TWI797892B - Photosensitive resin composition and organic EL element partition wall - Google Patents

Abstract

A high-sensitivity photosensitive resin composition containing a black agent is provided, which can form a thick film pattern with high optical density (OD value). A photosensitive resin composition comprising (A) a first resin having an epoxy group and a phenolic hydroxyl group, (B) a second resin with a weight average molecular weight of 3,000 to 80,000, (D) a radiation-sensitive compound, and (E ) black agent photosensitive resin composition, the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 μm film thickness, and the alkali dissolution rate of the second resin is faster than that of the first resin Below 5%.

Description

Photosensitive resin composition and organic EL element partition walls

The present invention relates to a photosensitive resin composition containing a black agent, an organic EL element partition wall, an organic EL element insulating film, and an organic EL element using the same.

In a display device such as an organic EL display (OLED), in order to improve display characteristics, a partition wall material is used in the partition part of the colored pattern in the display area or the edge of the peripheral part of the display area. In the manufacture of an organic EL display device, in order not to make the pixels of the organic substance contact each other, partition walls are first formed, and the pixels of the organic substance are formed between the partition walls. Generally, this partition wall is formed by photolithography using a photosensitive resin composition, and has insulating properties. Specifically, a coating device is used to coat a photosensitive resin composition on a substrate, and after removing volatile components by means of heating or the like, exposure is performed through a mask, and then in the case of a negative type, the unexposed part is exposed on a positive type. In this case, the exposed portion is removed with a developer such as an aqueous alkali solution to perform development, and the obtained pattern is subjected to heat treatment to form a partition wall (insulating film). Next, an organic material emitting red, green, and blue light is deposited between the partition walls by an inkjet method to form a pixel of an organic EL display device.

In this field, in recent years, due to miniaturization of display devices and diversification of displayed content, higher performance and higher definition of pixels are required. For the purpose of improving contrast in a display device and improving visibility, attempts have been made to impart light-shielding properties to partition wall materials using colorants. However, when a partition wall material has light-shielding property, there exists a tendency for a photosensitive resin composition to become low sensitivity, and as a result, exposure time becomes long, and there exists a possibility that productivity may fall. Therefore, higher sensitivity is required for the photosensitive resin composition used for formation of the partition wall material containing a coloring agent.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2001-281440) describes a composition as a radiation-sensitive resin composition exhibiting high light-shielding properties by heat treatment after exposure, which is composed of an alkali-soluble resin and a quinone disulfide. It is made by adding titanium black to the positive radiation-sensitive resin composition of azide compound.

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

Patent Document 3 (Japanese Unexamined Patent Publication No. 2010-237310) describes a composition as a radiation-sensitive resin composition that exhibits more light-shielding properties through heat treatment after exposure, and is composed of an alkali-soluble resin and a quinone disulfide. It is made by adding thermosensitive pigment to the positive radiation sensitive resin composition of azide compound.

Patent Document 4 (International Publication No. 2017/069172) describes a positive photosensitive resin composition, which contains (A) binder resin, (B) quinone diazide compound, and (C) selected from solvent black At least one black dye among the black dyes specified by the color index of 27~47. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2001-281440 [Patent Document 2] Japanese Patent Laid-Open No. 2002-116536 [Patent Document 3] Japanese Patent Laid-Open No. 2010-237310 [Patent Document 4] International Publication No. 2017/069172

[Problem to be Solved by the Invention]

In the photosensitive resin composition used for the formation of the colored partition wall material, in order to fully improve the light-shielding properties of the cured film, a considerable amount of coloring agent must be used. When such a large amount of colorant is used, the radiation irradiated to the film of the photosensitive resin composition is absorbed by the colorant, the effective intensity of the radiation in the film decreases, and the photosensitive resin composition is not fully exposed, resulting in a decrease in pattern formation.

In particular, if it is desired to use a photosensitive resin composition containing a black agent to form a thick film, for example, a film with a thickness of 2-3 μm, the absorption of radiation caused by the addition of the black agent to the radiation-sensitive compound will reach the bottom of the film at the exposed part radiation dose was significantly reduced. Therefore, in the positive type, the alkali solubility of the film bottom of the exposed part is insufficient, and resin residues are generated during development, or a large amount of photosensitive resin composition is consumed in order to obtain a film with a desired thickness, that is, the remaining film rate decreases. . On the other hand, in the negative type, insolubilization of the film bottom of the exposed part is insufficient, and the film may be peeled off during development. Therefore, in the photosensitive resin composition containing black agent, there is an urgent need for a photosensitive resin composition that can impart a high optical density (OD value) to the cured film and increase the thickness of the cured film.

The object of the present invention is to provide a high-sensitivity photosensitive resin composition containing a black agent, which can form a thick film pattern with a high optical density (OD value) [Means to solve the problem]

The present inventors found that by using the first resin having epoxy groups and phenolic hydroxyl groups in combination with the second resin having a predetermined weight average molecular weight, the alkali dissolution rate of the second resin is significantly lower than that of the first resin The second resin is selected for the method of dissolution speed, and thick-film patterns can be formed even in the case of using a photosensitive resin composition containing black agent.

(式(4)中，R ³為氫原子或碳原子數1~5之烷基，R ⁴為選自由碳原子數1~20之直鏈烷基、碳原子數3~20之分支烷基、碳原子數3~12之環狀烷基、碳原子數6~20之芳基、經酸性官能基以外之基取代之碳原子數1~20之直鏈烷基、經酸性官能基以外之基取代之碳原子數3~20之分支烷基、經酸性官能基以外之基取代之碳原子數3~12之環狀烷基，及經酸性官能基以外之基取代之碳原子數6~20之芳基所成群組中之基)。 [4] 如[1]~[3]中任一項記載之感光性樹脂組成物，其中其中前述第2樹脂具有式(3)所示之結構單元，

(式(3)中，R ²為氫原子或碳原子數1~5之烷基，b為1~5之整數)。 [5] 如[1]~[4]中任一項記載之感光性樹脂組成物，其中前述第2樹脂具有式(5)所示之結構單元，

(式(5)中，R ⁵及R ⁶各自獨立為氫原子、碳原子數1~3之烷基、完全或部分氟化之碳原子數1~3之氟烷基，或鹵素原子，R ⁷為氫原子、碳原子數1~6之直鏈烷基、碳原子數3~12之環狀烷基、苯基，或經選自由羥基、碳原子數1~6之烷基及碳原子數1~6之烷氧基所成群組中之至少1種所取代之苯基)。 [6] 如[1]~[5]中任一項記載之感光性樹脂組成物，其中前述第1樹脂，為1分子中具有至少2個環氧基之化合物與羥基苯甲酸化合物的反應物，且為具有式(2)之結構的化合物，

(式(2)中，a為1~5之整數，＊表示與1分子中具有至少2個環氧基之化合物之去除反應之環氧基的殘基之結合部位)。 [7] 如[6]中記載之感光性樹脂組成物，其中前述1分子中具有至少2個環氧基之化合物為酚醛清漆型環氧樹脂。 [8] 如[1]~[7]中任一項記載之感光性樹脂組成物，其中前述黑色劑為以溶劑黑27~47之比色指數(C.I.)所規定之染料。 [9] 如[1]~[8]中任一項記載之感光性樹脂組成物，其中前述感放射線化合物為光酸產生劑。 [10] 如[1]~[9]中任一項記載之感光性樹脂組成物，其中前述感光性樹脂組成物進一步包含(C)相異於前述第1樹脂及前述第2樹脂之任一者之重量平均分子量為3000~80000的第3樹脂，前述第2樹脂之鹼溶解速度為前述第3樹脂之鹼溶解速度之5%以下。 [11] 如[10]中記載之感光性樹脂組成物，其中前述第3樹脂為具有酚性羥基之聚合性單體與其他聚合性單體之共聚物。 [12] 如[1]~[11]中任一項記載之感光性樹脂組成物，其中以樹脂成分之合計質量為基準，包含前述第1樹脂20質量%~90質量%。 [13] 如[1]~[12]中任一項記載之感光性樹脂組成物，其中以樹脂成分之合計質量為基準，包含前述第2樹脂5質量%~50質量。 [14] 如[10]或[11]中記載之感光性樹脂組成物，其中以樹脂成分之合計質量為基準，包含前述第3樹脂5質量%~50質量。 [15] 如[1]~[14]中任一項記載之感光性樹脂組成物，其中以樹脂成分之合計100質量份為基準，包含前述感放射線化合物1質量份~40質量份。 [16] 如[1]~[15]中任一項記載之感光性樹脂組成物，其中以樹脂成分之合計100質量份為基準，包含前述黑色劑10質量份~150質量份。 [17] 一種有機EL元件間隔壁，其包含如[1]~[16]中任一項記載之感光性樹脂組成物之硬化物。 [18] 一種有機EL元件絕緣膜，其包含如[1]~[16]中任一項記載之感光性樹脂組成物之硬化物。 [19] 一種有機EL元件，其包含如[1]~[16]中任一項記載之感光性樹脂組成物之硬化物。 [發明效果] That is, the present invention includes the following aspects. [1] A photosensitive resin composition comprising: (A) a first resin having an epoxy group and a phenolic hydroxyl group, (B) a second resin having a weight average molecular weight of 3,000 to 80,000, (D) a radiation-sensitive compound , and (E) black agent, the optical density (OD value) of the cured film of the photosensitive resin composition is more than 0.5 per 1 μm film thickness, and the alkali dissolution rate of the second resin is the alkali dissolution rate of the first resin less than 5% of the [2] The photosensitive resin composition described in [1], wherein the second resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. [3] The photosensitive resin composition as described in [1] or [2], wherein the second resin has a structural unit represented by formula (4),

(In formula (4), R ³ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ⁴ is a branched alkyl group selected from a straight chain alkyl group with 1 to 20 carbon atoms and a branched alkyl group with 3 to 20 carbon atoms , cyclic alkyl groups with 3 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, linear alkyl groups with 1 to 20 carbon atoms substituted by groups other than acidic functional groups, and substituted by groups other than acidic functional groups A branched alkyl group with 3 to 20 carbon atoms substituted by a radical, a cyclic alkyl group with 3 to 12 carbon atoms substituted by a group other than an acidic functional group, and a branched alkyl group with 6 to 2 carbon atoms substituted by a group other than an acidic functional group The base in the group formed by the aryl group of 20). [4] The photosensitive resin composition described in any one of [1] to [3], wherein the second resin has a structural unit represented by formula (3),

(In formula (3), R ² is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and b is an integer of 1 to 5). [5] The photosensitive resin composition described in any one of [1] to [4], wherein the second resin has a structural unit represented by formula (5),

(In formula (5), R5 and ^R6 are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, ^a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom, R ⁷ is a hydrogen atom, a linear alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and carbon atoms A phenyl group substituted by at least one of the group consisting of alkoxy groups with numbers 1 to 6). [6] The photosensitive resin composition according to any one of [1] to [5], wherein the first resin is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound , and is a compound having the structure of formula (2),

(In the formula (2), a is an integer of 1 to 5, and * represents a bonding site of an epoxy group residue that reacts with the removal of a compound having at least two epoxy groups in one molecule). [7] The photosensitive resin composition as described in [6], wherein the compound having at least two epoxy groups in one molecule is a novolak-type epoxy resin. [8] The photosensitive resin composition as described in any one of [1] to [7], wherein the aforementioned black agent is a dye specified by the color index (CI) of solvent black 27 to 47. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the radiation-sensitive compound is a photoacid generator. [10] The photosensitive resin composition described in any one of [1] to [9], wherein the photosensitive resin composition further contains (C) any one of the first resin and the second resin that is different from the aforementioned first resin and the aforementioned second resin. The weight average molecular weight of the third resin is 3000~80000, the alkali dissolution rate of the second resin is 5% or less of the alkali dissolution rate of the third resin. [11] The photosensitive resin composition as described in [10], wherein the third resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. [12] The photosensitive resin composition according to any one of [1] to [11], which contains 20% by mass to 90% by mass of the first resin based on the total mass of the resin components. [13] The photosensitive resin composition according to any one of [1] to [12], which contains 5% by mass to 50% by mass of the second resin based on the total mass of the resin components. [14] The photosensitive resin composition described in [10] or [11], which contains 5% by mass to 50% by mass of the aforementioned third resin based on the total mass of the resin components. [15] The photosensitive resin composition according to any one of [1] to [14], which contains 1 to 40 parts by mass of the radiation-sensitive compound based on 100 parts by mass of the total resin components. [16] The photosensitive resin composition according to any one of [1] to [15], which contains 10 to 150 parts by mass of the black agent based on 100 parts by mass of the total resin components. [17] A partition wall for an organic EL element comprising a cured product of the photosensitive resin composition according to any one of [1] to [16]. [18] An insulating film for an organic EL element comprising a cured product of the photosensitive resin composition described in any one of [1] to [16]. [19] An organic EL device comprising a cured product of the photosensitive resin composition according to any one of [1] to [16]. [Invention effect]

According to the present invention, a high-sensitivity photosensitive resin composition containing a black agent can be provided, which can form a thick film pattern with a high optical density (OD value).

