JP6484055B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition.

In the lithography technology, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light or electron beam through a mask on which a predetermined pattern is formed. After the exposure, the exposed resist film is subjected to a development process to form a resist pattern of a predetermined shape.
A resist material in which the exposed portion changes to a property of being dissolved in the developer is referred to as a positive type, and a resist material in which the exposed portion is changed to a property not to be dissolved in the developer is referred to as a negative type.

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, miniaturization of patterns is rapidly progressing with advances in lithography technology.
Generally as a method of refinement | miniaturization, wavelength-shortening of the exposure light source is performed. Specifically, conventionally, ultraviolet rays represented 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 been started.
In addition, studies are being made on F2 excimer lasers having a shorter wavelength than these excimer lasers, electron beams, EUV (extreme ultraviolet), X-rays, and the like.

The resist material is required to have such lithography characteristics as sensitivity to the exposure light source and resolution capable of reproducing a pattern of fine dimensions.
As a resist material satisfying such requirements, a chemically amplified resist containing a base resin whose alkali solubility changes by the action of an acid and an acid generator which generates an acid upon exposure to light is used. For example, a positive-type 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, and the acid generator generates an acid by exposure when forming a resist pattern. And the exposed part becomes alkali soluble.

  As a specific example of such a positive type chemically amplified resist, for example, one containing a resin having a structural unit derived from a (meth) acrylate having an acid dissociable, dissolution inhibiting group as a base resin is known. See Patent Documents 1 and 2).

Unexamined-Japanese-Patent No. 2003-241385 JP, 2006-096965, A

  However, when a pattern is formed using a positive resist composition as described in Patent Documents 1 and 2, a low exposure dose is obtained in the case of not performing post-exposure heating (PEB) or in the case of a PEB process at a low temperature. In some cases, it may be difficult to form a pattern in the above, or it may be difficult to form a pattern of a desired cross-sectional shape. If PEB is not performed or a good pattern can be formed by low-temperature PEB treatment, shortening of the pattern formation time can improve the throughput of various products or semifinished products provided with a resist pattern.

  Also, when a pattern is formed using a positive resist composition as described in Patent Documents 1 and 2, exposure and development are performed after a while for a while after the resist composition is applied on a support. Then, it may be difficult to form a pattern of desired dimensions.

  The present invention has been made in view of the above problems, and can form a resist pattern having a desired cross-sectional shape with a low exposure amount, and leave the coating film of the photosensitive resin composition for a while. An object of the present invention is to provide a positive photosensitive resin composition capable of forming a pattern of a desired dimension even when exposure and development are performed later.

  The present inventors (A) contain an alkali-soluble resin, an OH group protected by a protective group of a specific structure, and have a hydrophilic group of a predetermined structure in an exposed state (B) non-alkali By using the photosensitive resin composition containing soluble resin, it discovers that said subject can be solved and came to complete this invention. Specifically, the present invention provides the following.

（式（Ｉ）中、Ｒ^１は、水素原子、又は−Ｏ−若しくは−Ｓ−で中断されてもよい炭素原子数１〜２０の炭化水素基であり、Ｒ^２及びＲ^３は、それぞれ独立に、−Ｏ−又は−Ｓ−で中断されてもよい炭素原子数１〜２０の炭化水素基であり、Ｒ^１とＲ^２とは互いに結合して環を形成してもよく、Ｒ^２とＲ^３とは、互いに結合して環を形成してもよい。）
で表される基を有し、
感光性樹脂組成物が露光された場合に、（Ｂ）非アルカリ可溶性樹脂中の式（Ｉ）で表される基の全部又は一部が脱保護されてＯＨ基に変化し、且つ、
露光された前記感光性樹脂組成物中に含まれる、脱保護された前記（Ｂ）非アルカリ可溶性樹脂が、下記式（ＩＩ−１）〜（ＩＩ−３）：
−Ｒ^４−ＯＨ・・・（ＩＩ−１）
−（Ｒ^５−Ｏ）_ｍ−Ｒ^６・・・（ＩＩ−２）
−（Ｒ^７−ＳＯ_２）_ｎ−Ｒ^８・・・（ＩＩ−３）
（式（ＩＩ−１）中、Ｒ^４は、炭素原子数１〜２０のアルキレン基である。式（ＩＩ−２）中、Ｒ^５は炭素原子数２〜４のアルキレン基であり、Ｒ^６は水素原子、炭素原子数１〜５０の炭化水素基又は−Ｒ^９−Ｃ（＝Ｏ）−Ｏ−Ｈ［Ｒ^９は２価の有機基である］であり、ｍは２〜２０の整数である。式（ＩＩ−３）中、Ｒ^７は炭素原子数１〜４のアルキレン基であり、Ｒ^８は炭素原子数１〜５０の炭化水素基であり、ｎは１〜２０の整数である。式（ＩＩ−２）中の複数のＲ^５は、同一であっても異なっていてもよい。式（ＩＩ−３）においてｎが２〜２０の整数である場合、式（ＩＩ−３）中の複数のＲ^７は、同一であっても異なっていてもよい。）
で表される基の少なくとも１種を有する、感光性樹脂組成物である。 An embodiment of the present invention is a photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a non-alkali-soluble resin,
(B) The non-alkali soluble resin has the following formula (I):

(In formula (I), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by —O— or —S—, and R ² and R ³ are each independently And a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -O- or -S-, and R ¹ and R ² may combine with each other to form a ring, and R ² and R ² And R ³ may combine with each other to form a ring).
With a group represented by
When the photosensitive resin composition is exposed, all or a part of the group represented by the formula (I) in the (B) non-alkali soluble resin is deprotected to change to an OH group, and
The deprotected (B) non-alkali soluble resin contained in the exposed photosensitive resin composition has the following formulas (II-1) to (II-3):
-R ⁴ -OH (II-1)
_{^{- (R 5 -O) m -R}} 6 ··· (II-2)
-(R ^7- SO ₂ ) _n- R ⁸ (II-3)
(In the formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms. In the formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, R ⁶ Is a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, or -R ⁹ -C (= O) -O-H (where R ⁹ is a divalent organic group), and m is an integer of 2 to 20 In formula (II-3), R ⁷ is an alkylene group having 1 to 4 carbon atoms, R ⁸ is a hydrocarbon group having 1 to 50 carbon atoms, and n is an integer of 1 to 20. When n is an integer of 2 to 20 in formula (II-3), a plurality of R ^{5 s in} formula (II-2) may be the same or different. A plurality of R ⁷ in) may be the same or different.)
It is a photosensitive resin composition which has at least 1 sort (s) of group represented by these.

  According to the present invention, a resist pattern having a desired cross-sectional shape can be formed with a low exposure amount, and even if exposure and development are performed after the coating film of the photosensitive resin composition is left for a while, it is desirable. It is possible to provide a positive photosensitive resin composition capable of forming a pattern of the above dimensions.

«Photosensitive resin composition»
The photosensitive resin composition according to the present invention comprises (A) an alkali-soluble resin and (B) a non-alkali-soluble resin having a specific functional group. The photosensitive resin composition may contain (C) a compound that generates an acid or a radical by the action of light, and / or (D) a compound that generates an imidazole compound by heating. Furthermore, the photosensitive resin composition may contain (S) a solvent. Hereinafter, essential or optional components contained in the photosensitive resin composition will be described in order.

<(A) Alkali-soluble resin>
The photosensitive resin composition contains (A) an alkali-soluble resin. Here, with an alkali-soluble resin, a resin film with a film thickness of 1 μm is formed on a substrate by a resin solution (solvent: propylene glycol monomethyl ether acetate) with a resin concentration of 20 mass%, and a 2.38 mass% TMAH aqueous solution is obtained. When it is immersed for 1 minute, it means something that dissolves by 0.01 μm or more.

  (A) The alkali-soluble resin is at least one resin selected from the group consisting of (A1) novolak resin, (A2) polyhydroxystyrene resin, (A3) acrylic resin, and (A4) cardo resin preferable.

Moreover, it is preferable that (A) alkali-soluble resin has an unsaturated double bond and / or an epoxy group. (A) The alkali-soluble resin usually has an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. For example, by reacting with a compound containing an unsaturated double bond or an epoxy group, such as a phenolic hydroxyl group and allyl bromide, (meth) acrylic acid halide, epichlorohydrin, etc., to etherify or acylate the phenolic hydroxyl group As a result, an unsaturated double bond or an epoxy group can be introduced into the alkali-soluble resin having a phenolic hydroxyl group. When the alkali-soluble resin is a resin having a carboxyl group, the carboxyl group is reacted with a compound having an unsaturated double bond such as (meth) acrylic acid ester containing an epoxy group and an epoxy group. Thus, unsaturated double bonds can be introduced into the resin having a carboxyl group.
(A) Alkali-soluble resin may have an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, which may be protected by a protecting group which is partially or entirely removed by exposure. In this case, as the protective group, a group represented by the formula (I) described later which is a water-repellent protective group which the (B) non-alkali soluble resin essentially has is preferable.
(A) As a unit having a protected alkali-soluble group which may be contained in an alkali-soluble resin, for example, a (meth) acrylic acid in which a carboxyl group is protected by a group represented by formula (I) And a unit derived from hydroxystyrene in which the phenolic hydroxyl group is protected by the group represented by the formula (I).
(A) When a part or all of the alkali-soluble group possessed by the alkali-soluble resin is protected by a protecting group, the photosensitive resin composition is to be described later in (C) to promote deprotection upon exposure. It is preferable to include a compound that generates an acid or a radical depending on the action.

[(A1) novolak resin]
The novolak resin (A1) 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 above-mentioned 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- Trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phlorogricinol, 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, as an acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used.

  The flexibility of the novolak resin can be further improved by using o-cresol, substituting the hydrogen atom of the hydroxyl group in the resin with another substituent, or using bulky aldehydes. It is.

  Although the mass mean molecular weight of (A1) novolak resin is not specifically limited in the range which does not inhibit the object of the present invention, it is preferred that it is 1000-50000.

[(A2) polyhydroxystyrene resin]
Examples of the hydroxystyrene-based compound constituting the (A2) polyhydroxystyrene resin include p-hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and the like.
Furthermore, it is preferable to make the (A2) polyhydroxystyrene resin into a copolymer of a hydroxystyrene compound and a styrene compound. As a styrene compound which comprises such a styrene resin, styrene, chlorostyrene, chloromethylstyrene, vinyl toluene, alpha-methylstyrene etc. are mentioned.

  Although the mass mean molecular weight of (A2) polyhydroxy styrene resin is not specifically limited in the range which does not inhibit the object of the present invention, it is preferred that it is 1000-50000.

[(A3) acrylic resin]
As the acrylic resin (A3), 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 esters, (meth) acrylamides, allyl compounds, vinyl ethers, Examples thereof include vinyl esters, styrenes, and epoxy group-containing unsaturated compounds having no alicyclic group.

  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, itaconic acid; anhydrides of these dicarboxylic acids A thing;

  Examples of (meth) acrylic acid esters are linear or branched such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate and the like Linear 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, phenyl (meth) acrylate;

  Moreover, as (A) alkali-soluble resin, what has an epoxy group is also preferable. For this reason, as a (meth) acrylic acid ester, an epoxy group containing (meth) acrylic acid ester is also preferable. Preferred examples of the epoxy group-containing (meth) acrylic acid ester include alicyclic epoxy group-containing unsaturated compounds having a structure represented by the following formulas (a3-1) to (a3-16). Among these, the compounds represented by the following formulas (a3-1) to (a3-6) are preferable, and the compounds represented by the following formulas (a3-1) to (a3-4) are more preferable.

In the above formulae, ^Ra4 represents a hydrogen atom or a methyl group, ^Ra5 represents a divalent aliphatic saturated hydrocarbon group having 1 to ⁶ carbon atoms, and ^Ra6 represents a divalent hydrocarbon having 1 to 10 carbon atoms Represents a group, and n represents an integer of 0 to 10. As R ^a5 , 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 is preferable. As R ^a6 , 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, a cyclohexylene group, -CH ₂ -Ph-CH _2- (Ph is Phenylene group is preferred).

  Further, an epoxy group-containing unsaturated compound having no alicyclic group is also suitably used as a monomer for introducing the epoxy group into the (A3) acrylic resin. Examples of epoxy group-containing unsaturated compounds having no alicyclic group include glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl ( (Meth) acrylic acid epoxy alkyl esters such as meta) acrylate; α-ethyl glycidyl glycidyl, α-n-propyl acrylic acid glycidyl, α-n-butyl acrylic acid glycidyl, α-ethyl acrylic acid 6,7-epoxy Α-alkyl acrylic acid epoxy alkyl esters such as heptyl; and the like. Among these, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, and 6,7-epoxyheptyl (meth) acrylate are preferable.

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

  As allyl compounds, allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; etc. It 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-ethyl butyl vinyl ether, hydroxyethyl vinyl ether Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butyl aminoethyl 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.

  As vinyl esters, vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl Examples include acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

  As styrenes, styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy Alkylstyrenes such as methylstyrene and acetoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene; 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.

