JP5715967B2 - Positive photosensitive resin composition, method for forming cured film, cured film, liquid crystal display device, and organic EL display device - Google Patents

Description

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

  In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. As a material for forming an interlayer insulating film, a photosensitive resin composition is widely used because a material having a small number of steps for obtaining a required pattern shape and sufficient flatness is preferable (Patent Documents). 1 and 2).

  Among the electronic components, for example, a TFT type liquid crystal display element has a transparent electrode film (ITO) formed on the interlayer insulating film, and a metal such as molybdenum (Mo) or titanium (Ti) on the transparent electrode film (ITO). Therefore, the interlayer insulating film is exposed to high temperature conditions in the transparent electrode film forming process, or the resist used for forming the electrode pattern is formed. Since it will be exposed to peeling liquid and NMP (N-methylpyrrolidone) used at the time of liquid crystal aligning film formation, sufficient tolerance with respect to these is required.

  In addition, if the interlayer insulating film has poor adhesion to the transparent electrode film or the wiring (metal) formed on the transparent electrode film, the display on the panel is liable to be defective. Is also required. Since the interlayer insulating film may be subjected to a dry etching process, sufficient resistance to dry etching is also required (see Patent Document 2 and Patent Document 3).

As a highly sensitive photosensitive resin composition for an interlayer insulating film, for example, Patent Document 4 includes (A1) a resin containing a structural unit having an acid dissociable group and (A3) an epoxy group or an oxetane group. A resin containing a structural unit and an acid-dissociable group, and (B) a positive photosensitive resin composition containing a compound that generates an acid upon irradiation with actinic rays or radiation, or (A1) having an acid-dissociable group A positive electrode for forming an interlayer insulating film containing a resin containing a structural unit, (A2) a resin containing a structural unit having an epoxy group or an oxetane group, and (B) a compound that generates an acid upon irradiation with actinic rays or radiation Type photosensitive resin compositions have been proposed.
Patent Document 5 discloses (A1) a resin containing a structural unit having an acid-dissociable group, and (A2) a polymer or copolymer having a structural unit derived from an epoxy group-containing radical polymerizable monomer. (B) A positive photosensitive resin composition comprising a compound having two or more epoxy groups in a molecule and (C) a compound capable of generating an acid upon irradiation with actinic rays having a wavelength of 300 nm or more. Proposed.
Furthermore, in Patent Document 6, (A) (a1) a norbornene compound having an acetal structure or a ketal structure or a (meth) acrylate compound having an acetal or ketal structure, (a2) a structural unit having a specific crosslinking group, And (a3) a copolymer comprising an olefinic unsaturated compound other than (a1) and (a2), and (B) formation of an interlayer insulating film containing a compound that generates an acid having a pKa of 4.0 or less upon irradiation with radiation. Radiation-sensitive resin compositions for use have been proposed.

JP 2001-354822 A JP 2000-241832 A JP 2005-345757 A Japanese Patent No. 4637221 Japanese Patent No. 4676542 Japanese Patent No. 4207604

  However, the photosensitive resin compositions proposed in Patent Documents 4 to 6 are not highly resistant to a resist stripping solution or N-methylpyrrolidone (NMP) used after the formation of an interlayer insulating film. Since the adhesion to films and metals is poor and the resistance to dry etching is not high, display defects in liquid crystal display devices are likely to occur, and improvements have been demanded.

The present invention has been made in view of the above circumstances, and solves the following problems.
That is, the problems to be solved by the present invention are high sensitivity, high resistance to a stripping solution and NMP, good adhesion to a transparent electrode film and metal, and excellent dry etching resistance. A positive photosensitive resin composition capable of obtaining a cured film in which display defects are unlikely to occur, a cured film obtained by curing the photosensitive resin composition, a method for forming the same, and an organic EL provided with the cured film A display device and a liquid crystal display device are provided.

The above-described problems of the present invention have been solved by means described in the following <1>, <12>, <15>, <17> or <18>. It is described below together with <2> to <11>, <13>, <14> and <16> which are preferred embodiments.
<1> (Component A) a copolymer having at least (a1) a structural unit having a residue in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group, (Component B) A copolymer having at least (b1) a structural unit having an acid group and (b2) a structural unit having a crosslinkable group, without a structural unit having a residue in which the acid group is protected with an acid-decomposable group; A positive photosensitive resin composition comprising (Component C) a photoacid generator and (Component D) a solvent;
<2> The positive photosensitive resin composition according to <2>, wherein the structural unit (a1) is a structural unit having a residue in which a carboxyl group is protected in the form of an acetal or a ketal.
<3> The positive photosensitive resin composition according to <1> or <2> above, wherein the structural unit (a1) is a structural unit represented by the formula (a1-1).

（式中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数１〜６のアルキル基を表し、Ｒ³は炭素数１〜６のアルキル基又は炭素数４〜７のシクロアルキル基を表し、Ｒ²とＲ³とは連結して環を形成してもよい。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms. R ² and R ³ may be linked to form a ring.

<4> The positive photosensitive resin composition according to any one of the above <1> to <3>, wherein the structural unit (a2) is a structural unit having an epoxy group and / or an oxetanyl group.
<5> The positive photosensitive resin composition according to any one of the above <1> to <5>, wherein the acid group of the structural unit (b1) is a carboxyl group or a phenolic hydroxyl group,
<6> The positive photosensitive resin composition according to any one of the above <1> to <5>, wherein the structural unit (b2) is a structural unit having an epoxy group and / or an oxetanyl group.
<7> The positive photosensitive resin composition according to any one of the above <1> to <6>, wherein the component B further has a structural unit represented by the formula (b3),

（式中、Ｒ⁴は水素原子又はメチル基を表す。）

(In the formula, R ⁴ represents a hydrogen atom or a methyl group.)

<8> the weight ratio between the content W _B content W _A and component B in component A, W _A / W _B = 98 / 2-20 / 80, any of the above <1> to the <7> Or a positive photosensitive resin composition according to any one of the above,
<9> The positive photosensitive resin composition according to any one of <1> to <8>, wherein the component C is an oxime sulfonate photoacid generator represented by the formula (c1),

（式（ｃ１）中、Ｒ⁵及びＲ⁶はそれぞれ独立に、一価の有機基を表し、Ｒ⁵及びＲ⁶は連結して環を形成していてもよく、Ｒ⁷はアルキル基、シクロアルキル基又はアリール基を表す。）

(In formula (c1), R ⁵ and R ⁶ each independently represents a monovalent organic group, R ⁵ and R ⁶ may be linked to form a ring, R ⁷ is an alkyl group, Represents an alkyl group or an aryl group.)

  <10> Any of the above <1> to <9>, wherein Component C is a compound represented by Formula (OS-3), Formula (OS-4), Formula (OS-5), or Formula (c4) Or a positive photosensitive resin composition according to any one of the above,

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

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

（式中、Ｒ^B1はアルキル基、アルコキシ基又はハロゲン原子を表し、Ｒ^B2はアルキル基又はアリール基を表す。）

(Wherein R ^B1 represents an alkyl group, an alkoxy group or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.)

<11> The positive photosensitive resin composition according to any one of the above <1> to <10>, further comprising a photosensitizer.
<12> (1) Layer forming step of forming a film-like layer on a substrate using the positive photosensitive resin composition according to any one of the above <1> to <11>, (2) Application A solvent removing step of removing the solvent from the exposed photosensitive resin composition, (3) an exposure step of exposing the photosensitive resin composition from which the solvent has been removed with active light, and (4) an exposed photosensitive resin composition. A cured film forming method comprising: a developing step of developing with an aqueous developer; and (5) a post-baking step of thermally curing the developed photosensitive resin composition,
<13> The method for forming a cured film according to the above <12>, comprising a step of exposing the developed photosensitive resin composition to the entire surface after the development step and before the post-baking step.
<14> (6) The method for forming a cured film according to the above <12> or <13>, further comprising a dry etching step of performing dry etching on a substrate having a cured film obtained by thermosetting,
<15> A cured film formed by the method according to any one of <12> to <14>,
<16> The cured film according to <15>, which is an interlayer insulating film,
<17> An organic EL display device comprising the cured film according to <15> or <16> above,
<18> A liquid crystal display device comprising the cured film according to <15> or <16>.

  According to the present invention, it has high sensitivity, high resistance to a stripping solution and NMP, good adhesion to a transparent electrode film and metal, excellent dry etching resistance, and display failure hardly occurs in a display device. Positive photosensitive resin composition capable of obtaining cured film, cured film obtained by curing said photosensitive resin composition, method for forming the same, and organic EL display device and liquid crystal display device provided with said cured film Could be provided.

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

Hereinafter, the present invention will be described in detail.
In the specification, the description of “lower limit to upper limit” represents “more than the lower limit and less than the upper limit”, and the description of “upper limit to lower limit” represents “the upper limit and less than the lower limit”. That is, it represents a numerical range including an upper limit and a lower limit.
Further, “(Component A) (copolymer) having at least (a1) a structural unit having a residue in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group” is simply “ “Component A” or the like is also referred to, and “(a1) a structural unit having a residue in which an acid group is protected by an acid-decomposable group” or the like is also simply referred to as “structural unit (a1)” or the like.
In addition, “(meth) acrylate” when referring to both or one of “acrylate” and “methacrylate”, and “(meth) acrylic” when referring to both or one of “acryl” and “methacryl”, respectively. There are things to do.

