WO2022145188A1

WO2022145188A1 - Photosensitive resin composition and organic el element partition

Info

Publication number: WO2022145188A1
Application number: PCT/JP2021/045203
Authority: WO
Inventors: 恭裕石田; 健太郎古江; 拓樹倉本
Original assignee: 昭和電工株式会社
Priority date: 2020-12-28
Filing date: 2021-12-08
Publication date: 2022-07-07
Also published as: JPWO2022145188A1; TW202244100A; TWI802156B

Abstract

The present invention provides a photosensitive resin composition that is highly sensitive and contains a black colorant, the composition making it possible to form a thick film pattern having a high optical density (OD value) and limited surface roughness. Provided is a photosensitive resin composition containing (A) a first resin, (B) a second resin that differs from the first resin and has a phenolic hydroxyl group, (C) a third resin that differs from both the first resin and the second resin and has a phenolic hydroxyl group, (D) a radiation-sensitive compound, and (E) a black colorant, wherein: the optical density (OD value) of a cured coating obtained from the photosensitive resin composition is 0.5 or higher per 1 μm of film thickness; and the phenolic hydroxyl group equivalent of the second resin is 1.1 to 5.0 times the phenolic hydroxyl group equivalent of the third resin.

Description

Photosensitive resin composition and organic EL element partition wall

The present invention relates to a photosensitive resin composition containing a blackening agent, and 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), a partition material is used at the interval portion of the coloring pattern in the display region or the edge of the peripheral portion of the display region in order to improve the display characteristics. In the manufacture of an organic EL display device, in order to prevent the pixels of the organic substance from coming into contact with each other, a partition wall is first formed, and the pixels of the organic substance are formed between the partition walls. The partition walls are generally formed by photolithography using a photosensitive resin composition and have insulating properties. Specifically, the photosensitive resin composition is applied onto the substrate using a coating device, the volatile components are removed by means such as heating, and then exposed through a mask, and then, in the case of a negative type, the unexposed portion is exposed. In the case of the positive type, the exposed portion is developed by removing it with a developing solution such as an alkaline aqueous solution, and the obtained pattern is heat-treated to form a partition wall (insulating film). Next, an organic substance that emits light of three colors of red, green, and blue is formed between the partition walls by an inkjet method or the like to form pixels of an organic EL display device.

In recent years, due to the miniaturization of display devices and the diversification of displayed contents, there is a demand for higher performance and higher definition of pixels in this field. Attempts have been made to make the partition material have a light-shielding property by using a colorant for the purpose of increasing the contrast in the display device and improving the visibility. However, when the partition wall material is provided with a light-shielding property, the photosensitive resin composition tends to have low sensitivity, and as a result, the exposure time may be long and the productivity may be lowered. Therefore, the photosensitive resin composition used for forming the partition wall material containing the colorant is required to have higher sensitivity.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2001-281440) describes a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting high light-shielding properties by heat treatment after exposure. The composition to which titanium black is added is described.

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

Patent Document 3 (Japanese Unexamined Patent Publication No. 2010-237310) describes a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition that exhibits light-shielding properties by heat treatment after exposure. The composition to which the heat-sensitive dye is added is described.

US Pat. Described are positive photosensitive resin compositions containing a seed black dye.

Japanese Unexamined Patent Publication No. 2001-281440 Japanese Patent Application Laid-Open No. 2002-116536 Japanese Unexamined Patent Publication No. 2010-237310 International Publication No. 2017/069172

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

In particular, when an attempt is made to form a thick film, for example, a film having a thickness of 2 to 3 μm using a photosensitive resin composition containing a blackening agent, the bottom of the film of the exposed portion is absorbed by radiation by a radiation-sensitive compound in addition to the blackening agent. The amount of radiation that reaches is significantly reduced. Therefore, in the positive type, the alkali solubility at the bottom of the film in the exposed portion is insufficient and a resin residue is generated during development, or a large amount of the photosensitive resin composition is consumed in order to obtain a film having a desired thickness. The residual film ratio may decrease. On the other hand, in the negative type, the insolubilization of the bottom of the film in the exposed portion is not sufficient, and the film may peel off during development. Therefore, in a photosensitive resin composition containing a blackening agent, a photosensitive resin composition capable of increasing the thickness of the cured film while imparting a high optical density (OD value) to the cured film is eagerly desired.

When microscopically non-uniform dissolution of the resin occurs in the developing process, the surface area of the resin in that portion, that is, the contact area with the developing solution increases, and the dissolution rate of the resin locally increases. As a result, the film may be melted non-uniformly in the developing process, resulting in roughening of the surface of the film after development, deterioration of the pattern shape, and the like. This is remarkable in the thick film developing process, which generally requires a long development time or the use of a high-concentration developer.

An object of the present invention is to provide a highly sensitive photosensitive resin composition containing a blackening agent, which has a high optical density (OD value) and can form a thick film pattern in which surface roughness is suppressed. That is.

The present inventors have a photosensitive resin composition containing a blackening agent by using at least two kinds of resins having phenolic hydroxyl groups in combination and setting the ratio of the phenolic hydroxyl group equivalents of these resins to a predetermined range. It has been found that a thick film pattern in which surface roughness is suppressed can be formed even when an object is used.

That is, the present invention includes the following aspects.
[1]
(A) First resin,
(B) A second resin having a phenolic hydroxyl group, which is different from the first resin,
(C) A third resin having a phenolic hydroxyl group, which is different from both the first resin and the second resin.
A photosensitive resin composition containing (D) a radiation-sensitive compound and (E) a blackening agent, wherein the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 μm of the film thickness. A photosensitive resin composition, wherein the phenolic hydroxyl group equivalent of the second resin is 1.1 to 5.0 times the phenolic hydroxyl group equivalent of the third resin.
[2]
The second resin contains the same structural unit as at least one of the structural units of the third resin and other structural units, and contains a total of 30 mol% to 95 mol% of structural units common to the third resin. The photosensitive resin composition according to [1], wherein the alkali dissolution rate of the second resin is smaller than the alkali dissolution rate of the third resin.
[3]
The photosensitive resin composition according to [1] or [2], wherein the second resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer.
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the third resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. ..
[5]
The second resin is the formula (17).

(In the formula (17), R ³⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³⁹ is a linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group having 3 to 20 carbon atoms. , A cyclic alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a linear alkyl group having 1 to 20 carbon atoms substituted with a group other than the acidic functional group, and a group other than the acidic functional group. A branched alkyl group having 3 to 20 carbon atoms substituted with, a cyclic alkyl group having 3 to 12 carbon atoms substituted with a group other than the acidic functional group, and a carbon atom substituted with a group other than the acidic functional group. It is a group selected from the group consisting of 6 to 20 aryl groups.)
The photosensitive resin composition according to any one of [1] to [4], which has a structural unit represented by.
[6]
The second resin is the formula (10).

(In the formula (10), ^R15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5).
The photosensitive resin composition according to any one of [1] to [5], which has a structural unit represented by.
[7]
The second resin is the formula (11).

(In the formula (11), R ¹⁶ and R ¹⁷ are independently hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a completely or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, respectively. , Or a halogen atom, where R18 is a hydrogen atom, a linear alkyl group having 1 to ⁶ carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, and 1 to 6 carbon atoms. It is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.)
The photosensitive resin composition according to any one of [1] to [6], which has a structural unit represented by.
[8]
The photosensitive resin composition according to any one of [1] to [7], wherein the first resin is a resin having an epoxy group and a phenolic hydroxyl group.
[9]
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 has the formula (9).

(In the formula (9), d is an integer of 1 to 5, and * represents the bond portion of the compound having at least two epoxy groups in one molecule to the residue excluding the epoxy group involved in the reaction. .)
The photosensitive resin composition according to any one of [1] to [8], which is a compound having the structure of.
[10]
The photosensitive resin composition according to [9], wherein the compound having at least two epoxy groups in one molecule is a novolak type epoxy resin.
[11]
The photosensitive resin composition according to any one of [1] to [10], wherein the blackening agent is a dye defined by a color index (CI) of Solvent Black 27 to 47.
[12]
The photosensitive resin composition according to any one of [1] to [11], wherein the radiation-sensitive compound is a photoacid generator.
[13]
The photosensitive resin composition according to any one of [1] to [12], which contains 20% by mass to 90% by mass of the first resin based on the total mass of the resin components.
[14]
The photosensitive resin composition according to any one of [1] to [13], which contains 5% by mass to 50% by mass of the second 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 5% by mass to 50% by mass of the third resin based on the total mass of the resin components.
[16]
The photosensitive resin composition according to any one of [1] to [15], which comprises 1 part by mass to 40 parts by mass of the radiation-sensitive compound based on a total of 100 parts by mass of the resin components.
[17]
The photosensitive resin composition according to any one of [1] to [16], which contains 10 parts by mass to 150 parts by mass of the blackening agent based on a total of 100 parts by mass of the resin components.
[18]
An organic EL device partition wall containing a cured product of the photosensitive resin composition according to any one of [1] to [17].
[19]
An organic EL device insulating film containing a cured product of the photosensitive resin composition according to any one of [1] to [17].
[20]
An organic EL device containing a cured product of the photosensitive resin composition according to any one of [1] to [17].

According to the present invention, there is provided a highly sensitive photosensitive resin composition containing a blackening agent, which has a high optical density (OD value) and can form a thick film pattern in which surface roughness is suppressed. be able to.

The present invention will be described in detail below.

In the present disclosure, "alkali-soluble" means that the photosensitive resin composition or its components, or the film or cured film of the photosensitive resin composition can be dissolved in 2.38% by mass of an aqueous solution of tetramethylammonium hydroxide. Means. The "alkali-soluble functional group" means a group that imparts such alkali solubility to the photosensitive resin composition or a component thereof, or a film or a cured film of the photosensitive resin composition. Examples of the alkali-soluble functional group include a phenolic hydroxyl group, a carboxy group, a sulfo group, a phosphoric acid group, an acid anhydride group, a mercapto group and the like.

In the present disclosure, the "radical polymerizable functional group" means an ethylenically unsaturated group, and the "radical polymerizable compound" means a compound having one or more ethylenically unsaturated groups.

In the present disclosure, the "structural unit" means an atomic group constituting a part of the basic structure of a polymer, and this atomic group may have a pendant atom or a pendant atomic group. 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 novolak resin, one molecule of phenol (C ₆ H ₅ OH) and 1 molecule. It means the following units formed by the condensation reaction of molecular formaldehyde (HCHO). Regarding a structural unit having a pendant group (side group), a structural unit having a pendant group used for forming a cross-linking site or a group derived from the pendant group and a structural unit having a free pendant group not involved in the formation of a cross-linking site. Are considered to be different from each other. For a polymer having a branched molecular chain (branched chain), the structural unit including the branch point (branched unit) and the structural unit contained in the linear molecular chain are considered to be different from each other.

In the present disclosure, "(meth) acrylic" means acrylic or methacrylic, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acryloyl" means acryloyl or methacryloyl.

In the present disclosure, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin or polymer mean standard polystyrene-equivalent values measured by gel permeation chromatography (GPC).

In the present disclosure, the phenolic hydroxyl group equivalent is a theoretical value calculated from the molecular weight and composition ratio of the structural units constituting the resin. Specifically, the phenolic hydroxyl group equivalent is determined by the following formula when the resin is a (co) polymer of n kinds of monomers i (natural numbers of i = 1 to n).

Means the value calculated by. In the formula, the total copolymerization ratio (molar basis) of the monomers i (i = 1 to n) is 1.

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

In the present disclosure, the "resin component" means the first resin (A), the second resin (B), and the third resin (C).

In the present disclosure, the "solid content" includes an optional component such as a resin component, a radiation-sensitive compound (D), a blackening agent (E), and a dissolution accelerator (F), and is a liquid basic compound (G) and a solvent. It means the total mass of the components excluding (H).

The photosensitive resin composition of one embodiment is different from the first resin (A) and the first resin (A), and has a second resin (B), a first resin (A) and a second resin having a phenolic hydroxyl group. It contains a third resin (C) having a phenolic hydroxyl group, a radiation-sensitive compound (D), and a blackening agent (E), which are different from any of (B).

[First resin (A)]
The first resin (A) is not particularly limited, but preferably has an alkali-soluble functional group and is alkali-soluble. The alkali-soluble functional group is not particularly limited, and examples thereof include a carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, and a mercapto group. The first resin (A) may be a resin having two or more kinds of alkali-soluble functional groups. In the present disclosure, the first resin (A) is a resin different from the second resin (B) and the third resin (C) described later in terms of the resin skeleton and / or the alkali-soluble functional group. In one embodiment, the first resin (A) is a resin that is the main component among the resin components, that is, the resin component has a larger mass than each of the second resin (B) and the third resin (C). include.