The present invention will be described in detail below.

The term "alkali-soluble" in this disclosure means that the photosensitive resin composition or its components, or the film or cured film of the photosensitive resin composition can be dissolved in a 2.38% by mass tetramethylammonium hydroxide aqueous solution. The term "alkali-soluble functional group" means a group that imparts alkali solubility to the photosensitive resin composition or its components, or the coating or cured coating of the photosensitive resin composition. As an alkali-soluble functional group, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group, a mercapto group etc. are mentioned, for example.

The term "radical polymerizable functional group" in this disclosure means an ethylenically unsaturated group, and the term "radical polymerizable compound" means a compound having one or more ethylenically unsaturated groups.

The term "structural unit" in this disclosure refers to an atomic group constituting a part of the basic structure of a polymer. The atomic group may also have pendant atoms or pendant atomic groups. For example, in the case of a radical (co)polymer, it means a unit derived from a radically polymerizable compound used as a monomer, and in the case of a phenol novolac resin, it means a unit derived from one molecule of phenol (C ₆ H ₅ OH) and 1 molecule of formaldehyde (HCHO) formed by the condensation reaction of the following units. Regarding the structural unit having a pendant group (side group), a structural unit having a pendant group or a group derived from it used in the formation of a crosslinking site and a structural unit having a free pendant group not participating in the formation of a crosslinking site , are considered different from each other. With regard to polymers having branched molecular chains (branches), structural units including branch points (branch units) and structural units contained in linear molecular chains are regarded as different from each other.

The so-called "(meth)acryl" in this disclosure means acrylic or methacryl, the so-called "(meth)acrylate" means acrylate or methacrylate, and the so-called "(meth)acryl " means acryl or methacryl.

In this disclosure, the number average molecular weight (Mn) and weight average molecular weight (Mw) of a resin or polymer refer to standard polystyrene conversion values measured by gel permeation chromatography (GPC, gel permeation chromatography).

。 式中，單體i (i=1~n)之共聚合比(莫耳基準)之合計為1。 In this disclosure, the phenolic hydroxyl equivalent is a theoretical value calculated from the molecular weight and composition ratio of the structural units constituting the resin. Specifically, when the resin is a (co)polymer of n types of monomer i (a natural number from i=1 to n), the phenolic hydroxyl equivalent means the value calculated by the following formula:

. In the formula, the total of the copolymerization ratios (molar basis) of monomer i (i=1~n) is 1.

In the case of (c) a resin having an epoxy group and a phenolic hydroxyl group described later, the phenolic hydroxyl equivalent means a value calculated by the following formula: Phenolic hydroxyl equivalent = (Epoxy equivalent weight of raw material + molecular weight of added carboxylic acid)/(number of phenolic hydroxyl groups of carboxylic acid).

In this disclosure, carboxyl group content (mmol/g) refers to the following value: Weigh an appropriate amount of the sample, dissolve it in a mixed solvent of toluene/methanol=7/3 (mass ratio), add a few drops of phenolphthalein solution, and use 0.1mol/L ethanolic potassium hydroxide solution was titrated to obtain the acid value, based on the obtained acid value by the following formula: Carboxyl content (mmol/g)=acid value/56.1 The calculated value.

The "resin component" in this disclosure refers to the first resin (A), the second resin (B) and the third resin (C) which is an optional component.

The so-called "solid content" in this disclosure refers to any components including the resin component, radiation-sensitive compound (D), black agent (E), and dissolution accelerator (F), and removes the basic compound (G) and solvent of the liquid The total mass of the components of (H).

In this disclosure, the alkali dissolution rate of a resin or a photosensitive resin composition is determined by the following procedure. Add MEGAFACE (registered trademark) as a leveling agent in an amount of 0.1 parts by mass per 100 parts by mass of resin solids in a 20% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of resin or photosensitive resin composition F-559 (fluorine-based surfactant, manufactured by DIC Corporation). The obtained mixture was applied on a glass substrate (70 mm×70 mm×0.7 mm) so that the dry film thickness became 5.0 μm, vacuum-dried for 30 seconds, and then the film was dried at a temperature of 120° C. for 120 seconds. After drying, alkali image development was performed with 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution. The developing time is adjusted to be in the range of 8~400 seconds, the time when the film will not completely dissolve. The value obtained by dividing the decrease (nm) of the film after development by the development time (second) was defined as the alkali dissolution rate (nm/second).

A photosensitive resin composition according to an embodiment, comprising a first resin (A) having an epoxy group and a phenolic hydroxyl group, a second resin (B) having a weight average molecular weight of 3000-80000, and a radiation-sensitive compound (D), and black agent (E).

The alkali dissolution rate of the second resin (B) is 5% or less of the alkali dissolution rate of the first resin (A). The alkali dissolution rate of the second resin (B) is preferably 3% or less of the alkali dissolution rate of the first resin (A), more preferably 1% or less. Since the second resin (B) has a significantly lower alkali dissolution rate than the first resin (A), it acts as a resin component with low alkali solubility during development to suppress excessive dissolution of the unexposed part, while on the other hand, it is Partly accompanied by the dissolution of other resin components with high alkali solubility and any dissolution accelerators, they are released from the film into the developer solution, so the sensitivity and residual film rate of the photosensitive resin composition can be improved. Thereby, depending on the application, the content of the radiation-sensitive compound (D) in the photosensitive resin composition can be reduced, and as a result, the photosensitive resin composition can be made suitable for forming a thick film.

[the first resin (A)] The first resin (A) is a resin having an epoxy group and a phenolic hydroxyl group. Resins having epoxy groups and phenolic hydroxyl groups can be obtained, for example, by combining epoxy groups of compounds having at least two epoxy groups in one molecule (hereinafter sometimes referred to as "epoxy compounds"), and hydroxybenzene It is obtained by reacting the carboxyl group of the formic acid compound. Resins with epoxy groups and phenolic hydroxyl groups can form crosslinks by reacting with phenolic hydroxyl groups when they are heated to improve the chemical resistance and heat resistance of the film. The phenolic hydroxyl group imparts alkali solubility to the resin during development.

One of the epoxy groups of the epoxy compound reacts with the carboxyl group of the hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group, as shown in Reaction Formula 1 below.

Examples of compounds having at least two epoxy groups in one molecule include novolac epoxy resins such as phenol novolak epoxy resins and cresol novolak epoxy resins, bisphenol epoxy resins, bisphenol epoxy resins, and bisphenol epoxy resins. Phenol type epoxy resin, epoxy resin containing naphthalene skeleton, alicyclic epoxy resin, heterocyclic epoxy resin, etc. These epoxy compounds should just have 2 or more epoxy groups in 1 molecule, and only 1 type may be used, and 2 or more types may be used in combination. These compounds are of thermosetting type, so as common knowledge of the industry, their structures cannot be described in a single sense due to differences in the presence or absence of epoxy groups, types of functional groups, degree of polymerization, and the like. An example of the structure of a novolak type epoxy resin is shown in Formula (1). In formula (1), for example, R ¹ is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 2 carbon atoms, or a hydroxyl group, and m is an integer of 1 to 50.

As a phenol novolak type epoxy resin, Epiclon (registered trademark) N-770 (made by DIC Corporation), jER(registered trademark)-152 (made by Mitsubishi Chemical Corporation), etc. are mentioned, for example. As a cresol novolak type epoxy resin, Epiclon (registered trademark) N-695 (made by DIC Corporation), EOCN (registered trademark)-102S (made by Nippon Kayaku Co., Ltd.), etc. are mentioned, for example. Examples of bisphenol-type epoxy resins include jER (registered trademark) 828, jER (registered trademark) 1001 (manufactured by Mitsubishi Chemical Corporation), YD-128 (trade name, manufactured by Nippon Steel Chemical & Materials Co., Ltd.) Bisphenol A type epoxy resin such as jER (registered trademark) 806 (manufactured by Mitsubishi Chemical Co., Ltd.), YDF-170 (trade name, manufactured by Nippon Steel Chemical & Materials Co., Ltd.) and other bisphenol F type epoxy resin resin etc. As a biphenol type epoxy resin, jER (registered trademark) YX-4000, jER (registered trademark) YL-6121H (made by Mitsubishi Chemical Corporation), etc. are mentioned, for example. Examples of the epoxy resin containing a naphthalene skeleton include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (trade name, manufactured by DIC Corporation), and the like. As an alicyclic epoxy resin, EHPE (registered trademark)-3150 (made by Daicel Chemical Industry Co., Ltd.), etc. are mentioned, for example. As a heterocyclic epoxy resin, TEPIC (registered trademark), TEPIC-L, TEPIC-H, TEPIC-S (made by Nissan Chemical Industries, Ltd.) etc. are mentioned, for example.

The compound having at least two epoxy groups in one molecule is preferably a novolak type epoxy resin, more preferably a cresol novolak type epoxy resin. A photosensitive resin composition containing a novolak-type epoxy resin, especially a resin having an epoxy group and a phenolic hydroxyl group derived from a cresol novolac-type epoxy resin, has excellent pattern formation and adjustment of alkali solubility Easy, less exhaust.

Hydroxybenzoic acid compound is a compound in which at least one of the 2-6 positions of benzoic acid is substituted by a hydroxyl group, such as 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-nitro Among benzoic acid, 3-hydroxy-4-nitrobenzoic acid, and 4-hydroxy-3-nitrobenzoic acid, dihydroxybenzoic acid compounds are preferable from the viewpoint of improving alkali developability. These hydroxybenzoic acid compounds may be used alone or in combination of two or more.

之結構。式(2)中，a為1~5之整數，＊表示與1分子中具有至少2個環氧基之化合物之去除反應之環氧基的殘基之結合部位。 In one embodiment, the resin having an epoxy group and a phenolic hydroxyl group is a reactant of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and has the formula (2)

The structure. In formula (2), a is an integer of 1 to 5, and * represents a bonding site of an epoxy group residue that reacts with the removal of a compound having at least two epoxy groups in one molecule.

In the method for obtaining a resin having epoxy groups and phenolic hydroxyl groups from epoxy compounds and hydroxybenzoic acid compounds, 0.2 to 1.0 equivalents of hydroxybenzoic acid compounds can be used relative to 1 equivalent of epoxy groups in epoxy compounds, which is relatively It is more preferable to use 0.3-0.9 equivalent, and it is more preferable to use 0.4-0.8 equivalent. If the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and if it is 1.0 equivalent or less, the molecular weight increase by a side reaction can be suppressed.

A catalyst may also be used in order to accelerate the reaction of the epoxy compound and the hydroxybenzoic acid compound. The amount of the catalyst used may be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture composed of epoxy compounds and hydroxybenzoic acid compounds. The reaction temperature can be set at 60-150° C., and the reaction time can be set at 3-30 hours. As the catalyst used in this reaction, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenyl Phosphine, chromium octoate, zirconium octoate, etc.

The number average molecular weight of the resin having epoxy groups and phenolic hydroxyl groups is preferably 500-8000, more preferably 800-6000, and still more preferably 1000-5000. The weight average molecular weight of the resin having epoxy groups and phenolic hydroxyl groups is preferably 500-30,000, more preferably 2,000-25,000, and still more preferably 3,000-20,000. If the number average molecular weight is 500 or more, or the weight average molecular weight is 500 or more, the alkali development speed is suitable and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good. When the number average molecular weight is 8000 or less, or the weight average molecular weight is 30000 or less, applicability and alkali developability are favorable.

The phenolic hydroxyl equivalent of the resin having an epoxy group and a phenolic hydroxyl group is preferably 60-300, more preferably 80-250, and still more preferably 100-200. When the phenolic hydroxyl equivalent of the resin which has an epoxy group and a phenolic hydroxyl group is 60 or more, the film thickness of an unexposed part can be fully maintained at the time of alkali image development. When the phenolic hydroxyl equivalent of the resin which has an epoxy group and a phenolic hydroxyl group is 300 or less, desired alkali solubility can be acquired.

