JP2015176124A - positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which has high radiation sensitivity, is excellent in development adhesion, and is capable of forming a fine pattern and reducing the amount of outgassing generated after curing, a cured film comprising the composition, and use of the cured film.SOLUTION: The photosensitive resin composition of the present invention contains an alkali-soluble resin (A) containing at least one functional group selected from the group consisting of a carboxyl group and a sulfone group, a compound (B) which generates an acid upon irradiation with active rays having a wavelength of 300 nm or more, and at least one basic compound (C) selected from the group consisting of nitrogen-containing heterocyclic compounds represented by formulae (c1)-(c3).

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, the present invention relates to a positive photosensitive resin composition suitably used for an interlayer insulating film in an organic electroluminescence (organic EL) element or the like, a cured film made of the composition, and a use of the cured film.

  Thin film transistors (TFT) type liquid crystal display elements, organic EL display elements, organic EL lighting, magnetic head elements, integrated circuit elements, solid-state image sensors and other electronic components are generally used to insulate between wirings arranged in layers. An interlayer insulating film is provided. As the material for forming the interlayer insulating film, a photosensitive or radiation-sensitive resin composition (hereinafter referred to as these) is preferable because it has a small number of steps for obtaining a required pattern shape and has sufficient flatness. Are collectively referred to as “photosensitive resin composition”) (see Patent Document 1 and Patent Document 2).

  As a conventional material for forming an interlayer insulating film, a combination of an acrylic resin and a quinone diad (Patent Document 3), a combination of a phenol resin and a quinone diazide (Patent Document 4), and the like are known. However, the conventional material has a problem that outgas is generated by the heating process after the film formation, and the TFT and the light emitting element are deteriorated.

  In recent years, display devices such as liquid crystal display elements and organic EL display elements tend to make pixels finer in order to display full high-definition images, and accordingly, wiring is made finer and more complicated. When forming a fine pattern using a photosensitive material, the exposure amount is generally reduced, but if the exposure amount is too small, the pattern is easily peeled off. Therefore, in forming a fine pattern, it is important that the photosensitive resin composition has high photosensitivity and excellent development adhesion after exposure.

JP 2001-354822 A JP 2001-343743 A JP-A-2005-320542 JP 2003-255546 A

  An object of the present invention is a photosensitive resin composition having high photosensitivity, excellent development adhesion, capable of forming a fine pattern, and capable of reducing the amount of outgas generation after curing, and the composition And a use of the cured film.

  As a result of intensive studies to solve the above problems, the present inventor has achieved high photosensitivity by using a photosensitive resin composition containing a specific alkali-soluble resin, a specific photoacid generator, and a specific basic compound. The present inventors have found that improvement in development adhesion and reduction of outgas can be realized, and the present invention has been completed. That is, the present invention includes the following aspects, for example.

  [1] An alkali-soluble resin (A) containing at least one functional group selected from the group consisting of a carboxyl group and a sulfone group, a compound (B) that generates an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more, A photosensitive resin composition comprising at least one basic compound (C) selected from the group consisting of nitrogen-containing heterocyclic compounds represented by the following formulas (c1) to (c3).

式（ｃ１）〜（ｃ３）中、Ｒ¹は、独立に炭素数１〜８のアルキル基、モノアルキルアミノ基、ジアルキルアミノ基、メルカプト基、ヒドロキシル基、シアノ基、ホルミル基、炭素数６〜１８の置換もしくは非置換の芳香族炭化水素基、炭素数４〜１８の置換もしくは非置換の脂環式炭化水素基、または炭素数４〜１８の置換もしくは非置換の複素環基を示し、隣接する２つのＲ¹が結合して環構造を形成してもよく；Ｘ¹は、炭素原子または窒素原子を示し、Ｘ¹が炭素原子の場合、Ｘ¹は前記Ｒ¹を有していてもよく；Ｘ²は、炭素原子、窒素原子または酸素原子を示し、Ｘ²が炭素原子または窒素原子の場合、Ｘ²は前記Ｒ¹を有していてもよく；ｐは０〜４の整数を示し；ｑは０〜３の整数を示し；ｒは０〜６の整数を示し；ｓは０または２を示す。

In formulas (c1) to (c3), R ¹ is independently an alkyl group having 1 to 8 carbon atoms, a monoalkylamino group, a dialkylamino group, a mercapto group, a hydroxyl group, a cyano group, a formyl group, or 6 to 6 carbon atoms. 18 substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted alicyclic hydrocarbon group having 4 to 18 carbon atoms, or substituted or unsubstituted heterocyclic group having 4 to 18 carbon atoms, adjacent to each other R ¹ may be bonded to form a ring structure; X ¹ represents a carbon atom or a nitrogen atom, and when X ¹ is a carbon atom, X ¹ may have R ¹ Well, X ² represents a carbon atom, a nitrogen atom or an oxygen atom, and when X ² is a carbon atom or a nitrogen atom, X ² may have R ¹ ; p is an integer of 0 to 4 Q represents an integer of 0 to 3; r represents an integer of 0 to 6; s represents 0 or It is shown.

  [2] The alkali-soluble resin (A) is (a-1) at least one compound selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, and an unsaturated sulfonic acid, and (a-2) At least one radical polymerizable compound selected from the group consisting of a radical polymerizable compound having an oxiranyl group and a radical polymerizable compound having an oxetanyl group; and (a-3) the above (a-1) and (a-2) The photosensitive resin composition according to item [1], wherein the photosensitive resin composition is produced using a radically polymerizable compound other than (1).

[3] The photosensitive resin composition according to any one of items [1] to [2], wherein X ¹ is a carbon atom.
[4] The photosensitive resin composition according to any one of items [1] to [3], wherein X ² is a nitrogen atom.

