JP2020077642A - Photosensitive resin composition, organic el element barrier rib, and organic el element - Google Patents

Abstract

To provide a high-sensitivity photosensitive resin composition which is used for forming a barrier rib of an organic EL element and contains a colorant.SOLUTION: The photosensitive resin composition for an organic EL element barrier rib according to one embodiment contains: (A) a binder resin; (B) at least one organic low-molecular compound which has a molar volume of 130 cm/mol or less and is selected from the group consisting of an aromatic carboxylic acid and a compound having a plurality of phenolic hydroxyl groups; (C) a radiation-sensitive compound; and (D) a colorant selected from the group consisting of a black dye and a black pigment.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition for an organic EL device partition, an organic EL device partition using the same, and an organic EL device. More specifically, the present invention relates to a photosensitive resin composition for a partition wall of an organic EL element containing a black colorant, an partition wall for an organic EL element using the same, and an organic EL element.

  BACKGROUND ART In a display device such as an organic EL display (OLED), a partition material is used at intervals between colored patterns in a display area or edges around a display area in order to improve display characteristics. In manufacturing an organic EL display device, in order to prevent pixels of an organic material from contacting each other, partition walls are first formed, and pixels of the organic material are formed between the partition walls. This partition is generally formed by photolithography using a photosensitive resin composition and has an insulating property. Specifically, a photosensitive resin composition is applied onto a substrate using a coating device, and after removing volatile components by means such as heating, exposure is performed through a mask, and then, in the case of a negative type, an unexposed portion is exposed. In the case of a positive type, the exposed portion is developed by removing it with a developing solution such as an alkaline aqueous solution, and the obtained pattern is heat-treated to form a partition wall (insulating film). Next, an organic material that emits light of three colors of red, green, and blue is formed between the partition walls by an inkjet method or the like to form a pixel of the organic EL display device.

  In recent years, due to the miniaturization of display devices and the diversification of contents to be displayed in the field, higher performance and higher definition of pixels have been demanded. For the purpose of enhancing the contrast and improving the visibility of a display device, an attempt has been made to impart a light-shielding property to a partition material by using a coloring agent. However, when the partition wall material has a light-shielding property, the photosensitive resin composition tends to have low sensitivity, and as a result, the exposure time becomes longer and the productivity may be reduced. Therefore, the photosensitive resin composition used for forming the partition wall material containing the colorant is required to have higher sensitivity.

  Patent Document 1 (Japanese Patent Laid-Open No. 2001-281440) discloses a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting high light-shielding properties by heat treatment after exposure. To Titanium Black.

  Patent Document 2 (Japanese Unexamined Patent Publication No. 2002-116536) discloses a carbon black in a radiation-sensitive resin composition containing an [A] alkali-soluble resin, a [B] 1,2-quinonediazide compound, and a [C] colorant. Describes a method for blackening the partition wall material.

  Patent Document 3 (JP 2010-237310A) discloses a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting light-shielding properties by heat treatment after exposure. A composition containing a thermal dye is described.

JP, 2001-281440, A JP 2002-116536 A JP, 2010-237310, A

  In the photosensitive resin composition used for forming the colored partition wall material, it is necessary to use a considerable amount of the colorant in order to sufficiently enhance the light-shielding property of the cured film. When a large amount of the colorant is used in this way, the radiation applied to the film of the photosensitive resin composition is absorbed by the colorant, so that the effective intensity of the radiation in the film is reduced and the photosensitive resin composition Is not sufficiently exposed, and as a result, the pattern formability deteriorates.

  In forming the partition walls in the organic EL element, it is important that the material forming the partition walls is highly sensitive from the viewpoint of productivity and the like. However, when a black photosensitive resin composition containing a colorant is used, it is necessary to increase the exposure time, for example, because exposure failure occurs under the normally used exposure conditions, which reduces productivity. It was a factor to make.

  It is common to use ghi rays for exposure by using an ultrahigh pressure mercury lamp including g rays (wavelength 436 nm), h rays (wavelength 405 nm) and i rays (wavelength 365 nm) in the partition wall material application of organic EL devices. Is. However, there is a demand for exposure using only i-rays because the manufacturer's facilities and equipment are limited. When only i-line is used for exposure, the total irradiation energy is reduced, so that the reaction rate of the radiation-sensitive compound, for example, the photo-acid generator is decreased, and the insoluble residue of the binder resin in the development process, the deterioration of pattern formability, etc. May occur. Therefore, it is desired to further increase the sensitivity of the photosensitive resin composition containing a colorant and increase the degree of freedom of radiation used for exposure.

  The present invention has been made based on the above circumstances, and an object thereof is to provide a highly sensitive photosensitive resin composition containing a colorant, which is used for forming partition walls of an organic EL element. ..

  The present inventors can increase the sensitivity of the photosensitive resin composition by adding a specific organic low molecular weight compound to the photosensitive resin composition containing a colorant, specifically, at the time of development. It has been found that it is possible to provide a photosensitive resin composition having excellent alkali developability and pattern formability by promoting dissolution of a binder resin and utilizing low irradiation energy exposure, for example, exposure using only i-line. It was

（式（１）において、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して水素原子、炭素原子数１〜５のアルキル基、式（２）

（式（２）において、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して水素原子、炭素原子数１〜５のアルキル基、炭素原子数５〜１０のシクロアルキル基又は炭素原子数６〜１２のアリール基であり、式（２）の＊は、芳香環を構成する炭素原子との結合部を表す。）で表されるアルケニル基、炭素原子数１〜２のアルコキシ基又は水酸基であり、かつＲ^１、Ｒ^２及びＲ^３の少なくとも１つは式（２）で表されるアルケニル基であり、Ｑは式−ＣＲ^４Ｒ^５−で表されるアルキレン基、炭素原子数５〜１０のシクロアルキレン基、芳香環を有する２価の有機基、脂環式縮合環を有する２価の有機基又はこれらを組み合わせた２価基であり、Ｒ^４及びＲ^５は、それぞれ独立して水素原子、炭素原子数１〜５のアルキル基、炭素原子数２〜６のアルケニル基、炭素原子数５〜１０のシクロアルキル基又は炭素原子数６〜１２のアリール基である。）
の構造単位を有するポリアルケニルフェノール樹脂、
（ｂ）式（３）

（式（３）において、Ｒ^１１は水素原子又は炭素原子数１〜５のアルキル基であり、ａは１〜４の整数、ｂは１〜４の整数であり、ａ＋ｂは２〜５の範囲内であり、Ｒ^１２は水素原子、メチル基、エチル基及びプロピル基からなる群より選択される少なくとも１種である。）
で表される構造単位を有するヒドロキシポリスチレン樹脂誘導体、
（ｃ）エポキシ基及びフェノール性水酸基を有するアルカリ水溶液可溶性樹脂、及び
（ｄ）アルカリ可溶性官能基を有する重合性単量体とその他の重合性単量体のアルカリ水溶液可溶性共重合体
からなる群より選択される少なくとも１種を含有する、［１］〜［１２］のいずれかに記載の感光性樹脂組成物。
［１４］
［１］〜［１３］のいずれかに記載の感光性樹脂組成物の硬化物を含む有機ＥＬ素子隔壁。
［１５］
［１］〜［１３］のいずれかに記載の感光性樹脂組成物の硬化物を含む有機ＥＬ素子。 That is, the present invention includes the following aspects.
[1]
(A) binder resin,
(B) at least one organic low molecular compound selected from the group consisting of aromatic carboxylic acids and compounds having a plurality of phenolic hydroxyl groups, having a molar volume of 130 cm ³ / mol or less,
A photosensitive resin composition for organic EL device partition walls, comprising (C) a radiation-sensitive compound, and (D) a colorant selected from the group consisting of black dyes and black pigments.
[2]
The photosensitive resin composition according to [1], wherein the organic low molecular weight compound (B) is an aromatic carboxylic acid having a pKa of 2.5 to 4.5.
[3]
The photosensitive resin composition according to any one of [1] or [2], wherein the organic low molecular weight compound (B) is a compound having a plurality of phenolic hydroxyl groups having a pKa of 7.5 to 10.
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein groups other than a carboxy group and a phenolic hydroxyl group are not bonded to carbon atoms constituting the aromatic ring of the organic low molecular weight compound (B). ..
[5]
The compound having a plurality of phenolic hydroxyl groups is an aromatic polyol selected from the group consisting of catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol and phloroglucinol, [1] to [4] ] The photosensitive resin composition in any one of these.
[6]
The aromatic carboxylic acid is a polyvalent carboxylic acid selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, and trimesic acid; or 2,3-dihydroxybenzoic acid, 2, It is an aromatic hydroxycarboxylic acid selected from the group consisting of 4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, and gallic acid. The photosensitive resin composition according to any one of [1] to [5].
[7]
0.1 parts by mass to 20 parts by mass of the binder resin (A), the organic low-molecular compound (B), the radiation-sensitive compound (C) and the colorant (D) are used as a reference. The photosensitive resin composition according to any one of [1] to [6], which contains an organic low molecular compound (B).
[8]
The radiation-sensitive compound (C) is at least one photoacid generator selected from the group consisting of quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts, [1] to [7] The photosensitive resin composition according to any one of claims.
[9]
The photosensitive resin composition according to any one of [1] to [8], wherein the binder resin (A) has an alkali-soluble functional group.
[10]
1 part by mass to 70 parts by mass of the colorant, based on a total of 100 parts by mass of the binder resin (A), the organic low molecular weight compound (B), the radiation-sensitive compound (C) and the colorant (D). The photosensitive resin composition according to any one of [1] to [9], which contains (D).
[11]
5 parts by mass to 50 parts by mass of the radiation sensitive material based on 100 parts by mass of the binder resin (A), the organic low molecular weight compound (B), the radiation sensitive compound (C) and the colorant (D) in total. The photosensitive resin composition according to any one of [1] to [10], which contains a photoacid generator as the compound (C).
[12]
The photosensitive resin composition according to any one of [1] to [11], wherein the cured film of the photosensitive resin composition has an optical density (OD value) of 0.5 or more per 1 μm of film thickness.
[13]
The binder resin (A) is
(A) Formula (1)

(In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formula (2)

(In the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. Or an aryl group having 6 to 12 carbon atoms, wherein * in the formula (2) represents a bonding portion with a carbon atom constituting an aromatic ring), and an alkenyl group having 1 to 2 carbon atoms. An alkoxy group or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the formula (2), Q is an alkylene group represented by the formula —CR ⁴ R ⁵ —, A cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group combining these, and R ⁴ and R ⁵ are , Each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .. )
A polyalkenylphenol resin having a structural unit of
(B) Formula (3)

(In the formula (3), R ¹¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is an integer of 1 to 4, b is an integer of 1 to 4, and a + b is in the range of 2 to 5. And R ¹² is at least one selected from the group consisting of hydrogen atom, methyl group, ethyl group and propyl group.)
A hydroxypolystyrene resin derivative having a structural unit represented by
From the group consisting of (c) an alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group, and (d) an alkali aqueous solution-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. The photosensitive resin composition according to any one of [1] to [12], which contains at least one selected.
[14]
An organic EL device partition wall containing a cured product of the photosensitive resin composition according to any one of [1] to [13].
[15]
An organic EL device containing the cured product of the photosensitive resin composition according to any one of [1] to [13].

  ADVANTAGE OF THE INVENTION According to this invention, the highly sensitive photosensitive resin composition containing a coloring agent used for the partition formation of an organic EL element can be provided.

  The present invention will be described in detail below.

  In the present disclosure, “alkali-soluble” means that the photosensitive resin composition or the coating or cured coating thereof can be dissolved in an alkaline aqueous solution, for example, a 2.38 mass% tetramethylammonium hydroxide aqueous solution. The “alkali-soluble functional group” means a group that imparts such alkali-solubility to the photosensitive resin composition or the film or cured film thereof.

