JP2013054253A - Positive photosensitive resin composition, method for forming cured film, cured film, liquid crystal display device, organic electroluminescence (el) display device, and polyfunctional cyclic carbonate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition that gives a cured film having high durability against a stripping liquid or NMP (N-methylpyrolidone) and excellent PED (post exposure delay) characteristics, to provide a cured film and a production method of the film, a liquid crystal display device and an organic EL display device using the positive photosensitive resin composition, and to provide a novel polyfunctional cyclic carbonate compound.SOLUTION: The positive photosensitive resin composition comprises: (component A) a resin having an acid decomposable group and a crosslinking group; (component B) a radiation-sensitive acid generator; and (component C) a compound having no amino group but having two or more cyclic carbonate structures. The polyfunctional cyclic carbonate compound is expressed by formula (3), where L represents an arylene group having the valence of (n+1), m represents 0 or 1, and n represents an integer of 1 to 5.

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, an organic EL display device, and a polyfunctional cyclic carbonate compound.

An organic EL display device, a liquid crystal display device, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
For example, Patent Documents 1 to 3 are known as such photosensitive resin compositions.

JP 2009-98673 A JP 2011-75750 A JP 2002-363146 A

However, the photosensitive resin compositions proposed in Patent Documents 1 to 3 are not highly resistant to a resist stripping solution or N-methylpyrrolidone (NMP) used after forming an interlayer insulating film. The display troubles in are likely to occur, and improvement has been demanded.
In recent years, as the apparatus becomes larger, a process margin, particularly PED (Post Exposure Delay) characteristics are required. The PED characteristic is the pattern shape stability with respect to the time from exposure to development.

An object of the present invention is to provide a positive photosensitive resin composition having high resistance to a stripping solution and NMP of a cured film obtained and having excellent PED characteristics, a cured film using the positive photosensitive resin composition, and a method for producing the same An object of the present invention is to provide a liquid crystal display device and an organic EL display device.
Another object of the present invention is to provide a novel polyfunctional cyclic carbonate compound.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <14>, <15>, <16>, <18>, <19> or <20>. It is described below together with <2> to <13>, <17>, <21> and <22> which are preferred embodiments.
<1> (Component A) a resin having an acid-decomposable group and a crosslinkable group, (Component B) a radiation-sensitive acid generator, and (Component C) having no amino group and having two or more cyclic carbonate structures A positive photosensitive resin composition comprising a compound,
<2> The positive photosensitive resin composition according to <1>, wherein the component C is a compound represented by the following formula (1):

（式（１）中、Ｌは２価以上のアルキレン基、２価以上のアリーレン基、エステル結合、エーテル結合、ウレタン結合、及び、ウレア結合よりなる群から選ばれた基又はこれらを２以上組み合わせた基を表し、ｍは０又は１を表し、ｎは１以上の整数を表す。）

(In Formula (1), L is a group selected from the group consisting of a divalent or higher valent alkylene group, a divalent or higher arylene group, an ester bond, an ether bond, a urethane bond, and a urea bond, or a combination of two or more thereof. M represents 0 or 1, and n represents an integer of 1 or more.)

<3> The above <1> or <2>, wherein L is a group selected from the group consisting of an alkylene group, an arylene group, an ester bond, and an ether bond, or a group obtained by combining two or more of these. Positive photosensitive resin composition,
<4> The positive photosensitive resin composition according to any one of <1> to <3>, wherein Component C is a compound having two cyclic carbonate structures,
<5> The positive photosensitive resin composition according to any one of the above <1> to <4>, wherein m is 0 and n is 1.
<6> The positive photosensitive resin composition according to any one of <1> to <4>, wherein Component C is a compound represented by the following formula (2):

（式（２）中、ｎは１〜５の整数を表す。）

(In formula (2), n represents an integer of 1 to 5)

<7> The positive photosensitive resin composition according to any one of <1> to <6>, wherein the component A further has an acid group,
<8> The positive electrode according to any one of <1> to <7>, wherein the component A is a resin having an acid-decomposable group that decomposes with an acid to generate a carboxyl group, a crosslinkable group, and a carboxyl group. Type photosensitive resin composition,
<9> In any one of the above items <1> to <8>, wherein the component A has a structural unit represented by the following formula (a1-1) or formula (a1-2) as an acid-decomposable group The positive photosensitive resin composition as described,

<10> The positive photosensitive resin composition according to any one of the above <1> to <9>, wherein the crosslinkable group is an oxetanyl group or an epoxy group,
<11> The positive photosensitive resin composition according to any one of the above <1> to <10>, wherein Component B is a compound having an oxime sulfonate group,
<12> (Component D) The positive photosensitive resin composition according to any one of the above <1> to <11>, further containing a basic compound,
<13> The content of component A is 1 to 99% by weight, the content of component B is 0.1 to 10% by weight, the content of component C is 1 to 30% by weight, and the content of component D The positive photosensitive resin composition according to <12>, wherein the amount is 0.001 to 2% by weight,
<14> (1) An application step of applying the positive photosensitive resin composition according to any one of the above <1> to <13> on a substrate, (2) an applied photosensitive resin composition An exposure step of exposing with an actinic ray, (3) a development step of developing the exposed photosensitive resin composition with an aqueous developer, and (4) a post-baking step of thermosetting the developed photosensitive resin composition, A method for forming a cured film comprising:
<15> A cured film formed by the method according to <14> above,
<16> A cured film formed by applying at least one of light and heat to the positive photosensitive resin composition according to any one of <1> to <13> above,
<17> The cured film according to <15> or <16>, which is an interlayer insulating film,
<18> A liquid crystal display device comprising the cured film according to any one of the above <15> to <17>,
<19> An organic EL display device comprising the cured film according to any one of <15> to <17> above,
<20> A polyfunctional cyclic carbonate compound represented by the following formula (3):

（式（３）中、Ｌは（ｎ＋１）価のアリーレン基を表し、ｍは０又は１を表し、ｎは１〜５の整数を表す。）

(In formula (3), L represents an (n + 1) -valent arylene group, m represents 0 or 1, and n represents an integer of 1 to 5)

<21> The polyfunctional cyclic carbonate compound according to <20>, wherein m is 0 and n is 1.
<22> The polyfunctional cyclic carbonate compound according to <20>, which is a compound represented by the following formula (4).

（式（４）中、ｎは１〜５の整数を表す。）

(In formula (4), n represents an integer of 1 to 5)

According to the present invention, a positive photosensitive resin composition having high resistance to a stripping solution and NMP of the cured film obtained and having excellent PED characteristics, a cured film using the positive photosensitive resin composition, and a method for producing the same In addition, a liquid crystal display device and an organic EL display device could be provided.
Moreover, according to this invention, the novel polyfunctional cyclic carbonate compound was able to 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) a resin having an acid-decomposable group and a crosslinkable group” or the like is also simply referred to as “Component A” or the like, and “(a1) a structure having a residue in which an acid group is protected by an acid-decomposable group”. The “unit” 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”) includes (Component A) a resin having an acid-decomposable group and a crosslinkable group, and (Component B) a radiation-sensitive material. And an acid generator (hereinafter, also simply referred to as “initiator”) and (Component C) a compound having no amino group and having two or more cyclic carbonate structures.