  [5] The basic compound (C) is pyridine, 4-dimethylaminopyridine, 4-phenylpyridine, 2,4′-dipyridyl, 5- (4-aminophenyl) -2,4′-bipyridine, imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylbenzimidazole, 1,8-diazabicyclo [5.4.0] -undecene-7, and 1,5-diazabicyclo [4.3 The photosensitive resin composition according to any one of items [1] to [4], comprising at least one compound selected from the group consisting of .0] -nonene-5.

  [6] Items [1] to [5], wherein the content of the basic compound (C) is 0.001 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). The photosensitive resin composition of any one of these.

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the alkali-soluble resin (A) has a weight average molecular weight of 3,000 to 100,000. .
[8] A cured film formed using the photosensitive resin composition according to any one of items [1] to [7].

[9] A semiconductor element comprising the cured film according to item [8].
[10] An electronic device comprising the cured film according to item [8].
[11] A display device comprising the semiconductor element according to item [9] or the electronic device according to item [10].

[12] An organic EL device comprising the photosensitive resin composition according to item [8].
[13] An organic EL display device comprising the organic EL element according to item [12].
[14] An organic EL lighting device comprising the organic EL element according to item [12].

  The photosensitive resin composition of the present invention has high photosensitivity, excellent development adhesion, can form a fine pattern, and can reduce the amount of outgas generated after curing. Therefore, if the photosensitive resin composition of the present invention is used, a highly reliable organic EL display element or the like can be provided.

Hereinafter, the photosensitive resin composition according to the present invention will be described in detail.
The photosensitive resin composition of the present invention generates an acid by irradiation with an alkali-soluble resin (A) containing at least one functional group selected from the group consisting of a carboxyl group and a sulfone group, and an actinic ray having a wavelength of 300 nm or more. And a basic compound (C) selected from the group consisting of specific nitrogen-containing heterocyclic compounds (B) (hereinafter also referred to as “photoacid generator (B)”). . In the present specification, “(meth) acryl” or the like means either or both of “acryl” and “methacryl”.

[Alkali-soluble resin (A)]
The alkali-soluble resin (A) used in the present invention is not particularly limited as long as it contains at least one functional group selected from the group consisting of a carboxyl group and a sulfone group and is soluble in an alkaline aqueous solution. ,
(A-1) at least one compound selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride and an unsaturated sulfonic acid;
(A-2) at least one radical polymerizable compound selected from the group consisting of a radical polymerizable compound having an oxiranyl group and a radical polymerizable compound having an oxetanyl group;
(A-3) A resin produced using a radical polymerizable compound other than (a-1) and (a-2).

<Component (a-1)>
Examples of the unsaturated carboxylic acid in component (a-1) include monocarboxylic acids such as (meth) acrylic acid, crotonic acid and 4-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid Dicarboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] mono [(meth) Acryloyloxyalkyl] esters; mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.

As an unsaturated carboxylic acid anhydride in a component (a-1), the anhydride of the said dicarboxylic acid etc. are mentioned, for example.
Examples of the unsaturated sulfonic acid in component (a-1) include isoprene sulfonic acid, styrene-3-sulfonic acid, styrene-4-sulfonic acid, α-methylstyrene-3-sulfonic acid, and α-methylstyrene-4. -Sulphonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-[(meth) acryloyloxy] ethanesulfonic acid, allylalkylsulfosuccinic acid, and salts thereof.

  Among the examples of the component (a-1), acrylic acid, methacrylic acid, 2- (methacryloyloxy) ethanesulfonic acid and maleic anhydride are copolymerization reactivity, solubility in alkaline aqueous solution and easy availability. It is preferably used from the point of view.

  The said component (a-1) may be used individually by 1 type, or may be used in combination of 2 or more type. The content of the structural unit derived from the component (a-1) in the alkali-soluble resin (A) (hereinafter referred to as “structural unit (a-1)” and the same shall apply to other components) is the structural unit. Preferably it is 1-30 weight% with respect to the sum total of (a-1), (a-2), and (a-3), More preferably, it is 5-20 weight%. When the content of the structural unit (a-1) is within the above range, the actinic ray sensitivity and alkali developability of the composition can be enhanced.

<Component (a-2)>
Examples of the radically polymerizable compound having an oxiranyl group in the component (a-2) include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylic acid. Glycidyl, (meth) acrylic acid-3,4-epoxybutyl, acrylic acid-3-methyl-3,4-epoxybutyl, methacrylic acid-3-ethyl-3,4-epoxybutyl, (meth) acrylic acid-5 , 6-epoxyhexyl, methacrylic acid-5-methyl-5,6-epoxyhexyl, methacrylic acid-5-ethyl-5,6-epoxyhexyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethyl Acrylic acid-6,7-epoxyheptyl, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxy Cycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, 3,4-epoxycyclohexylbutyl (meth) acrylate, 3, Epoxy group-containing (meth) acrylic compounds such as 4-epoxycyclohexylhexyl (meth) acrylate;
o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl Vinyl benzyl glycidyl ethers such as benzyl glycidyl ether;
vinyl phenyl glycidyl ethers such as o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, p-vinyl phenyl glycidyl ether;
Etc.

  Examples of the radically polymerizable compound having an oxetanyl group in the component (a-2) include 3-[(meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-methyloxetane, 3- [(Meth) acryloyloxymethyl] -3-ethyloxetane, 3-[(meth) acryloyloxymethyl] -3-phenyloxetane, 3- [2- (meth) acryloyloxyethyl] oxetane, 3- [2- ( (Meth) acryloyloxyethyl] -3-ethyloxetane, 3- [2- (meth) acryloyloxyethyl] -3-ethyloxetane, 3- [2- (meth) acryloyloxyethyl] -3-phenyloxetane, 2- [(Meth) acryloyloxymethyl] oxetane, 2-[(meth) acryloyl Oxymethyl] -2-methyloxetane, 2-[(meth) acryloyloxymethyl] -2-ethyloxetane, 2-[(meth) acryloyloxymethyl] -2-phenyloxetane, 2- [2- (meth) acryloyl Oxetane group-containing (meth) acrylic group such as oxyethyl] oxetane, 2- [2- (meth) acryloyloxyethyl] -2-ethyloxetane, 2- [2- (meth) acryloyloxyethyl] -2-phenyloxetane Compounds and the like.