  In the present disclosure, “radical polymerizable functional group” refers to one or more ethylenically unsaturated groups, and “radical polymerizable compound” refers to a compound having one or more ethylenically unsaturated groups.

  In the present disclosure, “(meth) acrylic” means acrylic or methacrylic, and “(meth) acrylate” means acrylate or methacrylate.

The photosensitive resin composition according to one embodiment is selected from the group consisting of (A) a binder resin, (B) a molar volume of 130 cm ³ / mol or less, and an aromatic carboxylic acid and a compound having a plurality of phenolic hydroxyl groups. At least one organic low molecular compound, (C) a radiation-sensitive compound, and (D) a colorant selected from the group consisting of a black dye and a black pigment.

(A) Binder Resin The binder resin (A) is not particularly limited, but preferably has an alkali-soluble functional group and is alkali-soluble. The alkali-soluble functional group is not particularly limited, and examples thereof include a carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, and a mercapto group. A binder resin having two or more kinds of alkali-soluble functional groups may be used.

  Examples of the binder resin (A) include acrylic resin, polystyrene resin, epoxy resin, polyamide resin, phenol resin, polyimide resin, polyamic acid resin, polybenzoxazole resin, polybenzoxazole resin precursor, silicone resin, cyclic olefin polymer. , Cardo resins, derivatives of these resins, and those obtained by binding an alkali-soluble functional group to these resins. As the binder resin (A), it is also possible to use a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group. These resins can be used alone or in combination of two or more kinds. The binder resin (A) may have a radically polymerizable functional group. In one embodiment, the binder resin (A) has a (meth) acrylic group, an allyl group or a methallyl group as a radically polymerizable functional group.

In one embodiment, the binder resin (A) contains at least one selected from the following resin components (a) to (k).
(A) Polyalkenylphenol resin (b) Hydroxypolystyrene resin derivative (c) Alkaline aqueous solution-soluble resin having epoxy group and phenolic hydroxyl group (d) Polymerizable monomer having alkali-soluble functional group and other polymerizable monomer Aqueous alkaline solution-soluble copolymer (e) polyimide resin (f) polyamic acid resin (g) polybenzoxazole resin (h) polybenzoxazole resin precursor (i) silicone resin (j) cyclic olefin polymer (k) cardo resin

の構造単位を有することが好ましい。このような樹脂を含有することにより、得られる感光性樹脂組成物の現像特性を向上させるとともに、アウトガスを低減することができる。 (A) Polyalkenylphenol Resin A polyalkenylphenol resin can be obtained by converting a hydroxyl group of a known phenol resin into an alkenyl ether, and further subjecting the alkenyl ether group to Claisen rearrangement. Among them, formula (1)

It is preferable to have the structural unit of By containing such a resin, it is possible to improve the developing characteristics of the obtained photosensitive resin composition and reduce outgas.

（式（２）において、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して水素原子、炭素原子数１〜５のアルキル基、炭素原子数５〜１０のシクロアルキル基又は炭素原子数６〜１２のアリール基であり、式（２）の＊は、芳香環を構成する炭素原子との結合部を表す。）で表されるアルケニル基、炭素原子数１〜２のアルコキシ基又は水酸基であり、かつＲ^１、Ｒ^２及びＲ^３の少なくとも１つは式（２）で表されるアルケニル基であり、Ｑは式−ＣＲ^４Ｒ^５−で表されるアルキレン基、炭素原子数５〜１０のシクロアルキレン基、芳香環を有する２価の有機基、脂環式縮合環を有する２価の有機基又はこれらを組み合わせた２価基であり、Ｒ^４及びＲ^５は、それぞれ独立して水素原子、炭素原子数１〜５のアルキル基、炭素原子数２〜６のアルケニル基、炭素原子数５〜１０のシクロアルキル基又は炭素原子数６〜１２のアリール基である。式（１）の構造単位が１分子中に２つ以上存在するときは、それぞれの式（１）の構造単位は同一でも異なってもよい。 In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a formula (2).

(In the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. Or an aryl group having 6 to 12 carbon atoms, wherein * in the formula (2) represents a bonding portion with a carbon atom constituting an aromatic ring), and an alkenyl group having 1 to 2 carbon atoms. An alkoxy group or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the formula (2), Q is an alkylene group represented by the formula —CR ⁴ R ⁵ —, A cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group combining these, and R ⁴ and R ⁵ are , Each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .. When two or more structural units of formula (1) are present in one molecule, the respective structural units of formula (1) may be the same or different.

R ¹ , R ² and R ³ in the formula (1) are hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group represented by the formula (2), an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group. And at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the formula (2). In R ¹ , R ² and R ³ of the formula (1), specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec. -Butyl group, t-butyl group, n-pentyl group and the like can be mentioned. Specific examples of the alkoxy group having 1 to 2 carbon atoms include methoxy group and ethoxy group.

In the alkenyl group represented by the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 5 carbon atoms. A cycloalkyl group having 10 to 10 or an aryl group having 6 to 12 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like. Can be mentioned. Examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group and cycloheptyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group and a naphthyl group. It is preferable that R ⁶ , R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkenyl group represented by the formula (2) is preferably an allyl group or a methallyl group from the viewpoint of reactivity, more preferably the allyl group.

Most preferably, any one of R ¹ , R ² and R ³ is an allyl group or a methallyl group and the other two are hydrogen atoms.

Q in the formula (1) represents an alkylene group represented by the formula —CR ⁴ R ⁵ —, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, and an alicyclic condensed ring 2 It is a valent organic group or a divalent group obtained by combining these. R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a carbon atom having 6 to 6 carbon atoms. 12 aryl groups. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like. Can be mentioned. Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group. Examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group and cycloheptyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group and a naphthyl group. R ⁴ and R ⁵ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably both are hydrogen atoms.

で表される基等を挙げることができる。脂環式縮合環を有する２価の有機基の具体例として、ジシクロペンタジエニレン基等を挙げることができる。 Specific examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group and a cycloheptylene group. Specific examples of the divalent organic group having an aromatic ring include phenylene group, tolylene group, naphthylene group, biphenylene group, fluorenylene group, anthracenylene group, xylylene group, 4,4-methylenediphenyl group, formula (6)

And the like. Specific examples of the divalent organic group having an alicyclic condensed ring include a dicyclopentadienylene group and the like.

で表される構造単位を有するものが挙げられる。式（４）において、Ｒ^１、Ｒ^２及びＲ^３は式（１）と同様である。好ましいＲ^１、Ｒ^２及びＲ^３は、式（１）における好ましいＲ^１、Ｒ^２及びＲ^３と同様である。 When a polyalkenylphenol resin is used as the binder resin (A), a particularly preferable polyalkenylphenol resin from the viewpoints of alkali developability, outgassing, etc., wherein Q in the formula (1) is —CH ₂ —, that is, the formula (4) )

Those having a structural unit represented by In formula (4), R ¹ , R ² and R ³ are the same as in formula (1). Preferred ^R 1, ^{R 2} and ^{R 3} are the same as the preferred ^R 1, ^{R 2} and ^{R 3} in Formula (1).

で表される構造単位を有するポリアルケニルフェノール樹脂であることが特に好ましい。式（７）において、Ｒ^１ａ、Ｒ^２ａ及びＲ^３ａは、それぞれ独立して水素原子、炭素原子数１〜５のアルキル基である。好ましいＲ^１ａ、Ｒ^２ａ及びＲ^３ａは、式（１）における好ましいＲ^１、Ｒ^２及びＲ^３と同様である。 The structural unit represented by formula (1) or formula (4) is preferably 50 to 100 mol% in the polyalkenylphenol resin, more preferably 70 to 100 mol%, and further preferably 80 to 100 mol%. It is 100 mol%. It is preferable that the structural unit represented by the formula (1) or the formula (4) is 50 mol% or more in the polyalkenylphenol resin because the heat resistance is improved. The phenolic hydroxyl group in the polyalkenylphenol resin is ionized in the presence of the basic compound and can be dissolved in water. Therefore, from the viewpoint of alkali developability, the phenolic hydroxyl group needs to be present in a certain amount or more. Therefore, the polyalkenylphenol resin containing the structural unit represented by the formula (4) has the structural unit represented by the formula (4) and the formula (7).

A polyalkenylphenol resin having a structural unit represented by is particularly preferable. In formula (7), R ^1a , R ^2a, and R ^3a are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferred ^{R 1a, R 2a} and ^{R 3a} are the same as the preferred ^R 1, ^{R 2} and ^{R 3} in Formula (1).

  In a polyalkenylphenol resin having a structural unit represented by the formula (4) and a structural unit represented by the formula (7), the number of structural units represented by the formula (4) is x, and in the formula (7) When the number of structural units represented is y, 0.5 ≦ x / (x + y) <1, 0 <y / (x + y) ≦ 0.5, and x + y is preferably 2 to 50, more preferably Is 3 to 40, and more preferably 5 to 25.

  When a polyalkenylphenol resin is used as the binder resin (A), the polyalkenylphenol resin preferably has a number average molecular weight of 500 to 5,000, more preferably 800 to 3,000, and still more preferably 900 to 2,000. When the number average molecular weight is 500 or more, the alkali developing rate is appropriate and the dissolution rate difference between the exposed and unexposed areas is sufficient, so that the pattern resolution is good, and when it is 5000 or less, the alkali developing property is good. ..

の構造単位を有するヒドロキシポリスチレン樹脂誘導体を使用することもできる。このような樹脂を含有することにより、得られる感光性樹脂組成物の現像特性を向上させるとともに、アウトガスの低減にも寄与することができる。 (B) Hydroxypolystyrene resin derivative As the binder resin (A), the compound represented by the formula (3)

It is also possible to use a hydroxypolystyrene resin derivative having the structural unit of By containing such a resin, it is possible to improve the developing characteristics of the obtained photosensitive resin composition and contribute to the reduction of outgas.

In the formula (3), R ¹¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is an integer of 1 to 4, b is an integer of 1 to 4, and a + b is in the range of 2 to 5. And R ¹² is at least one selected from the group consisting of hydrogen atom, methyl group, ethyl group and propyl group.

で表される構造単位を有する共重合体であることが好ましい。 When a hydroxypolystyrene resin derivative is used as the binder resin (A), the structural unit represented by the formula (3) and the formula (5) from the viewpoints of alkali developability and outgassing.

It is preferably a copolymer having a structural unit represented by:

In the formula (5), R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c is an integer of 1 to 5.

  The hydroxypolystyrene resin derivative having the structural unit represented by the formula (3) and the hydroxypolystyrene resin derivative having the structural unit represented by the formula (3) and the structural unit represented by the formula (5) are, for example, Aromatic vinyl compounds having a phenolic hydroxyl group such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenylphenol, either alone or in combination of two types. It can be obtained by reacting a part of the polymer or copolymer obtained by polymerizing the above by a known method with formaldehyde by a known method or further by reacting with formaldehyde.

  As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene or m-hydroxystyrene is preferably used.

  When a hydroxypolystyrene resin derivative is used as the binder resin (A), the hydroxypolystyrene resin derivative preferably has a number average molecular weight of 1,000 to 20,000, more preferably 3,000 to 10,000, and further preferably 4,000 to 9000. When the number average molecular weight is 1,000 or more, it is suitable as a resin for the photosensitive material because the alkali solubility is suitable, and when it is 20,000 or less, the coatability and the developability are good.

