WO2021246448A1

WO2021246448A1 - Positive-type photosensitive resin composition and partition wall of organic electroluminescent element

Info

Publication number: WO2021246448A1
Application number: PCT/JP2021/021043
Authority: WO
Inventors: 良和新井; 拓樹倉本; 尚平西澤
Original assignee: 昭和電工株式会社
Priority date: 2020-06-03
Filing date: 2021-06-02
Publication date: 2021-12-09
Also published as: JPWO2021246449A1; WO2021246444A1; TWI775466B; TWI789776B; WO2021246449A1; TW202210946A; TWI810578B; TW202210938A; JPWO2021246448A1; TW202204436A; JPWO2021246444A1

Abstract

Provided is a high-sensitivity photosensitive resin composition that has improved process stability and contains black colorant. This positive photosensitive resin composition includes: a resin blend (A1) that includes a resin (a1-1) having a plurality of phenolic hydroxyl groups, at least some of the plurality of phenolic hydroxyl groups being protected by an acid-degradable group (1), and a resin (a1-2) having a plurality of phenolic hydroxyl groups, at least some of the of the plurality of phenolic hydroxyl groups being protected by an acid-degradable group (2) that differs from the acid-degradable group (1); at least one type of colorant (B) selected from the group consisting of black dyes and black pigments; and a photoacid generator (C).

Description

Positive type photosensitive resin composition and organic EL element partition wall

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

Japanese Unexamined Patent Publication No. 2001-281440 Japanese Unexamined Patent Publication No. 2002-116536 Japanese Unexamined Patent Publication No. 2010-237310

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 the formation of partition walls in organic EL devices, it is important that the material forming the partition walls has high sensitivity from the viewpoint of productivity and the like. However, when a black photosensitive resin composition containing a colorant is used, exposure defects occur under normally used exposure conditions, so that it is necessary to lengthen the exposure time, for example, which reduces productivity. It was a factor to make it. Therefore, it is strongly desired to reduce the exposure amount of the photosensitive resin composition, reduce the energy cost, and increase the throughput.

As a method for increasing the sensitivity of the photosensitive resin composition, it is possible to use the resin composition as a chemical amplification system. However, in general, the chemical amplification system has a problem that the sensitivity is high but the process stability is poor.

An object of the present invention is to provide a highly sensitive photosensitive resin composition containing a black colorant, which has improved process stability.

By using the positive photosensitive resin composition as a chemical amplification system containing a plurality of resins having different acid degradability, the present inventors have high sensitivity and high sensitivity despite containing a black colorant. , Found that it is possible to provide improved process stability.

That is, the present invention includes the following aspects.
[1]
The resin (a1-1) having a plurality of phenolic hydroxyl groups and at least a part of the plurality of phenolic hydroxyl groups being protected by an acid-degradable group (1) and the plurality of phenolic hydroxyl groups. It has a resin (a1-2) in which at least a part of the phenolic hydroxyl groups of the above is protected by an acid-degradable group (2) different from the acid-degradable group (1), and optionally, a plurality of phenolic hydroxyl groups. , A resin (a1-3) in which at least a part of the plurality of phenolic hydroxyl groups is protected with an acid-degradable group (3) different from the acid-degradable groups (1) and (2), and the acid. The degradable groups (1) to (3) are independently group I: tert-butoxycarbonyl group and 1,1-dimethyl-propoxycarbonyl group;
Group II: Group represented by the formula (1) -CR ¹ R ² R ³ (1)
(In the formula (1), R ¹ is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are independent of 1 to 10 carbon atoms. A saturated or unsaturated linear or branched hydrocarbon group of 10 or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or ^{both R 2} and R ³ are alicyclics having 3 to 20 ring members. Structure may be formed);
Group III: 2-tetrahydropyranyl group;
Group IV: 2-tetrahydrofuranyl group;
Group V: Group represented by the formula (2) -CHR ⁴ - ^{OR 5} (2)
(In the formula (2), R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁵ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms);
Resin blend (A1) selected from the group consisting of
At least one colorant (B) selected from the group consisting of black dyes and black pigments, and
A positive photosensitive resin composition containing a photoacid generator (C).
[2]
The positive photosensitive resin composition according to [1], wherein each of the acid-degradable groups (1) to (3) is selected from a different group from the groups I to IV, V-1 and V-2.
Group I: tert-butoxycarbonyl group and 1,1-dimethyl-propoxycarbonyl group;
Group II: A group represented by the above formula (1);
Group III: 2-tetrahydropyranyl group;
Group IV: 2-tetrahydrofuranyl group;
Group V-1: Group represented by the formula (2-1) -CHR ⁴ - ^{OR 5} (2-1)
(In the formula (2-1), R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁵ is a linear or branched alkyl group having 1 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms);
Group V-2: 1-cyclohexyloxyethyl group [3]
The resin (a1-1) has the formula (3).

(In the formula (3), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is the acid-degradable group (1), l is an integer of 0 to 5, and m is an integer of 0 to 5. Yes, but l + m is an integer from 1 to 5))
The resin (a1-1) has at least one of the monomer units in which m is an integer of 1 or more.
The resin (a1-2) has the formula (4).

(In the formula (4), R ⁸ is a hydrogen atom or a methyl group, R ⁹ is the acid-degradable group (2), n is an integer of 0 to 5, and o is an integer of 0 to 5. Yes, where n + o has a monomeric unit represented by an integer of 1 to 5), and the resin (a1-2) has at least the monomeric unit in which o is an integer of 1 or more. Have one
The resin (a1-3) is the formula (5).

(In the formula (5), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is the acid-degradable group (3), p is an integer of 0 to 5, and q is an integer of 0 to 5. However, p + q has a monomer unit represented by an integer of 1 to 5), and the resin (a1-3) has at least the monomer unit in which q is an integer of 1 or more. The positive photosensitive resin composition according to any one of [1] and [2], which has one.
[4]
The resin (a1-1) contains 60 mol% to 100 mol% of the monomer unit represented by the formula (3) with respect to all the monomer units thereof, and the resin (a1-2) contains 60 mol% to 100 mol% of the monomer unit. The monomer unit represented by the formula (4) is contained in an amount of 60 mol% to 100 mol% with respect to all the monomer units, and the resin (a1-3) is based on the total monomer units. The positive photosensitive resin composition according to [3], which contains 60 mol% to 100 mol% of the monomer unit represented by the formula (5).
[5]
The positive photosensitive resin composition according to any one of [1] to [4], wherein the acid-degradable group (1) is a 2-tetrahydrofuranyl group.
[6]
The positive photosensitive resin composition according to [5], wherein the acid-degradable group (2) is selected from the group V-1 or V-2.
[7]
The positive photosensitive resin composition according to [6], wherein the acid-degradable group (3) comprises the resin (a1-3) selected from the group I, II, or III.
[8]
5 mol% to 95 mol% of the phenolic hydroxyl group of the resin (a1-1) is protected by the acid-degradable group (1), and 5 mol% to 5 mol% of the phenolic hydroxyl group of the resin (a1-2). 95 mol% is protected by the acid-degradable group (2), and 5 mol% to 95 mol% of the phenolic hydroxyl group of the resin (a1-3) is protected by the acid-degradable group (3). The positive photosensitive resin composition according to any one of [1] to [7].
[9]
The mass ratio of the resin (a1-2) to the resin (a1-1) (mass of resin (a1-2) / mass of resin (a1-1)) is 5/95 to 50/33. 1] The positive photosensitive resin composition according to any one of [8].
[10]
The resins (a1-1), (a1-2) and (a1-3) are represented by the formula (12).