In this disclosure, the phenolic hydroxyl equivalents of the first resin (A), the second resin (B) described later, and the third resin (C) of an optional component described later mean the amount after exposure of the photosensitive resin composition and the development. value at the previous point in time. Whether or not there is a change in the original phenolic hydroxyl equivalent value of these resins and the phenolic hydroxyl equivalent value at the time point after exposure of the photosensitive resin composition and before development can be judged by the following procedure using NMR . With respect to 100 parts by mass of the resin to be measured, 30 parts by mass of the radiation-sensitive compound used in the mixed photosensitive resin composition and 1 part by mass of methyltriphenylsilane as an internal standard were added to DMSO-d6. This modulation test composition. ^{The 1} H-NMR of the obtained test composition was measured, and the integrated value S1 of the phenolic hydroxyl group was calculated when the integrated value of the internal standard was set to 1.00. Furthermore, the test composition was irradiated with ultraviolet rays of 1000mJ/cm ² using an exposure device equipped with an ultra-high pressure mercury lamp, and heated at 120°C for 5 minutes using an oil bath, and then the ¹ H-NMR of the test composition was measured to calculate the internal standard The integral value S2 of the phenolic hydroxyl group when the integral value is set as 1.00. The resin whose integral value change ratio (absolute value of (S2-S1)/S1) is less than 10% is regarded as the one with no change in the value of phenolic hydroxyl equivalent.

The content of the first resin (A) in the photosensitive resin composition is based on the total mass of the resin component, the radiation-sensitive compound (D) and the black agent (E), preferably 5-60% by mass, more preferably 10 to 55% by mass, more preferably 10 to 50% by mass. When the content of the first resin (A) is 5% by mass or more based on the above-mentioned total mass, it is suitable for the residual film rate, heat resistance, sensitivity, and the like. If the content of the first resin (A) is 60 mass% or less based on the above total mass, the optical density (OD value) of the film after curing can be 0.5 or more per 1 μm film thickness, and light-shielding can be maintained even after curing sex.

The photosensitive resin composition, based on the total mass of the resin components, preferably contains 20 mass % to 90 mass % of the first resin (A), more preferably contains 25 mass % to 70 mass %, contains 30 mass % to 55 mass % % is better. When the content of the first resin (A) is 20% by mass or more based on the total mass of the resin components, desired alkali solubility can be obtained. When the content of the first resin (A) is 90% by mass or less based on the total mass of the resin components, high sensitivity can be imparted to the photosensitive resin composition.

唑樹脂、聚苯并

唑樹脂前驅物、聚矽氧樹脂、環狀烯烴聚合物、卡多樹脂(cardo resin)，及此等樹脂之衍生物，以及使鹼可溶性官能基鍵結於此等樹脂者。作為第2樹脂(B)，可使用具有酚性羥基之聚合性單體的均聚物或共聚物。作為第2樹脂(B)，可單獨使用此等樹脂之任一者，或可組合此等樹脂之2種以上使用。第2樹脂(B)亦可具有自由基聚合性官能基。一實施態樣中，第2樹脂(B)具有(甲基)丙烯醯氧基、烯丙基或甲基烯丙基作為自由基聚合性官能基。 [Second Resin (B)] The second resin (B) is a resin having a weight average molecular weight of 3,000 to 80,000. The second resin (B) is different from the first resin (A) and is not particularly limited as long as the alkali dissolution rate satisfies the above relationship. The so-called "different" here means that the structures of the structural units of a certain resin and other resins are different from each other, or when a certain resin contains one or more common structural units with other resins, the total of the common structural units contains less than 70 moles %, resins with only different molecular weights are regarded as the same resins. As the second resin (B), for example, acrylic resin, polystyrene resin, epoxy resin, polyamide resin, phenol resin, polyimide resin, polyamide resin, polybenzo

Azole resin, polybenzo

Azole resin precursors, polysiloxane resins, cyclic olefin polymers, cardo resins, and derivatives of these resins, and those in which alkali-soluble functional groups are bonded to these resins. As the second resin (B), a homopolymer or a copolymer of a polymerizable monomer having a phenolic hydroxyl group can be used. As the second resin (B), any one of these resins may be used alone, or two or more of these resins may be used in combination. The second resin (B) may have a radical polymerizable functional group. In one embodiment, the second resin (B) has a (meth)acryloxy group, an allyl group, or a methallyl group as a radically polymerizable functional group.

The weight average molecular weight of the second resin (B) is 3000-80000, preferably 4000-30000, more preferably 5000-15000. Since the weight average molecular weight is 3000~80000, the alkali developing speed is suitable and the difference between the dissolution speed of the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good, and the coatability and alkali developing property are also good.

The number average molecular weight of the second resin (B) is preferably from 1,000 to 20,000, more preferably from 1,500 to 15,000, and still more preferably from 2,000 to 10,000. If the number average molecular weight is 1000 or more, the alkali developing speed is suitable and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good. When the number average molecular weight is 20000 or less, applicability and alkali developability are favorable. The polydispersity (Mw/Mn) of the second resin (B) is preferably from 1.0 to 3.5, more preferably from 1.1 to 3.0, still more preferably from 1.2 to 2.8. By making the polydispersity into the said range, the photosensitive resin composition excellent in pattern formation property and alkali developability can be obtained.

When the second resin (B) has a phenolic hydroxyl group as the alkali-soluble functional group, the phenolic hydroxyl equivalent of the second resin (B) is preferably 250-700, more preferably 260-600, and even more preferably 270-550. When the phenolic hydroxyl equivalent of the 2nd resin (B) is 250 or more, the film thickness of an unexposed part can be fully maintained at the time of alkali image development. If the phenolic hydroxyl equivalent of the 2nd resin (B) is 700 or less, desired alkali solubility will be acquired.

The carboxyl group content of the second resin (B) is preferably from 0.0 to 0.5 mmol/g, more preferably from 0.0 to 0.1 mmol/g, still more preferably from 0.00 to 0.05 mmol/g. Since the alkali solubility of a carboxyl group is higher than that of a phenolic hydroxyl group, it is unfavorable to contain a large amount in the 2nd resin (B) of a low alkali solubility component. With the carboxyl group content of the second resin (B) being 0.0-0.5 mmol/g, the alkali dissolution rate of the second resin (B), which is a low-alkali-soluble component, can be precisely controlled.

The second resin (B) is preferably a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. Examples of the polymerizable functional group of the polymerizable monomer include radical polymerizable functional groups, such as CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CHCO-, CH ₂ = C(CH ₃ )CO-, -OC-CH=CH-CO-, etc.

A copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer can be produced, for example, by radically polymerizing a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. After the copolymer is synthesized by radical polymerization, a derivative having a phenolic hydroxyl group added thereto can also be used. Examples of polymerizable monomers having phenolic hydroxyl groups include 4-hydroxystyrene, 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxy Phenylacrylamide, 4-hydroxyphenylmaleimide, etc. Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide ; Acrylonitrile; Ether compounds of vinyl alcohol such as vinyl-n-butyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso Propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tertiary butyl (meth)acrylate ester, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, epoxy Propyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, cyclohexyl (meth)acrylate ) acrylate, isocamphoryl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate and other (meth)acrylates; maleic anhydride, horse Maleic acid derivatives such as monoesters of maleic acid; N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide. From the point of view of heat resistance, etc., copolymers of polymerizable monomers having phenolic hydroxyl groups and other polymerizable monomers can have alicyclic structure, aromatic structure, polycyclic structure, inorganic ring structure, heterocyclic structure, etc. One or more cyclic structures such as cyclic structures are preferred.

式(3)中，R ²為氫原子或碳原子數1~5之烷基，b為1~5之整數。作為如此之具有酚性羥基之聚合性單體，以4-羥基苯基甲基丙烯酸酯特佳。 As a polymerizable monomer which has a phenolic hydroxyl group, what forms the structural unit represented by formula (3) is preferable.

In formula (3), R ² is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and b is an integer of 1 to 5. As such a polymerizable monomer having a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is particularly preferable.

(式(4)中，R ³為氫原子或碳原子數1~5之烷基，R ⁴為選自由碳原子數1~20之直鏈烷基、碳原子數3~20之分支烷基、碳原子數3~12之環狀烷基、碳原子數6~20之芳基、經酸性官能基以外之基取代之碳原子數1~20之直鏈烷基、經酸性官能基以外之基取代之碳原子數3~20之分支烷基、經酸性官能基以外之基取代之碳原子數3~12之環狀烷基，及經酸性官能基以外之基取代之碳原子數6~20之芳基所成群組中之基)。 本揭示中，所謂酸性官能基，為與2.38質量%之氫氧化四甲基銨水溶液顯示酸鹼反應的基，具體而言，可舉例酚性羥基、羧基、磺酸基、磷酸基、酸酐基及巰基。藉由使用如此之聚合性單體，可賦予第2樹脂(B)鹼低溶解性。 As another polymerizable monomer, a polymerizable monomer forming a structural unit represented by formula (4) is preferable.

(In formula (4), R ³ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ⁴ is a branched alkyl group selected from a straight chain alkyl group with 1 to 20 carbon atoms and a branched alkyl group with 3 to 20 carbon atoms , cyclic alkyl groups with 3 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, linear alkyl groups with 1 to 20 carbon atoms substituted by groups other than acidic functional groups, and substituted by groups other than acidic functional groups A branched alkyl group with 3 to 20 carbon atoms substituted by a radical, a cyclic alkyl group with 3 to 12 carbon atoms substituted by a group other than an acidic functional group, and a branched alkyl group with 6 to 2 carbon atoms substituted by a group other than an acidic functional group The base in the group formed by the aryl group of 20). In this disclosure, the so-called acidic functional group is a group that exhibits an acid-base reaction with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, specifically, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an acid anhydride group. and mercapto. By using such a polymerizable monomer, low alkali solubility can be imparted to the second resin (B).

In ^R of formula (4), specific examples of an alkyl group with 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Tertiary butyl, n-pentyl, etc. R ³ is preferably methyl.

In R in formula ( ⁴ ), as a straight-chain alkyl group with 1 to 20 carbon atoms and a branched alkyl group with 3 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl , n-butyl, isobutyl, sec-butyl, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-hexadecyl, etc. Examples of the cyclic alkyl group having 3 to 12 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, isobornyl, adamantyl, and dicyclopentyl. wait. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, 4-(benzyloxymethoxy)phenyl, biphenyl, naphthyl, fenyl, anthracenyl, and phenanthrenyl. R ⁴ is preferably tertiary butyl, cyclohexyl, isobornyl, dicyclopentyl, phenyl, or 4-(benzyloxymethoxy)phenyl.

式(5)中，R ⁵及R ⁶各自獨立為氫原子、碳原子數1~3之烷基、完全或部分氟化之碳原子數1~3之氟烷基，或鹵素原子，R ⁷為氫原子、碳原子數1~6之直鏈烷基、碳原子數3~12之環狀烷基、苯基，或經選自由羥基、碳原子數1~6之烷基及碳原子數1~6之烷氧基所成群組中之至少1種所取代之苯基。R ⁵及R ⁶為氫原子較佳。R ⁷為碳原子數3~12之環狀烷基或苯基較佳。作為如此之其他聚合性單體，以苯基馬來醯亞胺及環己基馬來醯亞胺特佳。 As another polymerizable monomer, a polymerizable monomer forming a structural unit represented by formula (5) is also preferable.

In formula (5), R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom, and R ⁷ It is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and the number of carbon atoms A phenyl group substituted by at least one of the group consisting of 1 to 6 alkoxy groups. R ⁵ and R ⁶ are preferably hydrogen atoms. R ⁷ is preferably a cyclic alkyl group or a phenyl group with 3 to 12 carbon atoms. As such other polymerizable monomers, phenylmaleimide and cyclohexylmaleimide are particularly preferable.

4-Hydroxyphenyl methacrylate is used as the polymerizable monomer having a phenolic hydroxyl group, and a combination of tertiary butyl methacrylate, cyclohexyl methacrylate, and isocamyl methyl is used as the other polymerizable monomer. At least one member selected from the group consisting of acrylate, dicyclopentyl methacrylate, phenyl methacrylate, and 4-(benzyloxymethoxy)phenyl methacrylate, and selected from the group consisting of phenyl It is particularly preferred to use at least one of the group consisting of maleimide and cyclohexylmaleimide. By using a resin obtained by radically polymerizing these polymerizable monomers as the second resin (B) with low alkali solubility, it is possible to reduce outgassing while improving shape retention.