(Positive photosensitive resin composition)
The positive photosensitive resin composition of the present invention (hereinafter also simply referred to as “photosensitive resin composition”) has (resin A) a residue in which at least (a1) an acid group is protected with an acid-decomposable group. A copolymer having a structural unit and (a2) a structural unit having a crosslinkable group, (component B) having no structural unit having a residue in which an acid group is protected by an acid-decomposable group, and at least (b1) It contains a copolymer having a structural unit having an acid group and (b2) a structural unit having a crosslinkable group, (Component C) a photoacid generator, and (Component D) a solvent.
The photosensitive resin composition of this invention becomes the thing excellent in the sensitivity by containing 2 specific resin components (component A and component B) and a photo-acid generator. In addition, the photosensitive resin composition of the present invention has high resistance to a stripping solution, particularly a stripping solution containing monoethanolamine and NMP, by containing two specific resin components and a photoacid generator. It is possible to form a cured film that has good adhesion to a metal, is excellent in dry etching resistance, and is less likely to cause display defects even in a display device.
The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).
Furthermore, the photosensitive resin composition of the present invention can be suitably used as a positive photosensitive resin composition for dry etching resists.

In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Moreover, the method of introducing the structural unit contained in the copolymer such as Component A or Component B used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. In the polymer reaction method, after a polymerization reaction is performed, a necessary functional group is introduced into the constituent unit using a reactive group contained in the constituent unit of the obtained copolymer. Here, as the functional group, a protective group for protecting an acid group such as a carboxyl group or a phenolic hydroxyl group and simultaneously decomposing and releasing them in the presence of a strong acid, a crosslinkable group such as an epoxy group or oxetanyl group, Examples thereof include alkali-soluble groups (acid groups) such as phenolic hydroxyl groups and carboxyl groups.

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

Component A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, the component A may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, a structural unit derived from styrene or a vinyl compound.
Component A preferably contains 50 mol% or more of monomer units derived from (meth) acrylic acid and / or its ester, more preferably 80 mol% or more, more preferably 90 mol%, based on all monomer units. % Or more is more preferable, and 100 mol% is particularly preferable.

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

<Structural unit (a1)>
Component A has (a1) at least a structural unit having a residue in which an acid group is protected with an acid-decomposable group. When Component A has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
The “residue in which an acid group is protected with an acid-decomposable group” in the present invention refers to a residue in which a carboxyl group is protected in the form of an acetal, a residue in which an acid group is protected in the form of a ketal, It is a residue protected with a tertiary alkyl group or a residue whose acid group is protected with a tertiary alkyl carbonate group.
Preferred examples of the acid group include a carboxyl group and a phenolic hydroxyl group.
Specific examples of the residue in which the acid group is protected with an acid-decomposable group include, for example, an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group. And tertiary alkyl functional groups such as t-butyl ester groups and t-butyl carbonate groups.

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

Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a residue protected in the form of an acetal or ketal represented by the formula (A1). In addition, when the carboxyl group is a residue protected in the form of an acetal or ketal represented by the formula (A1), the residue as a whole is —C (═O) —O—CR ¹ R ² (OR ³ ) Structure.

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

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

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

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

In formula (A1), R ¹ , R ² and R ³ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include, for example, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, tetrahydrofuranyl group, adamantyl group and tetrahydropyrani And the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the radical polymerizable monomer used to form a monomer unit having a residue in which a phenolic hydroxyl group is protected in the form of an acetal or ketal include, for example, 1-alkoxyalkyl protected form of hydroxystyrene, hydroxy Protected tetrahydropyranyl of styrene, 1-alkoxyalkyl protected of α-methylhydroxystyrene, protected tetrahydropyranyl of α-methyl-hydroxystyrene, protected tetrahydrofuranyl of α-methylhydroxystyrene, 4-hydroxyphenyl methacrylate 1-alkoxyalkyl protectors, tetrahydropyranyl protectors of 4-hydroxyphenyl methacrylate, and tetrahydrofuranyl protectors of 4-hydroxyphenyl methacrylate. Among these, a 1-alkoxyalkyl protector of α-methylhydroxystyrene or a tetrahydrofuranyl protector of α-methylhydroxystyrene is preferable.

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

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

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

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

  Among these, the structural unit (a1) is preferably a structural unit represented by the following formula (a1-1) from the viewpoint of sensitivity.

（式（ａ１−１）中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数１〜６のアルキル基を表し、Ｒ³は炭素数１〜６のアルキル基又は炭素数４〜７のシクロアルキル基を表し、Ｒ²とＲ³とは連結して環を形成してもよい。）

(In formula (a1-1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or 4 to 4 carbon atoms). 7 represents a cycloalkyl group, and R ² and R ³ may be linked to form a ring.)

In formula (a1-1), R ¹ is preferably a methyl group.
In formula (a1-1), R ² is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
In formula (a1-1), R ³ is preferably an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and more preferably an ethyl group or a cyclohexyl group.
Wherein (a1-1), the case of forming a ring and R ² and R ³ are groups R ² and R ³ are linked is preferably an alkylene group having 3 to 6 carbon atoms 1,3-propylene group or 1,4-butylene group is more preferable.

  The content of monomer units forming the structural unit (a1) in all monomer units constituting Component A is preferably 10 to 80 mol%, more preferably 10 to 70 mol%, and more preferably 20 to 70 mol%. Is particularly preferred. By containing the structural unit (a1) at the above ratio, a highly sensitive photosensitive resin composition can be obtained.

<Structural unit (a2)>
Component A has at least a structural unit (a2) having a crosslinkable group.
The crosslinkable group may be any one that forms a covalent bond by reacting with the acid group described above, or any one that forms a covalent bond by the action of heat or light between the crosslinkable groups. Particularly preferred are those that form a covalent bond with heat.
As the structural unit (a2) having a crosslinkable group that reacts with an acid group to form a covalent bond, a structural unit having a group having an epoxy group, an oxetanyl group, or an N-alkoxymethyl group is preferable. An ethylenically unsaturated bond is preferred as the one that forms a covalent bond by the action of heat or light. Among these crosslinkable groups, those that react with an acid group to form a covalent bond are preferred.
The crosslinkable group is particularly preferably contained in Component A as a structural unit having an epoxy group or an oxetanyl group. In addition, the structural unit (a2) may include both an epoxy group and an oxetanyl group, or may include three groups of an epoxy group, an oxetanyl group, and an ethylenically unsaturated bond.
The structural unit having an epoxy group or oxetanyl group is preferably a structural unit having an alicyclic epoxy group or oxetanyl group, and more preferably a structural unit having an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring. Specifically, for example, 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3 -An epoxy cyclopentyl group etc. are mentioned preferably.
The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.
The structural unit having an epoxy group or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may include one or more epoxy groups and one or more oxetanyl groups. Well, it may have 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 oxetanyl groups, It is more preferable to have one or two oxetanyl groups in total, and it is even more preferable to have one epoxy group and one 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, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, cycloaliphatic described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Examples include compounds containing an epoxy skeleton That.

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

  As an example of the radical polymerizable monomer used for forming a structural unit having an epoxy group or an oxetanyl group, a monomer containing a methacrylic ester structure and a monomer containing an acrylate structure are preferable.

  Among these radical polymerizable monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs of JP-A-2001-330953. (Meth) acrylic acid ester having an oxetanyl group described in 0011 to 0016, and particularly preferable is a (meth) acrylic acid ester having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. is there. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid (3-ethyloxetane). -3-yl) methyl, most preferred are acrylic acid (3-ethyloxetane-3-yl) methyl and methacrylic acid (3-ethyloxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Moreover, as a crosslinkable group, N-alkoxymethyl group is mentioned preferably and N-alkoxymethylamide group is mentioned more preferably. As the structural unit having an N-alkoxymethyl group, a structural unit represented by the following formula (a2-1) is preferable.

（式（ａ２−１）中、Ｒ^a1は水素原子又はメチル基を表し、Ｒ^a2は炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基を表し、Ｒ^a3は水素原子、炭素数１〜２０のアルキル基、又は炭素数６〜２０のアリール基を表す。）

(In formula (a2-1), R ^a1 represents a hydrogen atom or a methyl group, R ^a2 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ^a3 represents a hydrogen atom or carbon. Represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.)

R ^a1 in formula (a2-1) represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.
R ^a2 in formula (a2-1) represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group may be substituted. An atom, a hydroxyl group, an amino group, a nitro group, and a cyano group are mentioned. R ^a2 is more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a cyclohexyl group or an n-hexyl group. A butyl group, i-butyl group, cyclohexyl group or n-hexyl group is more preferred, and a methyl group, n-butyl group or i-butyl group is particularly preferred.
R ^a3 in formula (a2-1) represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the alkyl group or aryl group may be substituted. Examples thereof include a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, and an alkoxy group having 1 to 20 carbon atoms. R ^a3 is more preferably a hydrogen atom or an alkoxymethyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

  Examples of the radical polymerizable monomer used to form the structural unit represented by the formula (a2-1) include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N- n-butoxymethyl (meth) acrylamide and Ni-butoxymethyl (meth) acrylamide are preferable, Nn-butoxymethyl (meth) acrylamide and Ni-butoxymethyl (meth) acrylamide are more preferable, and N-n -Butoxymethylacrylamide is particularly preferred.

  Preferable specific examples of the structural unit (a2) include the following structural units.