(C) Alkaline Aqueous Solution Soluble Resin Having Epoxy Group and Phenolic Hydroxyl Group As the binder resin (A), an alkaline aqueous solution soluble resin having an epoxy group and a phenolic hydroxyl group can be used. Such an alkaline aqueous solution-soluble resin is, for example, an epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as “epoxy compound”) and a carboxy of a hydroxybenzoic acid compound. It can be obtained by reacting a group. When the alkaline aqueous solution-soluble resin has an epoxy group, it can form a crosslink by reacting with a phenolic hydroxyl group during heating, and can improve the chemical resistance and heat resistance of the coating film. The phenolic hydroxyl group contributes to the solubility in the alkaline aqueous solution at the time of development.

An example of the reaction in which one of the epoxy groups of the epoxy compound and the carboxy group of the hydroxybenzoic acid compound react to form a compound having a phenolic hydroxyl group is shown in the following reaction formula 1.

Examples of the compound having at least two epoxy groups in one molecule include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin. , Heterocyclic epoxy resins and the like. These epoxy compounds may have two or more epoxy groups in one molecule, and may be used alone or in combination of two or more. Since these compounds are thermosetting, it is common knowledge for those skilled in the art that their structures cannot be uniquely described due to differences in the presence or absence of epoxy groups, types of functional groups, degree of polymerization and the like. Formula (9) shows an example of the structure of the novolac type epoxy resin. In the formula (9), for example, R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms or a hydroxyl group, and m is an integer of 1 to 50.

  Examples of the phenol novolac type epoxy resin include EPLICLON (registered trademark) N-770 (manufactured by DIC Corporation) and jER (registered trademark) -152 (manufactured by Mitsubishi Chemical Corporation). Examples of the cresol novolac type epoxy resin include EPICLON (registered trademark) N-695 (manufactured by DIC Corporation) and EOCN (registered trademark) -102S (manufactured by Nippon Kayaku Co., Ltd.). Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resins such as jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), YD-128 (trade name, manufactured by Nippon Steel & Sumitomo Metal Corporation). , JER (registered trademark) 806 (manufactured by Mitsubishi Chemical Co., Ltd.), YDF-170 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like. Examples of the biphenol type epoxy resin include jER (registered trademark) YX-4000 and jER (registered trademark) YL-6121H (manufactured by Mitsubishi Chemical Corporation). Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (trade name, manufactured by DIC Corporation). Examples of the alicyclic epoxy resin include EHPE (registered trademark) -3150 (manufactured by Daicel Chemical Industries, Ltd.). Examples of the heterocyclic epoxy resin include TEPIC (registered trademark), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.) and the like.

  The compound having at least two epoxy groups in one molecule is preferably a cresol novolac type epoxy resin. A photosensitive resin composition containing an alkali aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group derived from a cresol novolac type epoxy resin is excellent in pattern formability, easy to adjust alkali solubility, and less outgas. ..

  The hydroxybenzoic acid compound is a compound in which at least one of 2- to 6-positions of benzoic acid is substituted with a hydroxyl group, and for example, salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid. 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitro Benzoic acid, 4-hydroxy-3-nitrobenzoic acid and the like can be mentioned, and dihydroxybenzoic acid compounds are preferable from the viewpoint of enhancing the alkali developability. These hydroxybenzoic acid compounds may be used alone or in combination of two or more.

の構造を有する。式（８）において、ｄは１〜５の整数であり、＊は、１分子中に少なくとも２個のエポキシ基を有する化合物のエポキシ基を除く残基との結合部を表す。 In one embodiment, the alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule with a hydroxybenzoic acid compound, and has the formula (8):

It has the structure of. In the formula (8), d is an integer of 1 to 5, and * represents a bond with a residue of the compound having at least two epoxy groups in one molecule, excluding the epoxy groups.

  In the method for obtaining an alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group from an epoxy compound and a hydroxybenzoic acid compound, 0.2 to 1.0 equivalent of the hydroxybenzoic acid compound is used for 1 equivalent of the epoxy group of the epoxy compound. Can be used, and preferably 0.3 to 0.9 equivalent, more preferably 0.4 to 0.8 equivalent is used. When the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and when it is 1.0 equivalent or less, increase in molecular weight due to side reaction can be suppressed.

  A catalyst may be used to accelerate the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of the catalyst used may be 0.1 to 10% by mass based on the mass of the reaction raw material mixture composed of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature may be 60 to 150 ° C., and the reaction time may be 3 to 30 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, zirconium octanoate and the like.

  The number average molecular weight of the alkaline aqueous solution-soluble resin having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and even more preferably 1000 to 5000. When the number average molecular weight is 500 or more, the alkali solubility is appropriate, and therefore it is good as a resin for the photosensitive material. When the number average molecular weight is 8,000 or less, the coatability and developability are good.

(D) Alkaline Aqueous Solution Soluble Copolymer of Polymerizable Monomer Having Alkali-Soluble Functional Group and Other Polymerizable Monomer As the binder resin (A), a polymerizable monomer having an alkali-soluble functional group and other An aqueous alkaline solution-soluble copolymer of a polymerizable monomer can be used. Examples of the alkali-soluble functional group include a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group and the like. Examples of the polymerizable functional group contained in the polymerizable monomer include radically polymerizable functional groups, for example, CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, CH ₂ ═CHCO—, CH. _{2 = C (CH 3) CO} -, - OC-CH = CH-CO- and the like.

  Aqueous solution-soluble copolymers of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers include, for example, a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. It can be produced by radical polymerization. You may use the derivative which added the alkali-soluble functional group, after synthesize | combining a copolymer by radical polymerization. Examples of the polymerizable monomer having an alkali-soluble functional group include 4-hydroxystyrene, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth). ) Acrylic acid, β-styryl (meth) acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid , 4-hydroxyphenylmethacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimidopropionic acid, 4-maleimidobutyric acid, 6-maleimidohexanoic acid and the like. Be done. Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, acrylamide, acrylonitrile, vinyl-n-butyl ether and the like. Ether compound of vinyl alcohol, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester (Meth) acrylic acid ester such as 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, isobornyl (meth) acrylate, maleic anhydride, Mention may be made of N-substituted maleimides such as maleic acid monoester, phenylmaleimide and cyclohexylmaleimide. From the viewpoint of heat resistance and the like, an aqueous alkaline solution-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer has an alicyclic structure, an aromatic structure, a polycyclic structure, and an inorganic structure. It is preferable to have one or more cyclic structures such as a cyclic structure and a heterocyclic structure.

で表される構造単位を形成するものが好ましい。式（１０）において、Ｒ^１５は水素原子又は炭素原子数１〜５のアルキル基であり、ｅは１〜５の整数である。そのようなアルカリ可溶性官能基を有する重合性単量体として、４−ヒドロキシフェニルメタクリレートが特に好ましい。 The polymerizable monomer having an alkali-soluble functional group is represented by the formula (10)

What forms the structural unit represented by is preferable. In formula (10), R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5. 4-Hydroxyphenyl methacrylate is particularly preferable as the polymerizable monomer having such an alkali-soluble functional group.

で表される構造単位を形成するものが好ましい。式（１１）において、Ｒ^１６及びＲ^１７は、それぞれ独立して水素原子、炭素原子数１〜３のアルキル基、完全若しくは部分的にフッ素化された炭素原子数１〜３のアルキル基、又はハロゲン原子であり、Ｒ^１８は、水素原子、炭素原子数１〜６の直鎖若しくは環状アルキル基、フェニル基、又はヒドロキシ基、炭素原子数１〜６のアルキル基及び炭素原子数１〜６のアルコキシ基からなる群より選択される少なくとも１種で置換されたフェニル基である。そのようなその他の重合性単量体として、フェニルマレイミド及びシクロヘキシルマレイミドが特に好ましい。 The other polymerizable monomer has the formula (11)

What forms the structural unit represented by is preferable. In formula (11), R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a completely or partially fluorinated alkyl group having 1 to 3 carbon atoms, or A halogen atom, R ¹⁸ is a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and a carbon atom having 1 to 6 carbon atoms. It is a phenyl group substituted with at least one selected from the group consisting of alkoxy groups. As such other polymerizable monomers, phenylmaleimide and cyclohexylmaleimide are particularly preferable.

（式（１０）において、Ｒ^１５は水素原子又は炭素原子数１〜５のアルキル基であり、ｅは１〜５の整数である。）
で表される構造単位、及び式（１１）

（式（１１）において、Ｒ^１６及びＲ^１７は、それぞれ独立して水素原子、炭素原子数１〜３のアルキル基、完全若しくは部分的にフッ素化された炭素原子数１〜３のアルキル基、又はハロゲン原子であり、Ｒ^１８は、水素原子、炭素原子数１〜６の直鎖若しくは環状アルキル基、フェニル基、又はヒドロキシル基、炭素原子数１〜６のアルキル基及び炭素原子数１〜６のアルコキシ基からなる群より選択される少なくとも１種で置換されたフェニル基である。）
で表される構造単位を有する。 In one embodiment, the alkali aqueous solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer has the formula (10)

(In the formula (10), R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5.)
And a structural unit represented by the formula (11)

(In the formula (11), R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a completely or partially fluorinated alkyl group having 1 to 3 carbon atoms, Or a halogen atom, R ¹⁸ is a hydrogen atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, or a hydroxyl group, an alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. A phenyl group substituted with at least one selected from the group consisting of
It has a structural unit represented by.

  It is particularly preferable to use 4-hydroxyphenyl methacrylate as the polymerizable monomer having an alkali-soluble functional group and phenylmaleimide or cyclohexylmaleimide as the other polymerizable monomer. By using a resin obtained by radically polymerizing these polymerizable monomers, shape retention and developability can be improved and outgassing can be reduced.

  The polymerization initiator for producing an alkali-soluble copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer by radical polymerization is not limited to '-Azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyano Valeric acid), azo polymerization initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile) (AVN), dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylper) (Oxy) hexane, tert-butyl cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc. has a 10-hour half-life temperature of 100 to 170 ° C. Or a peroxide polymerization initiator such as benzoyl peroxide, lauroyl peroxide, 1,1′-di (t-butylperoxy) cyclohexane or t-butylperoxypivalate can be used. . The amount of the polymerization initiator used is generally 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, 40 parts by mass or less, and 20 parts by mass with respect to 100 parts by mass of the mixture of the polymerizable monomers. It is preferably not more than 15 parts by mass or not more than 15 parts by mass.

  An RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator. The RAFT agent is not limited to the following, but a thiocarbonylthio compound such as dithioester, dithiocarbamate, trithiocarbonate, xanthate can be used. The RAFT agent can be used in the range of 0.005 to 20 parts by mass, and preferably in the range of 0.01 to 10 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer.

  The weight average molecular weight (Mw) of the alkali-soluble copolymer of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer can be 3000 to 80,000, and is preferably 4000 to 70,000. It is preferably 5000 to 60,000 and more preferably. The number average molecular weight (Mn) can be 1,000 to 30,000, preferably 1,500 to 25,000, and more preferably 2,000 to 20,000. The polydispersity (Mw / Mn) may be 1.0 to 3.5, preferably 1.1 to 3.0, and more preferably 1.2 to 2.8. By setting the weight average molecular weight, number average molecular weight and polydispersity within the above ranges, a photosensitive resin composition having excellent alkali solubility and developability can be obtained.

  In the present disclosure, when the alkali aqueous solution-soluble copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer also corresponds to the hydroxypolystyrene resin derivative (b), The polymerizable monomer having a soluble functional group and the other polymerizable monomer are treated as an aqueous alkaline solution-soluble copolymer (d). When the aqueous alkaline solution-soluble copolymer (d) of a polymerizable monomer having an alkaline soluble functional group and another polymerizable monomer also corresponds to the aqueous alkaline solution soluble resin (c) having an epoxy group and a phenolic hydroxyl group. Is treated as an aqueous alkaline solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. That is, the hydroxypolystyrene resin derivative (b) and the alkaline aqueous solution-soluble resin (c) having an epoxy group and a phenolic hydroxyl group are soluble in an alkaline aqueous solution of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers. Those corresponding to the copolymer (d) are excluded.