As a polymerization initiator when producing a copolymer of a polymerizable monomer having a phenolic hydroxyl group and other polymerizable monomers by radical polymerization, although not limited to the following, 2,2'-azo can be used Bisisobutyronitrile, 2,2'-Azobis(2-methylbutyronitrile), Dimethyl 2,2'-Azobis(2-methylpropionate), 4,4'-Azo Azo polymerization initiators such as bis(4-cyanovalerenic acid), 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN), dicumyl peroxide, 2,5-Dimethyl-2,5-bis(tertiary butylperoxy)hexane, tertiary butylcumyl peroxide, di-tertiary butyl peroxide, 1,1 , 3,3-Tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc., peroxide polymerization initiators with a half-life of 10 hours and a temperature of 100~170°C, or benzoyl peroxide, peroxide Peroxide polymerization initiators such as lauryl, 1,1'-di(tertiary butylperoxy)cyclohexane, tertiary butylperoxypivalate, etc. The amount of the polymerization initiator used is generally not less than 0.01 parts by mass, not less than 0.05 parts by mass, or not less than 0.5 parts by mass, but not more than 40 parts by mass and not more than 20 parts by mass with respect to 100 parts by mass of the mixture of polymerizable monomers Or less than 15 parts by mass is preferred.

RAFT (Reversible Addition Fragmentation Transfer) agent can also be used together with polymerization initiator. As the RAFT agent, although not limited to the following ones, thiocarbonylsulfur compounds such as dithioesters, dithiocarbamates, trithiocarbonates, and xanthates can be used. The RAFT agent can be used in the range of 0.005 to 20 parts by mass, preferably in the range of 0.01 to 10 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer.

(式(4)中，R ³為氫原子或碳原子數1~5之烷基，R ⁴為選自由碳原子數1~20之直鏈烷基、碳原子數3~20之分支烷基、碳原子數3~12之環狀烷基、碳原子數6~20之芳基、經酸性官能基以外之基取代之碳原子數1~20之直鏈烷基、經酸性官能基以外之基取代之碳原子數3~20之分支烷基、經酸性官能基以外之基取代之碳原子數3~12之環狀烷基，及經酸性官能基以外之基取代之碳原子數6~20之芳基所成群組中之基)。 式(4)之R ³及R ⁴如上述。 In one embodiment, the second resin (B) has a structural unit represented by formula (4).

(In formula (4), R ³ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ⁴ is a branched alkyl group selected from a straight chain alkyl group with 1 to 20 carbon atoms and a branched alkyl group with 3 to 20 carbon atoms , cyclic alkyl groups with 3 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, linear alkyl groups with 1 to 20 carbon atoms substituted by groups other than acidic functional groups, and substituted by groups other than acidic functional groups A branched alkyl group with 3 to 20 carbon atoms substituted by a radical, a cyclic alkyl group with 3 to 12 carbon atoms substituted by a group other than an acidic functional group, and a branched alkyl group with 6 to 2 carbon atoms substituted by a group other than an acidic functional group The base in the group formed by the aryl group of 20). R ³ and R ⁴ in formula (4) are as above.

(式(3)中，R ²為氫原子或碳原子數1~5之烷基，b為1~5之整數)。 R ²以甲基較佳。b為1較佳。b為1時，OH基位於4位較佳。 In one embodiment, the second resin (B) has a structural unit represented by formula (3).

(In formula (3), R ² is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and b is an integer of 1 to 5). R ² is preferably methyl. b is preferably 1. When b is 1, the OH group is preferably at the 4th position.

(式(5)中，R ⁵及R ⁶各自獨立為氫原子、碳原子數1~3之烷基、完全或部分氟化之碳原子數1~3之氟烷基，或鹵素原子，R ⁷為氫原子、碳原子數1~6之直鏈烷基、碳原子數3~12之環狀烷基、苯基，或經選自由羥基、碳原子數1~6之烷基及碳原子數1~6之烷氧基所成群組中之至少1種所取代之苯基)。 R ⁵及R ⁶以氫原子較佳。R ⁷以苯基或環己基較佳。 In one embodiment, the second resin (B) has a structural unit represented by formula (5).

(In formula (5), R5 and ^R6 are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, ^a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom, R ⁷ is a hydrogen atom, a linear alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and carbon atoms A phenyl group substituted by at least one of the group consisting of alkoxy groups with numbers 1 to 6). R ⁵ and R ⁶ are preferably hydrogen atoms. R ⁷ is preferably phenyl or cyclohexyl.

The second resin (B) is preferably a copolymer comprising the structural unit represented by the above formula (3), the structural unit represented by the formula (4), and the structural unit represented by the formula (5).

The photosensitive resin composition, based on the total mass of the resin components, preferably contains the second resin (B) at 5 mass % to 50 mass %, more preferably at 8 mass % to 45 mass %, and at 10 mass % to 40 mass % % content is better. If the content of the second resin (B) is 5% by mass or more based on the total mass of the resin components, the contrast due to the difference in dissolution rate from the first resin (A) can be sufficiently obtained. If the content of the second resin (B) is 50% by mass or less on the basis of the total mass of the resin components, the dissolution of the coating film during development can be made more uniform microscopically, and as a result, the torsion on the surface of the coating film can be effectively suppressed. crack.

[the third resin (C)] The photosensitive resin composition may further contain, as an optional component, a third resin (C) having a weight average molecular weight of 3,000 to 80,000 different from any one of the first resin (A) and the second resin (B). The weight average molecular weight of the third resin (C) is preferably from 4,000 to 70,000, more preferably from 5,000 to 60,000. Since the weight average molecular weight is 3000~80000, the alkali developing speed is suitable and the difference between the dissolution speed of the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good, and the coatability and alkali developing property are also good.

The number average molecular weight of the third resin (C) is preferably from 1,000 to 30,000, more preferably from 1,500 to 25,000, and still more preferably from 2,000 to 20,000. If the number average molecular weight is 1000 or more, the alkali developing speed is suitable and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good. When the number average molecular weight is 30000 or less, applicability and alkali developability are favorable. The polydispersity (Mw/Mn) of the third resin (C) is preferably from 1.0 to 3.5, more preferably from 1.1 to 3.0, still more preferably from 1.2 to 2.8. By making polydispersity into the said range, the photosensitive resin composition excellent in pattern formation property and alkali developability can be obtained.

The alkali dissolution rate of the 2nd resin (B) is 5% or less of the alkali dissolution rate of the 3rd resin (C). The alkali dissolution rate of the second resin (B) is preferably 4% or less of the alkali dissolution rate of the third resin (C), more preferably 3% or less. Since the third resin (C) has higher alkali solubility than the second resin (B), it is possible to adjust the dissolution rate of the exposed part and the unexposed part of the cured film, thereby improving the patterning property.

The alkali dissolution rate of the third resin (C) is preferably lower than the alkali dissolution rate of the first resin (A), and it is better below 90% of the alkali dissolution rate of the first resin (A). It is better if the alkali dissolution rate is below 80%. Thereby, the dissolution of the film during development can be made more uniform microscopically, and as a result, cracks on the surface of the film can be effectively suppressed.

When the third resin (C) has a phenolic hydroxyl group as the alkali-soluble functional group, the phenolic hydroxyl equivalent of the third resin (C) is preferably 107-240, more preferably 140-235, and still more preferably 170-230. When the phenolic hydroxyl equivalent of the 3rd resin (C) is 107 or more, the film thickness of an unexposed part can be fully maintained at the time of alkali image development. If the phenolic hydroxyl equivalent of the 3rd resin (C) is 240 or less, desired alkali solubility can be acquired.

The third resin (C) is preferably a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. The method for producing a polymerizable monomer having a phenolic hydroxyl group, other polymerizable monomers, and a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer is as described in the second resin (B).

In the manufacture of the third resin (C), 4-hydroxyphenyl methacrylate is used as a polymerizable monomer having a phenolic hydroxyl group, and as the other polymerizable monomer, a polymer selected from phenylmaleimide and At least one of the group consisting of cyclohexylmaleimide is particularly preferred. By using a resin obtained by radically polymerizing these polymerizable monomers as the third resin (C), it is possible to reduce outgassing while improving shape retention and developability. In the production of the third resin (C), it is preferable not to use a polymerizable monomer forming the structural unit represented by formula (4).

(式(3)中，R ²為氫原子或碳原子數1~5之烷基，b為1~5之整數)；

(式(5)中，R ⁵及R ⁶各自獨立為氫原子、碳原子數1~3之烷基、完全或部分氟化之碳原子數1~3之氟烷基，或鹵素原子，R ⁷為氫原子、碳原子數1~6之直鏈烷基、碳原子數3~12之環狀烷基、苯基，或經選自由羥基、碳原子數1~6之烷基及碳原子數1~6之烷氧基所成群組中之至少1種所取代之苯基)。 第3樹脂(C)，以不包含式(4)所示之結構單元較佳。 In one embodiment, the third resin (C) has a structural unit represented by formula (3) and a structural unit represented by formula (5).

(In formula (3), R ² is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and b is an integer of 1 to 5);

(In formula (5), R5 and ^R6 are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, ^a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom, R ⁷ is a hydrogen atom, a linear alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and carbon atoms A phenyl group substituted by at least one of the group consisting of alkoxy groups with numbers 1 to 6). The third resin (C) preferably does not contain the structural unit represented by formula (4).

The photosensitive resin composition, based on the total mass of the resin components, preferably contains the third resin (C) at 5 mass % to 50 mass %, more preferably at 8 mass % to 45 mass %, and at 10 mass % to 40 mass % % is better. If the content of the third resin (C) is 5% by mass or more based on the total mass of the resin components, the dissolution of the coating film during development can be made more uniform microscopically, and as a result, the torsion on the surface of the coating film can be effectively suppressed. crack. If the content of the third resin (C) is 50% by mass or less based on the total mass of the resin components, then the contrast due to the difference in dissolution rate between the first resin (A) and the second resin (B) can be maintained. graphics.

[Radiation sensitive compound (D)] As the radiation-sensitive compound (D), a photoacid generator, a photobase generator, or a photopolymerization initiator can be used. The photoacid generator is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, γ-rays, and electron beams. The photoacid generator can be used in a positive-type photosensitive resin composition in which the portion irradiated with radiation has increased solubility in an aqueous alkali solution. A photobase generator is a compound which generates a base when irradiated with radiation. The photobase generator can be used in a negative-type photosensitive resin composition in which the portion irradiated with radiation is less soluble in aqueous alkali solution. The photopolymerization initiator is a compound that generates radicals when irradiated with radiation. Photopolymerization initiator, when the photosensitive resin composition contains a binder resin having a radically polymerizable functional group or a radically polymerizable compound, the radically polymerizable functional group or free radical of the binder resin at the portion irradiated with radiation Radical polymerization of a polymerizable compound can be used for a negative photosensitive resin composition in which a polymer insoluble in aqueous alkali solution is formed in this part.

<Photoacid generator> From the point of view of obtaining high-sensitivity and high-resolution patterns, the radiation-sensitive compound (D) is preferably a photoacid generator. As the photoacid generator, at least one selected from the group consisting of quinonediazide compounds, percite salts, phosphonium salts, diazonium salts, and iodonium salts can be used. In one embodiment, the photoacid generator is a compound or salt with high sensitivity to i-line (365 nm).

It is preferable to use a quinone diazide compound as a photoacid generator. Examples of quinone diazide compounds include those in which sulfonic acid of quinone diazide is ester-bonded to a polyhydroxy compound, those in which sulfonic acid of quinone diazide is bonded to a polyamine compound through sulfonamide, Sulfonic acid of quinonediazide is bonded to polyhydroxypolyamine-based compounds through ester linkage or sulfonamide linkage. From the viewpoint of the comparison between the exposed part and the unexposed part, it is preferable that 20 mol% or more of the functional groups of the polyol or polyamino compound be substituted with quinonediazide.

As polyols, 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, Methylene Reference-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, trade name, manufactured by 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 (above, trade name, Asahi organic material industry Co., Ltd.), 2,6-dimethoxymethyl-4-tertiary butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyl Acyloxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.), etc., but not limited to these.

Examples of polyamine-based compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane , 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, etc., but not limited thereto.