(In the formula (12), R ²¹ and R ²² are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and fully or partially fluorinated alkyl groups having 1 to 3 carbon atoms, respectively. Alternatively, it is a halogen atom, and R ²³ is a hydrogen atom, a linear group having 1 to 6 carbon atoms, a cyclic alkyl group having 4 to 12 carbon atoms, a phenyl group, or a hydroxy group, and an alkyl group having 1 to 6 carbon atoms. And a phenyl group substituted with at least one selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms.)
The positive photosensitive resin composition according to any one of [1] to [9], which is a copolymer having a monomer unit represented by.
[11]
The photoacid generator (C) has the formula (13).

(In formula (13), R ²⁴ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, and R ²⁵ and R ²⁶ are independent of each other. It is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, an acetoxy group, a carboxy group, or an alkoxycarbonyl group, and R ²⁵ and R ²⁶ are bonded to each other to have 3 to 10 ring members. The ring structure may be formed, and the ring structure may have a substituent.)
The positive photosensitive resin composition according to any one of [1] to [10], which is a compound represented by.
[12]
The positive photosensitive resin composition according to any one of [1] to [11], which comprises the resin blend (A1) in an amount of 30% by mass to 90% by mass based on the total mass of the resin components.
[13]
The positive photosensitive resin composition according to any one of [1] to [12], which contains the colorant (B) in an amount of 10 parts by mass to 150 parts by mass based on a total of 100 parts by mass of the resin components.
[14]
The positive photosensitive resin according to any one of [1] to [13], which contains 0.1 part by mass to 85 parts by mass of the photoacid generator (C) based on a total of 100 parts by mass of the resin components. Composition.
[15]
The positive photosensitive resin composition according to any one of [1] to [14], wherein the optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of the film thickness. ..
[16]
The positive photosensitive resin composition according to any one of [1] to [15], further comprising a resin (D) having an epoxy group and a phenolic hydroxyl group.
[17]
An organic EL device partition wall containing a cured product of the positive photosensitive resin composition according to any one of [1] to [16].
[18]
An organic EL device insulating film containing a cured product of the positive photosensitive resin composition according to any one of [1] to [16].
[19]
An organic EL device containing a cured product of the positive photosensitive resin composition according to any one of [1] to [16].

According to the present invention, it is possible to provide a highly sensitive photosensitive resin composition containing a black colorant, which has improved process stability.

The present invention will be described in detail below.

In the present disclosure, "alkali-soluble" and "alkali aqueous solution-soluble" mean that the positive photosensitive resin composition or its components, or the film or cured film of the positive photosensitive resin composition is an alkaline aqueous solution, for example, 2.38 mass. It means that it can be dissolved in a% aqueous solution of tetramethylammonium hydroxide. The "alkali-soluble functional group" means a group that imparts such alkali solubility to a positive photosensitive resin composition or a component thereof, or a film or a cured film of a positive 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 "acid-degradable group" means a group that decomposes (deprotects) to generate an alkali-soluble functional group by heating as necessary in the presence of an acid.

In the present disclosure, the "radical polymerizable functional group" refers to one or more ethylenically unsaturated groups.

In the present disclosure, the "monomer unit" means a unit derived from a radically polymerizable monomer.

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 "resin component" means a resin blend (A1), a resin (D) having an epoxy group and a phenolic hydroxyl group, and a third resin (E).

The positive photosensitive resin composition of one embodiment has a plurality of phenolic hydroxyl groups, and at least a part of the plurality of phenolic hydroxyl groups is protected by an acid-degradable group (1) (a1-1). A resin (a1-2) having a plurality of phenolic hydroxyl groups and having at least a part of the plurality of phenolic hydroxyl groups protected by an acid-degradable group (2) different from the acid-degradable group (1). It contains a resin blend (A1) containing the above, at least one colorant (B) selected from the group consisting of black dyes and black pigments, and a photoacid generator (C).

[Resin blend (A1)]
The resin blend (A1) has a plurality of phenolic hydroxyl groups, and at least a part of the plurality of phenolic hydroxyl groups is protected by different acid-degradable groups selected from specific acid-degradable groups, or two or more thereof. Contains resin. The resin blend (A1) contains two resins having a plurality of phenolic hydroxyl groups and at least a portion of the plurality of phenolic hydroxyl groups protected by different acid-degradable groups selected from specific acid-degradable groups. In this case, for convenience, the respective resins are referred to as resins (a1-1) and (a1-2), and when three types are contained, they are referred to as resins (a1-1), (a1-2) and (a1-3). The same applies when 4 or more types are contained. For example, when 4 types are contained, they are called resins (a1-1), (a1-2), (a1-3) and (a1-4), and when 5 types are contained, the resin ( They are called a1-1), (a1-2), (a1-3), (a1-4) and (a1-5), and their acid-degradable groups are different from each other. The generic name of these resins is the resin (a1). The phenolic hydroxyl group is an alkali-soluble functional group, and a part of the phenolic hydroxyl group is protected by an acid-decomposable group, so that the alkali solubility of the resin (a1) before exposure is suppressed. The resin (a1) may have an alkali-soluble functional group other than the phenolic hydroxyl group, and the alkali-soluble functional group may be protected by an acid-degradable group like the phenolic hydroxyl group. By performing post-exposure bake (PEB, post exposure bake) as necessary in the presence of the acid generated during the exposure, the decomposition (deprotection) of the acid-degradable group is promoted, and the phenolic hydroxyl group is regenerated. This promotes alkaline dissolution of the resin (a1) in the exposed portion during development. The resin (a1) may have an alkali-soluble functional group other than the phenolic hydroxyl group, for example, a carboxy group, a sulfo group, a phosphoric acid group, an acid anhydride group, a mercapto group and the like.

<Protection of phenolic hydroxyl groups by acid-degradable groups>
Various resins contained in the resin blend (A1) (a1) (for example, a resin (a1-1), (a1-2)) is one of the phenolic hydroxyl groups of the base resin _(a b 1) having a plurality of phenolic hydroxyl groups It can be obtained by protecting the portion with an acid-degradable group, and the acid-degradable group is different with respect to various resins (a1). The resin (a1) having a phenolic hydroxyl group protected by an acid-degradable group has a partial structure of Ar—OR, where Ar represents a phenol-derived aromatic ring and R represents an acid-degradable group.