  Among the examples of the component (a-2), glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3- (methacryloyloxymethyl) -3-methyloxetane, 3- ( (Methacryloyloxymethyl) -3-ethyloxetane is preferable from the viewpoint of good copolymerization reactivity with other radical polymerizable monomers and good developability of the photosensitive resin composition.

  The said component (a-2) may be used individually by 1 type, or may be used in combination of 2 or more type. The content of the structural unit (a-2) in the alkali-soluble resin (A) is preferably 10 to 80 with respect to the total of the structural units (a-1), (a-2) and (a-3). % By weight, more preferably 20 to 60% by weight. When content of a structural unit (a-2) is the said range, the cure reactivity at the time of hardening of the coating film of a composition can be improved.

<Component (a-3)>
Examples of radical polymerizable compounds other than the components (a-1) and (a-2) include, for example:
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as (meth) acrylic acid t-butyl;
(Meth) acrylic acid cyclohexyl, (meth) acrylic acid-2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid-2- (Meth) acrylic acid alicyclic alkyl esters such as (tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxy) ethyl, isobornyl (meth) acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate and aralkyl esters of (meth) acrylic acid;
Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Unsaturation containing one oxygen atom such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, methacrylic acid (tetrahydro-2H-pyran) -2-yl, methacrylic acid [(tetrahydro-2H-pyran) -2-yl] methyl Hetero 5-membered ring methacrylate and unsaturated hetero 6-membered ring methacrylate;
4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyl Oxymethyl-2,2-diethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-cyclopentyl -1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4 -(Meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- ( (Ii) non-oxygen containing two oxygen atoms such as acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxybutyl-2-methyl-2-ethyl-1,3-dioxolane, etc. Saturated hetero five-membered ring (meth) acrylic acid ester;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, 4-isopropenylphenol;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate can be mentioned.

Among examples of the component (a-3), methyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tetrahydrofurfuryl methacrylate, methacrylic acid (Tetrahydro-2H-pyran) -2-yl, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, 1,3-butadiene, etc. However, it is preferable at the point which makes copolymerization reactivity and the developability of the photosensitive resin composition favorable.

  The said component (a-3) may be used individually by 1 type, or may be used in combination of 2 or more type. The content of the structural unit (a-3) in the alkali-soluble resin (A) is preferably 10 to 85 with respect to the total of the structural units (a-1), (a-2) and (a-3). % By weight, more preferably 30 to 70% by weight. When the content of the structural unit (a-3) is in the above range, the actinic ray sensitivity and alkali developability of the composition can be improved and the heat resistance of the coating film can be improved.

<Molecular weight of alkali-soluble resin (A)>
The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of the alkali-soluble resin (A) by GPC (gel permeation chromatography) is preferably 3,000 to 100,000, more preferably 5,000 to 50, 000. When Mw of alkali-soluble resin (A) is the said range, the radiation sensitivity and alkali developability of the photosensitive resin composition can be improved.

<Method for producing alkali-soluble resin (A)>
Although the manufacturing method of alkali-soluble resin (A) is not specifically limited, Preferably the said component (a-1), (a-2) and (a-3) is a polymerization initiator in a solvent. A method of radical copolymerization in the presence of.

  Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, and aromatic carbonizations. Examples include hydrogens, ketones, and other esters.

  As the polymerization initiator, those known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (methyl 2-methylpropionate), 2,2′-azobis- (2,4-dimethylvalero). Nitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and the like; benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t -Organic peroxides such as -butylperoxy) cyclohexane; and hydrogen peroxide.

  In the production of the alkali-soluble resin (A), a molecular weight adjusting agent can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan and thioglycolic acid; dimethylxanthogen Xanthogens such as sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

[Photoacid generator (B)]
The photoacid generator (B) used in the present invention is a compound that generates an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more. The photosensitive resin composition of this invention can be used as a positive photosensitive resin composition by including a photo-acid generator (B). The photoacid generator (B) is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with the actinic ray. The photoacid generator (B) is contained in the photosensitive resin composition in the form of a photoacid generator (hereinafter also referred to as “photoacid generator (B)”), which is a compound as described later. It may be in the form of a photoacid generating group incorporated as part of the soluble resin (A) or other polymer, or both forms.
Preferred photoacid generators (B) include, for example, quinonediazide compounds, oxime sulfonate compounds, sulfonimide compounds and the like.

<Quinonediazide compound>
As the quinonediazide compound, a compound obtained by esterifying a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid halide is preferable. Examples of the compound having a phenolic hydroxyl group include compounds in which the ortho position and the para position of the phenolic hydroxyl group are each independently a hydrogen atom or a substituent represented by the following formula (1).

式（１）中、Ｒ²、Ｒ³及びＲ⁴は、それぞれ独立して、炭素数１〜１０のアルキル基、カルボキシル基、フェニル基又は置換フェニル基である。但し、Ｒ²、Ｒ³及びＲ⁴のうち２つ以上が結合して環構造を形成してもよい。

In formula (1), R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group. However, two or more of R ² , R ³ and R ⁴ may be bonded to form a ring structure.

In the substituent represented by the above formula (1), when R ² , R ³ and R ⁴ are alkyl groups having 1 to 10 carbon atoms, part or all of the hydrogen atoms of the alkyl group are substituted. It may be. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, and n-heptyl. Group, n-octyl group, trifluoromethyl group, 2-carboxyethyl group and the like. Moreover, a hydroxyl group etc. are mentioned as a substituent of a substituted phenyl group. Examples of the ring structure formed by R ² , R ^3, and R ⁴ include a cyclopentane structure, a cyclohexane structure, an adamantane structure, and a fluorene structure.