Examples of polyhydroxypolyamine-based compounds include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, and the like, but are not limited thereto.

The quinonediazide compound is preferably 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate of a polyhydroxy compound.

When the quinonediazide compound is irradiated with ultraviolet light or the like, it undergoes a reaction shown in Reaction Formula 2 below to generate a carboxyl group. By generating carboxyl groups, the exposed part (film) becomes soluble in aqueous alkali solution, and alkali developability is produced in this part.

When the radiation-sensitive compound (D) is a photoacid generator, the content of the photoacid generator in the photosensitive resin composition may be 1 to 40 parts by mass based on 100 parts by mass of the total resin components, preferably 1 to 40 parts by mass. 5-35 parts by mass, more preferably 10-30 parts by mass. The content of the photoacid generator is based on the total of 100 parts by mass. If it is 1 part by mass or more, the alkali developability will be good, and if it is 40 parts by mass or less, film reduction due to heating at 300° C. or higher can be suppressed.

<Photobase Generator> A photobase generator can also be used as a radiation sensitive compound (D). As a photobase generator, at least 1 sort(s) chosen from the group which consists of an amide compound and an ammonium salt can be used. In one embodiment, the photobase generator is a compound or salt highly sensitive to i-line (365 nm).

As the amide compound, for example, 2-nitrophenylmethyl-4-methacryloxypiperidine-1-carboxylate, 9-anthracenylmethyl-N,N-dimethylaminoformic acid ester, 1-(anthraquinone-2-yl)ethylimidazole carboxylate, (E)-1-[3-(2-hydroxyphenyl)-2-acryloyl]piperidine, etc. As the ammonium salt, for example, 1,2-diisopropyl-3-(bisdimethylamino)methylene)guanidinium 2-(3-benzoylphenyl)propionate, (Z) -{[bis(dimethylamino)methylene (methylidene)]amino}-N-cyclohexylamino)methanamine ion tetrakis(3-fluorophenyl)borate, 1,2-dicyclohexyl- 4,4,5,5-Tetramethylbiguanide n-butyltriphenylborate, etc.

When the radiation-sensitive compound (D) is a photobase generator, the content of the photobase generator in the photosensitive resin composition may be 1 to 40 parts by mass based on 100 parts by mass of the total resin components, preferably 1 to 40 parts by mass. 5-35 parts by mass, more preferably 10-30 parts by mass. The content of the photobase generator is based on the above total 100 parts by mass. If it is 1 part by mass or more, the alkali developability will be good, and if it is 40 parts by mass or less, the reduction of the film caused by heating at 300° C. or higher can be suppressed.

<Photopolymerization Initiator> A photopolymerization initiator can also be used as a radiation-sensitive compound (D). As the photopolymerization initiator, a group selected from benzyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine oxide compounds, oxime ester compounds, acridine compounds, benzophenone compounds, At least one selected from the group consisting of acetophenone compounds, aromatic ketoester compounds, and benzoate compounds. In one embodiment, the photopolymerization initiator is a compound highly sensitive to i-line (365 nm). From the perspective of high sensitivity during exposure, the photopolymerization initiator is preferably α-hydroxy ketone compound, α-amino ketone compound, acyl phosphine oxide compound, oxime ester compound, acridine compound or benzophenone compound. An α-amino ketone compound, an acyl phosphine oxide compound or an oxime ester compound is more preferable.

The benzyl ketal compound may, for example, be 2,2-dimethoxy-1,2-diphenylethan-1-one. Examples of α-hydroxyketone compounds include 1-(4-cumyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- 1-keto, 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 α-aminoketone compounds include 2-dimethylamino-2-methyl-1-phenylpropane-1-one, 2-diethylamino-2-methyl-1-phenylpropane -1-one, 2-methyl-2-morpholinyl-1-phenylpropane-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propane- 1-keto, 2-dimethylamino-1-(4-ethylphenyl)-2-methylpropan-1-one, 2-dimethylamino-1-(4-isopropylphenyl)- 2-methylpropan-1-one, 1-(4-butylphenyl)-2-dimethylamino-2-methylpropan-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)-butane -1-ketone, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butane-1-one, 2-dimethylamino-2-[(4- Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone. As the acylphosphine oxide compound, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, Phosphine or bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide. Examples of oxime ester compounds 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- Diketo-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-dioxolane-4 -yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime. The acridine compound may, for example, be 1,7-bis(acridin-9-yl)-n-heptane. As the benzophenone compound, for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4 -Phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone, alkylated benzophenone, 3,3',4,4'-tetra(tertiary butyl peroxycarbonyl) benzophenone, 4-methylbenzophenone, dibenzyl ketone or fennelone. Examples of the acetophenone compound include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-tertiary butyldichloroacetophenone, benzylidene phenone ketone or 4-azidobenzylideneacetophenone. The aromatic ketoester compound may, for example, be methyl 2-phenyl-2-oxyacetate. As the benzoate compound, for example, ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate or 2- Methyl benzoylbenzoate.

When the 1st resin (A), the 2nd resin (B), or the 3rd resin (C) of an arbitrary component, or these 2 or more types have cationic polymerizable groups, such as an epoxy group, as a photopolymerization initiator, A photocationic polymerization initiator that generates cationic species or Lewis acid by light can be used. As photocationic polymerization initiators, for example, triphenylconium, diphenyl-4-(phenylsulfanyl)phenylconium, diphenyliumium, bis(dodecylconium), etc. Odonium such as phenyl)iodonium, diazonium such as phenyldiazonium, 1-benzyl-2-cyanopyridinium, 1-(naphthylmethyl)-2-cyanopyridinium, etc. Fe cations of pyridinium, (2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe, etc., the anion part is BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , [BX ₄ ] ^- (X is a phenyl group substituted with at least two fluorine atoms or a trifluoromethyl group) and the like.

When the radiation-sensitive compound (D) is a photopolymerization initiator, the content of the photopolymerization initiator in the photosensitive resin composition may be 1 to 40 parts by mass based on 100 parts by mass of the resin components in total. Preferably it is 1.5-35 mass parts, More preferably, it is 2-30 mass parts. The content of the photopolymerization initiator is based on the above-mentioned total of 100 parts by mass. If it is 1 part by mass or more, the alkali developability will be good, and if it is 40 parts by mass or less, the reduction of the film caused by heating at 300°C or higher can be suppressed. .

When the radiation-sensitive compound (D) is a photopolymerization initiator, the photosensitive resin composition may further contain a radically polymerizable compound. Resins and compounds having plural ethylenically unsaturated groups which are radically polymerizable compounds crosslink the film to increase its hardness.

From the viewpoint of reactivity at the time of exposure, hardness of the film, heat resistance, etc., it is preferable to use a compound having plural (meth)acrylic groups as the radical 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 ester, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane Methylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate base) 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 triglyceride (Meth)acrylate, Pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Ethoxylated pentaerythritol tri(meth)acrylate, Ethoxylated pentaerythritol tetra(meth)acrylate , dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate , Pentaerythritol deca(meth)acrylate, pentaerythritol undeca(meth)acrylate, pentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2, 2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-para((meth)acryloxyethyl)iso Cyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloxyethoxy ) phenyl] fluorine, 9,9-bis[4-(3-(meth)acryloxypropoxy) phenyl] fennel or 9,9-bis(4-(meth)acryloxy Phenyl) oxane or their acid-modified, ethylene oxide-modified or propylene oxide-modified forms.

The content of the radically polymerizable compound in the photosensitive resin composition can be set at 15 to 65 parts by mass, preferably 20 to 60 parts by mass, with respect to a total of 100 parts by mass of the resin components, preferably 20 to 60 parts by mass, and 25 Parts by mass to 50 parts by mass are better. If the content of the radically polymerizable compound is within the above range, the alkali developability will be favorable, and the heat resistance of the cured film can be improved.

[Black agent (E)] The black agent (E) is selected from the group consisting of black dyes and black pigments. A black dye and a black pigment can also be used together. Visibility of display devices such as organic EL displays can be improved by forming black partition walls in organic EL elements using a photosensitive resin composition containing a black agent (E).

In one embodiment, the black agent (E) contains a black dye. As the black dye, the dye specified by the color index (C.I.) of solvent black 27~47 can be used. The black dye is preferably defined by the C.I. of Solvent Black 27, 29 or 34. When at least one of the dyes specified in the C.I. of solvent black 27~47 is used as the black dye, the light-shielding property of the film of the cured photosensitive resin composition can be maintained. Compared with the photosensitive resin composition containing black pigment, the photosensitive resin composition containing black dye has less colorant residue during development, and can form high-definition patterns on the film.

When the black agent (E) is a black dye, the content of the black dye in the photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass based on 100 parts by mass of the total resin components , and more preferably 20 to 80 parts by mass. When the content of the black dye is 10 parts by mass or more based on the above-mentioned total of 100 parts by mass, the light-shielding properties of the cured film can be maintained. When the content of the black dye is 150 parts by mass or less on the basis of 100 parts by mass of the above-mentioned total, the remaining film rate, heat resistance, sensitivity, etc. are suitable.

A black pigment can also be used as a black agent (E). Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene-based pigments, lactam-based pigments, and the like. Can be used for surface treatment of these black pigments. Examples of commercially available perylene-based pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34 manufactured by BASF Corporation. As an example of a commercially available lactam-based pigment, Irgaphor (registered trademark) black S0100CF manufactured by BASF Corporation may be mentioned. In view of having high light-shielding properties, the black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene-based pigments, and lactamide-based pigments. In the negative-type photosensitive resin composition in which the radiation-sensitive compound (D) is a photopolymerization initiator, it is advantageous that the black agent (E) is a black pigment that hardly inhibits polymerization.

When the black agent (E) is a black pigment, the content of the black pigment in the photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass based on 100 parts by mass of the total resin components , and more preferably 20 to 80 parts by mass. When the content of the black pigment is 10 parts by mass or more based on the above-mentioned total of 100 parts by mass, sufficient light-shielding properties can be obtained. When the content of the black pigment is 150 parts by mass or less on the basis of 100 parts by mass of the above-mentioned total, the residual film rate, sensitivity, etc. are suitable.

When the black agent (E) contains both the black dye and the black pigment, the total amount of the black dye and the black pigment in the photosensitive resin composition is preferably 10 to 150 parts by mass based on 100 parts by mass of the total resin components , more preferably 15 to 100 parts by mass, more preferably 20 to 80 parts by mass. When the total amount of the black dye and the black pigment is 10 parts by mass or more based on 100 parts by mass of the above-mentioned total, sufficient light-shielding properties can be obtained. When the total amount of the black dye and the black pigment is 150 parts by mass or less based on the above-mentioned total of 100 parts by mass, the remaining film rate, sensitivity, etc. are suitable.

[optional ingredient] The photosensitive resin composition may contain, as optional components, a dissolution accelerator (F), a basic compound (G), a solvent (H), a thermosetting agent, a surfactant, a second colorant other than the black agent (E), etc. . In this disclosure, arbitrary components are defined as those that do not meet any of (A) to (E).

[Dissolution Accelerator (F)] The photosensitive resin composition may contain a dissolution accelerator (F) in order to improve the solubility of the alkali-soluble part during development, for example. As the dissolution accelerator (F), a low-molecular compound having an alkali-soluble functional group is used. Among them, compounds having at least one group selected from carboxyl groups and phenolic hydroxyl groups are preferred.

For example, as a low-molecular-weight compound having a carboxyl group, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, diethylacetic acid, heptanoic acid, octanoic acid, etc.; oxalic acid , malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid (brassilic acid), methylmalonic acid, ethyl Aliphatic dicarboxylic acids such as malonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; 1,2,3-tricarballylic acid, ornithic acid Aliphatic tricarboxylic acids such as benzoic acid, toluic acid, anisic formic acid, hemimellitic acid, trimethylbenzoic acid, etc.; phthalic acid, isophthalic acid, p-phthalic acid, etc. Aromatic polycarboxylic acids such as phthalic acid, trimellitic acid, trimellitic acid, 1,2,3,4-mellophanic acid, pyromellitic acid, etc.; dihydroxybenzoic acid, trihydroxybenzoic acid Aromatic hydroxycarboxylic acids such as gallic acid; phenylacetic acid, hydrosolanic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamic acid , benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umbellic acid and other carboxylic acids.