  The proportion of units containing a carboxyl group in the acrylic resin (A3) is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and still more preferably 10 to 40% by mass.

[(A4) cardo resin]
(A4) Cardo resin is a resin having a cardo structure. The (A4) cardo resin as the (A) alkali-soluble resin is not particularly limited, and can be appropriately selected from those conventionally blended in photosensitive compositions. Among them, a resin represented by the following formula (a-1) which is a resin having a (meth) acryloyl group is preferable.

In the above formula (a-1), X ^a represents a group represented by the following formula (a-2) or (a-2 ′).

In the above formulas (a-2) and (a-2 ′), R ^a1 independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, and R ^a2 is independently Is ^a hydrogen atom or a methyl group, and Wa is a group represented by the following formula (a-3).

Further, in the above formula ^{(a-1), Y} a represents the residue obtained by removing dicarboxylic acid anhydride from the acid anhydride group (-CO-O-CO-). Examples of dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Phthalic anhydride, glutaric anhydride and the like can be mentioned.

Further, in the above formula ^(a-1), Z a represents a residue obtained by removing two acid anhydride groups from a tetracarboxylic acid dianhydride. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and the like.
Moreover, x shows the integer of 0-20 in said Formula (a-1).

1000-50000 are preferable and, as for the mass mean molecular weight (Mw: the measured value by polystyrene conversion of gel permeation chromatography (GPC) of the alkali-soluble resin demonstrated above), 3000-10000 are more preferable.
In addition, about a mass mean molecular weight of (A4) cardo resin, 1000-40000 are preferable and 2000-30000 are more preferable.

  The content of the (A) alkali-soluble resin in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. (A) relative to the total of (A) the mass of the alkali-soluble resin, (B) the mass of the non-alkali-soluble resin, and the mass of (B ') other non-alkali-soluble resins described later in the photosensitive resin composition 30 mass% or more is preferable, as for the ratio of the mass of alkali-soluble resin, 50 mass% or more is more preferable, and 50-70 mass% is especially preferable.

<(B) Non-alkali soluble resin>
The photosensitive resin composition contains (B) a non-alkali soluble resin. (B) The non-alkali soluble resin contains an OH group protected by a water-repellent protecting group which is deprotected by exposure of a specific structure. For this reason, the photosensitive resin composition containing (B) a non-alkali soluble resin is very difficult to conform to the alkaline developer in the non-exposed state, and although it contains (A) an alkali soluble resin, it is It hardly dissolves in the solution.

  With regard to an OH group protected by a water-repellent protecting group which is deprotected by exposure to light, the OH group may be a hydroxyl group or an OH group contained in a carboxyl group.

  (B) In the non-alkali soluble resin, part or all of the water repellent protective group described above is deprotected in the exposed state. For this reason, when the photosensitive resin composition is exposed, it becomes easy to conform to the alkaline developer.

  Moreover, (B) non-alkali soluble resin has a hydrophilic functional group of a specific structure in a deprotected state. The hydrophilic functional group contributes to the improvement of the contrast and promotes the dissolution of (A) the alkali-soluble resin in an alkali developer. For this reason, when the photosensitive resin composition containing (B) non-alkali soluble resin is exposed, the alkali developer is well compatible with the photosensitive resin composition, and (A) the alkali soluble resin is an alkaline developer. Since it is dissolved well, the exposed portion in the photosensitive resin composition is well removed by the alkaline developer.

（式（Ｉ）中、Ｒ^１は、水素原子、又は−Ｏ−若しくは−Ｓ−で中断されてもよい炭素原子数１〜２０の炭化水素基であり、Ｒ^２及びＲ^３は、それぞれ独立に、−Ｏ−又は−Ｓ−で中断されてもよい炭素原子数１〜２０の炭化水素基であり、Ｒ^１とＲ^２とは互いに結合して環を形成してもよく、Ｒ^２とＲ^３とは、互いに結合して環を形成してもよい。） The above-mentioned OH group protected by a water-repellent protecting group which is deprotected by exposure is specifically a group represented by the following formula (I).

(In formula (I), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by —O— or —S—, and R ² and R ³ are each independently And a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -O- or -S-, and R ¹ and R ² may combine with each other to form a ring, and R ² and R ² And R ³ may combine with each other to form a ring).

In formula (I), R ¹ , R ² and R ³ 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 or an aromatic hydrocarbon group, or may be a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

When R ¹ , R ² , and R ³ are aliphatic hydrocarbon groups, the aliphatic hydrocarbon group may have a chain structure or a cyclic structure, whether it is a chain or cyclic group. It may be The aliphatic hydrocarbon group may have an unsaturated bond. As an aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable.

When R ¹ , R ² and R ³ are a chain aliphatic hydrocarbon group, 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 and n-icosyl are included.

When R ¹ , R ² and R ³ are a cyclic aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group is a cycloalkyl group, specific examples thereof include a cyclopropyl group, a cyclobutyl group, A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, and a cyclododecyl group can be mentioned.

As specific examples where R ¹ , R ² and R ³ are cyclic aliphatic hydrocarbon groups, and the cyclic aliphatic hydrocarbon group is a polycyclic group, the following polycyclic aliphatic A group in which one hydrogen atom has been removed from a hydrocarbon can be mentioned.

When R ¹ , R ² and R ³ are aromatic hydrocarbon groups, specific examples thereof include phenyl group, naphthyl group, anthryl group, biphenylyl group, phenanthrenyl group and fluorenyl group.

When R ¹ , R ² and R ³ are a combination of 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 group And ethyl) and 2- (β-naphthyl) ethyl.

When R ¹ , R ² and R ³ are a hydrocarbon group containing an aromatic ring, the aromatic ring is a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms It may be substituted by one or more substituents selected from the group consisting of an alkanoyl group having 2 to 10 carbon atoms and an alkanoyl group 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 (I), a hydrogen atom is preferable as R ¹ . As R ² , a methyl group is preferable. As R ³ , an ethyl group, an isobutyl group, a cyclohexyl group, a 2-ethyl-n-hexyl group or an octadecyl group is preferable.

When R ² and R ³ bond to each other to form a ring, the ring is a heterocycle containing an oxygen atom bonded to R ³ . The number of carbon atoms in the heterocycle containing an oxygen atom is preferably 3 to 7, and more preferably 4 to 6. The heterocycle may further contain a hetero atom other than the oxygen atom bonded to R ³ . As a hetero atom in that case, an oxygen atom, a sulfur atom, a nitrogen atom etc. are mentioned.

When R ¹ and R ² bond together to form a ring, the ring is preferably a 3- to 12-membered saturated aliphatic hydrocarbon ring. When the ring formed by combining R ¹ and R ² is a six-membered saturated aliphatic hydrocarbon ring, the group represented by the formula (I) is a group represented by the following formula. In the following formulae, R ³ has the same meaning as in formula (I).

Below, the suitable example of group represented by Formula (I) is shown.

As the group represented by the formula (I), a group in which R ² and R ³ are bonded to each other to form a ring containing an oxygen atom is preferable. Therefore, as the group represented by formula (I), the following groups are preferable among the above-mentioned groups.

Among the groups containing a ring containing these oxygen atoms, the following groups are more preferable.

When the photosensitive resin composition is exposed, the (B) non-alkali soluble resin has the following formulas (II-1) to (II-3):
-R ⁴ -OH (II-1)
_{^{- (R 5 -O) m -R}} 6 ··· (II-2)
-(R ^7- SO ₂ ) _n- R ⁸ (II-3)
(In the formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms. In the formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, R ⁶ Is a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, or -R ⁹ -C (= O) -O-H (wherein R ⁹ is a divalent organic group), and m is 2 to 20 In the formula (II-3), R ⁷ is an alkylene group having 1 to 4 carbon atoms, R ⁸ is a hydrocarbon group having 1 to 50 carbon atoms, and n is an integer of 1 to 20 A plurality of R ^{5 s} in the formula (II-2) may be the same or different.When n is an integer of 2 to 20 in the formula (II-3), a plurality of R ^{5 s} Several R ⁷ in 3) may be the same or different.)
And at least one of the groups represented by

  The groups represented by the above formulas (II-1) to (II-3) are hydrophilic functional groups and contribute to the improvement of the contrast during development, and the exposed photosensitive resin composition is alkaline When in contact with the developer, the dissolution of the (A) alkali-soluble resin in the alkali developer is promoted.

  When the end of the group represented by the above formula (II-1) or (II-2) is an OH group, the (B) non-alkali soluble resin before exposure is a formula wherein the end is an OH group It may have a group represented by II-1) or Formula (II-2).

  In addition, it contains a group represented by the formula (II-1) or the formula (II-2) in which the terminal is an OH group in a state protected by a protective group which can be deprotected at the terminal OH group ( B) Non-alkali soluble resin may be used. In this case, when the (B) non-alkali soluble resin is exposed, a group represented by the formula (II-1) or the formula (II-2) in which the end is an OH group is generated.

In formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms. The alkylene group may be linear or branched. As the said alkylene group, a linear alkylene group is preferable. Specific examples of the linear alkylene group having 1 to 20 carbon atoms include methylene, ethane-1,2-diyl, n-propane-1,3-diyl 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 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-1,1 - diyl group, and a n- icosanoic -1,20- diyl group.

  Preferred examples of the group represented by the formula (II-1) include 2-hydroxyethyl group, 3-hydroxy-n-propyl group, 4-hydroxy-n-butyl group, 5-hydroxy-n-pentyl group 6-hydroxy-n-hexyl group, 7-hydroxy-n-heptyl group, 8-hydroxy-n-octyl group, 9-hydroxy-n-nonyl group, and 10-hydroxy-n-decyl group. Among these, 2-hydroxyethyl, 3-hydroxy-n-propyl, 4-hydroxy-n-butyl, 5-hydroxy-n-pentyl and 6-hydroxy-n-hexyl are more preferable. .

In formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, R ⁶ is a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, or —R ⁹ —C (= O) -O-H (wherein R ⁹ is a divalent organic group).

As R ⁵ , ethane-1,2-diyl group, n-propane-1,2-diyl group, n-propane-1,3-diyl group, and n-butane-1,4-diyl group are preferable, The ethane-1,2-diyl group and the n-propane-1,2-diyl group are more preferred.

When R ⁶ in the formula (II-2) is a hydrocarbon group, the number of carbon atoms in the hydrocarbon group is 1 to 50, preferably 1 to 12, and more preferably 1 to 8. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or may be a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. .

When R ⁶ is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may be linear, cyclic or may contain a linear structure and a cyclic structure. The aliphatic hydrocarbon group may have an unsaturated bond. As an aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable. Preferred examples of the hydrocarbon group of R ⁶ are the same as the preferred examples of the hydrocarbon group of R ¹ , R ² and R ³ .

R ⁹ in the formula (II-2) is a divalent organic group. The organic group may contain a hetero atom such as N, S, O or a halogen atom. The organic group may be linear, cyclic, or may include a linear structure and a cyclic structure. 1-50 are preferable and, as for the carbon atom number of the said organic group, 1-12 are more preferable. As the organic group, a hydrocarbon group containing no hetero atom is preferable, and an aliphatic hydrocarbon group is preferable. When R ⁹ is a divalent aliphatic hydrocarbon group, the aliphatic hydrocarbon group is preferably an alkylene group, and more preferably a linear alkylene group. Preferred examples in the case where R ⁹ is a linear alkylene group are the same as the aforementioned R ⁴ . When R ⁹ is a linear alkylene group, a linear alkylene group having 1 to 6 carbon atoms is particularly preferable.

In formula (II-3), R ⁷ is an alkylene group having 1 to 4 carbon atoms, and R ⁸ is a hydrocarbon group having 1 to 50 carbon atoms. Preferred examples of R ⁷ are the same as R ⁵ in formula (II-2). Preferred examples of R ⁸ are the same as R ⁶ in formula (II-2).

  (B) The non-alkali soluble resin has a group represented by the formula (I) and has at least one of the groups represented by the formulas (II-1) to (II-3) in an exposed state As long as it is a thing, the main frame is not specifically limited. For example, the main skeleton may be linear, star-shaped, or dendritic (brush-like).

  As a preferable main skeleton, a main skeleton consisting of carbon-carbon bonds contained in a polymer of a monomer having an unsaturated bond, and a skeleton of an acetylene diol derivative can be mentioned.

  Among these, a main skeleton composed of carbon-carbon bonds contained in a polymer of monomers having unsaturated bonds is preferable. As a polymer of a monomer having an unsaturated bond having such a main skeleton, a copolymer of a monomer having an unsaturated bond containing a (meth) acrylic acid ester, a monomer such as (poly) cycloolefin, etc. The polymer of a saturated alicyclic compound, the polymer of a maleimide derivative, and the copolymer of the said unsaturated alicyclic compound and the said maleimide derivative are mentioned. When it becomes a copolymer, it may be copolymerized with maleic anhydride.

