JP6240147B2 - Photosensitive resin composition, method for producing cured film using the same, cured film, liquid crystal display device, and organic EL display device - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a method for producing a cured film, a cured film, an organic EL display device, and a liquid crystal display device. More specifically, a positive photosensitive resin composition suitable for forming a flattening 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 producing a cured film using the above.

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

  In addition to the properties of the cured film, such as insulating properties, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputtering suitability, the interlayer insulating film in the above display device is desired to have high transparency. Yes. For this reason, an attempt has been made to use an acrylic resin having excellent transparency as a film forming component. For example, those described in Patent Documents 1 to 3 are known.

JP 2011-209681 A JP 2009-288343 A JP 2008-286924 A

  However, in recent years, there has been a demand for a photosensitive resin composition that can improve chemical resistance and cured film adhesion while maintaining higher sensitivity. The present invention is intended to solve such problems, and provides a photosensitive resin composition capable of improving chemical resistance and cured film adhesion while maintaining higher sensitivity. The purpose is to do.

（一般式（ａ４−１）中、Ｒ⁴は水素原子またはメチル基を表し、Ｗは二価の連結基を表し、Ｚは一価の有機基を表す。）
＜３＞前記構成単位（ａ４）が下記一般式（ａ４−２）で表される、＜２＞に記載の感光性樹脂組成物。
一般式（ａ４−２）

（一般式（ａ４−２）中、Ｒ⁴は水素原子またはメチル基を表し、Yは二価の連結基を表し、Ｚは一価の有機基を表す。）
＜４＞前記構成単位(ａ２) に含まれる架橋性基が、エポキシ基、オキセタニル基および−ＮＨ−ＣＨ₂−ＯＲ（Ｒは炭素数１〜２０のアルキル基）から選ばれる少なくとも１種である、＜１＞〜＜３＞のいずれかに記載の感光性樹脂組成物。
＜５＞前記酸分解性基がアセタールの形で保護された構造を有する基である、＜１＞〜＜４＞のいずれか１項に記載の感光性樹脂組成物。
＜６＞前記構成単位（ａ１）が、下記一般式（Ａ２’）で表される繰り返し単位である、＜１＞〜＜５＞のいずれかに記載の感光性樹脂組成物。

（一般式（Ａ２’）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³は、アルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
＜７＞（１）＜１＞〜＜６＞のいずれかに記載の感光性樹脂組成物を基板上に塗布する工程、
（２）塗布された感光性樹脂組成物から溶剤を除去する工程、
（３）溶剤が除去された感光性樹脂組成物を活性光線で露光する工程、
（４）露光された感光性樹脂組成物を水性現像液で現像する工程、および、
（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程を含む、硬化膜の製造方法。
＜８＞前記現像工程後、ポストベーク工程前に、全面露光する工程を含む、＜７＞に記載の硬化膜の製造方法。
＜９＞＜１＞〜＜６＞のいずれかに記載の感光性樹脂組成物を硬化してなる硬化膜。
＜１０＞＜７＞または＜８＞に記載の硬化膜の製造方法で得られた硬化膜。
＜１１＞層間絶縁膜である、＜９＞または＜１０＞に記載の硬化膜。
＜１２＞＜９＞〜＜１１＞のいずれかに記載の硬化膜を有する、液晶表示装置または有機ＥＬ表示装置。As a result of the study by the present inventors under such circumstances, chemical resistance and cured film adhesion are maintained while maintaining high sensitivity by blending a structural unit having a blocked isocyanate group into the photosensitive resin composition. Found that it can be good. Although the following mechanism is not clear, by containing a polymer containing a structural unit having a blocked isocyanate group in the photosensitive resin composition, the affinity between the composition of the present invention and the interface of the base substrate is caused by the blocked isocyanate group. It is presumed that the adhesiveness of the cured film can be improved because the properties of the composition of the present invention and the base substrate are easily bonded. Moreover, the structural unit which has a block isocyanate group is uniformly distributed in the composition of this invention by making the photosensitive resin composition contain the structural unit which has a blocked isocyanate group as a polymer, The composition of this invention It is presumed that the group derived from the structural unit having a blocked isocyanate group is evenly distributed in the cured film obtained by curing the product, and the chemical resistance can be improved.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <12>.
<1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group (excluding a blocked isocyanate group and OH group) Or (2) a polymer having the structural unit (a1) and a polymer having the structural unit (a2),
(B) a photoacid generator,
(C) contains a solvent,
In the polymer component, at least one of a polymer having the structural unit (a1) and the structural unit (a2), a polymer having the structural unit (a1), and a polymer having the structural unit (a2). (A4) at least one structural unit having a blocked isocyanate group is contained,
(3) A photosensitive resin composition comprising at least one polymer containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2).
<2> The photosensitive resin composition according to <1>, wherein the structural unit (a4) is represented by the following general formula (a4-1).
Formula (a4-1)

(In general formula (a4-1), R ⁴ represents a hydrogen atom or a methyl group, W represents a divalent linking group, and Z represents a monovalent organic group.)
<3> The photosensitive resin composition according to <2>, wherein the structural unit (a4) is represented by the following general formula (a4-2).
Formula (a4-2)

(In general formula (a4-2), R ⁴ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and Z represents a monovalent organic group.)
<4> The crosslinkable group contained in the structural unit (a2) is at least one selected from an epoxy group, an oxetanyl group, and —NH—CH ₂ —OR (R is an alkyl group having 1 to 20 carbon atoms). <1>-<3> The photosensitive resin composition in any one of.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the structural unit (a1) is a repeating unit represented by the following general formula (A2 ′).

(In the general formula (A2 ′), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a simple group. Represents a bond or an arylene group.)
<7> (1) The process of apply | coating the photosensitive resin composition in any one of <1>-<6> on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) developing the exposed photosensitive resin composition with an aqueous developer, and
(5) The manufacturing method of a cured film including the post-baking process of thermosetting the developed photosensitive resin composition.
<8> The method for producing a cured film according to <7>, including a step of exposing the entire surface after the developing step and before the post-baking step.
<9> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <6>.
<10> A cured film obtained by the method for producing a cured film according to <7> or <8>.
<11> The cured film according to <9> or <10>, which is an interlayer insulating film.
<12> A liquid crystal display device or an organic EL display device having the cured film according to any one of <9> to <11>.

  According to the present invention, it is possible to provide a photosensitive resin composition capable of improving chemical resistance and cured film adhesion while maintaining high sensitivity.