  In one embodiment, the binder resin (A) is a phenol novolac resin, a cresol novolac resin, a triphenylmethane type phenol resin, a phenol aralkyl resin, a biphenyl aralkyl phenol resin, a phenol-dicyclopentadiene copolymer resin, or a derivative thereof. Including phenol resin. The preferred number average molecular weight when using a phenol resin as the binder resin (A) varies depending on the resin structure, but is generally 100 to 50,000, more preferably 500 to 30,000, and further preferably 800 to 10,000. is there. If the number average molecular weight is 100 or more, the alkali developing rate is appropriate, and the difference in dissolution rate between the exposed and unexposed areas is sufficient, so the pattern resolution is good, and if it is 50,000 or less, the alkali developability is good. .

(E) Polyimide resin, (f) Polyamic acid resin, (g) Polybenzoxazole resin, (h) Polybenzoxazole resin precursor In one embodiment, the binder resin (A) is (e) polyimide resin, (f). ) At least one selected from polyamic acid resin, (g) polybenzoxazole resin, and (h) polybenzoxazole resin precursor. The polyamic acid resin becomes a resin having a polyimide structure by dehydration ring closure. The polybenzoxazole resin precursor becomes a polybenzoxazole resin by dehydration ring closure.

  (E) The polyimide resin has a structural unit represented by the formula (12). The (f) polyamic acid resin and (h) polybenzoxazole resin precursor have a structural unit represented by the formula (13). (G) The polybenzoxazole resin has a structural unit represented by the formula (14). The polyimide resin may have both the structural unit represented by the formula (12) and the structural unit represented by the formula (13), and the polybenzoxazole resin includes the structural unit represented by the formula (14) and the formula unit. You may have both of the structural units represented by (13).

In formula (12), R ¹⁹ is a 4- to 10-valent organic group, R ²⁰ is a 2- to 8-valent organic group, and R ²¹ and R ²² are each independently a hydroxyl group, a carboxy group, or a sulfo group. Or a mercapto group, and f and g are each independently an integer of 0 to 6.

In the formula (13), R ²³ is a divalent to octavalent organic group, R ²⁴ is a divalent to octavalent organic group, and R ²⁵ and R ²⁶ are each independently a hydroxyl group, a sulfo group or a mercapto group. Or —COOR ²⁷ , R ²⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, h and i are each independently an integer of 0 to 6, provided that h + i> 0. Is. In the case of polyamic acid resin, h is an integer of 1 or more, and at least one of R ²⁵ is —COOR ²⁷ . In the case of the polybenzoxazole resin precursor, i is an integer of 1 or more, and at least one of R ²⁶ is a phenolic hydroxyl group.

In formula (14), R ²⁸ is a divalent to octavalent organic group, R ²⁹ is a divalent to octavalent organic group, and R ³⁰ and R ³¹ are each independently a hydroxyl group, a carboxy group, or a sulfo group. Or a mercapto group, and j and k are each independently an integer of 0 to 6.

R <^19> -(R < ²¹ _> ) _f of Formula (12) represents the residue of an acid dianhydride. R ¹⁹ is a 4- to 10-valent organic group, and is preferably an organic group having 5 to 40 carbon atoms including an aromatic ring or a cycloaliphatic group.

  Examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetra Carboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2 , 3-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis (3 , 4-Dicarboxyphenyl) fluorenic acid dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Aromatic tetracarboxylic dianhydrides such as hexafluoropropane dianhydride; Butanetetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride And the like, and combinations of two or more thereof.

R _< ^23> -(R _< ^25> ) _{h of} Formula (13) and R _< ^28> -(R _< ³⁰ _> ) _j of Formula (14) respectively represent the residue of an acid. R ²³ and R ²⁸ are each independently a divalent to octavalent organic group, and preferably an organic group having 5 to 40 carbon atoms, including an aromatic ring or a cycloaliphatic group.

Examples of the acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, and triphenyldicarboxylic acid; trimellitic acid, trimesic acid. Aromatic dicarboxylic acids such as diphenyl ether tricarboxylic acid and biphenyl tricarboxylic acid; pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2 , 2 ', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 2,2 ', 3,3'-benzophenonetetracarboxylic acid, 2,2-bis ( 3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1- Bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) ether, 1, 2,5,6-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, etc. Aromatic tetracarboxylic acids; aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and the like, and combinations of two or more thereof. In the above tricarboxylic acid and tetracarboxylic acid, one or two carboxy groups correspond to R ²⁵ in formula (13) or R ³⁰ in formula (14). These acids may be in the form of esters or anhydrides.

^R 20 of formula _{^{(12) - (R 22)}} g, R 24 of formula (13) ^{- (R} _{26) i,} and ^R 29 of formula (14) ^- a ^(R _{31) k} is the residue of each diamine Represent R ²⁰ , R ²⁴ and R ²⁹ are each independently a divalent to octavalent organic group, and preferably an organic group having 5 to 40 carbon atoms, including an aromatic ring or a cycloaliphatic group.

Examples of the diamine corresponding to R ^{20 of} formula (12) and R ²⁴ of formula (13) related to the polyamic acid resin include, for example, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4 ′. -Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine , Bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diamino Biphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-Tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, aromatic diamine such as 9,9-bis (4-aminophenyl) fluorene, or at least one hydrogen atom of the aromatic ring of these aromatic diamines is an alkyl group or a halogen atom. Substituted compounds; cyclodiamine, aliphatic diamines such as methylenebiscyclohexylamine, and combinations of two or more thereof.

Examples of the diamine corresponding to R ^{24 of} the formula (13) and R ²⁹ of the formula (14) related to the polybenzoxazole resin precursor include, for example, an ortho position with respect to an amino group on the aromatic ring of the aromatic diamine. Examples thereof include a bisaminophenol compound having a phenolic hydroxyl group, and a combination of two or more thereof.

  Polyimide resin, polyamic acid resin, polybenzoxazole resin, and polybenzoxazole resin precursors, their ends are monoamines having an acidic group, acid anhydride, acid chloride, by being sealed with a monocarboxylic acid, It may have an acidic group at the end of the main chain.

  Polyamic acid resin, for example, a method of reacting a tetracarboxylic dianhydride and a diamine, after producing a diester from a tetracarboxylic dianhydride and an alcohol, a method of reacting the diester and diamine in the presence of a condensing agent, A diester can be produced from tetracarboxylic dianhydride and an alcohol, the remaining dicarboxylic acid can be converted to an acid chloride, and then the resulting intermediate can be reacted with a diamine.

  The polybenzoxazole resin precursor can be synthesized, for example, by subjecting a bisaminophenol compound and a polycarboxylic acid such as dicarboxylic acid, tricarboxylic acid or tetracarboxylic acid to a condensation reaction. Specifically, a method of reacting an intermediate obtained by reacting a dehydration condensation agent such as dicyclohexylcarbodiimide (DCC) with a polyvalent carboxylic acid with a bisaminophenol compound, and a tertiary amine such as pyridine was added. Examples include a method of dropping a dicarboxylic acid dichloride solution into a solution of a bisaminophenol compound.

  The polyimide resin can be synthesized, for example, by heating the polyamic acid resin obtained by the above-mentioned method or by dehydration ring closure by a chemical treatment with an acid or a base.

  The polybenzoxazole resin can be synthesized, for example, by heating the polybenzoxazole resin precursor obtained by the above-mentioned method or by dehydration ring closure by a chemical treatment such as acid or base.

  The number average molecular weight of the polyimide resin, polyamic acid resin, polybenzoxazole resin, and polybenzoxazole resin precursor is preferably 500 to 8000, more preferably 800 to 6000, and more preferably 1000 to 5000. Is more preferable. When the number average molecular weight is 500 or more, the alkali solubility is appropriate, and therefore it is good as a resin for the photosensitive material. When the number average molecular weight is 8,000 or less, the coatability and developability are good.

(I) Silicone Resin In one embodiment, the binder resin (A) comprises (i) a silicone resin. The silicone resin can be synthesized by hydrolyzing and condensing at least one compound selected from the organosilane represented by the formula (15) and the organosilane represented by the formula (16). By using the organosilane represented by the formulas (15) and (16), a photosensitive resin composition having excellent sensitivity and resolution can be obtained.

The organosilane represented by the formula (15) is shown below.

In the formula (15), R ³² is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 16 carbon atoms, and R ³³ is a hydrogen atom, An alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms or an aryl group having 6 to 16 carbon atoms, and p is an integer of 0 to 3. When p is 2 or more, a plurality of R ^32's may be the same or different. When p is 2 or less, a plurality of R ^33's may be the same or different.

  Examples of the organosilane represented by the formula (15) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, and methyltriisosilane. Propoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane Silane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryl Roxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p -Hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoro Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane Silane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-full Trifunctional silanes such as oleenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane; dimethyldimethoxysilane, dimethyl Diethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, di (1-naphthyl) ) Difunctional silanes such as dimethoxysilane and di (1-naphthyl) diethoxysilane; trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) ) Monofunctional silanes such as dimethylethoxysilane, and combinations of two or more thereof.

The organosilane represented by the formula (16) is shown below.

In formula (16), R ^{34 to} R ³⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 16 carbon atoms. , N is in the range of 2-8. When n is 2 or more, a plurality of R ³⁵ and R ³⁶ may be the same or different.

Specific examples of the organosilane represented by the formula (16) include Methyl silicate 51 manufactured by Fuso Chemical Co., Ltd. (R ^{34 to} R ³⁷ are methyl groups, n is 4 on average), and M silicate 51 manufactured by Tama Chemical Co., Ltd. ^(R 34 ^{to R 37} is a methyl group, n represents an average 3-5), silicate ^{40 (R} 34 ~R ³⁷ is an ethyl group, n represents an average 4-6), silicate ^{45 (R} 34 ~R ³⁷ is an ethyl group, n is an average of 6 to 8), Methyl silicate 51 (R ^{34 to} R ³⁷ is a methyl group, n is an average of 4) manufactured by Colcoat Co., Ltd., methyl silicate 53A (R ^{34 to} R ³⁷ is a methyl group, and n is an average of 7), Ethyl silicate 40 (R ^{34 to} R ³⁷ are ethyl groups, n is 5 on average) and the like. It is also possible to use two or more of these in combination.

  The silicone resin can be synthesized by hydrolyzing and partially condensing the organosilanes represented by the formulas (15) and (16). Due to the partial condensation, residual silanol groups are present in the silicone resin. Examples of the hydrolysis and partial condensation include a method in which a solvent, water, a catalyst, etc. are added to the organosilane mixture as necessary, and the mixture is heated and stirred at 50 ° C. to 150 ° C. for about 0.5 to 100 hours. If necessary, the hydrolysis by-product (alcohol such as methanol) or the condensation by-product (water) may be distilled off.

  As the catalyst, an acid catalyst or a base catalyst is preferably used. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acids or anhydrides thereof, and ion exchange resins. Examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino group. Examples thereof include alkoxysilanes and ion exchange resins. After hydrolysis and partial condensation, the catalyst may be optionally removed by washing with water, treatment with an ion exchange resin, or a combination thereof. The storage stability of the photosensitive resin composition can be increased by removing the catalyst.

  The weight average molecular weight (Mw) of the silicone resin is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography). When the weight average molecular weight is 1,000 or more, the film-forming property can be improved, and when it is 100,000 or less, the alkali developability is good.

(J) Cyclic Olefin Polymer In one embodiment, the binder resin (A) comprises (j) a cyclic olefin polymer. The cyclic olefin polymer is a homopolymer or copolymer of a cyclic olefin monomer having a cyclic structure (alicyclic or aromatic ring) and a carbon-carbon double bond. The cyclic olefin polymer may have a structural unit derived from a monomer other than the cyclic olefin monomer.