（式（ＩＩＩ−１）中、Ｘ^１は、不飽和二重結合を有する単量体に由来する３価の有機基であり、Ｒ^１０は、前述の式（ＩＩ−１）〜（ＩＩ−３）、及び下記式（ＩＩ−４）〜下記式（ＩＩ−７）：
−Ｒ^４−ＯＲ^１１・・・（ＩＩ−４）
−（Ｒ^５−Ｏ）_ｍ−Ｒ^１２・・・（ＩＩ−５）
−Ｒ^４−Ｏ−Ｒ^１３−Ｃ（＝Ｏ）−Ｏ−Ｒ^１１・・・（ＩＩ−６）
−（Ｒ^５−Ｏ）_ｍ−Ｒ^１４−Ｃ（＝Ｏ）−Ｏ−Ｒ^１２・・・（ＩＩ−７）
で表される基から選択される基であり、
式（ＩＩ−４）及び式（ＩＩ−６）中、Ｒ^４は炭素原子数１〜２０のアルキレン基であり、Ｒ^１１は感光性樹脂組成物が露光された場合に、脱保護され得る保護基であり、Ｒ^１３は２価の有機基であり、
式（ＩＩ−５）及び式（ＩＩ−７）中、Ｒ^５は炭素原子数２〜４のアルキレン基であり、複数のＲ^５は、同一であっても異なっていてもよく、ｍは２〜２０の整数であり、Ｒ^１２は感光性樹脂組成物が露光された場合に、脱保護され得る保護基であり、Ｒ^１４は２価の有機基である。）
で表される構成単位と、下記式（ＩＩＩ−２）：

（式（ＩＩＩ）−２中、Ｘ^２は、不飽和二重結合を有する単量体に由来する３価の有機基であり、Ｒ^１５は、式（Ｉ）で表される基及び下記式（ＩＶ−１）〜下記式（ＩＶ−４）：
−Ｒ^４−ＯＲ^１６・・・（ＩＶ−１）
−（Ｒ^５−Ｏ）_ｍ−Ｒ^１６・・・（ＩＶ−２）
−Ｒ^４−Ｏ−Ｒ^１３−Ｃ（＝Ｏ）−Ｏ−Ｒ^１６・・・（ＩＶ−３）
−（Ｒ^５−Ｏ）_ｍ−Ｒ^１４−Ｃ（＝Ｏ）−Ｏ−Ｒ^１６・・・（ＩＶ−４）
で表される基から選択される基であり、
式（ＩＶ−１）〜式（ＩＶ−４）中、Ｒ^４、Ｒ^５、Ｒ^１３、Ｒ^１４は前述の通りであり、末端部分構造の−ＯＲ^１６は式（Ｉ）で表される基である。）
で表される構成単位と、を含む（Ｂ−１）コポリマーが好ましい。 As the non-alkali soluble resin (B) which is a polymer of monomers having such unsaturated bonds, monomers having unsaturated double bonds are polymerized by reaction between unsaturated double bonds. A linear polymer that can be produced or a linear polymer obtained by chemically modifying the linear polymer,
The following formula (III-1):

(In the formula (III-1), X ¹ is a trivalent organic group derived from a monomer having an unsaturated double bond, and R ¹⁰ is a group represented by any of the above-mentioned formulas (II-1) to (II-) 3) and the following formula (II-4) to the following formula (II-7):
-R ⁴ -OR ¹¹ (II-4)
-(R ^5- O) _m- R ¹² (II-5)
-R ⁴ -O-R ¹³ -C (= O) -O-R ¹¹ (II-6)
_{^{- (R 5 -O) m -R}} 14 -C (= O) -O-R 12 ··· (II-7)
A group selected from the groups represented by
In formulas (II-4) and (II-6), R ⁴ is an alkylene group having 1 to 20 carbon atoms, and R ¹¹ is a protection which can be deprotected when the photosensitive resin composition is exposed. R ¹³ is a divalent organic group,
In formula (II-5) and formula (II-7), R ⁵ is an alkylene group having 2 to 4 carbon atoms, and plural R ^{5 s} may be the same or different, and m is 2 an integer from to 20, R ¹² in the case where the photosensitive resin composition has been exposed, a protecting group which can be deprotected, R ¹⁴ is a divalent organic group. )
And a structural unit represented by the following formula (III-2):

(In Formula (III) -2, X ² is a trivalent organic group derived from a monomer having an unsaturated double bond, R ¹⁵ is a group represented by Formula (I), and the following formula (IV-1) to the following formula (IV-4):
-R ⁴ -OR ¹⁶ (IV-1)
-(R ^5- O) _m- R ¹⁶ (IV-2)
-R ⁴ -O-R ¹³ -C (= O) -O-R ¹⁶ (IV-3)
_{^{- (R 5 -O) m -R}} 14 -C (= O) -O-R 16 ··· (IV-4)
A group selected from the groups represented by
In formulas (IV-1) to (IV-4), R ⁴ , R ⁵ , R ¹³ and R ¹⁴ are as described above, and -OR ^{16 of the} terminal partial structure is a group represented by formula (I) It is. )
And the structural unit represented by (B-1) copolymer is preferable.

  1-70 mass% is preferable, and, as for the quantity of the unit which consists of said Formula (III-1) in this (B-1) copolymer, 5-40 mass% is more preferable. 10-90 mass% is preferable, and, as for the single quantity which consists of said Formula (III-2) in this polymer, 30-70 mass% is more preferable. The (B-1) copolymer preferably comprises a unit represented by the above formula (III-1) and a unit represented by the above formula (III-2). Hereinafter, the unit represented by Formula (III-1) and the unit represented by Formula (III-2) are demonstrated.

(Unit represented by formula (III-1))
The unit represented by the formula (III-1) is a unit which gives the hydrophilic group represented by the above-mentioned formulas (II-1) to (II-3) to the exposed (B-1) copolymer. It is.

The unit represented by the formula (III-1) is a trivalent organic group derived from an unsaturated double bond as the functional group R ¹⁰ bonded to X ¹ , the above-mentioned formulas (II-1) to (II) -3), and the following formula (II-4) to the following formula (II-7):
-R ⁴ -OR ¹¹ (II-4)
-(R ^5- O) _m- R ¹² (II-5)
-R ⁴ -O-R ¹³ -C (= O) -O-R ¹¹ (II-6)
_{^{- (R 5 -O) m -R}} 14 -C (= O) -O-R 12 ··· (II-7)
And a group selected from the group consisting of

In formulas (II-4) to (II-7), R ⁴ , R ⁵ and m are as defined above. R ¹³ and R ¹⁴ are the same as R ⁹ described above. R ¹¹ is a protective group which can be deprotected when the photosensitive resin composition is exposed.

Such a protective group is a group conventionally employed as a protective group for a group containing an active hydrogen such as a hydroxyl group possessed by a resin component contained in a photosensitive resin composition, and is represented by the above-mentioned formula (I) It can select suitably from groups other than the group represented by a following formula contained in group. As such a group, a group represented by the following formula (b1), which is a protecting group to be deprotected by the action of an acid, can be mentioned.

（式（ｂ１）中、Ｒ^ｂ１は、炭素数１〜６の直鎖状、分岐状、又は環状のアルキル基を表し、ｏは０又は１を表す。）

(In formula (b1), R ^b1 represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and o represents 0 or 1).

Preferred examples of R ^b1 being a linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and pentyl. Groups, isopentyl groups, neopentyl groups and the like. Moreover, a cyclopentyl group, a cyclohexyl group etc. are mentioned as a suitable example in case R ^b1 is a cyclic ^| annular alkyl group. Specific examples of the acid dissociable, dissolution inhibiting group represented by the formula (b1) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group and the like.

Examples of the trivalent organic group derived from a monomer having an unsaturated double bond of X ¹ include, for example, the following (x-1) to (x-22). R ^b2 represents a hydrogen atom or a methyl group. * Is a bond. In addition, the code | symbol of "*" is abbreviate | omitted in two bonds which couple | bond with the principal chain of a (B-1) copolymer among the bonds which a trivalent organic group has.

  As a unit represented by Formula (III-1), the unit derived from (meth) acrylic acid ester or a styrene derivative is preferable.

（式（ｂ２）〜（ｂ８）中、Ｒ^ｂ２は水素原子又はメチル基を表す。Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、ｍ、及びｎは前述と同様である。） With regard to the unit represented by the formula (III-1), examples of the unit derived from the (meth) acrylic acid ester include units represented by the following formulas (b2) to (b8).

(In the formulas (b2) to (b8), R ^b2 represents a hydrogen atom or a methyl group. R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , m, and n are as defined above) It is similar.)

  Among the units represented by the formulas (b2) to (b8), the unit represented by the formula (b2) or the formula (b3) is preferable, and the unit represented by the formula (b2) is particularly preferable.

（式（ｂ９）〜（ｂ１５）中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、ｍ、及びｎは前述と同様であり、ｐは０又は１である。） As for the unit represented by the formula (III-1), examples of units derived from a styrene derivative include units represented by the following formulas (b9) to (b15).

(In the formulas (b9) to (b15), R ⁴ , R ⁵ , R ⁶ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , m and n are as defined above, and p is 0 or 1) .)

  In formulas (b9) to (b15), p is 0 or 1, preferably 1. Among the units represented by the formulas (b9) to (b15), the unit represented by the formula (b9) or the formula (b10) is preferable, and the unit represented by the formula (b9) is more preferable. In the units represented by the formulas (b9) to (b15), the substituent on the benzene ring is bonded in the para position relative to the position at which the benzene ring is bonded to the main chain of the (B-1) copolymer preferable.

(Unit represented by formula (III-2))
The unit represented by the formula (III-2) essentially contains the group represented by the formula (I) which is the above-mentioned water-repellent protecting group. For this reason, when (B-1) copolymer containing the unit represented by Formula (III-2) is mix | blended with the photosensitive resin composition, the photosensitive resin composition which is not exposed does not adapt to an alkaline developing solution. On the other hand, the exposed photosensitive resin composition is well adapted to the alkaline developer.

The unit represented by Formula (III-2) is a group represented by the above-mentioned Formula (I) as a functional group R ¹⁵ bonded to X ² which is a trivalent organic group derived from an unsaturated double bond And the following formula (IV-1) to the following formula (IV-4):
-R ⁴ -OR ¹⁶ (IV-1)
-(R ^5- O) _m- R ¹⁶ (IV-2)
-R ⁴ -O-R ¹³ -C (= O) -O-R ¹⁶ (IV-3)
_{^{- (R 5 -O) m -R}} 14 -C (= O) -O-R 16 ··· (IV-4)
And a group selected from the groups represented by

In formulas (IV-1) to (IV-4), R ⁴ , R ⁵ , R ¹³ and R ¹⁴ are as defined above, and -OR ^{16 of the} terminal partial structure is a group represented by formula (I) is there.

Examples of the trivalent organic group derived from a monomer having an unsaturated double bond of X ² include, for example, the above formulas (x-1) to (x-22).

  As a unit represented by Formula (III-2), the unit derived from (meth) acrylic acid ester or a styrene derivative is preferable.

（式（ｂ１６）〜（ｂ２０）中、Ｒ^ｂ２、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^１３、Ｒ^１４、及びｍは前述と同様である。） As for the unit represented by the formula (III-2), examples of the unit derived from the (meth) acrylic acid ester include units represented by the following formulas (b16) to (b8).

(In the formulas (b16) to (b20), R ^b2 , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and m are as defined above).

  Among the units represented by the formulas (b16) to (b20), the unit represented by the formula (b16) or the formula (b17) is preferable, and the unit represented by the formula (b16) is particularly preferable.

（式（ｂ２１）〜（ｂ２５）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^１３、Ｒ^１４、及びｍは前述と同様である。） With regard to the unit represented by the formula (III-2), examples of units derived from a styrene derivative include units represented by the following formulas (b21) to (b25).

(In the formulas (b21) to (b25), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and m are as defined above.)

  Among the units represented by the formulas (b21) to (b25), the unit represented by the formula (b21) or the formula (b22) is preferable, and the unit represented by the formula (b21) is more preferable. In the units represented by the formulas (b21) to (b25), the substituent on the benzene ring is bonded in the para position relative to the position at which the benzene ring is bonded to the main chain of the (B-1) copolymer preferable.

  When the (B-1) copolymer contains a unit other than the unit represented by Formula (III-1) and the unit represented by Formula (III-2), the unit has an unsaturated double bond The unit is not particularly limited as long as it is a unit derived from a monomer and does not inhibit the object of the present invention. The units other than the unit represented by the formula (III-1) and the unit represented by the formula (III-2) are constituent units of various resins conventionally blended in the photosensitive resin composition. It may be suitably selected from a large number of units adopted as.

  Moreover, the (B-2) homopolymer demonstrated below can also be used conveniently as (B) non-alkali soluble resin. Preferred examples of the (B-2) homopolymer include a homo only composed of any one of the units represented by the following formulas (b17) to (b20) and (b22) to (b25). Polymer is mentioned.

（式（ｂ１７）〜（ｂ２０）中、Ｒ^ｂ２、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^１３、Ｒ^１４、及びｍは前述と同様である。）

(In the formulas (b17) to (b20), R ^b2 , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and m are as defined above).