From the viewpoint of sensitivity, the content ratio of the monomer units forming the structural unit (a2) in Component A is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, based on all monomer units constituting Component A. 20-60 mol% is still more preferable.
From the viewpoint of adhesion and resistance to resist stripping solution and NMP, the content ratio of the monomer units forming the structural unit (a2) in Component A is preferably 10 to 70 mol% with respect to all monomer units constituting Component A. 10-60 mol% is more preferable, and 10-50 mol% is still more preferable.

<Other structural units (a3)>
Component A may further have another structural unit (a3) as long as the effects of the present invention are not hindered.
Examples of the radical polymerizable monomer used to form the structural unit (a3) include compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (however, the above-described configuration). Units (a1) and (a2) are excluded.)
Moreover, it is preferable that the component A further has a structural unit which has an acid group as a structural unit (a3) from a viewpoint of a sensitivity.
The acid group is more preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group, and still more preferably a structural unit having a carboxyl group.
The structural unit (a3) is preferably a structural unit derived from at least one selected from the group consisting of acrylic acid, methacrylic acid, p-hydroxystyrene, and α-methyl-p-hydroxystyrene. Alternatively, a structural unit derived from methacrylic acid is more preferable, and a structural unit derived from methacrylic acid is particularly preferable.

Moreover, as a preferable example of the structural unit (a3), the hydroxyl group-containing unsaturated carboxylic acid ester, the alicyclic structure-containing unsaturated carboxylic acid ester, styrene, N-substituted maleimide, and methyl (meth) acrylate are selected. Also included are structural units derived from at least one kind.
Among these, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ² ] from the viewpoint of improving electrical characteristics. ^{, 6} ] decan-8-yloxyethyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid esters containing an alicyclic structure such as 2-methylcyclohexyl (meth) acrylate, Alternatively, a hydrophobic monomer such as styrene is preferable. From the viewpoint of sensitivity, 2-hydroxyethyl (meth) acrylate and N-substituted maleimide are preferable. Among these, (meth) acrylic acid esters having an alicyclic structure are more preferable. From the viewpoint of etching resistance, styrenes such as styrene and α-methylstyrene are preferable.
These structural units (a3) can be used individually by 1 type or in combination of 2 or more types.

  The content ratio of the monomer units forming the structural unit (a3) in the case where the structural unit (a3) is contained in all the monomer units constituting the component A is preferably 1 to 50 mol%, more preferably 5 to 40 mol%. Preferably, 5 to 30 mol% is particularly preferable.

The weight average molecular weight of component A in the present invention is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and further preferably 4,000 to 30,000. Preferably, it is 10,000-16,000. In addition, it is preferable that the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.
Component A may be used alone or in combination of two or more.

  The content of Component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, and preferably 30 to 95% by weight, based on the total solid content of the photosensitive resin composition. More preferably, it is 30 to 70% by weight. When the content is within this range, the pattern formability upon development is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.

(Component B) It does not have a structural unit having a residue protected with an acid-decomposable group, and has at least (b1) a structural unit having an acid group and (b2) a structural unit having a crosslinkable group. Copolymer The positive photosensitive resin composition of the present invention has, in addition to Component A, (Component B) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and at least (b1). It contains a copolymer having a structural unit having an acid group and (b2) a structural unit having a crosslinkable group.
Component B does not have a structural unit having a residue in which an acid group is protected with an acid-decomposable group, which is the structural unit (a1) in Component A.
The structural unit (b1) and the structural unit (b2) may be the same structural unit, but are preferably different structural units.
Furthermore, component B is preferably alkali-soluble.

Component B is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, the component A may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, a structural unit derived from styrene or a vinyl compound.
Component B preferably contains 50 mol% or more, more preferably 80 mol% or more of monomer units derived from (meth) acrylic acid and / or its ester, based on all monomer units, more preferably 90 mols % Or more is more preferable, and 100 mol% is particularly preferable.
In addition, the method for introducing the structural unit contained in Component B may be a polymerization method, a polymer reaction method, or a combination of these two methods, as in Component A.

<Structural unit (b1)>
Component B has (b1) at least a structural unit having an acid group.
The structural unit (b1) is more preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group, and still more preferably a structural unit having a carboxyl group.

Examples of the radical polymerizable monomer used to form the structural unit having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Preferable examples include unsaturated carboxylic acids such as dicarboxylic acids such as itaconic acid.
Moreover, as a radically polymerizable monomer used in order to form the structural unit which has a carboxylic anhydride residue, maleic anhydride, itaconic anhydride, etc. can be mentioned as a preferable thing, for example.

  Examples of the radical polymerizable monomer used to form a structural unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and α-methyl-p-hydroxystyrene, and JP-A-2008-40183. Compounds described in paragraphs 0011 to 0016 of the publication, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of the patent No. 2888454, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, 4-hydroxy An addition reaction product of benzoic acid and glycidyl acrylate can be mentioned as a preferable example.

Among these, methacrylic acid, acrylic acid, compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, 4- An addition reaction product of hydroxybenzoic acid and glycidyl methacrylate, and an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable. Compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, Patent No. Preferably, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate. , Acrylic acid, methacrylic acid, p-hydro It is more preferably a structural unit derived from at least one selected from the group consisting of styrene and α-methyl-p-hydroxystyrene, more preferably a structural unit derived from acrylic acid or methacrylic acid, A structural unit derived from methacrylic acid is particularly preferred. These structural units can be used individually by 1 type or in combination of 2 or more types.
Preferable specific examples of the structural unit (b1) include the following structural units.

  Among these, the structural unit (b1) is preferably (b1-1), (b1-2), (b1-11) or (b1-12), and (b1-1) or (b1−) 2) is more preferable, and (b1-1) is particularly preferable.

<Structural unit (b2)>
Component B has (b2) at least a structural unit having a crosslinkable group.
The crosslinkable group may be any one that forms a covalent bond by reacting with the acid group described above, or any one that forms a covalent bond by the action of heat or light between the crosslinkable groups.
The structural unit (b2) in the component B is synonymous with the structural unit (a2) in the component A, and the preferred embodiment is also the same.

From the viewpoint of sensitivity, the content ratio of the monomer units forming the structural unit (b1) in Component B is preferably 5 to 50 mol%, more preferably 5 to 45 mol%, based on all monomer units constituting Component B. 5 to 40 mol% is more preferable.
From the viewpoint of adhesion and resistance to resist stripping solution and NMP, the content ratio of the monomer units forming the structural unit (b2) in the component B is preferably 10 to 90 mol% with respect to all monomer units constituting the component B. 15-85 mol% is more preferable, and 20-80 mol% is still more preferable.

<Other structural units (b3)>
Component B may further have another structural unit (b3) as long as the effects of the present invention are not hindered.
Examples of the radical polymerizable monomer used for forming the structural unit (b3) include the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (however, the above-described structure). Units (b1) and (b2) and structural units having a residue in which an acid group is protected with an acid-decomposable group are excluded.
Moreover, the radically polymerizable monomer mentioned above can also be used as a structural unit (a3) in the component A.

As a radically polymerizable monomer used for forming the structural unit (b3), styrenes such as styrene and α-methylstyrene are preferable from the viewpoint of etching resistance, and styrene or α-methylstyrene is more preferable.
Moreover, it is preferable that the component B further has a structural unit represented by the following formula (b3) from the viewpoint of etching resistance. R ⁴ is preferably a hydrogen atom.

（式中、Ｒ⁴は水素原子又はメチル基を表す。）

(In the formula, R ⁴ represents a hydrogen atom or a methyl group.)

Examples of the structural unit (b3) preferably include structural units derived from at least one selected from the group consisting of (meth) acrylic acid esters, styrenes, and N-substituted maleimides, and (meth) More preferred are structural units derived from at least one selected from the group consisting of acrylates and styrenes.
Among them, as a radical polymerizable monomer used for forming the structural unit (b3), an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate is used. Preferred examples include (meth) acrylic acid esters, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and styrene. Can be illustrated more preferably, methyl (meth) acrylate can be illustrated more preferably, and methyl methacrylate can be illustrated particularly preferably.
The structural unit (b3) can be used alone or in combination of two or more.

  The content ratio of the monomer unit forming the structural unit (b3) in the case where the structural unit (b3) is contained in all monomer units constituting the component B is preferably 1 to 60 mol% from the viewpoint of dry etching resistance. 3-55 mol% is more preferable and 5-50 mol% is still more preferable.

The weight average molecular weight of Component B in the present invention is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and further preferably 4,000 to 30,000. Preferably, it is 10,000-16,000. In addition, it is preferable that the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.
Component B may be used alone or in combination of two or more.

The content of Component B in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, and preferably 30 to 95% by weight, based on the total solid content of the photosensitive resin composition. More preferably, it is 30 to 70% by weight. When the content is within this range, the pattern formability upon development is good.
Further, the content ratio of Component A and Component B in the photosensitive resin composition of the present invention is preferably (Content of Component A) / (Content of Component B) = 0.5-2, It is more preferable that it is 0.8-1.2, and it is still more preferable that it is 0.9-1.1. The effect of this invention can be exhibited more as it is the said range.

  In the photosensitive resin composition of the present invention, resins other than Component A and Component B may be used in combination as long as the effects of the present invention are not hindered. However, the content of the resin other than Component A and Component B is preferably less than the content of Component A and the content of Component B from the viewpoint of developability.

  As such a resin other than Component A and Component B, 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.

In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 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, etc. Is mentioned.
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.