Examples of low-molecular compounds having phenolic hydroxyl groups include catechol, resorcinol, hydroquinone, propyl gallate, dihydroxynaphthalene, leucoquinizarine, 1,2,4- Triol, thracenetriol, gallicol, phloroglucinol, tetrahydroxybenzophenone, phenolphthalein, phenolphthalein, ginseng (4-hydroxyphenyl) methane, 1,1,1-ginseng (4- Hydroxyphenyl) ethane, α,α,α'-reference (4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, etc.

The content of the dissolution accelerator (F) may be 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 3 to 12 parts by mass, based on 100 parts by mass of the total resin components. If the content of the dissolution accelerator (F) is at least 0.1 parts by mass based on the above-mentioned total of 100 parts by mass, the dissolution of the resin component can be effectively promoted, and if it is at most 20 parts by mass, excessive dissolution of the resin component can be suppressed, improving Pattern formation, surface quality, etc. of the film.

[Basic compound (G)] The photosensitive resin composition may contain a basic compound (G) in order to secure the long-term reliability of the organic EL device. The basic compound (G) functions as a quencher of acidic components or acidic sites such as carboxylic acids and phenolic hydroxyl groups contained in the photosensitive resin composition, or acidic gases generated from photoacid generators. When the film is used as an organic EL element, by using the basic compound (G), reduction in emission luminance, shrinkage of pixels, generation of dark spots, etc. can be prevented.

、吡唑、嗒

、喹

啉、嘌呤、吡咯啶、哌啶、嗎啉、4-甲基嗎啉、哌

、1,4-二甲基哌

、1,4-二吖雙環[2.2.2]辛烷、1,5-二吖雙環[4.3.0]-5-壬烯、1,8-二吖雙環[5.4.0]-7-十一烯，及2,4,6-參[雙(甲氧基甲基)胺基]-1,3,5-三

。As the basic compound (G), for example, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, 3-(2-ethylhexyloxy)propylamine, di -n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, triethylamine Amine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, Tri-n-decylamine, tricyclohexylamine, triphenylamine, aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline Aniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, butylenediamine, hexamethylenediamine , 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl amine, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2-(4-aminophenyl )-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis[1-(4-aminophenyl) )-1-methylethyl]benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene, poly(4-vinylpyridine), poly(2- pyridine), poly(N-2-pyrrolidone), polyethyleneimine, polyallylamine, poly(dimethylaminoethylacrylamide), formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrole Pyridone, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea, Imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2 -Phenylpyridine, 4-Phenylpyridine, N-Methyl-4-Phenylpyridine, Nicotine, Nicotinic Acid, Nicotinamide, Quinoline, 8-Oxyquinoline, Acridine, Pyridine

, pyrazole, click

, quinine

morpholine, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperidine

, 1,4-Dimethylpiperene

, 1,4-diacribicyclo[2.2.2]octane, 1,5-diacribicyclo[4.3.0]-5-nonene, 1,8-diacribicyclo[5.4.0]-7-deca One ene, and 2,4,6-para[bis(methoxymethyl)amino]-1,3,5-tri

.

The content of the basic compound (G) is preferably not more than 4 parts by mass, more preferably not more than 3 parts by mass, and still more preferably not more than 2 parts by mass, based on 100 parts by mass of the total solid content excluding the basic compound (G) the following.

[Solvent (H)] The photosensitive resin composition can be used in a solution state by being dissolved in a solvent (however, when a black pigment is included, the pigment is in a dispersed state). For example, by mixing the radiation-sensitive compound ( Optional components such as D), black agent (E), optional dissolution accelerator (F), basic compound (G), thermosetting agent, surfactant, etc., can prepare a photosensitive resin composition in a solution state. The photosensitive resin composition can adjust the viscosity suitable for the coating method used by changing the amount of solvent.

As the solvent (H), for example, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether, etc.; Ethylene glycol alkyl ether acetate of cellulosic agent acetate, ethyl cellosolve acetate, etc.; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether , diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other diethylene glycol compounds; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetate compounds such as acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl- Ketones such as 2-pentanone and cyclohexanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethoxyacetic acid Ethyl ester, ethyl glycolate, methyl 2-hydroxy-2-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, esters of diethyl carbonate, etc.; N-methyl-2-pyrrole Amide compounds such as pyridone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. The solvent (H) may be used alone or in combination of two or more.

[Thermohardener] As the thermosetting agent, a thermal radical generating agent can be used. As a preferable thermal free radical generating agent, organic peroxides can be exemplified, specifically, dicumyl peroxide, 2,5-dimethyl-2,5-bis(tertiary butyl peroxide) oxy)hexane, tertiary butylcumyl peroxide, di-tertiary butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene peroxide Organic peroxides with a 10-hour half-life temperature of 100-170°C, such as hydrogen.

The content of the thermosetting agent is preferably at most 5 parts by mass, more preferably at most 4 parts by mass, and still more preferably at most 3 parts by mass, based on 100 parts by mass of the total solid content excluding the thermosetting agent.

[Surfactant] The photosensitive resin composition may contain a surfactant, for example, to improve applicability, to improve the smoothness of the film, or to improve the developability of the film. As the surfactant, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonylphenyl ether; non-ionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; MEGAFACE (registered trademark) F-251, same F-281, same F-430, same F-444, same R-40, same F-553, same F-554, same F-555, same F-556, same F-557, same as F-558, same as F-559 (above, trade name, manufactured by DIC Corporation), Surflon (registered trademark) S-242, same as S-243, same as S-386, same as S-420, Fluorine-based surfactants such as S-611 (above, trade name, manufactured by AGC SEIMI CHEMICAL Co., Ltd.); organosiloxane polymers KP323, KP326, KP341 (above, trade name, manufactured by Shin-Etsu Chemical Co., Ltd. )wait. These may be used individually, and may use 2 or more types.

The content of the surfactant is preferably not more than 2 parts by mass, more preferably not more than 1 part by mass, and still more preferably not more than 0.5 parts by mass, based on 100 parts by mass of the total solid content excluding the surfactant.

[the second coloring agent] The photosensitive resin composition may contain a second colorant other than the black agent (E). As a 2nd coloring agent, dye, an organic pigment, an inorganic pigment etc. are mentioned, It can use according to the objective. The 2nd coloring agent can be used in the content which does not impair the effect of this invention.

Examples of dyes include azo-based dyes, benzoquinone-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, cyanine-based dyes, squarylium-based dyes, croconium-based dyes, merocyanidin-based dyes, and stilbene-based dyes. Dye series dyes, diphenylmethane series dyes, triphenylmethane series dyes, fluorescent yellow matrix dyes, spiropyran series dyes, phthalocyanine series dyes, indigo series dyes, fulginic anhydride series dyes, nickel complexes Department of dyes, and azulene dyes.

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

[Manufacturing method of photosensitive resin composition] The photosensitive resin composition can be prepared by mixing the first resin (A), the second resin (B), the third resin (C) of any component, the radiation-sensitive compound (D), the black agent (E), and if necessary The above-mentioned optional components such as a dissolution accelerator (F) and a basic compound (G) are dissolved or dispersed in a solvent (H) and mixed to prepare. Depending on the purpose of use, the solid content concentration of the photosensitive resin composition can be appropriately determined. For example, the solid content concentration of the photosensitive resin composition may be set to 1 to 60% by mass, 3 to 50% by mass, or 5 to 40% by mass.

A well-known method can be used for the dispersion mixing method at the time of using a pigment. For example, ball type of ball mill, sand mill, bead mill, paint shaker, rocking mill, etc., blade type of kneader, paddle mixer, planetary mixer, Henschel mixer, etc. , roll type of three-roll mixer, etc., as others, grinder, colloid mill, ultrasonic wave, homogenizer, rotation/revolution mixer, etc. can also be used. From the viewpoint of dispersion efficiency and fine dispersion, it is better to use a bead mill.

The prepared photosensitive resin composition is usually filtered before use. As the filtering means, for example, a microporous filter with a pore size of 0.05 to 1.0 μm can be cited.

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

[Use of photosensitive resin composition] When using the photosensitive resin composition 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 coated on the surface of the substrate, and the solvent can be removed by means such as heating to form a film. The coating method of the coating composition on the surface of the substrate 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 coating the coating composition on the surface of the substrate, the solvent is usually removed by heating to form a film (pre-baking). Although the heating conditions vary depending on the type of ingredients and the blending ratio, etc., they are usually heated at 70 to 130°C, for example, for 30 seconds to 20 minutes on a heating plate, and 1 to 60 minutes in an oven. In this way, a film can be obtained. In one embodiment, the formed film has a thickness of 2-3 μm.

Then irradiate the pre-baked film with radiation (for example, visible light, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, gamma rays, synchrotron radiation, etc.) through a mask with a specified pattern (exposure step). When a quinonediazide compound is used as a radiation-sensitive compound, preferred radiation is ultraviolet to visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-line. In another embodiment, the radiation is ghi rays.

After the exposure step, the film is developed by contacting the film with a developer to remove unnecessary parts and form a pattern on the film (development step). As the developer, inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc.; primary amines such as ethylamine and n-propylamine; diethylamine can be used. , di-n-propylamine and other secondary amines; triethylamine and methyldiethylamine and other secondary amines; dimethylethanolamine and triethanolamine and other alcohol amines; tetramethylammonium hydroxide, hydroxide Quaternary ammonium salts such as tetraethylammonium, choline, etc.; An aqueous solution of an alkali compound such as a cyclic amine such as ]-5-nonane. It can also be used in alkaline aqueous solution, and the aqueous solution obtained by adding an appropriate amount of water-soluble organic solvents such as methanol and ethanol, and surfactants can be used as a developing solution. The developing time is usually 30~180 seconds. The image development method may be any one of a liquid coating method, a spray method, and a dipping method. After developing, wash with running water for 30-90 seconds, remove unnecessary parts, and air-dry with compressed air or nitrogen to form patterns on the film.

Afterwards, the patterned film is heat-treated by a heating device such as a heating plate or an oven at, for example, 100-350°C for 20-200 minutes to obtain a cured film (post-baking, heat treatment step) . In the heat treatment, the temperature may be kept constant, or the temperature may be raised continuously, or may be raised stepwise.

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. Thereby, sufficient light-shielding properties can be obtained. The OD value of the cured film of the photosensitive resin composition is preferably at least 0.7, more preferably at least 1.0.

[Manufacturing method of organic EL element partition wall or organic EL element insulating film] One embodiment is a method for manufacturing an organic EL element partition wall or an organic EL element insulating film, which includes: a step of dissolving or dispersing a photosensitive resin composition in a solvent to prepare a coating composition; coating the coating composition The step of forming a film on the base material, the step of removing the solvent contained in the film to dry the film, the step of exposing the film to the dried film by irradiating radiation through a photomask, and developing the exposed film by contacting the developer. A step of forming a pattern on the coating, and a step of heating the patterned coating at a temperature of 100°C to 350°C to form organic EL element partition walls or organic EL element insulating films.

[Organic EL element partition wall] One embodiment is an organic EL element partition including a cured product of a photosensitive resin composition.

[Organic EL element insulating film] One embodiment is an insulating film for an organic EL element, which includes a cured product of a photosensitive resin composition.

[Organic EL element] One embodiment is an organic EL device including a hardened photosensitive resin composition. [Example]

Hereinafter, although this invention is concretely demonstrated based on an Example and a comparative example, this invention is not limited to these Examples.

(1) Evaluation of physical properties The evaluation of the physical properties of the resin or photosensitive resin composition was carried out by the following procedures.

[Alkali dissolution rate] Add MEGAFACE (registered trademark) as a leveling agent in an amount of 0.1 mass per 100 mass parts of resin solids in a 20% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of resin or photosensitive resin composition F-559 (fluorine-based surfactant, manufactured by DIC Corporation). The obtained mixture was coated on a glass substrate (70 mm×70 mm×0.7 mm) so that the dry film thickness was 5.0 μm, vacuum-dried for 30 seconds, and then the film was dried at a temperature of 120° C. for 120 seconds. After drying, alkali image development was performed with 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution. The developing time is adjusted to be in the range of 8~400 seconds, the time when the film will not completely dissolve. The amount of reduction (nm) of the film after development was divided by the development time (second) to determine the alkali dissolution rate (nm/second).