（式（ｂ２２）〜（ｂ２５）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^１３、Ｒ^１４、及びｍは前述と同様である。）

(In the formulas (b22) to (b25), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ¹³ , R ¹⁴ and m are as defined above.)

  As the homopolymer (B-2), a homopolymer consisting of only the units represented by the above formulas (b17), (b18), (b22) or (b23) is more preferable.

As the homopolymer (B-2), those containing one or more kinds of groups represented by the following formula as a unit represented by the above-mentioned formula (I) are preferable.

  The content of the (B) non-alkali soluble resin in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. (B) relative to the total of the mass of (A) alkali-soluble resin, the mass of (B) non-alkali-soluble resin, and the mass of (B ') other non-alkali-soluble resins described later in the photosensitive resin composition 70 mass% or less is preferable, as for the ratio of the mass of non-alkali soluble resin, 50 mass% or less is more preferable, and 1 to 50 mass% is especially preferable.

<(B ') Other non-alkali soluble resin>
The photosensitive resin composition may contain (B ′) another non-alkali soluble resin which is a non-alkali soluble resin other than the (B) non-alkali soluble resin, within the range not impairing the object of the present invention.

  The other non-alkali soluble resin (B ') is not particularly limited as long as it is a resin other than the (A) alkali soluble resin which does not correspond to the (B) non alkali soluble resin. (B ') As other non-alkali soluble resins, structural units derived from the various (meth) acrylic acid derivatives and hydroxystyrene derivatives described above, (meth) acrylic acid, and unsaturated groups other than (meth) acrylic acid Selected from the group consisting of carboxylic acids, (meth) acrylic esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and epoxy group-containing unsaturated compounds having no alicyclic group What is comprised from the structural unit derived from the monomer to be

  Moreover, it is preferable that (B ') other non-alkali soluble resin contains the structural unit which has an epoxy group. As a monomer which gives the structural unit which has an epoxy group, the alicyclic epoxy group containing unsaturated compound and glycidyl (meth) acrylate of the structure represented by above-mentioned Formula (a3-1)-(a 3-16) preferable.

  Furthermore, since it is easy to obtain a photosensitive resin composition having good developability, it is preferable that the (B ') and other non-alkali soluble resins have increased solubility in an alkaline developer upon exposure. That is, it is preferable that the (B ') other non-alkali soluble resin has an alkali soluble group such as a carboxyl group or a phenolic hydroxyl group protected by a protective group which can be deprotected by exposure. Deprotection may occur by the action of a compound that generates an acid or a radical by the action of (C) light described later.

  The content of (B ') other non-alkali soluble trees in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. (B) relative to the total of the mass of (A) alkali-soluble resin, the mass of (B) non-alkali-soluble resin, and the mass of (B ') other non-alkali-soluble resins described later in the photosensitive resin composition 70% by mass or less is preferable, 50% by mass or less is more preferable, 1 to 50% by mass is more preferable, and 10 to 50% by mass is particularly preferable. Mass% is most preferred.

<(C) Compound that generates acid or radical by the action of light>
The photosensitive resin composition preferably contains a compound that generates an acid or a radical by the action of (C) light. When the photosensitive resin composition does not contain a compound that generates an acid or a radical by the action of (C) light, (A) the alkali-soluble resin and (B) the protective group possessed by the non-alkali-soluble resin are well removed. In order to protect, the kind of light source used at the time of exposure is limited. However, when the photosensitive resin composition contains a compound that generates an acid or a radical by the action of (C) light, (A) an alkali-soluble resin or (B) regardless of the type of light source used for exposure. The protective group possessed by the non-alkali soluble resin can be well deprotected.

  For this reason, when the photosensitive resin composition contains a compound that generates an acid or a radical by the action of (C) light, it is easy to form a good pattern of the shape with a low exposure amount.

  (C) The compound which generates an acid or a radical by the action of light may be a nonionic organic compound or an ionic organic compound. Examples of nonionic organic compounds include halogen-containing compounds, diazo ketones, sulfone compounds, and sulfonic acid compounds. Examples of the nonionic organic compound include onium salts and the like. (C) As a compound which generates an acid or a radical by the action of light, two or more kinds may be used in combination. (C) When using in combination of 2 or more types as a compound which generates an acid or a radical by the effect | action of light, you may use combining an nonionic organic compound and an ionic organic compound.

（式（Ｃ１）中、Ｒ^ｃ１は、置換基を有してもよい炭素原子数１〜１０の脂肪族炭化水素基、置換基を有してもよい炭素原子数１〜８のパーフルオロアルキル基、又は置換基を有してもよい炭素原子数６〜１６の芳香族炭化水素基を表す。） [Nonionic Organic Compound]
(C) Nonionic organic compounds that can be used as compounds that generate acids or radicals by the action of light are represented by the following formulas (C1), (C2), (C3), and (C4) Compounds can be mentioned.

(In formula (C1), R ^c1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a perfluoroalkyl having 1 to 8 carbon atoms which may have a substituent A group or an aromatic hydrocarbon group having 6 to 16 carbon atoms which may have a substituent.

（式（Ｃ２）中、Ａは−Ｏ−又は−Ｓ−を表し、Ｒ^ｃ２は炭素原子数１〜８のパーフルオロアルキル基を表し、２つのＲ^ｃ３は、同一でも異なっていてもよく、それぞれ独立に、水素原子又は炭素原子数１〜４のアルキル基を表す。）

(In formula (C2), A represents -O- or -S-, R ^c2 represents a C 1-8 perfluoroalkyl group, and two R ^{c3 s} may be the same or different, And each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

（式（Ｃ３）中、Ｒ^ｃ４は、水素原子、ハロゲン原子、水酸基、シアノ基、炭素原子数１〜１０のアルキル基、炭素原子数１〜４のアルコキシ基、又はアシル基を表し、Ｒ^ｃ５は、炭素原子数１〜２０の炭化水素基、又は炭素原子数１〜２０のハロゲン化炭化水素基を表し、当該炭化水素基又は当該ハロゲン化炭化水素基は、−Ｏ−、−Ｓ−、又はカルボニル基を含んでいてもよい。当該炭化水素基又は当該ハロゲン化炭化水素基がカルボニル基を含む場合、カルボニル基に含まれる炭素原子の数は、当該炭化水素基又は当該ハロゲン化炭化水素基の炭素原子数に含まれない。）

(In the formula ^{(C3), R c4} represents a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an acyl ^{group, R c5} Represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group or the halogenated hydrocarbon group is —O—, —S—, When the hydrocarbon group or the halogenated hydrocarbon group contains a carbonyl group, the number of carbon atoms contained in the carbonyl group is the hydrocarbon group or the halogenated hydrocarbon group concerned. Not included in the number of carbon atoms in

（式（Ｃ４）中、Ｒ^ｃ６は、式（Ｃ３）中の、Ｒ^ｃ５と同様である。）

(In formula (C4), R ^c6 is the same as R ^c5 in formula (C3).)

  The compounds represented by formulas (C1) to (C4) will be sequentially described below.

(Compound represented by formula (C1))
In Formula (C1), when R ^c1 is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group may have an oxo group (= O). When R ^c1 is a perfluoroalkyl group, the perfluoroalkyl group preferably has no substituent. When R ^c1 is an aromatic hydrocarbon group, examples of the substituent which the aromatic hydrocarbon group may have include a halogen atom and an alkyl group having 1 to 4 carbon atoms.

Specific examples of the compound represented by the formula (C1) include compounds of the following formula.

(Compound represented by formula (C2))
Specific examples of the compound represented by the formula (C2) include compounds of the following formula.

(Compound represented by formula (C3))
Specific examples of the compound represented by the formula (C3) include compounds of the following formula.

(Compound represented by formula (C4))
Preferred examples of the compound represented by formula (C4) include compounds of the following formula and compounds described in JP2007-328090A and JP2007-328234A.

[Ionic organic compounds]
(C) As an ionic organic compound which can be used as a compound which generates an acid or a radical by the action of light, it is represented by the following formulas (C5), (C6), (C7), and (C8) Compounds are mentioned.

（式（Ｃ５）中、Ｒ^ｃ７、Ｒ^ｃ８、及びＲ^ｃ９は、それぞれ独立に、水酸基、炭素原子数１〜６のアルキル基、又は炭素原子数１〜６のアルコキシ基を表す。ａ、ｂ、及びｃは、それぞれ独立に０〜３の整数を表し、ａ、ｂ、及びｃのいずれかが２以上のとき、複数のＲ^ｃ７、Ｒ^ｃ８、又はＲ^ｃ９は、それぞれ異なっていても同一でもよい。Ｚ⁻は、有機対イオンを表す。）

(In formula (C5), R ^c7 , R ^c8 and R ^c9 each independently represent a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. And c each independently represent an integer of 0 to 3, and when any of a, b and c is 2 or more, plural R ^c7 , R ^c8 or R ^c9 are identical even if they are different from each other Z ⁻ represents an organic counter ion.)

（式（Ｃ６）中、Ｒ^ｃ１０、及びＲ^ｃ１１は、それぞれ独立に、水酸基、炭素原子数１〜６のアルキル基、又は炭素原子数１〜６のアルコキシ基を表し、ｄ及びｅは、それぞれ独立に０又は１である。Ｚ⁻は有機対イオンを表す。）

(In formula (C6), R ^c10 and R ^c11 each independently represent a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and d and e each represent Independently 0 or 1. Z ⁻ represents an organic counter ion.)

（式（Ｃ７）中、Ｒ^ｃ１２、及びＲ^ｃ１３は、それぞれ独立に、炭素原子数１〜６のアルキル基、又は炭素原子数３〜１０のシクロアルキル基を表すか、Ｒ^ｃ１２とＲ^ｃ１３とが互いに結合して、それらが結合する硫黄原子とともに炭素数３〜７の環を形成してもよい。当該環を構成するメチレン基は、カルボニル基、−Ｏ−、又は−Ｓ−に置き換わっていてもよい。Ｒ^ｃ１４は水素原子を表し、且つＲ^ｃ１５は炭素原子数１〜６のアルキル基、炭素原子数３〜１０のシクロアルキル基、又は置換されていてもよい芳香族炭化水素基を表すか、Ｒ^１４とＲ^ｃ１５とが互いに結合してこれらが結合している炭素原子とともに環を形成してもよい。Ｚ⁻は、有機対イオンを表す。）

(In formula (C7), R ^c12 and R ^c13 each independently represent an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, or R ^c12 and R ^c13 and May combine with each other to form a ring having 3 to 7 carbon atoms with the sulfur atom to which they are attached.The methylene group constituting the ring is substituted with a carbonyl group, -O-, or -S- R ^c14 represents a hydrogen atom, and R ^c15 represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group which may be substituted. Or R ¹⁴ and R ^c15 may be bonded to each other to form a ring with the carbon atom to which they are bonded.Z ⁻ represents an organic counter ion.

（式（Ｃ８）中、Ａは、−Ｏ−、又は−Ｓ−を表す。２つのＲ^ｃ１６は、それぞれ独立に、メチル基、又はフェニル基を表す。Ｒ^ｃ１７は、炭素原子数１〜８のパーフルオロアルキル基を表す。）

(In formula (C8), A represents -O- or -S-. Two R ^c16 each independently represent a methyl group or a phenyl group. R ^c17 has 1 to 8 carbon atoms Represents a perfluoroalkyl group of

  The compounds represented by formulas (C5) to (C8) will be sequentially described below.

(Compound represented by formula (C5))
The following organic cations are mentioned as a suitable example of the organic cation which constitutes a compound denoted by a formula (C5).

The organic counter ion (Z ⁻ ), which is an anion constituting the compound represented by the formula (C5), is preferably an organic acid anion, and more preferably an organic sulfonate anion. As a preferable example of an organic counter ion (Z < ^- >), the anion represented by a following formula (C9) is mentioned.

（式（Ｃ９）中、Ｒ^ｃ１８〜Ｒ^ｃ２２は、それぞれ独立に、水素原子、ハロゲン原子、ホルミル基、炭素原子数１〜１６のアルキル基、炭素原子数１〜１６のアルコキシ基、炭素原子数１〜８のハロゲン化アルキル基、炭素原子数６〜１２のアリール基、炭素原子数７〜１２のアラルキル基、シアノ基、炭素原子数１〜４のアルキルチオ基、炭素原子数１〜４のアルキルスルホニル基、水酸基、ニトロ基、又は下式（Ｃ１０）：
−（Ｃ＝Ｏ）−Ｏ−Ｒ^ｃ２３−Ｒ^ｃ２４ （Ｃ１０）
で表される基である。式（Ｃ１０）中、Ｒ^ｃ２３は、メチレン基の一部が−Ｏ−又は−Ｓ−で置換されていてもよい炭素原子数１〜１６の直鎖脂肪族アルキレン基を表し、Ｒ^ｃ２４は炭素原子数３〜２０の脂環式炭化水素基を表す。）

In the formula (C9), R ^{c18 to} R ^c22 each independently represent a hydrogen atom, a halogen atom, a formyl group, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, or the like 1 to 8 halogenated alkyl group, aryl group having 6 to 12 carbon atoms, aralkyl group having 7 to 12 carbon atoms, cyano group, alkylthio group having 1 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms A sulfonyl group, a hydroxyl group, a nitro group, or the following formula (C10):
-(C = O) -O-R ^c23 -R ^c24 (C10)
Is a group represented by In formula (C10), R ^c23 represents a linear aliphatic alkylene group having 1 to 16 carbon atoms in which a part of methylene groups may be substituted by -O- or -S-, and R ^c24 is carbon It represents an alicyclic hydrocarbon group having 3 to 20 atoms. )

Preferred examples of R ^{c18 to} R ^c22 each having 1 to 8 carbon atoms as a halogenated alkyl group include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, and perfluorobutyl group. Groups are mentioned.