Examples of the first resin (A) include acrylic resin, polystyrene resin, epoxy resin, polyamide resin, phenol resin, polyimide resin, polyamic acid resin, polybenzoxazole resin, polybenzoxazole resin precursor, silicone resin, and cyclic olefin. Examples thereof include polymers, cardo resins, and derivatives of these resins, and those having an alkali-soluble functional group bonded to these resins. As the first resin (A), a homopolymer or a copolymer of a polymerizable monomer having an alkali-soluble functional group can also be used. As the first resin (A), any one of these resins can be used alone, or two or more of these resins can be used in combination. The first resin (A) may have a radically polymerizable functional group. In one embodiment, the first resin (A) has a (meth) acryloyloxy group, an allyl group or a methallyl group as a radically polymerizable functional group.

In one embodiment, the first resin (A) comprises at least one selected from the following resins (a) to (l).
(A) Polyalkenylphenol resin having a specific structure (b) Hydroxypolystyrene resin derivative having a specific structure (c) Resin having an epoxy group and a phenolic hydroxyl group (d) Polymerizable monomer having an alkali-soluble functional group and other polymerization Copolymer of sex monomer (e) Polygonic acid resin (f) Polyamic acid resin (g) Polybenzoxazole resin (h) Polybenzoxazole resin precursor (i) Silicone resin (j) Cyclic olefin polymer (k) Cardo Resin (l) Phenolic resin

(A) Polyalkenylphenol resin The polyalkenylphenol resin (a) can be obtained by converting a hydroxyl group of a known phenol resin into an alkenyl ether and further rearranging the alkenyl ether group by Claisen rearrangement. Above all, equation (1)

Polyalkenylphenol resin having the structural unit of is preferable. By containing such a resin, the development characteristics of the obtained photosensitive resin composition can be improved and the outgas can be reduced.

In the formula (1), R ¹ , R ² and R ³ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and formula (2).

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

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

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

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

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

Specific examples of the cycloalkylene group having 5 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group and the like. Specific examples of the divalent organic group having an aromatic ring include a phenylene group, a tolylen group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthrasenylene group, a xylylene group, a 4,4-methylenediphenyl group, and the formula (3).

The group represented by is mentioned. Specific examples of the divalent organic group having an alicyclic condensed ring include a dicyclopentadienylene group and the like.

When the polyalkenylphenol resin (a) is used as the first resin (A), the Q of the formula (1) is _−CH2− as the polyalkenylphenol resin (a) which is particularly preferable from the viewpoint of alkali developability, outgas and the like. Something, that is, equation (4)

Those having a structural unit represented by. In the formula (4), R ¹ , R ² and R ³ are the same as those in the formula (1). Preferred R ¹ , R ² and R ³ are similar to preferred R ¹ , R ² and R ³ in formula (1).

The structural unit represented by the formula (1) or the formula (4) is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and further preferably 70 to 100 mol% in the polyalkenylphenol resin (a). Is 80-100 mol%. It is preferable that the structural unit represented by the formula (1) or the formula (4) is 50 mol% or more in the polyalkenylphenol resin (a) because the heat resistance is improved. Since the phenolic hydroxyl group in the polyalkenylphenol resin (a) is ionized in the presence of the basic compound and can be dissolved in water, it is necessary to have a certain amount or more of the phenolic hydroxyl group from the viewpoint of alkali developability. be. Therefore, the polyalkenylphenol resin (a) containing the structural unit of the formula (4) has the structural unit represented by the formula (4) and the formula (5).

It is particularly preferable that it is a polyalkenylphenol resin having a structural unit represented by. In the formula (5), R ^1a , R ^2a and R ^3a are independently hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Preferred R ^1a , R ^2a and R ^3a are similar to preferred R ¹ , R ² and R ³ in formula (1).

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

The number average molecular weight of the polyalkenylphenol resin (a) is preferably 500 to 5000, more preferably 800 to 3000, and even more preferably 900 to 2000. The weight average molecular weight of the polyalkenylphenol resin (a) is preferably 500 to 30,000, more preferably 3,000 to 25,000, and even more preferably 5,000 to 20,000. When the number average molecular weight is 500 or more or the weight average molecular weight is 500 or more, the alkali development speed is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good. When the number average molecular weight is 5000 or less or the weight average molecular weight is 30,000 or less, the coatability and the alkali developability are good.

The phenolic hydroxyl group equivalent of the polyalkenylphenol resin (a) is preferably 60 to 400, more preferably 80 to 350, and even more preferably 100 to 300. When the phenolic hydroxyl group equivalent of the polyalkenylphenol resin (a) is 60 or more, the film thickness of the unexposed portion can be sufficiently maintained during alkaline development. When the phenolic hydroxyl group equivalent of the polyalkenylphenol resin (a) is 400 or less, desired alkali solubility can be obtained.

(B) Hydroxystyrene resin derivative As the first resin (A), the formula (6)

A hydroxypolystyrene resin derivative (b) having the structural unit of can also be used. By containing such a resin, it is possible to improve the developing characteristics of the obtained photosensitive resin composition and also contribute to the reduction of outgas.

In formula (6), R ¹¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a is an integer of 1 to 4, b is an integer of 1 to 4, and a + b is within the range of 2 to 5. R ¹² is at least one selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group and a propyl group.

When the hydroxypolystyrene resin derivative (b) is used as the first resin (A), the structural unit represented by the formula (6) and the formula (7) in terms of alkali developability and outgas.

It is preferable that the copolymer has a structural unit represented by.

In the formula (7), R ¹³ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and c is an integer of 1 to 5.

A hydroxypolystyrene resin derivative (b) having a structural unit represented by the formula (6), and a hydroxypolystyrene resin derivative having a structural unit represented by the formula (6) and a structural unit represented by the formula (7) ( b) is an aromatic vinyl compound having a phenolic hydroxyl group such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol and the like. Of these, styrene is reacted with a part of the polymer or copolymer obtained by polymerizing one or two or more kinds by a known method by a known method, for example, the method described in JP2013-151705. It can be obtained by allowing it to react, or by further reacting it with alcohol.

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

The number average molecular weight of the hydroxypolystyrene resin derivative (b) is preferably 1000 to 20000, more preferably 3000 to 10000, and further preferably 4000 to 9000. The weight average molecular weight of the hydroxypolystyrene resin derivative (b) is preferably 1000 to 100,000, more preferably 5,000 to 75,000, and even more preferably 10,000 to 50,000. When the number average molecular weight is 1000 or more or the weight average molecular weight is 1000 or more, the alkali development speed is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good. When the number average molecular weight is 20000 or less, or the weight average molecular weight is 100,000 or less, the coatability and alkali developability are good.

The phenolic hydroxyl group equivalent of the hydroxypolystyrene resin derivative (b) is preferably 60 to 400, more preferably 80 to 350, and even more preferably 100 to 300. When the phenolic hydroxyl group equivalent of the hydroxypolystyrene resin derivative (b) is 60 or more, the film thickness of the unexposed portion can be sufficiently maintained during alkaline development. When the phenolic hydroxyl group equivalent of the hydroxypolystyrene resin derivative (b) is 400 or less, desired alkali solubility can be obtained.

(C) Resin having an epoxy group and a phenolic hydroxyl group As the first resin (A), a resin (c) having an epoxy group and a phenolic hydroxyl group can also be used. Such a resin (c) is, for example, an epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter, may be referred to as “epoxy compound”) and a carboxy of a hydroxybenzoic acid compound. It can be obtained by reacting the groups. When the resin (c) having an epoxy group and a phenolic hydroxyl group has an epoxy group, a crosslink can be formed by a reaction with the phenolic hydroxyl group at the time of heating, and the chemical resistance and heat resistance of the coating film can be improved. The phenolic hydroxyl group imparts alkali solubility during development to the resin.

The following reaction formula 1 shows an example of a reaction in which one of the epoxy groups of the epoxy compound reacts with the carboxy group of the hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group.

Examples of the compound having at least two epoxy groups in one molecule include novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolac type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, and naphthalene skeleton-containing epoxy. Examples thereof include a resin, an alicyclic epoxy resin, and a heterocyclic epoxy resin. These epoxy compounds may have two or more epoxy groups in one molecule, and may be used alone or in combination of two or more. Since these compounds are thermosetting, it is not possible to unambiguously describe their structures due to differences in the presence or absence of epoxy groups, the types of functional groups, the degree of polymerization, etc., as is common knowledge of those skilled in the art. An example of the structure of the novolak type epoxy resin is shown in the equation (8). In the formula (8), for example, R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a hydroxyl group having 1 to 2 carbon atoms, and m is an integer of 1 to 50.

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

The compound having at least two epoxy groups in one molecule is preferably a novolak type epoxy resin, and more preferably a cresol novolak type epoxy resin. The photosensitive resin composition containing a novolak type epoxy resin, particularly a resin (c) having an epoxy group and a phenolic hydroxyl group derived from a cresol novolak type epoxy resin, has excellent pattern forming properties and is easy to adjust alkali solubility. And there is little outgas.

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

In one embodiment, the resin (c) having an epoxy group and a phenolic hydroxyl group is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and is of the formula (9).

Has the structure of. In the formula (9), d is an integer of 1 to 5, and * represents the bond portion of the compound having at least two epoxy groups in one molecule to the residue excluding the epoxy group involved in the reaction.

In the method for obtaining the resin (c) having an epoxy group and a phenolic hydroxyl group from the epoxy compound and the hydroxybenzoic acid compound, 0.2 to 1.0 equivalent of the hydroxybenzoic acid compound is used with respect to 1 equivalent of the epoxy group of the epoxy compound. It is possible to use 0.3 to 0.9 equivalents, more preferably 0.4 to 0.8 equivalents. 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, an increase in molecular weight due to a side reaction can be suppressed.

A catalyst may be used to accelerate the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of the catalyst used can be 0.1 to 10 parts by mass based on 100 parts by mass of the reaction raw material mixture composed of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature can be 60 to 150 ° C. and the reaction time can be 3 to 30 hours. Examples of the catalyst used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanate, zirconium octanate and the like.

The number average molecular weight of the resin (c) having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and further preferably 1000 to 5000. The weight average molecular weight of the resin (c) having an epoxy group and a phenolic hydroxyl group is preferably 500 to 30,000, more preferably 2000 to 25,000, and even more preferably 3000 to 20000. When the number average molecular weight is 500 or more or the weight average molecular weight is 500 or more, the alkali development speed is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good. When the number average molecular weight is 8000 or less, or the weight average molecular weight is 30,000 or less, the coatability and the alkali developability are good.

The phenolic hydroxyl group equivalent of the resin (c) having an epoxy group and a phenolic hydroxyl group is preferably 60 to 300, more preferably 80 to 250, and further preferably 100 to 200. When the phenolic hydroxyl group equivalent of the resin (c) having an epoxy group and a phenolic hydroxyl group is 60 or more, the film thickness of the unexposed portion can be sufficiently maintained during alkaline development. When the phenolic hydroxyl group equivalent of the resin (c) having an epoxy group and a phenolic hydroxyl group is 300 or less, desired alkali solubility can be obtained.

(D) Polymer of polymerizable monomer having an alkali-soluble functional group and other polymerizable monomer As the first resin (A), the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomer A monomeric copolymer (d) can be used. Examples of the alkali-soluble functional group include a carboxy group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group and the like. Examples of the polymerizable functional group of the polymerizable monomer include radically 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- and the like can be mentioned.

The copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer may be, for example, a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. It can be produced by radical polymerization. After synthesizing the copolymer by radical polymerization, a derivative to which an alkali-soluble functional group is added may be used. Examples of the polymerizable monomer having an alkali-soluble functional group include 4-hydroxystyrene, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chlor (meth) acrylic acid, and β-frill (meth). ) Acrylic acid, β-styryl (meth) acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, silicic acid, α-cyanosilicic acid, itaconic acid, crotonic acid, propioleic acid , 4-Hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxyphenylmaleimide, 3-maleimide propionic acid, 4-maleimide fatty acid, 6-maleimide hexane acid and the like. Be done. Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl-n-butyl ether and the like. Ether compounds of vinyl alcohol; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl ( Meta) acrylate, tert-butyl (meth) acrylate, phenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2 , 2-Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopenta Examples thereof include (meth) acrylic acid esters such as nyl (meth) acrylates; maleic acid derivatives such as maleic anhydride and maleic acid monoesters; and N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide. From the viewpoint of heat resistance and the like, the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer has an alicyclic structure, an aromatic structure, a polycyclic structure, and an inorganic substance. It is preferable to have one or more kinds of cyclic structures such as a cyclic structure and a heterocyclic structure.