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

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

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

The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is a polymer component (A) containing a polymer satisfying at least one of the following (1) and (2) ( Hereinafter, also referred to as (A) polymer component or (A) component).
(1) (a1) a structural unit having an acid group protected with an acid-decomposable group (hereinafter also referred to as structural unit (a1)), and (a2) a crosslinkable group (however, a blocked isocyanate group and OH) A polymer having a structural unit (excluding a group) (hereinafter also referred to as a structural unit (a2)), or (2) a weight having the structural unit (a1). A polymer having a coalescence and the structural unit (a2) (hereinafter also referred to as polymer (2)),
(B) a photoacid generator,
(C) contains a solvent,
In the polymer component (A), at least a polymer having the structural unit (a1) and the structural unit (a2), a polymer having the structural unit (a1), and a polymer having the structural unit (a2). 1 includes (a4) at least one structural unit having a blocked isocyanate group (hereinafter also referred to as structural unit (a4)),
(3) At least one polymer that includes the structural unit (a4) and does not include the structural unit (a1) and the structural unit (a2) (hereinafter also referred to as polymer (3)) is included.
The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition.
Hereinafter, the composition of the present invention will be described in detail.

<(A) Polymer component>
The composition of this invention contains at least one of the said polymer (1) and the said polymer (2) as (A) polymer component. The composition of the present invention includes a polymer having the structural unit (a1) and the structural unit (a2), a polymer having the structural unit (a1), and the structural unit in the polymer component (A). At least one of the structural units (a4) is contained in at least one of the polymers having (a2), or the polymer (3) is further contained in the polymer component (A).
The composition of this invention may contain polymers other than these as (A) polymer component.
The polymer component (A) in the present invention includes, in addition to the (1) polymer and / or the polymer (2), other polymers added as necessary, unless otherwise specified. means.

<< Structural Unit (a1) >>
The component (A) has at least a structural unit (a1) having a group in which an acid group is protected with an acid-decomposable group. When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). A functional group) or a group that is relatively difficult to be decomposed by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).

(A1) The structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group protected with an acid-decomposable group, or a protected phenolic group protected with an acid-decomposable group. A structural unit having a hydroxyl group is preferred.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in this order. To do.

<<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a group.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group as a structural unit which can be used for the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, (a1-1-1) used as a structural unit having a carboxyl group, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) ethylene The structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.

<<<<< (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. Examples include leuoxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid. For example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or unsaturated polyhydric carboxylic acid anhydride It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.

<<<<< (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride reacts a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, from the viewpoint of developability.

<<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable group can be used.
Among these acid-decomposable groups, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. Basic properties of the photosensitive resin composition, in particular, sensitivity and pattern shape, contact hole formation, photosensitive resin It is preferable from the viewpoint of the storage stability of the composition. Furthermore, it is more preferable from a viewpoint of a sensitivity that a carboxyl group is a protected carboxyl group protected in the form of the acetal represented with the following general formula (a1-10) among acid-decomposable groups. In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected carboxyl group is — (C═O) —O—CR ^101. The structure is R ¹⁰² (OR ¹⁰³ ).

（式（ａ１−１０）中、Ｒ¹⁰¹およびＲ¹⁰²は、それぞれ独立に水素原子またはアルキル基を表し、但し、Ｒ¹⁰¹とＲ¹⁰²とが共に水素原子の場合を除く。Ｒ¹⁰³は、アルキル基を表す。Ｒ¹⁰¹またはＲ¹⁰²と、Ｒ¹⁰³とが連結して環状エーテルを形成してもよい。）Formula (a1-10)

(In formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms, and R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.)

In the general formula (a1-10), R ^{101 to} R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched, or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

  The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

  The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, (alpha) -methylphenyl group, a naphthyl group etc. can be illustrated. Examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
As said alkoxy group, a C1-C6 alkoxy group is preferable, More preferably, it is C1-C4, and a methoxy group or an ethoxy group is more preferable.
In addition, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

In the general formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a silyl group, a cumenyl group, and a 1-naphthyl group.

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.

In the general formula (a1-10), it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10), a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph numbers 0037 to 0040 of JP2011-221494A.

（一般式（Ａ２’）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、少なくともＲ¹およびＲ²のいずれか一方がアルキル基またはアリール基であり、Ｒ³は、アルキル基またはアリール基を表し、Ｒ¹またはＲ²と、Ｒ³とが連結して環状エーテルを形成してもよく、Ｒ⁴は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
Ｒ¹およびＲ²がアルキル基の場合、炭素数は１〜１０のアルキル基が好ましい。Ｒ¹およびＲ²がアリール基の場合、フェニル基が好ましい。Ｒ¹およびＲ²は、それぞれ独立に、水素原子または炭素数１〜４のアルキル基が好ましい。
Ｒ³は、アルキル基またはアリール基を表し、炭素数１〜１０のアルキル基が好ましく、１〜６のアルキル基がより好ましい。
Ｘは単結合またはアリーレン基を表し、単結合が好ましい。The 1st preferable aspect of the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group is a structural unit represented by the following general formula.
General formula (A2 ')

(In the general formula (A2 ′), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a simple group. Represents a bond or an arylene group.)
When R ¹ and R ² are alkyl groups, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.

（式中、Ｒ¹²¹は水素原子または炭素数１〜４のアルキル基を表し、Ｌ¹はカルボニル基またはフェニレン基を表し、Ｒ¹²²〜Ｒ¹²⁸はそれぞれ独立に、水素原子または炭素数１〜４のアルキル基を表す。）
Ｒ¹²¹は水素原子またはメチル基が好ましい。
Ｌ¹はカルボニル基が好ましい。
Ｒ¹²²〜Ｒ¹²⁸は、水素原子が好ましい。The 2nd preferable aspect of the structural unit (a1-1) which has the protected carboxyl group protected by the said acid-decomposable group is a structural unit of the following general formula.

(Wherein R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ^{122 to} R ¹²⁸ each independently represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of
R ¹²¹ is preferably a hydrogen atom or a methyl group.
L ¹ is preferably a carbonyl group.
R ^{122 to} R ¹²⁸ are preferably a hydrogen atom.

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

<<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>>
The structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic component in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a hydroxyl group.

<<<< (a1-2-1) Structural unit having phenolic hydroxyl group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a structural unit in a hydroxystyrene-based structural unit and a novolac-based resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is, It is preferable from the viewpoint of sensitivity. Moreover, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.

（一般式（ａ１−２０）中、Ｒ²²⁰は水素原子またはメチル基を表し、Ｒ²²¹は単結合または二価の連結基を表し、Ｒ²²²はハロゲン原子または炭素数１〜５の直鎖または分岐鎖状のアルキル基を表し、ａは１〜５の整数を表し、ｂは０〜４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ²²²が２以上存在する場合、これらのＲ²²²は相互に異なっていてもよいし同じでもよい。）Formula (a1-20)

(In General Formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a straight chain having 1 to 5 carbon atoms or Represents a branched alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R ²²² is 2 or more, these R ²²² may be different or the same.)

In the general formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R ²²¹ represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R ²²¹ may be exemplified alkylene groups, specific examples R ²²¹ is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group, etc. are mentioned. Among these, it is preferable that R ²²¹ is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Moreover, although a represents the integer of 1-5, from the viewpoint of the effect of this invention and the point that manufacture is easy, it is preferable that a is 1 or 2, and it is more preferable that a is 1. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²²¹ is defined as the reference (first position).
R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
Specific examples include fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;

<<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
The acid-decomposable group that can be used for the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group has a protected carboxyl group protected with the acid-decomposable group. Similarly to the acid-decomposable group that can be used for the unit (a1-1), a known one can be used and is not particularly limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10). When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of the acetal represented by the general formula (a1-10), the entire protected phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R. The structure is ¹⁰² (OR ¹⁰³ ).
Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

Moreover, as a radically polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of acetal, for example, paragraph number 0042 of JP2011-215590A is disclosed. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.

  Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.

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

  Preferable specific examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group include the following structural units, but the present invention is not limited thereto.

<<< Preferred Aspect of Structural Unit (a1) >>>
When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1). The mol% is preferable, and 30 to 90 mol% is more preferable.
When the polymer containing the structural unit (a1) contains the following structural unit (a2), the single structural unit (a1) is contained in the polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, 3-70 mol% is preferable, and 10-60 mol% is more preferable. In particular, when the acid-decomposable group that can be used for the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, 20 to 50 mol% is preferable.

The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred when developing quickly. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred when developing quickly. Conversely, when it is desired to delay development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<< Structural Unit (a2) >>
The component (A) has a structural unit having (a2) a crosslinkable group (excluding a blocked isocyanate group and an OH group). The crosslinkable group in this invention is at least 1 sort (s) chosen from carboxylic acid or phenolic hydroxyl group, and the group which can start a crosslinking reaction above 90 degreeC, for example. However, the OH group is excluded from the crosslinkable group of the present invention because it has low crosslinking reactivity with the carboxylic acid and the phenolic hydroxyl group and cannot sufficiently improve the chemical resistance. Preferred embodiments of the structural unit having a crosslinking group include an epoxy group, an oxetanyl group, a group represented by —NH—CH ₂ —O—R (where R is an alkyl group having 1 to 20 carbon atoms), and an ethylenically unsaturated group. And a structural unit containing at least one selected from the group consisting of an epoxy group, an oxetanyl group, and —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms). It is preferably at least one selected from the group described above. Among them, in the photosensitive resin composition of the present invention, the component (A) preferably includes a structural unit containing at least one of an epoxy group and an oxetanyl group, and includes a structural unit containing an epoxy group. Is particularly preferred. In more detail, the following are mentioned.

<<< (a2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
The (A) polymer component preferably contains a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group.
The structural unit (a2-1) having an epoxy group and / or oxetanyl group is preferably a structural unit having an alicyclic epoxy group and / or oxetanyl group, and more preferably a structural unit having an oxetanyl group. preferable.
The structural unit (a2-1) having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and one or more epoxy groups and one It may have an oxetanyl group, two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy skeleton.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer containing a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.

Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraph Nos. 0034 to 0035 of Japanese Patent No. 4168443 and paragraph numbers 0011 to 0016 of JP-A No. 2001-330953. The (meth) acrylic acid ester having an oxetanyl group described in (1), and (meth) acrylic acid ester having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953 is particularly preferable. Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl, most preferred are (3-ethyloxetane-3-yl) methyl acrylate and (3-ethyloxetane-3-yl) methyl methacrylate. These structural units can be used individually by 1 type or in combination of 2 or more types.
As the structural unit (a2-1) having the epoxy group and / or oxetanyl group, the description in paragraph numbers 0053 to 0055 of JP2011-215590A can be referred to.

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

  In the present invention, an oxetanyl group is preferable from the viewpoint of sensitivity. From the viewpoint of transmittance (transparency), an alicyclic epoxy group and an oxetanyl group are preferred. As mentioned above, in this invention, as an epoxy group and / or an oxetanyl group, an alicyclic epoxy group and an oxetanyl group are preferable, and an oxetanyl group is especially preferable.

<<< (a2-2) Structural unit having an ethylenically unsaturated group >>>
As one of the structural unit (a2) having a crosslinking group, there may be mentioned a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a2-2)”). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms. A structural unit having a side chain is more preferred.

  Other (a2-2) Regarding the structural unit having an ethylenically unsaturated group, description of paragraph numbers 0077 to 0090 of JP2011-215580A and description of paragraph numbers 0013 to 0031 of JP2008-256974 can be referred to. The contents of which are incorporated herein by reference.

（上記式中、Ｒ¹は水素原子またはメチル基を表し、Ｒ²は炭素数１〜２０のアルキル基を表す。）
Ｒ²は、炭素数１〜９のアルキル基が好ましく、炭素数１〜４のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。
Ｒ²の具体例としては、メチル基、エチル基、ｎ−ブチル基、ｉ−ブチル基、シクロヘキシル基、およびｎ−ヘキシル基を挙げることができる。中でもｉ−ブチル基、ｎ−ブチル基、メチル基が好ましい。<<< constituent unit having a group represented by (a2-3) -NH—CH ₂ —O—R (where R is an alkyl group having 1 to 20 carbon atoms) >>
The copolymer used in the present invention is also preferably a structural unit (a2-3) having a group represented by —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms). By having the structural unit (a2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit (a2) is more preferably a structural unit having a group represented by the following general formula (1).
General formula (1)

(In the above formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)
R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

<<< Preferred Aspect of Structural Unit (a2) >>>
When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is 5 to 90 in the polymer containing the structural unit (a2). Mol% is preferable and 20-80 mol% is more preferable.
When the polymer containing the structural unit (a2) contains the structural unit (a1), the structural unit (a2) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, 3-70 mol% is preferable, and 10-60 mol% is more preferable.
In this invention, it is preferable to contain 3-70 mol% of structural units (a2) in all the structural units of (A) component irrespective of any aspect, and it is more preferable to contain 10-60 mol%. preferable.
Within the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency, chemical resistance and ITO sputtering resistance.

<< (a4) Structural Unit Having Blocked Isocyanate Group >>
The composition of the present invention includes (a4) a polymer containing a structural unit having a blocked isocyanate group, thereby improving chemical resistance and cured film adhesion (particularly cured film adhesion after the PCT test). be able to.
The following mechanism is not clear, but by blending a polymer containing a structural unit having a blocked isocyanate group in the photosensitive resin composition, the affinity between the composition of the present invention and the interface of the base substrate is caused by the blocked isocyanate group. It is presumed that the adhesiveness of the cured film can be improved because the properties of the composition of the present invention and the base substrate are easily bonded. Moreover, the structural unit which has a block isocyanate group is uniformly distributed in the composition of this invention by making the photosensitive resin composition contain the structural unit which has a blocked isocyanate group as a polymer, The composition of this invention It is presumed that the group derived from the structural unit having a blocked isocyanate group is evenly distributed in the cured film obtained by curing the product, and the chemical resistance can be improved.
In the present invention, the blocked isocyanate group is a protecting group obtained by reacting a compound having a hydrogen atom capable of reacting with an isocyanate group (usually called a blocking agent) to protect the isocyanate group. The introduced protecting group is a hydrogen atom removed from the blocking agent and is usually called a blocking group. For example, in the structure represented by A—C (═O) —NH—, A is a protecting group.