[molecular weight] Regarding the weight average molecular weight (Mw) and number average molecular weight (Mn) of the first resin (A), the second resin (B), the third resin (C) and other resins, the following measurement conditions were used using polystyrene Calibration curves prepared with standard substances were used to calculate. Device name: Shodex (registered trademark) GPC-101 Column: Shodex (registered trademark) LF-804 Mobile Phase: Tetrahydrofuran Flow rate: 1.0mL/min Detector: Shodex (registered trademark) RI-71 Temperature: 40°C

(2) Raw materials Raw materials used in Examples and Comparative Examples were manufactured or obtained as follows.

[Manufacturing example 1] The first resin (A): Manufacture of resin (N770OH70) having epoxy group and phenolic hydroxyl group 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent, and EPICLON (registered trademark) N-770 as a compound having at least 2 epoxy groups in 1 molecule were added to a 300 mL 3-necked flask (DIC Co., Ltd. product phenol novolac type epoxy resin, epoxy equivalent 188) 37.6g, and it melt|dissolved at 60 degreeC in nitrogen atmosphere. 20.1 g of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) as a hydroxybenzoic acid compound (0.65 equivalent to 1 equivalent of epoxy) and triphenyl triphenyl as a reaction catalyst were added thereto. Phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.173 g (0.660 mmol) was 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 obtain a solution of 286.5 g of a resin (N770OH70) having an epoxy group and a phenolic hydroxyl group. The number average molecular weight of the obtained reactant was 2400, the weight average molecular weight was 5400, the epoxy equivalent was 2000, and the phenolic hydroxyl equivalent was 142.

[Production Example 2] Production of the first resin (A): a resin (N695OH70) having an epoxy group and a phenolic hydroxyl group 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) as a solvent, and EPICLON (registered trademark) N-695 as a compound having at least 2 epoxy groups in 1 molecule were added to a 300 mL 3-necked flask. (DIC Co., Ltd. product cresol novolak type epoxy resin, epoxy equivalent 214) 37.8g, and it melt|dissolved at 60 degreeC under nitrogen atmosphere. 20.1 g of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) as a hydroxybenzoic acid compound (0.65 equivalent to 1 equivalent of epoxy) and triphenyl triphenyl as a reaction catalyst were added thereto. Phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.166 g (0.660 mmol), 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 obtain a solution of 274.2 g of a resin (N695OH70) having an epoxy group and a phenolic hydroxyl group. The number average molecular weight of the obtained reactant was 3000, the weight average molecular weight was 5100, the epoxy equivalent was 2200, and the phenolic hydroxyl equivalent was 161.

[Production Example 3] Second Resin (B): Production of Second Resin (B-TBMA42.5%) Having Phenolic Hydroxyl Group 17.3 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 6.15 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and tertiary butylmethyl 13.8 g of acrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester TB") was completely dissolved in 56.0 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2 2.69 g of '-azobis(isobutyrate) dimethyl ester (manufactured by Fujifilm Wako Pure Chemical Co., Ltd. "V-601") was completely dissolved in isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 4.05 in g. In a 300 mL 3-necked flask, the resulting two solutions were simultaneously dropped into 100 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, and then It was allowed to react under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was dropped into 1000 g of 80:20 mixture of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 36.5 g of white powder. The obtained second resin B-TBMA42.5% having phenolic hydroxyl groups had a number average molecular weight of 4100, a weight average molecular weight of 7600, and a phenolic hydroxyl group equivalent of 384.

[Production Example 4] Second Resin (B): Production of Second Resin (B-PhMA41%) Having Phenolic Hydroxyl Group 17.0 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 5.83 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and phenylmethyl 14.4 g of acrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH") was completely dissolved in 60.0 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent, and 2,2 2.72 g of '-azobis(isobutyrate) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 4.08 in g. In a 300 mL 3-necked flask, the obtained two solutions were simultaneously dropped into 95.9 g of isopropyl acetate (manufactured by Shinko Organic Chemical Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, Then, it was made to react at 89 degreeC under reflux for 4 hours. The reaction solution cooled to room temperature was dropped into a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 36.5 g of white powder. The obtained second resin B-PhMA41% having phenolic hydroxyl groups had a number average molecular weight of 4300, a weight average molecular weight of 7800, and a phenolic hydroxyl group equivalent of 390.

[Production Example 5] Second Resin (B): Production of Second Resin (B-PhMA53%) Having Phenolic Hydroxyl Group 12.5 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 5.90 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and phenylmethyl 18.9 g of acrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH") was completely dissolved in 56.0 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent, and 2,2 2.72 g of '-azobis(isobutyrate) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 4.08 in g. In a 300 mL 3-necked flask, the resulting two solutions were simultaneously dropped into 100 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, and then It was allowed to react under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was dropped into a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 36.5 g of white powder. The obtained second resin (B-PhMA53%) having phenolic hydroxyl groups had a number average molecular weight of 4400, a weight average molecular weight of 7500, and a phenolic hydroxyl equivalent of 531.

[Production Example 6] Second Resin (B): Production of Second Resin (B-PhMA 20%) Having Phenolic Hydroxyl Group 24.6 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 5.71 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and phenylmethyl 6.89 g of acrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH") was completely dissolved in 55.8 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent, and 2,2 '-Dimethyl azobis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") 2.83 g is completely dissolved in isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 4.23 in g. In a 300 mL 3-necked flask, the resulting two solutions were simultaneously dropped into 100 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, and then It was allowed to react under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was dropped into a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 36.4 g of white powder. The obtained second resin B-PhMA 20% having phenolic hydroxyl groups had a number average molecular weight of 3600, a weight average molecular weight of 7200, and a phenolic hydroxyl group equivalent of 270.

[Production Example 7] The third resin (C): Copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer 25.5 g of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko Co., Ltd.) and 4.50 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) were completely dissolved in the solvent. In 77.1 g of 1-methoxy-2-propyl acetate (manufactured by DAICEL Co., Ltd.), 3.66 g of V-601 (manufactured by Fujisoft Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in In 14.6 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.). In a 300 mL 3-necked flask, the resulting two solutions were simultaneously dropped into 1-methoxy-2-propyl acetate (manufactured by DAICEL Co., Ltd.) heated to 85°C over a period of 2 hours under a nitrogen atmosphere. ) 61.2g, and then allowed to react at 85°C for 3 hours. The reaction solution cooled to room temperature was dropped into 815 g of toluene to precipitate a 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. The obtained copolymer PCX-02e of the polymerizable monomer having phenolic hydroxyl group and other polymerizable monomers had a number average molecular weight of 3100, a weight average molecular weight of 6700, and a phenolic hydroxyl group equivalent of 210.

[Manufacture Example 8] Manufacture of a copolymer of glycidyl methacrylate and methacrylic acid (GMA-MAA) Make glycidyl methacrylate (GMA) 99.5g (0.7 mol) and methacrylic acid (MAA) 8.6g (0.1 mol) completely dissolve in propylene glycol monomethyl ether (PGME) 72.1g respectively, make 7.6 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 7.6 g of PGME. In a 500 mL 3-necked flask, the obtained two solutions were dropped into PGME 172.6 g heated to 80° C. over 2 hours under a nitrogen atmosphere, and then stirred for 2 hours to make them react. In this way, in the form of a PGME solution with a solid content of 30% by mass, the molar ratio of glycidyl methacrylate to methacrylic acid is 7:1. Copolymer (GMA-MAA). The obtained GMA-MAA has a carboxyl group and an epoxy group in the molecule, so it has high self-reactivity, that is, it is easy to undergo ring-opening polymerization of the epoxy group, so if it is reprecipitated and vacuum-dried, the molecular weight will be high and it cannot be separated. Leave. The PGME solution of GMA-MAA has low stability, and the viscosity of the solution increases with time as the molecular weight increases.

[Production Example 9] Second Resin (B): Production of Second Resin (B-CHMA20%) Having Phenolic Hydroxyl Group 24.5 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 7.11 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and cyclohexylmethyl 5.68 g of acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 69.3 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2'-azo 2.72 g of dimethyl bis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 10.87 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.). In a 300 mL 3-necked flask, the resulting two solutions were simultaneously dropped into 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, and then It was allowed to react under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was dropped into a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 39.1 g of white powder. The obtained second resin B-CHMA 20% having phenolic hydroxyl groups had a number average molecular weight of 3,500, a weight average molecular weight of 7,200, and a phenolic hydroxyl equivalent of 271.

[Production Example 10] Second Resin (B): Production of Second Resin (B-CHMA40%) Having Phenolic Hydroxyl Group 17.14 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 14.39 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and cyclohexylmethyl 5.75 g of acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 69.3 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2'-azo 2.72 g of dimethyl bis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 10.87 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.). In a 300 mL 3-necked flask, the resulting two solutions were simultaneously dropped into 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, and then It was allowed to react at 89°C under reflux for 4 hours. The reaction solution cooled to room temperature was dropped into a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 39.1 g of white powder. The obtained second resin B-CHMA 40% having phenolic hydroxyl groups had a number average molecular weight of 3900, a weight average molecular weight of 7500, and a phenolic hydroxyl group equivalent of 387.

[Production Example 11] Second Resin (B): Production of Second Resin (B-BOM32%) Having Phenolic Hydroxyl Group 17.3 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 29.0 g of N,N-diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), tetrahydrofuran (dehydrated) (manufactured by Kanto Chemical Co., Ltd.) 160 g was placed in a 500 mL 3-necked flask, and stirred under a nitrogen atmosphere until the solid was completely dissolved. The solution was cooled to 0° C., and 26.4 g of benzyl chloromethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the solution. After completion|finish of dripping, it heated to 70 degreeC and made it react for 5 hours. After the reaction solution returned to room temperature, unnecessary substances were removed by filtration, 200 mL of ethyl acetate (special grade manufactured by Junzheng Chemical Co., Ltd.) was added, and THF was distilled off. The organic layer was washed once with 300 mL of saturated aqueous hydrogen carbonate solution, and washed twice with 200 mL of pure water. After drying over sodium sulfate, the solvent was distilled off completely. The crude product was purified by silica gel column chromatography using a developing solvent of hexane:ethyl acetate=50:1 to obtain 31.2 g of PQMA-BOM.

12.1 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 3.45 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and PQMA-BOM12. 3 g was completely dissolved in 41.8 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2'-azobis(isobutyrate) dimethyl (Fuji Wako Pure Chemicals Co., Ltd. "V-601") 2.14 g was completely dissolved in 8.54 g of isopropyl acetate (Shenko Organic Chemicals Co., Ltd.). In a 300 mL 3-necked flask, the obtained two solutions were simultaneously dropped into 69.7 g of isopropyl acetate (manufactured by Shinko Organic Chemical Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, Then, it was made to react at 89 degreeC under reflux for 4 hours. The reaction solution cooled to room temperature was dropped into a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 29.3 g of white powder. The obtained second resin B-BOM32% having phenolic hydroxyl groups had a number average molecular weight of 3600, a weight average molecular weight of 6900, and a phenolic hydroxyl equivalent of 431.

[Production Example 12] Second Resin (B): Production of Second Resin (B-IBMA 20%) Having Phenolic Hydroxyl Group 23.1 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 8.86 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), and isocamyl methyl 5.35 g of acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 69.2 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 2.72 g of dimethyl azabis(isobutyrate) (manufactured by Fujisoft Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 10.83 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.). In a 300 mL 3-necked flask, the resulting two solutions were simultaneously dropped into 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, and then It was allowed to react at 89°C under reflux for 4 hours. The reaction solution cooled to room temperature was dropped into a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 39.1 g of white powder. The obtained second resin B-IBMA 20% having phenolic hydroxyl groups had a number average molecular weight of 3600, a weight average molecular weight of 7100, and a phenolic hydroxyl group equivalent of 288.

[Production Example 13] Second Resin (B): Production of Second Resin (B-TCDMA 20%) Having Phenolic Hydroxyl Group 23.1 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 8.79 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and dicyclopentyl 5.37 g of methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 69.2 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2'- 2.72 g of dimethyl azobis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 10.83 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.) . In a 300 mL 3-necked flask, the resulting two solutions were simultaneously dropped into 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Co., Ltd.) heated to 89° C. under a nitrogen atmosphere for 2 hours, and then It was allowed to react under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was dropped into a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 39.1 g of white powder. The obtained second resin B-TCDMA 20% having phenolic hydroxyl groups had a number average molecular weight of 3800, a weight average molecular weight of 8000, and a phenolic hydroxyl group equivalent of 287.

[the first resin (A)] As the first resin (A), N770OH70 of Production Example 1 and N695OH70 of Production Example 2 were used.