  As the monomer constituting the cyclic olefin polymer, a cyclic olefin monomer having a protic polar group, a cyclic olefin monomer having a polar group other than protic, a cyclic olefin monomer having no polar group, And monomers other than cyclic olefins. The monomer other than the cyclic olefin may have a protic polar group or a polar group other than this, and may not have a polar group.

Examples of the cyclic olefin monomer having a protic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2.2.1]. Hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo [2.2.1] hept-2 -Ene, 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . Carboxy group-containing cyclic olefin such as 1 ^7,10 ] dodec-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy) Phenyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene and other hydroxyl group-containing cyclic olefins, and combinations of two or more thereof.

Examples of the cyclic olefin monomer having a polar group other than protic are 5-acetoxybicyclo [2.2.1] hept-2-ene and 5-methoxycarbonylbicyclo [2.2.1] hept-2. -Ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 8-acetoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.11 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . Cyclic olefins having an ester group such as 1 ^7,10 ] dodec-3-ene; cyclic olefins having an N-substituted imide group such as N-phenyl- (5-norbornene-2,3-dicarboximide); 8- Cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . Cyclic olefins having a cyano group such as 1 ^7,10 ] dodec-3-ene and 5-cyanobicyclo [2.2.1] hept-2-ene; 8-chlorotetracyclo [4.4.0.1 ^{2] , 5} . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . Cyclic olefins having a halogen atom, such as [ ^17,10 ] dodeca-3-ene, and combinations of two or more thereof.

As the cyclic olefin monomer having no polar group, for example, bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5- Butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2- ene, 5-vinyl - bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^{2, 5]} deca-3,7-diene, tetracyclo [8.4.0.1 ^11,14 . 0 ^3,7 ] Pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] deca-3-ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano -1,4,4a, 5,10,10a hexa hydro anthracene, 8-phenyl - tetracyclo [4.4. 0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] Tetradeca-3,5,7,12-tetraene, pentacyclo [7.4.0.1 ^3,6 . 1 ^{10, 13} . 0 ^2,7] pentadeca-4,11-diene, pentacyclo [9.2.1.14,7.0 ^2,10. [0 ^3,8 ] Pentadeca-5,12-diene and the like, and combinations of two or more thereof.

  Specific examples of monomers other than cyclic olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1. -Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl -1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like α-olefins having 2 to 20 carbon atoms; 1,4-hexadiene Chain olefins such as non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene, and combinations of two or more thereof.

  The cyclic olefin polymer can be synthesized by polymerizing the above-mentioned monomer by ring-opening polymerization or addition polymerization. As the polymerization catalyst, for example, a metal complex such as molybdenum, ruthenium, or osmium, or a combination of two or more thereof is preferably used. Hydrogenation treatment may be performed on the cyclic olefin polymer. As the hydrogenation catalyst, those generally used for hydrogenation of olefin compounds can be used, and examples thereof include a Ziegler type homogeneous catalyst, a precious metal complex catalyst, and a supported precious metal catalyst.

  The weight average molecular weight (Mw) of the cyclic olefin polymer is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography). When the weight average molecular weight is 1,000 or more, the film-forming property can be improved, and when it is 100,000 or less, the alkali developability is good.

(K) Cardo Resin In one embodiment, the binder resin (A) comprises (k) cardo resin. The cardo resin has a cardo structure, that is, a skeleton structure in which another two cyclic structures are bonded to a quaternary carbon atom forming the cyclic structure. Examples of the skeleton structure in which another two cyclic structures are bonded to the quaternary carbon atom forming the cyclic structure include a fluorene skeleton, a bisphenolfluorene skeleton, a bisaminophenylfluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. Examples thereof include a fluorene skeleton. An example of the cardo structure is a fluorene ring to which a benzene ring is bonded.

  The cardo resin can be synthesized by polymerizing monomers by reacting functional groups of monomers having a cardo structure. Examples of the method for polymerizing the monomer having a cardo structure include a ring-opening polymerization method and an addition polymerization method. Examples of the monomer having a cardo structure include bis (glycidyloxyphenyl) fluorene type epoxy resin, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl). ) A bisphenol compound containing a cardo structure such as fluorene; 9,9-bis (cyanoalkyl) fluorene compound such as 9,9-bis (cyanomethyl) fluorene; 9,9-bis (3-aminopropyl) fluorene such as 9,9 -Bis (aminoalkyl) fluorene compounds and the like, and combinations of two or more thereof. The cardo resin may be a copolymer of a monomer having a cardo structure and another copolymerizable monomer.

  The weight average molecular weight (Mw) of the cardo resin is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography). When the weight average molecular weight is 1,000 or more, the film-forming property can be improved, and when it is 100,000 or less, the alkali developability is good.

  As the binder resin (A), one type of resin may be used alone, or two or more types of resin may be used in combination.

  The content of the binder resin (A) in the photosensitive resin composition is 100 parts by mass in total of the (A) binder resin, (B) organic low-molecular compound, (C) radiation-sensitive compound, and (D) colorant. As a standard, it may be 5 to 60 parts by mass, preferably 10 to 55 parts by mass, and more preferably 10 to 50 parts by mass. When the content of the binder resin (A) is 5 parts by mass or more based on 100 parts by mass in total, the residual film rate, heat resistance, sensitivity, etc. are appropriate. When the content of the binder resin (A) is 60 parts by mass or less based on 100 parts by mass in total, the optical density (OD value) of the coating film after firing may be 0.5 or more per 1 μm of film thickness. Therefore, the light-shielding property can be maintained even after firing.

  The binder resin (A) preferably contains at least one selected from the resin components (a) to (k), and when it contains a plurality of the resin components (a) to (k), any combination may be used. It is possible. The binder resin (A) more preferably contains at least one selected from the resin components (a) to (d), and further preferably at least selected from the resin components (a), (c), and (d). Two types, and more preferably resin components (c) and (d). In another preferred embodiment, the binder resin (A) contains at least one selected from (a), (b), and (c).

  The amount of at least one resin component selected from (a) to (d) relative to 100 parts by mass of the binder resin (A) is preferably 0.5 parts by mass or more, more preferably 50 parts by mass or more, and further preferably Is 88 parts by mass or more. When the amount of at least one resin component selected from (a) to (d) with respect to 100 parts by mass of the binder resin (A) is 0.5 parts by mass or more, the heat resistance of the resin composition is good.

  You may use together 4 types of resin component (a)-(d). When four kinds are used in combination, the proportion of the polyalkenylphenol resin (a) in the binder resin (A) is 5 to 50% by mass, the proportion of the hydroxypolystyrene resin derivative (b) is 5 to 30% by mass, epoxy group and phenol. The ratio of the aqueous alkaline solution-soluble resin (c) having a functional hydroxyl group is 10 to 80% by mass, and the aqueous alkaline solution-soluble copolymer (d) of the polymerizable monomer having an alkaline soluble functional group and the other polymerizable monomer is The proportion is preferably 10 to 80% by mass.

(B) Organic Low-Molecular Compound The organic low-molecular compound (B) has a molar volume of 130 cm ³ / mol or less at 20 ° C. and 1 atm, and is selected from the group consisting of aromatic carboxylic acids and compounds having a plurality of phenolic hydroxyl groups. To be done. In the present disclosure, the “low molecular weight compound” refers to a compound having a molecular weight of 1,000 or less. The organic low molecular weight compound (B) may be used alone or in combination of two or more kinds.

  In the present disclosure, an aromatic hydroxycarboxylic acid having a plurality of phenolic hydroxyl groups is treated as an aromatic carboxylic acid. That is, a compound having a plurality of phenolic hydroxyl groups does not have a carboxy group.

The organic low molecular weight compound (B) has a carboxy group or a plurality of phenolic hydroxyl groups and is alkali-soluble. In addition, since the organic low molecular weight compound (B) has a small molar volume of 130 cm ³ / mol or less, the organic low molecular weight compound (B) quickly elutes from the film formed using the photosensitive resin composition into an alkaline developing solution. Elution of the organic low molecular weight compound (B) from the coating film breaks the entanglement of the polymer chains of the binder resin (A) and promotes the dissolution of the alkali-soluble portion of the binder resin (A) during development. In this way, the organic low molecular weight compound (B) can impart excellent alkali developability and pattern formability to the photosensitive resin composition even at low irradiation energy exposure. In addition, the organic low molecular weight compound (B) is excellent in compatibility or dispersibility with the binder resin (A) and other components because the molar volume of the organic low molecular weight compound (B) is as small as 130 cm ³ / mol. ) Can be uniformly dissolved or dispersed in the photosensitive resin composition and the coating film formed using the same. This also has an advantageous effect on enhancing the smoothness and uniformity of the coating surface and reducing the outgas caused by the organic low molecular weight compound (B).

  Since the organic low molecular weight compound (B) is an aromatic compound, it is unlikely to be modified or decomposed during exposure and heat treatment. Therefore, it is possible to form a high-quality coating and reduce the outgas caused by the decomposition product of the organic low molecular weight compound (B). The carboxy group or the plurality of phenolic hydroxyl groups of the organic low molecular weight compound (B) may contribute to the improvement of the adhesion of the coating film to the substrate.

Molar volume of the organic low-molecular compound (B), 20 ° C., at 1 atm, or less 130 cm ³ / mol, it is preferably 75~120cm ³ / mol, more preferably 80~110cm ³ / mol , 85 to 100 cm ³ / mol is more preferable.

  In one embodiment, the organic low molecular weight compound (B) is an aromatic carboxylic acid having a pKa (acid dissociation constant) of 2.5 to 4.5 at 25 ° C. The pKa of the aromatic carboxylic acid is preferably 2.7 to 4.2, more preferably 2.8 to 4.0. The aromatic carboxylic acid having a pKa in the above range effectively promotes the dissolution of the binder resin (A) and imparts excellent alkali developability and pattern formability to the photosensitive resin composition even at low irradiation energy exposure. can do. The aromatic carboxylic acid having a pKa of 2.5 or more has a solubility to such an extent that the effect of suppressing the dissolution of the binder resin (A) in the unexposed area by the photoacid generator, for example, a diazonaphthoquinone compound, is not lost. Even in the positive type photosensitive resin composition, excellent pattern formability is achieved by maintaining the film thickness of the unexposed area at a sufficient level without excessively dissolving the film of the unexposed area during development. can do.

  In one embodiment, the organic low molecular weight compound (B) is a compound having a plurality of phenolic hydroxyl groups having a pKa of 7.5 to 10 at 25 ° C. The pKa of the compound having a plurality of phenolic hydroxyl groups is preferably 7.8 to 9.8, and more preferably 8.0 to 9.6. The compound having a plurality of phenolic hydroxyl groups having a pKa in the above range effectively promotes the dissolution of the binder resin (A), and provides an excellent alkali developability and pattern formability even at low irradiation energy exposure to a photosensitive resin. It can be applied to the composition. Since the pKa of the compound having a phenolic hydroxyl group is sufficiently high so that the effect of suppressing the dissolution of the binder resin (A) in the unexposed portion by the photo-acid generator, for example, a diazonaphthoquinone compound, is not lost, a positive photosensitive resin is used. Excellent pattern formability can also be achieved in the composition.

  The organic low molecular weight compound (B) is preferably a compound in which groups other than the carboxy group and the phenolic hydroxyl group are not bonded to the carbon atoms constituting the aromatic ring. Since such a compound has a large number / molar volume ratio of the carboxy group and the phenolic hydroxyl group, the solubility of the organic low molecular weight compound (B) in the developing solution is further increased to dissolve the binder resin (A). It can be promoted more effectively.