The photosensitive resin composition of the present invention is a positive photosensitive resin composition.
The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).
The photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as the (Component B) radiation-sensitive acid generator. A 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
On the other hand, the oxime sulfonate compound acts as a catalyst for the deprotection of the acidic group protected by the acid generated in response to actinic rays, so that the acid generated by the action of one photon is It contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as a power of 10, and high sensitivity is obtained as a result of so-called chemical amplification.

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

(Component A) Resin Having Acid-Decomposable Group and Crosslinkable Group The photosensitive resin composition of the present invention contains (Component A) a resin having an acid-decomposable group and a crosslinkable group.
(Component A) The resin having an acid-decomposable group and a crosslinkable group is preferably a resin having a structural unit having an acid group protected with an acid-decomposable group and a structural unit having a crosslinkable group. .
In the present invention, the “acid-decomposable group” means a functional group capable of generating an acid group protected by the acid-decomposable group by decomposing in the presence of an acid.
The acid group generated by the decomposition of the acid-decomposable group is preferably a carboxy group or a phenolic hydroxyl group, and more preferably a carboxy group.
The acid-decomposable group is preferably a residue whose acid group is protected with an acetal or ketal.
Component A preferably further has an acid group, more preferably a structural unit having an acid group, a structural unit having an acid-decomposable group, a structural unit having an oxetanyl group or an epoxy group, and A resin having a structural unit having an acid group is more preferable.

Component A is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group in the molecule is decomposed.
In the present invention, the component A is “alkali-soluble” is formed by applying a solution containing the component A after decomposition of the acid-decomposable group onto a substrate and heating at 90 ° C. for 2 minutes. It means that the dissolution rate in a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. indicated by the coating film (thickness: 3 μm) is 0.01 μm / second or more. The alkali solubility is preferably such that the dissolution rate is 0.005 μm / second or more.
In addition, in the present invention, the component A is “alkali insoluble” means that a coating film (thickness 3 μm) formed by applying a solution containing the component A on a substrate and heating at 90 ° C. for 2 minutes. It means that the dissolution rate with respect to a 0.4 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. is less than 0.01 μm / second. The alkali insolubility is preferably such that the dissolution rate is less than 0.005 μm / second.
Component A does not exclude the introduction of acidic groups as long as it remains entirely insoluble in alkali. Examples of the case where an acidic group is introduced into component A include a case where it has a structural unit (a3) described later.

Component A is preferably an acrylic polymer.
The “acrylic polymer” in the present invention is an addition polymerization type resin, is a polymer containing monomer units derived from (meth) acrylic acid and / or its ester, and (meth) acrylic acid and / or its You may have monomer units other than the monomer unit derived from ester, for example, the monomer unit derived from styrene, the monomer unit derived from a vinyl compound, etc.
Component A is preferably a monomer unit derived from (meth) acrylic acid and / or an ester thereof in an amount of 50 mol% or more, more preferably 80 mol% or more based on all monomer units in the polymer. Particularly preferred is a polymer consisting only of monomer units derived from (meth) acrylic acid and / or its ester.
The “monomer unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic monomer unit”. Moreover, (meth) acrylic acid shall mean methacrylic acid and / or acrylic acid.

<Structural Unit (a1) Having Acid Group Protected with Acid-Decomposable Group>
Component A preferably has a structural unit (a1) having an acid group protected with an acid-decomposable group (hereinafter, also simply referred to as “structural unit (a1)”) from the viewpoint of sensitivity.
Preferred examples of the acid group in the structural unit (a1) include a carboxy group and a phenolic hydroxyl group.

(1-1) A structural unit having a residue in which a carboxy group is protected with an acid-decomposable group (1-1) As a structural unit having a residue in which a carboxy group is protected with an acid-decomposable group, It is preferable that it is a structural unit which has the residue in which the carboxy group contained in the structural unit as described in 1-1-1) and (1-1-2) was protected by the acid-decomposable group.

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

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

(1-1) Structural unit having a residue in which a carboxy group is protected with an acid-decomposable group The structural unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferably the above-mentioned (1-1- 1) A structural unit having a residue in which a carboxy group contained in the structural unit described in (1-1-2) 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 (1-1), a structural unit having a residue in which a carboxy group is protected with an acetal, or a residue in which a carboxy group is protected with a ketal has sensitivity, pattern shape, or contact hole formability. It is preferable from the viewpoint.

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

（式（Ａ１）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、アルキル基、又は、アリール基を表し、少なくともＲ¹及びＲ²のいずれか一方が前記アルキル基、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。）

(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 the alkyl group or 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.)

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

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

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

（式（Ａ２）中、Ｒ¹及びＲ²は、それぞれ独立に水素原子、アルキル基又はアリール基を表し、少なくともＲ¹及びＲ²のいずれか一方が前記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, and at least ^one of R ¹ and R ² is the alkyl group or aryl group, and R ³ Represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene Represents a group.)

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, 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.

  As the structural unit (1-1) having a residue in which a carboxy group is protected with an acid-decomposable group, a structural unit represented by the following formula (5) is more preferable.

（式（５）中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基を表し、Ｌ¹はカルボニル基又はフェニレン基を表し、Ｒ²¹〜Ｒ²⁷はそれぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。）

(In Formula (5), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ^{21 to} R ²⁷ each independently represents a hydrogen atom or a carbon number. Represents 1 to 4 alkyl groups.)

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

The structural unit (1-1) may be a residue in which a carboxy group is protected with a tertiary alkyl group represented by the formula (A3). The sensitivity is inferior to that of a residue protected with an acetal or ketal, but it is preferable in terms of excellent storage stability. In addition, when the carboxy group is a residue protected with a tertiary alkyl group represented by the formula (A3), the entire residue 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. 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.

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

(1-2-1) Structural Unit Having Phenolic Hydroxyl Group Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolac-based 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, and a linear or branched alkylene group having 1 to 6 carbon atoms is preferable. 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, from the viewpoint of the effect of this invention and the point that manufacture is easy, it is preferable that a is 1 or 2, and it is more preferable that a is 1. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 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.