  In addition to the above, the resin other than the component A and the component B may be a resin having a part of the structural units (a1), (a2), (a3), (b1), (b2), and (b3). Good. Examples of these resins include a resin composed only of the structural unit (a1), a resin composed only of the structural unit (a3), and the like.

  Resins other than these component A and component B may contain only 1 type, and may contain 2 or more types.

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

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

  Examples of diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl-4- (2′-hydroxy-1) '-Tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-) Tetradecaoxy) phenyliodonium p-toluenesulfonate and the like.

  Examples of triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoro. Lomethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

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

  Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, and bis (p-toluenesulfonyl) diazomethane.

  Examples of imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-ene-dicarboximide, succinimide trifluoromethyl sulfonate, phthalimido trifluoromethyl sulfonate, N-hydroxynaphthalimide methane sulfonate, N- Hydroxy-5-norbornene-2,3-dicarboximide propane sulfonate and the like.

  The photosensitive resin composition of the present invention preferably contains an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following formula (c0) as (Component C) a photoacid generator. Note that the wavy line represents the bonding position with another chemical structure.

  The oxime sulfonate compound having at least one oxime sulfonate residue represented by the formula (c0) is preferably a compound represented by the following formula (c1).

（式（ｃ１）中、Ｒ⁵及びＲ⁶はそれぞれ独立に、一価の有機基を表し、Ｒ⁵及びＲ⁶は連結して環を形成していてもよく、Ｒ⁷はアルキル基、シクロアルキル基又はアリール基を表す。）

(In formula (c1), R ⁵ and R ⁶ each independently represents a monovalent organic group, R ⁵ and R ⁶ may be linked to form a ring, R ⁷ is an alkyl group, Represents an alkyl group or an aryl group.)

In formula (c1), R ⁵ represents an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or a 2-thienyl group. Represents an alkoxy group having 1 to 4 carbon atoms or a cyano group. When R ⁵ is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups include a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a nitro group. It may be substituted with a substituent selected from the group consisting of groups.
In formula (c1), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents an alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, an anthranyl group optionally substituted with W, a dialkylamino group, a morpholino group, or a cyano group. R ⁶ and R ⁵ may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be bonded to a benzene ring.
In formula (c1), R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents an alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

The alkyl group having 1 to 6 carbon atoms represented by R ⁵ may be a linear or branched alkyl group, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- A butyl group, a tert-butyl group, an n-pentyl group, an isoamyl group, an n-hexyl group, or a 2-ethylbutyl group is exemplified.
Examples of the halogenated alkyl group having 1 to 4 carbon atoms represented by R ⁵ include a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁵ include a methoxy group and an ethoxy group.
When R ⁵ represents a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups are a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, or a carbon atom having 1 to 4 carbon atoms. Alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group), alkoxy groups having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group) , N-propoxy group, i-propoxy group, n-butoxy group) and a nitro group may be substituted.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁶ include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group and n-octyl. An oxy group, n-decyloxy group, etc. are mentioned.
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁶ include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.
Specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁶ include trifluoromethoxy group, pentafluoroethoxy group, perfluoro-n-propoxy group, perfluoro-n-butoxy group, perfluoro group. Examples include a fluoro-n-amyloxy group.

Specific examples of the phenyl group optionally substituted by W represented by R ⁶ include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group , P- ( -Butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i -Amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2, 4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group And p-biphenylyl group.

Specific examples of the naphthyl group optionally substituted by W represented by R ⁶ include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted with W represented by R ⁶ include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

Examples of the dialkylamino group represented by R ⁶ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.

In formula (c1), R ⁷ represents an alkyl group, a cycloalkyl group or an aryl group, represents an alkyl group, a cycloalkyl group or an aryl group, has 1 to 10 carbon atoms, and has 3 to 10 carbon atoms. Cycloalkyl group, halogenated alkyl group having 1 to 5 carbon atoms, halogenated cycloalkyl group having 3 to 10 carbon atoms, phenyl group optionally substituted with W, naphthyl optionally substituted with W An anthranyl group which may be substituted with a group or W is preferred. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁷ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl. Group, t-butyl group, n-amyl group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .
Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁷ include trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro-n-butyl group, perfluoro group. Examples include a fluoro-n-amyl group.
Specific examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷ include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, and an isobornyl group.
Specific examples of the halogenated cycloalkyl group having 3 to 10 carbon atoms represented by R ⁷ include a perfluorocyclopentyl group, a perfluorocyclohexyl group, and a perfluorocycloheptyl group.

Specific examples of the phenyl group optionally substituted with W represented by R ⁷ include o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p -Ethylphenyl group, p- (n-propyl) phenyl group, p- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s- Butyl) phenyl group, p- (t-butyl) phenyl group, p- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group , M-methoxyphenyl group, p-methoxyphenyl group, o-ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group , P- ( -Butoxy) phenyl group, p- (i-butoxy) phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i -Amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2, 4-difluorophenyl group, 2,4,6-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group And p-biphenylyl group.

Specific examples of the naphthyl group optionally substituted by W represented by R ⁷ include 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5 -Methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2- Naphthyl group, 4-methyl-2-naphthyl group, 5-methyl-2-naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group, 8-methyl-2-naphthyl group, etc. It is done.

Specific examples of the anthranyl group optionally substituted with W represented by R ⁷ include a 2-methyl-1-anthranyl group, a 3-methyl-1-anthranyl group, a 4-methyl-1-anthranyl group, 5 -Methyl-1-anthranyl group, 6-methyl-1-anthranyl group, 7-methyl-1-anthranyl group, 8-methyl-1-anthranyl group, 9-methyl-1-anthranyl group, 10-methyl-1- Anthranyl group, 1-methyl-2-anthranyl group, 3-methyl-2-anthranyl group, 4-methyl-2-anthranyl group, 5-methyl-2-anthranyl group, 6-methyl-2-anthranyl group, 7- Examples thereof include a methyl-2-anthranyl group, an 8-methyl-2-anthranyl group, a 9-methyl-2-anthranyl group, and a 10-methyl-2-anthranyl group.

An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy having 1 to 5 carbon atoms represented by W Specific examples include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and the number of carbon atoms represented by R ⁶ or R ^7. The thing similar to what was mentioned as a specific example of the halogenated alkoxy group of 1-5 is mentioned.

R ⁵ and R ⁶ may be bonded to each other to form a 5-membered ring or a 6-membered ring.
When R ⁵ and R ⁶ are bonded to each other to form a 5-membered ring or 6-membered ring, examples of the 5-membered ring or 6-membered ring include carbocyclic groups and heterocyclic ring groups. It may be a cyclopentane, cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered ring or 6-membered ring may be bonded to an optionally substituted benzene ring, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene, and thiol. Xanthene ring system. The 5-membered or 6-membered ring may contain a carbonyl group, examples of which include cyclohexadienone, naphthalenone and anthrone ring systems.

One of the suitable embodiments of the compound represented by the formula (c1) is a compound represented by the following formula (c1-1). The compound represented by the formula (c1-1) is a compound in which R ⁵ and R ⁶ in the formula (c1) are bonded to form a 5-membered ring.

（式（ｃ１−１）中、Ｒ⁷は、式（ｃ１）におけるＲ⁷と同義であり、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｔは、０〜３の整数を表し、ｔが２又は３であるとき、複数のＸは同一でも異なっていてもよい。）

(In the formula (c1-1), R ⁷ has the same meaning as R ⁷ in the formula (c1), X is an alkyl group, an alkoxy group or a halogen atom, t represents an integer of 0 to 3, When t is 2 or 3, the plurality of X may be the same or different.)

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.
t is preferably 0 or 1.
In formula (c1-1), t is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁷ is a linear alkyl group having 1 to 10 carbon atoms, 7,7 A compound having a -dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (c1-1) include the following compound (i), compound (ii), compound (iii), compound (iv) and the like. One species may be used alone, or two or more species may be used in combination. Compounds (i) to (iv) can be obtained as commercial products.
It can also be used in combination with other types of photoacid generators.

As one of the preferable embodiments of the compound represented by the formula (c1),
R ⁵ represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group, or an anthranyl group;
R ⁶ represents a cyano group;
R ⁷ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, or a carbon atom number of 1 Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

  The compound represented by the formula (c1) is also preferably a compound represented by the following formula (c1-2).

In formula (c1-2), R ⁸ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and L represents an integer of 0 to 5. Represent. R ⁷ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, 1 to 1 carbon atoms Represents an alkyl group having 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ⁷ in the formula (c1-2) 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 may be methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group. Particularly preferred.
The halogen atom represented by R ⁸ is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms represented by R ⁸ is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by R ⁸ is preferably a methoxy group or an ethoxy group.
As L, 0-2 are preferable, and 0-1 are particularly preferable.

Among the compounds represented by formula (c1), as a preferred embodiment of the compound included in the compound represented by formula (c1-2), in formula (c1), R ⁵ is a phenyl group or 4-methoxy. This is an embodiment in which a phenyl group is represented, R ⁶ represents a cyano group, and R ⁷ represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tolyl group.

  Hereinafter, among the compounds represented by the formula (c1), particularly preferred examples of the compounds included in the compound represented by the formula (c1-2) are shown, but the present invention is not limited to these.

α- (methylsulfonyloxyimino) benzylcyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = methyl group)
α- (Ethylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)
α- (n-butylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = 4-tolyl group)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = methyl group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = 4-tolyl group)

  The compound having at least one oxime sulfonate residue represented by the formula (c0) is represented by the following formula (OS-3), formula (OS-4), or formula (OS-5). An oxime sulfonate compound is preferred.