  Examples of the compound having a phenolic hydroxyl group include a compound group represented by the following formula.

上記ナフトキノンジアジドスルホン酸ハライドとしては、４−ナフトキノンジアジドスルホン酸ハライドまたは５−ナフトキノンジアジドスルホン酸ハライドを用いることができる。４−ナフトキノンジアジドスルホン酸ハライドから得られたエステル化合物（キノンジアジド化合物）は、ｉ線（波長３６５ｎｍ）領域に吸収を持つため、ｉ線露光に適している。また、５−ナフトキノンジアジドスルホン酸ハライドから得られたエステル化合物（キノンジアジド化合物）は、広範囲の波長領域に吸収が存在するため、広範囲の波長での露光に適している。特に好ましいキノンジアジド化合物の例として、４，４’−［１−［４−［１−（４−ヒドロキシフェニル）−１−メチルエチル］フェニル］エチリデン］ビスフェノールと１，２−ナフトキノンジアジド−５−スルホン酸クロリドとのエステル、１，１，１−トリ（ｐ−ヒドロキシフェニル）エタンと１，２−ナフトキノンジアジド−５−スルホン酸クロリドとのエステルを挙げることができる。

As the naphthoquinone diazide sulfonic acid halide, 4-naphthoquinone diazide sulfonic acid halide or 5-naphthoquinone diazide sulfonic acid halide can be used. An ester compound (quinonediazide compound) obtained from 4-naphthoquinonediazidesulfonic acid halide is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. In addition, an ester compound (quinonediazide compound) obtained from 5-naphthoquinonediazidesulfonic acid halide is suitable for exposure in a wide range of wavelengths because absorption exists in a wide range of wavelengths. Examples of particularly preferred quinonediazide compounds include 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfone. Mention may be made of esters with acid chlorides and esters of 1,1,1-tri (p-hydroxyphenyl) ethane with 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

<Oxime sulfonate compound>
As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (2) is preferable.

式（２）中、Ｒ^B1は、アルキル基、シクロアルキル基またはアリール基であり、これらの基の水素原子の一部または全部が置換基で置換されていてもよい。

In Formula (2), R ^B1 is an alkyl group, a cycloalkyl group, or an aryl group, and part or all of the hydrogen atoms of these groups may be substituted with a substituent.

In the above formula (2), the alkyl group of R ^B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ^B1 includes an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group). Group) and the like. The aryl group for R ^B1 is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ^B1 may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate group represented by the above formula (2) is more preferably an oxime sulfonate compound represented by the following formula (2-1).

式（２−１）において、Ｒ^B1は式（２）におけるＲ^B1と同義である。Ｘは、アルキル基、アルコキシ基またはハロゲン原子である。ｍは０〜３の整数を示し、ｍが２または３であるとき、複数のＸは同一でも異なっていてもよい。Ｘとしてのアルキル基は、炭素数１〜４の直鎖状または分岐状アルキル基が好ましい。

In the formula (2-1), R ^B1 has the same meaning as R ^B1 in the formula (2). X is an alkyl group, an alkoxy group, or a halogen atom. m represents an integer of 0 to 3, and when m is 2 or 3, a plurality of X may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  In the above formula (2-1), the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. In particular, in the formula (2-1), a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

  Specific examples of the oxime sulfonate compound represented by the above formula (2) include, for example, compounds (2-1-i) represented by the following formulas (2-1-i) to (2-1-v), respectively. , Compound (2-1-ii), compound (2-1-iii), compound (2-1-iv), compound (2-1-v) and the like.

これらは、１種単独で用いても、２種類以上を組み合わせて用いてもよく、成分（Ｂ）としての他の光酸発生剤と組み合わせて使用することもできる。

These may be used singly or in combination of two or more, and may be used in combination with other photoacid generators as component (B).

  Compound (2-1-i) [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], Compound (2-1-ii) [(5H-octylsulfonyl) Oxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (2-1-iii) [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) ) Acetonitrile], Compound (2-1-iv) [(5-p-Toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] and Compound (2-1-v) [ (5-n-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-( - methoxyphenyl) acetonitrile] can be obtained as a commercial product.

<Sulfonimide compound>
Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl). Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenyl Reimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2 2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-en-2,3-dicarboxylimide N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide, N- (campus Phonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2 , 3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicar Boxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene- 2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [ 2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bi Chlo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6- Oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethyl Sulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (phenylsulfonyloxy) naphthyl dicarboxylimide, N- ( 2-trifluoromethylphenylsulfonyloxy) naphthyl dicar Xylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluoro) Butylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxyl Examples include silimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, and the like.

  A photo-acid generator (B) may be used individually by 1 type, or may be used in combination of 2 or more type. As content of the photo-acid generator (B) in the photosensitive resin composition of this invention, Preferably it is 0.1-30 mass parts with respect to 100 mass parts of alkali-soluble resin (A), More preferably, it is 1- 20 parts by mass. When the content of the photoacid generator (B) is in the above range, the actinic ray sensitivity of the photosensitive resin composition can be optimized and a cured film can be formed.

[Basic compound (C)]
The basic compound (C) used in the present invention is at least one selected from the group consisting of nitrogen-containing heterocyclic compounds represented by the following formulas (c1) to (c3). Hereinafter, the compounds represented by the formulas (c1), (c2) and (c3) are also referred to as “compound (c1)”, “compound (c2)” and “compound (c3)”, respectively.