Examples of aromatic carboxylic acids include phthalic acid (molar volume 114.4 cm ³ / mol, pKa 2.95), isophthalic acid (molar volume 114.4 cm ³ / mol, pKa 3.53), terephthalic acid (molar volume 114.4 cm). ^{3 /mol,pKa3.49),} hemimellitic acid (molar volume 127cm ³ /mol,pKa2.8), trimellitic acid (molar volume 127.0cm ³ /mol,pKa2.84), and trimesic acid (molar volume 127 0.0 cm ^{3 /} mol, pKa 2.98), a polyvalent carboxylic acid selected from the group consisting of 2,3-dihydroxybenzoic acid (molar volume 98.8 cm ³ / mol, pKa 2.96), 2,4-dihydroxybenzoic acid. Acid (molar volume 98.8 cm ³ / mol, pKa 3.32), 2,5-dihydroxybenzoic acid (molar volume 98.8 cm ³ / mol, pKa 3.01), 3,5-dihydroxybenzoic acid (molar volume 98. 8cm ³ /mol,pKa3.96),2,3,4- trihydroxybenzoic acid (molar volume 97.2cm ³ /mol,pKa3.3), and gallic acid (molar volume 97.2cm ³ / mol, pKa4. Aromatic hydroxycarboxylic acids selected from the group consisting of 33) and the like. The aromatic carboxylic acid is preferably 2,4-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, or trimellitic acid from the viewpoint of easily adjusting the solubility in a developing solution, and the pattern after development It is more preferable to use 2,4-dihydroxybenzoic acid or 2,3,4-trihydroxybenzoic acid in terms of good adhesion.

Examples of the compound having a plurality of phenolic hydroxyl groups include catechol (molar volume 86.2 cm ³ / mol, pKa 9.50), resorcinol (mol volume 86.2 cm ³ / mol, pKa 9.45), hydroquinone (molar volume 86.45). 2cm ³ /mol,pKa9.58),1,2,4- benzene triol (molar volume 84.7cm ³ /mol,pKa9.58), pyrogallol (molar volume 84.7cm ³ /mol,pKa9.28) and furo An aromatic polyol selected from the group consisting of loglucinol (molar volume 84.7 cm ³ / mol, pKa 9.06) and the like can be mentioned. The compound having a plurality of phenolic hydroxyl groups is preferably 1,2,4-benzenetriol or phloroglucinol from the viewpoint of easily adjusting the solubility in a developing solution, and has good pattern adhesion after development. From the viewpoint, phloroglucinol is more preferable.

  The molar volume and pKa of the organic low molecular weight compound (B) can be examined using a database such as SciFinder (registered trademark) provided by CAS (Chemical Abstract Service).

  The content of the organic low-molecular weight compound (B) in the photosensitive resin composition is 100 masses of the (A) binder resin, (B) organic low-molecular weight compound, (C) radiation-sensitive compound, and (D) colorant. The amount can be 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, and more preferably 3 to 12 parts by mass, based on parts. When the content of the organic low molecular weight compound (B) is 0.1 parts by mass or more based on the total 100 parts by mass, the dissolution of the binder resin (A) can be effectively promoted, and 20 parts by mass. If it is below, excessive dissolution of the binder resin (A) can be suppressed and the pattern formability, surface quality and the like of the coating film can be improved.

(C) Radiation Sensitive Compound As the radiation sensitive compound, a photoacid generator, a photobase generator or a photopolymerization initiator can be used. Photoacid generators include compounds that generate an acid when exposed to radiation. The photo-acid generator increases the solubility of a portion irradiated with radiation in an alkaline aqueous solution, and thus can be used in a positive photosensitive resin composition in which the portion is dissolved. Photobase generators include compounds that generate a base when exposed to radiation. The photobase generator reduces the solubility of a portion irradiated with radiation in an alkaline aqueous solution, and thus can be used in a negative photosensitive resin composition in which the portion is insolubilized. The photopolymerization initiator includes a compound that generates a radical when irradiated with radiation. The photopolymerization initiator, when the photosensitive resin composition contains a binder resin or a radically polymerizable compound having a radically polymerizable functional group, a radically polymerizable functional group or a radically polymerizable compound of a portion of the binder resin irradiated with radiation. It can be used for a negative photosensitive resin composition in which the radical polymerization proceeds to form a cured product insoluble in an alkaline aqueous solution in that portion.

  It is preferable that the radiation-sensitive compound (C) is a photo-acid generator in that a pattern having high sensitivity and high resolution can be obtained. As the photoacid generator, at least one selected from the group consisting of quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts can be used. In one embodiment, the photoacid generator is a compound or salt sensitive to i-line (365 nm).

  It is preferable to use a quinonediazide compound as the photoacid generator. Examples of the quinonediazide compound include a polyhydroxy compound in which a sulfonic acid of quinonediazide is bound with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bound in a sulfonamide, and a polyhydroxypolyamino compound in which a sulfonic acid of quinonediazide is bound to an ester or a sulfonamide bond. The ones that have been made are listed. From the viewpoint of the contrast between the exposed area and the unexposed area, it is preferable that 20 mol% or more of all the functional groups of the polyhydroxy compound or the polyamino compound be substituted with quinonediazide.

  Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ. , BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-. PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-. HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above, brand name, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR. -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.) 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and the like, but are not limited thereto.

  Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′- Examples include, but are not limited to, diaminodiphenyl sulfide.

  Examples of the polyhydroxy polyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine.

  Specific examples of the quinonediazide compound include 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester of polyhydroxy compound.

  When quinonediazide compound is irradiated with ultraviolet light or the like, the quinonediazide compound produces a carboxy group through the reaction shown in the following reaction formula 2. By the formation of the carboxy group, the exposed portion (coating) can be dissolved in the alkaline aqueous solution, and the alkali developability occurs in the portion.

  When the radiation-sensitive compound (C) is a photoacid generator, the content of the radiation-sensitive compound (C) in the photosensitive resin composition is (A) binder resin, (B) organic low molecular compound, (C). It can be 5 to 50 parts by mass, preferably 10 to 45 parts by mass, and more preferably 15 to 40 parts by mass, based on 100 parts by mass of the total of the radiation-sensitive compound and the (D) colorant. .. When the content of the radiation-sensitive compound (C) is 5 parts by mass or more based on the total 100 parts by mass, the alkali developability is good, and when it is 50 parts by mass or less, the coating film is formed by heating at 300 ° C. or more. Can be suppressed.

  A photobase generator may be used as the radiation-sensitive compound (C). As the photobase generator, at least one selected from the group consisting of amide compounds and ammonium salts can be used. In one embodiment, the photobase generator is a compound or salt sensitive to i-line (365 nm).

  Examples of the amide compound include 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate, 9-anthrylmethyl-N, N-dimethylcarbamate, 1- (anthraquinone-2-yl) ethylimidazole carboxylate. , (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine and the like. Examples of the ammonium salt include 1,2-diisopropyl-3- (bisdimethylamino) methylene) guanidium 2- (3-benzoylphenyl) propionate and (Z)-{[bis (dimethylamino) methylidene] amino} -N. -Cyclohexylamino) methanaminium tetrakis (3-fluorophenyl) borate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidinium n-butyltriphenylborate and the like can be mentioned.

  When the radiation-sensitive compound (C) is a photobase generator, the content of the radiation-sensitive compound (C) in the photosensitive resin composition is (A) binder resin, (B) organic low molecular compound, (C). It can be 0.1 to 25 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 15 based on the total 100 parts by mass of the radiation-sensitive compound and the (D) colorant. It is a mass part. When the content of the radiation-sensitive compound (C) is 0.1 parts by mass or more based on the total 100 parts by mass, the alkali developability is good, and when it is 20 parts by mass or less, heating at 300 ° C. or more is performed. It is possible to suppress the reduction of the coating film due to

  A photopolymerization initiator may be used as the radiation-sensitive compound (C). As a photopolymerization initiator, a benzyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine oxide compound, an oxime ester compound, an acridine compound, a benzophenone compound, an acetophenone compound, an aromatic ketoester compound and a benzoic acid ester compound. At least one selected from the group can be used. In one embodiment, the photoinitiator is a compound sensitive to i-line (365 nm). Since the sensitivity at the time of exposure is high, the photopolymerization initiator is preferably an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine oxide compound, an oxime ester compound, an acridine compound or a benzophenone compound, and an α-aminoketone compound. More preferably, it is an acylphosphine oxide compound or an oxime ester compound.

  Examples of the benzyl ketal compound include 2,2-dimethoxy-1,2-diphenylethan-1-one. Examples of the α-hydroxyketone compound include 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one or 2-hydroxy-1- [4- [4- (2-hydroxy- 2-Methylpropionyl) benzyl] phenyl] -2-methylpropan-1-one. Examples of the α-aminoketone compound include 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, and 2-methyl-2-. Morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- (4-ethylphenyl) -2- Methylpropan-1-one, 2-dimethylamino-1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropane-1 -One, 2-dimethylamino-1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one, 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-benzyl -2-Dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl ] -1-butanone is mentioned. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide or bis (2,6-dimethoxybenzoyl)-(2 , 4,4-Trimethylpentyl) phosphine oxide. Examples of the oxime ester compound include 1-phenylpropane-1,2-dione-2- (O-ethoxycarbonyl) oxime, 1-phenylbutane-1,2-dione-2- (O-methoxycarbonyl) oxime, 1,3-Diphenylpropane-1,2,3-trione-2- (O-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] octane-1,2-dione-2- (O-benzoyl) Oxime, 1- [4- [4- (carboxyphenyl) thio] phenyl] propane-1,2-dione-2- (O-acetyl) oxime, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyl) oxime, 1- [9-ethyl-6- [2-methyl-4- [1- (2,2-dimethyl-1,3-) Dioxolan-4-yl) methyloxy] benzoyl] -9H-carbazol-3-yl] ethanone-1- (O-acetyl) oxime. Examples of the acridine compound include 1,7-bis (acridin-9-yl) -n-heptane. Examples of the benzophenone compound include benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone and alkyl. Benzophenone, 3,3 ′, 4,4′-tetrakis (t-butylperoxycarbonyl) benzophenone, 4-methylbenzophenone, dibenzyl ketone or fluorenone. Examples of the acetophenone compound include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone and 4-azidobenzalacetophenone. Examples of the aromatic ketoester compound include methyl 2-phenyl-2-oxyacetate. Examples of the benzoic acid ester compound include ethyl 4-dimethylaminobenzoate, (2-ethyl) hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, and methyl 2-benzoylbenzoate.

  When the radiation-sensitive compound (C) is a photopolymerization initiator, the content of the radiation-sensitive compound (C) in the photosensitive resin composition is (A) binder resin, (B) organic low molecular compound, (C). It can be 0.1 to 25 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1 to 15 based on the total 100 parts by mass of the radiation-sensitive compound and the (D) colorant. It is a mass part. When the content of the radiation-sensitive compound (C) is 0.1 parts by mass or more based on the total 100 parts by mass, the alkali developability is good, and when it is 20 parts by mass or less, heating at 300 ° C. or more is performed. It is possible to suppress the reduction of the coating film due to

  When the radiation-sensitive compound (C) is a photopolymerization initiator, the photosensitive resin composition may further contain a radically polymerizable compound. The resin and compound having a plurality of ethylenically unsaturated groups as the radically polymerizable compound can crosslink the coating to increase its hardness.