When R ^{c18 to} R ^c22 is an aryl group having 6 to 12 carbon atoms, the aryl group may be substituted with an alkyl group or an alkoxy group. Preferred examples of the aryl group include phenyl group, tolyl group, methoxyphenyl group and naphthyl group.

Preferred examples of R ^{c18 to} R ^{c22 which} are aralkyl groups having 7 to 12 carbon atoms include benzyl, chlorobenzyl and methoxybenzyl.

Preferred examples of R ^{c18 to} R ^c22 each having 1 to 4 carbon atoms as an alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, and an n-butylthio group.

Preferred examples of R ^{c18 to} R ^c22 each having 1 to 4 carbon atoms as an alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an isopropylsulfonyl group, and an n-butylsulfonyl group. Can be mentioned.

Moreover, in Formula (C9), when two or more are groups represented by Formula (C10) among R ^{c18 to} R ^c22 , groups represented by a plurality of Formulas (C10) are the same and are the same. May also be different.

R ^c23 is a linear aliphatic alkylene group having 1 to 16 carbon atoms in which a part of methylene groups may be substituted by -O- or -S-. As preferable groups, an alkyleneoxy group having 1 to 15 carbon atoms, an alkyleneoxy alkylene group having 2 to 14 carbon atoms, an alkylene thio group having 1 to 15 carbon atoms, an alkylene thio alkylene group having 2 to 14 carbon atoms, etc. Can be mentioned.

Preferred examples of R ^c23 include groups represented by the following formulas (C10-1) to (C10-15).

-CH ₂ - (C10-1)
-CH ₂ CH ₂ - (C10-2)
-CH ₂ CH ₂ CH _2- (C10-3)
_{-CH 2 CH 2 CH 2 CH 2} - (C10-4)
-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- (C10-5)
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 - (C10-6)
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 - (C10-7)
-CH ₂ -O- (C10-8)
_{-CH 2 -O-CH 2 - (} C10-9)
_{-CH 2 -O-CH 2 CH 2} - (C10-10)
_{-CH 2 CH 2 -O-CH 2} CH 2 - (C10-11)
-CH ₂ -S- (C10-12)
_{-CH 2 -S-CH 2 - (} C10-13)
_{-CH 2 -S-CH 2 CH 2} - (C10-14)
_{-CH 2 CH 2 -S-CH 2} CH 2 - (C10-15)

Among R ^c23 , an unsubstituted linear alkylene group having 1 to 8 carbon atoms (for example, a group represented by formulas (C10-1) to (C10-7)) is preferable.

As a group preferable as R ^c24 , the following formulas may be mentioned.

Among the above-mentioned groups, a group of the following formula is more preferable as R ^c24 .

Specific examples of the anion represented by the formula (C9) include the following.

The anion represented by a following formula (C11) is also mentioned as a preferable example of organic counter ion (Z < ^- >).
R ^c25 -SO ₃ ^- (C11)
(In formula (C11), R ^c25 represents a perfluoroalkyl group having 1 to 25 carbon atoms, a naphthyl group which may have a substituent, or an anthryl group which may have a substituent.)

  As a substituent which a naphthyl group or an anthryl group may have, a C1-C4 alkyl group and a C1-C4 alkoxy group are mentioned.

Preferred examples of the anion represented by the formula (C11) include the following.

Furthermore, the anion represented by a following formula (C12) is also mentioned as a preferable example of an organic counter ion (Z < ^- >).
R ^c26 -SO ₂ -N ^-- SO ₂ -R ^c27 (C12)
(In the formula (C12), each of R ^c26 and R ^c27 independently represents a perfluoroalkyl group having 1 to 20 carbon atoms, or the number of carbon atoms which may have an alkyl group having 1 to 4 carbon atoms 6 to 20 represent an aryl group.)

R ^c26 and R ^c27 may be different groups or may be the same group, and are preferably the same group.

Preferred examples of the anion represented by the formula (C12) include the following.
CF ₃ -SO ₂ -N ^-- SO ₂ -CF _{3
^{C 2 F 5 -SO 2 -N -}} -SO 2 -C 2 F 5
CF ₃ -SO ₂ -N ^-- SO ₂ -C ₂ F _{5
^{n-C 4 F 9 -SO 2}} -N - -SO 2 -n-C 4 F 9
^{_{n-C 8 F 17 -SO 2}} -N - -SO 2 -n-C 8 F 17
^{_{n-C 10 F 21 -SO 2}} -N - -SO 2 -n-C 10 F 21
^{_{n-C 12 F 25 -SO 2}} -N - -SO 2 -n-C 12 F 25
^{_{n-C 16 F 33 -SO 2}} -N - -SO 2 -n-C 16 F 33
^{_{n-C 20 F 41 -SO 2}} -N - -SO 2 -n-C 20 F 41

(Compound represented by formula (C6))
As a suitable example of the organic cation which comprises the compound represented by Formula (C6), the following organic cation is mentioned.

Preferred examples of the organic counter ion (Z ⁻ ) constituting the compound represented by the formula (C6) are the same as those described for the formula (C5).

(Compound represented by formula (C7))
As a suitable example of the organic cation which comprises the compound represented by Formula (C7), the following organic cation is mentioned.

Preferred examples of the organic counter ion (Z ⁻ ) constituting the compound represented by the formula (C7) are the same as those described for the formula (C5).

(Compound represented by formula (C8))
As a suitable example of the organic cation which comprises the compound represented by Formula (C8), the following organic cation is mentioned.

The organic counter ion (Z < ^- >) which comprises the compound represented by Formula (C8) is a C1-C8 perfluoro alkane sulfonate ion.

  The content of the compound that generates an acid or a radical by the action of (C) light in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. The content of the compound for generating an acid or a radical by the action of (C) light in the photosensitive resin composition is 0.1 to 20% by mass based on the mass of the solid content of the photosensitive resin composition. Preferably, 3 to 10% by mass is more preferable.

（式（Ｄ１）中、Ｒ^ｄ１、Ｒ^ｄ２、及びＲ^ｄ３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。）
で表されるイミダゾール化合物を発生する化合物（以下、（Ｄ）成分とも記す。）を含有してもよい。 <(D) Compound that generates imidazole compound by heating>
The photosensitive resin composition has the following formula (D1) by heating (D):

(In formula (D1), R ^d1 , R ^d2 and R ^d3 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 sulfonato group, Represents a phosphino group, a phosphinyl group, a phosphonato group, or an organic group)
The compound which generate | occur | produces the imidazole compound represented by these (Hereafter, it describes also as (D) component.) May be included.

  When the photosensitive resin composition contains a compound that generates an imidazole compound by heating (D), (A) the alkali-soluble resin has a pattern formed after development, for example, by heating to a temperature of about 150 ° C. Promote the crosslinking reaction of unsaturated double bond and epoxy group, or promote the condensation reaction between carboxyl groups or hydroxyl group-carboxyl group derived from (A) alkali-soluble resin and (B) non-alkali-soluble resin Can be

  Therefore, by heating the pattern formed using the photosensitive resin composition containing the compound that generates the imidazole compound by heating (D), the chemical resistance and solvent resistance of the pattern, and the support of the pattern can be obtained. Adhesion can be improved.

^Examples of the organic group as R ^d1 , R ^d2 and R ^d3 include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group. The organic group may contain a bond or a 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 forming a cyclic structure.

R ^d1 and R ^d2 may be combined to form a cyclic structure, and may further include a bond of a heteroatom. The cyclic structure may, for example, be a heterocycloalkyl group or a heteroaryl group, which may be a fused ring.

The bond contained in the organic group of R ^d1 , R ^d2 , and R ^d3 is not particularly limited as long as the effects of the present invention are not impaired, and the organic group contains a heteroatom such as oxygen atom, nitrogen atom, or silicon atom It may contain a bond. 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, an imino bond (-N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond and the like.

As a bond containing a hetero atom which the organic group of R ^d1 , R ^d2 and R ^d3 may have, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond from the viewpoint of heat resistance of an imidazole compound , 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.

If ^{R d1,} R ^d2, and an organic group ^{R d3} is a substituent other than a hydrocarbon ^{group, R d1,} R ^d2, and ^{R d3} is not particularly limited as long as the effects of the present invention are not impaired. Specific examples of R ^d1 , R ^d2 and R ^d3 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 and a silanol group. Alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfonato group, phosphino group, phosphinyl group, phosphonato group, alkyl ether group, alkenyl An ether group, an alkyl thioether group, an alkenyl thioether group, an aryl ether group, an aryl thioether group etc. are mentioned. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. The hydrocarbon group contained in the above-mentioned substituent may be linear, branched or cyclic.

As R ^d1 , R ^d2 and R ^d3 , 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 are preferable, and a hydrogen atom is preferable. Is more preferred.

  The component (D) is not particularly limited as long as it is a compound that can generate the imidazole compound represented by the above formula (D1) by heating. About the compound (thermal base generator) which generate | occur | produces an amine by the effect | action of a heat | fever conventionally mix | blended with various compositions, The frame | skeleton derived from the amine generated at the time of heating is represented by said imidazole (D1) Substitution of the skeleton derived from the compound gives a compound used as the component (D1).

（式（Ｄ２）中、Ｒ^ｄ１、Ｒ^ｄ２、及びＲ^ｄ３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^ｄ４及びＲ^ｄ５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^ｄ６、Ｒ^ｄ７、Ｒ^ｄ８、Ｒ^ｄ９、及びＲ^ｄ１０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^ｄ６、Ｒ^ｄ７、Ｒ^ｄ８、Ｒ^ｄ９、及びＲ^ｄ１０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 (D) component, following formula (D2):

(In formula (D2), R ^d1 , R ^d2 and R ^d3 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 sulfonato group, And p represents a phosphino group, a phosphinyl group, a phosphonato group, or an organic group, R ^d4 and R ^d5 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 Sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, or organic group, and R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 each independently represent a hydrogen atom , Halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitro And a sulfino group, a sulfino group, a sulfo group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, and R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R Two or more of ^d10 may combine to form a cyclic structure, and may include a heteroatom bond.)
The compound represented by these is mentioned.

In Formula (D2), R ^d1 , R ^d2 and R ^d3 are the same as those described for Formula (D1).

In formula (D2), R ^d4 and R ^d5 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 , Phosphino group, phosphinyl group, phosphono group, phosphonato group, or organic group.

The organic group in R ^d4 and ^{R d5,} include those exemplified for ^{R d1,} R ^d2, and ^{R d3.} The organic group may contain a hetero atom in the organic group, as in the case of R ^d1 , R ^d2 and R ^d3 . The organic group may be linear, branched or cyclic.

Among the above, R ^d4 and R ^d5 each independently represent 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 aryloxy alkyl group, aralkyl group having 7 to 20 carbon atoms, alkyl group having 2 to 11 carbon atoms having cyano group, alkyl group having 1 to 10 carbon atoms having hydroxyl group, 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 (-COOR, -OCOR: R represents a hydrocarbon group ), An aryl group having 6 to 20 carbon atoms, an electron donating group and / or an aryl group having 6 to 20 carbon atoms substituted with an electron withdrawing group, a benzyl group substituted with an electron donating group and / or an electron withdrawing group A cyano group is preferably a methylthio group. More preferably, both ^Rd4 and ^Rd5 are hydrogen atoms, or ^Rd4 is a methyl group, and ^Rd5 is a hydrogen atom.

In the formula (D2), R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 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 And 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.

As the organic group in R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 , those exemplified for R ^d1 , R ^d2 and R ^d3 can be mentioned. The organic group, as in the case of R ^d1 and R ^d2, which may contain a binding and substituent other than a hydrocarbon group such as a heteroatom in the organic group. The organic group may be linear, branched or cyclic.

Two or more of R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 may be combined to form a cyclic structure, and may include a heteroatom bond. As a cyclic structure, a heterocycloalkyl group, a heteroaryl group etc. are mentioned, A condensed ring may be sufficient. For example, R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 are ^benzenes to which two or more of them are bonded and R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 are bonded. Ring atoms may be shared to form a fused ring of naphthalene, anthracene, phenanthrene, indene and the like.

