JP2017037108A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition capable of forming a pattern good in contrast and heat resistance, a pattern forming method using the photosensitive composition and a patterned film formed by using the photosensitive composition.SOLUTION: In a photosensitive composition containing (A1) a resin component, (A2) a resin composition and (B) a radical generator or containing (A3) a resin component and (B) the radical generator, (A1) the resin component which is a resin containing a structural unit having a ring structure in a main chain, (A2) the resin component which is a resin having an acid group protected by a protective group, (A3) the resin component which is a resin containing the structural unit having the ring structure in the main chain and having the acid group protected by the protective group and (B) the radical generator containing a naphthalic acid derivative with predetermined structure are used.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive composition.

In lithography technology, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed with radiation such as light or an electron beam through a mask on which a predetermined pattern is formed. After being performed, a process of forming a resist pattern having a predetermined shape is performed by developing the exposed resist film.
A resist material in which the exposed portion changes to a property that dissolves in the developer is referred to as a positive type, and a resist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative type.

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology.
As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but at present, mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has started.
Further, studies have been made on F2 excimer lasers having a shorter wavelength than these excimer lasers, electron beams, EUV (extreme ultraviolet rays), X-rays, and the like.

Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern with fine dimensions.
As a resist material satisfying such requirements, a chemically amplified resist containing a base resin whose alkali solubility is changed by the action of an acid and an acid generator that generates an acid upon exposure is used. For example, a positive chemically amplified resist contains, as a base resin, a resin whose alkali solubility is increased by the action of an acid and an acid generator. When a resist pattern is formed, an acid is generated from the acid generator by exposure. The exposed part becomes alkali-soluble.

  Specific examples of such positive chemically amplified resists include those containing, as a base resin, a resin having a structural unit derived from a (meth) acrylic acid ester having an acid dissociable, dissolution inhibiting group. (Patent Documents 1 and 2).

JP 2003-241385 A JP 2006-096965 A

  Regarding the positive resist composition, for the purpose of expanding the range of processing conditions of products having a resist pattern and further miniaturization for resist pattern formation, the contrast and heat resistance of the pattern to be formed, There is a need for further improvements.

  The present invention has been made in view of the above problems, a photosensitive composition capable of forming a pattern with good contrast and heat resistance, a pattern forming method using the photosensitive composition, and the photosensitive composition. It is an object of the present invention to provide a patterned film formed using an object.

  The present inventors include (A1) a resin component, (A2) a resin component, and (B) a radical generator, or (A3) a resin component and (B) a radical generator. In the composition, (A1) a resin component containing a structural unit having a ring structure in the main chain, (A2) a resin component having an acid group protected by a protecting group, and a ring in the main chain A resin component containing a structural unit having a structure and having an acid group protected by a protecting group (A3) and a (B) radical generator containing a naphthalic acid derivative having a predetermined structure are used. As a result, the inventors have found that the above problems can be solved, and have completed the present invention. Specifically, the present invention provides the following.

The first aspect of the present invention includes (A1) a resin component, (A2) a resin component, and (B) a radical generator.
A photosensitive composition comprising (A3) a resin component and (B) a radical generator,
(A1) The resin component is a resin containing a structural unit having a ring structure in the main chain,
(A2) the resin component is a resin having an acid group protected by a protecting group;
(A3) A photosensitive composition in which the resin component is a resin containing a structural unit having a ring structure in the main chain and having an acid group protected by a protecting group.

The second aspect of the present invention is a step of coating the photosensitive composition according to the first aspect on a support to form a coating film,
A step of selectively exposing a coating film,
Developing the exposed coating film with an alkaline developer, and
A step of baking the coating film patterned by development,
Is a pattern forming method.

  According to the present invention, a photosensitive composition capable of forming a pattern with good contrast and heat resistance, a pattern forming method using the photosensitive composition, and a patterned pattern formed using the photosensitive composition. Membranes can be provided.

≪Photosensitive composition≫
The photosensitive composition contains (A1) a resin component, (A2) a resin component, and (B) a radical generator, or (A3) a resin component and (B) a radical generator.
The resin component (A2) and the resin component (A3) have an acid group protected by a protective group. When the photosensitive composition is exposed, the protected acid group contained in (A2) resin component or (A3) resin component is deprotected by the action of (B) radical generator.
For this reason, the photosensitive composition concerning this invention can be used as a positive photosensitive composition in which an exposure part is solubilized with respect to an alkali developing solution.

Hereinafter, the photosensitive composition containing (A1) resin component, (A2) resin component, and (B) radical generator is referred to as a first composition. A photosensitive composition containing (A3) a resin component and (B) a radical generator is referred to as a second composition.
Hereinafter, a 1st composition and a 2nd composition are demonstrated in order.

≪First composition≫
The first composition includes (A1) a resin component, (A2) a resin component, and (B) a radical generator. (A1) The resin component is a resin containing a structural unit having a ring structure in the main chain. (A2) The resin component is a resin having an acid group protected by a protecting group. Hereinafter, essential or optional components contained in the first composition will be described.

<(A1) resin component>
(A1) The resin component is a polymer containing a structural unit having a ring structure in the main chain. When the first composition contains the resin component (A1), it is easy to form a pattern with good contrast and heat resistance.

  The polymer containing a structural unit having a ring structure in the main chain is not particularly limited as long as it is a resin having a predetermined ring structure in the main chain. As a suitable example of the polymer containing a structural unit having a ring structure in the main chain, a polymer containing a structural unit derived from maleimide (hereinafter also referred to as “structural unit (A2a)”) (hereinafter referred to as “polymer (A2)”). And a polymer containing a structural unit represented by the following formula (A-1) (hereinafter also referred to as “structural unit (A1a)”) (hereinafter also referred to as “polymer (A1)”). Can be mentioned.

  The maleimide-derived structural unit (A2a) contained in the polymer (A2) is not particularly limited as long as it is obtained by polymerizing a monomer having a maleimide skeleton. Examples of the monomer having a maleimide skeleton include N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

  In particular, the photosensitive composition containing the polymer (A1) containing the structural unit (A1a) having a ring structure in the main chain has good solubility in a developer.

In formula (A-1), ring A is a C 4-6 saturated aliphatic cyclic group having one oxygen atom as a ring constituent atom. Ring A is preferably a saturated aliphatic cyclic group having 4 or 5 carbon atoms having one oxygen atom as a ring constituent atom, more preferably a tetrahydrofuran ring or a tetrahydropyran ring, still more preferably A tetrahydropyran ring in a structural unit represented by the following formula (A-3) (hereinafter also referred to as “structural unit (A1a1)”) or a structural unit represented by the following formula (A-4) (hereinafter referred to as “structural unit”). It is also a tetrahydrofuran ring in the unit (A1a2) ”.

  The polymer containing the structural unit represented by the above formula (A-1) in the main chain (polymer (A1)) is usually a structural unit represented by the above formula (A-1) in the main chain (constituent unit ( A plurality of A1a)). In the plurality of structural units (A1a), ring A contained in each structural unit (A1a) may be the same or different from each other in one main chain constituting the polymer (A1). Specifically, one main chain constituting the polymer (A1) is a structural unit represented by the above formula (A-1) contained in the main chain, for example, the above formula (A-3). It may have only the structural unit represented, may have only the structural unit represented by the above formula (A-4), or may be represented by the above formula (A-3). And a structural unit represented by the above formula (A-4).

In the above formula (A-1), formula (A-3) and formula (A-4), R ¹ and R ² are each independently a hydrogen atom or —COOR, and R is each independently a hydrogen atom or a substituent. It is a C1-C25 hydrocarbon group which may have. R ¹ and R ² are preferably —COOR. When one main chain constituting the polymer containing the structural unit represented by the above formula (A-1) (polymer (A1)) contains a plurality of rings A, -COOR bonded to each ring A is Each is independent, and the same or different groups as —COOR may be bonded to each ring A.

The hydrocarbon group of R ¹ and R ² in good to 25 carbon atoms which may have a substituent represented, not particularly limited. Specific examples of the hydrocarbon group include linear or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl and 2-ethylhexyl. Group; aryl group such as phenyl; alicyclic group such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; 1-methoxyethyl, 1 -An alkyl group substituted with alkoxy such as ethoxyethyl; an alkyl group substituted with an aryl group such as benzyl; and the like.

When R ¹ and R ² are hydrocarbon groups, the hydrocarbon group preferably has 8 or less carbon atoms. As a hydrocarbon group having 8 or less carbon atoms, it is difficult to desorb by an acid or heat, so that a free bond at the end of the hydrocarbon group is bonded to a primary carbon atom or a secondary carbon atom. The hydrocarbon group is preferred. As such a hydrocarbon group, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 5 carbon atoms is preferable. .
Specific examples of such a hydrocarbon group include methyl, ethyl, cyclohexyl, benzyl and the like, and a methyl group is preferable.

When a plurality of structural units (A1a) are contained in one main chain constituting the polymer (polymer (A1)) containing the structural unit represented by formula (A-1) (structural unit (A1a)) R ¹ and R ² bonded to each structural unit (A1a) may be the same or different between the structural units (A1a).
When the same or different ring A is contained between the structural units (A1a), R ¹ and R ² are independent of each other without depending on the type of each ring A to be bonded.

Specifically, when a plurality of structural units represented by the formula (A-3) (structural unit (A1a1)) are contained in one main chain constituting the polymer (A1), each structural unit ( R ¹ and R ² in A1a1) may be the same or different between the structural units (A1a1).

When one main chain constituting the polymer (A1) contains a plurality of structural units represented by the above formula (A-4) (structural unit (A1a2)), R ¹ in each structural unit (A1a2) And R ² may be the same or different between the structural units (A1a2).
Furthermore, in one main chain constituting the polymer (A1), a structural unit represented by the above formula (A-3) (structural unit (A1a1)) and a structural unit represented by the above formula (A-4) ( If the structural unit (A1A2)) and is contained, the ^{R 1} and ^{R 2} in ^{R 1} and ^{R 2} and each of the structural units in each of the structural units (A1a1) (A1a2) or different may be the same Also good.

（式（Ａ−５）及び式（Ａ−６）中、Ｒ^１及びＲ^２はそれぞれ独立に上記と同様である。） The structural unit represented by the above formula (A-3) (structural unit (A1a1)) is a repeating unit represented by the following formula (A-5) (hereinafter also referred to as “repeating unit (ar1)”). It may be a part. The structural unit represented by the above formula (A-4) (structural unit (A1a2)) is a repeating unit represented by the following formula (A-6) (hereinafter also referred to as “repeating unit (ar2)”). It may be a part.

(In Formula (A-5) and Formula (A-6), R ¹ and R ² are each independently the same as described above.)

（上記式中、Ｒはそれぞれ独立に上記と同様である。） Examples of the monomer that gives each repeating unit represented by the above formulas (A-5) and (A-6) include 1,6-dienes represented by the following formulas.

(In the above formula, each R is independently the same as above.)

  In a monomer composition that gives a polymer (polymer (A1)) containing a structural unit represented by the above formula (A-1) (structural unit (A1a)) in the main chain, a repeating unit containing the structural unit (A1a) The content ratio of the monomer (A1ma) that gives the structural unit (A1a1) and the structural unit (A1a2) is preferably 1% by mass to 60% by mass with respect to the total amount of monomers in the monomer composition. %, More preferably 5% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass.

  The polymer (A1) preferably has a repeating unit (A1b) having an acid group in the side chain. If the polymer (A1) has a repeating unit (A1b) having an acid group in the side chain, a photosensitive composition having excellent alkali developability can be obtained. As the monomer (A1mb) constituting the repeating unit (A1b) having an acid group in the side chain, for example, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, itaconic acid, ω- Monomers having a carboxyl group such as carboxy-polycaprolactone monoacrylate; monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride. Of these, (meth) acrylic acid is preferred.

  In the monomer composition giving the polymer (A1), the content ratio of the monomer (A1mb) constituting the repeating unit (A1b) having an acid group in the side chain is based on the total amount of monomers in the monomer composition. Preferably they are 1 mass%-50 mass%, More preferably, they are 5 mass%-40 mass%, More preferably, they are 10 mass%-35 mass%.

  Preferably, the polymer (A1) has a repeating unit (A1c) having a carbon double bond in the side chain. The repeating unit (A1c) having a carbon double bond in the side chain is formed by reacting part or all (preferably part) of the acid group of the repeating unit (A1b) having an acid group in the side chain as a reaction point. It can be obtained by adding a compound having a heavy bond.

  When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxyl group, the compound having a carbon double bond is a compound having an epoxy group and a double bond, an isocyanate group and a double bond. Or the like. Examples of the compound having an epoxy group and a double bond include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinyl. Examples include benzyl glycidyl ether and 4-hydroxybutyl acrylate glycidyl ether. Examples of the compound having an isocyanate group and a double bond include 2-isocyanatoethyl (meth) acrylate. When the acid group of the repeating unit (A1b) having an acid group in the side chain is a carboxylic anhydride group, a compound having a hydroxyl group and a double bond can be used as the compound having a carbon double bond. Examples of the compound having a hydroxyl group and a double bond include 2-hydroxyethyl (meth) acrylate.

  The polymer (A1) may further have another repeating unit (A1e) derived from the monomer (A1ma), the monomer (A1mb) and / or another monomer (A1me) copolymerizable with the monomer (A1mc).

Examples of the other monomer (A1me) may further include a repeating unit having two or more oxyalkylene groups in the side chain. Examples of the repeating unit having two or more oxyalkylene groups in the side chain include a repeating unit represented by the following formula.

In the above formula, R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or a methyl group, preferably a hydrogen atom. R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. And preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. More preferably, it is a linear alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a linear alkyl group having 1 to 5 carbon atoms, A phenyl group or a biphenyl group, particularly preferably a methyl group, a phenyl group or a biphenyl group. The alkyl group, alkenyl group, and aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The oxyalkylene group represented by AO has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 2. The repeating unit having two or more oxyalkylene groups in the side chain may contain one or more oxyalkylene groups. x represents an integer of 0-2. y represents 0 or 1; n represents the average addition mole number of an oxyalkylene group and is 2 or more, preferably 2 to 100, more preferably 2 to 50, and further preferably 2 to 15.

（上記式中、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、ＡＯ、ｘ、ｙ及びｎは、上記で説明した通りである。） The repeating unit having two or more oxyalkylene groups in the side chain is composed of a monomer having two or more oxyalkylene groups in the side chain. As this monomer, the monomer represented by a following formula is mentioned, for example.

(In the above formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , AO, x, y and n are as described above.)

  Examples of the monomer having two or more oxyalkylene groups in the side chain include ethoxylated o-phenylphenol (meth) acrylate (EO 2 mol), phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate (EO 4 mol). ), Methoxypolyethylene glycol (meth) acrylate (EO 9 mol), methoxypolyethylene glycol (meth) acrylate (EO 13 mol), methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, 2 -Ethylhexyl diethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolypropylene Examples include propylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate (EO 4-17 mol), nonylphenoxypolypropylene glycol (meth) acrylate (PO 5 mol), EO-modified cresol (meth) acrylate (EO 2 mol), and the like. . These monomers may be used alone or in combination of two or more. Among them, ethoxylated o-phenylphenol (meth) acrylate (EO 2 mol), methoxypolyethylene glycol (meth) acrylate (EO 9 mol), and methoxypolyethylene glycol (meth) acrylate (EO 13 mol) are preferable. More preferred are ethoxylated o-phenylphenol acrylate (EO 2 mol), methoxy polyethylene glycol acrylate (EO 9 mol), and methoxy polyethylene glycol acrylate (EO 13 mol). In the present specification, for example, “EO2 mole”, “PO5 mole” and the like represent the average number of moles added of the oxyalkylene group.

  As other monomer (A1me), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, biphenyl (meth) acrylate, methoxy Ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylene glycol (meth) acrylate, 2-ethylhexyl ethylene glycol (meth) acrylate, methoxypropylene Glycol (meth) acrylate, phenoxyethyl (meth) acrylate, biphenoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, Tricyclodecyloxyethyl (meth) acrylate, nonylphenoxyethylene glycol (meth) acrylate, nonylphenoxypropylene glycol, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, etc. (Meth) acrylic acid esters; (meth) acryloylmorpholine (morpholino (meth) acrylate), (meth) acrylamide, N-methyl (meth) acrylami N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-isobutyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nt-octyl (meth) acrylamide, diacetone (meth) Acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, N-triphenylmethyl ( (Meth) acrylic acid amides such as meth) acrylamide and N, N-dimethyl (meth) acrylamide; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; butadiene such as butadiene and isoprene or substituted butadiene Compounds, ethylene, propylene, vinyl chloride, ethylene, or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like. These monomers may be used alone or in combination of two or more.

  The content ratio of the monomer (A1me) giving other repeating units (A1e) in the monomer composition giving the polymer (A1) is preferably 0% by mass to 55% by mass with respect to the total amount of monomers in the monomer composition. More preferably, it is 5 mass%-50 mass%, More preferably, it is 10 mass%-45 mass%.

  The polymer (A1) may be a random copolymer or a block copolymer. As a polymer (A1), it can use individually or in combination of 2 or more types.