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

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

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group represented by R ¹ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
In the formulas (OS-3) to (OS-5), the aryl group represented by R ¹ is preferably an aryl group having 6 to 30 carbon atoms in total which may have a substituent.
In the formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent. There may be at least one heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be condensed.
Examples of the substituent that the alkyl group, aryl group or heteroaryl group represented by R ¹ may have include a halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryl Examples thereof include an oxycarbonyl group and an aminocarbonyl group.

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

In the formulas (OS-3) to (OS-5), the alkyl group represented by R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent. It is more preferable that it is a C1-C6 alkyl group which may have a group.
As the alkyl group represented by R ² , a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are preferable, and a methyl group is more preferable.

In the formulas (OS-3) to (OS-5), the aryl group represented by R ² is preferably an aryl group having 6 to 30 carbon atoms in total which may have a substituent.
The aryl group represented by R ² is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.

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

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.

In the formulas (OS-3) to (OS-5), the alkyl group represented by R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
The alkyloxy group represented by R ⁶ is preferably a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group.
Examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
Examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

Examples of the substituent that the alkyl group or alkyloxy group represented by R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. And aminocarbonyl group.

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

  The compound represented by the formula (OS-3) is particularly preferably a compound represented by the following formula (OS-6), formula (OS-10), or formula (OS-11), The compound represented by the formula (OS-4) is particularly preferably a compound represented by the following formula (OS-7), and the compound represented by the formula (OS-5) is represented by the following formula (OS −8) or a compound represented by the formula (OS-9) is particularly preferable.

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

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

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

  As another preferred embodiment of the oxime sulfonate compound having at least one oxime sulfonate residue represented by the formula (c0), a compound represented by the following formula (OS-1) may be mentioned.

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

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

In the formula (OS-2), R ¹ , R ² , R ^{21 to} R ²⁴ are respectively synonymous with R ¹ , R ² , R ^{21 to} R ²⁴ in the formula (OS-1), and preferred examples are also included. The same is true.
Among these, the aspect in which R ¹ in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), and R ¹ is The embodiment which is a cyano group, a phenyl group or a naphthyl group is most preferred.

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

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

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

It is preferable that the photosensitive resin composition of the present invention does not contain a 1,2-quinonediazide compound as a (component C) photoacid generator that is sensitive to actinic rays. The reason is that the 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is 1 or less and is less sensitive than the oxime sulfonate compound.
On the other hand, the oxime sulfonate compound acts as a catalyst for the deprotection of the acidic group protected in response to the actinic ray, so that the acid generated by the action of one photon Contributing to the deprotection reaction, the quantum yield exceeds 1, for example, a large value such as a power of 10, and it is assumed that high sensitivity is obtained as a result of so-called chemical amplification.

  The content of the (Component C) photoacid generator in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the phase content of Component A and Component B. 0.5 to 10 parts by weight is more preferable.

(Component D) Solvent The photosensitive resin composition of the present invention contains (Component D) a solvent.
The photosensitive resin composition of the present invention is a liquid obtained by dissolving or dispersing component A, component B and component C, which are essential components, and optional components of various additives described below, which are preferable components, in (component D) a solvent. It is preferable to be prepared as
As the (component D) solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene Examples include glycol monoalkyl ether acetates, esters, ketones, amides, and lactones.

  Examples of the (Component D) solvent used in the photosensitive resin composition of the present invention include (1) ethylene glycol such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Monoalkyl ethers; (2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether; (3) ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl Ethylene glycol monoalkyl ethers such as ether acetate and ethylene glycol monobutyl ether acetate (4) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; (5) propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol Propylene glycol dialkyl ethers such as monomethyl ether and diethylene glycol monoethyl ether;

  (6) Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; (7) diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl Diethylene glycol dialkyl ethers such as methyl ether; (8) diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, etc. (9) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether; (10) Dipropylene glycol dimethyl ether Dipropylene glycol dialkyl ethers such as dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

  (11) Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate; (12) methyl lactate, lactic acid Lactic acid esters such as ethyl, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate; (13) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, N-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate , Ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate and the like; (14) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, Ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxypropionmethyl, 3-methoxypropionethyl, 3-ethoxypropionmethyl, 3-ethoxypropionethyl, 3-methoxybutylacetate, 3- Others such as methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate Esters;

  (15) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; (16) N-methylformamide, N, N-dimethyl Examples include amides such as formamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone; and (17) lactones such as γ-butyrolactone.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents. , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.
Of the above-mentioned solvents, diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferable.
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, preferably a combination of two types, and a combination of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. More preferably.

  The content of the (Component D) solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight per 100 parts by weight of the total content of Component A and Component B. 000 parts by weight is more preferable, and 150 to 1,500 parts by weight is even more preferable.

<Other ingredients>
The photosensitive resin composition of the present invention can contain other components.
As other components, the photosensitive resin composition of the present invention preferably contains a photosensitizer from the viewpoint of sensitivity, and preferably contains a basic compound from the viewpoint of liquid storage stability. From the viewpoint of physical properties, it is preferable to contain a crosslinking agent, from the viewpoint of substrate adhesion, it is preferable to contain an adhesion improving agent, and from the viewpoint of applicability, it is preferable to contain a surfactant.
Furthermore, if necessary, the photosensitive resin composition of the present invention includes a development accelerator, an antioxidant, a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, an ultraviolet absorber, and a thickener. And known additives such as organic or inorganic suspending agents can be added.
Hereinafter, other components that can be contained in the photosensitive resin composition of the present invention will be described.

[Photosensitizer]
The photosensitive resin composition of the present invention preferably contains a photosensitizer.
By containing the photosensitizer, it is effective for improving the exposure sensitivity, and is particularly effective when the exposure light source is a mixed line of g and h lines.
As the photosensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyrylbenzene derivatives are preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.
As an acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.
As the thioxanthone derivative, thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2-chlorothioxanthone are preferable.
As the coumarin derivative, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.
Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.
Among these, an anthracene derivative is preferable, and 9,10-dialkoxyanthracene (an alkoxy group having 1 to 6 carbon atoms) is more preferable.
Specific examples of the photosensitizer include the following. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

  The content of the photosensitizer in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total content of Component A and Component B. More preferably, it is 10 weight part. When the content of the photosensitizer is 0.1 parts by weight or more, desired sensitivity is easily obtained, and when it is 10 parts by weight or less, the transparency of the coating film is easily secured.

[Basic compounds]
The photosensitive resin composition of the present invention preferably contains a basic compound from the viewpoint of liquid storage stability.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

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

The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.
It is preferable that content of the basic compound in the photosensitive resin composition of this invention is 0.001-1 weight part with respect to 100 weight part of total content of the component A and the component B, 0.002- More preferably, it is 0.2 parts by weight.

[Crosslinking agent]
It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
Examples of the crosslinking agent include a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, or A blocked isocyanate crosslinking agent can be added.
Among these crosslinking agents, compounds having two or more epoxy groups or oxetanyl groups in the molecule are preferable, and epoxy resins are particularly preferable.
The addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.05 to 50 parts by weight, preferably 0.5 to 44 parts by weight with respect to the total solid content of the photosensitive resin composition. More preferably, it is 3 to 40 parts by weight. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.

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

These are available as commercial products. For example, as bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1051, EPICLON1051 And bisphenol F-type epoxy resins such as JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Co., Ltd.), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.) As the phenol novolac type epoxy resin, JER152, JER154, JER157S70, JER157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (or higher) The cresol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.) and the like, and as an aliphatic epoxy resin, ADEKA RESIN EP-408 S, EP-4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, Daicel Chemical Industries, Ltd.) ))). In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol 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- 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH -300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.) and the like.
These can be used alone or in combination of two or more.

  Among these, an epoxy resin is preferable, 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.
Among these,
The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to the photosensitive resin composition of the present invention is 1-50 when the total content of Component A and Component B is 100 parts by weight. Part by weight is preferable, and 3 to 30 parts by weight is more preferable.

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

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

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

-Compound having at least one ethylenically unsaturated double bond-
As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate is preferably used. be able to.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.
These compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.

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

-Block isocyanate-based crosslinking agent-
The blocked isocyanate crosslinking agent is not particularly limited as long as it is a compound having a blocked isocyanate group (block isocyanate compound), but is a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. Is preferred.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said block isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.
In addition, the skeleton of the blocked isocyanate-based crosslinking agent is not particularly limited, and includes a hexamethylene diisocyanate (HDI) skeleton, an isophorone diisocyanate (IPDI) skeleton, and a prepolymer type skeleton derived from HDI or IPDI. A compound can be preferably used.

The blocking agent for the isocyanate group in the blocked isocyanate group is not particularly limited, and active methylene compounds such as diester compounds, active hydrogen compounds such as oxime compounds, lactam compounds, and amine compounds can be preferably used. Among these, an active methylene compound is particularly preferable from the viewpoint of reactivity.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the oxime compound include cyclohexanone oxime, benzophenone oxime, acetoxime, and the like.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the amine compound include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
In addition, the said active hydrogen compound reacts with an isocyanate group as shown in a following formula, and forms a blocked isocyanate group.
R—NCO + HR ′ → R—NH—C (═O) —R ′
(Wherein HR ′ represents an active hydrogen compound, H in HR ′ represents an active hydrogen atom, R represents a moiety other than the isocyanate group in the isocyanate compound, and R ′ represents the active hydrogen compound in the active hydrogen compound) It represents a part other than the active hydrogen atom.)