[the second resin (B)] As the second resin (B), 42.5% of B-TBMA in Production Example 3, 41% of B-PhMA in Production Example 4, 53% of B-PhMA in Production Example 5, 20% of B-PhMA in Production Example 6, and 20% of Production Example 9 were used. B-CHMA 20% of production example 10, B-CHMA 40% of production example 11, B-BOM 32% of production example 11, B-IBMA 20% of production example 12 and B-TCDMA 20% of production example 13.

[the third resin (C)] As the third resin (C), PCX-02e of Production Example 7 was used.

[Other resins] As other resins, Shonol (registered trademark) BRG-558 (phenol novolak resin manufactured by AICA Industry Co., Ltd., phenolic hydroxyl equivalent 107), EPICLON (registered trademark) N-770 (phenol novolac type manufactured by DIC Co., Ltd. Epoxy resin, epoxy equivalent 188) and the GMA-MAA of manufacturing example 8.

Table 1 shows the structural unit ratio, phenolic hydroxyl equivalent, alkali dissolution rate, and weight average molecular weight (Mw) of the resin. In Table 1, PQMA represents a structural unit derived from 4-hydroxyphenyl methacrylate, and CHMI represents a structural unit derived from N-cyclohexylmaleimide.

[Radiation sensitive compound (D)] As the radiation-sensitive compound (D), TS-150A (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl ] Ethylene] bisphenol (TrisP-PA) and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonic acid acid) ester, manufactured by Toyo Gosei Kogyo Co., Ltd.). The structure of TS-150A is shown below.

[Black agent (E)] As a black agent, VALIFAST (registered trademark) BLACK 3820 (a black dye specified in C.I. of Solvent Black 27, manufactured by Oriental Chemical Industry Co., Ltd.) was used as a black dye.

[Dissolution Accelerator (F)] Phloroglucinol (phloroglucinol) was used as the dissolution accelerator (F).

[Basic compound (G)] Tri-n-octylamine (TOA) was used as the basic compound (G).

[Solvent (H)] As the solvent (H), use a mixed solvent of γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate (PGMEA) and diethyl carbonate (DEC) (GBL:PGMEA:DEC=35:45: 20 (mass ratio)), or a mixed solvent of γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate (PGMEA), diethyl carbonate (DEC) and propylene glycol monomethyl ether (PGME) ( GBL:PGMEA:DEC:PGME=35:35:20:10 (mass ratio)). The mass ratio values of GBL and PGME also include those used in Production Example 1, 2 or 8.

(3) Evaluation method The evaluation methods used in Examples and Comparative Examples are as follows.

[Solubility] <Solubility in exposed part> Bar-coat the photosensitive resin composition on a glass substrate (size 100mm×100mm×1mm) so that the dry film thickness becomes 2.7 μm, and heat it at 120°C for 120 seconds on a hot plate. Solvent dried (pre-baked). After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, manufactured by FILMETRICS Co., Ltd.), an exposure device equipped with an ultra-high pressure mercury lamp (trade name Multilight ML-251A/B, manufactured by Ushio Electric Co., Ltd. ) through a band-pass filter for mercury exposure (trade name HB0365, manufactured by Asahi Spectroscopic Co., Ltd.) and a quartz mask (with lines and spaces of 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, and 500 μm (L/S ) pattern person) to 100mJ/cm ² for exposure. The exposure amount was measured using an ultraviolet cumulative dosimeter (trade name UIT-150, light receiving unit UVD-S365, manufactured by Ushio Electric Co., Ltd.). Thereafter, using a rotary developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), alkali development was performed in a range of 20 seconds to 200 seconds with a 2.38% by mass tetramethylammonium hydroxide aqueous solution until the film on the exposed portion disappeared. Therefore, in Table 2, according to the development time, the solubility of the exposed part is marked as 2.70 μm (only Comparative Example 2 is marked as exceeding 2.70 μm due to pattern peeling).

<Solubility of unexposed part> The photosensitive resin composition was bar-coated on a glass substrate (100 mm x 100 mm x 1 mm in size) so that the dry film thickness was 2.7 μm, and the solvent was dried by heating at 120° C. for 120 seconds on a hot plate (pre-baking). After measuring the dry film thickness with an optical film thickness measuring device (F20-NIR, manufactured by FILMETRICS Co., Ltd.), tetramethylammonium hydroxide was added to 2.38% by mass using a rotary developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). For aqueous solution, alkali development is carried out at the same developing time as the solubility of the exposed part. 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 (μm) dissolved before and after development was calculated as the solubility of the unexposed part.

<Poor solubility> What subtracted the solubility (micrometer) of an unexposed part from the solubility (micrometer) of an exposed part was made into poor solubility (micrometer). The greater the difference in solubility, the higher the sensitivity, which means excellent pattern formation.

[OD value of hardened film] The photosensitive resin composition was spin-coated on a glass substrate (100 mm×100 mm×1 mm in size) so that the dry film thickness was about 1.5 μm, and the solvent was dried by heating at 120° C. for 120 seconds on a hot plate. Thereafter, a film was obtained by curing at 250° C. for 60 minutes in a nitrogen atmosphere. Measure the OD value of the cured film with a transmission densitometer (BMT-1, manufactured by SAKATA INX ENG. Co., Ltd.), correct it with the OD value of glass only, and convert it into the OD value per 1 μm of film thickness. The thickness of the film was measured using an optical film thickness measuring device (F20-NIR, manufactured by FILMETRICS Co., Ltd.).

(4) Preparation and evaluation of photosensitive resin composition [Examples 1-14, Comparative Examples 1-4] Add the radiation-sensitive compound (D), black agent (E), dissolution accelerator (F), and basic compound (G) solvents listed in Table 2 to the solution obtained by mixing and dissolving the resin components in the composition listed in Table 2. (H), further mixing. After visually confirming the dissolution of the components, it was filtered through a microporous filter with a pore size of 0.22 μm to prepare a photosensitive resin composition with a solid content concentration of about 12% by mass. The parts by mass of the compositions in Table 2 are solid content conversion values. Table 2 also describes the alkali dissolution rate of the photosensitive resin composition. Table 2 shows the evaluation results of the photosensitive resin compositions of Examples 1-14 and Comparative Examples 1-4. Since pattern peeling occurred during development in Comparative Example 3, the correct solubility could not be measured, so the numerical values of solubility in Table 2 were added in parentheses. In Comparative Example 4, the stability of the PGME solution of GMA-MAA was low and could not be evaluated.

[產業上之可利用性]

[Industrial availability]

The photosensitive resin composition of the present disclosure can be suitably used for radiation lithography for forming partition walls or insulating films between organic EL elements. An organic EL element provided with a partition wall or an insulating film formed of the photosensitive resin composition of the present disclosure is suitable for use as an electronic component of a display device showing good contrast.

Claims (18)

A photosensitive resin composition comprising: (A) a first resin having an epoxy group and a phenolic hydroxyl group, (B) a second resin with a weight average molecular weight of 3000-80000, (D) a radiation-sensitive compound, and ( E) Black agent, the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 μm film thickness, and the alkali dissolution rate of the second resin is 5% of the alkali dissolution rate of the first resin Hereinafter, the aforementioned second resin has a structural unit represented by formula (4),

(In formula (4), R ³ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ⁴ is a branched alkyl group selected from a straight chain alkyl group with 1 to 20 carbon atoms and a branched alkyl group with 3 to 20 carbon atoms , cyclic alkyl groups with 3 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, linear alkyl groups with 1 to 20 carbon atoms substituted by groups other than acidic functional groups, and substituted by groups other than acidic functional groups A branched alkyl group with 3 to 20 carbon atoms substituted by a radical, a cyclic alkyl group with 3 to 12 carbon atoms substituted by a group other than an acidic functional group, and a branched alkyl group with 6 to 2 carbon atoms substituted by a group other than an acidic functional group 20 aryl groups), the aforementioned alkali dissolution rate is defined as follows: in the 20 mass % propylene glycol monomethyl ether acetate (PGMEA) solution of the aforementioned first resin or the aforementioned second resin, each resin 100 parts by mass of solid content was added in an amount of 0.1 part by mass as a leveling agent, MEGAFACE (registered trademark) F-559 (fluorine-based surfactant, manufactured by DIC Co., Ltd.), and the resulting dry film thickness was 5.0 μm. The mixture was coated on a glass substrate (70mm×70mm×0.7mm), vacuum-dried for 30 seconds, and then dried at a temperature of 120°C for 120 seconds. After drying, 2.38% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution was used. The developing time is adjusted to be in the range of 8~400 seconds, and the film will not be completely dissolved in the time solution for alkali development. At this time, the value obtained by dividing the reduction (nm) of the film after development by the developing time (seconds) ( nm/sec) is defined as the alkali dissolution rate. The photosensitive resin composition according to claim 1, wherein the second resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. The photosensitive resin composition according to claim 1 or 2, wherein the aforementioned second resin has a structural unit represented by formula (3),

(In formula (3), R ² is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and b is an integer of 1 to 5). The photosensitive resin composition according to claim 1 or 2, wherein the aforementioned second resin has a structural unit represented by formula (5),

(In formula (5), R5 and ^R6 are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, ^a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom, R ⁷ is a hydrogen atom, a linear alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and carbon atoms A phenyl group substituted by at least one of the group consisting of alkoxy groups with numbers 1 to 6). The photosensitive resin composition according to claim 1 or 2, wherein the first resin is a reactant of a compound having at least 2 epoxy groups in one molecule and a hydroxybenzoic acid compound, and has a structure of formula (2) compound of

(In the formula (2), a is an integer of 1 to 5, and * represents a bonding site of an epoxy group residue that reacts with the removal of a compound having at least two epoxy groups in one molecule). The photosensitive resin composition according to claim 5, wherein the compound having at least 2 epoxy groups in one molecule is a novolak type epoxy resin. Such as the photosensitive resin composition of claim 1 or 2, which The aforementioned black agent is a dye specified by the color index (C.I.) of solvent black 27~47. The photosensitive resin composition according to claim 1 or 2, wherein the radiation-sensitive compound is a photoacid generator. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition further comprises (C) a compound having a weight average molecular weight of 3000 to 80000 different from any one of the first resin and the second resin The third resin, the alkali dissolution rate of the aforementioned second resin is less than 5% of the alkali dissolution rate of the aforementioned third resin, and the aforementioned alkali dissolution rate is defined as follows: 20% by mass of propylene glycol monomethyl in the aforementioned second resin or the aforementioned third resin Add MEGAFACE (registered trademark) F-559 (fluorine-based surfactant, manufactured by DIC Co., Ltd. ), the resulting mixture was coated on a glass substrate (70mm×70mm×0.7mm) in such a way that the dry film thickness became 5.0 μm, and after vacuum drying for 30 seconds, the film was dried at a temperature of 120°C for 120 seconds. After drying, use 2.38 Mass% tetramethylammonium hydroxide (TMAH) aqueous solution, the development time is adjusted to be in the range of 8 to 400 seconds, and the time solution that the film will not completely dissolve is used for alkali development. At this time, the reduction of the film after development ( The value (nm/sec) obtained by dividing the value (nm/sec) by the developing time (sec) was defined as the alkali dissolution rate. The photosensitive resin composition as claimed in claim 9, wherein the aforementioned third resin is a polymerizable monomer having a phenolic hydroxyl group and other polymerizable Copolymer of monomers. The photosensitive resin composition according to claim 1 or 2, wherein based on the total mass of the resin components, 20% to 90% by mass of the first resin is contained. The photosensitive resin composition according to claim 1 or 2, wherein based on the total mass of the resin components, it contains 5% by mass to 50% by mass of the aforementioned second resin. The photosensitive resin composition according to claim 9, wherein the third resin is contained by 5% by mass to 50% by mass of the aforementioned third resin based on the total mass of the resin components. The photosensitive resin composition according to Claim 1 or 2, wherein 1 to 40 parts by mass of the aforementioned radiation-sensitive compound is contained based on 100 parts by mass of the total resin components. The photosensitive resin composition according to Claim 1 or 2, wherein 10 to 150 parts by mass of the black agent is contained based on 100 parts by mass of the total resin components. A partition wall for an organic EL element, comprising a cured product of the photosensitive resin composition according to any one of Claims 1 to 15. An insulating film for an organic EL element, comprising a cured product of the photosensitive resin composition according to any one of Claims 1 to 15. An organic EL element, which comprises a cured product of the photosensitive resin composition according to any one of claims 1 to 15.