  The weight average molecular weight of the polymer (A1) is preferably a value measured by gel permeation chromatography (GPC) with a tetrahydrofuran (THF) solvent, preferably 3,000 to 200,000, more preferably It is 3,500-100,000, More preferably, it is 4,000-50,000. If it is such a range, the photosensitive composition which can ensure heat resistance and has a viscosity suitable for film formation can be obtained.

  The polymer (A1) can be obtained by polymerizing the monomer composition giving the polymer (A1) by any appropriate method. Examples of the polymerization method include a solution polymerization method.

  The monomer composition that provides the polymer (A1) can comprise any suitable solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl. Examples include esters such as acetate; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more. The polymerization concentration when polymerizing the monomer composition is preferably 5% by mass to 90% by mass, more preferably 5% by mass to 50% by mass, and further preferably 10% by mass to 50% by mass. .

  The monomer composition that provides the polymer (A1) can comprise any suitable polymerization initiator. Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, and t-amyl peroxy-2. Organic peroxides such as ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexanecarbonitrile), Examples thereof include azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2′-azobis (2-methylpropionate). The content of the polymerization initiator is preferably 0.1 parts by mass to 15 parts by mass, and more preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of all monomers in the monomer composition.

  The polymerization temperature when polymerizing the polymer (A1) by the solution polymerization method is preferably 40 ° C to 150 ° C, more preferably 60 ° C to 130 ° C.

  When obtaining the polymer (A1) having the repeating unit (A1c) having a carbon double bond in the side chain, the compound having the carbon double bond is added to the obtained polymer after the polymerization. Any appropriate method can be adopted as a method for adding a compound having a carbon double bond. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having a carbon double bond is reacted with part or all (preferably part) of the acid group of the repeating unit (A1b) having an acid group in the side chain. Thus, a repeating unit (A1c) having a carbon double bond in the side chain can be formed.

  The addition amount of the compound having a carbon double bond is preferably 5 parts by mass or more with respect to 100 parts by mass of the polymer after the polymerization (that is, the polymer before adding the compound having a carbon double bond). More preferably, it is 10 mass parts or more, More preferably, it is 15 mass parts or more, Most preferably, it is 20 mass parts or more. If it is such a range, the photosensitive composition excellent in exposure sensitivity can be obtained. If such a photosensitive composition is used, it is easy to form a dense cured coating film, and a pattern excellent in substrate adhesion tends to be obtained. Further, when the addition amount of the compound having a carbon double bond is within the above range, a photosensitive composition having a sufficient hydroxyl group generated by the addition of the compound having a carbon double bond and having excellent solubility in an alkali developer is obtained. be able to. The upper limit of the addition amount of the compound having a carbon double bond is preferably 170 parts by mass or less with respect to 100 parts by mass of the polymer after the polymerization (that is, the polymer before adding the compound having a carbon double bond). More preferably, it is 150 mass parts or less, More preferably, it is 140 mass parts or less. If the addition amount of the compound having a carbon double bond is within the above range, the storage stability and solubility of the photosensitive composition can be maintained.

  Examples of the polymerization inhibitor include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol. Examples of the catalyst include tertiary amines such as dimethylbenzylamine and triethylamine.

  (A1) When the resin component has an acid group to be described later such as a carboxyl group, the acid group may be protected by a protecting group to be described later.

  (A1) The resin component may have a crosslinking group. The cross-linking group is a functional group that can be cross-linked thermally when the patterned film to be formed is post-baked. Suitable groups as such a crosslinking group include an epoxy group, an oxetanyl group, and a group containing an unsaturated double bond (vinyl group, (meth) acryloyl group, etc.). A film having excellent mechanical properties and chemical resistance can be formed by thermal crosslinking between crosslinking groups during post-baking.

  (A1) The method for introducing a crosslinking group into the resin component is not particularly limited. For example, when the (A1) resin component has a functional group containing an active hydrogen atom such as a carboxyl group, a hydroxyl group, or an amino group, epichlorohydrin, (meth) acryloyl chloride, (meth) acrylic anhydride, allyl halide, etc., and active hydrogen A crosslinking group can be introduced into the resin component (A1) by reacting with a functional group containing an atom according to a conventional method.

In particular, when the resin component (A1) contains the structural unit (A1a) represented by the formula (A-1) and at least one of R ¹ and R ² is a carboxyl group, the carboxyl group, epichlorohydrin, allyl halide A cross-linking group is introduced into the resin component (A1) by reacting a compound having a cross-linking group such as the above and a compound having reactivity with a carboxyl group according to a conventional method.

  (A1) When preparing a resin component, a crosslinking group can be introduce | transduced into (A1) resin component by copolymerizing the monomer which has the above-mentioned crosslinking group and unsaturated double bond.

  The crosslinking group is preferably an epoxy group from the viewpoint of reactivity. Suitable examples of the monomer having an epoxy group and an unsaturated double bond include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxyphenyl (meth) acrylate. 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate, and the like.

  An aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group is also preferably used for introducing a crosslinking group. Examples of the aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group include an ester group (—O—CO—, such as epoxy alkyl (meth) acrylate and epoxyalkyloxyalkyl (meth) acrylate). (Meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to the oxy group (—O—) in (). Such a chain aliphatic epoxy group possessed by the (meth) acrylate ester may contain one or a plurality of oxy groups (—O—) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

  Specific examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meta And epoxyalkyloxyalkyl (meth) acrylates such as acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate.

  From the viewpoint of the transparency and mechanical properties of the formed film, a (meth) acrylic acid ester having a cycloaliphatic epoxy group is also preferably used for introducing a crosslinking group. Preferable examples of the (meth) acrylic acid ester having a cyclic aliphatic epoxy group include compounds represented by the following formulas (a-1) to (a-15). Among these, compounds represented by the following formulas (a-1) to (a-5) are preferable, and compounds represented by the following formulas (a-1) to (a-3) are more preferable.

In the above formula, R ^a9 represents a hydrogen atom or a methyl group, R ^a10 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a11 represents a divalent divalent hydrocarbon having 1 to 10 carbon atoms. A hydrocarbon group is shown, t shows the integer of 0-10. R ^a10 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a11 , for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, and a cyclohexylene group are preferable.

  Furthermore, when the (A1) resin component has an unsaturated double bond, an epoxy group can be introduced into the (A1) resin component as a crosslinking group by oxidizing the unsaturated bond according to a conventional method.

  Moreover, (A1) resin component may have a carboxyl group couple | bonded with an aromatic group. For example, when preparing the resin component (A1), by copolymerizing a monomer having a carboxyl group and an unsaturated double bond bonded to the aromatic group, the (A1) resin component is converted into an aromatic group. A linking carboxyl group can be introduced.

Specific examples of the monomer having a carboxyl group bonded to an aromatic group and an unsaturated double bond include vinyl benzoic acid such as o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid. : Vinylnaphthalenecarboxylic acid such as 1-vinylnaphthalene-2-carboxylic acid and 4-vinylnaphthalene-2-carboxylic acid; o- (meth) acryloyloxybenzoic acid, m- (meth) acryloyloxybenzoic acid, and p -(Meth) acryloyloxybenzoic acid such as (meth) acryloyloxybenzoic acid; 1- (meth) acryloyloxynaphthalene-2-carboxylic acid, 1- (meth) acryloyloxynaphthalene-3-carboxylic acid, 1- (meth ) Acryloyloxynaphthalene-4-carboxylic acid, 1- (meth) acryloyloxynaphthalene-5-carboxylic acid 1- (meth) acryloyloxynaphthalene-6-carboxylic acid, 1- (meth) acryloyloxynaphthalene-7-carboxylic acid, 1- (meth) acryloyloxynaphthalene-8-carboxylic acid, 2- (meth) acryloyloxy Naphthalene-1-carboxylic acid, 2- (meth) acryloyloxynaphthalene-3-carboxylic acid, 2- (meth) acryloyloxynaphthalene-4-carboxylic acid, 2- (meth) acryloyloxynaphthalene-5-carboxylic acid, 2 -(Meth) acryloyloxynaphthalene-6-carboxylic acid, (meth) acryloyloxynaphthalene-7-carboxylic acid, and (meth) acryloyloxynaphthalenecarboxylic acid such as 2- (meth) acryloyloxynaphthalene-8-carboxylic acid Acid; o-allyloxybenzoic acid, m Allyloxybenzoic acid and allyloxycarboxylic acid such as p-allyloxybenzoic acid; 1-allyloxynaphthalene-2-carboxylic acid, 1-allyloxynaphthalene-3-carboxylic acid, 1-allyloxynaphthalene-4-carboxylic acid, 1-allyloxynaphthalene-5-carboxylic acid, 1-allyloxynaphthalene-6-carboxylic acid, 1-allyloxynaphthalene-7-carboxylic acid, 1-allyloxynaphthalene-8-carboxylic acid, 2-allyloxynaphthalene- 1-carboxylic acid, 2-allyloxynaphthalene-3-carboxylic acid, 2-allyloxynaphthalene-4-carboxylic acid, 2-allyloxynaphthalene-5-carboxylic acid, 2-allyloxynaphthalene-6-carboxylic acid, 2 Allyloxynaphthalene-7-carboxylic acid and 2-allylthio And allyloxynaphthalene carboxylic acid such as xinaphthalene-8-carboxylic acid.
These monomers can be used in combination of two or more.

  The content of the resin component (A1) in the first composition is preferably 1 to 50% by mass and more preferably 5 to 40% by mass with respect to the mass of the solid content of the first composition.

<(A2) resin component>
(A2) The resin component is not particularly limited as long as it is a resin having an acid group protected by a protecting group. The acidic group is not particularly limited as long as it is a group showing acidity according to the Bronsted definition. Suitable acidic groups include carboxyl groups and phenolic hydroxyl groups.

As a suitable example of the (A2) resin component that is not protected by a protecting group, a polymer of a monomer having an unsaturated double bond containing an unsaturated carboxylic acid such as (meth) acrylic acid (acrylic resin) ), A polymer of a monomer having an unsaturated double bond containing hydroxystyrenes (polyhydroxystyrene resin), and a novolak resin obtained by condensing phenols.
In addition, the basic skeleton of the resin component (A2) is not limited to the basic skeleton of these resins.
(A2) The novolak resin, hydroxystyrene resin, and acrylic resin, which are preferably used as the resin component, will be described later.

(A2) The resin component may be prepared using a monomer protected by a protective group, or at least a part of the acidic group in the resin having an acidic group is protected by a protective group according to a conventional method. It may be prepared. When the (A2) resin component is an acrylic resin or a polyhydrostyrene resin, the (A2) resin component is preferably produced by polymerizing a monomer containing an unsaturated carboxylic acid protected by a protecting group. .
Examples of the unsaturated carboxylic acid include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. Of these unsaturated carboxylic acids, (meth) acrylic acid is preferred.

  The protecting group is not particularly limited as long as it has been used as a protecting group for an acidic group in a resin conventionally blended in a photosensitive composition. Groups represented by the following formulas (a1), (a2), and (a3), vinyloxyethyl groups, or trialkylsilyl groups are preferred.

In the formula (a1), R ^a1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by —O— or —S—, and R ^a2 and R ^a3 are each independently to a hydrocarbon group of -O- or -S- carbon atoms which may be interrupted by from 1 to ^20, it may be bonded to each other and ^{R a1} and ^{R a2} to form a ^{ring, R a2} and R ^a3 may be bonded to each other to form a ring.

In the formula (a2), R ^a4 , R ^a5 , and R ^a6 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear structure having 1 to 10 carbon atoms. Alternatively, it is a branched fluorinated alkyl group. Any two groups out of R ^a4 , R ^a5 and R ^a6 may be bonded to each other to form a ring.

In the above formula (a3), R ^a7 is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and o is 0 or 1.

In formula (a1), R ^a1 , R ^a2 , and R ^a3 are hydrocarbon groups having 1 to 20 carbon atoms. 1-10 are preferable, as for the carbon atom number of the said hydrocarbon group, 1-8 are more preferable, and 1-6 are especially preferable. The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

When R ^a1 , R ^a2 , and R ^a3 are aliphatic hydrocarbon groups, the aliphatic hydrocarbon group includes a chain structure and a cyclic structure ^regardless of whether it is a chain or a ring. May be. The aliphatic hydrocarbon group may have an unsaturated bond. As the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable.

When R ^a1 , R ^a2 , and R ^a3 are chain aliphatic hydrocarbon groups, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n- Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n- Nonadecyl group and n-icosyl group are mentioned.

Specific examples of the case where R ^a1 , R ^a2 and R ^a3 are cyclic aliphatic hydrocarbon groups and the cyclic aliphatic hydrocarbon group is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, Examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group.

Specific examples of the case where R ^a1 , R ^a2 , and R ^a3 are cyclic aliphatic hydrocarbon groups and the cyclic aliphatic hydrocarbon group is a polycyclic group include the following polycyclic aliphatic groups: A group obtained by removing one hydrogen atom from a hydrocarbon can be mentioned.

When R ^a1 , R ^a2 , and R ^a3 are aromatic hydrocarbon groups, specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a biphenylyl group, a phenanthrenyl group, and a fluorenyl group.

When R ^a1 , R ^a2 , and R ^a3 are a group obtained by combining an aliphatic hydrocarbon group and an aromatic hydrocarbon group, examples of the group include an aralkyl group. Specific examples of the aralkyl group include benzyl group, phenethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, α-naphthylmethyl group, β-naphthylmethyl group, 2- (α-naphthyl). ) Ethyl group and 2- (β-naphthyl) ethyl group.

When R ^a1 , R ^a2 and R ^a3 are hydrocarbon groups containing an aromatic ring, the aromatic ring is a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. , An alkanoyl group having 2 to 10 carbon atoms, and one or more substituents selected from the group consisting of alkanoyloxy groups having 2 to 10 carbon atoms. When a plurality of substituents are present on the aromatic ring, the plurality of substituents may be the same or different.

In formula (a1), R ^a1 is preferably a hydrogen atom. R ^a2 is preferably a methyl group. R ^a3 is preferably an ethyl group, an isobutyl group, a cyclohexyl group, a 2-ethyl-n-hexyl group, or an octadecyl group.

When R ^a2 and R ^a3 are bonded to each other to form a ring, the ring is a heterocycle including an oxygen atom bonded to R ^a3 . About the heterocyclic ring containing an oxygen atom, 3-7 are preferable and, as for the carbon atom number, 4-6 are more preferable. The heterocycle may further contain a hetero atom other than an oxygen atom bonded to R ^a3 . In this case, examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

When R ^a1 and R ^a2 are bonded to each other to form a ring, the ring is preferably a 3- to 12-membered saturated aliphatic hydrocarbon ring. When the ring formed by combining R ^a1 and R ^a2 is a 6-membered saturated aliphatic hydrocarbon ring, the group represented by the formula (a1) is a group represented by the following formula. In the following formula, R ^a3 is the same as formula (a1).

  Below, the suitable example of group represented by a formula (a1) is shown.

In the formula (a2), when R ^a4 , R ^a5 and R ^a6 are alkyl groups, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl Group, and n-decyl group.

In the formula (a2), when two arbitrary groups out of R ^a4 , R ^a5 and R ^a6 are bonded to each other to form a ring, the ring is an aliphatic hydrocarbon ring having 5 to 20 carbon atoms Is preferred. The aliphatic hydrocarbon ring may be a monosialkane or a polycycloalkane such as a bicycloalkane, tricycloalkane, and tetracycloalkane. Specific examples of the aliphatic hydrocarbon ring include monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclodecane.

The ring formed by combining any two groups out of R ^a4 , R ^a5 and R ^a6 may have a substituent. Examples of the substituent include a polar group such as a hydroxyl group, a cyano group, and an oxygen atom (═O), and a linear or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (═O) is particularly preferable.

Preferable examples of the group represented by the formula (a2) include the following groups.

  Specific examples of the protecting group represented by the above formula (a3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include those having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

  (A2) In the resin component, the content of the structural unit having an acidic group protected by a protecting group is preferably 1 to 85% by mass and more preferably 2 to 80% by mass with respect to the mass of the (A2) resin component. Preferably, 3-75 mass% is especially preferable. When the content of the structural unit having an acidic group protected by a protecting group is within such a range, it is easy to obtain a first composition having good developability.

(A2) The resin component may have a carboxyl group bonded to an aromatic group.
For example, when the resin component (A2) is an acrylic resin or a polyhydroxystyrene resin, by copolymerizing a carboxyl group bonded to an aromatic group and a monomer having an unsaturated double bond, ( A2) A carboxyl group bonded to an aromatic group can be introduced into the resin component.

  Specific examples of the monomer having a carboxyl group bonded to an aromatic group and an unsaturated double bond include (A1) the specific examples described above for introduction of a carboxyl group bonded to an aromatic group into the resin component, and It is the same.

  In addition, when the (A2) resin component is based on a novolak resin, a hydroxy aromatic carboxylic acid is condensed with other phenols, whereby (A2) a carboxyl group bonded to the aromatic group is added to the resin component. Can be introduced.

Suitable examples of hydroxy aromatic carboxylic acids include hydroxybenzoic acids such as salicylic acid, m-hydroxybenzoic acid, and p-hydroxybenzoic acid; 1-hydroxy-2-naphthoic acid, 1-hydroxy-3-naphthoic acid, 1-hydroxy-4-naphthoic acid, 1-hydroxy-5-naphthoic acid, 1-hydroxy-6-naphthoic acid, 1-hydroxy-7-naphthoic acid, 1-hydroxy-8-naphthoic acid, 2-hydroxy-1 -Naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-4-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-7-naphthoic acid, and Examples include hydroxynaphthoic acid such as 2-hydroxy-8-naphthoic acid.
These hydroxy aromatic carboxylic acids may be used in combination of two or more.