式（ｃ１）〜（ｃ３）中、Ｒ¹は、独立に炭素数１〜８のアルキル基、モノアルキルアミノ基、ジアルキルアミノ基、メルカプト基、ヒドロキシル基、シアノ基、ホルミル基、炭素数６〜１８の置換もしくは非置換の芳香族炭化水素基、炭素数４〜１８の置換もしくは非置換の脂環式炭化水素基、または炭素数４〜１８の置換もしくは非置換の複素環基を示し、隣接する２つのＲ¹が結合して環構造を形成してもよい。

In formulas (c1) to (c3), R ¹ is independently an alkyl group having 1 to 8 carbon atoms, a monoalkylamino group, a dialkylamino group, a mercapto group, a hydroxyl group, a cyano group, a formyl group, or 6 to 6 carbon atoms. 18 substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted alicyclic hydrocarbon group having 4 to 18 carbon atoms, or substituted or unsubstituted heterocyclic group having 4 to 18 carbon atoms, adjacent to each other Two R ¹ may be bonded to form a ring structure.

X ¹ represents a carbon atom or a nitrogen atom, preferably a carbon atom. When X ¹ is a carbon atom, X ¹ is may have the R ^1.
X ² represents a carbon atom, a nitrogen atom or an oxygen atom, preferably a nitrogen atom. When X ² is a carbon atom or a nitrogen atom, X ² may have R ¹ .

  p represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, q represents an integer of 0 to 3, r represents an integer of 0 to 6, and preferably 0. It is an integer of ˜2, more preferably 0 or 1, and s represents 0 or 2.

Examples of the alkyl group having 1 to 8 carbon atoms in R ¹ include straight groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, and n-octyl group. Examples thereof include branched alkyl groups such as chain alkyl groups, i-propyl groups, i-butyl groups, t-butyl groups, neopentyl groups, 2-hexyl groups, and 3-hexyl groups.

Examples of the monoalkylamino group in R ¹ include a methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, and an n-hexylamino group.

Examples of the dialkylamino group in R ¹ include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a di-n-butylamino group, and an N-methyl-N-cyclohexylamino group.

Examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 18 carbon atoms in R ¹ include a phenyl group, a p-methylphenyl group, a p-aminophenyl group, a p-phenyl-phenyl group, and pentamethylphenyl. Group, α-naphthyl group, β-naphthyl group, anthracenyl group, phenanthryl group, acenaphthyl group, phenalenyl group, tetramethylnaphthyl group, indanyl group, biphenylyl group and the like.

Examples of the substituted or unsubstituted alicyclic hydrocarbon group having 4 to 18 carbon atoms in R ¹ include a cyclobutane group, a cyclopentane group, a cyclohexane group, and a 2,3,4,5,6-pentamethylcyclohexyl group. , Cycloheptane group, cyclooctane group, norbornane group, 2-methylnorbornane group, adamantane group, 2-methyladamantane group and the like.

Examples of the substituted or unsubstituted heterocyclic group having 4 to 18 carbon atoms in R ¹ include a pyridyl group, a pyrimidyl group, a furyl group, a thienyl group, a tetrahydrofuryl group, a dioxolanyl group, a benzoxazol-2-yl group, Examples thereof include a tetrahydropyranyl group, a pyrrolidyl group, an imidazolicyl group, a pyrazolysyl group, a thiazolysyl group, an inchazolysyl group, an oxazolyl group, an isoxazolyl group, a piperidyl group, a piperazyl group, and a morpholinyl group.

  Examples of the compound (c1) include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 4-dimethylaminopyridine, 2-phenylpyridine, 4-phenylpyridine, 2,4. Examples include '-dipyridyl and 5- (4-aminophenyl) -2,4'-bipyridine.

  Examples of the compound (c2) include imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1,2-dimethylimidazole, 4-methyl-2-phenyl. Examples include imidazole, benzimidazole, and 2-phenylbenzimidazole.

Examples of the compound (c3) include 1,8-diazabicyclo [5.4.0] -undecene-7 and 1,5-diazabicyclo [4.3.0] -nonene-5.
Among the examples of the basic compound (C), pyridine, 4-dimethylaminopyridine, 4-phenylpyridine, 2,4′-dipyridyl, 5- (4-aminophenyl) -2,4′-bipyridine, imidazole , 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylbenzimidazole, 1,8-diazabicyclo [5.4.0] -undecene-7, and 1,5-diazabicyclo [4. 3.0] -Nonene-5 is preferred.

  A basic compound (C) may be used individually by 1 type, or may be used in combination of 2 or more type. As content of the basic compound (C) in the photosensitive resin composition of this invention, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of alkali-soluble resin (A), More preferably, it is 0.002. ~ 3 parts by mass. When content of a basic compound (C) exists in the said range, while improving the curing reactivity at the time of hardening, the outgas after hardening can be reduced.

[Other ingredients]
The photosensitive resin composition of the present invention is a component other than the above components (A) to (C), as long as it does not impair the effects of the present invention. An agent (F), a crosslinking agent, a dehydrating agent, an adhesion assistant, an ultraviolet absorber, a plasticizer, a thickener, an acid diffusion controller, a storage stabilizer, an antifoaming agent, and the like may be contained.

<Surfactant (E)>
Surfactant (E) can be added to improve the applicability of the composition, reduce coating unevenness, and improve the developability of the actinic ray-irradiated area. Examples of such surfactant (E) include nonionic surfactants, fluorine surfactants, silicone surfactants, and the like.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and the like Polyoxyethylene aryl ethers; polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; 57, no. (Meth) acrylic acid copolymers such as 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hex Fluoroalkanes such as fluorodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates Fluorine alkyl esters and the like.

  Commercially available fluorosurfactants include, for example, F-top EF301, 303, 352 (manufactured by Shin-Akita Kasei), MegaFuck F171, 172, 173 (manufactured by Dainippon Ink), Florard FC430, 431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC-101, 102, 103, 104, 105, 106 (Asahi Glass), FTX-218 (Neos), and the like.