An acid-degradable group is a group that decomposes (deprotects) to produce an alkali-soluble functional group by heating as necessary in the presence of an acid. The acid-degradable group is selected from the groups described in the following groups IV to V.
Group I: tert-butoxycarbonyl group and 1,1-dimethyl-propoxycarbonyl group;
Group II: Group represented by the formula (1) -CR ¹ R ² R ³ (1)
(In the formula (1), R ¹ is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ² and R ³ are independent of 1 to 10 carbon atoms. A saturated or unsaturated linear or branched hydrocarbon group of 10 or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or ^{both R 2} and R ³ are alicyclics having 3 to 20 ring members. The structure may be formed.);
Group III: 2-tetrahydropyranyl group;
Group IV: 2-tetrahydrofuranyl group;
Group V: Group represented by the formula (2) -CHR ⁴ - ^{OR 5} (2)
(In the formula (2), R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁵ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.)
Since these acid-degradable groups have different easiness of deprotection by acid, the part where the alkali solubility is rapidly improved mainly in the exposed part by combining the resins protected by different acid-decomposable groups, and the part where the alkali solubility is gradually improved. A portion that develops solubility can coexist in. Therefore, the process window of PEB conditions can be expanded. These acid-degradable groups can be used alone or in combination of two or more. When each of the various resins (for example, resins (a1-1) and (a1-2)) has a plurality of acid-degradable groups, at least one acid-degradable group may be different. In one embodiment, each of the various resins (a1) has a single acid degradable group. The 2-tetrahydropyranyl group, the 2-tetrahydrofuranyl group, and the group represented by the formula (2) form an acetal structure together with an oxygen atom derived from a phenolic hydroxyl group.

In the formula (1) Examples of the linear or branched saturated or unsaturated hydrocarbon group of R ^1, R ² and having 1 to 10 carbon atoms represented by R ^3, methyl, ethyl radical, n -Saturated hydrocarbon groups such as propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group, unsaturated hydrocarbons such as ethenyl group, propenyl group, butenyl group, ethynyl group and propynyl group. A hydrogen group can be mentioned. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ² and R ³ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecyl group. Saturated monocyclic hydrocarbon group such as cyclododecyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, unsaturated monocyclic hydrocarbon group such as cyclodecenyl group, bicyclo [2.2.1] Saturated polycyclic hydrocarbon groups such as heptanyl group, bicyclo [2.2.2] octanyl group, tricyclo [3.3.1.1 ^3,7 ] decanyl group, bicyclo [2.2.1] heptenyl group, bicyclo [2.2.2] Examples thereof include unsaturated polycyclic hydrocarbon groups such as an octenyl group. Examples of the alicyclic structure having 3 to 20 ring members formed by R ² and R ³ include a monocyclic cycloalkane structure such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, and a cyclohexane structure, a norbornane structure, and an adamantan structure. A polycyclic cycloalkane structure can be mentioned. Examples of the group represented by the formula (2) include a 1-alkoxyalkyl group. Examples of the 1-alkoxyalkyl group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxyethyl group, 1-n-butoxyethyl group and 1-isobutoxyethyl group. Groups include 1- (2-ethylhexyloxy) ethyl groups and 1-cyclohexyloxyethyl groups, with 1-n-propoxyethyl groups being preferred.

Each of the acid-degradable groups of the plurality of kinds of resins (a1) contained in the resin blend (A1) is selected from the above groups I to IV and different groups from the following groups V-1 and V-2. Is preferable.
Group V-1: Group represented by the formula (2-1) -CHR ⁴ - ^{OR 5} (2-1)
(In the formula (2-1), R ⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁵ is a linear or branched alkyl group having 1 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms.);
Group V-2: 1-cyclohexyloxyethyl group

Groups I and II are groups of groups that are empirically difficult to deprotect compared to groups that form an acetal structure with oxygen atoms derived from phenolic hydroxyl groups. In investigating the ease of deprotection of a group forming an acetal structure together with an oxygen atom derived from a phenolic hydroxyl group, the present inventors activate de-acetalization of a phenol protected by an acid-degradable group. As a result of computationally simulating the energy and the bond dissociation energy between (phenol oxygen) and (acid-degradable group carbon), the activation energy of deacetalization correlates with the above bond dissociation energy, and it is easy to deprotect. Found that the electronic effect on the reaction center was dominant rather than the steric effect of the acid-degradable group. Groups III, IV, V-1 and V-2 are classified based on the ease of deprotection of acid-degradable groups based on this finding. The larger the group number, the easier it is to deprotect.

Since a highly sensitive positive photosensitive resin composition can be obtained even at a low exposure amount, at least one of the acid-decomposable groups of the resin (a1) forms an acetal structure together with an oxygen atom derived from a phenolic hydroxyl group. It is preferably selected from Group III, IV or V. The acetal structure is easier to deprotect than the carboxy group protected by the alkyl group, that is, the ester structure, and can be deprotected with a weak photoacid generator. Therefore, the deprotection reaction of the positive photosensitive resin composition Can be made easier to control. In addition, the deprotected carboxy group has too high alkali solubility, so that the alkali dissolution delaying effect of the other blended resins is not sufficiently exhibited. Among them, the 2-tetrahydrofuranyl group has excellent pattern-forming properties, and the acid-degradable group (1) of the resin (a1-1) is used as the 2-tetrahydrofuranyl group, and the acid-degradable group of the other resin (a1) is used. By selecting from Group III or V, it is possible to obtain a positive photosensitive resin composition which provides excellent pattern forming property and improved process stability of PEB in spite of containing a black colorant.

From the viewpoint of the process stability of PEB, the resin blend (A1) is preferably an acid-degradable resin selected from the group V-1 or V-2 with the resin (a1-1) protected by a 2-tetrahydrofuranyl group. It comprises a resin (a1-2) protected by a group (2), more preferably selected from the group V-1 or V-2 with a resin (a1-1) protected by a 2-tetrahydrofuranyl group. It contains a resin (a1-2) protected by an acid-degradable group (2) and a resin (a1-3) protected by an acid-degradable group (3) selected from groups I, II, or III. ..

The protection reaction of the phenolic hydroxyl group can be carried out under known conditions using a general protective agent. _{For example, by reacting the base resin (ab} 1) of the resin (a 1) with a protective agent in a solvent-free solvent or a solvent such as toluene or hexane at a reaction temperature of −20 to 50 ° C. in the presence of an acid or a base. , Resin (a1) can be obtained.

As the protective agent, a known protective agent capable of protecting the phenolic hydroxyl group can be used. As the protective agent, for example, isobutene can be used when the acid-degradable group is a tert-butyl group, and di-tert-butyl dicarbonate can be used when the acid-degradable group is a tert-butoxycarbonyl group. Ethyl vinyl ether when the acid-degradable group is 1-ethoxyethyl group, n-propyl vinyl ether when it is 1-n-propoxyethyl group, 2,3-dihydrofuran and 2-tetrahydropyrani when it is 2-tetrahydrofuranyl group. In the case of a le group, 3,4-dihydro-2H-pyran or the like can be used.

Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid. Salts of organic acids, such as pyridinium salts of p-toluenesulfonic acid, can also be used as the acid source. Examples of the base include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium hydrogencarbonate, potassium carbonate and cesium carbonate, and pyridine, N, N-dimethyl-4-amino. Examples thereof include amine compounds such as pyridine, triethylamine and diisopropylethylamine.