  (A2) The content of the unit containing a carboxyl group bonded to an aromatic group in the resin component is preferably 1 to 50% by mass and more preferably 5 to 40% by mass with respect to the mass of the (A2) resin component. .

  (A2) The resin component may have a crosslinking group. For example, when the resin component (A2) has a functional group containing an active hydrogen atom such as a carboxyl group, a hydroxyl group, and an amino group, epichlorohydrin, (meth) acryloyl chloride, (meth) acrylic anhydride, allyl halide, and the like, and active hydrogen By reacting with a functional group containing an atom according to a conventional method, a crosslinking group can be introduced into the resin component (A2).

  As an example, after reacting a part of the phenolic hydroxyl group of a polymer containing a unit derived from a novolak resin or hydroxystyrene with epichlorohydrin, (meth) acryloyl chloride, (meth) acrylic anhydride, allyl halide, etc., By protecting the remaining phenolic hydroxyl group with the above-mentioned protecting group, a resin component (A2) having a crosslinking group such as a glycidyl group, a (meth) acryloyl group, an allyl group, or the like can be obtained.

  Moreover, when the (A2) resin component has an unsaturated double bond, an epoxy group can be introduced into the (A2) resin component as a crosslinking group by oxidizing the unsaturated bond according to a conventional method.

  When the (A2) resin component is an acrylic resin or a polyhydroxystyrene resin, a monomer having a crosslinking group and an unsaturated double bond is copolymerized to form a crosslinking group in the (A2) resin component. Can be introduced.

  The crosslinking group is preferably an epoxy group from the viewpoint of reactivity. Preferable examples of the monomer having an epoxy group and an unsaturated double bond are the same as the specific examples described above with respect to (A1) introduction of a crosslinking group (epoxy group) into the resin component.

  The content of the unit containing a crosslinking group in the (A2) resin component is preferably 10 to 80% by mass and more preferably 20 to 70% by mass with respect to the mass of the (A2) resin component. (A2) When the amount of the resin component is included in such a range, a film having excellent mechanical properties and chemical resistance can be obtained by post-baking the formed film.

(A2) The resin component preferably further has an alcoholic hydroxyl group and / or a cyclic ether group. The cyclic ether group is a group that is not bonded to an oxygen atom.
Here, the cyclic ether group is a group in which one or two —CH ₂ — in a (poly) cycloalkyl group having 5 or more carbon atoms is substituted with —O—. The cyclic ether group does not contain an oxygen atom in an adjacent state. Moreover, what forms a protective group by combining with an acid group among cyclic ether groups is defined as a protective group, and is not included in a resin further having a cyclic ether group.
(A2) Since the resin component further has an alcoholic hydroxyl group and / or a cyclic ether group, the resolution of the first composition is improved.

The alcoholic hydroxyl group is preferably present in the resin component (A2) as a group represented by the following formula (a4). In the formula (a4), R ^a12 is an alkylene group having 1 to 20 carbon atoms which may be linear or branched.
-R ^a12 -OH (a4)
The cyclic ether group is preferably present in the resin component (A2) as a group represented by the following formula (a5). In the formula (a5), R ^a13 is a C 1-6 alkylene group which may be a single bond or linear or branched, and R ^a14 is a 5-membered ring or more, preferably It is a 5- to 8-membered cyclic ether group.
-R ^a13 -R ^a14 (a5)

  As an example, an alcoholic hydroxyl group or a cyclic ether group can be introduced into the resin component (A2) by the following method. (A2) The method of introducing an alcoholic hydroxyl group or a cyclic ether group into the resin component is not limited to the following method.

(A2) When the resin component or the acid group is not protected (A2) When the resin component has a phenolic hydroxyl group, the phenolic hydroxyl group and Hal-R ^a12 -OH (Hal is a halogen atom, R ^a12 is the same as formula (a4).) By reacting a halogenated alkanol represented by formula (A4) according to a conventional method to etherify the phenolic hydroxyl group, (A2) the alcoholic hydroxyl group is introduced into the resin component. be able to. Examples of halogenated alkanols include 2-chloroethanol, 3-chloro-n-propanol, 4-chloro-n-butanol, 2-bromoethanol, 3-bromo-n-propanol, and 4-bromo-n-butanol. Can be mentioned.
A cyclic group having a halogen atom at the terminal represented by the phenolic hydroxyl group and Hal-R ^a13 -R ^a14 (Hal is a halogen atom, and R ^a13 and R ^a14 are the same as those in formula (a5)). A cyclic ether group can be introduced into the resin component (A2) by reacting with an ether compound according to a conventional method to etherify the phenolic hydroxyl group. Examples of the cyclic ether compound having a halogen atom at the terminal include tetrahydrofurfuryl chloride.

When the (A2) resin component or the (A2) resin component in which the acidic group is not protected has a carboxyl group, the carboxyl group and HO—R ^a12 —OH (R ^a12 is the same as in the formula (a4)) The alcoholic hydroxyl group can be introduced into the resin component (A2) by carrying out esterification by reacting with an aliphatic glycol represented by the following formula. Aliphatic glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like.
In addition, the carboxyl group is reacted with a cyclic ether compound having a hydroxyl group at the terminal represented by HO—R ^a13 —R ^a14 (R ^a13 and R ^a14 are the same as those in formula (a5)) according to a conventional method. By performing esterification, a cyclic ether group can be introduced into the resin component (A2). Examples of the cyclic ether compound having a hydroxyl group at the terminal include tetrahydrofurfuryl alcohol, tetrahydro-4H-pyran-4-methanol, and tetrahydro-2H-pyran-3-methanol.

(A2) When the resin component is an acrylic resin or a polyhydroxystyrene resin, by copolymerizing a monomer having an unsaturated double bond and an alcoholic hydroxyl group or a cyclic ether group, (A2) resin component An alcoholic hydroxyl group or a cyclic ether group can be introduced into.
Preferable examples of the compound that can be used as a monomer having an unsaturated double bond and an alcoholic hydroxyl group or a cyclic ether group include compounds represented by the following formulas (x-1) to (x-22). Can be mentioned. In the formulas (x-1) to (x-22), R ^a15 is a group represented by the above formula (a4) or a group represented by the formula (a5), and R ^a16 represents a hydrogen atom or methyl It is a group.

  The content of the unit having an alcoholic hydroxyl group and / or a cyclic ether group in the resin component (A2) is preferably 1 to 30% by mass and more preferably 2 to 20% by mass with respect to the mass of the resin component (A2). preferable. (A2) The resolution of a 1st composition is favorable because the resin component contains the unit which has the amount of alcoholic hydroxyl groups and / or cyclic ether groups in this range.

  Hereinafter, a novolak resin, a polyhydroxystyrene resin, and an acrylic resin will be described as preferred examples of the resin component (A2).

(Novolac resin)
The novolak resin can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde under an acid catalyst.

Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2 , 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5- Examples include trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol and the like.
Examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde and the like.
The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used as the acid catalyst.

  In addition, it is possible to further improve the flexibility of the novolak resin by using o-cresol, by replacing the hydrogen atom of the hydroxyl group in the resin with another substituent, or by using bulky aldehydes. It is.

  The mass average molecular weight of the novolak resin is not particularly limited as long as the object of the present invention is not impaired, but it is preferably 1000 to 50000.

  A resin in which at least a part of the hydroxyl groups of the novolak resin is protected by a protecting group is used as the resin component (A2). As described above, a crosslinking group, a carboxyl group bonded to an aromatic group, an alcoholic hydroxyl group, and a cyclic ether group are introduced into the novolak resin as the resin component (A2) as necessary.

(Polyhydroxystyrene resin)
The polyhydroxystyrene resin is a polymer of a monomer containing a styrene compound. Examples of the hydroxystyrene compound constituting the polyhydroxystyrene resin include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, and the like.
Furthermore, the polyhydroxystyrene resin is preferably a copolymer of a hydroxystyrene compound and a styrene compound. Examples of the styrene compound constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene, and the like.

  The mass average molecular weight of the polyhydroxystyrene resin is not particularly limited as long as the object of the present invention is not impaired, but is preferably 1000 to 50000.

  A resin in which at least a part of the hydroxyl groups of the polyhydroxystyrene resin is protected by a protecting group is used as the resin component (A2). As described above, a crosslinking group, a carboxyl group bonded to an aromatic group, an alcoholic hydroxyl group, and a cyclic ether group are introduced into the polyhydroxystyrene resin (A2) as a resin component, as necessary.

(acrylic resin)
As the acrylic resin, a resin obtained by copolymerizing (meth) acrylic acid and another monomer having an unsaturated bond is preferable. Examples of monomers copolymerizable with (meth) acrylic acid include unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, Examples include vinyl esters and styrenes.

  Preferable examples of unsaturated carboxylic acids other than (meth) acrylic acid include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.

Examples of (meth) acrylic acid esters are linear or branched such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and t-octyl (meth) acrylate. Chain alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate , Furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and phenyl (meth) acrylate.
Of the (meth) acrylic acid esters having no epoxy group, (meth) acrylic acid esters having a group having an alicyclic skeleton are preferred.

  In the (meth) acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Examples of the (meth) acrylic acid ester having a group having an alicyclic skeleton include compounds represented by the following formulas (a-16) to (a-23). Among these, compounds represented by the following formulas (a-18) to (a-23) are preferable, and compounds represented by the following formula (a-18) or (a-19) are more preferable.

In the above formula, R ^a17 represents a hydrogen atom or a methyl group, R ^da18 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a19 represents a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 5. R ^a18 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group or a hexamethylene group. R ^a19 is preferably a methyl group or an ethyl group.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  As vinyl ethers, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether , Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenyl Examples include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  A resin in which at least a part of the carboxyl groups of the acrylic resin is protected by a protecting group is used as the resin component (A2). As described above, a crosslinking group, a carboxyl group bonded to an aromatic group, an alcoholic hydroxyl group, and a cyclic ether group are introduced into the acrylic resin (A2) as necessary.

  (A2) In the acrylic resin used as the resin component, the sum of the amount of units having a carboxyl group protected by a protecting group and the amount of units having a carboxyl group is based on the mass of (A2) resin component 1-85 mass% is preferable, and 1-30 mass% is more preferable.

  The content of the resin component (A2) in the first composition is preferably 50 to 90% by mass and more preferably 60 to 80% by mass with respect to the mass of the solid content of the first composition.

<(B) Radical generator>
The first composition contains (B) a radical generator (hereinafter also referred to as component (B)). The acid group protected by the protective group of the (A2) resin component is deprotected by a reaction involving a radical generated from the radical generator (B) by exposure.
(B) The radical generator is not particularly limited as long as it generates radicals by exposure, and can be appropriately selected from known radical generators.

  Suitable examples of known radical generators include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl]- 2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy 2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4- Benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2-ethylhexylbenzoic acid 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoylbenzoic acid Methyl, 2,4-diethylthioxanthone, 2-chloro Thioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone , Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercapto Benzothiazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) -imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzene Zophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n- Butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone P-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, α, α-dic Rho-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1 , 5-bis- (9-acridinyl) pentane, 1,3-bis- (9-acridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- 2- (4-Diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) Phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl- 6- (3-Bromo-4-methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine; methyl ethyl ketone peroxide, methyl Ketone peroxides such as isobutyl ketone peroxide and cyclohexanone peroxide; diacyl peroxides such as isobutyryl peroxide and bis (3,5,5-trimethylhexanoyl) peroxide; p-menthane hydroperoxide, 1, Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide; Dialkyl peroxides such as 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane; 1,1-bis (T-butylperoxy) -3, Peroxyketals such as 1,5-trimethylcyclohexane; peroxyesters such as t-butyl peroxyneodecanoate, 1,1,3,3-tetramethylperoxyneodecanoate; di-n-propylper Peroxydicarbonates such as oxydicarbonate and diisopropylperoxydicarbonate; azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyrate And azo compounds.

These radical polymerization initiators may be commercially available, such as IRGACURE 907, IRGACURE 651, IRGACURE 2959, IRGACURE 184, DAROCUR 1173, IRGACURE 250, IRGACURE 754, DAROCUR MBF, DAROCUR BP (special, (Made by Chemicals) etc. are commercially available.
These radical polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.

（式（Ｂ１）中、Ｒ^ｂ１は、１価の有機基であり、Ｒ^ｂ２、Ｒ^ｂ３、Ｒ^ｂ４、及びＲ^ｂ５は、それぞれ独立に、水素原子又は１価の有機基であり、Ｒ^ｂ２とＲ^ｂ３と、Ｒ^ｂ４とＲ^ｂ５と、又はＲ^ｂ４とＲ^ｂ５とは、それぞれ互いに結合して環を形成してもよい。） (B) As the radical generator, a naphthalic acid derivative represented by the following formula (B1) is also preferable. The content of the naphthalic acid derivative represented by the formula (B1) in the component (B) is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and 100% by mass. Most preferred.

(In Formula (B1), R ^b1 is a monovalent organic group, R ^b2 , R ^b3 , R ^b4 , and R ^b5 are each independently a hydrogen atom or a monovalent organic group, and R ^b2 And R ^b3 , R ^b4 and R ^b5 , or R ^b4 and R ^b5 may be bonded to each other to form a ring.)

The organic group as R ^b1 is not particularly limited as long as the object of the present invention is not impaired. The organic group may be a hydrocarbon group and may contain a hetero atom such as O, N, S, P, or a halogen atom. The structure of the organic group may be linear, branched, cyclic, or a combination of these structures.

As an organic group suitable as R ^b1 , an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, or 6 to 6 carbon atoms which may have a substituent. 20 aryl groups, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, an alkylaryl group having 7 to 20 carbon atoms which may have a substituent, a camphor-10-yl group, and The following formula (B1-1):
_{^{-R b6 - (O) a -R}} b7 - (O) b -Y b1 -R b8 ··· (B1-1)
(In Formula (B1-1), Y ^b1 is a single bond or an alkanediyl group having 1 to 4 carbon atoms. R ^b6 and R ^b7 each have 2 carbon atoms which may be substituted with a halogen atom. An alkanediyl group of ˜6, or an arylene group of 6 to 20 carbon atoms that may be substituted with a halogen atom, R ^b8 is an alkyl group of 1 to 18 carbon atoms that may be substituted with a halogen atom, An alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, and an aralkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom. A and b are each 0 or 1, and at least one of a and b is 1.)
The group represented by these is mentioned.

When the organic group as R ^b1 has a halogen atom as a substituent, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

When the organic group as R ^b1 is an alkyl group having 1 to 18 carbon atoms substituted with an alkylthio group, the alkylthio group preferably has 1 to 18 carbon atoms.
Examples of the alkylthio group having 1 to 18 carbon atoms include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group, and n-pentylthio group. , Isopentylthio group, tert-pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, and n-Octadecylthio group It is.

The organic group as R ^b1 is an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, and the aliphatic hydrocarbon group includes an unsaturated double bond. You may go out.
In addition, the structure of the aliphatic hydrocarbon group is not particularly limited, and may be linear, branched, cyclic, or a combination of these structures.

Preferable examples when the organic group as R ^b1 is an alkenyl group include an allyl group and a 2-methyl-2-propenyl group.

Preferable examples when the organic group as R ^b1 is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group. N-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-hexane-2-yl group, n-hexane-3-yl group, n-heptyl group, n-heptan-2-yl group N-heptan-3-yl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, n -Undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, and n- An octadecyl group is mentioned.

When the organic group as R ^b1 is an alicyclic hydrocarbon group, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, cyclohexane, Cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane, and adamantane Is mentioned. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

Preferable examples when the organic group as R ^b1 is an aliphatic hydrocarbon group substituted with a halogen atom include trifluoromethyl group, pentafluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, heptafluoro -N-propyl group, 3-bromopropyl group, nonafluoro-n-butyl group, tridecafluoro-n-hexyl group, heptadecafluoro-n-octyl group, 2,2,2-trifluoroethyl group, 1, 1-difluoroethyl group, 1,1-difluoro-n-propyl group, 1,1,2,2-tetrafluoro-n-propyl group, 3,3,3-trifluoro-n-propyl group, 2,2 , 3,3,3-pentafluoro-n-propyl group, 2-norbornyl-1,1-difluoroethyl group, 2-norbornyltetrafluoroethyl group, and 3-a A damantyl-1,1,2,2-tetrafluoropropyl group may be mentioned.

Preferable examples when the organic group as R ^b1 is an aliphatic hydrocarbon group substituted with an alkylthio group include 2-methylthioethyl group, 4-methylthio-n-butyl group, and 2-n-butylthio group. An ethyl group is mentioned.

Preferable examples in the case where the organic group as R ^b1 is an aliphatic hydrocarbon group substituted with a halogen atom and an alkylthio group include a 3-methylthio-1,1,2,2-tetrafluoro-n-propyl group Is mentioned.

Preferable examples when the organic group as R ^b1 is an aryl group include a phenyl group, a naphthyl group, and a biphenylyl group.

Preferable examples when the organic group as R ^b1 is an aryl group substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, and a trichlorophenyl group.