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

  Examples of the radical polymerizable monomer used to form a structural unit having a residue in which a phenolic hydroxyl group is protected with an acetal or ketal include, for example, a 1-alkoxyalkyl protector of hydroxystyrene, a hydroxystyrene Protected tetrahydropyranyl, 1-alkoxyalkyl protected α-methyl-hydroxystyrene, protected tetrahydropyranyl α-methyl-hydroxystyrene, protected tetrahydrofuranyl 4-α-methyl-hydroxystyrene, 4-hydroxyphenyl methacrylate 1-alkoxyalkyl protector, 4-hydroxyphenyl methacrylate tetrahydropyranyl protector, 4-hydroxyphenyl methacrylate protector of tetrahydrofuranyl, 4-hydroxybenzoic acid (1-methacryloylio) 1-alkoxyalkyl protector of (cimethyl) ester, tetrahydropyranyl protector of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, tetrahydrofuranyl protector of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 1-alkoxyalkyl protected form of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, tetrahydropyranyl protected form of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid (2-methacryloyl) Oxyethyl) ester tetrahydrofuranyl protected, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) 1-alkoxyalkyl protected, 4-hydroxybenzoic acid (3-methacryloylio) Cypropyl) ester tetrahydropyranyl protected, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester tetrahydrofuranyl protected, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester 1-alkoxy Protected alkyl, tetrahydropyranyl protected 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester, protected tetrahydrofuranyl 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester Etc. Of these, a 1-alkoxyalkyl protector of α-methyl-hydroxystyrene is preferred.

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

  A commercially available thing may be used for the radically polymerizable monomer used in order to form a structural unit (1-2), 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 (1-2) include the following structural units, but the present invention is not limited thereto. R represents a hydrogen atom or a methyl group.

A structural unit having a residue in which a carboxy group is protected with an acid-decomposable group develops faster than a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Therefore, when it is desired to develop quickly, a structural unit having a residue in which a carboxy group is protected with an acid-decomposable group is preferable. Conversely, when it is desired to delay development, it is preferable to use a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group.
Among these, component A particularly preferably has a structural unit represented by the following formula (a1-1) or formula (a1-2) as an acid-decomposable group.

  10-80 mol% is preferable and, as for the content rate of the monomer unit which forms a structural unit (a1) in all the monomer units which comprise the component A, 30-80 mol% is more preferable.

<Structural Unit (a2) Having Crosslinkable Group>
Component A preferably contains a structural unit (a2) having a crosslinkable group (hereinafter also referred to as “structural unit (a2)”).
The crosslinkable group is preferably an epoxy group and / or an oxetanyl group.
That is, component A preferably has a structural unit having an epoxy group and / or an oxetanyl group.
The structural unit having an epoxy group and / or oxetanyl group is preferably a structural unit having an alicyclic epoxy group and / or oxetanyl group, and more preferably a structural unit having an oxetanyl group.
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 constitutional unit having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one constitutional unit, one or more epoxy groups and one or more oxetanyl groups, two Although it may have the above epoxy groups or two or more oxetanyl groups and is not particularly limited, it preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and epoxy groups and / or oxetanyl groups. It is more preferable to have one or two groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

  Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 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.

  Examples of the radical polymerizable monomer used to form a structural unit having an epoxy group and / or an oxetanyl group are a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure. preferable.

  Among these monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs 0011 to 0016 of JP 2001-330953 A. (Meth) acrylic acid esters having an oxetanyl group, particularly preferred are (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Among these, preferred are 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 monomer units can be used singly or in combination of two or more.

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

  The content of the monomer unit forming the structural unit (a2) having a crosslinkable group in all the monomer units constituting Component A is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and more preferably 20 to 65 mol%. Mole% is particularly preferred. By containing in the above ratio, the physical properties of the cured film are improved.

<Constitutional Unit Having Acid Group (a3)>
Component A preferably contains a structural unit (a3) having an acid group (hereinafter also referred to as “structural unit (a3)”).
The acid group is preferably a carboxy group, a carboxylic anhydride residue and / or a phenolic hydroxyl group, more preferably a carboxy group and / or a phenolic hydroxyl group, and still more preferably a carboxy group.
Component A preferably contains a carboxy group, a carboxylic acid anhydride residue and / or a structural unit having a phenolic hydroxyl group as long as component A is not alkali-soluble, and has a carboxy group and / or a phenolic hydroxyl group. It is more preferable to contain a structural unit, and a structural unit having a carboxy group is still more preferable.
Examples of the radical polymerizable monomer used to form the structural unit having a carboxy group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, Preferred examples include 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. In particular, 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 preferable. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a3) include the following structural units.

  The content of monomer units forming the structural unit (a3) having an acid group in all monomer units constituting Component A is preferably 1 to 25 mol%, more preferably 2 to 25 mol%, and more preferably 3 to 20 mol. % Is particularly preferred. By containing in the above proportion, high sensitivity is obtained and developability is also improved.

<Other structural units (a4)>
Component A may contain a structural unit (a4) other than the structural units (a1) to (a3) (hereinafter also referred to as “structural unit (a4)”) as long as the effects of the present invention are not hindered. Good.
Examples of the radical polymerizable monomer used to form the structural unit (a4) include the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (provided that the above (a1) ) To (a3) monomer units are excluded.).
Among these, (meth) acrylic acid esters containing alicyclic structures such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl acrylate, methyl (meth) acrylate, (meth) Preferred examples include 2-hydroxyethyl acrylate and styrene. Among these, 2-hydroxyethyl (meth) acrylate can be illustrated more preferably.
These structural units (a4) can be used individually by 1 type or in combination of 2 or more types.

  The content of the monomer unit forming the structural unit (a4) in the case where the component A has the structural unit (a4) in all monomer units constituting the component A is preferably 1 to 50 mol%, and preferably 5 to 40 mol%. Is more preferable, and 5 to 30 mol% is particularly preferable.

  The weight average molecular weight of Component A is preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. In addition, 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).

  Various methods for synthesizing the component A are known. For example, the component A is used to form at least the structural unit (a1), the structural unit (a2), and the structural unit (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. Further, a chain transfer agent such as α-methylstyrene dimer or thiol compound may be used during the polymerization.

The photosensitive resin composition of this invention can contain the component A individually by 1 type or in combination of 2 or more types.
The content of Component A in the photosensitive resin composition of the present invention is preferably 1 to 99% by weight, and preferably 1 to 97% by weight, based on the total solid content of the photosensitive resin composition. More preferably, it is more preferably 1 to 95% by weight, and particularly preferably 1 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.
In addition, in the photosensitive resin composition of this invention, you may use together resin other than the component A in the range which does not prevent the effect of this invention. However, the content of the resin other than Component A is preferably smaller than the content of Component A from the viewpoint of developability.

(Component B) Radiation-sensitive acid generator The photosensitive resin composition of the present invention contains (Component B) a radiation-sensitive acid generator.
The radiation-sensitive acid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid, but is not limited to its chemical structure. . Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
The radiation-sensitive acid generator used in the present invention is preferably a radiation-sensitive acid generator that generates an acid having a pKa of 4 or less, and more preferably a radiation-sensitive acid generator that generates an acid having a pKa of 3 or less. In addition, about pKa, a value can be calculated | required by a well-known measuring method, a well-known calculation method, and / or literature value.
Examples of the radiation-sensitive acid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more.

Specific examples of 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 and the like;

  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, etc .;

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

  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, bis (p-toluenesulfonyl) diazomethane, and the like;

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-dicarboximidopropane sulfonate and the like;
The compound shown below as an oxime sulfonate compound.