In another embodiment, the radically polymerizable monomer having a radically polymerizable monomer having a phenolic hydroxyl group is protected with an acid-degradable group and then having a radically polymerizable monomer protected with an acid-degradable group. The resin (a1) can also be obtained by polymerizing or copolymerizing other radically polymerizable monomers as needed. The protection of the phenolic hydroxyl group of the radically polymerizable monomer having the phenolic hydroxyl group can be carried out in the same manner as the protection of the phenolic hydroxyl group of _{the base resin (ab 1).}

<Base resin ( _ab 1)>
As the base resin ( _ab 1) of the resin (a 1), a homopolymer or a copolymer of a radically polymerizable monomer having a phenolic hydroxyl group can be used. These base resins ( _ab 1) can be used alone or in combination of two or more. The base resin ( _ab 1) may further have a radically polymerizable functional group. Examples of the radically polymerizable functional group include (meth) acryloyloxy group, allyl group and metharyl group.

<Alkaline aqueous solution-soluble copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer: base resin ( _ab 1-1)>
In one embodiment, the base resin ( _ab 1) of the resin (a 1) is an alkaline aqueous solution-soluble copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer: a base resin. It is (a _b 1-1), and (a _b 1-1) has a plurality of phenolic radicals. In this embodiment, the resin (a1) is obtained by protecting at least a part of a plurality of phenolic hydroxyl groups of _{the base resin (ab 1-1) with an acid-degradable group.} The base resin ( _ab 1-1) may further have an alkali-soluble functional group other than the phenolic hydroxyl group, for example, a carboxy group, a sulfo group, a phosphate group, an acid anhydride group, or a mercapto group. At least one of the radically polymerizable monomer having a phenolic hydroxyl group and the other radically polymerizable monomer has CH ₂ = CHCO- or CH ₂ = C (CH ₃ ) CO- as a polymerizable functional group. Is preferable. The other radically polymerizable monomer has, as a polymerizable functional group, for example, CH ₂ = CH-, CH ₂ = C (CH ₃ )-, CH ₂ = CHCO-, CH ₂ = C (CH ₃ ) CO-. , -OC-CH = CH-CO- and the like, preferably having a radically polymerizable functional group.

The base resin ( _ab 1-1) can be produced, for example, by radically polymerizing a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer. After synthesizing the copolymer by radical polymerization, a phenolic hydroxyl group may be added to the copolymer. Examples of the radically polymerizable monomer having a phenolic hydroxyl group include 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, 4-hydroxystyrene, and 4-hydroxyphenyl. Maleimide and the like can be mentioned. Examples of other radically polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene and p-ethylstyrene, acrylamide, acrylic nitrile, vinyl-n-butyl ether and the like. Vinyl alcohol ether compounds, alkyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates, dimethylaminoethyl (meth) acrylates, diethylaminoethyl (meth) acrylates, glycidyl (meth) acrylates, 2,2,2-trifluoro Ethyl (meth) acrylates, 2,2,3,3-tetrafluoropropyl (meth) acrylates, (meth) acrylic acids such as isobornyl (meth) acrylates, N-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide, maleic acid Anhydrous, maleic acid monoester, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chlor (meth) acrylic acid, β-frill (meth) acrylic acid, β-styryl (meth) acrylic acid, Maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, silicic acid, α-cyanosylate, itaconic acid, crotonic acid, propiole acid, 3-maleimide propionic acid, 4-maleimide butyric acid, 6 -Maleimidohexanoic acid and the like can be mentioned. From the viewpoint of heat resistance and the like, the base resin ( _ab 1-1) has one or more rings such as an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic ring structure and a heterocyclic structure. It is preferable to have a formula structure.

As a radically polymerizable monomer having a phenolic hydroxyl group which is a raw material of the base resin ( _{ab 1-1), the formula (14)}

(In formula (14), R ²⁷ is a hydrogen atom or a methyl group, and a is an integer of 1 to 5).
Those forming a monomer unit represented by are preferable. a is preferably an integer of 1 to 3, and more preferably 1. As the radically polymerizable monomer having such a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is particularly preferable.

As another radically polymerizable monomer, the formula (12)

(In the formula (12), R ²¹ and R ²² are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and fully or partially fluorinated alkyl groups having 1 to 3 carbon atoms, respectively. Alternatively, it is a halogen atom, and R ²³ is a hydrogen atom, a linear group having 1 to 6 carbon atoms, a cyclic alkyl group having 4 to 12 carbon atoms, a phenyl group, or a hydroxy group, and an alkyl group having 1 to 6 carbon atoms. And a phenyl group substituted with at least one selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms.)
Those forming a monomer unit represented by are preferable. In the formula (12), ^{it is preferable that R 21} and R ²² are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, respectively. R ²³ is at least one selected from the group consisting of a cyclic alkyl group having 4 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. It is preferably a phenyl group substituted with a species. Phenylmaleimide and cyclohexylmaleimide are particularly preferred as such other radically polymerizable monomers.

In one embodiment, the base resin ( _ab 1-1) preferably has a monomer unit represented by the formula (14) and a monomer unit represented by the formula (12).

In the base resin ( _ab 1-1), 4-hydroxyphenylmethacrylate may be used as the radically polymerizable monomer having a phenolic hydroxyl group, and phenylmaleimide or cyclohexylmaleimide may be used as the other radically polymerizable monomer. Especially preferable. By using a resin obtained by radically polymerizing these radically polymerizable monomers, shape retention and developability can be improved and outgas can be reduced.

The polymerization initiator for producing the base resin ( _ab 1-1) by radical polymerization is not limited to the following, but is limited to 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,2'-azobis). 2-Methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovalerian acid), 2,2'-azobis (2,4-dimethyl) Valeronitrile) (AVN), 1,1'-azobis (1-acetoxy-1-phenylethane), dimethyl-2,2'-azobis (2-methylbutyrate), dimethyl-2,2'-azobis (2) , 4-dimethylpentanoate) and other azo polymerization initiators, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert -A peroxide polymerization initiator having a 10-hour half-life temperature of 100 to 170 ° C. such as butyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, or benzoyl peroxide, a peroxide. Peroxide polymerization initiators such as lauroyl oxide, 1,1'-di (tert-butylperoxy) cyclohexane, and tert-butylperoxypivalate can be used. 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, and 40 parts by mass or less with respect to 100 parts by mass of the total amount of the radically polymerizable monomer. It is preferably 20 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 radically polymerizable monomer, and is preferably used in the range of 0.01 to 10 parts by mass. ..

The weight average molecular weight (Mw) of the base resin ( _ab 1-1) can be 3000 to 80000, preferably 4000 to 70,000, and more preferably 5000 to 60,000. The number average molecular weight (Mn) can be 1000 to 30000, preferably 1500 to 25000, and more preferably 2000 to 20000. The polydispersity (Mw / Mn) can be 1.0 to 3.5, preferably 1.1 to 3.0, and more preferably 1.2 to 2.8. By setting the weight average molecular weight, the number average molecular weight and the polydispersity within the above ranges, a positive photosensitive resin composition having excellent alkali solubility and developability can be obtained.

In one embodiment, the various resins (resins (a1-1), (a1-2), etc.) contained in the resin blend (A1) are 5 mol% to 95 mol%, preferably 10 mol% of each phenolic hydroxyl group. % -80 mol%, more preferably 25 mol% -70 mol% is protected with an acid-degradable group. By setting the ratio of the phenolic hydroxyl group protected by the acid-decomposable group to 5 mol% or more, it is possible to impart a chemical amplification function to the photosensitive resin composition and realize high sensitivity. By reducing the proportion of phenolic hydroxyl groups protected by acid-degradable groups to 95 mol% or less, the residual amount of unreacted acid-degradable groups is reduced, the solubility of the exposed area is improved, and high sensitivity is achieved. can do. The ratio of phenolic hydroxyl groups protected by acid-decomposable groups is calculated from the weight reduction rate (%) of resins (a1-1), (a1-2), etc. by a thermogravimetric differential thermal analyzer (TG / DTA). Will be done.