As a polymerizable monomer having an alkali-soluble functional group, the formula (10)

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

As another polymerizable monomer, the formula (11)

A polymerizable monomer forming a structural unit represented by is preferable. In formula (11), R ¹⁶ and R ¹⁷ are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and fully or partially fluorinated fluoroalkyl groups having 1 to 3 carbon atoms, respectively. Alternatively, R ¹⁸ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, and 1 to 6 carbon atoms. It is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms. R ¹⁶ and R ¹⁷ are preferably hydrogen atoms. R ¹⁸ is preferably a cyclic alkyl group or a phenyl group having 3 to 12 carbon atoms. Phenylmaleimide and cyclohexylmaleimide are particularly preferred as such other polymerizable monomers.

It is particularly preferable to use 4-hydroxyphenylmethacrylate as the polymerizable monomer having an alkali-soluble functional group, and to use at least one selected from the group consisting of phenylmaleimide and cyclohexylmaleimide as the other polymerizable monomer. By using a resin obtained by radically polymerizing these polymerizable monomers, shape retention and developability can be improved and outgas can be reduced.

The polymerization initiator for producing a copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer by radical polymerization is not limited to the following, but 2. 2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-) Cyanovaleric acid), azo polymerization initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile) (AVN), dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butyl). Peroxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, etc. have a 10-hour half-life temperature of 100 to 170. Peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di (tert-butylperoxy) cyclohexane, and tert-butylperoxypivalate can be used. can. The amount of the polymerization initiator used is generally 0.01 part by mass or more, 0.05 part by mass or more or 0.5 part by mass or more, 40 parts by mass or less, 20 parts by mass with respect to 100 parts by mass of the mixture of the polymerizable monomer. It is preferably parts by mass or less or 15 parts by mass or less.

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

In one embodiment, the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer is represented by the formula (10).

(In the formula (10), ^R15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5).
Structural unit represented by and formula (11)

(In the formula (11), R ¹⁶ and R ¹⁷ are independently hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a completely or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, respectively. , Or a halogen atom, where R18 is a hydrogen atom, a linear alkyl group having 1 to ⁶ carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, and 1 to 6 carbon atoms. It is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.)
It has a structural unit represented by.

The number average molecular weight of the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer is preferably 1000 to 30,000, more preferably 1500 to 25,000, and further. It is preferably 2000 to 20000. The weight average molecular weight of the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer is preferably 3000 to 80,000, more preferably 4000 to 70000, and further. It is preferably 5000 to 60,000. When the number average molecular weight is 1000 or more or the weight average molecular weight is 3000 or more, the alkali development speed is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good. When the number average molecular weight is 30,000 or less or the weight average molecular weight is 80,000 or less, the coatability and the alkali developability are good. The polydispersity (Mw / Mn) of the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer is preferably 1.0 to 3.5, and more. It is preferably 1.1 to 3.0, and more preferably 1.2 to 2.8. By setting the degree of polydispersity within the above range, a photosensitive resin composition having excellent pattern forming property and alkali developability can be obtained.

When the alkali-soluble functional group of the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is a phenolic hydroxyl group, the polymerizable monomer having an alkali-soluble functional group The phenolic hydroxyl group equivalent of the copolymer (d) of the above and other polymerizable monomers is preferably 60 to 400, more preferably 80 to 350, and further preferably 100 to 300. When the phenolic hydroxyl group equivalent of the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer is 60 or more, the film thickness of the unexposed portion is sufficient during alkaline development. Can be retained. When the phenolic hydroxyl group equivalent of the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer is 400 or less, the desired alkali solubility can be obtained.

In the present disclosure, when the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer also corresponds to the hydroxypolystyrene resin derivative (b), the alkali-soluble functional group It shall be treated as a copolymer (d) of the polymerizable monomer having the above and other polymerizable monomers. If the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and the other polymerizable monomer also corresponds to the resin (c) having an epoxy group and a phenolic hydroxyl group, the alkali-soluble functional group It shall be treated as a copolymer (d) of the polymerizable monomer having the above and other polymerizable monomers. That is, the hydroxypolystyrene resin derivative (b) and the resin (c) having an epoxy group and a phenolic hydroxyl group are copolymers (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers. Excludes those that fall under.

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

The polyimide resin (e) has a structural unit represented by the formula (12). The polyamic acid resin (f) and the polybenzoxazole resin precursor (h) have a structural unit represented by the formula (13). The polybenzoxazole resin (g) has a structural unit represented by the formula (14). The polyimide resin (e) may have both a structural unit represented by the formula (12) and a structural unit represented by the formula (13), and the polybenzoxazole resin (g) is represented by the formula (14). It may have both the structural unit to be used and the structural unit represented by the formula (13).

In formula (12), R ¹⁹ is a 4- to 10-valent organic group, R ²⁰ is a 2- to 8-valent organic group, and R ²¹ and R ²² are independently hydroxyl groups, carboxy groups, and sulfo groups, respectively. Alternatively, it is a mercapto group, and f and g are independently integers of 0 to 6.

In formula (13), R ²³ is a 2- to 8-valent organic group, R ²⁴ is a 2- to 8-valent organic group, and R ²⁵ and R ²⁶ are independently hydroxyl groups, sulfo groups, and mercapto groups, respectively. , Or -COOR ²⁷ , R ²⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and h and i are independently integers of 0 to 6, except h + i> 0. Is. In the case of the polyamic acid resin (f), h is an integer of 1 or more, and at least one of R ²⁵ is −COOR ²⁷ . In the case of the polybenzoxazole resin precursor (h), i is an integer of 1 or more, and at least one of R ²⁶ is a phenolic hydroxyl group.

In formula (14), R ²⁸ is a 2- to 8-valent organic group, R ²⁹ is a 2- to 8-valent organic group, and R ³⁰ and R ³¹ are independently hydroxyl groups, carboxy groups, and sulfo groups, respectively. Alternatively, it is a mercapto group, and j and k are independently integers of 0 to 6.

In formula (12), R ^19- (R ²¹ ) _f represents the residue of acid dianhydride. R ¹⁹ is a 4- to 10-valent organic group, preferably an organic group having 5 to 40 carbon atoms including an aromatic ring or a cyclic aliphatic group.

Examples of the acid dianhydride include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride. 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetra Carboxydic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis ( 3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2) , 3-Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis (3) , 4-Dicarboxyphenyl) Fluoleic dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] Fluoleic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Aromatic tetracarboxylic acid dianhydrides such as hexafluoropropane dianhydride; aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Things, etc., and combinations of two or more of these can be mentioned.

R ^23- (R ²⁵ ) _h of the formula (13) and R ^28- (R ³⁰ ) _j of the formula (14) each represent an acid residue. Each of R ²³ and R ²⁸ is an independently 2 to 8-valent organic group, and is preferably an organic group having 5 to 40 carbon atoms including an aromatic ring or a cyclic aliphatic group.

Examples of the acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyldicarboxylic acid; trimellitic acid and trimesic acid. , Diphenyl ether tricarboxylic acid, aromatic tricarboxylic acids such as biphenyltricarboxylic acid; pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2 , 2', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis ( 3,4-Dicarboxyphenyl) Hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1- Bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) ether, 1, 2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, etc. Aromatic tetracarboxylic acids; butane tetracarboxylic acids, aliphatic tetracarboxylic acids such as 1,2,3,4-cyclopentanetetracarboxylic acids, and combinations of two or more thereof. In the above tricarboxylic acids and tetracarboxylic acids, one or two carboxy groups correspond to R ²⁵ in formula (13) or R ³⁰ in formula (14). These acids may be in the form of esters or acid anhydrides.

R ^20- (R ²² ) _g of formula (12), R ^24- (R ²⁶ ) _i of formula (13), and R ^29- (R ³¹ ) _k of formula (14) each contain diamine residues. show. R ²⁰ , R ²⁴ and R ²⁹ are each independently 2 to 8 valent organic groups, and are preferably organic groups having 5 to 40 carbon atoms including an aromatic ring or a cyclic aliphatic group.

Examples of the diamine corresponding to R ²⁰ of the formula (12) and R ²⁴ of the formula (13) according to the polyamic acid resin (f) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3 , 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6 -Naphthalenediamine, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (tri) An aromatic diamine such as fluoromethyl) -4,4'-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, or at least one of the hydrogen atoms in the aromatic ring of these aromatic diamines is an alkyl group or Compounds substituted with halogen atoms; aliphatic diamines such as cyclohexyldiamine and methylenebiscyclohexylamine, and combinations of two or more thereof can be mentioned.

As the diamine corresponding to R ²⁴ of the formula (13) and R ²⁹ of the formula (14) according to the polybenzoxazole resin precursor (h), for example, with respect to the amino group on the aromatic ring of the aromatic diamine. Examples thereof include bisaminophenol compounds having a phenolic hydroxyl group at the ortho position, and combinations of two or more of these.

The polyimide resin (e), the polyamic acid resin (f), the polybenzoxazole resin (g), and the polybenzoxazole resin precursor (h) are monoamines having acidic groups at their ends, acid anhydrides, acid chlorides, and the like. It may have an acidic group at the end of the main chain by being sealed with a monocarboxylic acid or the like.

The polyamic acid resin (f) is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine, forming a diester from the tetracarboxylic acid dianhydride and an alcohol, and then reacting the diester with the diamine in the presence of a condensing agent. It can be synthesized by a method of forming a diester from tetracarboxylic acid dianhydride and an alcohol, acid chlorideizing the remaining dicarboxylic acid, and then reacting the obtained intermediate with a diamine.

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

The polyimide resin (e) can be synthesized, for example, by heating the polyamic acid resin (f) obtained by the above method or dehydrating and closing the ring by a chemical treatment such as an acid or a base.

The polybenzoxazole resin (g) can be synthesized, for example, by heating the polybenzoxazole resin precursor (h) obtained by the above method or dehydrating and closing the ring by a chemical treatment such as an acid or a base.

The number average molecular weight of the polyimide resin (e), the polyamic acid resin (f), the polybenzoxazole resin (g), and the polybenzoxazole resin precursor (h) is preferably 500 to 8000, more preferably 800 to 800. It is 6000, more preferably 1000 to 5000. When the number average molecular weight is 500 or more, it is suitable as a resin for a photosensitive material because it has appropriate alkali solubility. When the number average molecular weight is 8000 or less, the coatability and developability are good.

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

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

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

Examples of the organosilane represented by the formula (15) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane; methyltrimethoxysilane, methyltriethoxysilane, and methyltriiso. Propoxysilane, methyltri n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxy Silane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacry Propylpropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p) -Hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoro Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyllin-propoxysilane, 2-naphthyltrimethoxy Silane, 1-anthrasenyltrimethoxysilane, 9-anthrasenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-f Trifunctional silanes such as ruolenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane; dimethyldimethoxysilane, Dimethyldiethoxysilane, dimethyldiacetoxysilane, din-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, di (1-) Bifunctional silanes such as naphthyl) dimethoxysilane, di (1-naphthyl) diethoxysilane; trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxy) Monofunctional silanes such as propyl) dimethylethoxysilane and combinations of two or more of these can be mentioned.

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

In the formula (16), R ³⁴ to R ³⁷ are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, alkanoyl groups having 2 to 6 carbon atoms, or aryl groups having 6 to 16 carbon atoms. , N is in the range of 2-8. When n is 2 or more, the plurality of R ³⁵ and R ³⁶ may be the same or different.

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

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

As the catalyst, an acid catalyst or a base catalyst is preferably used. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or its anhydride, ion exchange resin and the like. Examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide and amino groups. Examples thereof include an alkoxysilane having an ion exchange resin and an ion exchange resin. The catalyst may be removed after hydrolysis and partial condensation, if necessary, by washing with water, treatment with an ion exchange resin, or a combination thereof. By removing the catalyst, the storage stability of the photosensitive resin composition can be improved.

The weight average molecular weight of the silicone resin (i) is preferably 1000 to 100,000, more preferably 1000 to 50,000. When the weight average molecular weight is 1000 or more, the film-forming property can be improved, and when the weight average molecular weight is 100,000 or less, the alkali developability is good.