As the blocking agent used in the present invention, for example, the blocking agent described in paragraph 0009 of JP-A-5-186564, the blocking agent described in paragraph 0022 of JP-A-2002-275231 can be used, These contents are incorporated herein.
Specifically, compounds having a phenolic hydroxyl group such as phenol, naphthol, cresol, xylenol, halogen-substituted phenol; oxime compounds such as acetoxime, formaldoxime, cyclohexaneoxime, methylethylketoxime; pyrazole, methylpyrazole, dimethylpyrazole, etc. Compounds having a pyrazole structure of: alcohol compounds such as methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate, etc .; activity of ethyl acetoacetate, diethyl malonate, acetylacetone, etc. Compound having methylene; mercaptan compound such as alkyl mercaptan and aryl mercaptan; α-lactam, β-lactam Beam, .gamma.-lactam, lactam compounds such as δ- lactams, other imide compounds, imidazole compounds, primary amines, secondary amines, and the like.

The blocking group used in the present invention is preferably a group derived from a compound having a phenolic hydroxyl group, an oxime compound or an alcohol compound, more preferably a group derived from an oxime compound or an alcohol compound, and an oxime group. More preferred are groups derived from compounds.
In the polymer component (A) used in the present invention, at least one type of blocked isocyanate group may be included in the structural unit having one (a4) blocked isocyanate group, but two or more types are included. Moreover, it is more preferable that 1 type is included.
The upper limit of the number of blocked isocyanate groups in the structural unit having one blocked isocyanate group is not particularly defined, but for example, preferably 5 or less in the structural unit having one blocked isocyanate group, and one blocked isocyanate group It is more preferable that the number is 3 or less in the structural unit having, and 1 is particularly preferable.

（一般式（ａ４−１）中、Ｒ⁴は水素原子またはメチル基を表し、Ｗは二価の連結基を表し、Ｚは一価の有機基を表す。）As the structural unit (a4) having a blocked isocyanate group used in the present invention, a vinyl polymer is preferable, and a repeating unit represented by the following general formula (a4-1) is more preferable.
Formula (a4-1)

(In general formula (a4-1), R ⁴ represents a hydrogen atom or a methyl group, W represents a divalent linking group, and Z represents a monovalent organic group.)

In general formula (a4-1), W represents a divalent linking group. Examples of the divalent linking group include a linear, branched or cyclic alkylene group, —O—, —COO—, —S—, —NR—, —CO—, —NRCO—, —SO ₂ — and the like. And those composed of a combination of these groups. Here, R represents a hydrogen atom or a C1-C4 alkyl group, and a hydrogen atom is preferable. As the divalent linking group, — (CH ₂ ) _m — (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and a cyclic group having 5 to 10 carbon atoms. An alkylene group or a group composed of at least one of these groups and —O—, —COO—, —S—, —NH— and —CO— is preferable.

In general formula (a4-1), Z is a group (blocking group described above) that is eliminated by heating. Here, the group that is eliminated by heating refers to a group that is eliminated when heated at 90 to 250 ° C., for example.
In general formula (a4-1), Z is not particularly limited, but for example, a monovalent organic group is preferable. As a monovalent organic group, an alkyl group or an aryl group is mentioned, for example, The group which consists of a C1-C20 alkyl group, a C6-C20 aryl group, or these combination is preferable. Specific examples of such a monovalent organic group include —N═R ′, —OR ′, —NR ′, —SR ′, or at least one of these groups, —O—, —CO—, and —COOR ′. What consists of a combination with one is preferable. Here, R ′ is a straight chain having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms (preferably a straight chain having 1 to 7 carbon atoms, carbon A branched alkyl group having 3 to 7 carbon atoms or a cyclic alkyl group having 3 to 7 carbon atoms), an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), or an aryl group having 6 to 10 carbon atoms and the carbon number. Are preferably a combination of 1 to 10 alkylene groups.
When the monovalent organic group represents —NR ′, it is preferable that —NR ′ forms a heterocyclic structure. The hetero atom in the heterocyclic structure preferably contains a nitrogen atom, more preferably contains two or more nitrogen atoms, and more preferably contains two nitrogen atoms. As the heterocyclic structure, a 5- to 8-membered ring structure is preferable, and a 5- to 7-membered ring structure is more preferable. A condensed ring may be used, but a single ring is preferable. When the monovalent organic group represents -NR ', the substituent has a -CO group or an alkyl group (preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group). It is preferable.
In general formula (a4-1), the formula weight of Z is preferably 20 to 300, and more preferably 30 to 150. It is preferable that the formula amount of Z is not too large because unnecessary components of the final cured film can be reduced.
Here, the formula weight of Z means the mass of the Z portion per one structural unit having a blocked isocyanate group.

（一般式（ａ４−２）中、Ｒ⁴は水素原子またはメチル基を表し、Ｘはアリーレン基または−Ｃ（＝Ｏ）−基を表し、Ｙは二価の連結基を表し、Ｚは一価の有機基を表す。）As the structural unit (a4) having a blocked isocyanate group used in the present invention, a repeating unit represented by the following general formula (a4-1-2) is more preferable.
General formula (a4-1-2)

(In general formula (a4-2), R ⁴ represents a hydrogen atom or a methyl group, X represents an arylene group or —C (═O) — group, Y represents a divalent linking group, and Z represents one Represents a valent organic group.)

  In general formula (a4-2), X represents an arylene group or —C (═O) — group. When X is an arylene group, a phenylene group is preferred.

In General Formula (a4-2), Y represents a divalent linking group. Examples of the divalent linking group include a linear, branched or cyclic alkylene group, —O—, —COO—, —S—, —NR—, —CO—, —NRCO—, —SO ₂ — and the like. And those composed of a combination of these groups. Here, R represents a hydrogen atom or a C1-C4 alkyl group, and a hydrogen atom is preferable. As the divalent linking group, — (CH ₂ ) _m — (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and a cyclic group having 5 to 10 carbon atoms. An alkylene group or a group composed of at least one of these groups and —O—, —COO—, —S—, —NH— and —CO— is preferable.
In General Formula (a4-2), Z represents a monovalent organic group, and is synonymous with Z in General Formula (a4-2) described above, and a preferable range is also the same.

（一般式（ａ４−２）中、Ｒ⁴は水素原子またはメチル基を表し、Ｙは二価の連結基を表し、Ｚは一価の有機基を表す。）
一般式（ａ４−２）中、ＹおよびＺは、上述した一般式（ａ４−１−２）中のＹおよびＺと同義であり、好ましい範囲も同様である。As the structural unit (a4) having a blocked isocyanate group used in the present invention, a repeating unit represented by the following general formula (a4-2) is more preferable.
Formula (a4-2)

(In general formula (a4-2), R ⁴ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and Z represents a monovalent organic group.)
In General Formula (a4-2), Y and Z have the same meanings as Y and Z in General Formula (a4-1-2) described above, and preferred ranges are also the same.

Specific examples of the structural unit (a4) having a blocked isocyanate group are listed below, but the present invention is not limited thereto. In the following specific examples, Rx is a hydrogen atom or a methyl group.