Among the above, R ^d6 , R ^d7 , R ^d8 , R ^d9 and R ^d10 each independently represent 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シ ク ロ 13 cycloalkenyl group, C7-C16 aryloxyalkyl group, C7-C20 aralkyl group, cyano-containing C2-C11 alkyl group, hydroxyl group-containing C1-10 alkyl group Group, alkoxy group having 1 to 10 carbon atoms, amide group having 2 to 11 carbon atoms, alkylthio group having 1 to 10 carbon atoms, acyl group having 1 to 10 carbon atoms, ester group having 2 to 11 carbon atoms, 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 benzyl group substituted with electron withdrawing group, cyano group, methyl group Thio is preferably a nitro group.

^{Also, R d6, R d7, R} d8, R d9, and as ^{R d10} combines two or more of ^{them, R d6, R d7, R} d8, R d9, and ^{R d10} are attached It is also preferable to share a benzene ring atom to form a fused ring of naphthalene, anthracene, phenanthrene, indene or the like from the viewpoint of increasing the absorption wavelength.

（式（Ｄ３）中、Ｒ^ｄ１、Ｒ^ｄ２、及びＲ^ｄ３は、式（Ｄ１）及び（Ｄ２）と同義である。Ｒ^ｄ４〜Ｒ^ｄ９は式（Ｄ２）と同義である。Ｒ^ｄ１１は、水素原子又は有機基を示す。Ｒ^ｄ６及びＲ^ｄ７が水酸基となることはない。Ｒ^ｄ６、Ｒ^ｄ７、Ｒ^ｄ８、及びＲ^ｄ９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 (D2), the following formula (D3):

(In the formula ^{(D3), R d1, R} d2, and ^{R d3} are ^{.R d11} is as defined for formula (D1) and (D2) ^.R d4 ^{to R d9} are the same as in formula (D2) is, R ^d6 and R ^d7 are not a hydroxyl group, and two or more of R ^d6 , R ^d7 , R ^d8 and R ^d9 are combined to form a cyclic structure. And may contain a hetero atom bond.)
The compound represented by is preferable.

Since the compound represented by Formula (D3) has a substituent -O-R ^d11 , it is excellent in the solubility with respect to the organic solvent.

In formula (D3), ^Rd11 is a hydrogen atom or an organic group. When R ^d11 is an organic group, examples of the organic group include those exemplified for R ^d1 , R ^d2 and R ^d3 . The organic group may contain a hetero atom in the organic group. The organic group may be linear, branched or cyclic. As ^Rd11 , a hydrogen atom or a C1-C12 alkyl group is preferable, and a methyl group is more preferable.

  Specific examples of the compound particularly suitable as the component (D) are shown below.

  Moreover, the imidazole compound represented by following formula (D4) is also suitable as a compound which generate | occur | produces an imidazole compound by (D) heating.

（式（Ｄ４）中、Ｒ^ｄ１２は水素原子又はアルキル基であり、Ｒ^ｄ１３は置換基を有してもよい芳香族基であり、Ｒ^ｄ１４は置換基を有してもよいアルキレン基である。Ｒ^ｄ１、Ｒ^ｄ２及びＲ^ｄ３は、式（Ｄ１）と同様である。）

(In Formula (D4), R ^d12 is a hydrogen atom or an alkyl group, R ^d13 is an aromatic group which may have a substituent, and R ^d14 is an alkylene group which may have a substituent R ^d1 , R ^d2 and R ^d3 are the same as in formula (D1).)

In formula (D4), R ^d12 is a hydrogen atom or an alkyl group. When R ^d12 is an alkyl group, the alkyl group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.

Specific examples of the alkyl group suitable as R ^d12 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 Groups, 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 (D4), ^Rd13 is an aromatic group which may have a substituent. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent, or may be an aromatic heterocyclic group which may have a substituent.

  The type of 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, or may be formed by condensation of two or more aromatic hydrocarbon groups, or two or more aromatic hydrocarbon groups. May be formed by bonding by a single bond. The aromatic hydrocarbon group is preferably a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group or a phenanthrenyl group.

  The type of 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, pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzothiazolyl and benzoimidazolyl are preferable.

  As a substituent which a phenyl group, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group And sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group and organic group. When the phenyl group, the polycyclic aromatic hydrocarbon group, or the 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. The organic group may contain a bond or a 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 forming a cyclic structure.

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

  When the substituent which 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 is an oxygen atom, a nitrogen atom, a silicon atom And a bond containing the hetero atom of 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, an imino bond (-N = C (-R)-, -C (= NR)-: R represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond and the like.

  As a bond containing a hetero atom which the organic group may have, from the viewpoint of the heat resistance of the imidazole compound represented by the formula (1), an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an 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 is a hydrogen atom Or a monovalent organic group is shown), a carbonate bond, a sulfonyl bond or a sulfinyl bond is preferable.

  When the organic group is a substituent other than a hydrocarbon group, the type of the substituent other than a 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 and 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 Groups, sulfonato groups, phosphino groups, phosphinyl groups, phosphonato groups, alkyl ether groups, alkenyl ether groups, alkyl thioether groups, alkenyl thioether groups, aryl ether groups, aryl thioether groups and the like. The hydrogen atom contained in the said substituent may be substituted by the hydrocarbon group. The hydrocarbon group contained in the above-mentioned substituent may be linear, branched or cyclic.

  As a substituent which a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms And the aryloxy group having 1 to 12 carbon atoms, the arylamino group having 1 to 12 carbon atoms, and a halogen atom are preferable.

As ^Rd13 , an imidazole compound represented by the formula (D4) can be easily and inexpensively synthesized, and since the solubility of the imidazole compound in water and organic solvents is good, it may be substituted phenyl. Preferred is a group, a furyl group or a thienyl group.

In formula (D4), R ^d14 is 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. A hydroxyl group, an alkoxy group, an amino group, a cyano group, a halogen atom etc. are mentioned as a specific example of the substituent which the alkylene group may have. The alkylene group may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferable. Although the carbon atom number of an alkylene group is not specifically limited, 1-20 are preferable, 1-10 are preferable and 1-5 are more preferable. The number of carbon atoms of the alkylene group does not include the carbon atom of the substituent bonded to the alkylene group.

  The alkoxy group as a substituent bonded to an alkylene group may be a linear alkoxy group or a branched alkoxy group. Although the carbon atom number of the alkoxy group as a substituent is not specifically limited, 1-10 are preferable, 1-6 are more preferable, and 1-3 are especially preferable.

  The amino group as a substituent bonded to an alkylene group may be a monoalkylamino group or a dialkylamino group. The alkyl group contained in the monoalkylamino group or the dialkylamino group may be a linear alkyl group or a branched alkyl group. Although the carbon atom number of the alkyl group contained in a monoalkyl amino group or a dialkylamino group is not specifically limited, 1-10 are preferable, 1-6 are more preferable, and 1-3 are especially preferable.

Specific examples of the alkylene group suitable as R ^d14 include methylene group, ethane-1,2-diyl group, n-propane-1,3-diyl group, n-propane-2,2-diyl group, 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 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-icosan-1,20-diyl group.

Among the imidazole compounds represented by the above formula (D4), compounds represented by the following formula (D4-1) are preferable from the viewpoint of being inexpensive and easily synthesizable, and having excellent solubility in water and organic solvents. The compound represented by the formula (D4-1), wherein R ^d14 is a methylene group is more preferable.

（式（Ｄ４−１）中、Ｒ^ｄ１２、及びＲ^ｄ１４は、式（Ｄ４）と同様であり、Ｒ^ｄ１、Ｒ^ｄ２及びＲ^ｄ３は、式（Ｄ１）と同様である。Ｒ^ｄ１５、Ｒ^ｄ１６、Ｒ^ｄ１７、Ｒ^ｄ１８、及びＲ^ｄ１９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、又は有機基であり、ただし、Ｒ^ｄ１５、Ｒ^ｄ１６、Ｒ^ｄ１７、Ｒ^ｄ１８、及びＲ^ｄ１９のうち少なくとも１つは水素原子以外の基である。）

(In the formula ^{(D4-1), R d12,} and ^{R d14} is similar to the formula ^{(D4), R d1, R} d2 and ^{R d3} are ^{.R d15, R d16} is similar to the formula (D1) , R ^d17 , R ^d18 and R ^d19 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, an amino group, an ammonio group, or an organic group, provided that at least one of R ^d15 , R ^d16 , R ^d17 , R ^d18 , and R ^d19 is a hydrogen atom Other groups)

When R ^d15 , R ^d16 , R ^d17 , R ^d18 , and R ^d19 are organic groups, the organic groups are the same as the organic groups that R ^d13 in formula (D4) has as a substituent. R ^d15 , R ^d16 , R ^d17 and R ^d18 are preferably hydrogen atoms in terms of the solubility of the imidazole compound in the solvent.

Among ^{them, R d15, R d16, R} d17, R d18, and at least one of ^{R d19} is preferably the following substituent ^group, the ^{R d19} is the following substituent group are particularly preferred. When R ^d19 is a substituent ^described below, R ^d15 , R ^d16 , R ^d17 and R ^d18 are preferably hydrogen atoms.
-O-R ^d20
(R ^d20 is a hydrogen atom or an organic group)

When R ^d20 is an organic group, the organic group is the same as the organic group that R ^d13 in Formula (D4) has as a substituent. As ^Rd20 , an alkyl group is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is particularly preferable, and a methyl group is most preferable.

（式（Ｄ４−１−１）において、Ｒ^ｄ１２は式（Ｄ４）と同様である。Ｒ^ｄ２１、Ｒ^ｄ２２、Ｒ^ｄ２３、Ｒ^ｄ２４、及びＲ^ｄ２５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、又は有機基であり、ただし、Ｒ^ｄ２１、Ｒ^ｄ２２、Ｒ^ｄ２３、Ｒ^ｄ２４、及びＲ^ｄ２５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 above formula (D4-1), a compound represented by the following formula (D4-1-1) is preferable.

In (Equation ^{(D4-1-1), R d12} is similar to the formula ^{(D4) .R d21, R d22} , R d23, R d24, and ^{R d25} are each independently a hydrogen atom, a hydroxyl group, a mercapto Group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, amino group, ammonio group, or organic group, ^{However, R d21, R d22, R} d23, R d24, and at least one of ^{R d25} is a group other than a hydrogen atom.)

Among the compounds represented by formula ^(D4-1-1), a group ^{R d21, R d22, R d23} , R d24, and at least one of ^{R d25,} represented by ^{-O-R d20} described above It is particularly preferable that ^{Rd 25} be a group represented by —O—R ^d20 . When R ^d25 is a group represented by —O—R ^d20 , it is preferable that R ^d21 , R ^d22 , R ^d23 and R ^{d24 be} a hydrogen atom.

  The synthesis method of the imidazole compound represented by the above formula (D4) is not particularly limited. For example, the above-mentioned formula (1) is produced by reacting the halogen-containing carboxylic acid derivative represented by the following formula (D5) with the imidazole compound represented by the above-mentioned formula (D1) according to a conventional method to carry out imidazolylation. The imidazole compound represented by these can be synthesize | combined.

（式（Ｄ５）中、Ｒ^ｄ１２、Ｒ^ｄ１３、及びＲ^ｄ１４は、式（Ｄ４）と同様であり、Ｈａｌはハロゲン原子である。）

(In the formula (D5), R ^d12 , R ^d13 and R ^d14 are the same as the formula (D4), and Hal is a halogen atom.)

In addition, when the imidazole compound is a compound represented by the formula (D4) and R ^d14 is a methylene group, that is, when the imidazole compound is a compound represented by the following formula (D6), it will be described below The imidazole compound can also be synthesized by the method by the Michael addition reaction.

（式（Ｄ６）中、Ｒ^ｄ１２、及びＲ^ｄ１３は式（１）と同様であり、Ｒ^ｄ１、Ｒ^ｄ２、及びＲ^ｄ３は式（Ｄ１）と同様である。）

(In formula (D6), R ^d12 and R ^d13 are the same as in formula (1), and R ^d1 , R ^d2 and R ^d3 are the same as in formula (D1).)

  Specifically, for example, a 3-substituted acrylic acid derivative represented by the following formula (D7) and an imidazole compound represented by the above formula (D1) are mixed in a solvent to cause a Michael addition reaction. Thus, an imidazole compound represented by the above formula (D6) is obtained.

（式（Ｄ７）中、Ｒ^ｄ１２、及びＲ^ｄ１３は、式（Ｄ４）と同様である。）

(In Formula (D7), R ^d12 and R ^d13 are the same as in Formula (D4).)

  Moreover, the imidazole compound represented by a following formula (D9) is obtained by adding the 3-substituted acrylic acid derivative containing an imidazolyl group represented by following formula (D8) in the solvent containing water.

（式（Ｄ８）及び式（Ｄ９）中、Ｒ^ｄ１３は、式（Ｄ４）と同様であり、Ｒ^ｄ１、Ｒ^ｄ２、及びＲ^ｄ３は式（Ｄ１）と同様である。）

(In Formula (D8) and Formula (D9), ^Rd13 is the same as Formula (D4), and ^Rd1 , ^Rd2 , and ^Rd3 are the same as Formula (D1).