  Preferred examples of the oxime sulfonate compound, that is, the compound having an oxime sulfonate residue include compounds containing an oxime sulfonate residue represented by the formula (B-1).

In Formula (B-1), R ⁵ represents an alkyl group, an aryl group, or a heteroaryl group, and a wavy line represents a bonding position with another chemical structure. Any group may be substituted, and the alkyl group in R ⁵ may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
The alkyl group of R ⁵ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged type fat It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^5, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.
The heteroaryl group for R ⁵ is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the heteroaryl group in R ⁵ may have include a halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, aminocarbonyl Group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group.
The heteroaryl group in R ⁵ may be such that at least one ring is a heteroaromatic ring, and for example, a heteroaromatic ring and a benzene ring may be condensed.
The heteroaryl group in R ⁵ may have a substituent, a group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring And a group in which one hydrogen atom is removed from the ring selected from the above.
The compound containing an oxime sulfonate residue represented by the formula (B-1) is more preferably an oxime sulfonate compound represented by the following formula (B-2).

In formula (B-2), R ⁵ has the same meaning as R ⁵ in formula (B-1), X represents an alkyl group, an alkoxy group, or a halogen atom, and m represents an integer of 0 to 3. And when m 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.
m is preferably 0 or 1.
In formula (B-1), m is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferred.

  Specific examples of the oxime sulfonate compound include the following compound (i), compound (ii), compound (iii), compound (iv), and the like. These may be used alone or in combination of two or more. be able to. Compounds (i) to (iv) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

  The radiation sensitive acid generator is preferably a radiation sensitive acid generator represented by the formula (II).

In the formula (II), R ^4A 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, a cyano group or a nitro group, and L is an integer of 0 to 5 Represents. R ^3A 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 It represents a 10 alkyl group, 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 ^3A in the formula (II) includes methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro group, A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and a methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group is particularly preferable. .
The halogen atom represented by R ^4A is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms represented by R ^4A is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by R ^4A is preferably a methoxy group or an ethoxy group.
As L, 0-2 are preferable, and 0-1 are particularly preferable.

As a preferred embodiment of the compound included in the photoacid generator represented by the formula (II), R ^3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tolyl group, R ^4A represents a hydrogen atom or a methoxy group, and L is an embodiment of 0 to 1.

  Hereinafter, although the especially preferable example of the compound included by the radiation sensitive acid generator represented by Formula (II) is shown, this invention is not limited to these.

α- (Methylsulfonyloxyimino) benzyl cyanide (R ^3A = methyl group, R ^4A = hydrogen atom)
α- (Ethylsulfonyloxyimino) benzyl cyanide (R ^3A = ethyl group, R ^4A = hydrogen atom)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ^3A = n-propyl group, R ^4A = hydrogen atom)
α- (n-butylsulfonyloxyimino) benzyl cyanide (R ^3A = n-butyl group, R ^4A = hydrogen atom)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ^3A = 4-tolyl group, R ^4A = hydrogen atom)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = methyl group, R ^4A = methoxy group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = ethyl group, R ^4A = methoxy group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-propyl group, R ^4A = methoxy group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-butyl group, R ^4A = methoxy group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = 4-tolyl group, R ^4A = methoxy group)

  The compound containing an oxime sulfonate residue represented by the formula (B-1) is also preferably a compound represented by the formula (OS-1).

In the formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or hetero Represents an aryl group. R ² represents an alkyl group or an aryl group.
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 an aryl group is represented.
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 aforementioned functional groups may further have a substituent.

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

In said formula (OS-2), R < ¹ >, R < ² >, R < ²¹ > -R < ²⁴ > is synonymous with the thing in a formula (OS-1), respectively, and its preferable example is also the same.
Among these, the aspect in which R ¹ in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), and R ¹ is a cyano group. The embodiment which is a phenyl group or a naphthyl group is most preferable.

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

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

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

  The compound containing an oxime sulfonate residue represented by the formula (B-1) is an oxime sulfonate compound represented by the formula (OS-3), formula (OS-4) or formula (OS-5). Preferably there is.

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

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

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group, or heteroaryl group in R ¹ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, Examples include phenoxycarbonylethyl group and dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, An n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

In the formulas (OS-3) to (OS-5), the aryl group for R ¹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the aryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. , A sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group.

As the aryl group in R ¹ , a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, a p-phenoxyphenyl group, a p-methylthiophenyl group, p -Phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, p-dimethylaminocarbonylphenyl group.
Among these, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.

Further, the formula (OS-3) ~ (OS -5), as the heteroaryl group in R ^1, heteroaryl group having a total carbon number of 4-30 which may have a substituent is preferable.
Examples of the substituent that the heteroaryl group in R ¹ may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl. Group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group.

In the formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R ¹ may be a heteroaromatic ring. For example, a heteroaromatic ring and a benzene ring are condensed. May be.
The heteroaryl group in R ¹ may have a substituent, the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring And a group in which one hydrogen atom is removed from the ring selected from the above.

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

The alkyl group for R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and an alkyl group having 1 to 6 carbon atoms which may have a substituent. It is more preferable.
Specific examples of the alkyl group for R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, allyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, perfluorohexyl group, chloromethyl group, bromomethyl group, methoxymethyl group, benzyl group, phenoxyethyl group, methylthioethyl Group, phenylthioethyl group, ethoxycarbonylethyl group, phenoxycarbonylethyl group, dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromomethyl group, Methoxymethyl group and benzyl group are preferable, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and n-hexyl group are more preferable, and methyl group , An ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is particularly preferable.

The aryl group for R ² is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
Specific examples of the aryl group for R ² include phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group, p-methylthiophenyl group, p- Examples include a phenylthiophenyl group, a p-ethoxycarbonylphenyl group, a p-phenoxycarbonylphenyl group, and a p-dimethylaminocarbonylphenyl group.
Among these, a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group are preferable.
Examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among these, a chlorine atom and a bromine atom are preferable.

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

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group in R ⁶ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyl group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .

Examples of the alkyl group in R ⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, Examples include phenoxycarbonylethyl group and dimethylaminocarbonylethyl group.
Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, An n-decyl group, an n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

In the formulas (OS-3) to (OS-5), the alkyloxy group for R ⁶ is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.
Examples of the substituent that the alkyloxy group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. It is done.

Examples of the alkyloxy group in R ⁶ include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, an ethoxyethyloxy group, a methylthioethyloxy group, a phenylthioethyloxy group, and an ethoxy group. Examples thereof include carbonylethyloxy group, phenoxycarbonylethyloxy group, and dimethylaminocarbonylethyloxy group.
Among these, a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
In the formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group. It is done.
In the formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

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

  Moreover, the compound containing the oxime sulfonate residue represented by the formula (B-1) is an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11). Particularly preferred.