<<< Preferred Aspect of Structural Unit (a4) >>>
When the structural unit (a4) is contained in the polymer (1), the structural unit (a4) is preferably 0.1 to 30 mol% in the polymer containing the structural unit (a4), 20 mol% is more preferable, and 2 to 15 mol% is more preferable.
When the structural unit (a4) is contained in the polymer (2), that is, the structural unit (a4) is a polymer having the structural unit (a1) or a polymer having the structural unit (a2). When included in at least one, the structural unit (a4) is preferably 0.1 to 40 mol%, more preferably 1 to 30 mol%, and more preferably 2 to 25 mol in the polymer containing the structural unit (a4). % Is more preferable.
When the structural unit (a4) is contained in the polymer (3), the structural unit (a4) is preferably 1 to 90 mol%, preferably 2 to 70 mol in the polymer containing the structural unit (a4). % Is more preferable, and 3 to 50 mol% is more preferable.
In this invention, it is preferable to contain 0.1-30 mol% of structural units (a4) among all the structural units of (A) component irrespective of any aspect, and 1-20 mol% is contained. Is more preferable, and it is more preferable to contain 2-15 mol%. Moreover, content of a structural unit (a4) can also be 5 mol% or less among all the structural units of (A) component, and in this case, there exists an advantage that it is excellent in the residual film rate after a post-baking.
Within the above numerical range, the cured film obtained from the composition of the present invention has good transparency, chemical resistance and ITO sputtering resistance.

  When the structural unit (a4) is contained in at least one of the polymer (1), the polymer (2), and the polymer (3), the formula weight of the structural unit (a4) is 100. It is preferable that it is -500, and it is more preferable that it is 150-400.

The polymer containing the structural unit (a4) has, for example, a molecular weight of 8000 or more, preferably 9000 or more. Moreover, the upper limit of the molecular weight of the polymer containing the structural unit (a4) is not particularly limited, but is preferably 50000 or less, and more preferably 30000 or less.
By setting the molecular weight of the polymer containing the structural unit (a4) to 8000 or more, the structural unit having a blocked isocyanate group is more uniformly distributed in the composition of the present invention, and the composition of the present invention is cured. Even in the film, the group derived from the structural unit having a blocked isocyanate group is more uniformly distributed, and it is estimated that the chemical resistance effect of the present invention is more effectively exhibited over the entire film.
The composition of the present invention preferably contains substantially no polymer containing the structural unit (a4) having a molecular weight of less than 8000, and the content of the polymer containing the structural unit (a4) having a molecular weight of less than 8000. Is more preferably 0% by mass.

<< (a3) Other structural units >>
In the present invention, the component (A) may have another structural unit (a3) in addition to the structural unit (a1), the structural unit (a2), and the structural unit (a4). Good. The structural unit (a3) may be contained in any one of the polymer (1), the polymer (2), and the polymer (3). In addition to the polymer (1), the polymer (2) and the polymer (3), the composition of the present invention contains another polymer component having the structural unit (a3). May be. When the polymer (1), the polymer (2) and the polymer (3) contain other polymer having the structural unit (a3), the amount of the polymer component is In the coalescence component, it is preferably 60% by mass or less, more preferably 40% by mass or less, and further preferably 20% by mass or less.

  There is no restriction | limiting in particular as a monomer used as the said structural unit (a3), For example, styrenes, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid arylester, unsaturated dicarboxylic acid List acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds Can do. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes said structural unit (a3) can be used individually or in combination of 2 or more types.

  Hereinafter, preferred embodiments of the polymer component of the present invention will be described, but it is needless to say that the present invention is not limited to these.

(First embodiment)
The aspect in which the polymer (1) further has one or more structural units (a3).
(Second Embodiment)
The aspect in which the polymer having the structural unit (a1) in the polymer (2) further has one or more structural units (a3).
(Third embodiment)
The aspect in which the polymer having the structural unit (a2) in the polymer (2) further includes one or more structural units (a3).
(Fourth embodiment)
The aspect in which the polymer (3) further includes one or more structural units (a3).

(Fifth embodiment)
In any one of the first to fourth embodiments, the structural unit (a3) includes a structural unit containing at least an acid group.

(Sixth embodiment)
In any one of the first to fourth embodiments, as the structural unit (a3), at least one of the polymer (1), the polymer (2), and the polymer (3) is at least The aspect containing the structural unit containing an acid group.

(Seventh embodiment)
The aspect which has a polymer which has the said structural unit (a3) separately from the said polymer (1), the said polymer (2), and the said polymer (3). Examples of the structural unit (a3) in this case include a structural unit containing an acid group and a structural unit having a crosslinkable group other than the structural unit (a2).

(Eighth embodiment)
The form which consists of two or more combinations of the said 1st-7th embodiment.

  Specifically, the structural unit (a3) is styrene, methyl styrene, hydroxy styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy Benzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, ethylene glycol monoacetate It can be mentioned a structural unit due acetate mono (meth) acrylate. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

  In addition, a group having a styrene or an aliphatic cyclic skeleton as the structural unit (a3) is preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and the like.

  Furthermore, (meth) acrylic acid alkyl ester is preferable as the structural unit (a3) from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable. In the structural unit constituting the polymer (A), the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.

The structural unit (a3) preferably contains an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . For example, the compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.

  In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.

  The structural unit containing an acid group is preferably 1 to 80 mol%, more preferably 1 to 50 mol%, still more preferably 5 to 40 mol%, and particularly preferably 5 to 30 mol% of the structural units of all polymer components. 5 to 20 mol% is particularly preferable.

  In the present invention, apart from the polymer component (1) or the polymer component (2) or the polymer component (3), the structural unit (a1), the structural unit (a2), and the A polymer having other structural unit (a3) without including the structural unit (a4) may be included.

  As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.

For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
These polymers may contain only 1 type and may contain 2 or more types.

  SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON are commercially available as these polymers. UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncry 690, Joncry 678, Joncry 67, Joncry 586 (above, made by BASF) You can also.

<< (A) Molecular Weight of Polymer >>
(A) The molecular weight of the polymer is a weight average molecular weight in terms of polystyrene, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 50,000. 000 range. Various characteristics are favorable in the range of said numerical value. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< (A) Polymer Production Method >>
Various methods for synthesizing the component (A) are known. For example, at least the structural units represented by the structural unit (a1) and the structural unit (a3) are formed. Therefore, it can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer used for the purpose in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
(A-1) The polymer preferably contains 50 mol% or more, and 80 mol% or more of the structural units derived from (meth) acrylic acid and / or its ester with respect to all the structural units. More preferred.

  The photosensitive resin composition of the present invention preferably contains the component (A) in a proportion of 50 to 99.9 parts by mass and in a proportion of 70 to 98 parts by mass with respect to 100 parts by mass of the total solid content. More preferred.

<(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. Most preferred are photoacid generators that generate.

  Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A. It can be illustrated.