In one embodiment, the resin (a1) has a plurality of phenolic hydroxyl groups, and at least a part of the plurality of phenolic hydroxyl groups is protected by an acid-degradable group, and the radically polymerizable monomer having a phenolic hydroxyl group is obtained. Alkaline aqueous solution soluble homopolymer, or radical polymerizable monomer having phenolic hydroxyl group having multiple phenolic hydroxyl groups and having at least a part of the plurality of phenolic hydroxyl groups protected by an acid-degradable group and others. It is an alkaline aqueous solution-soluble copolymer with the radically polymerizable monomer of. The latter resin uses a copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer as a base resin ( _ab 1-1), and is a base resin (a). _b 1-1) has a plurality of phenolic hydroxyl groups, and at least a part of these phenolic hydroxyl groups is protected by an acid-degradable group.

In this embodiment, the resin (a1-1) is represented by the formula (3).

(In the formula (3), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is an acid-degradable group (1), l is an integer of 0 to 5, and m is an integer of 0 to 5. However, l + m is an integer of 1 to 5.)
It is preferable that the resin (a1-1) has at least one of the above-mentioned monomer units in which m is an integer of 1 or more. Acid-decomposable group of R ⁷ (1) are those selected from the acid-decomposable groups contained in the acid-decomposable group & I ~ V are preferred.

In this embodiment, the resin (a1-2) is represented by the formula (4).

(In the formula (4), R ⁸ is a hydrogen atom or a methyl group, R ⁹ is an acid-degradable group (2), n is an integer of 0 to 5, and o is an integer of 0 to 5. However, n + o is an integer of 1 to 5.)
It is preferable that the resin (a1-2) has at least one of the above-mentioned monomer units in which o is an integer of 1 or more. Acid-decomposable group of R ⁹ (2) are those selected from the acid-decomposable groups contained in the acid-decomposable group & I ~ V are preferred. However, the acid-degradable group (2) of ^{R 9} is different from the acid-degradable group (1) of ^{R 7.}

In this embodiment, any resin (a1-3) is used in the formula (5).

(In the formula (5), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is an acid-degradable group (3), p is an integer of 0 to 5, and q is an integer of 0 to 5. However, p + q is an integer of 1 to 5.)
It is preferable that the resin (a1-3) has at least one of the above-mentioned monomer units in which q is an integer of 1 or more. The acid-decomposable group (3) of R ¹¹ is preferably selected from the acid-decomposable groups contained in the acid-decomposable groups I to V. However, the acid-degradable group (3) of ^{R 11} is different from ^{the acid-degradable group (1) of R 7 and} the acid-degradable group (2) of R ^8.

The resin (a1) has the formula (12).

(In the formula (12), R ²¹ and R ²² are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and fully or partially fluorinated alkyl groups having 1 to 3 carbon atoms, respectively. Alternatively, it is a halogen atom, and R ²³ is a hydrogen atom, a linear group having 1 to 6 carbon atoms, a cyclic alkyl group having 4 to 12 carbon atoms, a phenyl group, or a hydroxy group, and an alkyl group having 1 to 6 carbon atoms. And a phenyl group substituted with at least one selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms.)
It is preferable to have a monomer unit represented by. Preferred examples of R ²¹ , R ²² and R ²³ are the same as described above.

In one embodiment, the resin (a1-1) preferably contains 60 mol% to 100 mol% of the monomer unit represented by the formula (3) with respect to all the monomer units of the resin (a1-1). Contains 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol%. By setting the monomer unit represented by the formula (3) to 60 mol% or more, the difference in alkali solubility between the exposed portion and the unexposed portion can be increased and the sensitivity can be increased. By setting the monomer unit represented by the formula (3) to 100 mol% or less, the balance between heat resistance and alkali solubility can be maintained. From the same viewpoint, in one embodiment, the resin (a1-2) contains 60 mol% or more of the monomer unit represented by the formula (4) with respect to all the monomer units of the resin (a1-2). It contains 100 mol%, preferably 70 mol% to 100 mol%, and more preferably 80 mol% to 100 mol%. From the same viewpoint, in one embodiment, the resin (a1-3) contains 60 mol% or more of the monomer unit represented by the formula (5) with respect to all the monomer units of the resin (a1-3). It contains 100 mol%, preferably 70 mol% to 100 mol%, and more preferably 80 mol% to 100 mol%.

In one embodiment, the monomer unit represented by the formula (3) and in which m is an integer of 1 or more, that is, at least one phenolic hydroxyl group is protected by the acid-degradable group (1). ) Is 5% to 95%, preferably 15% to 70%, more preferably 25% to 60% of the total number of monomer units of the resin (a1-1). be. By setting the ratio of the monomer unit to 5% or more, it is possible to impart a chemical amplification function to the photosensitive resin composition and realize high sensitivity. By setting the ratio of the monomer unit to 95% or less, the residual amount of unreacted acid-decomposable groups can be reduced, the solubility of the exposed portion can be improved, and high sensitivity can be realized. From the same viewpoint, in one embodiment, the monomer unit represented by the formula (4) and in which o is an integer of 1 or more, that is, at least one phenolic hydroxyl group is protected by the acid-degradable group (2). The number of monomeric units represented by the formula (4) is 5% to 95%, preferably 15% to 70%, more preferably 25% of the total number of monomeric units of the resin (a1-2). % To 60%. From the same viewpoint, in one embodiment, the monomer unit represented by the formula (5) and in which q is an integer of 1 or more, that is, at least one phenolic hydroxyl group is protected by the acid-degradable group (3). The number of monomeric units represented by the formula (5) is 5% to 95%, preferably 15% to 70%, more preferably 25% of the total number of monomeric units of the resin (a1-3). % To 60%.

In one embodiment, it is preferable that the resin (a1-1) is contained in an amount of 33 to 95% by mass based on the resin blend (A1). It is more preferably 40 to 90% by mass, still more preferably 50 to 85% by mass. By containing 33 to 95% by mass of the resin (a1-1) based on the resin blend (A1), the process stability of PEB can be improved.

In one embodiment, it is preferable that the resin (a1-2) is contained in an amount of 5 to 50% by mass based on the resin blend (A1). It is more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass. By containing 5 to 50% by mass of the resin (a1-2) based on the resin blend (A1), the process stability of PEB can be improved.

In one embodiment, it is preferable that the resin (a1-3) is contained in an amount of 0 to 32% by mass based on the resin blend (A1). It is more preferably 5 to 30% by mass, still more preferably 10 to 25% by mass. By containing 32% by mass or less of the resin (a1-3) based on the resin blend (A1), the process stability of PEB can be improved.

In one embodiment, the mass ratio of the resin (a1-2) to the resin (a1-1) (mass of the resin (a1-2) / mass of the resin (a1-1)) is 5/95 to 50/33. It is preferably 10/90 to 40/40, more preferably 15/85 to 35/50. By setting the mass ratio of the resin (a1-2) to the resin (a1-1) to 5/95 to 50/33, the process stability of PEB can be improved.