  These blocked isocyanate crosslinking agents are available as commercial products, for example, Duranate MF-K60X, MF-K60B, MF-B60X, 17B-60P, TPA-B80E, E402-B80B, SBN-70D, K6000 (or more , Manufactured by Asahi Kasei Chemicals Co., Ltd.), Death Module BL3272, BL3575 / 1, BL3475, BL3370, BL4265, BL5375, VPLS2376 / 1, VPLS2257, VPLS2578 / 1, VPLS2352 / 1, Sumidur BL3175 (above, Sumika Bayer Urethane) (Made by Co., Ltd.), Urehyper PUR-1804 (made by DIC Corporation), etc. can be used preferably. Among these, Duranate MF-K60X, MF-K60B, SBN-70D, and K6000 are particularly preferable.

  When the blocked isocyanate crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the blocked isocyanate crosslinking agent is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of component A. More preferably, it is -20 weight part, and it is still more preferable that it is 2-15 weight part. By adding in this range, high sensitivity and preferable alkali solubility during development can be obtained.

[Adhesion improver]
The photosensitive resin composition of the present invention preferably contains an adhesion improver from the viewpoint of substrate adhesion.
Adhesion improvers that can be used in the photosensitive resin composition of the present invention are inorganic substances that serve as substrates, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, molybdenum, titanium, indium tin oxide, gold, copper, and aluminum. It is a compound that improves the adhesion between the metal and the insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
Among these, a silane coupling agent can be preferably exemplified.
Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.
These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
The content of the adhesion improving agent in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, and 0.5 to 10 parts by weight with respect to 100 parts by weight of the total content of Component A and Component B. Is more preferable.

[Surfactant]
The photosensitive resin composition of the present invention preferably contains a surfactant from the viewpoint of applicability.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone surfactants. .

The photosensitive resin composition of the present invention more preferably contains a fluorine-based surfactant and / or a silicone-based surfactant as the surfactant.
As these fluorosurfactants and silicone surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, Surfactants described in JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 are listed. Commercially available surfactants can also be used.
Examples of commercially available surfactants that can be used include EFTOP EF301, EF303 (above, Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox series (produced by OMNOVA), etc. Fluorine type surfactant or silicone type surfactant can be mentioned. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

  In addition, as a surfactant, the structural unit A and the structural unit B represented by the following formula (1) are included, and the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.

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

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

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

The 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 weight or less, and 0.01 to 10 parts by weight with respect to 100 parts by weight of the total content of Component A and Component B. It is more preferable that it is 0.01 to 1 part by weight.

[Development accelerator]
The photosensitive resin composition of the present invention preferably contains a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, but a compound having at least one group selected from the group of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group is preferable. A compound having a carboxyl group or a phenolic hydroxyl group is more preferred, and a compound having a phenolic hydroxyl group is most preferred.
The molecular weight of the development accelerator is preferably 100 to 2,000, more preferably 150 to 1,500, and particularly preferably 150 to 1,000.

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

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 0.1 to 30 parts by weight when the total content of Component A and Component B is 100 parts by weight from the viewpoint of sensitivity and residual film ratio. Is preferable, 0.2 to 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

〔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, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, a phenolic antioxidant is particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used alone or in combination of two or more.
Examples of commercially available phenolic antioxidants include ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 and ADK STAB manufactured by ADEKA Corporation. AO-80, Adeka Stab AO-330, Sumitizer GM, sumilizer GS, sumizer MDP-S, sumizer BBM-S, sumizer ZX, NOGAIR10 NO. , IRGANOX 1135, IRGANOX 1330, IRGANOX 1726, IRGANOX 1425WL, I GANOX 1520L, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 565, IRGAMOD 295, Yoshinox BHT, Yoshinox BB, Yoshinox T 317, Yoshinox T 317, Yoshinox T 317 Is mentioned.
Among them, Adeka Stub AO-60, Adeka Stub AO-80 (manufactured by ADEKA Co., Ltd.) and Irganox 1098 (manufactured by Ciba Japan Co., Ltd.) are preferable.
The content of the antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by weight. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.

[Plasticizer]
The photosensitive resin composition of the present invention may contain a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
It is preferable that content of the plasticizer in the photosensitive resin composition of this invention is 0.1-30 weight part with respect to 100 weight part of total content of the component A and the component B, 1-10 weight part It is more preferable that

[Thermal radical generator]
The photosensitive resin composition of the present invention may contain a thermal radical generator, and when it contains an ethylenically unsaturated compound such as the aforementioned compound having at least one ethylenically unsaturated double bond, It is preferable to contain a thermal radical generator.
As the thermal radical generator in the present invention, a known thermal radical generator can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.
A thermal radical generator may be used individually by 1 type, and it is also possible to use 2 or more types together.
The content of the thermal radical generator in the photosensitive resin composition of the present invention is 0.01 to 50 parts by weight when the total content of Component A and Component B is 100 parts by weight from the viewpoint of improving film properties. Preferably, 0.1 to 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most preferable.

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

In the present invention, it is also preferable to use a sulfonic acid ester that does not substantially generate an acid by irradiation with exposure light and generates an acid by heat.
The fact that acid is not substantially generated by exposure light exposure can be determined by no change in the spectrum by IR spectrum or NMR spectrum measurement before and after the exposure of the compound.
The molecular weight of the sulfonic acid ester is preferably 230 to 1,000, and more preferably 230 to 800.
As the sulfonic acid ester that can be used in the present invention, a commercially available one may be used, or one synthesized by a known method may be used. The sulfonic acid ester can be synthesized, for example, by reacting a sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, when the total content of Component A and Component B is 100 parts by weight. preferable.

[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. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-T 9-512498. Examples of the compounds described in the first to page 47, line 2 are listed.
Specific examples include the following compounds.

Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
The content of the acid proliferating agent in the photosensitive resin composition is 10 to 1,000 parts by weight with respect to 100 parts by weight of the photoacid generator, from the viewpoint of dissolution contrast between the exposed part and the unexposed part. To 20 to 500 parts by weight is more preferable.

(Method for forming cured film)
Next, the formation method of the cured film of this invention is demonstrated.
The method for forming a cured film of the present invention is not particularly limited except that the positive photosensitive resin composition of the present invention is used, but preferably includes the following steps (1) to (5).
(1) Application process for applying the positive photosensitive resin composition of the present invention onto a substrate (2) Solvent removal process for removing the solvent from the applied photosensitive resin composition (3) Photosensitivity from which the solvent has been removed Exposure step of exposing the resin composition with actinic rays (4) Development step of developing the exposed photosensitive resin composition with an aqueous developer (5) Post-baking step of thermosetting the developed photosensitive resin composition In the method for forming a cured film of the invention, after the exposure in the exposure step, the developing step (4) may be performed without performing a heat treatment.
Moreover, it may further include a step of exposing the entire surface of the developed photosensitive resin composition before the post-baking step.
Moreover, it is preferable that the formation method of the cured film of this invention further includes the dry etching process which performs dry etching with respect to the board | substrate which has the cured film obtained by (6) thermosetting.
Each step will be described below in order.

In the coating step (1), it is preferable to apply the positive photosensitive resin composition of the present invention on a substrate to form a wet film containing a solvent.
In the solvent removal step (2), the solvent is removed from the applied film. In the solvent removal step, it is preferable to form a dry coating film on the substrate by removing the solvent, for example, under reduced pressure (vacuum) and / or heating.

In the exposure step (3), it is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm to 450 nm. In this step, the specific acid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group in the structural unit (a1) contained in Component A is decomposed to generate an acid group.
In the region where the acid catalyst is generated, post exposure bake (hereinafter also referred to as “PEB”) may be performed as necessary in order to accelerate the decomposition reaction. PEB can promote the generation of acid groups from acid-decomposable groups.
The acid-decomposable group in the structural unit (a1) in the specific resin has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from a photoacid generator by exposure to generate an acid group. There is no need. Therefore, it is preferable to perform the developing step after the exposure step without performing a heat treatment. More specifically, it is preferable to form a positive image by performing development in the development step (4) without performing PEB after the exposure step (3).
In addition, by performing PEB at a relatively low temperature, decomposition of the acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 90 ° C. or lower.

In the development step (4), it is preferable to develop the component A having a liberated acid group and the component B having an acid group using an alkaline developer. A positive image can be formed by removing an exposed area containing a photosensitive resin composition having an acid group that is easily dissolved in an alkaline developer.
In the post-baking step (5), the obtained positive image is heated, for example, by thermally decomposing the acid group in the structural unit (b1) and the acid-decomposable group in the structural unit (a1). The cured acid film can be crosslinked with the crosslinkable group in the structural unit (a2) and the structural unit (b2) to form a cured film. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.

The cured film obtained from the photosensitive resin composition of the present invention can be suitably used as a dry etching resist.
When the cured film obtained by thermal curing in the post-baking step (5) is used as a dry etching resist, dry etching processing such as ashing, plasma etching, ozone etching, or the like can be performed as the etching processing.
In the dry etching step (6), a reactive gas etching process in which the substrate is exposed to a reactive gas to perform etching, or a reactive ion etching (RIE) in which the reactive gas is ionized and radicalized by plasma to perform etching. A known dry etching process can be exemplified. These gas types and etching methods may be appropriately selected depending on the material to be dry-etched, desired speed and accuracy, and the like. A known apparatus can be used as an apparatus for performing dry etching.