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

（一般式（Ｂ１）中、Ｒ²¹は、アルキル基またはアリール基を表す。波線は他の基との結合を表す。）General formula (B1)

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

Any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group for R ²¹ is a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group, etc.). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate structure represented by the general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).

（式（Ｂ２）中、Ｒ⁴²は、アルキル基またはアリール基を表し、Ｘは、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍ４は、０〜３の整数を表し、ｍ４が２または３であるとき、複数のＸは同一でも異なっていてもよい。）

(In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 represents 2 or When X is 3, the plurality of X may be the same or different.)

Preferred ranges of R ^42, the same as the preferable range of the R ^21.
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

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

（式（Ｂ３）中、Ｒ⁴³は式（Ｂ２）におけるＲ⁴²と同義であり、Ｘ¹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、シアノ基またはニトロ基を表し、ｎ４は０〜５の整数を表す。）

(In formula (B3), R ⁴³ has the same meaning as R ⁴² in formula (B2), and X ¹ is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano A group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
As n4, 0-2 are preferable and 0-1 are especially preferable.

  As specific examples of the compound represented by the general formula (B1-3) and preferable examples of the oxime sulfonate compound, description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to. Incorporated in the description.

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

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. ^R102 represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ₂ —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ^{105 to} R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ^{121 to} R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ^{121 to} R ¹²⁴ may be bonded to each other to form a ring.
As R ^{121 to} R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and an embodiment in which at least two of R ^{121 to} R ¹²⁴ are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R ^{121 to} R ¹²⁴ are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.

  The compound represented by the general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.

  Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include the compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to 1). b-34), but the present invention is not limited thereto.

  In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (B1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.

（一般式（ＯＳ−３）〜一般式（ＯＳ−５）中、Ｒ²²、Ｒ²⁵およびＲ²⁸はそれぞれ独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ²³、Ｒ²⁶およびＲ²⁹はそれぞれ独立に水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ²⁴、Ｒ²⁷およびＲ³⁰はそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、Ｘ¹〜Ｘ³はそれぞれ独立に酸素原子または硫黄原子を表し、ｎ¹〜ｎ³はそれぞれ独立に１または２を表し、ｍ¹〜ｍ³はそれぞれ独立に０〜６の整数を表す。）

(In the general formula (OS-3) to general formula (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ^{1 to} X ³ each independently represents an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represents 1 or 2, and m ^{1 to} m ³ each independently represents an integer of 0 to 6 Represents.)

  Regarding the general formulas (OS-3) to (OS-5), for example, the description of paragraph numbers 0098 to 0115 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification.

  Moreover, the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is described in, for example, the general formula (OS-6) to paragraph 0117 described in JP2012-163937A. A compound represented by any of (OS-11) is particularly preferred, the contents of which are incorporated herein.

  Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.

  Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.

  In the photosensitive resin composition of the present invention, (B) the photoacid generator is based on 100 parts by mass of all resin components (preferably a solid content, more preferably a total of copolymers) in the photosensitive resin composition. 0.1 to 10 parts by mass is preferably used, and 0.5 to 10 parts by mass is more preferably used. Two or more kinds can be used in combination.

<(D) Solvent>
The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and optional components described below are dissolved in the solvent (D).
As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. Specific examples of the (D) solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and the paragraph numbers of JP2012-194290A. Examples include the solvents described in 0167 to 0168, the contents of which are incorporated herein.

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

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

  The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, and 60 to 90 parts by mass with respect to 100 parts by mass of the total resin components in the photosensitive resin composition. More preferably it is.

<Other ingredients>
In addition to the above-mentioned components, other crosslinking agents, alkoxysilane compounds, sensitizers, basic compounds, surfactants and antioxidants are preferably added to the photosensitive resin composition of the present invention as necessary. Can do. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added. Moreover, as these compounds, the description of paragraph number 0201-0224 of Unexamined-Japanese-Patent No. 2012-88459 can also be considered, for example, The content of these is integrated in this-application specification.

Other crosslinking agent It is preferable that the photosensitive resin composition of this invention contains other crosslinking agents other than an alicyclic epoxy compound as needed. By adding a crosslinking agent other than the alicyclic epoxy compound, the cured film obtained from the photosensitive resin composition of the present invention can be made stronger.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat (excluding the polymer component (A) above). 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 a compound having at least one ethylenically unsaturated double bond, A blocked isocyanate compound different from the structural unit (a4) having a blocked isocyanate group to be used can be added.
It is preferable that the addition amount of the crosslinking agent in the photosensitive resin composition of this invention is 0.01-50 mass parts with respect to 100 mass parts of total solids of the photosensitive resin composition, 0.1-30 It is more preferable that it is a mass part, and it is still more preferable that it is 0.5-20 mass parts. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used in combination, and in that case, the content is calculated by adding all the crosslinking agents.

<Low molecular crosslinkable compound>
Specific examples of the low molecular crosslinking compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.

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

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

  As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.

  Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.

  As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A and compounds having at least one ethylenically unsaturated double bond are also preferably used. The contents of which are incorporated herein by reference. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

Alkoxysilane Compound The photosensitive resin composition of the present invention may contain an alkoxysilane compound. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. As for carbon number of the alkoxy group which an alkoxysilane compound has, 1-5 are preferable.
The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.

Moreover, the compound represented by the following general formula is also preferably employable.
_{^{(R 1) 4-n -Si-}} (OR 2) n
In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms having no reactive group, R ² is an alkyl group or a phenyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 3 It is.
Specific examples thereof include the following compounds.

  In the above, Ph is a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and known compounds can be used.
As for content of the alkoxysilane compound in the photosensitive resin composition of this invention, 0.1-30 mass parts is preferable with respect to 100 mass parts of total solids in the photosensitive composition, 0.5-20 mass parts Is more preferable.

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

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

The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass, and 10 to 500 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition. It is more preferable that it is 50-200 mass parts.
Two or more kinds can be used in combination.

Basic Compound The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A-2011-221494, paragraphs 0204 to 0207, and the contents thereof are incorporated in the present specification.

  The basic compounds that can be used in the present invention may be used singly or in combination of two or more.

  Content of the basic compound in the photosensitive resin composition of this invention is 0.001-3 mass parts with respect to 100 mass parts of total solids in the photosensitive resin composition, when another basic compound is included. It is preferable that it is 0.005-1 mass part.

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

（式（Ｉ−１）中、Ｒ⁴⁰¹およびＲ⁴⁰³はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ⁴⁰²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴⁰⁴は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。）Formula (I-1)

(In Formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or C 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 mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. A numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 to 18 and s represents an integer of 1 to 10)

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

Formula (I-2)

  The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, based on 100 parts by mass of the total solid content in the photosensitive resin composition, and is 0.001 to 10 masses. More preferably, it is 0.01-3 mass parts.

Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing film thickness, with phenol-based antioxidants being the most preferred. preferable. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, the contents of which are incorporated herein. Preferred commercial products include ADK STAB AO-60, ADK STAB AO-80, IRGANOX 1726, IRGANOX 1035, and IRGANOX 1098.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

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

[Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, the description of paragraph numbers 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.