(J) Cyclic olefin polymer In one embodiment, the first resin (A) contains a cyclic olefin polymer (j). The cyclic olefin polymer (j) is a homopolymer or copolymer of a cyclic olefin monomer having an alicyclic structure and an ethylenically unsaturated double bond. The cyclic olefin polymer (j) may have a structural unit derived from a monomer other than the cyclic olefin monomer.

Examples of the monomer constituting the cyclic olefin polymer (j) include a cyclic olefin monomer having a protonic polar group, a cyclic olefin monomer having a polar group other than protonic, and a cyclic olefin monomer having no polar group. Examples thereof include a metric and a monomer other than the cyclic olefin. The monomer other than the cyclic olefin may have a protonic polar group or a polar group other than this, or may not have a polar group.

Examples of the cyclic olefin monomer having a protonic polar group include 5-hydroxycarbonylbicyclo [2.2.1] hept-2-ene and 5-methyl-5-hydroxycarbonylbicyclo [2.2.1]. Hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1] Hept-2-ene, 5-exo-6-end-dihydroxycarbonylbicyclo [2.2.1] Hept-2 -En, 8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-exo-9-end-dihydroxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^17,10 ] Carboxy group-containing cyclic olefins such as dodeca-3-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5- (4-hydroxy) Phenyl) bicyclo [2.2.1] hept-2-ene, 8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-methyl-8- (4-hydroxyphenyl) tetracyclo [4.4.0.1 ^2,5 . ^{17. 10} ] Hydroxyl-containing cyclic olefins such as dodeca-3-ene, and combinations of two or more thereof can be mentioned.

Examples of the cyclic olefin monomer having a polar group other than the protonic property include 5-acetoxybicyclo [2.2.1] hept-2-ene and 5-methoxycarbonylbicyclo [2.2.1] hept-2. -En, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 8-acetoxytetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, 8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Cyclic olefins with ester groups such as dodeca-3-ene; cyclic olefins with N-substituted imide groups such as N-phenyl- (5-norbornene-2,3-dicarboxyimide); 8- Cyanotetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-methyl-8-cyanotetracyclo [4.4.0.1 ^2,5 . Cyclic olefins with cyano groups such as ^17,10 ] dodeca-3-ene, 5-cyanobicyclo [2.2.1] hept-2-ene; 8-chlorotetracyclo [4.4.0.1 ² ] ^{, 5} . 17 and ¹⁰ ] Dodeca-3-ene, 8-methyl-8-chlorotetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Cyclic olefins having a halogen atom such as dodeca-3-ene, and combinations of two or more thereof can be mentioned.

Examples of the cyclic olefin monomer having no polar group include bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, and 5-en. Butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] hept-2- En, 5-vinyl-bicyclo [2.2.1] hept-2-ene, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene, tetracyclo [8.4.0.1] ^11,14 . 0 ^3,7 ] Pentadeca-3,5,7,12,11-pentaene, tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Deca-3-ene, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-en, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodeca-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ⁷ , 10] Dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . ^09,13 ] Pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo [4.4. 0.1 2, ⁵ . 1 ⁷ , 10] Dodeca-3-ene, tetracyclo [9.2.1.0 ^2,10 . 0 ^3,8 ] Tetradeca-3,5,7,12-Tetraene, Pentacyclo [7.4.0.1 ^3,6 . 1 ^{10, 13} . 0 ^2,7 ] Pentadeca-4,11-diene, pentacyclo [9.2.1.14, 7.0 ^2,10 . 0 ^3,8 ] Pentadeca-5,12-diene, etc., and combinations of two or more of these.

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

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

The weight average molecular weight of the cyclic olefin polymer (j) is preferably 1000 to 100,000, more preferably 1000 to 50,000. When the weight average molecular weight is 1000 or more, the film-forming property can be improved, and when the weight average molecular weight is 100,000 or less, the alkali developability is good.

(K) Cardo Resin In one embodiment, the first resin (A) contains a cardo resin (k). The cardo resin (k) has a cardo structure, that is, a skeletal structure in which two other cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure. Examples of the skeleton structure in which two other cyclic structures are bonded to the quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenylfluorene skeleton, a fluorene skeleton having an epoxy group, and an acrylic group. Examples include the fluoren skeleton. An example of a cardo structure is a fluorene ring bonded to a benzene ring.

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

The weight average molecular weight of the cardo resin (k) is preferably 1000 to 100,000, more preferably 1000 to 50,000. When the weight average molecular weight is 1000 or more, the film-forming property can be improved, and when the weight average molecular weight is 100,000 or less, the alkali developability is good.

(L) Phenol resin In one embodiment, the first resin (A) is a phenol novolac resin, a cresol novolak resin, a triphenylmethane type phenol resin, a phenol aralkyl resin, a biphenyl aralkyl phenol resin, a phenol-dicyclopentadiene copolymer. It contains a phenol resin (l) such as a resin or a derivative thereof. The number average molecular weight of the phenol resin (l) varies depending on the resin structure, but is preferably 100 to 50,000, more preferably 500 to 30,000, and even more preferably 800 to 10,000. When the number average molecular weight is 100 or more, the alkaline development rate is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good. When the number average molecular weight is 50,000 or less, the alkali developability is good.

The content of the first resin (A) in the photosensitive resin composition is preferably 5 to 60% by mass, based on the total mass of the resin component, the radiation-sensitive compound (D), and the blackening agent (E). It is 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 total mass, the residual film ratio, heat resistance, sensitivity and the like are appropriate. When the content of the first resin (A) is 60% by mass or less based on the total mass, the optical density (OD value) of the cured film can be 0.5 or more per 1 μm of the film thickness. , The light-shielding property can be maintained even after curing.

The photosensitive resin composition preferably contains the first resin (A) in an amount of 20% by mass to 90% by mass, more preferably 25% by mass to 70% by mass, and more preferably 30% by mass, based on the total mass of the resin components. It is more preferable to contain% to 55% by mass. If the content of the first resin (A) is 20% by mass or more based on the total mass of the resin components, the 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.

The first resin (A) is preferably at least one selected from the resins (a) to (l), and more preferably from the resins (a) to (d) from the viewpoint of heat resistance of the resin composition. It is at least one selected, and more preferably a resin (c), that is, a resin (c) having an epoxy group and a phenolic hydroxyl group.

[Second resin (B)]
As the second resin (B), a resin having a phenolic hydroxyl group, which is different from the first resin (A), can be used. The second resin (B) is not particularly limited as long as it is a resin having a phenolic hydroxyl group. As such a second resin (B), it is preferable to use (a) to (d) or (l) among the resins described in the first resin (A). However, the second resin (B) is a resin different from the first resin (A). Here, "different" means that the structures of the structural units of one resin and another resin are different from each other, or when a certain resin contains one or more common structural units with another resin, the common structural units are summed up. It means that it contains less than 70 mol%, and resins having different molecular weights are regarded as the same resin.

The phenolic hydroxyl group equivalent of the second resin (B) is 1.1 to 5.0 times the phenolic hydroxyl group equivalent of the third resin (C) described later. The phenolic hydroxyl group equivalent of the second resin (B) is preferably 1.2 to 4.0 times, preferably 1.3 to 2.5 times, the phenolic hydroxyl group equivalent of the third resin (C). Is more preferable. The second resin (B) suppresses excessive dissolution of the unexposed portion as a resin component having low alkali solubility during development, while the exposed portion contains other resin components having high alkali solubility and any dissolution accelerator. Since it is released from the coating film into the developing solution as it dissolves, the sensitivity and residual film ratio of the photosensitive resin composition can be increased. As a result, the content of the radiation-sensitive compound (D) in the photosensitive resin composition can be reduced depending on the application, and as a result, the photosensitive resin composition can be made suitable for forming a thick film. can. Further, the second resin (B) having a low alkali solubility and the third resin (C) having a higher alkali solubility than the second resin (B) are in a range in which the phenol hydroxyl group equivalents of these resins are in the above ratio. By combining with, the dissolution of the coating film during development can be made microscopically uniform, and as a result, the roughness of the coating film surface can be suppressed.

When the alkali-soluble functional group of the first resin (A) is a phenolic hydroxyl group, the phenolic hydroxyl group equivalent of the second resin (B) is 1.3 to 4. It is preferably 5 times, more preferably 1.4 to 4.0 times, and even more preferably 1.5 to 3.5 times. By setting the phenolic hydroxyl group equivalent of the first resin (A) and the phenolic hydroxyl group equivalent of the alkaline low solubility second resin (B) to have the above ratio, the dissolution of the coating film during development is slight. It can be visually made more uniform, and as a result, the roughness of the coating surface can be effectively suppressed.

In the present disclosure, the phenolic hydroxyl group equivalents of the first resin (A), the second resin (B) and the third resin (C) mean the values at the time after the exposure of the photosensitive resin composition and before the development. .. Whether or not there is a change between the original phenolic hydroxyl group equivalents of these resins and the phenolic hydroxyl group equivalents after exposure to the photosensitive resin composition and before development can be determined by the following procedure using NMR. You can judge. To 100 parts by mass of the resin to be measured, 30 parts by mass of the radiation-sensitive compound used in the photosensitive resin composition and 1 part by mass of methyltriphenylsilane as an internal standard are added and mixed in DMSO-d6. To prepare the test composition by. ¹ H-NMR of the obtained test composition is measured, and the integral value S1 of the phenolic hydroxyl group is calculated when the integral value of the internal standard is 1.00. Further, ¹ H-NMR of the test composition after irradiating the test composition with ultraviolet rays at 1000 mJ / cm ² with an exposure device incorporating an ultra-high pressure mercury lamp and heating at 120 ° C. for 5 minutes using an oil bath is performed. The measurement is performed, and the integral value S2 of the phenolic hydroxyl group is calculated when the integral value of the internal standard is 1.00. A resin in which the rate of change of these integrated values ((S2-S1) / absolute value of S1) is less than 10% is considered to have no change in the value of phenolic hydroxyl group equivalent.

The phenolic hydroxyl group equivalent of the second resin (B) is preferably 250 to 700, more preferably 260 to 600, and even more preferably 270 to 550. When the phenolic hydroxyl group equivalent of the second resin (B) is 250 or more, the film thickness of the unexposed portion can be sufficiently maintained during alkaline development. When the phenolic hydroxyl group equivalent of the second resin (B) is 700 or less, desired alkali solubility can be obtained.

The second resin (B) contains the same structural unit as at least one of the structural units of the third resin (C) described later and other structural units, and has a total of 30 structural units common to the third resin (C). It is preferably contained in an amount of mol% to 95 mol%, and the alkali dissolution rate of the second resin (B) is smaller than the alkali dissolution rate of the third resin (C). In this embodiment, since a part of the structural unit of the second resin (B) and the third resin (C) is common, the compatibility between the second resin (B) and the third resin (C) is high. Therefore, the dissolution of the coating film during development can be made more uniform microscopically, and as a result, the roughness of the coating film surface can be effectively suppressed. In this embodiment, the second resin (B) more preferably contains 40 mol% to 90 mol% of the structural units common to the third resin (C) in total, and more preferably 50 mol% to 85 mol%. More preferred. When a plurality of structural units are common between the second resin (B) and the third resin (C), the value of mol% above means the sum of mol% of these plurality of structural units. In the present disclosure, the alkali dissolution rate of the resin or the photosensitive resin composition is determined by the following procedure. In a 20% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of the resin or photosensitive resin composition, Megafuck (registered trademark) F-559 (fluorine-based surfactant, manufactured by DIC Co., Ltd.) as a leveling agent is added to the resin solid content. Add in an amount of 0.1 parts by mass per 100 parts by mass. The obtained mixture is applied to a glass substrate (70 mm × 70 mm × 0.7 mm) so that the dry film thickness is 5.0 μm, vacuum dried for 30 seconds, and then the film is dried at a temperature of 120 ° C. for 120 seconds. After drying, alkaline development is performed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution. The development time is adjusted in the range of 8 to 400 seconds so that the film does not completely melt. The value obtained by dividing the reduction amount (nm) of the film after development by the development time (seconds) is defined as the alkali dissolution rate (nm / sec). Since the alkali dissolution rate of the second resin (B) is smaller than the alkali dissolution rate of the third resin (C), the second resin (B) is less soluble in alkali than the third resin (C). Is guaranteed.

The second resin (B) is preferably a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. The copolymer of the polymerizable monomer having a phenolic hydroxyl group and the other polymerizable monomer is the polymerizable monomer having the alkali-soluble functional group described for the first resin (A) and other polymerizable monomers. Of the monomeric copolymer (d), at least a part, preferably all of the alkali-soluble functional groups, is a phenolic hydroxyl group. At least a portion of the structural units derived from the other polymerizable monomers confer the second resin (B) with lower alkali solubility than the third resin (C). The second resin (B) of this embodiment is the same as the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers described for the first resin (A). , It can be produced by radically polymerizing a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer.