Furthermore, it is preferable to include a step of exposing the entire surface of the developed photosensitive resin composition before the post-baking step, and the entire surface of the developed photosensitive resin composition is irradiated with actinic rays, preferably ultraviolet rays. If a process is added, a crosslinking reaction can be accelerated | stimulated with the acid which generate | occur | produces by irradiation of actinic light.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

[Method for preparing photosensitive resin composition]
A solvent is mixed with an essential component of the specific resin and the acid generator in a predetermined ratio and in any manner as required, and the mixture is stirred and dissolved to prepare a photosensitive resin composition. For example, a photosensitive resin composition can be prepared by preparing a solution in which a specific resin or an acid generator is previously dissolved in a solvent and then mixing them in a predetermined ratio. The solution of the photosensitive resin composition prepared as described above can be used after being filtered using a filter having a pore size of 0.1 μm or the like.

<Layer formation step and solvent removal step>
A desired dry coating film can be formed by forming a film-like layer on a predetermined substrate using the photosensitive resin composition and removing the solvent by reducing pressure and / or heating (pre-baking). Examples of the substrate include a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as necessary, and a transparent conductive circuit layer in manufacturing a liquid crystal display device. The method for forming a layer on the substrate is not particularly limited, and for example, a coating method such as a slit coating method, a spray method, a roll coating method, or a spin coating method can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a side of 1 m or more on each side.
In addition, (2) the heating conditions in the solvent removal step are such that the acid-decomposable group is decomposed in the structural unit (a1) in the component A in the unexposed area and the component A is not soluble in the alkaline developer. Yes, although it varies depending on the type and mixing ratio of each component, it is preferably about 70 to 120 ° C. for about 30 to 300 seconds.

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

  In the case of using a laser, 343 nm and 355 nm are preferably used for a solid (YAG) laser, 351 nm (XeF) is preferably used for an excimer laser, and 375 nm and 405 nm are preferably used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoints of stability and cost. The coating can be irradiated with the laser once or a plurality of times.

The energy density per pulse of the laser is preferably 0.1 mJ / cm ² or more and 10,000 mJ / cm ² or less. In order to sufficiently cure the coating film, 0.3 mJ / cm ² or more is more preferable, and 0.5 mJ / cm ² or more is most preferable. To prevent the coating film from being decomposed by an ablation phenomenon, 1,000 mJ / cm ² is preferable. cm ² or less is more preferable, and 100 mJ / cm ² or less is most preferable.
The pulse width is preferably 0.1 nsec or more and 30,000 nsec or less. In order not to decompose the color coating film due to the ablation phenomenon, 0.5 nsec or more is more preferable, and 1 nsec or more is most preferable, and in order to improve the alignment accuracy at the time of scanning exposure, 1,000 nsec or less is more preferable, Most preferred is 50 nsec or less.
Furthermore, the frequency of the laser is preferably 1 Hz to 50,000 Hz, more preferably 10 Hz to 1,000 Hz.
Furthermore, the frequency of the laser is more preferably 10 Hz or more, most preferably 100 Hz or more for shortening the exposure processing time, and more preferably 10,000 Hz or less for improving the alignment accuracy at the time of scan exposure. 000 Hz or less is most preferable.

Compared with a mercury lamp, a laser is preferable in that the focus can be easily reduced and a mask for forming a pattern in the exposure process is not necessary and the cost can be reduced.
The exposure apparatus that can be used in the present invention is not particularly limited, but commercially available exposure apparatuses include Callisto (buoy technology), AEGIS (buoy technology) and DF2200G (Dainippon). Screen Manufacturing Co., Ltd.) can be used. Further, devices other than those described above are also preferably used.
Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

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

The pH of the developer is not particularly limited as long as it can be developed, but it is preferably 10.0 to 14.0.
It is preferable to develop with a 0.2 to 2.38% by weight aqueous solution of tetramethylammonium hydroxide, and develop with a 0.4%, 0.5%, 0.7% or 2.38% by weight aqueous solution. More preferably.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, a shower method, and the like. After the development, washing with running water is performed for 10 to 90 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing process, 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, a shower rinse, a dip rinse, etc. can be mentioned.

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

<Dry etching process>
The dry etching step in the present invention is a step of performing dry etching on a substrate having a cured film obtained by thermosetting in the post-baking step. Since the cured film obtained from the photosensitive resin composition of the present invention is excellent in dry etching resistance, the amount of film loss is small even when exposed to dry etching conditions.
In the dry etching process, as described above,
Examples of dry etching materials that can be used in the present invention include silicon, silicon dioxide, silicon nitride, alumina, glass, glass-ceramics, gallium arsenide, indium phosphide, copper, aluminum, nickel, iron, steel, copper -Including but not limited to silicon alloys, indium-tin oxide coated glass; metal, semiconductor, and any substrate containing a patterned region of insulating material.
There is no restriction | limiting in particular as a generation method of plasma, Both a low pressure plasma method and an atmospheric plasma method are applicable.
In the plasma etching, for example, an inert gas selected from helium, argon, krypton, and xenon, O ₂ , CF ₄ , C ₂ F ₄ , N ₂ , CO ₂ , SF ₆ , CHF ₃ , at least O A reactive gas containing N, F, or Cl can be preferably used.
In the dry etching process, for example, when the base is a silicon-based layer such as SiN _x or SiO _2, it is preferable to use O ₂ and a fluorine-based reactive gas such as CF ₄ or SiF ₆ .
Further, the substrate in the dry etching process and the substrate in the coating process may be the same or different. For example, the substrate in the coating step may be a temporary substrate, and the cured film may be transferred to another substrate before the dry etching step.

Moreover, the cured film obtained by curing the photosensitive resin composition of the present invention can also be suitably used as a sacrificial layer during an etching process such as dry etching or wet etching. When peeling, peeling can be performed by a known dry plasma process such as ashing or a known wet process such as alkaline chemical treatment. Since the cured film of the present invention is cured through a baking process, peeling by a dry plasma process is particularly preferable.
Even when it is used as a planar resist as an etching resist, oxygen plasma treatment is preferably used, but the resist can be peeled and removed by heat treatment with a chemical solution.
The cured film obtained by curing the photosensitive resin composition of the present invention can be particularly suitably used as a dry etching resist.

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention, and can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
By the photosensitive resin composition of the present invention, a cured film having a high sensitivity, generation of residues during development, and a surface having excellent smoothness is obtained, and the cured film is used as an interlayer insulating film. Useful. In addition, the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency, can form a good pattern shape, and has excellent surface smoothness. It is useful for applications of display devices and liquid crystal display devices.
As an organic EL display device or a liquid crystal display device to which the photosensitive resin composition of the present invention can be applied, a cured film formed using the photosensitive resin composition of the present invention is formed as a planarizing film, a protective film, or an interlayer insulating film. There is no particular limitation except for the use as a known organic EL display device and a liquid crystal display device having various structures.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film, the protective film, and the interlayer insulating film, a microlens provided on the color filter in the spacer or the solid-state imaging device for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, an etching resist, Particularly preferably, it can be suitably used for a resist for dry etching and the like.

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

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

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

<Synthesis Example 1>
A flask equipped with a condenser and a stirrer was charged with 150 parts by weight of diethylene glycol ethyl methyl ether, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. In the solution, 41.3 parts by weight of 1-ethoxyethyl methacrylate, 31.0 parts by weight of 3-ethyl-3-oxetanylmethyl methacrylate, 5.6 parts by weight of methacrylic acid, 17-ethylhexyl methacrylate as monomer components. 0 parts by weight and 10.0 parts by weight of dimethyl-2,2′-azobis (2-methylpropionate) as a polymerization initiator were dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours. To the solution was further added 2.5 parts by weight of dimethyl-2,2′-azobis (2-methylpropionate), and the mixture was further stirred for 2 hours to complete the reaction. Thereby, copolymer A-1 was obtained. The weight average molecular weight was 11,000.

<Synthesis Examples 2-38>
Table 1 shows the same conditions as in Synthesis Example 1 except that the monomers used and the amounts thereof were changed.
Copolymers A-2 to A-15, a-1, a-2, B-1 to B-16, and b-1 to b-5 shown in Table 2 were respectively synthesized. The composition ratio (mol%) and the weight average molecular weight (Mw) of each synthesized copolymer are as shown in Tables 1 and 2.

Abbreviations in Table 1 and Table 2 are as follows.
MAEVE: 1-ethoxyethyl methacrylate MATHF: tetrahydro-2H-furan-2-yl methacrylate MACHOE: 1- (cyclohexyloxy) ethyl methacrylate MATHP: tetrahydro-2H-pyran-2-yl methacrylate PHSEVE: 1 of p-hydroxystyrene -Ethoxyethyl group protector OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (Osaka Organic Chemical Co., Ltd.)
GMA: glycidyl methacrylate NBMA: n-butoxymethyl acrylamide VBGE: p-vinylbenzyl glycidyl ether MAA: methacrylic acid PHS: p-hydroxystyrene HEMA: 2-ethylhexyl methacrylate AA: acrylic acid THF FMA: tetrahydrofurfuryl methacrylate St: styrene α- MeSt: α-methylstyrene MMA: methyl methacrylate DCPM: methacrylic acid (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl)

(Examples 1-68 and Comparative Examples 1-11)
The amount (solid content) described in Tables 3 to 5 was dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid content concentration was 27% by weight. Then, it filtered with the membrane filter with a hole diameter of 0.2 micrometer, and prepared the photosensitive resin composition of Examples 1-68 and Comparative Examples 1-11, respectively.