In one embodiment, the mass ratio of the resin (a1-3) to the resin (a1-1) (mass of the resin (a1-3) / mass of the resin (a1-1)) is 0/100 to 32/33. It is preferably 5/95 to 30/40, more preferably 10/90 to 25/50. By setting the mass ratio of the resin (a1-3) to the resin (a1-1) to 32/33 or less, the process stability of PEB can be improved.

In one embodiment, the mass ratio of the resin (a1-3) to the resin (a1-2) (mass of the resin (a1-3) / mass of the resin (a1-2)) is 0/100 to 32/5. It is preferably 5/95 to 30/10, more preferably 10/90 to 25/15. By setting the mass ratio of the resin (a1-3) to the resin (a1-2) to 32/5 or less, the process stability of PEB can be improved.

In one embodiment, the mass ratio of the resin (a1-1) to the resin (a1-2) to the resin (a1-3) (mass of resin (a1-1): mass of resin (a1-2): resin (a1) The mass) of -3) is preferably 95: 5: 0 to 33:35:32, more preferably 90: 5: 5 to 40:30, and 85: 10: 5 to 50. : 30:20 is more preferable. By setting the mass ratio of the resin (a1-1) to the resin (a1-2) to the resin (a1-3) to 95: 5: 0 to 33:35:32, the process stability of PEB can be improved. can.

In one embodiment, the positive photosensitive resin composition contains 10 parts by mass to 80 parts by mass, preferably 15 parts by mass to 60 parts by mass, more preferably the resin blend (A1) based on 100 parts by mass of the solid content. Includes 20 to 40 parts by mass. When the content of the resin blend (A1) is 10 parts by mass or more based on 100 parts by mass of the solid content, a chemical amplification function can be imparted to the photosensitive resin composition and high sensitivity can be realized. When the content of the resin blend (A1) is 80 parts by mass or less based on 100 parts by mass of the solid content, the residual amount of unreacted acid-decomposable groups is reduced, the solubility of the exposed part is enhanced, and the sensitivity is high. Can be realized. In the embodiment including the resin blend (A1), the "solid content" is a resin blend (A1), a colorant (B), a photoacid generator (C), and a resin having an arbitrary epoxy group and a phenolic hydroxyl group (A1). It means the total mass of the components including D), the third resin (E), the dissolution accelerator (F), and the optional component (G), excluding the solvent (H).

In one embodiment, the positive photosensitive resin composition contains 30% by mass to 90% by mass, preferably 40% by mass to 80% by mass, more preferably the resin blend (A1) based on the total mass of the resin components. Contains 45% by mass to 65% by mass. By setting the content of the resin blend (A1) to 30% by mass or more, it is possible to impart a chemical amplification function to the photosensitive resin composition and realize high sensitivity. By setting the content of the resin blend (A1) to 90% by mass or less, the solubility of the exposed portion can be enhanced and high sensitivity can be realized.

[Colorant (B)]
The colorant (B) is at least one selected from the group consisting of black dyes and black pigments. A black dye and a black pigment may be used in combination. For example, by forming a black partition wall on the organic EL element by using the positive photosensitive resin composition containing the colorant (B), the visibility of a display device such as an organic EL display can be improved.

In one embodiment, the colorant (B) 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 the black dye, the light-shielding property of the film of the positive photosensitive resin composition after firing can be maintained. The positive photosensitive resin composition containing a black dye has less residue of the colorant (B) during development as compared with the positive photosensitive resin composition containing a black pigment, and forms a high-definition pattern on the film. be able to.

A black pigment may be used as the colorant (B). Examples of the black pigment include carbon black, carbon nanotube, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigment, lactam pigment and the like. 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 one embodiment, the positive photosensitive resin composition comprises 10 parts by mass to 150 parts by mass, preferably 30 parts by mass to 100 parts by mass, based on a total of 100 parts by mass of the resin components. It preferably contains 40 parts by mass to 70 parts by mass. When the content of the colorant (B) is 10 parts by mass or more based on the total of 100 parts by mass, the light-shielding property of the film after firing can be maintained. When the content of the colorant (B) is 150 parts by mass or less based on the total of 100 parts by mass, the coating film can be colored without impairing the alkali developability.

[Photoacid generator (C)]
The positive photosensitive resin composition contains a photoacid generator (C). The photoacid generator (C) is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, γ-rays, and electron beams. The photoacid generator (C) promotes the decomposition of the acid-degradable group of the resin (a1) to regenerate the phenolic hydroxyl group and increase the alkali solubility of the resin (a1). Further, the presence of the acid generated from the photoacid generator (C) in the portion irradiated with radiation makes it easier for the resin in that portion to dissolve in the alkaline aqueous solution together with the acid. As a result, it is possible to form a pattern with high sensitivity and high resolution even with a low exposure amount. The photoacid generator (C) can be used alone or in combination of two or more.

The photoacid generator (C) preferably generates an acid having a pKa of 4 or less by irradiation, and more preferably an acid having a pKa of 3 or less. Such a photoacid generator (C) can produce an acid having an ability to decompose an acid-degradable group.

The photoacid generator (C) preferably generates an acid having a pKa of -15 or more by irradiation, and more preferably an acid having a pKa of -5 or more. Such a photoacid generator (C) does not excessively proceed with ring-opening polymerization of the epoxy group and the epoxy group of the resin (D) having a phenolic hydroxyl group, which will be described later, during exposure and heat treatment (PEB) after exposure. In addition, the alkali solubility of the resin (D) can be maintained during development.

Examples of the photoacid generator (C) include trichloromethyl-s-triazine compounds, sulfonium salts, phosphonium salts, diazonium salts, onium salts such as iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oximes. Examples include sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound because of its high sensitivity and high insulating property. The acid generated from the oxime sulfonate compound has an appropriate ability to decompose the acid-degradable group that forms an acetal structure together with the oxygen atom derived from the phenolic hydroxyl group. Therefore, when these are used in combination, the PEB is superior. Process stability can be obtained.

Examples of the oxime sulfonate compound include a compound represented by the formula (13).

In formula (13), R ²⁴ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, and R ²⁵ and R ²⁶ are independent of each other. It is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, an acetoxy group, a carboxy group, or an alkoxycarbonyl group. R ²⁵ and R ²⁶ may be bonded to form a ring structure having 3 to 10 ring members, and the ring structure may have a substituent.