  From the viewpoint of reactivity at the time of exposure, hardness of the coating, heat resistance, etc., it is preferable to use a compound having a plurality of (meth) acrylic groups as the radically polymerizable compound. Examples of such compounds include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylol. Propane tri (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, 1,3 -Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( (Meth) acrylate, 1,10-decanediol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, ethoxylated glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Acrylate, ethoxylated pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tri Pentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, pentapentaerythritol undeca (meth) acrylate, pentapentaerythritol dodeca (meth) acrylate, ethoxylated bisphenol A di (Meth) acrylate, 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 1,3,5-tris ((meth) acryloxyethyl) isocyanuric acid, 1, 3-bis ((meth) acryloxyethyl) isocyanuric acid, 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, 9,9-bis [4- (3- (meth)) Acryloxypropoxy) phenyl] fluorene or 9,9-bis (4- (meth) acryloxyphenyl) fluor Ren, an acid-modified product thereof, an ethylene oxide-modified product, or a propylene oxide-modified product thereof may be mentioned.

  Content of the radically polymerizable compound in a photosensitive resin composition can be 15 mass parts-65 mass parts with respect to 100 mass parts of binder resin (A), and is 20 mass parts-60 mass parts. It is preferable that the amount is 25 parts by mass to 50 parts by mass. When the content of the radically polymerizable compound is within the above range, the alkali developability is good, and the heat resistance of the cured film can be improved.

(D) Colorant The colorant (D) is selected from the group consisting of black dyes and black pigments. By forming a black partition in the organic EL element using the photosensitive resin composition containing the colorant (D), the visibility of a display device such as an organic EL display can be improved.

  In one embodiment the colorant (D) comprises a black dye. As the black dye, a dye defined by the color index (CI) of Solvent Black 27 to 47 can be used. The black dye is preferably C.I. of Solvent Black 27, 29 or 34. I. Is defined by. Solvent Black 27-47 C.I. I. When at least one kind of the dyes defined by the above is used as the black dye, the light-shielding property of the film of the photosensitive resin composition after firing can be maintained. The photosensitive resin composition containing a black dye has less residual colorant at the time of development and can form a high-definition pattern on a film, as compared with a photosensitive resin composition containing a black pigment.

  When the colorant (D) is a black dye, the content of the colorant (D) in the photosensitive resin composition is (A) binder resin, (B) organic low molecular compound, (C) radiation-sensitive compound, And 1 to 70 parts by mass, more preferably 5 to 60 parts by mass, further preferably 10 to 50 parts by mass, based on 100 parts by mass of the total of (D) colorant. When the content of the colorant (D) is 1 part by mass or more based on 100 parts by mass in total, the light-shielding property of the coating film after firing can be maintained. When the content of the colorant (D) is 70 parts by mass or less based on the total 100 parts by mass, the residual film rate, heat resistance, sensitivity, etc. are appropriate.

  A black pigment may be used as the colorant (D). Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigments and lactam pigments. It is also possible to use those obtained by subjecting these black pigments to surface treatment. Examples of commercially available perylene pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34 manufactured by BASF. Examples of commercially available lactam pigments include Irgaphor (registered trademark) Black S0100CF manufactured by BASF. The black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene pigments, and lactam pigments because it has high light-shielding properties. In the negative photosensitive resin composition in which the radiation-sensitive compound (C) is a photopolymerization initiator, it is advantageous that the colorant (D) is a black pigment that hardly inhibits polymerization.

  When the colorant (D) is a black pigment, the content of the colorant (D) in the photosensitive resin composition is (A) binder resin, (B) organic low molecular compound, (C) radiation-sensitive compound, And 1 to 70 parts by mass, more preferably 5 to 60 parts by mass, further preferably 10 to 50 parts by mass, based on 100 parts by mass of the total of (D) colorant. When the content of the colorant (D) is 1 part by mass or more based on 100 parts by mass in total, sufficient light-shielding property can be obtained. When the content of the colorant (D) is 70 parts by mass or less based on the total 100 parts by mass, the residual film rate, the sensitivity, etc. are appropriate.

(E) Optional component The photosensitive resin composition may include a thermosetting agent, a surfactant, a colorant other than (D), and the like as optional components. The optional component (E) is defined as not applicable to any of (A) to (D).

  A thermal radical generator can be used as the thermosetting agent. Examples of preferable heat radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and tert-butyl. Organic peroxides such as cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide and cumene hydroperoxide having a 10-hour half-life temperature of 100 to 170 ° C. Can be mentioned.

  The content of the thermosetting agent is the total of the binder resin (A), the organic low molecular weight compound (B), the radiation sensitive compound (C), the colorant (D), and other solid content (excluding the thermosetting agent). The amount is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass or less, based on 100 parts by mass.

  The photosensitive resin composition may contain a surfactant, for example, in order to improve coatability, improve smoothness of the coating, or improve developability of the coating. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Oxyethylene aryl ethers; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafac (registered trademark) F-251, F-281 and F-281 -430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559 (above, Product name, manufactured by DIC Corporation), Surflon (registered trademark) S-242, S-243, S-386, S-420, S-611 (trade name, manufactured by ACG Seimi Chemical Co., Ltd.) Fluorosurfactants such as; organosiloxane polymers KP323, KP326, KP341 (these are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  The content of the surfactant is the total of the binder resin (A), the organic low molecular weight compound (B), the radiation sensitive compound (C), the colorant (D), and other solids (excluding the surfactant). The amount is 2 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less, based on 100 parts by mass.

  The photosensitive resin composition may contain a second colorant other than the black dye and the black pigment. Examples of the second colorant include dyes, organic pigments, and inorganic pigments, which can be used according to the purpose. The second colorant can be used in a content that does not impair the effects of the present invention.

  Examples of the dye include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes. Examples thereof include dyes, fluoran dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgide dyes, nickel complex dyes, and azulene dyes.

  Examples of the pigment include C.I. I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment Blue 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Pigment Green 7, C.I. I. Pigment Brown 23, 25, 26 and the like.

(F) Solvent The photosensitive resin composition can be dissolved in a solvent and used in a solution state (however, when a black pigment is included, the pigment is in a dispersed state). For example, a low-molecular organic compound (B), a radiation-sensitive compound (C), a colorant (D), and optionally a thermosetting agent are added to a solution obtained by dissolving the binder resin (A) in a solvent (F). The solution-state photosensitive resin composition can be prepared by mixing the optional component (E) such as a surfactant at a predetermined ratio. The photosensitive resin composition can be adjusted to have a viscosity suitable for the coating method used by changing the amount of the solvent.

  As the solvent, for example, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, glycol ether such as ethylene glycol monoethyl ether, methyl cellosolve acetate, ethylene glycol alkyl ether acetate such as ethyl cellosolve acetate, diethylene glycol monomethyl ether, Diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol compounds such as diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol alkyl ether acetate compounds such as propylene glycol ethyl ether acetate, toluene, xylene, etc. Aromatic hydrocarbons, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, ketones such as cyclohexanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Esters such as ethyl ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, and amide compounds such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide Can be mentioned. These solvents may be used alone or in combination of two or more.

  The photosensitive resin composition comprises a binder resin (A), an organic low molecular weight compound (B), a radiation-sensitive compound (C), a colorant (D), and, if necessary, an optional component (E) in a solvent (F). It can be prepared by dissolving or dispersing and mixing. The solid content concentration of the photosensitive resin composition can be appropriately determined depending on the purpose of use. For example, the solid content concentration of the photosensitive resin composition may be 1 to 60% by mass, 3 to 50% by mass, or 5 to 40% by mass.

  A known method can be used as a dispersion mixing method when a pigment is used. For example, ball type such as ball mill, sand mill, bead mill, paint shaker, rocking mill, blade type such as kneader, paddle mixer, planetary mixer, and Henschel mixer, roll type such as three-roll mixer, etc. An ultrasonic wave, a homogenizer, a rotation / revolution mixer, etc. may be used. From the viewpoint of dispersion efficiency and fine dispersion, it is preferable to use a bead mill.

  The prepared photosensitive resin composition is usually filtered before use. Examples of filtration means include a Millipore filter having a pore size of 0.05 to 1.0 μm.

  The photosensitive resin composition thus prepared is also excellent in long-term storage stability.

  When the photosensitive resin composition is used for radiation lithography, first, the photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition can be applied to the surface of the substrate, and the solvent can be removed by means such as heating to form a film. The method of applying the coating composition onto the substrate surface is not particularly limited, and for example, a spray method, a roll coating method, a slit method, a spin coating method, etc. can be used.

  After applying the coating composition to the surface of the substrate, the solvent is usually removed by heating (prebaking) to form a film. The heating conditions vary depending on the type of each component, the mixing ratio, etc., but are usually 70 to 130 ° C., for example, 1 to 20 minutes on a hot plate, and 3 to 60 minutes in an oven to obtain a film. You can

  Next, the prebaked film is irradiated with radiation (eg, visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, gamma ray, synchrotron radiation) through a photomask having a predetermined pattern (exposure step). . When a quinonediazide compound is used as the radiation-sensitive compound, the preferred radiation is ultraviolet light to visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-line.

  After the exposure step, the coating is developed by bringing it into contact with a developing solution, and unnecessary portions are removed to form a pattern on the coating (developing step). Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine, diamine -Secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline And the like quaternary ammonium salt; cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane, etc. It is possible to use an aqueous solution of the alkali compound. An aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like to an alkaline aqueous solution can also be used as a developing solution. The developing time is usually 30 to 180 seconds. The developing method may be any of a puddle method, a shower method, a dipping method and the like. After development, washing with running water is carried out for 30 to 90 seconds to remove unnecessary portions and air drying with compressed air or compressed nitrogen can be performed to form a pattern on the coating.

  After that, the cured film can be obtained by subjecting the film on which the pattern is formed to a heat treatment such as a hot plate and an oven at, for example, 100 to 350 ° C. for 20 to 200 minutes (post-baking, heat treatment). Process). In the heat treatment, the temperature may be kept constant, the temperature may be continuously raised, or the temperature may be raised stepwise.

  The optical density (OD value) of the cured film of the photosensitive resin composition is preferably 0.5 or more per 1 μm of film thickness, more preferably 0.7 or more, and 1.0 or more. More preferable. When the OD value of the cured film is 0.5 or more per 1 μm of film thickness, sufficient light shielding property can be obtained.

  In one embodiment, the photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition, the coating composition is applied to a substrate to form a film, and the solvent contained in the film is removed. Drying the coating, exposing the coating by irradiating the dried coating with radiation through a photomask, and developing the exposed coating by contacting it with a developer to form a pattern on the coating. And a method for manufacturing an organic EL device partition wall, which comprises heat-treating the coating film on which the pattern is formed at a temperature of 100 ° C. to 350 ° C. to form the organic EL device partition wall.

  One embodiment is an organic EL device partition containing a cured product of a photosensitive resin composition.

  One embodiment is an organic EL device containing a cured product of a photosensitive resin composition.

  Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

The weight average molecular weight and the number average molecular weight of the binder resin (A) were calculated using a calibration curve prepared using a polystyrene standard substance under the following measurement conditions.
Device name: Shodex (registered trademark) GPC-101
Column: Shodex (registered trademark) LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: Shodex (registered trademark) RI-71
Temperature: 40 ° C

(1) Synthesis of binder resin (A)

[Production Example 1] Production of an aqueous alkaline solution-soluble resin (c1) having an epoxy group and a phenolic hydroxyl group In a 300 mL three-necked flask, 300 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent, and at least 2 per molecule. As a compound having one epoxy group, 150 g of EPICLON (registered trademark) N-695 (cresol novolac type epoxy resin manufactured by DIC Corporation, epoxy equivalent 210) was charged and dissolved at 60 ° C. in a nitrogen gas atmosphere. There, 70.4 g of 3,5-dihydroxybenzoic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound (0.65 equivalents relative to 1 equivalent of epoxy) and triphenylphosphine (Tokyo Kasei) as a reaction catalyst. 0.661g (2.52mmol) manufactured by Kogyo Co., Ltd. was added and reacted at 110 ° C for 24 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to recover 804.2 g (resin liquid c1). The number average molecular weight of the obtained reaction product was 3,000, and the weight average molecular weight was 8,100.