Preferable examples when the organic group as R ^b1 is an aryl group substituted with an alkylthio group include a 4-methylthiophenyl group, a 4-n-butylthiophenyl group, a 4-n-octylthiophenyl group, 4 -N-dodecylthiophenyl group is mentioned.

Preferable examples when the organic group as R ^b1 is an aryl group substituted with a halogen atom and an alkylthio group include 1,2,5,6-tetrafluoro-4-methylthiophenyl group, 1,2,5 , 6-tetrafluoro-4-n-butylthiophenyl group, 1,2,5,6-tetrafluoro-4-n-dodecylthiophenyl group.

Preferable examples when the organic group as R ^b1 is an aralkyl group include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group, and a triphenylmethyl group.

Preferable examples in the case where the organic group as R ^b1 is an aralkyl group substituted with a halogen atom include pentafluorophenylmethyl group, phenyldifluoromethyl group, 2-phenyltetrafluoroethyl group, 2- (pentafluorophenyl) ) Ethyl group.

A preferred example in the case where the organic group as R ^b1 is an aralkyl group substituted with an alkylthio group includes a p-methylthiobenzyl group.

As a suitable example when the organic group as R ^b1 is an aralkyl group substituted with a halogen atom and an alkylthio group, a 2- (2,3,5,6-tetrafluoro-4-methylthiophenyl) ethyl group is Can be mentioned.

As a suitable example in case the organic group as ^Rb1 is an alkylaryl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-tert-butylphenyl group, 4-n-hexylphenyl group, 4-cyclohexylphenyl group, 4-n-octylphenyl group, 4- (2-ethyl) -N-hexyl) phenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3, 5-dimethylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 2,6-di- tert-butylphenyl group, 2,4-di-tert-pentylphenyl group, 2,5-di-tert-pentylphenyl group, 2,5-di-tert-octylphenyl group, 2-cyclohexylphenyl group, 3- Examples include cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, and 2,4,6-triisopropylphenyl group.

The group represented by the formula (B1-1) is an ether group-containing group.
In the formula ^(B1-1), as the alkanediyl group having 1 to 4 carbon atoms represented by ^{Y b1,} methylene, ethane-1,2-diyl, ethane-1,1-diyl group, propane - 1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group Is mentioned.
In the formula (B1-1), the alkanediyl group having 2 to 6 carbon atoms represented by R ^b6 or R ^b7 includes an ethane-1,2-diyl group, a propane-1,3-diyl group, a propane- 1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,2-diyl group, pentane-1,5-diyl Group, pentane-1,3-diyl group, pentane-1,4-diyl group, pentane-2,3-diyl group, hexane-1,6-diyl group, hexane-1,2-diyl group, hexane-1 , 3-diyl group, hexane-1,4-diyl group, hexane-2,5-diyl group, hexane-2,4-diyl group, hexane-3,4-diyl group.

In the formula (B1-1), when R ^b6 or R ^b7 is an alkanediyl group having 2 to 6 carbon atoms substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and A fluorine atom is mentioned. Examples of the alkanediyl group substituted with a halogen atom include tetrafluoroethane-1,2-diyl group, 1,1-difluoroethane-1,2-diyl group, 1-fluoroethane-1,2-diyl group, 1,2-difluoroethane-1,2-diyl group, hexafluoropropane-1,3-diyl group, 1,1,2,2, -tetrafluoropropane-1,3-diyl group, 1,1,2, A 2, -tetrafluoropentane-1,5-diyl group may be mentioned.

Examples of the case where R ^b6 or R ^b7 in the formula (B1-1) is an arylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5-dimethyl- 1,4-phenylene group, biphenyl-4,4′-diyl group, diphenylmethane-4,4′-diyl group, 2,2, -diphenylpropane-4,4′-diyl group, naphthalene-1,2-diyl Group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-1 , 8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group.

In Formula (B1-1), when R ^b6 or R ^b7 is an arylene group substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Examples of the arylene group substituted with a halogen atom include a 2,3,5,6-tetrafluoro-1,4-phenylene group.

In the formula (B1-1), the alkyl group having 1 to 18 carbon atoms which may have a branch represented by R ^b8 includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, tert-pentyl group, n-hexyl group, n-hexane-2-yl group, n-hexane-3-yl group N-heptyl group, n-heptan-2-yl group, n-heptan-3-yl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group Examples include a syl group, an n-heptadecyl group, and an n-octadecyl group.

In Formula (B1-1), when R ^b8 is an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. It is done. Examples of alkyl groups substituted with halogen atoms include trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, nonafluoro-n-butyl, tridecafluoro-n-hexyl, heptadecafluoro. -N-octyl group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoro-n-propyl group, 1,1,2,2-tetrafluoro-n-propyl Group, 3,3,3-trifluoro-n-propyl group, 2,2,3,3,3-pentafluoro-n-propyl group, 1,1,2,2-tetrafluorotetradecyl group. .

In the formula (B1-1), when R ^b8 is an alicyclic hydrocarbon group having the number of carbon atoms, examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group include cyclohexane Propane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2 2.2] octane and adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

In the formula (B1-1), when R ^b8 is an aryl group, a halogenated aryl group, an aralkyl group, or a halogenated aralkyl group, suitable examples of these groups are the same as in the case where R ^b1 is these groups. It is.

Among the groups represented by formula (B1-1), a preferable group is a group in which the carbon atom bonded to the sulfur atom in the group represented by R ^b6 is substituted with a fluorine atom. Such suitable groups preferably have 2 to 18 carbon atoms.

R ^b1 is preferably a perfluoroalkyl group having 1 to 8 carbon atoms. In addition, a camphor-10-yl group is also preferable as R ^b1 because a high-definition resist pattern can be easily formed.

In the formula (B1), R ^{b2 to} R ^b5 are a hydrogen atom or a monovalent organic group. R ^b2 and R ^b3 , R ^b3 and R ^b4 , or R ^b4 and R ^b5 may be bonded to each other to form a ring. For example, acenaphthene skeleton may be formed by combining R ^b4 and R ^b5 to form a 5-membered ring together with a naphthalene ring.

Examples of the monovalent organic group include an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or an alkoxy group having 4 to 18 carbon atoms which may be substituted with a halogen atom and may have a branch; A heterocyclyloxy group; an alicyclic hydrocarbon group, a heterocyclic group (heterocyclyl group), or an alkylthio group having 4 to 18 carbon atoms which may be substituted with a halogen atom and may have a branch; heterocyclylthio group; Is preferred.
A group in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with -CO- is also preferable.
A group in which the alkoxy group is interrupted by an —O—CO— bond or an —O—CO—NH— bond is also preferable. Note that the left ends of the —O—CO— bond and the —O—CO—NH— bond are on the side close to the naphthalic acid mother nucleus in the alkoxy group.
Furthermore, the C4-C18 alkylthio group which may be substituted by an alicyclic hydrocarbon group, a heterocyclic group, or a halogen atom and may have a branch is also preferable as R ^{b2 to} R ^b5 .
A group in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with -CO- is also preferable.
A group in which the alkylthio group is interrupted by an —O—CO— bond or an —O—CO—NH— bond is also preferable. Note that the left end of the —O—CO— bond and the —O—CO—NH— bond is the side close to the naphthalic acid mother nucleus in the alkylthio group.

As R ^{b2 to} R ^b5 , R ^b2 is an organic group, R ^{b3 to} R ^b5 are hydrogen atoms, or R ^b3 is an organic group, and R ^b2 , R ^b4 , and R ^b5 are hydrogen atoms. Is preferred. Further, all of R ^{b2 to} R ^b5 may be hydrogen atoms.

Examples of when R ^{b2 to} R ^b5 are unsubstituted alkoxy groups include n-butyloxy group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, n-pentyloxy group, isopentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, isoheptyloxy group, tert-heptyloxy group, n-octyloxy group, isooctyloxy group, tert-octyloxy group, 2-ethylhexyl group N-nonyloxy group, n-decyloxy group, n-decyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, Examples include n-heptadecyloxy group and n-octadecyloxy group.

Examples of the case where R ^{b2 to} R ^b5 are unsubstituted alkylthio groups include n-butylthio group, sec-butylthio group, tert-butylthio group, isobutylthio group, n-pentylthio group, isopentylthio group, tert -Pentylthio group, n-hexylthio group, n-heptylthio group, isoheptylthio group, tert-heptylthio group, n-octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n- Examples include decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, and n-octadecylthio group. .

Examples of the alicyclic hydrocarbon constituting the main skeleton of the alicyclic hydrocarbon group that substitutes these groups when R ^{b2 to} R ^b5 are an alkoxy group or an alkylthio group include cyclopropane, cyclobutane, and cyclopentane. , Cyclohexane, cycloheptane, cyclooctane, cyclodecane, bicyclo [2.1.1] hexane, bicyclo [2.2.1] heptane, bicyclo [3.2.1] octane, bicyclo [2.2.2] octane , And adamantane. The alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from these alicyclic hydrocarbons.

When R ^{b2 to} R ^b5 are an alkoxy group or an alkylthio group, or a heterocyclic group that substitutes these groups, or R ^{b2 to} R ^b5 is a heterocyclyloxy group, the heterocyclic ring constituting the main skeleton of these groups Examples include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine , Piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, pyridine, indolizine, indole, indazole, purine, quinolidine, iso Norrin, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, perimidine, phenanthroline, carbazole, carboline, phenazine, antilysine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzo Examples include thiazole, benzothiadiazole, benzofuroxane, naphthimidazole, benzotriazole, and tetraazaindene. Of these heterocycles, a saturated heterocycle obtained by hydrogenating a ring having a conjugated bond is also preferable.
As the heterocyclic group substituted for the alkoxy group or the alkylthio group, or the heterocyclic group contained in the heterocyclyloxy group, a group in which one hydrogen atom has been removed from the above heterocyclic ring is preferable.

Examples of the case where R ^{b2 to} R ^b5 are alkoxy groups containing an alicyclic hydrocarbon group include a cyclopentyloxy group, a methylcyclopentyloxy group, a cyclohexyloxy group, a fluorocyclohexyloxy group, a chlorocyclohexyloxy group, and a cyclohexylmethyl group. Oxy group, methylcyclohexyloxy group, norbornyloxy group, ethylcyclohexyloxy group, cyclohexylethyloxy group, dimethylcyclohexyloxy group, methylcyclohexylmethyloxy group, norbornylmethyloxy group, trimethylcyclohexyloxy group, 1-cyclohexyl Butyloxy group, adamantyloxy group, menthyloxy group, n-butylcyclohexyloxy group, tert-butylcyclohexyloxy group, bornyloxy group, isobornyl Oxy group, decahydronaphthyloxy group, dicyclopentadienoxy group, 1-cyclohexylpentyloxy group, methyladamantyloxy group, adamantylmethyloxy group, 4-pentylcyclohexyloxy group, cyclohexylcyclohexyloxy group, adamantylethyloxy group And a dimethyladamantyloxy group.

Examples of when R ^{b2 to} R ^b5 are heterocyclyloxy groups include tetrahydrofuranyloxy group, furfuryloxy group, tetrahydrofurfuryloxy group, tetrahydropyranyloxy group, butyrolactonyloxy group, indolyloxy Groups.

Examples of the case where R ^{b2 to} R ^b5 are alkylthio groups containing an alicyclic hydrocarbon group include a cyclopentylthio group, a cyclohexylthio group, a cyclohexylmethylthio group, a norbornylthio group, and an isonorbornylthio group.

Examples of the case where R ^{b2 to} R ^b5 are heterocyclylthio groups include a furfurylthio group and a tetrahydrofuranylthio group.

Examples of the case where R ^{b2 to} R ^b5 are groups in which a methylene group at any position not adjacent to the oxygen atom of the alkoxy group is substituted with —CO— include a 2-ketobutyl-1-oxy group, 2-ketopentyl -1-oxy group, 2-ketohexyl-1-oxy group, 2-ketoheptyl-1-oxy group, 2-ketooctyl-1-oxy group, 3-ketobutyl-1-oxy group, 4-ketopentyl-1-oxy group 5-ketohexyl-1-oxy group, 6-ketoheptyl-1-oxy group, 7-ketooctyl-1-oxy group, 3-methyl-2-ketopentane-4-oxy group, 2-ketopentane-4-oxy group, Examples include 2-methyl-2-ketopentane-4-oxy group, 3-ketoheptane-5-oxy group, and 2-adamantanone-5-oxy group.

Examples of the case where R ^{b2 to} R ^b5 are groups in which a methylene group at any position not adjacent to the sulfur atom of the alkylthio group is substituted with —CO— include 2-ketobutyl-1-thio group, 2-ketopentyl -1-thio group, 2-ketohexyl-1-thio group, 2-ketoheptyl-1-thio group, 2-ketooctyl-1-thio group, 3-ketobutyl-1-thio group, 4-ketopentyl-1-thio group 5-ketohexyl-1-thio group, 6-ketoheptyl-1-thio group, 7-ketooctyl-1-thio group, 3-methyl-2-ketopentane-4-thio group, 2-ketopentane-4-thio group, Examples include 2-methyl-2-ketopentane-4-thio group and 3-ketoheptane-5-thio group.

Preferable examples of the naphthalic acid derivative represented by the formula (B1) include the following compounds.

The content of the component (B) in the first composition is relative to the mass of the solid content of the first composition.
0.1-20 mass% is preferable and 1-10 mass% is more preferable.

（式（Ｃ１）中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、ホスフィノ基、スルホナト基、ホスフィニル基、ホスホナト基、又は有機基を示す。）
で表される化合物である。 <(C) Compound that generates an imidazole compound by heating>
The first composition may contain (C) a compound that generates an imidazole compound by heating (hereinafter also referred to as component (C)). The imidazole compound generated by the component (C) is represented by the following formula (C1):

(In the formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, Represents a sulfonate group, a phosphinyl group, a phosphonate group, or an organic group.)
It is a compound represented by these.

  When the first composition contains (C) a compound that generates an imidazole compound by heating, a crosslinking reaction involving the acidic group of the resin contained in the photosensitive resin composition proceeds in the baking step, and at a low temperature. Even with baking, a pattern having excellent heat resistance and chemical resistance can be formed.

^Examples of the organic group for R ^c1 , R ^c2 , and R ^c3 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

R ^c1 and R ^c2 may be bonded to each other to form a cyclic structure, and may further include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring.

The bond contained in the organic group of R ^c1 , R ^c2 , and R ^c3 is not particularly limited as long as the effect of the present invention is not impaired, and the organic group includes a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Bonds may be included. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (—R) —, —C (= NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.

As the bond containing a hetero atom that the organic group of R ^c1 , R ^c2 , and R ^c3 may have, from the viewpoint of heat resistance of the imidazole compound, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond Amide bond, urethane bond, imino bond (-N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond, sulfinyl bond Is preferred.

When ^{R c1,} R ^c2, and an organic group of ^{R c3} is a substituent other than a hydrocarbon ^{group, R c1,} R ^c2, and ^{where R c3} not particularly limited as long as the effects of the present invention are not impaired. Specific examples of R ^c1 , R ^c2 and R ^c3 include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a silyl group, a silanol group, Alkoxy, alkoxycarbonyl, carbamoyl, thiocarbamoyl, nitro, nitroso, carboxylate, acyl, acyloxy, sulfino, sulfonate, phosphino, phosphinyl, phosphonate, alkyl ether, alkenyl Examples include an ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, and an aryl thioether group. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

R ^c1 , R ^c2 , and R ^c3 are preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom, and a hydrogen atom Is more preferable.

  The component (C) is not particularly limited as long as it is a compound that can generate the imidazole compound represented by the above formula (C1) by heating. Regarding the compound (thermal base generator) that has been conventionally compounded in various compositions and generates an amine by the action of heat, the skeleton derived from the amine generated upon heating is represented by the above formula (C1). By substituting the skeleton derived from the compound, the compound used as the component (C1) can be obtained.

（式（Ｃ２）中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホナト基、又は有機基を示す。Ｒ^ｃ４及びＲ^ｃ５は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基を示す。Ｒ^ｃ６、Ｒ^ｃ７、Ｒ^ｃ８、Ｒ^ｃ９、及びＲ^ｃ１０は、それぞれ独立に水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基を示す。Ｒ^ｃ６、Ｒ^ｃ７、Ｒ^ｃ８、Ｒ^ｃ９、及びＲ^ｃ１０は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。）
で表される化合物が挙げられる。 As a suitable component (C), the following formula (C2):

(In the formula (C2), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonate group, R ^c4 and R ^c5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, or a nitroso group. , A sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group, wherein R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 are each independently a hydrogen atom. , Halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitro A So group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^{In c10} , two or more of them may be bonded to form a cyclic structure, and may include a heteroatom bond.)
The compound represented by these is mentioned.

In the formula (C2), R ^c1 , R ^c2 , and R ^c3 are the same as those described for the formula (C1).

In the formula (C2), R ^c4 and R ^c5 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, or a sulfonate group. , A phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group.

Examples of the organic group in R ^c4 and R ^c5 include those exemplified for R ^c1 , R ^c2 , and R ^c3 . This organic group may contain a hetero atom in the organic group as in the case of R ^c1 , R ^c2 and R ^c3 . The organic group may be linear, branched or cyclic.