A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition from the viewpoint of sensitivity and residual film ratio. 1-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.
In addition, as other additives, a thermal radical generator described in paragraph Nos. 0120 to 0121 of JP2012-8223A, a nitrogen-containing compound and a thermal acid generator described in WO2011 / 136604A1, can be used. Is incorporated herein by reference.

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

[Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate;
(2) A step of removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.

In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound These substrates which may be mentioned are less if used while the above embodiment, normally, depending on the form of the final product, for example, multi-layered structure such as a TFT element is formed.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 μm.
Furthermore, before applying the composition used in the present invention to the substrate, it is possible to apply a so-called pre-wet method as described in JP-A-2009-145395.

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

In the exposure step (3), the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, and g-line (436 nm), i-line (365 nm), h-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mj / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, PEB is not necessarily performed. A positive image can also be formed by development.

In the developing step (4), a polymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide.
The pH of the developer is preferably 10.0 to 14.0.
The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid piling method and a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and crosslinked with an epoxy group, a crosslinking agent, etc. A cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on a hot plate, 30 to 120 minutes for an oven. It is preferable to By proceeding with such a crosslinking reaction, it is possible to form a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, and the crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

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

[Curing film]
The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the manufacturing method of the cured film of this invention.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.

[Liquid Crystal Display]
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. An apparatus can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be taken by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. -346054 can be used as the organic insulating film (212).
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, 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 conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and can be used as the second interphase insulating film (48) of JP 2011-145686 A or the interphase insulating film (520) of JP 2009-258758 A.

[Organic EL display device]
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

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

  Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4A of 9793, and the bank layer (221) and third interlayer insulating film (216b) described in FIG. 10 of JP 2010-27591A. ), Second interlayer insulating film (125) and third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14).

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

In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MACHOE: 1- (cyclohexyloxy) ethyl methacrylate MATHP: tetrahydro-2H-pyran-2-yl methacrylate GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)
PGME Propylene glycol monomethyl ether (Japan emulsifier)
MEDG diethylene glycol ethyl methyl ether): Hisolv EDM (manufactured by Toho Chemical Industry Co., Ltd.)

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

ＭＯＩ−ＢＰ：(昭和電工製)

Monomer MOI-BM having blocked isocyanate groups: (Showa Denko)

MOI-BP: (Made by Showa Denko)

[Synthesis of a4-1]
Commercially available Karenz AOI (manufactured by Showa Denko Co., Ltd.)) (42.3 g, 0.30 mol) and methyl ethyl ketoxime (27 g, 0.31 mol), bismuth tris (2-ethylhexanoate) (manufactured by Nitto Kasei Corporation, Neostan U-600, Bi content 18.0 to 19.0%) (0.1 g) and tetrahydrofuran (200 g) were added at room temperature, and the mixture was heated to 60 ° C. and stirred for 5 hours.
After cooling to room temperature, 500 ml of water was added to the reaction solution, and the organic layer was extracted with 200 ml of ethyl acetate. Magnesium sulfate was added to the obtained organic layer for dehydration, and after filtration, the filtrate was concentrated under reduced pressure to obtain 62.3 g (yield: 91.0%) of compound a4-1.
¹ H-NMR spectrum (300 MHz, CDCl ₃ ). δ = 6.65 (brs, 1H), 6.45 (d, 1H), 6.19 (dd, 1H), 5.83 (d, 1H), 4.31 (t, 2H), 3.59 (M, 2H), 2.49 (q, 2H), 2.02 (s. 3H), 1.18 (t, 3H).
[Synthesis of a4-2 to a4-12]
a4-2 to a4-12 were also synthesized in the same manner as a4-1.

<Synthesis Example of Polymer A-1>
PGMEA (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MATH (amount to be 30 mol% in all monomer components), GMA (amount to be 30 mol% in all monomer components), MOI-BM (10 mol% in all monomer components) in the solution Amount), MAA (amount to be 10 mol% in all monomer components), MMA (amount to be 20 mol% in all monomer components), V-65 (total 100 mol% of all monomer components) And 4 mol%) was dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, a polymer A-1 was obtained. The ratio of the total amount of PGMEA and other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared.
<Synthesis Example of Polymers A-2 to A-25>
Monomers and the like were changed as shown in the following table, and other polymers were synthesized. In the table below, PGMEA was used for all polymerization solvents A2 to A23, MEDG was used for the polymerization solvent A-24, and PGME was used for the polymerization solvent A-25. The solid content concentration was 40 parts by mass.

<Adjustment of photosensitive resin composition>
The polymer component, photoacid generator, alkoxysilane compound, crosslinking agent, sensitizer, basic compound, surfactant and other components were added to PGMEA so that the solid content ratio shown in the following table was obtained. The resulting mixture was dissolved and mixed until the concentration reached%, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various Examples and Comparative Examples. In addition, the addition amount in the following table | surface is a mass part.

  The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.

(Polymer component)
A-1 to A-25: Polymer described above

Ｂ−３：ＰＡＩ１０１（みどり化学（株）製）

Ｂ−４：下記の化合物

(Photoacid generator)
B-1: DTS-105, (triarylsulfonium salt) (manufactured by Midori Chemical Co., Ltd.)
B-2: CGI 1397 (manufactured by BASF Japan Ltd.)

B-3: PAI101 (manufactured by Midori Chemical Co., Ltd.)

B-4: The following compound

[Synthesis of B-4]
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated. The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain B-4 (2.3 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-4 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

(Sensitizer)
E-1: Dibutoxyanthracene having the following structure (manufactured by Kawasaki Kasei Co., Ltd.)

(Crosslinking agent)
F-1: JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol type epoxy compound)
F-2: JER828 (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol type epoxy compound)

(Alkoxysilane compound)
G-1: γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-2: Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Basic compound)
H-1: Diazabicyclononene (manufactured by Tokyo Chemical Industry Co., Ltd.)
H-2: 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
H-3: The following compound

(Surfactant)
I-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)

(Antioxidant)
J-1: Irganox 1098 (BASF)

<Evaluation of sensitivity>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a hot plate at 95 ° C. for 140 seconds to evaporate the solvent. A photosensitive resin composition layer having a thickness of 4.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (extra high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The optimum i-line exposure (Eopt) when resolving a 5 μm hole by these operations was taken as the sensitivity. C and above are practical levels.
A: 20mJ / cm ² less B: 20mJ / cm ² or more, 40 mJ / cm ² less than C: 40mJ / cm ² or more, 80 mJ / cm ² less than D: 80mJ / cm ² or more, 160 mJ / cm ² less than E: 160 mJ / cm ² or more

<Evaluation of chemical resistance (stripping solution resistance)>
After each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 4 A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
The obtained photosensitive resin composition layer is subjected to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
The cured film was immersed in monoethanolamine at 60 ° C. for 5 minutes, the film was pulled up and the liquid on the surface was wiped off, and the film thickness was measured immediately. The film thickness before immersion was compared with the film thickness after immersion, and the increased ratio was expressed in percent. The results are shown in the table below. The smaller the numerical value, the better the peeling liquid resistance of the cured film, and A or B is a practical level.
Swell ratio (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100
A: 100% or more and less than 105% B: 105% or more and less than 110% C: 110% or more D: 115% or more