[Production Example 2] Production of alkaline aqueous solution-soluble resin (c2) having epoxy group and phenolic hydroxyl group In a 300 mL three-necked flask, 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent was added per molecule. 37.6 g of EPICLON (registered trademark) N-770 (phenolic novolac type epoxy resin manufactured by DIC Corporation, epoxy equivalent 188) was charged as a compound having at least two epoxy groups and dissolved at 60 ° C. under a nitrogen gas atmosphere. .. There, 20.1 g of 3,5-dihydroxybenzoic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound (0.65 equivalents relative to 1 equivalent of epoxy) and triphenylphosphine (Tokyo Kasei) as a reaction catalyst. 0.173 g (0.660 mmol) manufactured by Kogyo Co., Ltd. was added and reacted at 110 ° C. for 21 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to recover 197.7 g (resin liquid c2). The number average molecular weight of the obtained reaction product was 2,400, and the weight average molecular weight was 8,300.

[Production Example 3] Production of an aqueous alkaline solution-soluble copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko KK) ) 28.0 g and N-cyclohexyl maleimide (manufactured by Nippon Shokubai Co., Ltd.) 7.89 g, and 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) 77.1 g, and V-601 (Fuji Co., Ltd.) as a polymerization initiator. 3.66 g of the film Wako Pure Chemical Industries, Ltd.) was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation). The obtained two solutions were simultaneously added to 61.2 g of 1-methoxy-2-propylacetate (manufactured by Daicel Corporation) heated to 85 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. After dropping, the mixture was reacted at 85 ° C. for 3 hours. The reaction solution cooled to room temperature was dropped into 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 90 ° C. for 4 hours to recover 32.4 g of white powder. This was dissolved in γ-butyrolactone to obtain a resin liquid having a solid content of 20 mass% (resin liquid d1). The resulting reaction product had a number average molecular weight of 6,100 and a weight average molecular weight of 1,1800.

(2) Raw Material (A) Binder Resin As the binder resin (A), the resin liquids c1, c2, and d1 synthesized in Production Examples 1 to 3 were used.

(B) Organic low-molecular compound The compounds shown in Table 1 were used as the organic low-molecular compound (B). Molar volume (cm ³ / mol) and pKa were quoted from Scifinder®.

(C) Radiation Sensitive Compound A quinonediazide compound TS150-A (α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene 1,2- which is a photoacid generator as a radiation sensitive compound. Naftoquinone diazide-5-sulfonic acid ester (manufactured by Toyo Gosei Co., Ltd.) was used, and the structure of TS-150A is shown below: The sulfonic acid esterification rate of TS-150A is about 50%.

(D) Colorant As a colorant, VALIFAST (registered trademark) BLACK 3804 (black dye defined by CI of Solvent Black 34 (manufactured by Orient Chemical Industry Co., Ltd.)) which is a black dye was used.

(E) Optional component Megafac (registered trademark) F-559 (fluorine-based surfactant (manufactured by DIC Corporation)) was used as a surfactant.

(F) Solvent γ-butyrolactone was used as the solvent.

(3) Preparation and Evaluation of Photosensitive Resin Composition [Examples 1-10, Comparative Examples 1-6]
Resin solution d1 22.5 parts by mass (solid content 4.5 parts by mass) and resin solution c1 21 parts by mass (solid content 4.2 parts by mass) were mixed and dissolved, and the obtained solution was as shown in Table 1. 5 parts by mass of each organic low-molecular compound (B) described, 22 parts by mass of TS-150A, 29.5 parts by mass of VALIFAST (registered trademark) BLACK 3804, and 0.14 parts by mass of Megafac (registered trademark) F-559. And a diluent solvent were added and further mixed. After visually confirming the dissolution, the solution was filtered through a Millipore filter having a pore size of 0.22 μm to prepare a photosensitive resin composition having a solid content concentration of 12% by mass.

  With respect to the photosensitive resin compositions prepared in each example and each comparative example, pattern formability and residue, surface condition, and ITO adhesion were evaluated. The results are shown in Table 2. The evaluation method is as follows.

[Pattern formability and residue]
On the ITO film of a glass substrate (size 70 mm × 70 mm × 0.7 mm) having an indium tin oxide (ITO) film, the photosensitive resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were respectively dried. Was about 1 to 2 μm, and the solvent was dried at 120 ° C. for 80 seconds. Furthermore, with an exposure device (trade name Multi-light ML-251A / B, manufactured by Ushio Inc.) incorporating an ultra-high pressure mercury lamp, a bandpass filter for mercury exposure (product name HB0365, manufactured by Asahi Bunko Co., Ltd.) and a quartz photo Only the i-line was exposed at 100 mJ / cm ² through the mask. The line & space (L / S) pattern of the photomask was 10 μm. The exposure amount was measured using an ultraviolet integrated photometer (trade name: UIT-150, light receiving part UVD-S365, manufactured by Ushio Inc.). The exposed film was alkali-developed for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). Then, a pattern sample was obtained by curing at 250 ° C. for 60 minutes in a nitrogen gas atmosphere. Observation using an optical microscope (VHX-6000, manufactured by Keyence Corporation) determined that there was no residue after alkali development including the edge portion of the pattern as “good”, and if there was residue, it was determined as “poor”. ..

  When both the pattern formability and the residue were good, the pattern formability and the residue were judged as "good", and the other cases were judged as "poor".

[Surface condition]
After forming the pattern in the same manner as described above, it was evaluated using an optical microscope (VHX-6000, manufactured by KEYENCE CORPORATION) whether the skin was orange-colored or mottled. Those in which the orange-colored skin-like portion and the color nonuniformity were not observed were judged to be “good”, and those in which any one of the orange-colored skin-like part and the color nonuniformity were observed were judged to be “poor”.

[ITO adhesion]
After forming the pattern in the same manner as above, whether the pattern was formed according to the photomask was evaluated using an optical microscope (VHX-6000, manufactured by Keyence Corporation). When the pattern remained on the photomask, it was judged as "good", and when the pattern was partially peeled off, it was judged as "bad".

[Examples 11 to 15]
A photosensitive resin composition having the composition shown in Table 3 was prepared in the same manner as in Example 1. The photosensitive resin composition prepared in each example was evaluated for film thickness, OD value after heating, unexposed area solubility, and residual film rate. The results are shown in Table 3. The evaluation method is as follows.

[Film thickness]
The 10 μm L / S portion of the pattern sample after pattern formability and residue confirmation was measured using a surface roughness meter (Surfcom 130A, manufactured by Tokyo Seimitsu Co., Ltd.).

[OD value after heating]
A glass substrate (size 100 mm × 100 mm × 1 mm) was spin-coated with the photosensitive resin composition of Examples 11 to 15 to a dry film thickness of about 1.5 μm, and heated on a hot plate at 120 ° C. for 80 seconds. The solvent was dried. Then, a coating was obtained by curing at 250 ° C. for 60 minutes in a nitrogen gas atmosphere. The OD value of the film after curing was measured with a transmission densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.), corrected with the OD value of only glass, and converted into an OD value per 1 μm of the film thickness. The thickness of the coating film was measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.).

[Unexposed area solubility]
A glass substrate with an ITO film (size: 70 mm × 70 mm × 0.7 mm) was bar-coated with the photosensitive resin composition of Examples 11 to 15 to a dry film thickness of 1.5 to 2.0 μm, and then a hot plate was used. The solvent was dried by heating at 120 ° C. for 80 seconds. After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.), 2.38 mass% tetramethyl using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.) Alkali development was carried out for 60 seconds with an ammonium hydroxide aqueous solution. The film thickness after alkali development was measured again using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.), and the film thickness dissolved before and after development was calculated as the solubility in the unexposed area.

[Rate of remaining film]
The coating film after the unexposed portion solubility measurement was cured at 250 ° C. for 60 minutes in a nitrogen gas atmosphere, and the coating film thickness after curing was measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmetrics Co., Ltd.) It was measured. The residual film rate was calculated from each measured value according to the following formula.
Residual film rate (%) = film thickness after dissolution (development) and curing process of unexposed area / film thickness before dissolution of unexposed area

  The photosensitive resin composition of the present invention can be suitably used for radiation lithography for forming partition walls of organic EL devices. The organic EL element provided with the partition wall formed from the photosensitive resin composition of the present invention is suitably used as an electronic component of a display device showing good contrast.

Claims (11)

(A) binder resin,
(B) at least one organic low molecular compound selected from the group consisting of aromatic carboxylic acids and compounds having a plurality of phenolic hydroxyl groups, having a molar volume of 130 cm ³ / mol or less,
A photosensitive resin composition for organic EL device partition, comprising (C) a radiation-sensitive compound, and (D) a colorant selected from the group consisting of a black dye and a black pigment, wherein the binder resin (A) comprises: An organic aqueous solution soluble resin (c) having an epoxy group and a phenolic hydroxyl group is contained, and the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 μm of film thickness, and the organic low molecule is The photosensitive resin composition for organic EL device partition walls, wherein the compound (B) is an aromatic carboxylic acid having a pKa of 2.5 to 4.5.   The photosensitive resin composition according to claim 1, wherein groups other than a carboxy group and a phenolic hydroxyl group are not bonded to carbon atoms constituting the aromatic ring of the organic low molecular weight compound (B).   The aromatic carboxylic acid is a polyvalent carboxylic acid selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, and trimesic acid; or 2,3-dihydroxybenzoic acid, 2, It is an aromatic hydroxycarboxylic acid selected from the group consisting of 4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, and gallic acid. The photosensitive resin composition according to claim 1 or 2.   0.1 parts by mass to 20 parts by mass of the binder resin (A), the organic low-molecular compound (B), the radiation-sensitive compound (C) and the colorant (D) are used as a reference. The photosensitive resin composition according to any one of claims 1 to 3, which comprises an organic low-molecular compound (B).   The radiation-sensitive compound (C) is at least one photoacid generator selected from the group consisting of a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt. The photosensitive resin composition as described in one item.   The photosensitive resin composition according to any one of claims 1 to 5, wherein the binder resin (A) has an alkali-soluble functional group.   1 part by mass to 70 parts by mass of the colorant, based on a total of 100 parts by mass of the binder resin (A), the organic low molecular weight compound (B), the radiation-sensitive compound (C) and the colorant (D). The photosensitive resin composition according to any one of claims 1 to 6, which comprises (D).   5 parts by mass to 50 parts by mass of the radiation sensitive material based on 100 parts by mass of the binder resin (A), the organic low molecular weight compound (B), the radiation sensitive compound (C) and the colorant (D) in total. The photosensitive resin composition according to any one of claims 1 to 7, which comprises a photoacid generator as a compound (C). The binder resin (A) is
(A) Formula (1)

(In the formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formula (2)

(In the formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms. Or an aryl group having 6 to 12 carbon atoms, wherein * in the formula (2) represents a bonding portion with a carbon atom constituting an aromatic ring), and an alkenyl group having 1 to 2 carbon atoms. An alkoxy group or a hydroxyl group, and at least one of R ¹ , R ² and R ³ is an alkenyl group represented by the formula (2), Q is an alkylene group represented by the formula —CR ⁴ R ⁵ —, A cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent group combining these, and R ⁴ and R ⁵ are , Each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .. )
At least one selected from the group consisting of a polyalkenylphenol resin having the structural unit of (1), and (d) a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer in an aqueous alkali solution. The photosensitive resin composition according to any one of claims 1 to 8, further comprising:   An organic EL device partition wall containing a cured product of the photosensitive resin composition according to claim 1.   An organic EL device containing the cured product of the photosensitive resin composition according to claim 1.