Among these, as R ^c4 and R ^c5 , each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, or 7 carbon atoms. -16 aryloxyalkyl group, C7-20 aralkyl group, C2-C11 alkyl group having a cyano group, C1-C10 alkyl group having a hydroxyl group, C1-C10 alkoxy group , An amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms (-COOR, -OCOR: R represents a hydrocarbon group. ), An aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or an electron withdrawing group substituted benzyl group A cyano group is preferably a methylthio group. More preferably, both R ^c4 and R ^c5 are hydrogen atoms, or R ^c4 is a methyl group and R ^c5 is a hydrogen atom.

In the formula (C2), R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, A group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group.

Examples of the organic group in R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 include those exemplified for R ^c1 , R ^c2 , and R ^c3 . As in the case of R ^c1 and R ^c2 , this organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

Two or more of R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 may be bonded to form a cyclic structure, and may include a hetero atom bond. Examples of the cyclic structure include a heterocycloalkyl group and a heteroaryl group, and may be a condensed ring. For example, R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 are benzene in which two or more of them are bonded and R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 are bonded. A ring atom may be shared to form a condensed ring such as naphthalene, anthracene, phenanthrene, and indene.

Among these, as R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 , each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, or 4 carbon atoms. -13 cycloalkenyl group, C7-16 aryloxyalkyl group, C7-20 aralkyl group, C2-C11 alkyl group having cyano group, C1-C10 alkyl having hydroxyl group Group, an alkoxy group having 1 to 10 carbon atoms, an amide group having 2 to 11 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, and 6 carbon atoms. -20 aryl group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group, methyl Thio is preferably a nitro group.

In addition, as R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 , two or more of them are bonded, and R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 are bonded. A case where a condensed ring such as naphthalene, anthracene, phenanthrene, or indene is formed by sharing the atoms of the benzene ring is also preferable from the viewpoint of increasing the absorption wavelength.

（式（Ｃ３）中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は、式（Ｃ１）及び（Ｃ２）と同義である。Ｒ^ｃ４〜Ｒ^ｃ９は式（Ｃ２）と同義である。Ｒ^ｃ１１は、水素原子又は有機基を示す。Ｒ^ｃ６及びＲ^ｃ７が水酸基となることはない。Ｒ^ｃ６、Ｒ^ｃ７、Ｒ^ｃ８、及びＲ^ｃ９は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。）
で表される化合物が好ましい。 Among the compounds represented by the above formula (C2), the following formula (C3):

(In the formula ^{(C3), R c1, R} c2, and ^{where R c3, .R c11} is as defined for formula (C1) and (C2) ^.R c4 ^{to R c9} is as defined for formula (C2) is Represents a hydrogen atom or an organic group, R ^c6 and R ^c7 do not become a hydroxyl group, and R ^c6 , R ^c7 , R ^c8 , and R ^c9 are bonded together to form a cyclic structure. And may contain a heteroatom bond.)
The compound represented by these is preferable.

Since the compound represented by the formula (C3) has the substituent —O—R ^c11 , the compound has excellent solubility in an organic solvent.

In Formula (C3), R ^c11 is a hydrogen atom or an organic group. When R ^c11 is an organic group, examples of the organic group include those exemplified for R ^c1 , R ^c2 , and R ^c3 . This organic group may contain a hetero atom in the organic group. The organic group may be linear, branched or cyclic. R ^c11 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group.

Specific examples of compounds particularly suitable as the component (C) are shown below.

（式（Ｃ４）中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は、式（Ｃ１）と同様であり、Ｒ^ｃ１２はそれぞれ独立に水素原子又は１価の有機基を表し、Ｒ^ｃ１３は置換基を有してもよい芳香族基を表し、前記Ｒ^ｃ１２は他方のＲ^ｃ１２又はＲ^ｃ１３と結合して環状構造を形成してもよい。） In addition, an imidazole compound represented by the following formula (C4) is also suitable as a compound that generates an imidazole compound by heating (C).

(In formula (C4), R ^c1 , R ^c2 and R ^c3 are the same as in formula (C1), R ^c12 independently represents a hydrogen atom or a monovalent organic group, and R ^c13 represents a substituent. It represents an aromatic group which may have, the ^{R c12} may be combined with other ^{R c12} or ^{R c13} to form a cyclic structure.)

In formula (C4), R ^c12 represents a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and may be, for example, an alkyl group that may have a substituent, an aromatic group that may have a substituent, or the like. When R ^c12 is an alkyl group, the alkyl group may have an ester bond or the like in the chain.

As an alkyl group, you may be the same as that of ^Rc14 etc. in below-mentioned formula (C4a), for example. 1-40 are preferable, as for the carbon atom number of an alkyl group, 1-30 are more preferable, 1-20 are especially preferable, and 1-10 are the most preferable.
Examples of the substituent that the alkyl group may have may be the same as the substituent that the alkylene group that is R ^c15 in formula (C4a) described later may have.

The aromatic group which may have a substituent is the same as R ^c13 in formula (C4a) described later, and is preferably an aryl group, more preferably a phenyl group. The aromatic group which may have a substituent as R ^c12 may be the same as or different from R ^c13 .
In formula (C4), one R ^c12 is preferably a hydrogen atom, one R ^c12 is a hydrogen atom, and the other R ^c12 has an alkyl group or a substituent which may have a substituent. It is more preferable that it is a good aromatic group.
In formula (C4), R ^c12 may combine with the other R ^c12 or R ² to form a cyclic structure. For example, at least one R ^c12 may be an alkyl group which may have a substituent, R ^c12 may be combined with other R ^c12 or R ² to form a ring structure.

  The imidazole compound represented by the formula (C4) may be a compound represented by the following formula (C4a).

（式（Ｃ４ａ）中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は式（Ｃ１）と同様であり、Ｒ^ｃ１４は水素原子又はアルキル基であり、Ｒ^ｃ１３は置換基を有してもよい芳香族基であり、Ｒ^ｃ１５は置換基を有してもよいアルキレン基であり、Ｒ^ｃ１５はＲ^ｃ１３と結合して環状構造を形成してもよい。）

(In formula (C4a), R ^c1 , R ^c2 and R ^c3 are the same as in formula (C1), R ^c14 is a hydrogen atom or an alkyl group, and R ^c13 is an aromatic group which may have a substituent. a ^{group, R c15} is an alkylene group which may have a ^{substituent, R c15} may form a ring structure bonded to ^{R c13.)}

In formula (C4a), R ^c14 represents a hydrogen atom or an alkyl group. When R ^c14 is an alkyl group, the alkyl group may be a linear alkyl group or a branched alkyl group. Although the carbon atom number of the said alkyl group is not specifically limited, 1-20 are preferable, 1-10 are preferable and 1-5 are more preferable.

Specific examples of the alkyl group suitable as R ^c14 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethyl-n-hexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group.

In formula (C4a), R ^c13 represents an aromatic group that may have a substituent. The aromatic group that may have a substituent may be an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group that may have a substituent.

  The type of the aromatic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensation of two or more aromatic hydrocarbon groups, and may be two or more aromatic hydrocarbon groups. May be formed by a single bond. As the aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthrenyl group are preferable.

  The kind of the aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. As the aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, an isoxazolyl group, an isothiazolyl group, a benzoxazolyl group, a benzothiazolyl group, and a benzoimidazolyl group are preferable.

  Examples of the substituent that the phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, and a nitroso group. , Sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, ammonio group, and organic group. When a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

  When the substituent that the aromatic group has is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group. The organic group may be any of linear, branched, cyclic, and a combination of these structures. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

  When the aromatic group has a substituent on the adjacent carbon atom, the two substituents bonded on the adjacent carbon atom may combine to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring and an aliphatic ring containing a hetero atom.

  When the substituent that the aromatic group has is an organic group, the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group includes an oxygen atom, a nitrogen atom, a silicon atom, and the like. A bond containing a hetero atom may be included. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (—R) —, —C (= NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.

  As the bond containing a hetero atom that the organic group may have, from the viewpoint of heat resistance of the imidazole compound represented by the formula (C4) or the formula (C4a), an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond , Ester bond, amide bond, amino bond (—NR—: R represents a hydrogen atom or a monovalent organic group) urethane bond, imino bond (—N═C (—R) —, —C (═NR) — : R represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, or a sulfinyl bond.

  When the organic group is a substituent other than a hydrocarbon group, the type of substituent other than the hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. Specific examples of substituents other than hydrocarbon groups include halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups, silanol groups, alkoxy groups. , Alkoxycarbonyl group, amino group, monoalkylamino group, dialkylaluminum group, monoarylamino group, diarylamino group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino Group, sulfonate group, phosphino group, phosphinyl group, phosphonate group, alkyl ether group, alkenyl ether group, alkyl thioether group, alkenyl thioether group, aryl ether group, aryl thioether group and the like. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be linear, branched, or cyclic.

  Examples of the substituent that the phenyl group, the polycyclic aromatic hydrocarbon group, or the aromatic heterocyclic group has include an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms. An alkoxy group, an aryloxy group having 1 to 12 carbon atoms, an arylamino group having 1 to 12 carbon atoms, and a halogen atom are preferable.

As R ^c13 , an imidazole compound represented by the formula (C4) or the formula (C4a) can be synthesized inexpensively and easily, and the solubility of the imidazole compound in water or an organic solvent is good. Preferred are a phenyl group, a furyl group, and a thienyl group.

In formula (C4a), R ^c15 represents an alkylene group which may have a substituent. The substituent which the alkylene group may have is not particularly limited as long as the object of the present invention is not impaired. Specific examples of the substituent that the alkylene group may have include a hydroxyl group, an alkoxy group, an amino group, a cyano group, and a halogen atom. The alkylene group may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred. The number of carbon atoms of the alkylene group is not particularly limited, preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The number of carbon atoms of the alkylene group does not include the carbon atom of the substituent that is bonded to the alkylene group.

  The alkoxy group as a substituent bonded to the alkylene group may be a linear alkoxy group or a branched alkoxy group. The number of carbon atoms of the alkoxy group as a substituent is not particularly limited, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.

  The amino group as a substituent bonded to the alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or dialkylamino group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or dialkylamino group is not particularly limited, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3.

Specific examples of the alkylene group suitable as R ^c15 include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, and n-butane. -1,4-diyl group, n-pentane-1,5-diyl group, n-hexane-1,6-diyl group, n-heptane-1,7-diyl group, n-octane-1,8-diyl Group, n-nonane-1,9-diyl group, n-decane-1,10-diyl group, n-undecane-1,11-diyl group, n-dodecane-1,12-diyl group, n-tridecane- 1,13-diyl group, n-tetradecane-1,14-diyl group, n-pentadecane-1,15-diyl group, n-hexadecane-1,16-diyl group, n-heptadecane-1,17-diyl group N-octadecane-1,18-diyl group , N-nonadecane-1,19-diyl group, and n-icosane-1,20-diyl group.

  Among the imidazole compounds represented by the above formula (C4), a compound represented by the following formula (C4-1a) is preferable because it can be synthesized inexpensively and easily.

（式（Ｃ４−１ａ）中、Ｒ^ｃ１、Ｒ^ｃ２、及び^Ｒｃ３は、式（Ｃ１）と同様であり、Ｒ^ｃ１２は、式（Ｃ４）と同様であり、Ｒ^ｃ１６、Ｒ^ｃ１７、Ｒ^ｃ１８、Ｒ^ｃ１９、及びＲ^ｃ２０は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^ｃ１６、Ｒ^ｃ１７、Ｒ^ｃ１８、Ｒ^ｃ１９、及びＲ^ｃ２０のうち少なくとも１つは水素原子以外の基である。Ｒ^ｃ１６、Ｒ^ｃ１７、Ｒ^ｃ１８、Ｒ^ｃ１９、及びＲ^ｃ２０のうち少なくとも２つが結合して環状構造を形成してもよい。Ｒ^ｃ１２はＲ^ｃ１８と結合して環状構造を形成してもよい。）

(In Formula (C4-1a), R ^c1 , R ^c2 , and ^Rc3 are the same as in Formula (C1), R ^c12 is the same as in Formula (C4), and R ^c16 , R ^c17 , R ^c18 , R ^c19, and ^{R c20} in each occurrence independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. ^{However, R c16, R c17, R c18} , R c19, and at least one non-hydrogen atom group of ^{R c 20} there ^{.R c16, R c17, R c18} , R c19, and may form a cyclic structure and at least two members out of ^{R c 20} .R ^{c 2} may form a cyclic structure bonded to ^{R c18.)}

^{R c16, R c17, R c18} , R c19, and ^{R c 20} is the same as the formula below (C4-1). In formula (C4-1a), R ^c12 may be bonded to R ^c18 to form a cyclic structure. For example, when R ^c12 is an alkyl group which may have a substituent, R ^c12 represents R ^It may combine with ^c18 to form a cyclic structure.

Among the imidazole compounds represented by the above formula (C4a) or formula (C4-1a), they can be synthesized inexpensively and easily, and are excellent in solubility in water and organic solvents, so that the following formula (C4-1) A compound represented by formula (C4-1) is preferred, and a compound in which R ^c15 is a methylene group is more preferred.

（式（Ｃ４−１）中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は式（Ｃ１）と同様であり、Ｒ^ｃ１４、及びＲ^ｃ１５は、式（Ｃ４ａ）と同様であり、Ｒ^ｃ１６、Ｒ^ｃ１７、Ｒ^ｃ１８、Ｒ^ｃ１９、及びＲ^ｃ２０は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^ｃ１６、Ｒ^ｃ１７、Ｒ^ｃ１８、Ｒ^ｃ１９、及びＲ^ｃ２０のうち少なくとも１つは水素原子以外の基である。Ｒ^ｃ１６、Ｒ^ｃ１７、Ｒ^ｃ１８、Ｒ^ｃ１９、及びＲ^ｃ２０のうち少なくとも２つが結合して環状構造を形成してもよい。Ｒ^ｃ１５はＲ^ｃ１８と結合して環状構造を形成してもよい。）

(In formula (C4-1), R ^c1 , R ^c2 , and R ^c3 are the same as in formula (C1), R ^c14 , and R ^c15 are the same as in formula (C4a), and R ^c16 , R ^c17 , ^{R c18, R c19,} and ^{R c20} in each occurrence independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group, or an organic group. ^However, at least one hydrogen atom of ^{R c16, R c17, R c18} , R c19, and ^{R c 20} except that the group ^{.R c16, R c17, R c18} , R c19, and at least two members to form a cyclic structure of ^{R c 20} Which may ^{.R c15} may form a ring structure bonded to ^{R c18.)}

When ^{R c16, R c17, R c18} , R c19, and ^{R c 20} is an organic group, the organic group, ^{R c13} in formula (C4a) is the same as the organic group having as a substituent. R ^c16 , R ^c17 , R ^c18 , and R ^c19 are preferably hydrogen atoms from the viewpoint of solubility of the imidazole compound in a solvent.

Among ^{them, R c16, R c17, R} c18, R c19, and at least one of ^{R c 20} is preferably the following substituent ^group, the ^{R c 20} is the following substituent group are particularly preferred. If R ^{c 20} is the following substituent ^{group, R c16, R c17, R} c18, and ^{R c19} is preferably a hydrogen atom.
-O-R ^c21
(R ^c21 is a hydrogen atom or an organic group.)

When R ^c21 is an organic group, the organic group is the same as the organic group that R ^c13 in formula (C4a) has as a substituent. R ^c21 is preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

（式（Ｃ４−１−１）において、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は式（Ｃ１）と同様であり、Ｒ^ｃ１４は、式（Ｃ４ａ）と同様であり、Ｒ^ｃ２２、Ｒ^ｃ２３、Ｒ^ｃ２４、Ｒ^ｃ２５、及びＲ^ｃ２６は、それぞれ独立に、水素原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基、又は有機基である。ただし、Ｒ^ｃ２２、Ｒ^ｃ２３、Ｒ^ｃ２４、Ｒ^ｃ２５、及びＲ^ｃ２６のうち少なくとも１つは水素原子以外の基である。） Among the compounds represented by the formula (C4-1), a compound represented by the following formula (C4-1-1) is preferable.

(In Formula (C4-1-1), R ^c1 , R ^c2 , and R ^c3 are the same as in Formula (C1), R ^c14 is the same as in Formula (C4a), and R ^c22 , R ^c23 , R ^c24 , R ^c25 and R ^c26 each independently represent a hydrogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, or a phosphinyl group. A group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, provided that at least one of R ^c22 , R ^c23 , R ^c24 , R ^c25 , and R ^c26 is a group other than a hydrogen atom. .)

Among the compounds represented by the formula (C4-1-1), at least one of R ^c22 , R ^c23 , R ^c24 , R ^c25 , and R ^c26 is a group represented by the aforementioned —O—R ^c21. It is preferable that R ^c26 is a group represented by —O—R ^c21 . When R ^c26 is a group represented by —O—R ^c21 , R ^c22 , R ^c23 , R ^c24 , and R ^c25 are preferably hydrogen atoms.

A method for synthesizing the imidazole compound represented by the above formula (C4) is not particularly limited. For example, a halide represented by R ^c13 CR ^c12 (Hal) R ^c12 (R ^c12 and R ^c13 are the same as ^those in the formula (C4), Hal is a halogen atom), and the formula (C1) described above. The imidazole compound represented by the above formula (C4) can be synthesized by reacting with the imidazole compound represented by formula (I) in accordance with a conventional method to perform imidazolylation.