The substituted or unsubstituted alkyl group R ^24, for example, for example, linear or branched alkyl group having 1 to 10 carbon atoms, preferably a methyl group, an ethyl group, or n- propyl .. The substituted or unsubstituted alkoxy group R ^24, for example, a straight-chain or branched alkoxy group having 1 to 5 carbon atoms is preferably a methoxy group or an ethoxy group. The substituent of the alkyl group and alkoxy group R ^24, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom), a cyano group, a nitro group, an aryl group having 6 to 20 carbon atoms, carbon Examples thereof include an alkoxy group having 1 to 10 atoms and a cycloalkyl group having 3 to 10 carbon atoms. The substituted or unsubstituted aryl group R ^24, for example, include an aryl group having 6 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group, or a naphthyl group. Examples of the substituent of the aryl group R ^24, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom) Can be mentioned. Examples of the halogen atom of R ²⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the unsubstituted aryl group of R ²⁵ and R ²⁶ include an aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferable. Examples of the unsubstituted heterocyclic group of R ²⁵ and R ²⁶ include a 2-benzoimidazolyl group, a 2-benzoxazolyl group, a 2-benzothiazolyl group, and a 2-indrill group. Examples of the substituents of the aryl group and the heterocyclic group of R ²⁵ and R ²⁶ include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom (fluorine atom, chlorine atom, etc.). Bromine atom and iodine atom). Examples of the alkoxycarbonyl group of R ²⁵ and R ^{26 include an ethoxycarbonyl group.} It is preferable ^{that R 25} is a cyano group, a carboxy group, or an alkoxycarbonyl group, particularly a cyano group, and R ²⁶ is a substituted aryl group, particularly a 4-methoxyphenyl group.

Examples of the oxime sulfonate compound having a ring structure formed by bonding R ²⁵ and R ^{26 include an oxime sulfonate compound represented by the formula (13a).}

In formula (13a), R ²⁴ is as described for formula (13), R ³⁷ is an alkyl group, an alkoxy group, or a halogen atom, respectively, and d represents an integer of 0 to 5. ..

Examples of the alkyl group of R ³⁷ include a linear or branched alkyl group having 1 to 10 carbon atoms, and a methyl group, an ethyl group, or an n-propyl group is preferable. Examples of the alkoxy group of R ³⁷ include a linear or branched alkoxy group having 1 to 5 carbon atoms, and a methoxy group or an ethoxy group is preferable. Examples of the halogen atom of R ³⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom or a fluorine atom is preferable. d is preferably 0 or 1.

Examples of the oxime sulfonate compound include (Z, E) -2- (4-methoxyphenyl) ([((4-methylphenyl) sulfonyl) oxy] imino) acetonitrile, 2- [2- (propylsulfonyloxyimino) thiophene. -3 (2H) -iriden] -2- (2-methylphenyl) acetonitrile, 2- [2- (4-methylphenylsulfonyloxyimino) thiophene-3 (2H) -iriden] -2- (2-methylphenyl) ) Examples include acetonitrile.

In one embodiment, the positive photosensitive resin composition contains 0.1 parts by mass to 85 parts by mass, preferably 5 parts by mass to 40 parts by mass of the photoacid generator (C) based on a total of 100 parts by mass of the resin components. It contains parts by mass, more preferably 10 parts by mass to 30 parts by mass. When the content of the photoacid generator (C) is 0.1 part by mass or more based on the total of 100 parts by mass, high sensitivity can be realized. When the content of the photoacid generator (C) is 85 parts by mass or less based on the total of 100 parts by mass, the alkali developability is good.

[Resin (D) having an epoxy group and a phenolic hydroxyl group]
The positive photosensitive resin composition may further contain a resin (D) having an epoxy group and a phenolic hydroxyl group. The resin (D) having an epoxy group and a phenolic hydroxyl group is an alkaline aqueous solution soluble resin. The resin (D) having an epoxy group and a phenolic hydroxyl group may have an alkali-soluble functional group other than the phenolic hydroxyl group. Phenolic hydroxyl groups and other alkali-soluble functional groups may be protected by acid-degradable groups. The resin (D) having an epoxy group and a phenolic hydroxyl group is, for example, a part of the epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter, may be referred to as “epoxy compound”). It can be obtained by reacting with the carboxy group of the hydroxyepoxide compound. The epoxy group of the resin (D) having an epoxy group and a phenolic hydroxyl group forms a crosslink by reacting with the phenolic hydroxyl group during heat treatment (post-baking) after development, whereby the chemical resistance and heat resistance of the coating film are formed. Can be improved. Since the phenolic hydroxyl group contributes to the solubility in the alkaline aqueous solution during development, the acid-degradable group is sufficiently decomposed (deprotected) in the resin (D) having the epoxy group and the phenolic hydroxyl group when exposed at a low exposure amount. ) Also functions as a dissolution accelerator for the resin blend (A1) that has not been formed, whereby the photosensitive resin composition can be made highly sensitive.

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 phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, naphthalene skeleton-containing epoxy resin, and alicyclic epoxy resin. , Heterocyclic epoxy resin and the like can be mentioned. 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 (21). In the formula (21), for example, R ³⁸ 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 e is an integer of 1 to 50.

Examples of the phenol novolac type epoxy resin include EPRICLON (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 Corporation), 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 at least one selected from the group consisting of a phenol novolac type epoxy resin and a cresol novolac type epoxy resin. preferable. The positive photosensitive resin composition containing an epoxy group derived from a novolak type epoxy resin and a resin (D) having a phenolic hydroxyl group has excellent pattern forming property, easy adjustment of alkali solubility, and outgassing. few.

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. The hydroxybenzoic acid compound can be used alone or in combination of two or more.

In one embodiment, the resin (D) 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 (22).

Has the structure of. In the formula (22), f 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 (D) having an epoxy group and a phenolic hydroxyl group from the epoxy compound and the hydroxybenzoic acid compound, 0.2 to 0.95 equivalent of the hydroxy benzoic 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. When the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and when it is 0.95 equivalent or less, the 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 (Mn) of the resin (D) having an epoxy group and a phenolic hydroxyl group is preferably 500 to 8000, more preferably 800 to 6000, and even more preferably 1000 to 5000. When the number average molecular weight is 500 or more, the alkali solubility is appropriate, so that it is good as a resin for a photosensitive material, and when it is 8000 or less, the coatability and developability are good.

In one embodiment, the positive photosensitive resin composition contains 5% by mass to 50% by mass, preferably 10% by mass or more of the resin (D) having an epoxy group and a phenolic hydroxyl group based on a solid content of 100% by mass. It contains 40% by mass, more preferably 15% by mass to 30% by mass. When the content of the resin (D) having an epoxy group and a phenolic hydroxyl group is 5% by mass or more based on 100% by mass of the solid content, dissolution of the exposed portion can be promoted and high sensitivity can be realized. The stability and durability of the film after thermosetting can be ensured. When the content of the resin (D) having an epoxy group and a phenolic hydroxyl group is 50% by mass or less based on 100% by mass of the solid content, the solubility of the unexposed portion is suppressed to a low level and the residual film ratio is kept high. Can be done.

[Third resin (E)]
The positive photosensitive resin composition may further contain a third resin (E) other than the resin (a1) and the resin (D) having an epoxy group and a phenolic hydroxyl group. The third resin (E) can be used alone or in combination of two or more.

Examples of the third resin (E) include acrylic resins other than the resin (a1), polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, and polybenzoxazole resin precursors. Examples thereof include silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins. In general, the acrylic resin means a (co) polymer of α-alkyl acrylic acid ester, but in the present disclosure, the acrylic resin is a (co) polymer of acrylic acid ester and a (co) polymer of α-alkyl acrylic acid ester. ) Includes polymers. For example, as a derivative of a phenol resin, a polyalkenylphenol resin in which an alkenyl group is bonded to a benzene ring, and as a derivative of a polystyrene resin, a hydroxypolystyrene resin derivative in which a phenolic hydroxyl group and a hydroxyalkyl group or an alkoxy group are bonded to a benzene ring may be used. Can be mentioned. These resins may or may not have alkali-soluble functional groups.