In the above table, the abbreviations of various additives are as follows.
C-1: Compound having the following structure (synthetic product)
C-2: Compound having the following structure (synthetic product)
C-3: Compound having the following structure (synthetic product)
C-4: CGI-1397 (manufactured by BASF)
C-5: Compound having the following structure (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
C-6: PAI-1001 (manufactured by Midori Chemical Co., Ltd.)
C-7: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

<Synthesis of C-1>
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 then reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and 50% by weight hydroxylamine aqueous solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (18 mL), and the mixture was heated to reflux for 10 hours. 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 C-1 (2.3 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of C-1 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

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

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

E-1: DBA (9,10-dibutoxyanthracene, manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
E-2: DETX (diethylthioxanthone)
F-1: 1,5-diazabicyclo [4,3,0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)
F-2: Compound having the following structure

G-1: JER157S65 (Mitsubishi Chemical Corporation)
G-2: JER1031S (Mitsubishi Chemical Corporation)
G-3: Denacol EX-612 (manufactured by Nagase ChemteX Corporation)
G-4: Denacol EX-321L (manufactured by Nagase ChemteX Corporation)
G-5: MF-K60X (manufactured by Asahi Kasei Chemicals Corporation)
H-1: 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
H-2: 3-glycidoxypropyltriethoxysilane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
H-3: 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
I-1: Compound having the following structure I-2: Silicone surfactant SH-8400 FLUID (manufactured by Toray Dow Corning Co., Ltd.)

<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 Tables 6-8. The smaller the numerical value, the better the peel resistance of the cured film, and A or B is preferred.
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

<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, 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 Tables 6-8. The smaller the numerical value, the better the NMP resistance of the cured film, and A or B is preferred.
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

<Adhesion of cured film>
After slit coating each photosensitive resin composition on an ITO (indium tin oxide) substrate, Mo (molybdenum) substrate, titanium (Ti) substrate, the solvent is removed by heating on a hot plate at 90 ° C./120 seconds, A photosensitive resin composition layer having a thickness of 4.0 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. Using a cutter on the cured film, cuts were made at intervals of 1 mm 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 Tables 6-8. The smaller the numerical value, the higher the adhesion to the base substrate, and A or B is preferred.
A: The transferred area is less than 1% B: The transferred area is 1% or more and less than 5% C: The transferred area is 5% or more

<Dry etching 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 is dry etched using a dry etching apparatus “CDE-80N (manufactured by Shibaura Mechatronics Co., Ltd.)” under the conditions of etching gas CF ₄ 50 ml / min, O ₂ 10 ml / min, output 400 mW, etching time 90 seconds. Went. The etching rate was calculated from the amount of film loss. The results are shown in Tables 6-8. As the numerical value is smaller, the dry etching resistance is higher, and A or B is preferable.
A: 30 Å / second or more and less than 35 Å / second B: 35 Å / second or more and less than 40 Å / second C: 40 Å / second or more and less than 45 Å / second

<Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness A photosensitive resin composition layer having a thickness of 4.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive composition layer was developed with an alkali developer (0.3 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
With these operations, the optimum i-line exposure (Eopt) when resolving a 13 μm line and space at 1: 1 was defined as sensitivity. The results are shown in Tables 6-8. The smaller the numerical value, the better. A and B are practically satisfactory levels, and C is not preferable from the viewpoint of productivity.
A: Less than 50 mJ / cm ² B: 50 mJ / cm ² or more and less than 300 mJ / cm ² C: 300 mJ / cm ² or more

<Display performance evaluation in display devices>
A liquid crystal display device using a thin film transistor (TFT) was manufactured by the following method (see FIG. 2). In the active matrix type liquid crystal display device described in FIG. 1 and FIG. 2 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, the bottom gate type TFT 1 was formed on the glass substrate 6, and the insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1. Next, after forming a contact hole in the insulating film 3, a wiring 2 (height of 1.0 μm) connected to the TFT 1 through the contact hole was formed on the insulating film 3.

Further, in order to flatten the unevenness due to the formation of the wiring 2, 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 compositions of Examples 1 to 57 and Comparative Examples 1 to 9 on a substrate and prebaking (90 ° C. × 2 on a hot plate). Then, i-line (365 nm) was irradiated from the mask with a high-pressure mercury lamp at 25 mJ / cm ² (illuminance 20 mW / cm ² ), and then developed with an alkaline aqueous solution to form a pattern at 60 ° C. at 60 ° C. Heat treatment was performed for a minute. 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.

When a drive voltage was applied to the obtained liquid crystal display device and a gray test signal was input, the gray display was visually observed to evaluate the presence or absence of display unevenness. The results are shown in Tables 6-8. A and B are levels at which there is no practical problem.
A: No unevenness at all (very good)
B: Slight unevenness is seen on the display, but practical level (good)
C: Strong unevenness is seen on the display (bad)

  The photosensitive resin composition of the present invention has high sensitivity, high resistance to a stripping solution and NMP, good adhesion with a transparent electrode film and metal, and excellent dry etching resistance. .

(Example 69)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is 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 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

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

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film, the photosensitive resin composition of Example 3 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process can be prevented.

  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 through the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 70)
An organic EL device was produced in the same manner as in Example 69 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 16. It was found that the organic EL display device had good display characteristics and high reliability.

(Example 71)
An organic EL device was produced in the same manner as in Example 69 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 31. It was found that the organic EL display device had good display characteristics and high reliability.

(Example 72)
In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 72 was obtained.
That is, using the photosensitive resin composition of Example 1, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 69.

  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 73)
A liquid crystal display device was produced in the same manner as in Example 72 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 16. It was found that the liquid crystal display device had good display characteristics and high reliability.

(Example 74)
A liquid crystal display device was produced in the same manner as in Example 72 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 31. It was found that the liquid crystal display device had good display characteristics and high reliability.

(Example 75)
A liquid crystal display device was produced in the same manner as in Example 72 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 60. It was found that the liquid crystal display device had good display characteristics and high reliability.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening 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 (18)

(Component A) a copolymer having at least (a1) a structural unit having a residue in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group,
(Component B) It does not have a structural unit having a residue protected with an acid-decomposable group, and has at least (b1) a structural unit having an acid group and (b2) a structural unit having a crosslinkable group. Copolymer,
(Component C) a photoacid generator, and
(Component D) contains a solvent ,
The crosslinkable groups in the structural unit (a2) and the structural unit (b2) are each independently an epoxy group, an oxetanyl group or an N-alkoxymethyl group,
Component C is a compound selected from the group consisting of trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. A positive photosensitive resin composition.   The positive photosensitive resin composition according to claim 1, wherein the structural unit (a1) is a structural unit having a residue in which a carboxy group is protected in the form of an acetal or a ketal. The positive photosensitive resin composition according to claim 1, wherein the structural unit (a1) is a structural unit represented by the formula (a1-1).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 4 to 7 carbon atoms. R ² and R ³ may be linked to form a ring.   The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the structural unit (a2) is a structural unit having an epoxy group and / or an oxetanyl group.   The positive photosensitive resin composition of any one of Claims 1-4 whose acid group of the said structural unit (b1) is a carboxyl group or a phenolic hydroxyl group.   The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the structural unit (b2) is a structural unit having an epoxy group and / or an oxetanyl group. The positive photosensitive resin composition of any one of Claims 1-6 in which the component B further has a structural unit represented by Formula (b3).

(In the formula, R ⁴ represents a hydrogen atom or a methyl group.) The weight ratio between the content W _B content W _A and component B in component A is _{W A / W B = 98 /} 2~20 / 80, according to any one of claims 1-7 Positive photosensitive resin composition. The positive photosensitive resin composition of any one of Claims 1-8 whose component C is an oxime sulfonate photoacid generator represented by Formula (c1).

(In formula (c1), R ⁵ and R ⁶ each independently represents a monovalent organic group, R ⁵ and R ⁶ may be linked to form a ring, R ⁷ is an alkyl group, Represents an alkyl group or an aryl group.) The component C is a compound represented by Formula (OS-3), Formula (OS-4), Formula (OS-5), or Formula (c4), according to any one of claims 1 to 9. Positive photosensitive resin composition.

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

(Wherein R ^B1 represents an alkyl group, an alkoxy group or a halogen atom, and R ^B2 represents an alkyl group or an aryl group.)   The positive photosensitive resin composition of any one of Claims 1-10 which further contains a photosensitizer. (1) A layer forming step of forming a film-like layer on a substrate using the positive photosensitive resin composition according to any one of claims 1 to 11,
(2) a solvent removal step of removing the solvent from the applied photosensitive resin composition;
(3) An exposure process in which the photosensitive resin composition from which the solvent has been removed is exposed to actinic rays,
(4) a developing step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
A method for forming a cured film comprising:   The formation method of the cured film of Claim 12 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process.   (6) The formation method of the cured film of Claim 12 or 13 which further includes the dry etching process of dry-etching with respect to the board | substrate which has a cured film obtained by thermosetting.   The cured film formed by the method of any one of Claims 12-14.   The cured film according to claim 15, which is an interlayer insulating film.   An organic EL display device comprising the cured film according to claim 15 or 16.   A liquid crystal display device comprising the cured film according to claim 15 or 16.

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