  The method for synthesizing the imidazole compound represented by the above formula (C4a) is not particularly limited. For example, by reacting a halogen-containing carboxylic acid derivative represented by the following formula (CI) with an imidazole compound represented by the aforementioned formula (C1) according to a conventional method, imidazolylation is carried out. An imidazole compound represented by (C4a) can be synthesized.

（式（Ｃ−Ｉ）中、Ｒ^ｃ１３、Ｒ^ｃ１４、及びＲ^ｃ１５は、式（Ｃ４ａ）と同様であり、Ｈａｌはハロゲン原子である。）

(In the formula (CI), R ^c13 , R ^c14 and R ^c15 are the same as in the formula (C4a), and Hal is a halogen atom.)

When the imidazole compound is a compound represented by the formula (C4a) and R ^c15 is a methylene group, that is, when the imidazole compound is a compound represented by the following formula (C4-2), The imidazole compound can also be synthesized by the method using the Michael addition reaction described.

（式（Ｃ４−２）中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は式（Ｃ１）と同様であり、Ｒ^ｃ１３、及びＲ^ｃ１４は、式（Ｃ４ａ）と同様である。）

(In the formula ^{(C4-2), R c1, R} c2, and ^{where R c3} is the same as the formula ^{(C1), R c13,} and ^{R c14} are the same as the formula (C4a).)

  Specifically, for example, a 3-substituted acrylic acid derivative represented by the following formula (C-II) and an imidazole compound represented by the above formula (C1) are mixed in a solvent to carry out Michael addition reaction. By generating it, an imidazole compound represented by the above formula (C4-2) is obtained.

（式（Ｃ−ＩＩ）中、Ｒ^ｃ１３、及びＲ^ｃ１４は、式（Ｃ４ａ）と同様である。）

(In formula (C-II), R ^c13 and R ^c14 are the same as in formula (C4a).)

  Moreover, the imidazole compound represented by a following formula (C4-3) is represented by adding the 3-substituted acrylic acid derivative containing the imidazolyl group represented by the following formula (C-III) in the solvent containing water. can get.

（式（Ｃ−ＩＩＩ）及び式（Ｃ４−３）中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は式（Ｃ１）と同様であり、Ｒ^ｃ１３は、式（Ｃ４）と同様である。）

(In Formula (C-III) and Formula (C4-3), R ^c1 , R ^c2 , and R ^c3 are the same as in Formula (C1), and R ^c13 is the same as in Formula (C4).)

  In this case, by hydrolysis of the 3-substituted acrylic acid derivative represented by the above formula (C-III), the imidazole compound represented by the above formula (C1) and the following formula (C-IV) are represented. 3-substituted acrylic acid is formed. A Michael addition reaction occurs between the 3-substituted acrylic acid represented by the following formula (C-IV) and the imidazole compound represented by the above formula (C1), and the above formula (C4-3) The imidazole compound represented is produced.

（式（Ｃ−ＩＶ）中、Ｒ^ｃ１３は、式（Ｃ４ａ）と同様である。）

(In formula (C-IV), R ^c13 is the same as in formula (C4a).)

Preferable specific examples of the imidazole compound represented by the formula (C4) or the formula (C4a) include the following.

  The content of the component (C) in the first composition is preferably 0.01 to 10% by mass and more preferably 0.1 to 5% by mass with respect to the mass of the solid content of the first composition. .

<(D) Crosslinking group-containing compound>
The first composition may contain (D) a crosslinking group-containing compound (hereinafter also referred to as component (D)). (D) The crosslinking group-containing compound is a compound containing a crosslinking group that can be thermally crosslinked when the patterned film formed by using the first composition is post-baked. Examples of the crosslinking group include an epoxy group, an oxetanyl group, and a group containing an unsaturated double bond (such as a vinyl group) as described above for the component (A). (D) The crosslinking group-containing compound may have two or more crosslinking groups, or may have a combination of different types of crosslinking groups. (D) The crosslinking group-containing compound may be a low molecular compound or a high molecular compound.
In addition, even if at least one of (A1) resin component and (A2) resin component has a crosslinking group, the first composition may contain (D) a crosslinking group-containing compound.

In the claims and specification of the present application, (A1) resin component, (A2) resin component, and (A3) resin component having a crosslinkable group are represented by (D) crosslinkable group-containing compound. Not applicable.
Hereinafter, the crosslinking group-containing low molecular compound and the crosslinking group-containing polymer compound will be described.

[Crosslinkable group-containing low molecular weight compound]
Preferable examples of the crosslinking group-containing low molecular weight compound include a bifunctional or higher polyfunctional epoxy compound, a bifunctional or higher polyfunctional oxetane compound, and a polymerizable monomer containing a vinyl group.

(Polyfunctional epoxy compound)
The polyfunctional epoxy compound is not particularly limited as long as it is a bifunctional or higher functional epoxy compound. Examples of polyfunctional epoxy compounds include bifunctional epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, naphthalene type epoxy resins, and biphenyl type epoxy resins; Glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; Glycidyl amine type epoxy such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmetaxylylenediamine, and tetraglycidylbisaminomethylcyclohexane Resins; heterocyclic epoxy resins such as triglycidyl isocyanurate; phloroglicinol triglycidyl ether, trihydroxybiphenyl tri Lysidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2, 3-epoxypropoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Trifunctional epoxy resins such as (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol; tetrahydroxyphenylethane tetraglycidyl ether, tetraglycidylbenzophenone, bisresorcinol tetraglycidyl Tetrafunctional ethers such as ether and tetraglycidoxybiphenyl Carboxymethyl resins.

  An alicyclic epoxy compound is also preferable as a polyfunctional epoxy compound in that a highly transparent film can be easily formed. Specific examples of the alicyclic epoxy compound include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate. Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, ε-caprolactone modified 3, 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3, 4-epoxycyclohex Rumethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate) , Epoxycyclohexahydrophthalic acid dioctyl, and epoxycyclohexahydrophthalic acid di-2-ethylhexyl, an epoxy resin having a tricyclodecene oxide group, and a compound represented by the following formula (a1).

  Epoxy group-containing fluorene compounds can also be suitably used as the polyfunctional epoxy compound. Examples of the epoxy group-containing fluorene compound include 9,9-bis [4- (glycidyloxy) phenyl] -9H-fluorene, 9,9-bis [4- [2- (glycidyloxy) ethoxy] phenyl] -9H. -Fluorene, 9,9-bis [4- [2- (glycidyloxy) ethyl] phenyl] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3-methylphenyl] -9H-fluorene, 9,9-bis [4- (glycidyloxy) -3,5-dimethylphenyl] -9H-fluorene, 9,9-bis (6-glycidyloxynaphthalen-2-yl) -9H-fluorene, etc. .

（式（ｄ１）中、Ｚは単結合、−Ｏ−、−Ｏ−ＣＯ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＣＢｒ_２−、−Ｃ（ＣＢｒ_３）_２−、−Ｃ（ＣＦ_３）_２−、及び−Ｒ^ｄ１９−Ｏ−ＣＯ−からなる群より選択される２価の基であり、Ｒ^ｄ１９は炭素原子数１〜８のアルキレン基であり、Ｒ^ｄ１〜Ｒ^ｄ１８は、それぞれ独立に、水素原子、ハロゲン原子、及び有機基からなる群より選択される基である。） Among the specific examples of these epoxy compounds, an alicyclic epoxy compound represented by the following formula (d1) is preferable because a film excellent in transparency and mechanical properties can be easily formed.

(In the formula (d1), Z represents a single bond, —O—, —O—CO—, —S—, —SO—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, — _{CBr 2 -, - C (CBr} 3) 2 -, - C (CF 3) 2 -, and a divalent radical selected from the group consisting of ^{-R d19 -O-CO-, R} d19 is a carbon atom (It is an alkylene group of ^formulas 1 to 8, and R ^{d1 to} R ^d18 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.)

In the formula (d1), R ^d19 is an alkylene group having 1 to 8 carbon atoms, and is preferably a methylene group or an ethylene group.

When R ^{d1 to} R ^d18 are organic groups, the organic group is not particularly limited as long as the object of the present invention is not ^impaired . The organic group may be a hydrocarbon group or a group composed of a carbon atom and a halogen atom, such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom together with a carbon atom and a hydrogen atom. It may be a group containing a hetero atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

  The organic group includes a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom and a halogen atom, a carbon atom and a hydrogen atom. And a group consisting of an oxygen atom and a halogen atom. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. 1-20 are preferable, as for the carbon atom number of an organic group, 1-10 are more preferable, and 1-5 are especially preferable.

  Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. N-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group Chain alkyl groups such as n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n Chain alkenyl groups such as -butenyl, 2-n-butenyl, and 3-n-butenyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl And a cycloalkyl group such as cycloheptyl group; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, α-naphthyl group, β-naphthyl group, biphenyl-4-yl group, biphenyl-3-yl Group, biphenyl-2-yl group, anthryl group, phenanthryl group and other aryl groups; benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, α-naphthylethyl group, and β-naphthylethyl group And aralkyl groups such as

  Specific examples of the halogenated hydrocarbon group include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, and perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogenated chain alkyl group such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromocyclohexyl group , And 4-bu Halogenated cycloalkyl group such as mocyclohexyl group; 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6 -Dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4- Halogenated aryl groups such as fluorophenyl group; 2-chlorophenylmethyl group, 3-chlorophenylmethyl group, 4-chlorophenylmethyl group, 2-bromophenylmethyl group, 3-bromophenylmethyl group, 4-bromophenylmethyl group, 2 -Fluorophenylmethyl group, 3-fluorophenyl Methyl group, a halogenated aralkyl group such as 4-fluorophenyl methyl group.

  Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom include hydroxy chain such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group. An alkyl group; a hydroxycycloalkyl group such as a 2-hydroxycyclohexyl group, a 3-hydroxycyclohexyl group, and a 4-hydroxycyclohexyl group; a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, 2,3- Hydroxyaryl groups such as dihydroxyphenyl group, 2,4-dihydroxyphenyl group, 2,5-dihydroxyphenyl group, 2,6-dihydroxyphenyl group, 3,4-dihydroxyphenyl group, and 3,5-dihydroxyphenyl group; 2-hydroxyphenylmethyl group, 3-hydroxy Hydroxy aralkyl groups such as enylmethyl group and 4-hydroxyphenylmethyl group; methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group N-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n- Tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-nonadecyloxy group, n-icosyloxy group, etc. A chain alkoxy group; vinyloxy group, 1-pro Chain alkenyloxy groups such as nyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, 2-n-butenyloxy group, and 3-n-butenyloxy group; phenoxy group, o-tolyloxy Group, m-tolyloxy group, p-tolyloxy group, α-naphthyloxy group, β-naphthyloxy group, biphenyl-4-yloxy group, biphenyl-3-yloxy group, biphenyl-2-yloxy group, anthryloxy group, And aryloxy groups such as phenanthryloxy group; benzyloxy group, phenethyloxy group, α-naphthylmethyloxy group, β-naphthylmethyloxy group, α-naphthylethyloxy group, β-naphthylethyloxy group, etc. Aralkyloxy group; methoxymethyl group, ethoxymethyl group, n-propylo group Xymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propyloxyethyl group, 3-methoxy-n-propyl group, 3-ethoxy-n-propyl group, 3-n-propyloxy-n Alkoxyalkyl groups such as -propyl group, 4-methoxy-n-butyl group, 4-ethoxy-n-butyl group, and 4-n-propyloxy-n-butyl group; methoxymethoxy group, ethoxymethoxy group, n- Propyloxymethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group, 2-n-propyloxyethoxy group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n- Propyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, and 4-n-pro Alkoxyalkoxy groups such as ruoxy-n-butyloxy group; alkoxyaryl groups such as 2-methoxyphenyl group, 3-methoxyphenyl group, and 4-methoxyphenyl group; 2-methoxyphenoxy group, 3-methoxyphenoxy group, and 4 -Alkoxyaryloxy groups such as methoxyphenoxy group; aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group and decanoyl group; benzoyl group , Α-naphthoyl group, β-naphthoyl group and other aromatic acyl groups; methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, n-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyl Carboni A chain alkyloxycarbonyl group such as a group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, and n-decyloxycarbonyl group; phenoxycarbonyl group, α-naphthoxycarbonyl group, And aryloxycarbonyl groups such as β-naphthoxycarbonyl group; formyloxy group, acetyloxy group, propionyloxy group, butanoyloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group An aliphatic acyloxy group such as a nonanoyloxy group and a decanoyloxy group; an aromatic acyloxy group such as a benzoyloxy group, an α-naphthoyloxy group, and a β-naphthoyloxy group.

R ^{d1 to} R ^d18 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. In particular, from the viewpoint of mechanical properties of the film formed using the first composition, it is more preferable that R ^{d1 to} R ^d18 are all hydrogen atoms.

Among the alicyclic epoxy compounds represented by the formula (d1), specific examples of suitable compounds include the following compounds 1 and 2.

(Polyfunctional oxetane compound)
Examples of the bifunctional or higher polyfunctional oxetane compound include 3,3 ′-(oxybismethylene) bis (3-ethyloxetane), 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl, 3,7-bis (3-oxetanyl) -5-oxanonane, 3,3 ′-[1,3- (2-methylenyl) propanediylbis (oxymethylene)] bis (3-ethyloxetane), 1,4- Bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 1,2-bis [(3-ethyl-3-oxetanyl) methoxymethyl] ethane, 1,3-bis [(3-ethyl-3-oxetanyl) ) Methoxymethyl] propane, ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dicyclopentenyl bis [(3-ethyl-3- Xetanyl) methyl] ether, triethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, tetraethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, tricyclodecanediyldimethylene bis [ (3-ethyl-3-oxetanyl) methyl] ether, trimethylolpropane tris [(3-ethyl-3-oxetanyl) methyl] ether, 1,4-bis [(3-ethyl-3-oxetanyl) methoxy] butane, 1,6-bis [(3-ethyl-3-oxetanyl) methoxy] hexane, pentaerythritol tris [(3-ethyl-3-oxetanyl) methyl] ether, pentaerythritol tetrakis [(3-ethyl-3-oxetanyl) methyl ] Ether, polyethylene glycol Rubis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl ] Ether, dipentaerythritol tetrakis [(3-ethyl-3-oxetanyl) methyl] ether, and the like.

Reaction product of dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether and caprolactone, reaction product of dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether and caprolactone , Ditrimethylolpropanetetrakis [(3-ethyl-3-oxetanyl) methyl] ether, reaction product of bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide, bisphenol A bis [( Reaction product of 3-ethyl-3-oxetanyl) methyl] ether and propylene oxide, reaction product of hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide, hydrogenated bisphenol A bis [( -Ethyl-3-oxetanyl) methyl] ether and propylene oxide reaction product, bisphenol F bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide reaction product, etc. are also polyfunctional oxetane compounds. Can be used as
(Polymerizable monomer containing unsaturated double bond)
The polymerizable monomer containing an unsaturated double bond includes a monofunctional monomer and a polyfunctional monomer. Hereinafter, the monofunctional monomer and the polyfunctional monomer will be described in order.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-methylol ( (Meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamide- 2-methylpropane sulfonic acid, tert-butylacrylamide sulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybuty (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers may be used alone or in combination of two or more.

  Polyfunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate Rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meta Acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, Examples thereof include polyfunctional monomers such as a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers may be used alone or in combination of two or more.

[Crosslinking group-containing polymer compound]
Preferable examples of the crosslinking group-containing polymer compound include an epoxy-containing resin and a resin containing an unsaturated double bond.

(Epoxy group-containing resin)
The epoxy group-containing resin may be a polymer obtained by polymerizing a monomer mixture containing an epoxy group-containing monomer or an epoxy group-containing monomer. The epoxy group-containing resin is obtained by introducing an epoxy group into a polymer having a reactive functional group such as a hydroxyl group, a carboxyl group, and an amino group using a compound having an epoxy group such as epichlorohydrin. May be. Since it is easy to obtain, prepare, adjust the amount of the epoxy group in the polymer, etc., the polymer having an epoxy group includes a monomer having an epoxy group or a monomer having an epoxy group A polymer obtained by polymerizing a body mixture is preferred.

  Preferred examples of the epoxy group-containing resin include novolac epoxy resins such as phenol novolac epoxy resin, brominated phenol novolac epoxy resin, orthocresol novolac epoxy resin, bisphenol A novolac epoxy resin, and bisphenol AD novolac epoxy resin. A cycloaliphatic epoxy resin such as an epoxidized product of a dicyclopentadiene type phenol resin; and an aromatic epoxy resin such as an epoxidized product of a naphthalene type phenol resin.

  In addition, among epoxy group-containing resins, since it is easy to prepare, a homopolymer of an epoxy group-containing (meth) acrylate ester or an epoxy group-containing (meth) acrylate ester and other single quantities A copolymer with the body is preferred.

  The (meth) acrylic acid ester having an epoxy group is a (meth) acrylic acid ester having an alicyclic epoxy group as described later, even if it is a (meth) acrylic acid ester having a chain aliphatic epoxy group. There may be. Moreover, the (meth) acrylic acid ester which has an epoxy group may contain the aromatic group. Among the (meth) acrylic acid ester having an epoxy group, an aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group and an aliphatic (meth) acrylic acid ester having an alicyclic epoxy group are preferable, Aliphatic (meth) acrylic acid esters having an alicyclic epoxy group are more preferred.