  Examples of the silicone surfactant include SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400FLUID (manufactured by Toray Dow Corning Silicone), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  As content when using the said surfactant (E), 0.01 to 10 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A), 0.05 to 5 mass parts is preferable. Less than the mass part is more preferable. By making content of surfactant (E) into the said range, the applicability | paintability of a composition can be optimized.

<Sensitizer (F)>
A sensitizer (F) can be added in order to further improve the sensitivity of the composition. The sensitizer (F) absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer (F) in an electronically excited state is brought into contact with the photoacid generator (B), and effects such as electron transfer, energy transfer, and heat generation occur, whereby the photoacid generator (B) is chemically Changes and decomposes to produce acid.

As the sensitizer (F), compounds having an absorption wavelength in the region of 350 nm to 450 nm, for example, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7 -Polynuclear aromatics such as dimethoxyanthracene and 9,10-dipropyloxyanthracene; xanthenes such as fluorescein, eosin, erythrosine, rhodamine B, and rose bengal; xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, etc. Xanthones; cyanines such as thiacarbocyanine and oxacarbocyanine;
Merocyanines such as merocyanine and carbomerocyanine; rhodocyanines; oxonols; thiazines such as thionine, methylene blue and toluidine blue; acridines such as acridine orange, chloroflavin and acriflavine; acridone, 10-butyl-2-chloroacryl Acridones such as Don; Anthraquinones such as Anthraquinone; Squariums such as Squarium; Styryls; Base styryls such as 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole; 7-Diethylamino 4- Methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [l] benzopyrano [6,7,8-ij] quinolizine-11-non, etc. And coumarins That.

  Among the examples of the sensitizer (F), polycyclic aromatics, acridones, styryls, base styryls, coumarins, and xanthones are preferable, and xanthones are more preferable. Of the xanthones, diethylthioxanthone and isopropylthioxanthone are particularly preferred.

  As content of the said sensitizer (F), 0.1 to 10 mass parts is preferable with respect to 100 mass parts of alkali-soluble resin (A), and 0.5 to 5 mass parts is preferable. More preferred. Sensitivity can be improved more by making content of a sensitizer into the said range.

[Preparation of photosensitive resin composition]
The photosensitive resin composition of the present invention is prepared, for example, by mixing the above components (A) to (C) and, if necessary, other components in a solvent (D) at a predetermined ratio. It is preferable to be used in a state dissolved or dispersed in

  The solid content concentration of the photosensitive resin composition of the present invention (referring to the ratio of the mass of the polymer contained in the polymer solution to the total mass of the polymer solution) depends on the purpose of use and the desired film thickness. Although it can set arbitrarily, Preferably it is 5 mass%-50 mass%, More preferably, it is 10 mass%-40 mass%, More preferably, it is 15 mass%-35 mass%. Actually, in the concentration range, a solid content concentration (a component other than the solvent in the composition solution) corresponding to a desired film thickness value or the like is set.

The solution-like photosensitive resin composition thus prepared is preferably used for forming a cured film after being filtered using a Millipore filter having a pore diameter of about 0.5 μm.
As the solvent (D) that can be used for the preparation of the photosensitive resin composition of the present invention, a solvent that can uniformly dissolve or disperse each component and does not react with each component is preferably used. Examples of such a solvent (D) include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether. Examples include propionates, aromatic hydrocarbons, ketones and esters.

Examples of alcohols include benzyl alcohol and diacetone alcohol;
Examples of ethers include dialkyl ethers such as tetrahydrofuran, diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether;
Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like;
Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, and the like;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 Examples include -propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

  Among these solvents, ethers such as dialkyl ethers, diethylene glycol alkyls, etc. from the viewpoints of excellent solubility or dispersibility, non-reactivity with each component, and facilitating film formation. Ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve Acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene Recall monoethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate , Ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate, methyl 3-methoxypropionate and ethyl 2-methoxypropionate are preferred. These solvents may be used alone or in combination of two or more.

  In addition to the above-mentioned solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol High-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate and the like can also be used in combination.

[Curing film]
The cured film of this invention is formed using the photosensitive resin composition of this invention mentioned above. The method for forming the cured film of the present invention is as follows.
(1) The process of forming the coating film of the photosensitive resin composition on a board | substrate,
(2) a step of irradiating at least a part of the coating film formed in step (1) with actinic rays;
(3) The process which develops the coating film irradiated with the actinic ray at the process (2), and the process of heating the coating film developed at the (4) process (3) are included. According to such a method for forming a cured film, since the photosensitive resin composition of the present invention is used, it is possible to form a cured film having excellent development adhesion and capable of forming a fine pattern, and The generation of outgas in the heating process during the formation of the cured film can be reduced. Hereinafter, each process is explained in full detail.

<Step (1)>
In this step, after the photosensitive linear resin composition of the present invention is applied on a substrate, the coating surface is preferably removed by heating (pre-baking) the coated surface to form a coating film. Examples of substrate materials that can be used include glass, quartz, silicon, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof.

  The method for applying the photosensitive resin composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like can be employed. . Of these, spin coating or slit die coating is preferred. Although the conditions for pre-baking (PB) vary depending on the types and blending ratios of each component, the temperature of PB is preferably 70 ° C. to 120 ° C., and the time of PB is preferably about 1 minute to 10 minutes. .

<Step (2)>
In this step, at least a part of the coating film formed in step (1) is exposed to an actinic ray for exposure. When exposing, it exposes normally through the photomask which has a predetermined pattern. Examples of the exposure light include ultraviolet light and visible light, and light with a wavelength of 200 to 500 nm is preferable, and light with a wavelength of 300 to 500 nm is preferably used. The irradiation amount of actinic rays varies depending on the type of each component in the photosensitive resin composition, the blending ratio, the thickness of the coating film, etc., but when using ultraviolet light having a wavelength of 350 nm as exposure light, the exposure amount is usually 10 ˜1500 mJ / cm ² . Examples of the light source include a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a halogen lamp, and a laser.