  In this case, the imidazole compound represented by the above formula (D1) and the 3-substituted acrylic acid represented by the following formula (D10) by hydrolysis of the 3-substituted acrylic acid derivative represented by the above formula (D8) And generate. Then, a Michael addition reaction occurs between the 3-substituted acrylic acid represented by the following formula (D10) and the imidazole compound represented by the above formula (D1), and the imidazole compound represented by the above formula (D9) Generates.

（式（Ｄ１０）中、Ｒ^ｄ１３は、式（Ｄ４）と同様である。）

(In the formula (D10), ^Rd13 is the same as the formula (D4).)

Preferable specific examples of the imidazole compound represented by the formula (D4) include the following.

  The content of the compound for generating the imidazole compound by heating (D) in the photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. The content of the compound for generating the imidazole compound by heating (D) in the photosensitive resin composition is preferably 0.1 to 20% by mass with respect to the mass of the solid content of the photosensitive resin composition, and 0. 1-5 mass% is more preferable.

<(S) Solvent>
The photosensitive resin composition may contain (S) a solvent, 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 the components to be used to form a uniform solution. Any one or more solvents selected from known solvents used for the photosensitive resin composition can be used as the (S) solvent.

  Specific examples of the solvent (S) include lactones such as γ-butyrolactone; acetones such as methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; ethylene glycol and diethylene glycol Propylene glycol, and polyhydric alcohols such as dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene glycol monopropionate, diethylene glycol monopropionate, propylene glycol mono Compound having an ester bond such as propionate or dipropylene glycol monopropionate; the above 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 ether such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or the like of the compound having an ester bond or monophenyl ether [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, ethyc acid Aromatic organic solvents such as benzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene; N, N, N ', N'-tetramethylurea, N-methyl-2-pyrrolidone, N, Nitrogen-containing polar solvents such as N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoramide, 1,3-dimethyl-2-imidazolidinone, N, N, 2-trimethylpropionamide and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

  (S) As a solvent, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), EL, γ-butyrolactone, N, N, N ′, N′-tetramethylurea, N, N-dimethylacetamide , N, N, 2-trimethylpropionamide is preferred. These organic solvents may be used alone or in combination of two or more. Moreover, the mixed solvent which mixed PGMEA and polar solvents other than said PGMEA is also preferable. The compounding ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, etc., but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be in the range.

  More specifically, when blending EL as a polar solvent, the weight ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably 1: 9-9: 1, More preferably, 2: 8-8: 2, More preferably, 3: 7-7: It is three.

As the solvent (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. In this case, the mass ratio of the former and the latter is preferably 70:30 to 95: 5 as the mixing ratio.
The amount of the solvent (S) to be used is not particularly limited, and is appropriately set in accordance with the applied film thickness within the range in which the photosensitive resin composition can be applied to a substrate or the like. Generally, it is used so that the solid content concentration of the photosensitive resin composition is in the range of 1 to 40% by mass, preferably 2 to 39% by mass, and more preferably 3 to 25% by mass.

<(E) Other ingredients>
The photosensitive resin composition may further contain other components as needed. For example, dissolution control agents, dissolution inhibitors, basic compounds, surfactants, dyes, pigments, plasticizers, photosensitizers, light absorbers, antihalation agents, storage stabilizers, antifoaming agents, adhesion assistants , Fluorescent substances, magnetic substances and the like.

«Pattern formation method»
The method for forming a pattern using the photosensitive resin composition described above is carried out in the same manner as in the case of using a conventional positive photosensitive resin composition.
As a preferable method of forming a pattern, a step of forming a photosensitive resin film on a support, a step of position-selectively exposing the formed photosensitive resin film, and a photosensitive exposed light Developing the photosensitive resin film with an alkaline developer to form a pattern.

  The method for applying the photosensitive resin composition on the support is not particularly limited, and for example, a spinner is suitably used. Prebaking is applied to the formed photosensitive resin film as required. Prebaking is performed, for example, at 80 to 120 ° C. for 40 to 120 seconds.

  Next, after exposing the photosensitive resin film using an exposure apparatus equipped with a desired light source, development with an alkaline developer is performed. In addition, when using the photosensitive resin composition demonstrated above, a pattern of a favorable shape can be formed, without performing post-exposure baking (PEB) with respect to the exposed photosensitive resin film, PEB may be applied to the resin film. PEB is typically performed at 80-120 ° C. for 40-120 seconds.

  The alkali developer is appropriately selected from those conventionally used in the photolithography method. As a preferable alkali developing solution, 0.1-10 mass% tetramethyl ammonium hydroxide aqueous solution is mentioned, for example. Preferably, water rinse is performed using pure water and drying is performed. Further, in some cases, a bake treatment (post bake) may be performed after the development treatment. Thus, 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 body, the board | substrate for electronic components, the thing in which the predetermined | prescribed wiring pattern was formed on this etc. can be illustrated, for example. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, aluminum or the like, a glass substrate, etc. may be mentioned. As a material of the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.

  As the support, an inorganic and / or organic film may be provided on the substrate as described above. Examples of inorganic films include inorganic antireflective films (inorganic BARCs). An organic antireflective film (organic BARC) may be mentioned as the organic film.

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

  When the photosensitive resin composition contains a compound that generates an imidazole compound by (D) heating, the pattern formed by the above method may be heated. As heating temperature in this case, 150 degreeC or more is typically preferable, and 150-300 degreeC is more preferable.

Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples. Example 12 is to be read as a reference example.

[Examples 1 to 67 and Comparative Examples 1 to 8]
In Examples and Comparative Examples, as the component (A) which is an alkali-soluble resin, a resin consisting of one or more units selected from the following A1 to A11, a novolak resin, or a cardo resin was used. The mass ratio of each structural unit in the resin used as component (A) is described in Tables 1 to 3.
In the case where the component (A) is a novolac resin or a cardo resin, the composition ratio is described as 100 in the column of "novolac resin" or "cardo resin".
Moreover, when component (A) contains a copolymer resin consisting of one or more units selected from the following A1 to A11 and a cardo resin, the composition ratio of the column of "cardo resin" is described as 100. The component ratio of each structural unit is described in Tables 1 to 3 so that the total of the component ratio of each structural unit contained in the copolymer resin is 100.
In this case, when preparing the photosensitive resin composition, a copolymer resin and a cardo resin were used as a copolymer resin: cardo resin at a mass ratio of 30:60.

  As a novolak resin, formaldehyde is used as a condensing agent with respect to mixed phenols of m-cresol / p-cresol = 60/40 as the proportion (molar ratio) of preparation of m-cresol and p-cresol, and oxalic acid catalyst The novolak resin obtained by subjecting the novolac resin obtained by the condensation reaction using a conventional method to a fractional treatment with a water-methanol mixed solvent, a Mw 5000 novolak resin was used.

  As cardo resin, resin (R1) obtained according to the following synthesis example was used.

[Resin (R1) Synthesis Example]
First, in a 500 ml four-necked flask, 235 g of bisphenol fluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethyl ammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid The solution was heated and dissolved at 90 to 100.degree. C. while blowing air at a rate of 25 ml / min. Next, the solution was gradually heated while keeping the solution cloudy, and was completely dissolved by heating to 120 ° C. At this time, the solution gradually became clear and viscous, but stirring was continued. During this time, the acid value was measured, and heating and stirring were continued until it was less than 1.0 mg KOH / g. It took 12 hours for the acid value to reach the target value. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by following formula (a-4) of colorless and transparent solid.

  Subsequently, 600 g of 3-methoxybutyl acetate is added to 307.0 g of the bisphenol fluorene type epoxy acrylate thus obtained and dissolved, and then 80.5 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide are dissolved. The mixture was mixed, heated gradually, and reacted at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain a resin (R1). The disappearance of the acid anhydride group was confirmed by IR spectrum. In addition, this resin (R1) is corresponded to resin represented by said Formula (a-1).

  In Examples and Comparative Examples, a resin having a tetrahydro-2H-pyran-2-yl-oxy group as a group represented by the formula (I), or a resin to be compared with the resin was used as the component (B) .

As the component (B), a resin consisting of one or more units selected from the following B1 to B8 was used. The mass ratio of each structural unit in the resin used as the component (B) is described in Tables 1 to 3.

In the examples, as (B ′) other non-alkali soluble resin (component (B ′)) other than the component (B), it comprises one or more units selected from the following B′1 to B′5: Resin was used. The mass ratio of each structural unit in the resin used as the component (B ') is described in Tables 1 to 3.

In Examples and Comparative Examples, the compound of the following formula was used as a compound which generates an acid or a radical by the action of light which is the component (C).

In Examples and Comparative Examples, the compounds D1 and D2 of the following formula were used as the compound (D) which generates an imidazole compound by heating.

(Preparation of photosensitive resin composition)
The solid content concentration of the components (A), (B), (B '), (C), and (D) components described in Tables 4 to 6 is such that the solid content concentration is 25 mass%, It was made to melt | dissolve in PGMEA and the photosensitive resin composition of each Example and the comparative example was obtained. With respect to the photosensitive resin compositions of the respective examples and comparative examples, the sensitivity, the pattern dimension in the case of forming a pattern after laying the photosensitive resin film, and the pattern shape were evaluated according to the following method. In addition, also about any evaluation item, the case where heating after exposure (PEB) was performed, and the case where it did not perform was evaluated. The evaluation results are shown in Tables 7-9. In Comparative Examples 1 and 2, no pattern was formed unless PEB was performed, and therefore, the pattern dimensions and pattern shape after being placed in the case where PEB was not performed were not evaluated. Further, in Comparative Example 4, no pattern could be formed regardless of the presence or absence of PEB, so the pattern dimensions and pattern shape after being placed were not evaluated. Moreover, since Example 16, 17, 38, 39 changed the light source, comparison with the other example of sensitivity evaluation was not performed.

<Sensitivity evaluation>
The photosensitive resin composition of each Example and Comparative Example was applied onto a silicon wafer with a film thickness capable of forming a pattern with a film thickness of 3 μm to form a photosensitive resin film. Prebaking was performed on the formed photosensitive resin film at 100 ° C. for 120 seconds. After prebaking, the photosensitive resin film was exposed to light beams of the types described in Tables 7 to 9 while changing the exposure amount stepwise through a mask for hole pattern formation of 10 μm diameter. In the test under the conditions of post-exposure heating (PEB), the exposed photosensitive resin film was heated at 100 ° C. for 120 seconds. Then, the exposed photosensitive resin film with or without PEB was developed using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 ° C. for 30 seconds. . Thereafter, the developed photosensitive resin film was washed with running water and blown with nitrogen to obtain a hole pattern.
Then, the minimum exposure amount required to form a hole pattern was determined, and used as an index of sensitivity. The results are shown in Tables 7 to 9 below.
○: 50mJ / cm ² or less △: 50mJ / cm ² ultra 300mJ / cm ² or less ×: 300mJ / cm ² more than

<Evaluation of dimensions after placement>
In the dimensional evaluation after placing, the photosensitive resin film was exposed with the lowest exposure amount measured in the sensitivity evaluation, and a hole pattern having holes of 10 μm diameter was formed by the same method as the sensitivity evaluation.
In the case where PEB is not performed, immediately after exposure, the diameter of holes in the pattern formed by developing the photosensitive resin film and the photosensitive resin film are developed by developing the photosensitive resin film one hour after exposure (after being placed) The difference with the diameter of the hole in the pattern was determined.
When PEB is performed, the diameter of the holes in the pattern formed by developing the photosensitive resin film immediately after exposure and PEB, and one hour after exposure and PEB (after being placed), the photosensitive resin film The difference with the diameter of the hole in the pattern formed by development was determined.
Based on the difference between the diameters of holes in the pattern when the photosensitive resin film is placed and when it is not placed, the pattern dimensions after placement are evaluated according to the following criteria. It was judged.
○: 0.5 μm or less Δ: more than 0.5 μm 1 μm or less ×: 1 μm or more

<Pattern shape evaluation>
A hole pattern having holes with a diameter of 10 μm was formed by the same method as in the conditions for not placing a photosensitive resin film in the dimensional evaluation after placing.
From an electron microscope observation image of the cross section of the formed hole, the taper angle which is an acute angle was determined among the angles formed by the surface of the silicon wafer and the side surface of the hole pattern. The closer the taper angle is to 90 °, the better the cross-sectional shape of the hole is a rectangular shape, and the better the pattern shape.
Using the obtained taper angle, the quality of the pattern shape was judged according to the following criteria.
:: 80 ° or more ○: 70 ° or more and less than 80 ° ×: less than 70 °

  According to Tables 1 to 9, it has an alkali-soluble resin (A) and a functional group represented by the formula (I), and in the exposed state has a hydrophilic group having a predetermined structure (B) It turns out that the photosensitive resin composition of the Example containing resin of a component is highly sensitive. Moreover, when using the photosensitive resin composition of an Example from Tables 1-9, even if it forms a pattern after laying down a photosensitive resin film, a pattern of a desired dimension can be formed and it heats after exposure. It can be seen that a pattern of good shape can be formed.