In one embodiment, the second resin (B) is represented by the formula (17).

(In the formula (17), R ³⁸ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³⁹ is a linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group having 3 to 20 carbon atoms. , A cyclic alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a linear alkyl group having 1 to 20 carbon atoms substituted with a group other than the acidic functional group, and a group other than the acidic functional group. A branched alkyl group having 3 to 20 carbon atoms substituted with, a cyclic alkyl group having 3 to 12 carbon atoms substituted with a group other than the acidic functional group, and a carbon atom substituted with a group other than the acidic functional group. It is a group selected from the group consisting of 6 to 20 aryl groups.)
It has a structural unit represented by. In the present disclosure, the acidic functional group is a group exhibiting an acid-base reaction with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, and specifically, a phenolic hydroxyl group, a carboxy group, a sulfo group, and a phosphoric acid. Groups include groups, acid anhydride groups, and mercapto groups.

Specific examples of the alkyl group having 1 to 5 carbon atoms in R ³⁸ of the formula (17) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-. Butyl group, n-pentyl group and the like can be mentioned. R ³⁸ is preferably a methyl group.

In ^R39 of the formula (17), the linear alkyl group having 1 to 20 carbon atoms and the branched alkyl group having 3 to 20 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group and an isopropyl group. , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n -Dodecyl group, n-hexadecyl group and the like can be mentioned. Examples of the cyclic alkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, an isobornyl group, an adamantyl group and a dicyclopentanyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 4- (benzyloxymethoxy) phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, an anthrasenyl group, a phenanthrenyl group and the like. R ³⁹ is preferably a tert-butyl group, a cyclohexyl group, an isobornyl group, a dicyclopentanyl group, a phenyl group, or a 4- (benzyloxymethoxy) phenyl group.

In one embodiment, the second resin (B) is represented by the formula (10).

(In the formula (10), ^R15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5).
It has a structural unit represented by. ^R15 is preferably a methyl group. e is preferably 1. When e is 1, the OH group is preferably at the 4-position.

In one embodiment, the second resin (B) is represented by the formula (11).

(In the formula (11), R ¹⁶ and R ¹⁷ are independently hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a completely or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, respectively. , Or a halogen atom, where R18 is a hydrogen atom, a linear alkyl group having 1 to ⁶ carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, and 1 to 6 carbon atoms. It is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.)
It has a structural unit represented by. R ¹⁶ and R ¹⁷ are preferably hydrogen atoms. R ¹⁸ is preferably a phenyl group or a cyclohexyl group.

The second resin (B) is a copolymer containing the structural unit represented by the above formula (17), the structural unit represented by the formula (10), and the structural unit represented by the formula (11). Is preferable.

The number average molecular weight of the second resin (B) is preferably 1000 to 30,000, more preferably 1500 to 25,000, and even more preferably 2000 to 20000. The weight average molecular weight of the second resin (B) is preferably 3000 to 80000, more preferably 4000 to 70,000, and further preferably 5000 to 60,000. When the number average molecular weight is 1000 or more or the weight average molecular weight is 3000 or more, the alkali development speed is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good. When the number average molecular weight is 30,000 or less or the weight average molecular weight is 80,000 or less, the coatability and the alkali developability are good. The polydispersity (Mw / Mn) of the second resin (B) is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2. It is 8.8. By setting the degree of polydispersity within the above range, a photosensitive resin composition having excellent pattern forming property and alkali developability can be obtained.

The photosensitive resin composition preferably contains the second resin (B) in an amount of 5% by mass to 50% by mass, more preferably 8% by mass to 45% by mass, and 10% by mass, based on the total mass of the resin components. It is more preferable to contain% to 40% by mass. When the content of the second resin (B) is 5% by mass or more based on the total mass of the resin components, a sufficient contrast due to the difference in dissolution rate from the first resin (A) can be obtained. When the content of the second resin (B) is 50% by mass or less based on the total mass of the resin components, the dissolution of the coating film during development can be made microscopically more uniform, and as a result, the coating film surface can be made more uniform. Roughness can be effectively suppressed.

[Third resin (C)]
As the third resin (C), among the resins described in the first resin (A), a resin having a phenolic hydroxyl group, which is different from both the first resin (A) and the second resin (B), is used. Can be done.

The phenolic hydroxyl group equivalent of the third resin (C) is preferably 107 to 240, more preferably 140 to 235, and even more preferably 170 to 230. When the phenolic hydroxyl group equivalent of the third resin (C) is 107 or more, the film thickness of the unexposed portion can be sufficiently maintained during alkaline development. When the phenolic hydroxyl group equivalent of the third resin (C) is 240 or less, desired alkali solubility can be obtained.

The third resin (C) is preferably a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. The copolymer of the polymerizable monomer having a phenolic hydroxyl group and the other polymerizable monomer is the polymerizable monomer having the alkali-soluble functional group described for the first resin (A) and other polymerizable monomers. Of the monomeric copolymer (d), at least a part, preferably all of the alkali-soluble functional groups, is a phenolic hydroxyl group.

The number average molecular weight of the third resin (C) is preferably 1000 to 30,000, more preferably 1500 to 25,000, and even more preferably 2000 to 20000. The weight average molecular weight of the third resin (C) is preferably 3000 to 80000, more preferably 4000 to 70,000, and further preferably 5000 to 60,000. When the number average molecular weight is 1000 or more or the weight average molecular weight is 3000 or more, the alkali development speed is appropriate and the difference in dissolution rate between the exposed portion and the unexposed portion is sufficient, so that the resolution of the pattern is good. When the number average molecular weight is 30,000 or less or the weight average molecular weight is 80,000 or less, the coatability and the alkali developability are good. The polydispersity (Mw / Mn) of the third resin (C) is preferably 1.0 to 3.5, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2. It is 8.8. By setting the degree of polydispersity within the above range, a photosensitive resin composition having excellent pattern forming property and alkali developability can be obtained.

The photosensitive resin composition preferably contains the third resin (C) in an amount of 5% by mass to 50% by mass, more preferably 8% by mass to 45% by mass, and 10% by mass, based on the total mass of the resin components. It is more preferable to contain% to 40% by mass. When 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 microscopically more uniform, and as a result, the coating surface surface. Roughness can be effectively suppressed. When the content of the third resin (C) was 50% by mass or less based on the total mass of the resin components, the contrast due to the difference in the dissolution rate between the first resin (A) and the second resin (B) was maintained. A pattern can be formed.

[Radiation-sensitive compound (D)]
As the radiation-sensitive compound (D), a photoacid generator, a photobase generator or a photopolymerization initiator can be used. A photoacid generator is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, γ-rays, and electron beams. Since the photoacid generator increases the solubility of the irradiated portion in the alkaline aqueous solution, it can be used in a positive photosensitive resin composition in which the portion is dissolved. A photobase generator is a compound that generates a base when irradiated with radiation. Since the photobase generator reduces the solubility of the irradiated portion in the alkaline aqueous solution, it can be used for a negative photosensitive resin composition in which the portion is insoluble. A photopolymerization initiator is a compound that generates radicals when irradiated with radiation. The photopolymerization initiator is a radical polymerization functional group or a radically polymerizable compound of the binder resin of the portion irradiated with radiation when the photosensitive resin composition contains a binder resin or a radically polymerizable compound having a radically polymerizable functional group. It can be used in a negative photosensitive resin composition in which radical polymerization of the above progresses and a polymer insoluble in an alkaline aqueous solution is formed in the portion thereof.

<Photoacid generator>
The radiation-sensitive compound (D) is preferably a photoacid generator in that a pattern with high sensitivity and high resolution can be obtained. As the photoacid generator, at least one selected from the group consisting of a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt can be used. In one embodiment, the photoacid generator is a compound or salt that is sensitive to i-rays (365 nm).

It is preferable to use a quinonediazide compound as a photoacid generator. The quinone-diazide compound includes a polyhydroxy compound in which quinone-diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone-diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone-diazide sulfonic acid is ester-bonded or a sulfonamide-bond. And so on. From the viewpoint of the contrast between the exposed portion and the unexposed portion, it is preferable that 20 mol% or more of the total functional group of the polyhydroxy compound or the polyamino compound is substituted with quinonediazide.

Examples of the polyhydroxy compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ. BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methyltris-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 (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIRC-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, asbestosic acid methyl ester, bisphenol A, Examples thereof include, but are not limited to, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

Examples of the polyamino compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diamino. Examples thereof include, but are not limited to, diphenyl sulfide.

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

The quinone diazide compound is preferably a 1,2-naphthoquinone diazide-4-sulfonic acid ester or a 1,2-naphthoquinone diazide-5-sulfonic acid ester of a polyhydroxy compound.

When the quinone diazide compound is irradiated with ultraviolet light or the like, it produces a carboxy group through the reaction shown in the following reaction formula 2. By generating a carboxy group, the exposed portion (coating) becomes soluble in an alkaline aqueous solution, and alkaline developability occurs in that portion.

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

<Photobase generator>
A photobase generator may be used as the radiation-sensitive compound (D). As the photobase generator, at least one selected from the group consisting of an amide compound and an ammonium salt can be used. In one embodiment, the photobase generator is a compound or salt that is sensitive to i-rays (365 nm).

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

When the radiation-sensitive compound (D) is a photobase generator, the content of the photobase generator in the photosensitive resin composition shall be 1 to 40 parts by mass based on a total of 100 parts by mass of the resin components. It is preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass. When the content of the photobase generator is 1 part by mass or more based on the total of 100 parts by mass, the alkali developability is good, and when it is 40 parts by mass or less, the film is reduced by heating at 300 ° C. or higher. Can be suppressed.

<Photopolymerization initiator>
A photopolymerization initiator may be used as the radiation-sensitive compound (D). The photopolymerization initiator comprises a benzyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine oxide compound, an oxime ester compound, an acridine compound, a benzophenone compound, an acetophenone compound, an aromatic ketoester compound and a benzoic acid ester compound. At least one selected from the group can be used. In one embodiment, the photopolymerization initiator is a compound that is highly sensitive to i-rays (365 nm). Since the photopolymerization initiator is highly sensitive at the time of exposure, the photopolymerization initiator is preferably an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine oxide compound, an oxime ester compound, an acridine compound or a benzophenone compound, and an α-aminoketone compound. , An acylphosphine oxide compound, or an oxime ester compound is more preferable.

Examples of the benzyl ketal compound include 2,2-dimethoxy-1,2-diphenylethane-1-one. Examples of the α-hydroxyketone compound include 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1 -Hydroxycyclohexylphenyl 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 can be mentioned. Examples of the α-aminoketone compound include 2-dimethylamino-2-methyl-1-phenylpropane-1-one, 2-diethylamino-2-methyl-1-phenylpropane-1-one, and 2-methyl-2-one. Morphorino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- (4-ethylphenyl) -2- Methylpropane-1-one, 2-dimethylamino-1- (4-isopropylphenyl) -2-methylpropane-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropane-1 -On, 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-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-benzyl -2-Dimethylamino-1- (4-dimethylaminophenyl) -butane-1-one, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4-morphonyl) phenyl ] -1-Butanone. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide or bis (2,6-dimethoxybenzoyl)-(2). , 4,4-trimethylpentyl) phosphine oxide. Examples of the oxime ester compound include 1-phenylpropane-1,2-dione-2- (O-ethoxycarbonyl) oxime, 1-phenylbutane-1,2-dione-2- (O-methoxycarbonyl) oxime, and the like. 1,3-Diphenylpropane-1,2,3-trion-2- (O-ethoxycarbonyl) oxime, 1- [4- (phenylthio) phenyl] octane-1,2-dione-2- (O-benzoyl) Oxime, 1- [4- [4- (carboxyphenyl) thio] phenyl] Propane-1,2-dione-2- (O-acetyl) oxime, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-Carbazole-3-yl] Etanone-1- (O-acetyl) oxime, 1- [9-ethyl-6- [2-methyl-4- [1- (2,2-dimethyl-1,3-) Dioxolan-4-yl) methyloxy] benzoyl] -9H-carbazole-3-yl] etanone-1- (O-acetyl) oxime. Examples of the acridine compound include 1,7-bis (acridine-9-yl) -n-heptane. Examples of the benzophenone compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone, and alkyl. Benzophenones, 3,3', 4,4'-tetrakis (tert-butylperoxycarbonyl) benzophenones, 4-methylbenzophenones, dibenzylketones or fluorenones can be mentioned. Examples of the acetophenone compound include 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-tert-butyldichloroacetophenone, benzalacetophenone or 4-azidobenzalacetophenone. Examples of the aromatic ketoester compound include 2-phenyl-2-methyl oxyacetate. Examples of the benzoic acid ester compound include ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-ethyl) hexyl, ethyl 4-diethylaminobenzoate or methyl 2-benzoylbenzoate.