<Step (3)>
In this step, the coating film exposed in the step (2) is developed to remove unnecessary portions (irradiated portions of actinic rays) and form a predetermined pattern. As the developer used in the development step, an aqueous alkali (basic compound) solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. .

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution. The concentration of alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the photosensitive resin composition, but is preferably about 10 seconds to 180 seconds. Following such development processing, for example, after washing with running water for 30 seconds to 90 seconds, a desired pattern can be formed by air drying with compressed air or compressed nitrogen.

<Process (4)>
In this step, the thin film patterned in step (3) is heated (post-baked) using a heating device such as a hot plate or oven to accelerate the curing reaction of the alkali-soluble resin (A) and cure. You can get things. As heating temperature, it is about 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device. For example, when the heating process is performed on a hot plate, the heating time is 5 to 30 minutes, and when the heating process is performed in an oven, the heating time is 30 to 90 minutes. it can. The step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the target cured film can be formed on the surface of the substrate.

[Usage]
Since the cured film of the present invention is formed using the photosensitive resin composition of the present invention, general properties such as surface hardness are sufficiently satisfied and the heat resistance is excellent. Therefore, the photosensitive resin composition or cured film of the present invention is suitably used for semiconductor elements, liquid crystal display elements, organic EL elements, electronic devices, and the like, and these include liquid crystal displays, organic EL displays, electronic papers, and the like. It is suitably used for display devices and organic EL lighting devices.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.
The Mw of the polymer was measured by GPC under the following conditions.
Apparatus: GPC-101 (Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined with mobile phase: tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodispersed polystyrene.

[Synthesis of alkali-soluble resin (A)]
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of methacrylic acid, 40 parts by weight of methyl methacrylate and 50 parts by weight of glycidyl methacrylate were charged, and after the atmosphere was replaced with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). Mw of the copolymer (A-1) was 8000. In addition, the solid content concentration of the obtained polymer solution was 34.7% by mass.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of methacrylic acid, 40 parts by weight of methyl methacrylate and 50 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate were charged, and after nitrogen substitution, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). Mw of the copolymer (A-2) was 10,000. Further, the solid content concentration of the obtained polymer solution was 34.9% by mass.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by mass of 2- (methacryloyloxy) ethanesulfonic acid, 40 parts by mass of methyl methacrylate and 50 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were charged, and after nitrogen substitution, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). Mw of the copolymer (A-3) was 20000. Further, the solid content concentration of the obtained polymer solution was 34.0% by mass.

[Preparation of positive photosensitive resin composition]
Components other than the alkali-soluble resin (A) used in Examples and Comparative Examples are shown below.
<Acid generator (B)>
(B-1) 4,4 ′-[1- [4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (48%) and 1,2-naphthoquinonediazide-5 Ester (B-2) 9,10-dimethoxyanthracene-2-sulfonic acid with sulfonic acid chloride [also known as 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid chloride] (52%) -P-nitrobenzyl ester <basic compound (C)>
(C-1) 4-dimethylaminopyridine (C-2) imidazole (C-3) 2-phenylbenzimidazole (C-4) 1-methylimidazole (C-5) 2-methylimidazole (C-6) 1 , 2-Dimethylimidazole (C-7) pyridine (C-8) 2,4′-dipyridyl (C-9) 4-phenylpyridine (C-10) 5- (4-aminophenyl) -2,4′- Bipyridine (C-11) 1,8-diazabicyclo (5.4.0) -undecene-7
(C-12) 1,5-diazabicyclo (4.3.0) -nonene-5
<Other basic compounds (c)>
(C-1) t-Butyl-4-hydroxy-1-piperidinecarboxylate <Solvent (D)>
(D-1) Diethylene glycol ethyl methyl ether (D-2) methyl 3-methoxypropionate <Surfactant (E)>
(E-1) Silicone-based surfactant (“SH8400 FLUID” manufactured by Toray Dow Corning)
<Sensitizer (F)>
(F-1) Isopropylthioxanthone.

[Example 1]
As a photoacid generator (B), a solution containing the copolymer (A-1) obtained in Synthesis Example 1 (an amount corresponding to 100 parts by mass (solid content) of the copolymer (A-1)) ( B-1) 17 parts by mass, 0.01 part by mass of (C-1) as basic compound (C), 300 parts by mass of (D-1) as solvent (D), (E-) as surfactant (E) 1) A positive photosensitive resin composition (S-1) was prepared by mixing 0.1 part by mass and filtering through a membrane filter having a pore size of 0.05 μm.

[Examples 2 to 23 and Comparative Examples 1 to 4]
The positive photosensitive compositions (S-2) to (S-23) and (CS-) were operated in the same manner as in Example 1 except that the types and blending amounts of the respective components were as described in Table 1. 1) to (CS-4) were prepared as Examples 2 to 23 and Comparative Examples 1 to 4, respectively.

[Evaluation]
Using the positive photosensitive resin compositions (S-1) to (S-23) and (CS-1) to (CS-4) prepared in Examples and Comparative Examples, the positive photosensitive resin compositions were used as follows. The various properties of the conductive resin composition and its coating film or interlayer insulating film were evaluated. The results are shown in Table 2.