（式（ＯＳ−６）〜（ＯＳ−１１）中、Ｒ¹はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ⁷は、水素原子又は臭素原子を表し、Ｒ⁸は水素原子、炭素数１〜８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒ⁹は水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒ¹⁰は水素原子又はメチル基を表す。）

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

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

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

In the photosensitive resin composition of the present invention, Component B is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of Component A.
Moreover, in the photosensitive resin composition of this invention, it is preferable that the component B is contained 0.1 to 10weight% with respect to the total solid content of the photosensitive resin composition, 0.2 to 10weight% More preferably it is contained.

The photosensitive resin composition of the present invention preferably contains a sensitizer in order to accelerate its decomposition in combination with a radiation-sensitive acid generator.
The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the radiation-sensitive acid generator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the radiation-sensitive acid generator undergoes a chemical change and decomposes to generate an acid.
Examples of preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the 350 nm to 450 nm regions.

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

  Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

(Component C) Compound having no amino group and having two or more cyclic carbonate structures The photosensitive resin composition of the present invention is (Component C) a compound having no amino group and having two or more cyclic carbonate structures. Containing.
In the cured film obtained by curing the photosensitive resin composition of the present invention, the cyclic carbonate structure in Component C is presumed to react with an acid group to form a crosslinked structure in the same manner as the crosslinkable group in Component A.
In addition, since the photosensitive resin composition of the present invention has no amino group (primary, secondary, and tertiary) in the molecule thereof, the generated acid is not quenched. A sensitive positive photosensitive composition can be obtained, and the resulting cured film has high resistance to a stripping solution and NMP, and is excellent in sensitivity and PED characteristics.
Component C has 2 or more cyclic carbonate structures, preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2.
The number of ring members in the cyclic carbonate structure is not particularly limited, but is preferably 5 or 6, and more preferably 5. That is, Component C preferably has 2 or more 5- or 6-membered cyclic carbonate structures, and more preferably 2 or more 5-membered cyclic carbonate structures.
Component C is preferably a compound represented by the following formula (1).

（式（１）中、Ｌは２価以上のアルキレン基、２価以上のアリーレン基、エステル結合、エーテル結合、ウレタン結合、及び、ウレア結合よりなる群から選ばれた基又はこれらを２以上組み合わせた基を表し、ｍは０又は１を表し、ｎは１以上の整数を表す。）

(In Formula (1), L is a group selected from the group consisting of a divalent or higher valent alkylene group, a divalent or higher arylene group, an ester bond, an ether bond, a urethane bond, and a urea bond, or a combination of two or more thereof. M represents 0 or 1, and n represents an integer of 1 or more.)

L in Formula (1) is preferably a group selected from the group consisting of a divalent or higher alkylene group, a divalent or higher arylene group, an ester bond, and an ether bond, or a combination of two or more thereof. A group in which two or more alkylene groups, two or more arylene groups, or two or more alkylene groups, two or more arylene groups, and a group selected from the group consisting of ether bonds are combined. More preferably, it is a divalent or higher valent arylene group.
The alkylene group and arylene group may have a substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, and a halogen atom.
The number of carbon atoms of L in formula (1) is preferably 1-20, more preferably 1-10, and even more preferably 2-6.
N in Formula (1) is preferably an integer of 1 to 9, more preferably an integer of 1 to 5, and particularly preferably 1.
Component C is a compound represented by Formula (1) in which m is 0 and n is 1, or a compound represented by Formula (2) below. preferable.

（式（２）中、ｎは１〜５の整数を表す。）

(In formula (2), n represents an integer of 1 to 5)

N in the formula (2) is preferably an integer of 1 to 3, particularly preferably 1.
In addition, the substitution position on the benzene ring in the formula (2) is not particularly limited and may be any position.

  As specific examples of Component C, the following C-1 to C-17 can be preferably exemplified, but the present invention is not limited thereto. In the chemical formula below, Me represents a methyl group.

  Among these, C-1 to C-11 and C-15 to C-17 are preferable, C-1 to C-3 and C-15 to C-17 are more preferable, and C-1 to C-3 and C-17 are preferable. -15 is particularly preferred.

Component C may use only 1 type in the photosensitive resin composition of this invention, and can also use 2 or more types together.
The content of component C is preferably 0.1 to 50% by weight, more preferably 0.2 to 40% by weight, and more preferably 1 to 30% with respect to the total solid content of the photosensitive resin composition. Weight percent is optimal. Within the above range, sufficient transparency of the formed film is obtained, and excellent sensitivity at the time of pattern formation is exhibited.

(Component D) Basic Compound The photosensitive resin composition of the present invention preferably contains (Component D) a basic compound.
(Component D) The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

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, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7 -Undecene and the like.

  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.
The content of the (Component D) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 2 parts by weight, and 0.002 to 0.2 parts by weight with respect to 100 parts by weight of Component A. More preferably, it is a part.
The photosensitive resin composition of the present invention has a component A content of 1 to 99% by weight, a component B content of 0.1 to 10% by weight, and a component C content of 1 to 30% by weight. And the content of component D is preferably 0.001 to 2% by weight. The photosensitive resin composition of the present invention has a component A content of 1 to 99% by weight and a component B content of 0.1 to 10% by weight based on the total solid content of the photosensitive resin composition. %, The content of component C is 1 to 30% by weight, and the content of component D is more preferably 0.001 to 2% by weight.

(Component E) Solvent The photosensitive resin composition of the present invention preferably contains (Component E) a solvent from the viewpoints of coatability and film formability.
The photosensitive resin composition of the present invention is prepared as a solution in which components A to C which are essential components, component D which is a preferred component, and optional components described below are further dissolved in (component E) solvent. Is preferred.
As the (component E) solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, Propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene Examples include glycol monoalkyl ether acetates, esters, ketones, amides, and lactones.

As the (component E) solvent used in the photosensitive resin composition of the present invention, for example,
(A) Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
(A) Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether;
(C) Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
(D) Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
(E) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether;

(F) 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;
(G) Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
(H) Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
(G) Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
(Co) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether;

(Sa) 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;
(L) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
(S) 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, propionate Aliphatic carboxylic acid esters such as isobutyl acid, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
(C) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl Other esters such as butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;
(So) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;

(Ta) Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
(H) Examples include 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.
These solvents can be used alone or in combination of two or more.

  The content of the (component E) solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight and more preferably 100 to 2,000 parts by weight per 100 parts by weight of component A. The amount is preferably 100 to 1,500 parts by weight.

<Other ingredients>
In addition to the components A to E, the photosensitive resin composition of the present invention includes, as necessary, optional components (component F) surfactant, (component G) antioxidant, (component) H) adhesion improver, (component I) plasticizer, and (component J) thermal radical generator, thermal acid generator, ultraviolet absorber, thickener, organic or inorganic precipitation inhibitor, etc. Known additives can be added.