  According to Comparative Examples 1, 2, and 4, when the photosensitive resin composition does not contain the component (A) which is an alkali-soluble resin, the sensitivity in the case where heating after exposure is not performed is significantly reduced. It can be seen that the composition can not be used to form a pattern of the desired shape. Further, in this case, it is understood from Comparative Example 4 that the sensitivity in the case of performing heating after exposure is also significantly reduced depending on the composition of the resin of the component (B).

  According to Comparative Examples 3 and 8, while the resin of the component (B) contained in the photosensitive resin composition has the functional group represented by the formula (I), the hydrophilicity of the predetermined structure in the exposed state It can be seen that the sensitivity in the case of not carrying out the post-exposure heating is significantly reduced when it does not have a sexulent group. Further, in this case, depending on the composition of the resin of the component (B) (that is, the composition having no group represented by general formulas (II-1) to (II-3) even after exposure) is desired. It can be seen that the pattern of the shape can not be formed.

  According to Comparative Example 5, when the photosensitive resin composition does not contain the resin of the component (B), it is understood that the sensitivity of the photosensitive resin composition is extremely low, and a pattern having a desired shape can not be formed.

  According to Comparative Example 6, the resin of the component (B) contained in the photosensitive resin composition does not have a functional group represented by the formula (I), and a hydrophilic group having a predetermined structure in an exposed state It is understood that the sensitivity of the photosensitive resin composition and the shape of the pattern to be formed are deteriorated.

  According to Comparative Example 7, the photosensitive resin composition does not contain the component (A) which is an alkali-soluble resin, contains a large amount of the functional group represented by the formula (I), and has a predetermined exposed state. It can be seen that when the resin of component (B) having a hydrophilic group of the structure is included, the sensitivity is significantly reduced.

Claims (11)

A photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a non-alkali-soluble resin,
The (B) non-alkali soluble resin is
A linear polymer which can be produced by polymerizing a monomer having an unsaturated double bond by reaction between unsaturated double bonds, or a linear polymer obtained by chemically modifying the linear polymer,
The following formula (III-1):

(In the formula (III-1), X ¹ is a trivalent organic group derived from a monomer having an unsaturated double bond, and R ¹⁰ is a group represented by the following formulas (II-1) to (II-2) ):
-R ⁴ -OH (II-1)
_{^{- (R 5 -O) m -R}} 6 ··· (II-2)
(In Formula (II-1), R ⁴ is an alkylene group having 1 to 20 carbon atoms.
In formula (II-2), R ⁵ is an alkylene group having 2 to 4 carbon atoms, R ⁶ is a hydrogen atom, and m is an integer of 2 to 20. Plural R ⁵ in the formula (II-2) may be the same or different. )
It is a group selected from the group represented by )
A structural unit represented by
The following formula (III-2):

(In Formula (III-2), X ² is a trivalent organic group derived from a monomer having an unsaturated double bond, and R ¹⁵ is a group represented by the following Formula (I):

(In formula (I), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by —O— or —S—, and R ² and R ³ are each independently And a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -O- or -S-, and R ¹ and R ² may combine with each other to form a ring, and R ² and R ² And R ³ may combine with each other to form a ring).
And the following formulas (IV-3) to (IV-4):
-R ⁴ -O-R ¹³ -C (= O) -O-R ¹⁶ (IV-3)
_{^{- (R 5 -O) m -R}} 14 -C (= O) -O-R 16 ··· (IV-4)
In formulas (IV-3) to (IV-4), R ⁴ is an alkylene group having 1 to 20 carbon atoms, R ⁵ is an alkylene group having 2 to 4 carbon atoms, and R ¹³ is divalent R ¹⁴ is a divalent organic group, and the terminal partial structure —OR ¹⁶ is a group represented by the above formula (I).
It is a group selected from the group represented by )
The photosensitive resin composition containing the polymer which consists of a structural unit represented by these.   A photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a non-alkali-soluble resin,
  The (B) non-alkali soluble resin has the following formula (I):

(In the formula (I), R ¹ Is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -O- or -S-; ² And R ³ Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -O- or -S-; ¹ And R ² And may combine with each other to form a ring, R ² And R ³ And may be bonded to each other to form a ring. )
With a group represented by
  When the photosensitive resin composition is exposed, all or a part of the group represented by the formula (I) in the (B) non-alkali soluble resin is deprotected to be converted to an OH group, ,
  The deprotected (B) non-alkali soluble resin contained in the exposed photosensitive resin composition has the following formulas (II-1) to (II-3):
-R ⁴ -OH (II-1)
-(R ⁵ -O) _m -R ⁶ ... (II-2)
-(R ⁷ -SO ₂ ) _n -R ⁸ ... (II-3)
(In the formula (II-1), R ⁴ Is an alkylene group having 1 to 20 carbon atoms. In the formula (II-2), R ⁵ Is an alkylene group having 2 to 4 carbon atoms, and R ⁶ Is a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, or -R ⁹ -C (= O) -O-H [R ⁹ Is a divalent organic group], and m is an integer of 2 to 20. In the formula (II-3), R ⁷ Is an alkylene group having 1 to 4 carbon atoms, and R ⁸ Is a hydrocarbon group having 1 to 50 carbon atoms, and n is an integer of 1 to 20. Several R in Formula (II-2) ⁵ May be the same or different. When n is an integer of 2 to 20 in formula (II-3), a plurality of R in formula (II-3) ⁷ May be the same or different. )
And at least one of the groups represented by
  The photosensitive resin composition is further subjected to (D) heating by the following formula (D1):

(In the formula (D1), R ^d1 , R ^d2 , And R ^d3 Each independently represents 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, a sulfonato group, a phosphinyl group, a phosphonato group, or an organic group. )
The photosensitive resin composition containing the compound which generate | occur | produces the imidazole compound represented by these.   A photosensitive resin composition comprising (A) an alkali-soluble resin and (B) a non-alkali-soluble resin,
  The (A) alkali-soluble resin contains (A4) cardo resin,
  The (B) non-alkali soluble resin has the following formula (I):

(In the formula (I), R ¹ Is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -O- or -S-; ² And R ³ Each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by -O- or -S-; ¹ And R ² And may combine with each other to form a ring, R ² And R ³ And may be bonded to each other to form a ring. )
With a group represented by
  When the photosensitive resin composition is exposed, all or a part of the group represented by the formula (I) in the (B) non-alkali soluble resin is deprotected to be converted to an OH group, ,
  The deprotected (B) non-alkali soluble resin contained in the exposed photosensitive resin composition has the following formulas (II-1) to (II-3):
-R ⁴ -OH (II-1)
-(R ⁵ -O) _m -R ⁶ ... (II-2)
-(R ⁷ -SO ₂ ) _n -R ⁸ ... (II-3)
(In the formula (II-1), R ⁴ Is an alkylene group having 1 to 20 carbon atoms. In the formula (II-2), R ⁵ Is an alkylene group having 2 to 4 carbon atoms, and R ⁶ Is a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, or -R ⁹ -C (= O) -O-H [R ⁹ Is a divalent organic group], and m is an integer of 2 to 20. In the formula (II-3), R ⁷ Is an alkylene group having 1 to 4 carbon atoms, and R ⁸ Is a hydrocarbon group having 1 to 50 carbon atoms, and n is an integer of 1 to 20. Several R in Formula (II-2) ⁵ May be the same or different. When n is an integer of 2 to 20 in formula (II-3), a plurality of R in formula (II-3) ⁷ May be the same or different. )
The photosensitive resin composition which has at least 1 sort (s) of group represented by these. The photosensitive resin composition is further subjected to (D) heating by the following formula (D1):

(In formula (D1), R ^d1 , R ^d2 and R ^d3 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 sulfonato group, a phosphinyl group, a phosphonato group, or an organic group)
The photosensitive resin composition of Claim 1 or 3 containing the compound which generate | occur | produces the imidazole compound represented by these. The compound which generates the imidazole compound represented by said Formula (D1) by said (D) heating is a following formula (D2):

(In formula (D2), R ^d1 , R ^d2 and R ^d3 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, And each of R ^d4 and R ^d5 independently represents 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, and a sulfonato group, a phosphinyl group, a phosphonato group or an organic group. Sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonato group, or organic group, and R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R ^d10 each independently represent a hydrogen atom , Halogen atom, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitro And a sulfino group, a sulfino group, a sulfo group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, and R ^d6 , R ^d7 , R ^d8 , R ^d9 , and R Two or more of ^d10 may combine to form a cyclic structure, and may include a heteroatom bond.)
The photosensitive resin composition of Claim 2 or 4 which is a compound represented by these. The compound which generates the imidazole compound represented by said Formula (D1) by said (D) heating is a following formula (D4):

(In formula (D4), R ^d1 , R ^d2 and R ^d3 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, .R ^d12 indicating a phosphinyl group, a phosphono group, or an organic group represents a hydrogen atom or an alkyl group, R ^d13 represents an aromatic group which may have a substituent group, R ^d14 is have a substituent Represents an alkylene group which may
The photosensitive resin composition of Claim 2 or 4 which is a compound represented by these.   The (B) non-alkali soluble resin is a linear polymer which can be formed by polymerizing a monomer having unsaturated double bonds by reaction between unsaturated double bonds, or the linear polymer is chemically modified A linear polymer,
  The (B) non-alkali soluble resin has the following formula (III-1):

(In the formula (III-1), X ¹ Is a trivalent organic group derived from a monomer having an unsaturated double bond, ¹⁰ Is a group represented by the following formulas (II-1) to (II-3):
-R ⁴ -OH (II-1)
-(R ⁵ -O) _m -R ⁶ ... (II-2)
-(R ⁷ -SO ₂ ) _n -R ⁸ ... (II-3)
(In the formula (II-1), R ⁴ Is an alkylene group having 1 to 20 carbon atoms. In the formula (II-2), R ⁵ Is an alkylene group having 2 to 4 carbon atoms, and R ⁶ Is a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, or -R ⁹ -C (= O) -O-H [R ⁹ Is a divalent organic group], and m is an integer of 2 to 20. In the formula (II-3), R ⁷ Is an alkylene group having 1 to 4 carbon atoms, and R ⁸ Is a hydrocarbon group having 1 to 50 carbon atoms, and n is an integer of 1 to 20. Several R in Formula (II-2) ⁵ May be the same or different. When n is an integer of 2 to 20 in formula (II-3), a plurality of R in formula (II-3) ⁷ May be the same or different. )
And the following formulas (II-6) to (II-7):
-R ⁴ -OR ¹³ -C (= O) -O-R ¹¹ ... (II-6)
-(R ⁵ -O) _m -R ¹⁴ -C (= O) -O-R ¹² ... (II-7)
(In the formula (II-6), R ⁴ Is an alkylene group having 1 to 20 carbon atoms, and R ¹¹ Is a protective group which can be deprotected when the photosensitive resin composition is exposed, R ¹³ Is a divalent organic group,
In the formula (II-7), R ⁵ Is an alkylene group having 2 to 4 carbon atoms, and a plurality of R ⁵ And m may be the same or different, m is an integer of 2 to 20, and R ¹² Is a protective group which can be deprotected when the photosensitive resin composition is exposed, R ¹⁴ Is a divalent organic group. )
It is a group selected from the group represented by )
And a structural unit represented by the following formula (III-2):

(In the formula (III-2), X ² Is a trivalent organic group derived from a monomer having an unsaturated double bond, ¹⁵ Is a group represented by the formula (I) and the following formulas (IV-3) to (IV-4):
-R ⁴ -OR ¹³ -C (= O) -O-R ¹⁶ ... (IV-3)
-(R ⁵ -O) _m -R ¹⁴ -C (= O) -O-R ¹⁶ ... (IV-4)
A group selected from the groups represented by
In the formulas (IV-3) to (IV-4), R ⁴ , R ⁵ , R ¹³ , R ¹⁴ Is the same as above, and the terminal partial structure -OR ¹⁶ Is a group represented by the above formula (I). )
The photosensitive resin composition of Claim 2 or 3 containing the structural unit represented by these.   The photosensitive resin composition according to any one of claims 1 to 7, wherein the photosensitive resin composition further contains a compound that generates an acid or a radical by the action of (C) light.   The photosensitive resin composition according to any one of claims 1 to 8, wherein the (A) alkali-soluble resin is a resin having an unsaturated double bond and / or an epoxy group. The photosensitive resin composition according to any one of claims 1 to 9 , further comprising (B ') another non-alkali soluble resin which is a non-alkali soluble resin other than the (B) non-alkali soluble resin. With respect to the total of the mass of the (A) alkali-soluble resin, the mass of the (B) non-alkali-soluble resin, and the mass of the (B ′) other non-alkali-soluble resin in the photosensitive resin composition The photosensitive resin composition of Claim 10 whose ratio of the mass of said (A) alkali-soluble resin is 50 mass% or more.