<Thickness change rate>
The positive photosensitive resin composition is applied onto a 4-inch non-alkali glass wafer using a slit die coater “TR6321005-CL” and prebaked at 90 ° C. or 110 ° C. for 2 minutes to obtain a film thickness of 3.0 μm. The coating film was formed. Subsequently, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. by a puddle method. The development time was 70 seconds. Subsequently, it was washed with ultrapure water for 1 minute and then dried. The film thickness after development was measured, and the film thickness change rate (%) was calculated from the following formula.
Film thickness change rate after development (%) = (film thickness after development / film thickness before development) × 100

<Actinic light sensitivity>
A film having a thickness of 3.0 μm was formed on a 4-inch non-alkali glass wafer in the same manner as in the evaluation of the film thickness change rate. Subsequently, after using a Canon exposure machine “PLA-501F” and irradiating the coating film with a variable exposure amount through a 1-60% halftone mask having a pattern of 5 mm × 10 mm, Development was performed at 25 ° C. with a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 25 ° C. The development time was 70 seconds. Next, running water was washed with ultrapure water for 1 minute and then dried to form a pattern on a 4-inch glass wafer. At this time, the exposure amount at which the pattern was completely dissolved was examined.

<Development adhesion>
A film having a thickness of 3.0 μm was formed on a 4-inch non-alkali glass wafer in the same manner as in the evaluation of the film thickness change rate. Subsequently, using a Canon exposure device “PLA-501F”, the exposure dose is varied with respect to the coating film through a mask having a 1 to 150 μm line-and-space (one-to-one) pattern. After the irradiation, a pattern was formed by the same operation as in the evaluation of the radiation sensitivity. At this time, the minimum line width of the line pattern closely contacting without peeling was examined at the exposure amount at which the space pattern was completely dissolved.

<Outgas amount>
By operating in the same manner as the evaluation of the film thickness change rate, a coating film was formed on a 4-inch non-alkali glass wafer so that the film thickness after post-baking was 2.0 μm, washed with water after development, and dried. . Subsequently, the glass wafer was cut to 1 × 5 cm and then post-baked at 230 ° C. for 30 minutes. The cut glass wafer is baked at 230 ° C. for 15 minutes using a P & T-GCMS apparatus consisting of “JTD-505” manufactured by Nippon Analysis Co., Ltd. and “GC-QP-2010” manufactured by Shimadzu Corporation, and chromatogram Was measured. Using the peak area of the measured chromatogram and the peak area of the standard sample C18, the outgas amount was calculated from the following formula.
Outgas amount (μg) = (peak area of chromatogram / peak area of standard sample) × introduction amount of standard sample

<Storage stability>
When the photosensitive resin composition was filled in a 30 ml screw tube and stored at 40 ° C., the number of days on which fluidity could be confirmed visually was examined.

  As is apparent from the results in Table 2, in Examples 1 to 23 using the positive photosensitive resin composition of the present invention, good adhesiveness was obtained with the same sensitivity as compared with the compositions of Comparative Examples 1 to 4. It was found that the amount of outgas after post-baking was reduced.

Claims (14)

An alkali-soluble resin (A) containing at least one functional group selected from the group consisting of a carboxyl group and a sulfone group, a compound (B) that generates an acid upon irradiation with actinic rays having a wavelength of 300 nm or more, and the following formula ( A photosensitive resin composition comprising at least one basic compound (C) selected from the group consisting of nitrogen-containing heterocyclic compounds represented by c1) to (c3).

[In the formulas (c1) to (c3),
R ¹ is independently an alkyl group having 1 to 8 carbon atoms, a monoalkylamino group, a dialkylamino group, a mercapto group, a hydroxyl group, a cyano group, a formyl group, or a substituted or unsubstituted aromatic carbon atom having 6 to 18 carbon atoms. A hydrogen group, a substituted or unsubstituted alicyclic hydrocarbon group having 4 to 18 carbon atoms, or a substituted or unsubstituted heterocyclic group having 4 to 18 carbon atoms, wherein two adjacent R ¹ groups are bonded to form a ring; May form a structure,
X ¹ represents a carbon atom or a nitrogen atom, and when X ¹ is a carbon atom, X ¹ may have R ¹ ,
X ² represents a carbon atom, a nitrogen atom or an oxygen atom, and when X ² is a carbon atom or a nitrogen atom, X ² may have the above R ¹ ,
p represents an integer of 0 to 4, q represents an integer of 0 to 3, r represents an integer of 0 to 6, and s represents 0 or 2. ] The alkali-soluble resin (A) is
(A-1) at least one compound selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride and an unsaturated sulfonic acid;
(A-2) at least one radical polymerizable compound selected from the group consisting of a radical polymerizable compound having an oxiranyl group and a radical polymerizable compound having an oxetanyl group;
(A-3) The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is produced using a radical polymerizable compound other than (a-1) and (a-2). The photosensitive resin composition according to claim ^1, wherein X ¹ is a carbon atom. The photosensitive resin composition according to claim 1, wherein X ² is a nitrogen atom.   The basic compound (C) is pyridine, 4-dimethylaminopyridine, 4-phenylpyridine, 2,4′-dipyridyl, 5- (4-aminophenyl) -2,4′-bipyridine, imidazole, 1-methyl. Imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylbenzimidazole, 1,8-diazabicyclo [5.4.0] -undecene-7, and 1,5-diazabicyclo [4.3.0] The photosensitive resin composition according to any one of claims 1 to 4, comprising at least one compound selected from the group consisting of -nonene-5.   The content of the basic compound (C) is 0.001 to 5 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). The photosensitive resin composition as described.   The photosensitive resin composition according to any one of claims 1 to 6, wherein the alkali-soluble resin (A) has a weight average molecular weight of 3,000 to 100,000.   A cured film formed using the photosensitive resin composition according to claim 1.   A semiconductor device comprising the cured film according to claim 8.   An electronic device comprising the cured film according to claim 8.   A display device comprising the semiconductor device according to claim 9 or the electronic device according to claim 10.   An organic EL device comprising the photosensitive resin composition according to claim 8.   An organic EL display device comprising the organic EL element according to claim 12.   An organic EL lighting device comprising the organic EL element according to claim 12.