(Component F) Surfactant The photosensitive resin composition of the present invention preferably contains (Component F) a surfactant.
As (Component F) 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, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by JEMCO), Mega Fuck (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Made by Co., Ltd.), Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), and the like.
In addition, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula (F-1), and is a polystyrene equivalent weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. Preferred examples include copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

（式（Ｆ−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 Formula (F-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 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 10% by weight to 80% by weight. A numerical value is represented, q represents a numerical value of 20% by weight or more and 90% by weight or less, r represents an integer of 1 to 18 and n represents an integer of 1 to 10)

The L is preferably a branched alkylene group represented by the following formula (F-2). R ⁵ in Formula (F-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 with respect to the coated surface. Two or three alkyl groups are more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by weight.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of (Component F) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, and preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of Component A. More preferred is 0.01 to 1 part by weight.

(Component G) Antioxidant The photosensitive resin composition of the present invention preferably contains (Component G) an antioxidant.
(Component G) As antioxidant, a well-known antioxidant can be contained. (Component G) By adding an antioxidant, there is an advantage that coloring of a 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-60 (manufactured by ADEKA), ADK STAB AO-80 (manufactured by ADEKA), and Irganox 1098 (manufactured by Ciba Japan Co., Ltd.). It is done.

The content of (Component G) antioxidant is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, based on the total solid content of the photosensitive resin composition. It is preferably 0.5 to 4% by weight. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation 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 for the photosensitive property of the present invention. You may add to a resin composition.

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

Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Of 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 (Component H) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of Component A.

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

(Component J) Thermal radical generator The photosensitive resin composition of the present invention may contain (Component J) a thermal radical generator, and is a compound having at least one ethylenically unsaturated double bond as described above. When such an ethylenically unsaturated compound is contained, it is preferable to contain (Component J) a thermal radical generator.
As the thermal radical generator in the present invention, a known thermal radical generator can be used.
The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film becomes tougher and heat resistance and solvent resistance may be improved.
Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon Examples thereof include compounds having a halogen bond, azo compounds, and bibenzyl compounds.
(Component J) A thermal radical generator may be used alone or in combination of two or more.
From the viewpoint of improving film properties, the amount of (Component J) thermal radical generator added to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight when component A is 100 parts by weight. 0.1 to 20 parts by weight is more preferable, and 0.5 to 10 parts by weight is most 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 preferably includes the following steps (1) to (4).
(1) Application step of applying the positive photosensitive resin composition of the present invention onto a substrate (2) An exposure step of exposing the applied photosensitive resin composition with actinic rays,
(3) a development step of developing the exposed photosensitive resin composition with an aqueous developer, and
(4) a post-baking step of thermosetting the developed photosensitive resin composition;
Each step will be described below in order.

In the coating step (1), the photosensitive resin composition of the present invention is coated on a substrate to form a wet film containing a solvent.
Moreover, when the positive photosensitive resin composition of this invention contains a solvent, the formation method of the cured film of this invention was apply | coated between the application process of (1), and the exposure process of (3). It is preferable to include a solvent removal step of removing the solvent from the photosensitive resin composition.
In the solvent removing step, the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.

  In the exposure step (2), the obtained coating film is irradiated with actinic rays having a wavelength of 300 nm or more and 450 nm or less. In this step, (Component B) the radiation-sensitive acid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in Component A is decomposed to produce an acid group.

  In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment (Post Exposure Bake (hereinafter also referred to as “PEB”)) can be performed as necessary. PEB can promote the formation of a carboxy group from an acid-decomposable group.

The acid-decomposable group in component A in the present invention has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from an acid generator by exposure to generate an acid group. Therefore, development without necessarily performing PEB Thus, a positive image can also be formed.
In addition, by performing PEB at a relatively low temperature, hydrolysis of an acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is performed 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 80 ° C. or lower.

In the developing step (3), the resin having a liberated acid group is developed using an alkaline developer. A positive image is formed by removing an exposed area made of a composition containing a resin having an acid group that is easily dissolved in an alkaline developer.
In the post-baking step of (4), the obtained positive image is heated to thermally decompose the acid-decomposable group in component A to generate an acid group and to crosslink with the crosslinkable group, thereby forming a cured film. Can be formed. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.

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

<Method for preparing photosensitive resin composition>
The essential components of component A to component C are mixed at a predetermined ratio and in an arbitrary manner, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a resin composition by preparing components A to C in advance as solutions in which each of components A to C is previously dissolved in a (component E) solvent and then mixing them in a predetermined ratio. The resin composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

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

  The heating condition of the solvent removal step is a range in which the acid-decomposable group in the component A in the unexposed part is decomposed and the component A is not soluble in the alkaline developer. However, it is preferably about 80 to 130 ° C. for about 30 to 120 seconds.

<Exposure process and development process (pattern formation method)>
In the exposure step, the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. After the exposure step, heat treatment (PEB) is performed as necessary, and then in the development step, the exposed area is removed using an alkaline developer to form an image pattern.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, or the like can be used. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.

  A basic compound is used for the developer used in the development step. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.

The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be either a liquid piling method or a dipping method. After the development, washing with running water is performed for 30 to 90 seconds, and a desired pattern can be formed.

<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, by performing heat treatment for 30 to 90 minutes, the acid-decomposable group in Component A is decomposed to generate an acid group, react with the crosslinkable group in Component A, and crosslink. A protective film or an interlayer insulating film having excellent 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 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 component B present in the unexposed portion, thereby performing a crosslinking step. It is preferable to function as a promoting catalyst.
That is, it is preferable that the method for forming a cured film of the present invention includes a re-exposure step in which re-exposure is performed with active light between the development step and the post-bake step.
The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable. A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for organic EL display devices and liquid crystal display devices.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a flattening film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to a planarization film and an interlayer insulating film, it can be suitably used for a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, or the like. .

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

(Polyfunctional cyclic carbonate compound)
The polyfunctional cyclic carbonate compound of the present invention is represented by the following formula (3). The polyfunctional cyclic carbonate compound of the present invention is a novel compound and is useful as an additive for a positive photosensitive resin composition.

（式（３）中、Ｌは（ｎ＋１）価のアリーレン基を表し、ｍは０又は１を表し、ｎは１〜５の整数を表す。）

(In formula (3), L represents an (n + 1) -valent arylene group, m represents 0 or 1, and n represents an integer of 1 to 5)

N in Formula (3) is preferably an integer of 1 to 3, and is particularly preferably 1.
L in Formula (3) is preferably an (n + 1) -valent phenylene group or an (n + 1) -valent naphthylene group, and more preferably an (n + 1) -valent phenylene group.
Moreover, although the arylene group in L of Formula (3) may have a substituent, it is preferable not to have. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, and a halogen atom.
Further, the polyfunctional cyclic carbonate compound of the present invention is a compound represented by the formula (3) in which the m is 0 and the n is 1, or is represented by the following formula (4). More preferably, it is a compound.

（式（４）中、ｎは１〜５の整数を表す。）

(In formula (4), n represents an integer of 1 to 5)

N in the formula (4) is preferably an integer of 1 to 3, particularly preferably 1.
In addition, the substitution position on the benzene ring in formula (4) is not particularly limited, and may be any position.

  As specific examples of component C, the following C-1 to C-3 and C-15 to C-17 can be preferably exemplified, but the present invention is not limited thereto. In the chemical formula below, Me represents a methyl group.