When the first resin (A), the second resin (B), or the third resin (C) or two or more of these have a cationically polymerizable group such as an epoxy group, the cationic species is lightly used as a photopolymerization initiator. Alternatively, a photocationic polymerization initiator that generates Lewis acid can be used. Examples of the photocationic polymerization initiator include triphenylsulfonium, sulfonium such as diphenyl-4- (phenylthio) phenylsulfonate, iodonium such as diphenyliodonium and bis (dodecylphenyl) iodinenium, and diazonium such as phenyldiazonium. Fe such as 1-benzyl-2-cyanopyridinium, pyridinium such as 1- (naphthylmethyl) -2-cyanopyridinium, (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe. It is a cation, and the anionic moiety is composed of BF _4- ^, PF _6- ^, SbF _6- , [BX ₄ ^]- ⁽ X is a phenyl group substituted with at least two or more fluorine atoms or a trifluoromethyl group) and the like. The onium salt to be added is mentioned.

When the radiation-sensitive compound (D) is a photopolymerization initiator, the content of the photopolymerization initiator in the photosensitive resin composition shall be 1 to 40 parts by mass based on a total of 100 parts by mass of the resin components. It is preferably 1.5 to 35 parts by mass, and more preferably 2 to 30 parts by mass. When the content of the photopolymerization initiator is 1 part by mass or more based on the total of 100 parts by mass, the alkali developability is good, and when it is 40 parts by mass or less, the film is reduced 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 a plurality of ethylenically unsaturated groups as radically polymerizable compounds can crosslink the coating film to increase its hardness.

It is preferable to use a compound having a plurality of (meth) acrylic groups as the radically polymerizable compound from the viewpoint of reactivity at the time of exposure, hardness of the film, heat resistance and the like. Such compounds include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, and trimethylol. Propanetri (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, dimethylolpropane tri (meth) acrylate, dimethylolpropane tetra (meth) acrylate, 1,3 -Butandiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( Meta) acrylate, 1,10-decanediol di (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate, ethoxylated glycerin tri (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, tri Pentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, pentapentaerythritol undeca (meth) acrylate, pentapentaerythritol dodeca (meth) acrylate, ethoxylated bisphenol A di (Meta) acrylate, 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 1,3,5-tris ((meth) acryloxyethyl) isocyanuric acid, 1, 3-Bis ((meth) acryloxyethyl) isocyanuric acid, 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, 9,9-bis [4- (3- (meth)) Acryloxypropoxy) phenyl] fluorene or 9,9-bis (4- (meth) acryloxyphenyl) fluor Examples thereof include len or an acid-modified product thereof, an ethylene oxide-modified product or a propylene oxide-modified product.

The content of the radically polymerizable compound in the photosensitive resin composition can be 15 parts by mass to 65 parts by mass and 20 parts by mass to 60 parts by mass with respect to 100 parts by mass of the total resin components. Is preferable, and 25 parts by mass to 50 parts by mass is more preferable. When the content of the radically polymerizable compound is in the above range, the alkali developability is good, and the heat resistance of the cured film can be improved.

[Black agent (E)]
The blackening agent (E) is selected from the group consisting of black dyes and black pigments. A black dye and a black pigment may be used in combination. By forming a black partition wall on the organic EL element using the photosensitive resin composition containing the blackening agent (E), the visibility of a display device such as an organic EL display can be improved.

In one embodiment, the black agent (E) contains a black dye. As the black dye, a dye specified by the color index (CI) of Solvent Black 27 to 47 can be used. The black dye is preferably C.I. I. It is specified in. Solvent Black 27-47 C.I. I. When at least one of the dyes specified in the above is used as a black dye, the light-shielding property of the film of the photosensitive resin composition after curing can be maintained. The photosensitive resin composition containing a black dye has less residual colorant during development as compared with the photosensitive resin composition containing a black pigment, and can form a high-definition pattern 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 10 parts by mass, based on a total of 100 parts by mass of the resin components. It is 15 to 100 parts by mass, 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 total of 100 parts by mass, the light-shielding property of the film after curing can be maintained. When the content of the black dye is 150 parts by mass or less based on the total of 100 parts by mass, the residual film ratio, heat resistance, sensitivity and the like are appropriate.

A black pigment may be used as the blackening agent (E). Examples of the black pigment include carbon black, carbon nanotube, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigment, and lactam pigment. Those having a surface treatment applied to these black pigments can also be used. Examples of commercially available perylene-based pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, 34, etc. manufactured by BASF. Examples of commercially available lactam pigments include Irgaphor® Black S0100CF manufactured by BASF. Since it has a high light-shielding property, the black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene-based pigments, and lactam-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 does not easily inhibit the 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 10 parts by mass, based on a total of 100 parts by mass of the resin components. It is 15 to 100 parts by mass, 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 total of 100 parts by mass, sufficient light-shielding property can be obtained. When the content of the black pigment is 150 parts by mass or less based on the total of 100 parts by mass, the residual film ratio, sensitivity and the like are appropriate.

When the black agent (E) contains both a black dye and a black pigment, the total amount of the black dye and the black pigment in the photosensitive resin composition is preferably 10 to 150 based on a total of 100 parts by mass of the resin components. It is by mass, more preferably 15 to 100 parts by mass, and even 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 the total 100 parts by mass, sufficient light-shielding property can be obtained. If the total amount of the black dye and the black pigment is 150 parts by mass or less based on the total 100 parts by mass, the residual film ratio, sensitivity and the like are appropriate.

[Arbitrary ingredient]
The photosensitive resin composition contains, 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 blackening agent (E), and the like. Can include. In the present disclosure, the optional component is defined as not applicable to any of (A) to (E).

[Dissolution accelerator (F)]
The photosensitive resin composition may contain a dissolution accelerator (F), for example, in order to improve the solubility of the alkali-soluble portion during development. As the dissolution accelerator (F), a small molecule compound having an alkali-soluble functional group is used. Of these, a compound having at least one group selected from a carboxy group and a phenolic hydroxyl group is preferable.

For example, low molecular weight compounds having a carboxy group include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and capric acid; oxalic acid and malon. Acids, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc. Aliphatic dicarboxylic acids; aliphatic tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemmellitic acid, and mesitylic acid; phthalic acid, isophthalic acid, Aromatic polycarboxylic acids such as terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid and gallic acid; phenylacetic acid, hydroatropic acid, hydrocay Examples thereof include other carboxylic acids such as dermal acid, mandelic acid, phenylsuccinic acid, atropic acid, silicic acid, methyl silicate, benzyl silicate, cinnamyldenacetic acid, kumalic acid and umbellic acid.

Low-molecular-weight compounds having a phenolic hydroxyl group include catechol, resorcinol, hydroquinone, propyl gallate, dihydroxynaphthalene, leukokinizarin, 1,2,4-benzenetriol, anthracentriol, pyrogallol, fluoroglucinol, tetrahydroxybenzophenone, and phenolphthal. Rain, phenolphthalin, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4 -Isopropylbenzene and the like can be mentioned.

The content of the dissolution accelerator (F) can be 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, and more preferably 3 to 3 parts by mass, based on 100 parts by mass of the total resin components. It is 12 parts by mass. If the content of the dissolution accelerator (F) is 0.1 part by mass or more based on the total of 100 parts by mass, the dissolution of the resin component can be effectively promoted, and if it is 20 parts by mass or less. It is possible to suppress excessive dissolution of the resin component and improve the pattern formability and surface quality of the coating film.

[Basic compound (G)]
The photosensitive resin composition can contain a basic compound (G) in order to ensure the long-term reliability of the organic EL device. The basic compound (G) acts as a quencher of an acidic component or moiety such as a carboxylic acid or a phenolic hydroxyl group contained in the photosensitive resin composition, or an acidic gas generated from a photoacid generator. When the coating film is used as an organic EL element, the use of the basic compound (G) can prevent a decrease in emission luminance, pixel shrinkage, generation of dark spots, and the like.

Examples of the basic compound (G) include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, 3- (2-ethylhexyloxy) propylamine, and di-n-. Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, triethylamine, 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, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, ethylenediamine, N , N, N', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'- Diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxy) Phenyl) 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 (dimethyl) Aminoethylacrylamide), formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, urea, methylurea, 1 , 1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea, imidazole, benzimidazole, 4-methyl Imidazole, 4-methyl-2-phenylimidazole, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenyl Pyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinolin, aclysine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholin, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] -5-nonen, 1,8-diazabicyclo [5.4.0] -7-undecene, and 2 , 4,6-Tris [bis (methoxymethyl) amino] -1,3,5-triazine.

The content of the basic compound (G) is preferably 4 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 3 parts by mass, based on 100 parts by mass of the total solid content excluding the basic compound (G). It is 2 parts by mass or less.

[Solvent (H)]
The photosensitive resin composition can be used in a solution state (however, when a black pigment is contained, the pigment is in a dispersed state) by dissolving it in a solvent. For example, a radiation-sensitive compound (D) and a blackening agent (E) are added to a solution obtained by dissolving the first resin (A), the second resin (B), and the third resin (C) in a solvent (H). , If necessary, prepare a photosensitive resin composition in a solution state by mixing arbitrary components such as a dissolution accelerator (F), a basic compound (G), a thermosetting agent, and a surfactant in a predetermined ratio. can do. The photosensitive resin composition can be adjusted to a viscosity suitable for the coating method used by changing the amount of the solvent.

Examples of the solvent (H) include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol. Diethylene glycol compounds such as monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol monoalkyl ether acetate compounds such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and cyclohexanone; ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropion Methyl acid, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Esters such as methyl acid, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, diethyl carbonate, etc .; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N -Amid compounds such as dimethylacetamide can be mentioned. The solvent (H) may be used alone or in combination of two or more.

[Thermosetting agent]
As the thermosetting agent, a thermal radical generator can be used. Preferred thermal radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl. Organic peroxides with a 10-hour half-life temperature of 100 to 170 ° C, such as cumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, etc. Can be mentioned.

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

[Surfactant]
The photosensitive resin composition may contain a surfactant, for example, in order to improve the coatability, the smoothness of the coating film, or the developability of the coating film. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and poly such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether. Oxyethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Megafuck® F-251, F-281, F 430, F-444, R-40, F-553, F-554, F-555, F-556, F-557, F-558, F-559 (above, Product name, manufactured by DIC Co., Ltd., Surfron (registered trademark) S-242, S-243, S-386, S-420, S-611 (above, product name, manufactured by AGC Seimi Chemical Co., Ltd.) Fluorobased surfactants such as; organosiloxane polymers KP323, KP326, KP341 (above, trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned. These may be used alone, or two or more kinds may be used.

The content of the surfactant is preferably 2 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 part by mass or less, based on 100 parts by mass of the total solid content excluding the surfactant. Is.

[Second colorant]
The photosensitive resin composition can contain a second colorant other than the blackening agent (E). Examples of the second colorant include dyes, organic pigments, inorganic pigments and the like, which can be used according to the purpose. The second colorant can be used in a content that does not impair the effects of the present invention.

Examples of dyes include azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilben dyes, diphenylmethane dyes, and triphenylmethane dyes. Examples thereof include dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, flugide dyes, nickel complex dyes, and azulene dyes.

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

[Manufacturing method of photosensitive resin composition]
The photosensitive resin composition includes a first resin (A), a second resin (B), a third resin (C), a radiation-sensitive compound (D), a blackening agent (E), and a dissolution accelerator (if necessary). It can be prepared by dissolving or dispersing the above optional components such as F) and the basic compound (G) in the solvent (H) and mixing them. 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 1 to 60% by mass, 3 to 50% by mass, or 5 to 40% by mass.

A known method can be used as the dispersion mixing method when a pigment is used. For example, ball type such as ball mill, sand mill, bead mill, paint shaker, rocking mill, blade type such as kneader, paddle mixer, planetary mixer, henschel mixer, roll type such as 3-roll mixer, etc. An ultrasonic wave, a homogenizer, a rotation / revolution mixer, or the like may be used. It is preferable to use a bead mill from the viewpoint of dispersion efficiency and fine dispersion.