<Evaluation of chemical resistance (NMP resistance)>
After each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 4 A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
The obtained photosensitive resin composition layer is subjected to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
The cured film was immersed in NMP at 80 ° C. for 10 minutes, and after the film was pulled up and the liquid on the surface was wiped off, the film thickness was measured immediately. The film thickness before immersion was compared with the film thickness after immersion, and the increased ratio was expressed in percent. The results are shown in the table below. The smaller the numerical value, the better the NMP resistance of the cured film, and A or B is a practical level.
Swell ratio (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100
A: 100% or more and less than 105% B: 105% or more and less than 110% C: 110% or more D: 115% or more

<Evaluation of cured film adhesion after PCT test>
After each photosensitive resin composition is slit-coated on an ITO (indium tin oxide) substrate, Mo (molybdenum) substrate, titanium (Ti) substrate, aluminum (Al) substrate, and copper (Cu) substrate, 90 ° C./120 The solvent was removed by heating on a second hot plate to form a photosensitive resin composition layer having a thickness of 4.0 μm. The obtained photosensitive resin composition layer is subjected to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. This cured film was treated for 150 hours under the conditions of a temperature of 121 ° C., a humidity of 100%, and a pressure of 2.1 atm using an unsaturated super accelerated life test apparatus PC-304R8 (manufactured by Hirayama Seisakusho). Using a cutter, the obtained cured film was cut at 1 mm intervals vertically and horizontally, and a tape peeling test was performed using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred to the back surface of the tape. The results are shown in the following table. The smaller the numerical value, the higher the adhesion to the base substrate, and A, B, or C is a practical level.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 3% C: The transferred area is 3% or more and less than 5% D: The transferred area is 5% or more

  As is clear from the above results, the photosensitive resin composition of the present invention was excellent in sensitivity, excellent in chemical resistance after thermosetting and post-PCT substrate adhesion, and both were above the practical level. On the other hand, the photosensitive resin composition of the comparative example was out of the practical level in chemical resistance or post-PCT substrate adhesion.

<Example 28>
Example 25 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The evaluation of sensitivity was the same level as in Example 1.

<Example 29>
Example 29 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure machine and 355 nm laser exposure was performed. Here, as the 355 nm laser exposure machine, “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.
The evaluation of sensitivity was the same level as in Example 1.

<Example 30>
In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

<Example 31>
A liquid crystal display device similar to that of Example 30 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit coating method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 30.

<Example 32>
Example 32 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a UV-LED light source exposure machine. The evaluation of sensitivity was the same level as in Example 1.

  As described above, it was found that the photosensitive resin compositions of the examples were excellent in the shape of the formed pattern regardless of the substrate and the exposure machine.

<Example 33>
A liquid crystal display device similar to that of Example 32 was changed to obtain the same liquid crystal display device. That is, after the photosensitive resin composition of Example 1 was applied by a slit and spin method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 27.

<Example 34>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C./30 minutes.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

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

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

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

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 (10)

(A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having an acid group protected by an acid-decomposable group, and (a2) a structural unit having a crosslinkable group (excluding a blocked isocyanate group and OH group) Or (2) a polymer having the structural unit (a1) and a polymer having the structural unit (a2),
(B) a photoacid generator,
(C) contains a solvent,
In the polymer component, at least one of a polymer having the structural unit (a1) and the structural unit (a2), a polymer having the structural unit (a1), and a polymer having the structural unit (a2). (A4) at least one structural unit having a blocked isocyanate group is contained,
(3) including at least one polymer including the structural unit (a4) and not including the structural unit (a1) and the structural unit (a2);
The photosensitive resin composition by which the said structural unit (a4) is represented by the following general formula (a4-1).
Formula (a4-1)

(In General Formula (a4-1), R ⁴ represents a hydrogen atom or a methyl group, W represents a divalent linking group, Z represents —N═R ′ , —SR ′, a heterocyclic group containing a nitrogen atom. Or a group consisting of a combination of these groups and at least one of -O-, -CO- and -COOR ',
The heterocyclic group containing a nitrogen atom is a heterocyclic group containing a nitrogen atom in which the nitrogen atom is bonded to the carbonyl group (—C (═O) —) side in the general formula (a4-1).
R ′ in —SR ′ and —COOR ′ is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a carbon number Represents a group consisting of an aryl group having 6 to 10 carbon atoms, or a combination of an aryl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms,
R ′ in —N═R ′ is a linear alkyl group having 1 to 10 carbon atoms including a carbon atom bonded to a nitrogen atom by a double bond, a branched alkyl group having 3 to 10 carbon atoms, or A cyclic alkyl group having 3 to 10 carbon atoms is represented. ) The photosensitive resin composition of Claim 1 by which the said structural unit (a4) is represented by the following general formula (a4-2).
Formula (a4-2)

(In General Formula (a4-2), R ⁴ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, Z represents —N═R ′ , —SR ′, a heterocyclic group containing a nitrogen atom. Or a group consisting of a combination of these groups and at least one of -O-, -CO- and -COOR ',
The heterocyclic group containing a nitrogen atom is a heterocyclic group containing a nitrogen atom in which the nitrogen atom is bonded to the carbonyl group (—C (═O) —) side in the general formula (a4-2),
R ′ in —SR ′ and —COOR ′ is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a carbon number Represents a group consisting of an aryl group having 6 to 10 carbon atoms, or a combination of an aryl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms,
R ′ in —N═R ′ is a linear alkyl group having 1 to 10 carbon atoms including a carbon atom bonded to a nitrogen atom by a double bond, a branched alkyl group having 3 to 10 carbon atoms, or A cyclic alkyl group having 3 to 10 carbon atoms is represented. ) Crosslinkable group contained in the structural unit (a2) is an epoxy group, an oxetanyl group and _-NH-CH 2 -OR (R is an alkyl group having 1 to 20 carbon atoms) is at least one selected from claims 3. The photosensitive resin composition according to 1 or 2. The photosensitive resin composition according to any one of claims 1 to 3, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal. The photosensitive resin composition of any one of Claims 1-4 whose said structural unit (a1) is a repeating unit represented by the following general formula (A2 ').

(In general formula (A2 ′), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single group. Represents a bond or an arylene group.) (1) The process of apply | coating the photosensitive resin composition of any one of Claims 1-5 on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) developing the exposed photosensitive resin composition with an aqueous developer, and
(5) The manufacturing method of a cured film including the post-baking process of thermosetting the developed photosensitive resin composition. The manufacturing method of the cured film of Claim 6 including the process of exposing the whole surface after the said image development process and before a post-baking process. The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-5. The cured film according to claim 8, which is an interlayer insulating film. A liquid crystal display device or an organic EL display device having the cured film according to claim 8.

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