  Among these, C-1 to C-3 and C-15 are preferable.

  Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Each abbreviation used in the following synthesis examples represents the following compound, respectively.
NBMA: n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate (FA-511A, manufactured by Hitachi Chemical Co., Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko KK)
HS-EDM: High Solve EDM (manufactured by Toho Chemical Industry Co., Ltd.)
α-methylstyrene dimer (Wako Pure Chemical Industries, Ltd.)
PHS: p-hydroxystyrene (synthetic product)
t-BuMA: t-butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

<Synthesis of MATHF (2-tetrahydrofuranyl methacrylate)>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (500 ml) was added, extracted with ethyl acetate (500 ml), dried over magnesium sulfate, insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Was distilled under reduced pressure to obtain 125 g of 2-tetrahydrofuranyl methacrylate (MATHF) as a colorless oily substance (yield 80%) of a boiling point (bp.) 54-56 ° C./3.5 mmHg fraction.

<Synthesis of Polymer A-1>
PGMEA (35.7 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MAA (1.72 g), MATHF (12.65 g), OXE-30 (11.05 g), HEMA (5.20 g), V-601 (3.47 g, 3 mol% with respect to the monomer) were added to the solution to PGMEA. (35.7 g) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby, a polymer A-1 was obtained. The weight average molecular weight was 15,000.

<Synthesis of Polymers A-2 to A-14>
Polymers A-2 to A-14 were respectively synthesized in the same manner as the synthesis of polymer A-1, except that each monomer, initiator, solvent, and amounts used thereof were changed to those shown in Table 1. did.

<Synthesis of Polymers Q-1 and Q-2>
HS-EDM (37.4 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. In the solution, MAA (6.9 g), MMA (5.8 g), St (22.9 g), NBMA (14.1 g), V-601 (8.28 g, 8 mol% based on monomer), α-methyl Styrene dimer (0.4 g) was dissolved in HS-EDM (37.4 g) and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours. V-601 (2.0 g, 2 mol% with respect to the monomer) was further added to the solution, and the mixture was further stirred for 2 hours to complete the reaction. Thereby, polymer Q-1 was obtained. The weight average molecular weight was 10,000.
Similarly, a polymer Q-2 was synthesized. Table 2 shows the types of monomers and solvents used and the amounts used. In addition, α-methylstyrene dimer which is a chain transfer agent was not used.

In Tables 1 and 2, the numerical values without particular units are in mol%. The numerical value of the initiator is mol% when the monomer component is 100 mol%. The solid content concentration was calculated by the following formula. When V-601 was used, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.
Monomer weight / (monomer weight + solvent weight) × 100 (unit: wt%)

<Synthesis of C-1>
Glycerol 1,2-carbonate (5.9 g, 0.05 mol) was dissolved in 30 mL of acetonitrile, triethylamine (5.0 g, 0.05 mol) was added, and the mixture was cooled to 0 ° C. and then phthaloyl chloride (5.1 g). , 0.025 mol) was added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature and stirred for 2 hours. Ethyl acetate (500 mL) and water (500 mL) were added, and the organic layer was extracted and concentrated. The crude product was subjected to silica gel column chromatography using ethyl acetate / hexane to isolate 6.13 g (yield 67%) of the desired product C-1.
¹ H-NMR (DMSO) δ = 4.41 (t, 2H), 4.45-4.57 (m, 6H), 5.09-5.19 (bs, 2H), 7.70-7.80 (bs, 4H). Colorless Oil

<Synthesis of C-2, C-3, C-6, C-10 and C-15>
C-2, C-3, C-6, C-10 and C-15 were isolated in the same manner as in the synthesis of C-1, except that the raw materials were changed. An example of each identification data is shown below.
C-2: ¹ H-NMR (DMSO) δ = 4.43-4.53 (m, 4H), 4.55-4.70 (m, 4H), 5.21-5.29 (bs, 2H), 7.77 (t, 1H), 8.23 (d , 2H), 8.49 (s, 1H). White Powder
C-3: ¹ H-NMR (DMSO) δ = 4.40-4.52 (m, 4H), 4.56-4.69 (m, 4H), 5.22-5.27 (bs, 2H), 8.09 (s, 4H). White Powder
C-6: ¹ H-NMR (DMSO) δ = 2.61 (s, 4H), 4.20-4.41 (m, 6H), 4.53 (t, 2H), 5.01-5.09 (bs, 2H). White Powder
C-10: ¹ H-NMR (DMSO) δ = 1.25 (s, 8H), 1.51 (t, 4H), 2.31 (t, 4H), 4.19-4.41 (m, 4H), 4.52 (t, 2H), 5.00-5.09 (bs, 2H)), White Powder
C-15 :: ¹ H-NMR (DMSO) δ = 4.39 (t, 2H), 4.4-4.57 (m, 6H), 5.03-5.11 (bs, 2H). White Powder

(Examples 1-22 and Comparative Examples 1-9)
(1) Preparation of photosensitive resin composition solution Each component shown in Table 3 below was mixed to obtain a uniform solution, and then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 μm. The photosensitive resin composition solution of Examples 1-22 and Comparative Examples 1-9 was prepared, respectively.

In addition, the unit of the addition amount in Table 3 is parts by weight.
Abbreviations in Table 3 are as follows.
NQD: TAS-200 (1,2-naphthoquinonediazide-4-sulfonic acid ester compound, manufactured by Toyo Gosei Co., Ltd.)
MX: Nicarax MX-270 (methoxymethyl crosslinking agent, manufactured by Sanwa Chemical Co., Ltd.)
JER1: JER150S70 (epoxy crosslinking agent, manufactured by Japan Epoxy Resin Co., Ltd.)
JER2: JER150S65 (epoxy crosslinking agent, manufactured by Japan Epoxy Resin Co., Ltd.)
JER3: JER828 (epoxy crosslinking agent, manufactured by Japan Epoxy Resin Co., Ltd.)
JER4: JER1002 (epoxy crosslinking agent, manufactured by Japan Epoxy Resin Co., Ltd.)
W-1: Megafax F-554 (fluorine-based surfactant, manufactured by DIC Corporation)
P-1: Oxime sulfonate having the following structure (synthetic product)
P-2: Oxime sulfonate having the following structure (PAI-101, manufactured by Midori Chemical Co., Ltd.)
P-3: Sulfonium sulfonate having the following structure (synthetic product)
S-1: Dibutoxyanthracene having the following structure (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
H-1: Monofunctional cyclic carbonate having the following structure H-2: Monofunctional cyclic carbonate having the following structure H-3: Bifunctional carbonate described in Japanese Patent No. 4044740

In the above formulae, Me represents a methyl group, OTs represents OSO ₂ C ₆ H ₄ -p-CH ₃ , and Bu represents an n-butyl group.