  Examples of (meth) acrylic acid ester containing an aromatic group and having an epoxy group include 4-glycidyloxyphenyl (meth) acrylate, 3-glycidyloxyphenyl (meth) acrylate, and 2-glycidyloxyphenyl (meth) acrylate. 4-glycidyloxyphenylmethyl (meth) acrylate, 3-glycidyloxyphenylmethyl (meth) acrylate, 2-glycidyloxyphenylmethyl (meth) acrylate, and the like.

  Examples of the aliphatic (meth) acrylic acid ester having a chain aliphatic epoxy group include an ester group (—O—CO—, such as epoxy alkyl (meth) acrylate and epoxyalkyloxyalkyl (meth) acrylate). (Meth) acrylic acid ester in which a chain aliphatic epoxy group is bonded to the oxy group (—O—) in (). Such a chain aliphatic epoxy group possessed by the (meth) acrylate ester may contain one or a plurality of oxy groups (—O—) in the chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and particularly preferably 3 to 10.

  Specific examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6, Epoxyalkyl (meth) acrylates such as 7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyloxy-n-butyl (meta And epoxyalkyloxyalkyl (meth) acrylates such as acrylate, 5-glycidyloxy-n-hexyl (meth) acrylate, and 6-glycidyloxy-n-hexyl (meth) acrylate.

  Specific examples of the aliphatic (meth) acrylic acid ester having an alicyclic epoxy group include the compounds represented by the formulas (a-1) to (a-15) described above for the (A1) resin component. It is done.

  As the polymer having an epoxy group, any of a homopolymer of (meth) acrylic acid ester having an epoxy group and a copolymer of (meth) acrylic acid ester having an epoxy group and another monomer is used. However, the content of the unit derived from the (meth) acrylic acid ester having an epoxy group in the polymer having an epoxy group is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. % Or more is particularly preferable, and 100% by mass is most preferable.

  When the polymer having an epoxy group is a copolymer of a (meth) acrylic acid ester having an epoxy group and another monomer, the other monomer has an unsaturated carboxylic acid or an epoxy group. Examples thereof include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and the like. These compounds can be used alone or in combination of two or more. From the viewpoint of the storage stability of the first composition and the chemical resistance of the film formed using the first composition to alkali and the like, (meth) acrylic acid ester having an epoxy group and other single amount The copolymer with the body preferably does not contain a unit derived from an unsaturated carboxylic acid.

  Examples of the unsaturated carboxylic acid include (meth) acrylic acid; (meth) acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.

  Examples of (meth) acrylic acid esters having no epoxy group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate and the like. Linear or branched alkyl (meth) acrylate; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (Meth) acrylate, furfuryl (meth) acrylate; (meth) acrylic acid ester having a group having an alicyclic skeleton.

  Examples of (meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, and N, N-aryl (meth) acrylamide. N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of allyl compounds include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Etc.

  Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxy Aliphatic vinyl ethers such as ethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4 Dichlorofe And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl Examples include phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

  Examples of styrenes include styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene. Alkyl styrene such as ethoxymethyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo Styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoro Methylstyrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  The molecular weight of the epoxy group-containing resin is not particularly limited as long as the object of the present invention is not hindered, but is preferably 3,000 to 30,000, more preferably 5,000 to 15,000, as a weight average molecular weight in terms of polystyrene. .

[Resins containing unsaturated double bonds]
Resins containing unsaturated double bonds include (meth) acrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monoethyl fumarate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene Glycol monoethyl ether (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra Tylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, Oligomers in which pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cardoepoxy diacrylate, etc. are polymerized; Polyester (meth) obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing monohydric acid or polybasic acid with monohydric alcohol Crylate: Polyurethane (meth) acrylate obtained by reacting a polyol with a compound having two isocyanate groups and then reacting with (meth) acrylic acid; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S Type epoxy resin, phenol or cresol novolac type epoxy resin, resol type epoxy resin, triphenolmethane type epoxy resin, polycarboxylic acid polyglycidyl ester, polyol polyglycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, dihydroxy Examples thereof include an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a benzene type epoxy resin with (meth) acrylic acid. Furthermore, a resin obtained by reacting an epoxy (meth) acrylate resin with a polybasic acid anhydride can be suitably used. In the present specification, “(meth) acryl” means “acryl or methacryl”.

  In addition, as a resin containing an ethylenically unsaturated group, a resin obtained by further reacting a reaction product of an epoxy compound and an unsaturated group-containing carboxylic acid compound with a polybasic acid anhydride, or an unsaturated carboxylic acid It is obtained by reacting at least part of the carboxy group contained in the polymer containing the unit derived from (meth) acrylic acid ester and / or (meth) acrylic acid epoxy alkyl ester having an alicyclic epoxy group. Resins (hereinafter collectively referred to as “resins containing structural units having an ethylenically unsaturated group”) can be suitably used. The ethylenically unsaturated group in the structural unit having an ethylenically unsaturated group is preferably a (meth) acryloyloxy group.

Among these, a resin containing a structural unit having an ethylenically unsaturated group or a compound represented by the following formula (d2) is preferable. The compound represented by the formula (d2) itself is preferable in terms of high crosslinkability.

In the above formula (d2), ^Xd represents a group represented by the following formula (d3).

In the formula (d3), R ^d20 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^d21 each independently represents a hydrogen atom or a methyl group, W represents a single bond or a group represented by the following structural formula (d4). In the formula (d3) and the formula (d4), “*” means a terminal of a bond of a divalent group.

In the above formula (d2), Y ^d represents a residue obtained by removing an acid anhydride group (—CO—O—CO—) from a dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Examples thereof include phthalic anhydride and glutaric anhydride.

In the above formula (d2), Z ^d represents a residue obtained by removing two acid anhydride groups from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like. Furthermore, in said formula (d2), a represents the integer of 0-20.

  The acid value of the resin containing an ethylenically unsaturated group is preferably 10 to 150 mgKOH / g, and more preferably 70 to 110 mgKOH / g, in terms of resin solids. An acid value of 10 mgKOH / g or more is preferable because sufficient solubility in a developer can be obtained. Moreover, it is preferable for the acid value to be 150 mgKOH / g or less because sufficient curability can be obtained and surface properties can be improved.

  Moreover, it is preferable that it is 1000-40000, and, as for the mass mean molecular weight of resin containing an ethylenically unsaturated group, it is more preferable that it is 2000-30000. A mass average molecular weight of 1000 or more is preferable because good heat resistance and film strength can be obtained. Moreover, it is preferable for the mass average molecular weight to be 40000 or less because good developability can be obtained.

5-60 mass% is preferable with respect to the mass of solid content of a 1st composition, and, as for content of (D) component in a 1st composition, 10-50 mass% is more preferable.
<(E) Aromatic carboxylic acid compound>
The first composition may contain (E) an aromatic carboxylic acid compound (hereinafter also referred to as component (E)). (E) The aromatic carboxylic acid compound has a carboxyl group bonded to an aromatic group. In the first composition containing the above-mentioned (A2) resin component, the first composition contains (E) the aromatic carboxylic acid compound and the above-mentioned (B) radical generator in combination, A1) The acid group protected by the protecting group in the resin component is easily deprotected by exposure.

(E) In the aromatic carboxylic acid compound, the aromatic group to which the carboxyl group is bonded may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
(E) When the aromatic carboxylic acid compound has two or more carboxyl groups, if at least one carboxyl group is bonded to the aromatic group, (E) the aromatic carboxylic acid compound is a carboxyl bonded to the aliphatic group. It may have a group.

(E) In the aromatic carboxylic acid compound, the aromatic group to which the carboxyl group is bonded may have one or more substituents in addition to the carboxyl group.
Examples of the substituent that the aromatic group may have include a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, a sulfonate group, a phosphinyl group, and a phosphonate group. Or an organic group.

  When the substituent on the aromatic group is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. This organic group may contain a bond or substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic. This organic group is usually monovalent, but can be a divalent or higher organic group when a cyclic structure is formed.

  The bond contained in the organic group is not particularly limited as long as the effects of the present invention are not impaired, and the organic group may contain a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (—R) —, —C (= NR)-: R represents a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond and the like.

  As the substituent on the aromatic group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen atom are preferable.

  The aromatic carboxylic acid compound may be a low molecular compound such as benzoic acid or naphthoic acid, or may be a high molecular compound having a carboxyl group bonded to an aromatic group. Hereinafter, the low-molecular aromatic carboxylic acid compound and the high-molecular aromatic carboxylic acid compound will be described in order.

(Low molecular aromatic carboxylic acid compound)
The low molecular aromatic carboxylic acid compound may be a monocarboxylic acid compound or a polyvalent carboxylic acid compound having two or more carboxyl groups. The aromatic group contained in the low molecular weight aromatic carboxylic acid compound may have a substituent other than the carboxyl group.

  The number of aromatic rings contained in the low molecular weight aromatic carboxylic acid compound is not particularly limited. Here, when the aromatic ring contained in the low-molecular aromatic carboxylic acid is a condensed ring, the number of aromatic rings among a plurality of rings constituting the condensed ring is the number of aromatic rings. For example, the number of aromatic rings is 2 for biphenyl carboxylic acid and naphthoic acid, and the number of aromatic rings is 3 for anthracene carboxylic acid. The number of aromatic rings contained in the low molecular weight aromatic carboxylic acid compound may be, for example, an integer of 1 to 5, or an integer of 1 to 3.

As a specific example of a low molecular weight aromatic carboxylic acid compound,
benzoic acid;
Hydroxybenzoic acids such as salicylic acid, m-hydroxybenzoic acid, and p-hydroxybenzoic acid;
alkylbenzoic acids such as o-methylbenzoic acid, m-methylbenzoic acid, and p-methylbenzoic acid;
Halogenated benzoic acids such as o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid, and p-bromobenzoic acid;
Alkoxybenzoic acids such as o-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxybenzoic acid, o-ethoxybenzoic acid, m-ethoxybenzoic acid, and p-ethoxybenzoic acid;
aminobenzoic acids such as o-aminobenzoic acid, m-aminobenzoic acid, and p-aminobenzoic acid;
acyloxybenzoic acids such as o-acetyloxybenzoic acid, m-acetyloxybenzoic acid, and p-acetyloxybenzoic acid;
Naphthoic acids such as 1-naphthoic acid and 2-naphthoic acid;
1-hydroxy-2-naphthoic acid, 1-hydroxy-3-naphthoic acid, 1-hydroxy-4-naphthoic acid, 1-hydroxy-5-naphthoic acid, 1-hydroxy-6-naphthoic acid, 1-hydroxy-7 -Naphthoic acid, 1-hydroxy-8-naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, 2-hydroxy-4-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2 Hydroxy naphthoic acids such as hydroxy-6-naphthoic acid, 2-hydroxy-7-naphthoic acid, and 2-hydroxy-8-naphthoic acid;
1-amino-2-naphthoic acid, 1-amino-3-naphthoic acid, 1-amino-4-naphthoic acid, 1-amino-5-naphthoic acid, 1-amino-6-naphthoic acid, 1-amino-7 -Naphthoic acid, 1-amino-8-naphthoic acid, 2-amino-1-naphthoic acid, 2-amino-3-naphthoic acid, 2-amino-4-naphthoic acid, 2-amino-5-naphthoic acid, 2 Amino naphthoic acids such as amino-6-naphthoic acid, 2-amino-7-naphthoic acid, and 2-amino-8-naphthoic acid;
1-methoxy-2-naphthoic acid, 1-methoxy-3-naphthoic acid, 1-methoxy-4-naphthoic acid, 1-methoxy-5-naphthoic acid, 1-methoxy-6-naphthoic acid, 1-methoxy-7 -Naphthoic acid, 1-methoxy-8-naphthoic acid, 2-methoxy-1-naphthoic acid, 2-methoxy-3-naphthoic acid, 2-methoxy-4-naphthoic acid, 2-methoxy-5-naphthoic acid, 2 -Methoxy-6-naphthoic acid, 2-methoxy-7-naphthoic acid, 2-methoxy-8-naphthoic acid, 1-ethoxy-2-naphthoic acid, 1-ethoxy-3-naphthoic acid, 1-ethoxy-4- Naphthoic acid, 1-ethoxy-5-naphthoic acid, 1-ethoxy-6-naphthoic acid, 1-ethoxy-7-naphthoic acid, 1-ethoxy-8-naphthoic acid, 2-ethoxy-1-naphthoic acid, 2- D Xyl-3-naphthoic acid, 2-ethoxy-4-naphthoic acid, 2-ethoxy-5-naphthoic acid, 2-ethoxy-6-naphthoic acid, 2-ethoxy-7-naphthoic acid, and 2-ethoxy-8- Alkoxy naphthoic acids such as naphthoic acid;
Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid;
1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1, Naphthalenedicarboxylic acids such as 8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid;
Biphenyl carboxylic acids such as 1,1′-biphenyl-4-carboxylic acid, 1,1′-biphenyl-3-carboxylic acid, and 1,1′-biphenyl-2-carboxylic acid;
1,1′-biphenyl-4,4′-dicarboxylic acid, 1,1′-biphenyl-3,3′-dicarboxylic acid, 1,1′-biphenyl-2,2′-dicarboxylic acid, 1,1′- Biphenyl dicarboxylic acids such as biphenyl-3,4'-dicarboxylic acid, 1,1'-biphenyl-2,4'-dicarboxylic acid, and 1,1'-biphenyl-2,3'-dicarboxylic acid,
Trivalent or higher aromatic polyvalent carboxylic acids such as pyromellitic acid, trimellitic acid, and mellitic acid;
Hydroxybenzene dicarboxylic acids such as 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, and 2-hydroxyisophthalic acid;
2,5-dihydroxyterephthalic acid, 2,6-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid, 3,4-dihydroxyphthalic acid, etc. Dihydroxybenzene dicarboxylic acid;
Bis (4-carboxyphenyl) ether;
Benzophenone-4,4′-dicarboxylic acid;
Bis (4-carboxyphenyl) sulfone;
2,2-bis (4-carboxyphenyl) hexafluoropropane;
4,4'-stilbene dicarboxylic acid;
Pyridine carboxylic acids such as pyridine-2-carboxylic acid, pyridine-3-carboxylic acid, and pyridine-4-carboxylic acid;
Pyridine dicarboxylic acids such as pyridine-2,5-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, and pyridine-2,4-dicarboxylic acid;
4-phenyl-2,5-pyridinedicarboxylic acid;
Pyrimidinecarboxylic acids such as pyrimidine-2-carboxylic acid, pyrimidine-4-carboxylic acid, pyrimidine-5-carboxylic acid, and pyrimidine-6-carboxylic acid;
2,6-pyrimidine dicarboxylic acid, and pyrimidine dicarboxylic acids such as 2,5-pyrimidine dicarboxylic acid.
These low molecular weight aromatic carboxylic acid compounds may be used alone or in combination of two or more.

  A reaction product of an aromatic diol represented by the following formula and a polyvalent aromatic carboxylic acid anhydride can also be suitably used as the low molecular weight aromatic carboxylic acid compound.

（式中、Ｒ^ｅ１は、それぞれ独立に、水素原子、炭素原子数１〜６の炭化水素基、又はハロゲン原子である。ｍは０〜５である。）

(In formula, R ^<e1> is a hydrogen atom, a C1-C6 hydrocarbon group, or a halogen atom each independently. M is 0-5.)

  Suitable examples of the polyvalent aromatic carboxylic acid anhydride include phthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride Etc.

(Polymer aromatic carboxylic acid compound)
The polymer aromatic carboxylic acid compound is not particularly limited as long as it is a polymer compound having a carboxyl group bonded to an aromatic group.
For example, a polymer of a monomer mixture including a monomer having a carboxyl group bonded to an aromatic group and an unsaturated double bond, and does not include an acid group protected by a protecting group. The polymer can be used as a polymer aromatic carboxylic acid compound.
As a preferable copolymer component used together with a monomer having a carboxyl group bonded to an aromatic group and an unsaturated double bond, (meth) acrylic as described above as a monomer for preparing an acrylic resin is used. Examples include acids, unsaturated carboxylic acids other than (meth) acrylic acid, (meth) acrylic esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes.
Moreover, the polyamic acid produced | generated by reaction with aromatic tetracarboxylic dianhydride and diamine can also be used as a polymeric aromatic carboxylic acid compound.

  1-50 mass% is preferable with respect to the mass of the solid content of a 1st composition, and, as for content of (E) component in a 1st composition, 5-40 mass% is more preferable.

<(F) Other ingredients>
The first composition may further contain other components as necessary. For example, dissolution control agent, dissolution inhibitor, basic compound, surfactant, dye, pigment, plasticizer, photosensitizer, light absorber, antihalation agent, storage stabilizer, antifoaming agent, adhesion aid , Phosphors, magnetic materials and the like.

<(S) Solvent>
The first composition may contain a solvent (S) as necessary for the purpose of adjusting coating properties and viscosity. As the component (S), any component can be used as long as it can dissolve each component to be used to form a uniform solution. Any one or more kinds of solvents selected from known solvents used in the photosensitive composition can be used as the (S) solvent.