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

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

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

After applying the coating composition to the surface of the substrate, the solvent is usually removed by heating to form a film (pre-bake). The heating conditions vary depending on the type of each component, the mixing ratio, etc., but a film is usually obtained by heat-treating at 70 to 130 ° C., for example, for 30 seconds to 20 minutes on a hot plate and 1 to 60 minutes in an oven. be able to. In one embodiment, the thickness of the formed coating is 2-3 μm.

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

After the exposure process, the film is developed by contacting it with a developing solution, unnecessary parts are removed, and a pattern is formed on the film (development process). Examples of the developing solution include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di-. Secondary amines such as n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alkaline amines such as dimethylethanolamine and triethanolamine; Fourth such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline Secondary ammonium salts; of alkaline compounds such as pyrrol, piperidine, cyclic amines such as 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane. An aqueous solution can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like to an alkaline aqueous solution can also be used as a developer. The development time is usually 30 to 180 seconds. The developing method may be any of a liquid filling method, a shower method, a dipping method and the like. After development, a pattern can be formed on the film by washing with running water for 30 to 90 seconds, removing unnecessary portions, and air-drying with compressed air or compressed nitrogen.

Then, a cured film can be obtained by heat-treating the patterned film with a heating device such as a hot plate or an oven at 100 to 350 ° C. for 20 to 200 minutes (post-baking, heat treatment). Process). In the heat treatment, the temperature may be kept constant, the temperature may be continuously increased, or the temperature may be increased stepwise.

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

[Manufacturing method of organic EL element partition wall or organic EL element insulating film]
One embodiment is to prepare a coating composition by dissolving or dispersing a photosensitive resin composition in a solvent, applying the coating composition to a substrate to form a film, and removing the solvent contained in the film. To dry the film, to expose the film by irradiating the dried film through a photomask, to develop the exposed film by contacting it with a developing solution, and to form a pattern on the film. A method for producing an organic EL element partition wall or an organic EL element insulating film, which comprises heat-treating a film on which a pattern is formed at a temperature of 100 ° C. to 350 ° C. to form an organic EL element partition wall or an organic EL element insulating film. Is.

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

[Organic EL element insulating film]
One embodiment is an organic EL device insulating film containing a cured product of a photosensitive resin composition.

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

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

(1) Physical property evaluation The physical property evaluation of the resin or the photosensitive resin composition was carried out by the following procedure.

[Alkaline dissolution rate]
In a 20% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of the resin or photosensitive resin composition, Megafuck (registered trademark) F-559 (fluorine-based surfactant, manufactured by DIC Co., Ltd.) as a leveling agent is added to the resin solid content. It was added in an amount of 0.1 parts by mass per 100 parts by mass. The obtained mixture was applied to a glass substrate (70 mm × 70 mm × 0.7 mm) so as to have a dry film thickness of 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, alkaline development was carried out with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution. The development time was adjusted in the range of 8 to 400 seconds so that the film did not completely melt. The reduction amount (nm) of the film after development was divided by the development time (seconds) to obtain the alkali dissolution rate (nm / sec).

[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, polystyrene is standard under the following measurement conditions. It was calculated using a calibration line prepared using the substance.
Device name: Shodex® GPC-101
Column: Leftox® LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: Chromatography (registered trademark) RI-71
Temperature: 40 ° C

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

[Production Example 1] First resin (A): Production of resin (N770OH70) having an epoxy group and a phenolic hydroxyl group 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as a solvent in a 300 mL three-necked flask. 37.6 g of EPICLON (registered trademark) N-770 (phenol novolak type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 188) was charged as a compound having at least two epoxy groups in one molecule, and the temperature was 60 ° C. under a nitrogen gas atmosphere. Dissolved in. There, 20.1 g (0.65 equivalent to 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound, and triphenylphosphine (Tokyo Kasei) as a reaction catalyst. (Manufactured by Kogyo Co., Ltd.) was added in an amount of 0.173 g (0.660 mmol), and the mixture 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 having an epoxy group and a phenolic hydroxyl group (N770OH70). The obtained reactants had a number average molecular weight of 2400, a weight average molecular weight of 5400, an epoxy equivalent of 2000, and a phenolic hydroxyl weight equivalent of 142.

[Production Example 2] First resin (A): Production of resin (N695OH70) having an epoxy group and a phenolic hydroxyl group 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as a solvent in a 300 mL three-necked flask. 37.8 g of EPICLON (registered trademark) N-695 (cresol novolac type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 214) was charged as a compound having at least two epoxy groups in one molecule, and the temperature was 60 ° C. under a nitrogen gas atmosphere. Dissolved in. There, 20.1 g (0.65 equivalent to 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound, and triphenylphosphine (Tokyo Kasei) as a reaction catalyst. (Manufactured by Kogyo Co., Ltd.) was added in an amount of 0.166 g (0.660 mmol), and the mixture was 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 having an epoxy group and a phenolic hydroxyl group (N695OH70). The obtained reactants had a number average molecular weight of 3000, a weight average molecular weight of 5100, an epoxy equivalent of 2200, and a phenolic hydroxyl weight equivalent of 161.

[Production Example 3] Second Resin (B): Production of Second Resin (B-TBMA 42.5%) Having a Phenolic Hydroxyl Group 4-Hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 17.3 g, N -Cycloxyl maleimide (manufactured by Nippon Catalyst Co., Ltd.) 6.15 g and tert-butyl methacrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester TB") 13.8 g, and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent. ) 2.69 g of 2,2'-azobis (isobutyric acid) dimethyl ("V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator in 56.0 g, and isopropyl acetate (Shinko Organic Chemical Industry Co., Ltd.) It was completely dissolved in 4.05 g (manufactured by the company). The two obtained solutions were simultaneously added dropwise to 100 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. The reaction was carried out under reflux at 89 ° C. for 4 hours. The reaction solution cooled to room temperature was added dropwise to a mixture of 1000 g of hexane and toluene at 80:20 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-TBMA 42.5% having a phenolic hydroxyl group 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-PhMA 41%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 17.0 g, N-cyclohexyl Maleimide (manufactured by Nippon Catalyst Co., Ltd.) 5.83 g and phenylmethacrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH") 14.4 g, and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 60.0 g as a solvent. In addition, 2.72 g of 2,2'-azobis (isobutyric acid) dimethyl (“V-601” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 4 as a polymerization initiator. Each was completely dissolved in 08 g. The two obtained solutions were simultaneously added dropwise to 95.9 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. Then, the reaction was carried out under reflux at 89 ° C. for 4 hours. The reaction solution cooled to room temperature was added dropwise to 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-PhMA 41% having a phenolic hydroxyl group 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-PhMA 20%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 24.6 g, N-cyclohexyl Maleimide (manufactured by Nippon Catalyst Co., Ltd.) 5.71 g and phenylmethacrylate (manufactured by Mitsubishi Chemical Co., Ltd. "Acryester PH") 6.89 g, and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 55.8 g as a solvent. 2.83 g of 2,2'-azobis (isobutyric acid) dimethyl (“V-601” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) 4 as a polymerization initiator. Each was completely dissolved in .23 g. The two obtained solutions were simultaneously added dropwise to 100 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. The reaction was carried out under reflux at 89 ° C. for 4 hours. The reaction solution cooled to room temperature was added dropwise to 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 a phenolic hydroxyl group 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 6] Third resin (C): Production of a copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer 4-hydroxyphenylmethacrylate (Showa Denko Co., Ltd.) Polymerization of 25.5 g of "PQMA" manufactured by the company) and 4.50 g of N-cyclohexylmaleimide (manufactured by Nippon Catalyst Co., Ltd.) into 77.1 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) as a solvent. As an initiator, 3.66 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.). The two obtained solutions were simultaneously placed in 61.2 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) heated to 85 ° C. in a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. The mixture was added dropwise, and then the reaction was carried out at 85 ° C. for 3 hours. The reaction solution cooled to room temperature was added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum dried at 90 ° C. for 4 hours to recover 32.4 g of white powder. The obtained polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer copolymer PCX-02e had a number average molecular weight of 3100, a weight average molecular weight of 6700, and a phenolic hydroxyl group equivalent of 210. ..

[Production Example 7] Production of a copolymer of glycidyl methacrylate and methacrylic acid (GMA-MAA) 99.5 g (0.7 mol) of glycidyl methacrylate (GMA) and 8.6 g (0.1 mol) of methacrylic acid (MAA). ) Was completely dissolved in 72.1 g of propylene glycol monomethyl ether (PGME), and 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. The two obtained solutions were simultaneously added dropwise to 172.6 g of PGME heated to 80 ° C. under a nitrogen gas atmosphere in a 500 mL three-necked flask over 2 hours, and then stirred for 2 hours to react. In this way, a copolymer of glycidyl methacrylate and methacrylic acid (GMA-MAA) having a molar ratio of glycidyl methacrylate and methacrylic acid of 7: 1 was obtained in the form of a PGME solution having a solid content of 30% by mass. Since the obtained GMA-MAA has a carboxy group and an epoxy group in the molecule, it has high self-reactivity, that is, ring-opening polymerization of the epoxy group easily proceeds. Therefore, when reprecipitation and vacuum drying are performed, the molecular weight is high. It became epoxide and could not be isolated. The PGME solution of GMA-MAA had low stability, and the viscosity of the solution increased as the molecular weight increased over time.

[Production Example 8] Second resin (B): Production of second resin (B-CHMA 20%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 24.5 g, N-cyclohexyl 7.11 g of maleimide (manufactured by Nippon Catalyst Co., Ltd.) and 5.68 g of cyclohexyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) were added to 69.3 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent, as a polymerization initiator. 2.72 g of 2,2'-azobis (isobutyric acid) dimethyl ("V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 10.87 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) are completely added. Dissolved in. The two obtained solutions were simultaneously added dropwise to 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. The reaction was carried out under reflux at 89 ° C. for 4 hours. The reaction solution cooled to room temperature was added dropwise to 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 a phenolic hydroxyl group had a number average molecular weight of 3500, a weight average molecular weight of 7200, and a phenolic hydroxyl group equivalent of 271.

[Production Example 9] Second resin (B): Production of second resin (B-CHMA 40%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 17.14 g, N-cyclohexyl 14.39 g of maleimide (manufactured by Nippon Catalyst Co., Ltd.) and 5.75 g of cyclohexyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) are added to 69.3 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent, as a polymerization initiator. 2.72 g of 2,2'-azobis (isobutyric acid) dimethyl ("V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 10.87 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) are completely added. Dissolved in. The two obtained solutions were simultaneously added dropwise to 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. The reaction was carried out under reflux at 89 ° C. for 4 hours. The reaction solution cooled to room temperature was added dropwise to 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 a phenolic hydroxyl group 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 10] Second resin (B): Production of second resin (B-BOM 32%) having a phenolic hydroxyl group 4-Hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko KK) 17.3 g, N, N -Diisopropylethylamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 29.0 g, tetrahydrofuran (dehydrated) (manufactured by Kanto Chemical Co., Ltd.) 160 g in a 500 mL three-necked flask until the solid is completely dissolved in a nitrogen gas atmosphere. Stirred. The solution was cooled to 0 ° C., and 26.4 g of benzyl chloromethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the solution. After completion of the dropping, the mixture was heated to 70 ° C. and reacted for 5 hours. After the reaction solution was brought to room temperature, unnecessary substances were removed by filtration, 200 mL of ethyl acetate (special grade manufactured by Junsei 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 twice with 200 mL of pure water. After drying over sodium sulfate, the solvent was completely distilled off. 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.

4-Hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 12.1 g, N-cyclohexyl maleimide (manufactured by Nippon Catalyst Co., Ltd.) 3.45 g, and PQMA-BOM 12.3 g are used as solvents for isopropyl acetate (Shinko). To 41.8 g of Organic Chemical Industry Co., Ltd.), 2.14 g of 2,2'-azobis (isobutyric acid) dimethyl ("V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator is added to isopropyl acetate (. It was completely dissolved in 8.54 g (manufactured by Shinko Organic Chemical Industry Co., Ltd.). The two obtained solutions were simultaneously added dropwise to 69.7 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. Then, the reaction was carried out under reflux at 89 ° C. for 4 hours. The reaction solution cooled to room temperature was added dropwise to 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-BOM having a phenolic hydroxyl group had a number average molecular weight of 3600, a weight average molecular weight of 6900, and a phenolic hydroxyl group equivalent of 431.