(2) Evaluation of sensitivity After the photosensitive resin composition solution was spin-coated on a silicon wafer having a silicon oxide film, it was pre-baked on a hot plate at 95 ° C. for 90 seconds to form a coating film having a thickness of 3 μm.
Next, it exposed through the predetermined | prescribed mask using i line | wire stepper (Canon Co., Ltd. product FPA-3000i5 ^<+> ). After the exposure, the resist film was developed with a 0.4% by weight aqueous tetramethylammonium hydroxide solution at 23 ° C. for 60 seconds and rinsed with ultrapure water for 1 minute. By these operations, the optimum exposure amount (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity. It can be said that the sensitivity when the chemically amplified photosensitive resin composition is used is high when the exposure amount is lower than 100 mJ / cm ² . In addition, when quinonediazide is used as a photoacid generator, it can be said that the sensitivity is high when the exposure amount is lower than 200 mJ / cm ² .

(3) Evaluation of chemical resistance (stripping solution resistance, NMP resistance) After a photosensitive resin composition solution is spin-coated on a silicon wafer having a silicon oxide film, the film is pre-baked on a hot plate at 95 ° C. for 90 seconds. A coating film having a thickness of 3 μm was formed. The obtained coating film was exposed to a cumulative irradiation amount of 200 mJ / cm ² (illuminance: 20 mW / cm ² ) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Was heated in an oven at 230 ° C. for 1 hour to obtain a cured film. The film thickness (T1) of the obtained cured film was measured. Next, the silicon wafer on which this cured film was formed was mixed in a monoethanolamine / dimethylsulfoxide (DMSO) = 7/3 mixed solution (stripping solution) or N-methylpyrrolidone (NMP) controlled at 25 ° C. After being soaked for 30 minutes, the film thickness (t1) of the cured film was measured, and the film thickness change rate {| t1-T1 | / T1} × 100 (%) due to immersion was calculated. If the rate of change is less than 5%, it can be said that the chemical resistance is good.

(4) Evaluation of transparency and heat-resistant transparency Same as (3) except that in the above (3) solvent resistance evaluation, a glass substrate “Corning 1737 (manufactured by Corning)” was used instead of a silicon wafer. Thus, a cured film was produced on the glass substrate. The minimum light transmittance of the obtained cured film was measured at a wavelength of 400 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”.
The cured film obtained above was further heated in an oven at 230 ° C. for 2 hours, and then the minimum light transmittance was measured by the same method as described above.
Table 4 shows the evaluation of the minimum light transmittance (evaluation of transparency and heat-resistant transparency). It can be said that transparency and heat-resistant transparency are so good that this value is near 100%.

(5) Evaluation of PED characteristics The PED characteristics are the shape stability of a pattern with respect to the time from exposure to development.
A circular pattern was cut through a mask for forming a 10 μm contact hole. Except for changing the holding time from exposure to development after 1 minute and 30 minutes and forming a circular pattern through a mask, the same operation as in the sensitivity evaluation was performed, and the diameter of the contact hole was changed. Compared. The closer this value is to 100%, the better the PED.
Fluctuation rate of contact hole diameter after 1 minute to 30 minutes (%) = [CH diameter after 1 minute (μm)] / [CH diameter after 30 minutes (μm)] × 100

  Table 4 shows the evaluation results in Examples 1 to 22 and Comparative Examples 1 to 9. In Comparative Example 9, the sensitivity evaluation did not sufficiently cure and the PED characteristics could not be evaluated.

(Example 23)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 to the organic EL element formed between the TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The 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. The insulating film 8 was formed by the same method as described above using the photosensitive resin composition of Example 7. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

(Example 24)
In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 332003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 58 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 23.
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.

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: planarization 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: Transparent ITO electrode, 20: Liquid crystal, 22: Color filter

Claims (22)

(Component A) a resin having an acid-decomposable group and a crosslinkable group;
(Component B) a radiation-sensitive acid generator;
(Component C) A positive photosensitive resin composition comprising an amino group and a compound having two or more cyclic carbonate structures. The positive photosensitive resin composition of Claim 1 whose component C is a compound represented by following formula (1).

(In Formula (1), L is a group selected from the group consisting of a divalent or higher valent alkylene group, a divalent or higher arylene group, an ester bond, an ether bond, a urethane bond, and a urea bond, or a combination of two or more thereof. M represents 0 or 1, and n represents an integer of 1 or more.)   The positive photosensitive resin composition according to claim 1, wherein L is a group selected from the group consisting of an alkylene group, an arylene group, an ester bond, and an ether bond, or a group obtained by combining two or more of these. object.   The positive photosensitive resin composition of any one of Claims 1-3 whose component C is a compound which has two cyclic carbonate structures.   The positive photosensitive resin composition according to any one of claims 1 to 4, wherein m is 0 and n is 1. The positive photosensitive resin composition of any one of Claims 1-4 whose component C is a compound represented by following formula (2).

(In formula (2), n represents an integer of 1 to 5)   The positive photosensitive resin composition according to any one of claims 1 to 6, wherein Component A further has an acid group.   The positive photosensitive resin composition according to any one of claims 1 to 7, wherein Component A is a resin having an acid-decomposable group capable of decomposing with an acid to form a carboxyl group, a crosslinkable group, and a carboxyl group. . The positive photosensitive property of any one of Claims 1-8 in which component A has a structural unit represented by the following formula (a1-1) or formula (a1-2) as an acid-decomposable group. Resin composition.

  The positive photosensitive resin composition according to claim 1, wherein the crosslinkable group is an oxetanyl group or an epoxy group.   The positive photosensitive resin composition according to any one of claims 1 to 10, wherein Component B is a compound having an oxime sulfonate group.   The positive photosensitive resin composition according to claim 1, further comprising (Component D) a basic compound. The content of component A is 1 to 99% by weight,
The content of component B is 0.1 to 10% by weight,
The content of component C is 1 to 30% by weight; and
The positive photosensitive resin composition according to claim 12, wherein the content of component D is 0.001 to 2% by weight. (1) A coating step of coating the positive photosensitive resin composition according to any one of claims 1 to 13 on a substrate,
(2) an exposure step of exposing the applied photosensitive resin composition with actinic rays,
(3) a development step of developing the exposed photosensitive resin composition with an aqueous developer, and
(4) a post-baking step of thermosetting the developed photosensitive resin composition;
A method for forming a cured film comprising:   A cured film formed by the method according to claim 14.   A cured film formed by applying at least one of light and heat to the positive photosensitive resin composition according to claim 1.   The cured film according to claim 15 or 16, which is an interlayer insulating film.   A liquid crystal display device comprising the cured film according to claim 15.   An organic EL display device comprising the cured film according to claim 15. The polyfunctional cyclic carbonate compound represented by following formula (3).

(In formula (3), L represents an (n + 1) -valent arylene group, m represents 0 or 1, and n represents an integer of 1 to 5)   21. The polyfunctional cyclic carbonate compound according to claim 20, wherein m is 0 and n is 1. The polyfunctional cyclic carbonate compound according to claim 20, which is a compound represented by the following formula (4).

(In formula (4), n represents an integer of 1 to 5)

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