  Specific examples of (S) solvent include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; ethylene glycol, diethylene glycol, Polyhydric alcohols such as propylene glycol and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene glycol monopropionate, diethylene glycol monopropionate, propylene glycol mono Compounds having an ester bond such as propionate or dipropylene glycol monopropionate; the polyhydric alcohols Monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether, dimethyl ether, diethyl ether, dipropyl ether, or in dibutyl ether [these are propylene glycol monomethyl ether (PGME) are preferable. ] Monoalkyl ethers or monophenyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc. of the compound having an ester bond [in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethoxy Esters such as ethyl propionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl Aromatic organic solvents such as benzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene; N, N, N ′, N′-tetramethylurea, N-methyl-2-pyrrolidone, N, Examples thereof include nitrogen-containing polar solvents such as N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N, N, 2-trimethylpropionamide and the like. These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.

  Moreover, since it is easy to obtain the photosensitive composition excellent in a sensitivity and resolution, it is preferable that (S) solvent contains an aprotic organic solvent. Among the specific examples of the above (S) solvent, lactones; ketones; monoalkyl ethers or monophenyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the compound having an ester bond; Formula ethers; esters having no hydroxyl group; aromatic organic solvents; nitrogen-containing polar solvents can be suitably used as the aprotic organic solvent.

  (S) The content of the aprotic organic solvent in the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.

  (S) Solvents include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, EL, γ-butyrolactone, N, N, N ′, N′-tetramethylurea, N, N— Dimethylacetamide and N, N, 2-trimethylpropionamide are preferred. These organic solvents may be used independently and may be used as 2 or more types of mixed solvents. Moreover, the mixed solvent which mixed PGMEA and polar solvents other than the said PGMEA is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range.

  (S) The usage-amount of a solvent is not specifically limited, In the range which can apply | coat a 1st composition to a board | substrate etc., it sets suitably according to a coating film thickness. Generally, it is used so that the solid content concentration of the photosensitive composition is 1 to 40% by mass, preferably 2 to 39% by mass, and more preferably 3 to 25% by mass.

≪Second composition≫
The second composition contains (A3) a resin component and (B) a radical generator. (A3) The resin component is a resin containing a structural unit having a ring structure in the main chain and having an acid group protected by a protecting group.
Hereinafter, essential or optional components contained in the second composition will be described in order.

<(A3) resin component>
The (A3) resin component is the same as the (A1) resin component described for the first composition except that the resin component has an acid group protected by a protecting group. That is, the resin component (A3) corresponds to a resin having an acid group protected by a protecting group among the resin components (A1) described above.
The content of the resin component (A3) in the second composition is preferably 50 to 90% by mass and more preferably 60 to 80% by mass with respect to the mass of the solid content of the second composition.

<(B) Radical generator>
(B) The example of the radical generator is as described for the first composition. The preferred use amount of the (B) radical generator in the second composition is also the same as in the first composition.

<(C) Compound that generates an imidazole compound by heating>
The second composition may also contain (C) a compound that generates an imidazole compound by heating. (C) About the example of the compound which generates an imidazole compound by heating, it is as having described about the 1st composition. The preferred amount of the compound that generates the imidazole compound by heating in the second composition (C) is also the same as in the first composition.

<(D) Crosslinking group-containing compound>
Similarly to the first composition, the second composition may contain (D) a crosslinking group-containing compound. (D) About the example of a crosslinking group containing compound, it is as having described about the 1st composition. The preferred use amount of the (D) crosslinking group-containing compound in the second composition is the same as in the first composition.

<(E) Aromatic carboxylic acid compound>
The second composition may also contain (E) an aromatic carboxylic acid compound. (E) Examples of the aromatic carboxylsan compound are as described for the first composition. The preferred use amount of the (E) aromatic carboxylic acid compound in the second composition is the same as in the first composition.

<(S) Solvent>
The 2nd composition may also contain the (S) solvent similarly to the 1st composition. (S) The example of the solvent is as described for the first composition. When the second composition contains the (S) solvent, the preferred solid content concentration of the second composition is the same as the preferred solid content concentration when the first composition contains the (S) solvent. is there.

<(F) Other ingredients>
The second composition may contain (F) other components in addition to the above components. Suitable examples of (F) other components are the same as (F) other components that the first composition may contain.

≪Pattern formation method≫
The pattern forming method using the photosensitive composition described above is performed in the same manner as in the case of using a conventional positive photosensitive resin composition.
As a preferable method of forming a pattern,
Applying a photosensitive composition on a support to form a coating film;
A step of selectively exposing the formed coating film;
And a step of developing the exposed coating film with an alkali developer.

  The method for applying the photosensitive composition on the support is not particularly limited, and for example, a spinner is preferably used. The formed coating film is pre-baked as necessary. Prebaking is performed at 80 to 120 ° C. for 40 to 120 seconds, for example.

Subsequently, after exposing a coating film using the exposure apparatus provided with a desired light source, it develops with an alkali developing solution.
The alkaline developer is appropriately selected from those conventionally used in photolithography. As a preferable alkaline developer, for example, a 0.1 to 10% by mass tetramethylammonium hydroxide aqueous solution may be mentioned. Preferably, the water is rinsed with pure water and dried. In some cases, a baking process (post-bake) may be performed after the development process. In this way, a resist pattern faithful to the mask pattern can be obtained.

  The support is not particularly limited as long as it is conventionally used for forming a resist pattern. As a preferable support, for example, a substrate for electronic components, a substrate on which a predetermined wiring pattern is formed, and the like can be exemplified. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As a material for the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.

  The support may be a substrate in which an inorganic and / or organic film is provided on the substrate as described above. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC).

  The wavelength used for exposure is not particularly limited. For example, g, h, i-line, ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, The exposure can be performed using soft X-rays or the like. Among these, g, h, i line, ArF excimer laser, KrF excimer laser, EUV, and EB are preferable. Further, (C) even when using a photosensitive resin composition that does not contain a compound that generates acid or radicals by the action of light, a pattern can be formed satisfactorily, so an ArF excimer laser (wavelength 193 nm), And EB (electron beam).

Furthermore, it is preferable to bake the coating film patterned by development according to the above method. By such baking, the formed pattern becomes tight. In particular, the photosensitive composition contains (C) a compound that generates an imidazole compound by heating, and / or (D) a crosslinking group-containing compound, (A1) a resin component, (A2) a resin component, or (A3). When a resin having a cross-linking group is included as a resin component, a cross-linking group feeling or cross-linking between acidic groups proceeds by baking to obtain a pattern having excellent heat resistance mechanical properties, chemical resistance, and adhesion to a support. Cheap.
The pattern formed by the above method may be heated. In this case, the heating temperature is typically preferably 150 ° C. or higher, and more preferably 150 to 300 ° C.

In addition, when the photosensitive composition contains (C) a compound that generates an imidazole compound by heating, the formed pattern is baked by imidazole in which the component (C) is represented by the above formula (C1) by thermal decomposition. It is preferably carried out at a temperature higher than the temperature at which the compound is generated.
(C) The temperature at which the compound generating the imidazole compound by heating generates the imidazole compound represented by the above formula (C1) by thermal decomposition can be measured by TG-DTA (thermogravimetric-differential thermal analysis). it can. Specifically, (C) In the TG curve obtained by TG-DTA analysis of a compound that generates an imidazole compound by heating, the inflection point on the coldest side on the baseline indicating the onset of weight loss due to thermal decomposition is shown. The temperature may be a temperature at which the imidazole compound represented by the formula (C1) is generated by thermal decomposition.
The upper limit of the baking temperature in this case is not particularly limited as long as the object of the present invention is not impaired. Baking is typically performed at a temperature of 300 ° C. or lower. Typically, the temperature is in the range of 150 to 300 ° C. and is equal to or higher than the temperature at which the imidazole compound represented by the formula (D1) is generated.
The baking time is not particularly limited, but is preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the scope of the present invention is not limited to these Examples.

[Examples 1 to 4, Comparative Example 1 and Comparative Example 2]
In Examples, the resin A1 prepared in Synthesis Example 1 below was used as the resin component (A1).

[Synthesis Example 1]
A separable flask equipped with a cooling tube was used as a reaction vessel. The reaction vessel was charged with propylene glycol monomethyl ether acetate (PGMEA) and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C.
On the other hand, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (MD) 40 parts by mass, methacrylic acid (MAA) 32 parts by mass, methyl methacrylate (MMA) 68 parts by mass, 60 parts by mass of cyclohexyl acid (CHMA), 2.6 parts by mass of t-butylperoxy-2-ethylhexanoate (PBO), and 40 parts by mass of PGMEA were mixed.
Further, 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of PGMEA were mixed in the chain transfer agent tank.
After the temperature of the reaction vessel was stabilized at 90 ° C., dropping from the monomer vessel and the chain transfer agent vessel to the reaction vessel was started to initiate polymerization. While maintaining the temperature at 90 ° C., dropping from the monomer tank and the chain transfer agent tank was performed over 135 minutes. The temperature was raised 60 minutes after the completion of the dropping, and the internal temperature of the reaction vessel was raised to 110 ° C. After maintaining at 110 ° C. for 3 hours, the contents of the reaction vessel were cooled to room temperature to obtain a resin A1 solution.

In Example 1, Example 2, Comparative Example 1, and Comparative Example 2, the following resin A2 was used as the resin component (A2). In Example 3, the following resin A3 was used as the resin component (A2). In addition, the value of the lower right of each structural unit represents content (mass%) of the structural unit in each resin.

In Example 2, the following (D1) was used as the component (D). In addition, the value of the lower right of each structural unit represents content (mass%) of the structural unit in each resin.

In Examples and Comparative Examples, the reaction in which an aromatic diol having the following structure and (2,3,3 ', 4'-biphenyltetracarboxylic dianhydride) are reacted at a molar ratio of 1: 1 as the component (E). Product E1 was used.

In Examples and Comparative Examples, naphthalic acid derivative B1 having the following structure was used as component (B).

  In Example 1 and Comparative Example 1, the imidazole compound (C1) obtained in Synthesis Example 2 below was used as the component (C).

[Synthesis Example 2]
In Synthesis Example 2, an imidazole compound (C1) having the following structure was synthesized.

First, 30 g of cinnamic acid derivative having the structure of the following formula was dissolved in 200 g of methanol, and then 7 g of potassium hydroxide was added to the methanol. The methanol solution was then stirred at 40 ° C. Methanol was distilled off and the residue was suspended in 200 g of water. To the obtained suspension, 200 g of tetrahydrofuran was mixed and stirred, and the aqueous phase was separated. Under ice cooling, 4 g of hydrochloric acid was added and stirred, and then 100 g of ethyl acetate was mixed and stirred. After allowing the mixture to stand, the oil phase was collected. The target product was crystallized from the oil phase, and the precipitate was collected to obtain an imidazole compound (C1) having the above structure.

The measurement result of ¹ H-NMR of the imidazole compound (C1) having the above structure is as follows.
¹ H-NMR (DMSO): 11.724 (s, 1H), 7.838 (s, 1H), 7.340 (d, 2H, J = 4.3 Hz), 7.321 (d, 1H, J = 7.2 Hz), 6.893 (d, 2H, J = 4.3 Hz), 6.876 (d, 1H, J = 6.1 Hz), 5.695 (dd, 1H, J = 4.3 J, 3.2J), 3.720 (s, 3H), 3.250 (m, 2H)

  In Examples and Comparative Examples, a mixed solvent composed of 50% by mass of propylene glycol monomethyl ether and 50% by mass of cyclohexanone was used as the (S) solvent.

(Preparation of photosensitive composition)
The components of the types and amounts listed in Table 1 were uniformly dissolved in the (S) solvent so that the solid content concentration was 20% by mass, and the photosensitive compositions of the examples and comparative examples were obtained.
Using the obtained photosensitive composition, the contrast and heat resistance were evaluated according to the following methods. These evaluation results are shown in Table 1.

<Contrast evaluation>
On the silicon wafer, the photosensitive composition of each Example and the comparative example was apply | coated with the film thickness which can form a pattern with a film thickness of 3 micrometers, and the coating film was formed. The formed coating film was pre-baked at 80 ° C. for 120 seconds. After pre-baking, the coating film was exposed through a 2 μm diameter hole pattern forming mask. The exposed coating film was developed using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass at 23 ° C. for 30 seconds. When the exposed and developed coating film was observed, a hole pattern with a diameter of 2 μm could be formed at an exposure amount of 100 mJ / cm ² , but a hole pattern with a diameter of ² μm could not be formed at an exposure amount of 50 mJ / cm ² The case where the pattern could be formed with an exposure amount of 50 mJ / cm ² was marked with “◎”.

<Heat resistance evaluation>
A post-baking process (curing process) was performed at 230 ° C. for 20 minutes for the developed pattern (however, a 10 μm diameter hole pattern) formed by the same method as the contrast evaluation. From the cured pattern, 5 μg of a sample for heat resistance evaluation was removed. Using a sample for heat resistance evaluation, a differential heat / thermogravimetric measurement device (TG / DTA-6200, manufactured by Seiko Instruments Inc.) is used for measurement under conditions of a heating rate of 10 ° C./min in an air stream. A TG curve was obtained. From the obtained TG curve, the 5% weight reduction temperature of the sample was determined. A 5% weight loss temperature of 270 ° C. or higher was evaluated as ◯, and 230 ° C. or lower was evaluated as x. The evaluation results of heat resistance are shown in Table 1.

  From Table 1, according to the examples, (A1) resin component which is a resin containing a structural unit having a ring structure in the main chain, and (A2) resin component which is a resin having an acid group protected by a protecting group It can be seen that a pattern having good contrast and heat resistance can be formed if the photosensitive composition contains (B) a radical generator.

  According to Comparative Examples 1 and 2, when the photosensitive composition does not contain the resin component (A1) which is a resin containing a structural unit having a ring structure in the main chain, the heat resistance of the pattern formed is remarkable. It can be seen that the contrast is slightly worse compared to the examples.

Claims (9)

(A1) includes a resin component, (A2) a resin component, and (B) a radical generator,
A photosensitive composition comprising (A3) a resin component and (B) a radical generator,
The (A1) resin component is a resin containing a structural unit having a ring structure in the main chain;
The (A2) resin component is a resin having an acid group protected by a protecting group,
The photosensitive composition in which the (A3) resin component is a resin containing a structural unit having a ring structure in the main chain and having an acid group protected by a protecting group. Further, (C) the following formula (C1) by heating:

(In the formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, Represents a sulfonate group, a phosphinyl group, a phosphonate group, or an organic group.)
The photosensitive composition of Claim 1 containing the compound which generate | occur | produces the imidazole compound represented by these. The compound that generates the imidazole compound represented by the formula (C1) by heating (C) is represented by the following formula (C2):

(In formula (C2), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, sulfonato group, a phosphinyl group, .R ^c4 and R ^c5 shows a phosphonato group, or an organic group, each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group , A sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group, wherein R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^c10 are each independently a hydrogen atom. , Halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitro A So group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, R ^c6 , R ^c7 , R ^c8 , R ^c9 , and R ^{In c10} , two or more of them may be bonded to form a cyclic structure, and may include a heteroatom bond.)
The photosensitive resin composition of Claim 2 which is a compound represented by these. The compound that generates the imidazole compound represented by the formula (C1) by heating (C) is represented by the following formula (C4):

(In formula (C4), R ^c1 , R ^c2 and R ^c3 are the same as those in formula (C1), R ^c12 independently represents a hydrogen atom or a monovalent organic group, and R ^c13 represents a substituent. represents an aromatic group which may have, said ^{R c12} may form a cyclic structure in combination with the other ^{R c12} or ^{R c13.)} The (B) radical generator is represented by the following formula (B1):

(In Formula (B1), R ^b1 is a monovalent organic group, R ^b2 , R ^b3 , R ^b4 , and R ^b5 are each independently a hydrogen atom or a monovalent organic group, and R ^b2 And R ^b3 , R ^b3 and R ^b4 , or R ^b4 and R ^b5 may be bonded to each other to form a ring.)
The photosensitive composition of any one of Claims 1-4 containing the compound represented by these. Whether the photosensitive composition further comprises (D) a crosslinking group-containing compound;
Whether at least one of the (A1) resin component and the (A2) resin component further has a crosslinking group,
The photosensitive composition of any one of Claims 1-5 in which the said (A3) resin component has a crosslinking group further. The photosensitive composition further comprises (E) an aromatic carboxylic acid compound having a carboxyl group bonded to an aromatic group,
Whether at least one of the (A1) resin component and the (A2) resin component further has a carboxyl group bonded to an aromatic group;
The photosensitive composition of any one of Claims 1-6 in which the said (A3) resin component has a carboxyl group couple | bonded with an aromatic group further. A step of coating the photosensitive composition according to any one of claims 1 to 7 on a support to form a coating film;
A step of selectively exposing the coating film;
Developing the exposed coating film with an alkaline developer; and
Baking the coating film patterned by development,
A pattern forming method including: The photosensitive composition is heated to the following formula (C1):

(In the formula (C1), R ^c1 , R ^c2 and R ^c3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, Represents a sulfonate group, a phosphinyl group, a phosphonate group, or an organic group.)
Including a compound that generates an imidazole compound represented by:
The coating film is baked at a temperature equal to or higher than the temperature at which the compound generating the imidazole compound represented by the formula (C1) by heating (C) generates the imidazole compound represented by the formula (C1) by thermal decomposition. The pattern formation method of Claim 8 performed.