[Production Example 11] Second resin (B): Production of second resin (B-IBMA 20%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 23.1 g, N-cyclohexyl Polymerization of 8.86 g of maleimide (manufactured by Nippon Catalyst Co., Ltd.) and 5.35 g of isobornyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) with 69.2 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent. As an initiator, 2.72 g of 2,2'-azobis (isobutyric acid) dimethyl ("V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to 10.83 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.). Each was completely dissolved. The two obtained solutions were simultaneously added dropwise to 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. The reaction was carried out under reflux at 89 ° C. for 4 hours. The reaction solution cooled to room temperature was added dropwise to 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 a phenolic hydroxyl group 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 12] Second resin (B): Production of second resin (B-TCDMA 20%) having a phenolic hydroxyl group 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) 23.1 g, N-cyclohexyl 8.79 g of maleimide (manufactured by Nippon Catalyst Co., Ltd.) and 5.37 g of dicyclopentanyl methacrylate (manufactured by Tokyo Kasei Co., Ltd.) were added to 69.2 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent. 2.72 g of 2,2'-azobis (isobutyric acid) dimethyl ("V-601" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 10.83 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a polymerization initiator. Each was completely dissolved. The two obtained solutions were simultaneously added dropwise to 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89 ° C. under a nitrogen gas atmosphere in a 300 mL three-necked flask over 2 hours. The reaction was carried out under reflux at 89 ° C. for 4 hours. The reaction solution cooled to room temperature was added dropwise to 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 a phenolic hydroxyl group had a number average molecular weight of 3800, a weight average molecular weight of 8000, and a phenolic hydroxyl group equivalent of 287.

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

[Second resin (B)]
As the second resin (B), B-TBMA 42.5% of Production Example 3, B-PhMA 41% of Production Example 4, B-PhMA 20% of Production Example 5, B-CHMA 20% of Production Example 8, and Production Example 9 B-CHMA 40%, B-BOM 32% of Production Example 10, B-IBMA 20% of Production Example 11, and B-TCDMA 20% of Production Example 12 were used.

[Third resin (C)]
As the third resin (C), PCX-02e of Production Example 6 was used.

[Other resins]
Other resins include Shonor (registered trademark) BRG-558 (Phenolic novolak resin manufactured by Aika Kogyo Co., Ltd., phenolic hydroxyl group equivalent 107), EPICLON (registered trademark) N-770 (Phenolic novolak type epoxy resin manufactured by DIC Co., Ltd.). Epoxy equivalent 188) and GMA-MAA of Production Example 7 were used.

Table 1 shows the structural unit ratio of the resin, the phenolic hydroxyl group equivalent, the alkali dissolution rate, and the weight average molecular weight (Mw). In Table 1, PQMA represents a structural unit derived from 4-hydroxyphenylmethacrylate, 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] ethylidene] bisphenol (TrisP-), which is a quinonediazide compound, is used. PA) and an ester of 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinonediazide-5-sulfonic acid), manufactured by Toyo Synthetic Industry Co., Ltd.) were used. The structure of TS-150A is shown below.

[Black agent (E)]
As the blackening agent, VALIFAST (registered trademark) BLACK 3820 (black dye specified by CI of Solvent Black 27, manufactured by Orient Chemical Industry Co., Ltd.), which is a black dye, was used.

[Dissolution accelerator (F)]
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), 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)) was used. The values of the mass ratios of GBL and PGME include those used in Production Examples 1, 2 or 7.

(3) Evaluation method The evaluation methods used in the examples and comparative examples are as follows.

[Solubility]
<Exposure part solubility>
The photosensitive resin composition was bar-coated on a glass substrate (size 100 mm × 100 mm × 1 mm) so that the dry film thickness was 2.7 μm, and heated on a hot plate at 120 ° C. for 120 seconds to dry the solvent (pre-bake). .. After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, manufactured by Filmometrics Co., Ltd.), an exposure device incorporating an ultra-high pressure mercury lamp (trade name: Multilight ML-251A / B, Ushio Denki Co., Ltd.) Band pass filter for mercury exposure (trade name HB0365, manufactured by Asahi Spectrometry Co., Ltd.) and photomask made of quartz (5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, 500 μm line & space (L / S)) It was exposed at 100 mJ / cm ² through the one having a pattern). The exposure amount was measured using an ultraviolet integrated photometer (trade name UIT-150 light receiving unit UVD-S365, manufactured by Ushio, Inc.). Then, using a spin developer (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), alkaline development was performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution in the range of 20 seconds to 200 seconds until the film on the exposed portion disappeared. rice field. Therefore, in Table 2, the solubility of the exposed part is expressed as 2.70 μm (more than 2.70 μm because the pattern was peeled off only in Comparative Example 2) together with the development time.

<Solubility in unexposed area>
The photosensitive resin composition was bar-coated on a glass substrate (size 100 mm × 100 mm × 1 mm) so that the dry film thickness was 2.7 μm, and heated on a hot plate at 120 ° C. for 120 seconds to dry the solvent (pre-bake). .. After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, manufactured by Filmometrics Co., Ltd.), 2.38% by mass hydroxylation using a spin developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). Alkaline development was carried out with an aqueous solution of tetramethylammonium for the same development time as the solubility in the exposed part. The film thickness after alkaline development was measured again using an optical film thickness measuring device (F20-NIR, manufactured by Filmometrics Co., Ltd.), and the film thickness (μm) dissolved before and after development was calculated as the unexposed portion solubility. ..

<Difference in solubility>
The difference in solubility (μm) was obtained by subtracting the solubility (μm) in the unexposed portion from the solubility (μm) in the exposed portion. The larger the solubility difference, the higher the sensitivity and the better the pattern forming property.

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

[Pattern formation]
The photosensitive resin composition was bar-coated on a glass substrate (size 100 mm × 100 mm × 1 mm) so that the dry film thickness was 2.7 μm, and heated on a hot plate at 120 ° C. for 120 seconds to dry the solvent (pre-bake). .. An exposure device (trade name: Multilight ML-251A / B, manufactured by Ushio, Inc.) incorporating an ultra-high pressure mercury lamp, a band pass filter for mercury exposure (trade name: HB0365, manufactured by Asahi Spectral Co., Ltd.) and a quartz photomask. Exposure was performed at 100 mJ / cm ² or less via (having a φ10 μm pattern). The exposure amount was measured using an ultraviolet integrated photometer (trade name UIT-150 light receiving unit UVD-S365, manufactured by Ushio, Inc.). After the exposure, alkali development was carried out for 60 seconds with a 2.38 mass% tetramethylammonium hydroxide aqueous solution using a spin developer (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). Further, the coating film was heated at 250 ° C. for 60 minutes in an inert oven (DN411I, manufactured by Yamato Kagaku Co., Ltd.) to cure. After curing, the film thickness of the film is measured using an optical film thickness measuring device (F20-NIR, manufactured by Filmometry Co., Ltd.), and the formed holes are observed with a microscope (VHX-6000, manufactured by KEYENCE Co., Ltd.). did. A film thickness of 3.0 μm or more and a hole diameter of 10 μm or more was judged to be good, and a film thickness of 2.9 μm or less or a hole diameter of 9 μm or less was judged to be defective.

[Rough surface]
Visual observation was performed with a microscope, and it was judged to be defective when unevenness of about 0.5 μm was observed on the entire surface of the coating film, and good when no unevenness was observed on the entire surface of the coating film.

(4) Preparation and Evaluation of Photosensitive Resin Compositions [Examples 1 to 9, Comparative Examples 1 to 4]
A radiation-sensitive compound (D), a blackening agent (E), a dissolution accelerator (F), and a basic compound shown in Table 2 are added to a solution obtained by mixing and dissolving a resin component having the composition shown in Table 2. (G) and the solvent (H) were added and further mixed. After visually confirming that the components were dissolved, the mixture was filtered through a millipore filter having a pore size of 0.22 μm to prepare a photosensitive resin composition having a solid content concentration of about 12% by mass. The mass part of the composition in Table 2 is a solid content conversion value. Table 2 also shows the alkali dissolution rate of the photosensitive resin composition. Table 2 shows the evaluation results of the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4. In Comparative Example 3, pattern peeling occurred during development, and accurate solubility could not be measured. Therefore, the numerical values related to solubility in Table 2 are shown in parentheses. Comparative Example 4 could not be evaluated because the stability of the PGME solution of GMA-MAA was low.

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

Claims

(A) First resin,
(B) A second resin having a phenolic hydroxyl group, which is different from the first resin,
(C) A third resin having a phenolic hydroxyl group, which is different from both the first resin and the second resin.
A photosensitive resin composition containing (D) a radiation-sensitive compound and (E) a blackening agent, wherein the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 μm of the film thickness. A photosensitive resin composition, wherein the phenolic hydroxyl group equivalent of the second resin is 1.1 to 5.0 times the phenolic hydroxyl group equivalent of the third resin.
The second resin contains the same structural unit as at least one of the structural units of the third resin and other structural units, and contains a total of 30 mol% to 95 mol% of structural units common to the third resin. The photosensitive resin composition according to claim 1, wherein the alkali dissolution rate of the second resin is smaller than the alkali dissolution rate of the third resin.
The photosensitive resin composition according to claim 1 or 2, 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 any one of claims 1 to 3, wherein the third resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. ..
The second resin is the formula (17).

(In the formula (17), R 38 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 39 is a linear alkyl group having 1 to 20 carbon atoms and a branched alkyl group having 3 to 20 carbon atoms. , A cyclic alkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, a linear alkyl group having 1 to 20 carbon atoms substituted with a group other than the acidic functional group, and a group other than the acidic functional group. A branched alkyl group having 3 to 20 carbon atoms substituted with, a cyclic alkyl group having 3 to 12 carbon atoms substituted with a group other than the acidic functional group, and a carbon atom substituted with a group other than the acidic functional group. It is a group selected from the group consisting of 6 to 20 aryl groups.)
The photosensitive resin composition according to any one of claims 1 to 4, which has a structural unit represented by.
The second resin is the formula (10).

(In the formula (10), R15 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e is an integer of 1 to 5).
The photosensitive resin composition according to any one of claims 1 to 5, which has a structural unit represented by.
The second resin is the formula (11).

(In the formula (11), R 16 and R 17 are independently hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a completely or partially fluorinated fluoroalkyl group having 1 to 3 carbon atoms, respectively. , Or a halogen atom, where R18 is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a hydroxy group, and 1 to 6 carbon atoms. It is a phenyl group substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group having 1 to 6 carbon atoms.)
The photosensitive resin composition according to any one of claims 1 to 6, which has a structural unit represented by.
The photosensitive resin composition according to any one of claims 1 to 7, wherein the first resin is a resin having an epoxy group and a phenolic hydroxyl group.
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 has the formula (9).

(In the formula (9), d is an integer of 1 to 5, and * represents the bond portion of the compound having at least two epoxy groups in one molecule to the residue excluding the epoxy group involved in the reaction. .)
The photosensitive resin composition according to any one of claims 1 to 8, which is a compound having the above-mentioned structure.
The photosensitive resin composition according to claim 9, wherein the compound having at least two epoxy groups in the one molecule is a novolak type epoxy resin.
The photosensitive resin composition according to any one of claims 1 to 10, wherein the blackening agent is a dye defined by a color index (CI) of Solvent Black 27 to 47.
The photosensitive resin composition according to any one of claims 1 to 11, wherein the radiation-sensitive compound is a photoacid generator.
The photosensitive resin composition according to any one of claims 1 to 12, which contains 20% by mass to 90% by mass of the first resin based on the total mass of the resin components.
The photosensitive resin composition according to any one of claims 1 to 13, which contains 5% by mass to 50% by mass of the second resin based on the total mass of the resin components.
The photosensitive resin composition according to any one of claims 1 to 14, which contains 5% by mass to 50% by mass of the third resin based on the total mass of the resin components.
The photosensitive resin composition according to any one of claims 1 to 15, which contains 1 part by mass to 40 parts by mass of the radiation-sensitive compound based on a total of 100 parts by mass of the resin component.
The photosensitive resin composition according to any one of claims 1 to 16, which contains 10 parts by mass to 150 parts by mass of the blackening agent based on a total of 100 parts by mass of the resin components.
An organic EL device partition wall containing a cured product of the photosensitive resin composition according to any one of claims 1 to 17.
An organic EL device insulating film containing a cured product of the photosensitive resin composition according to any one of claims 1 to 17.
An organic EL device containing a cured product of the photosensitive resin composition according to any one of claims 1 to 17.