In one embodiment, the third resin (E) is a resin having a plurality of phenolic hydroxyl groups, wherein the plurality of phenolic hydroxyl groups are not protected by an acid-degradable group, that is, all of the resin (a1). The acid-degradable group is deprotected. Since such a resin has excellent compatibility with the resin blend (A1) and has high alkali solubility, it can be suitably used for adjusting the alkali solubility of the coating film.

In one embodiment, the positive photosensitive resin composition contains 1 part by mass to 30 parts by mass, preferably 1 part by mass to 20 parts by mass, more preferably the third resin (E), based on 100 parts by mass of the solid content. Includes 1 to 10 parts by mass. When the content of the third resin (E) is 1 part by mass or more based on 100 parts by mass of the solid content, effective promotion of dissolution of the resin component, impartation of heat resistance, improvement of crosslinkability and the like can be expected. .. When the content of the third resin (E) is 30 parts by mass or less based on 100 parts by mass of the solid content, the above-mentioned expected performance can be imparted without impairing the pattern formability and surface quality of the coating film. can.

[Dissolution accelerator (F)]
The positive photosensitive resin composition may further contain a dissolution accelerator (F) for improving the solubility of the alkali-soluble portion in the developer during development. Examples of the dissolution accelerator (F) include organic low molecular weight compounds selected from the group consisting of a compound having a carboxy group and a compound having a phenolic hydroxyl group. The dissolution accelerator (F) can be used alone or in combination of two or more.

In the present disclosure, the "low molecular weight compound" means a compound having a molecular weight of 1000 or less. The organic low molecular weight compound has a carboxy group or a plurality of phenolic hydroxyl groups and is alkali-soluble.

Examples of such organic low molecular weight compounds 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 Other carboxylic acids such as dermal acid, mandelic acid, phenylsuccinic acid, atropic acid, silicic acid, methyl silicate, benzyl silicate, cinnamyldenacetic acid, kumalic acid, umbellic acid; catechol, resorcinol, hydroquinone, 1, Examples thereof include aromatic polyols such as 2,4-benzenetriol, pyrogallol, fluoroglucinol, and bisphenol.

The content of the dissolution accelerator (F) in the positive photosensitive resin composition can be 0.1 part by mass to 50 parts by mass, preferably 1 part by mass, based on 100 parts by mass of the total of the resin components. It is from 3 parts by mass to 35 parts by mass, and more preferably 2 parts by mass to 20 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 50 parts by mass or less. Excessive dissolution of the resin component can be suppressed, and the pattern forming property of the coating film, surface quality and the like can be improved.

[Arbitrary component (G)]
The positive photosensitive resin composition may contain a thermosetting agent, a surfactant, a colorant other than (B), or the like as an optional component (G). In the present disclosure, the optional component (G) is defined as not applicable to any of (A1) to (F).

A thermal radical generator can be used as the thermosetting agent. 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, and further preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the thermosetting agent. ..

The positive photosensitive resin composition can 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 ACG 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 surfactants can be used alone or in combination of two or more.

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.

The positive photosensitive resin composition can contain a second colorant other than the colorant (B). 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 disclosure 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. Among the dyes, red dyes are preferable. As red dyes, for example, VALUESTA (registered trademark) RED 3312 (red dye specified by CI of Solvent Red 122, manufactured by Orient Chemical Industry Co., Ltd.) and VALUESTA (registered trademark) RED 3311 (solvent red 8). A red dye specified by CI, manufactured by Orient Chemical Industry Co., Ltd.) can be mentioned.

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.

[Solvent (H)]
The positive photosensitive resin composition can be used in a solution state (however, when a black pigment is contained, the pigment is in a dispersed state) after being dissolved in the solvent (H). For example, a colorant (B) is added to a solution obtained by dissolving a resin blend (A1) and optionally a resin (D) having an epoxy group and a phenolic hydroxyl group and a third resin (E) in a solvent (H). ), And a photoacid generator (C), and if necessary, an optional component (G) such as a dissolution accelerator (F), a thermosetting agent, and a surfactant are mixed in a predetermined ratio to form a solution. A positive photosensitive resin composition can be prepared. The positive photosensitive resin composition can be adjusted to a viscosity suitable for the coating method used by changing the amount of the solvent (H).

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 acetate such as methyl cellosolve acetate and ethyl cellosolve acetate, and 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, diethylene glycol monobutyl ether, propylene glycol alkyl ether acetate compounds such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate, toluene, Aromatic hydrocarbons such as xylene, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, ketones such as cyclohexanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate , 2-Hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethers such as ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like. Examples include amide compounds. These solvents can be used alone or in combination of two or more.

[Positive photosensitive resin composition]
The positive photosensitive resin composition includes a resin blend (A1), a colorant (B), a photoacid generator (C), and if necessary, a resin (D) having an epoxy group and a phenolic hydroxyl group, and a third resin. (E), the dissolution accelerator (F), or the optional component (G) can be prepared by dissolving or dispersing in the solvent (H) and mixing. Depending on the purpose of use, the solid content concentration of the positive photosensitive resin composition can be appropriately determined. For example, the solid content concentration of the positive 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 because of dispersion efficiency and fine dispersion.

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

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

[How to use the positive photosensitive resin composition]
When the positive photosensitive resin composition is used for radiation lithography, first, the positive 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 surface of the substrate is not particularly limited, and for example, a spray method, a roll coating method, a slit method, a spin coating method 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.

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). .. 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 step, a heat treatment (PEB) may be performed to promote the decomposition of the acid-decomposable group. With PEB, the alkali solubility of the resin blend (A1) in the exposed portion can be further increased. The heating conditions vary depending on the type of each component, the mixing ratio, etc., but PEB is usually performed by heat-treating at 70 to 140 ° C., for example, for 30 seconds to 20 minutes on a hot plate and 1 to 60 minutes in an oven. be able to.

After the exposure step or PEB step, the film is developed by contacting it with a developing solution, unnecessary parts are removed, and a pattern is formed on the film (development step). Examples of the developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di. Secondary amines such as -n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline Tertiary ammonium salts such as pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonane and the like cyclic amines and the like. An aqueous solution of the alkaline compound of 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 developing solution. 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.

After that, 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 heat treatment is preferably performed in a nitrogen atmosphere.

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

One embodiment of the method for producing an organic EL element partition wall or an insulating film is to prepare a coating composition by dissolving or dispersing a positive photosensitive resin composition in a solvent, or applying the coating composition to a substrate to form a coating. The acid-degradable group of the resin blend (A1) is formed by forming the film, removing the solvent contained in the film to dry the film, and irradiating the dried film with radiation through a photomask to expose the film. At least a part of the film is decomposed, the film after exposure is developed by contacting it with a developing solution to form a pattern on the film, and the film on which the pattern is formed is heated at a temperature of 100 ° C to 350 ° C. It involves processing to form an organic EL element bulkhead or insulating film. The above PEB can also be performed after exposure and before development.

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

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

One embodiment is an organic EL device containing a cured product of a positive 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 this Example.

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

The weight average molecular weight and number average molecular weight of the resin (a1), the resin (D) having an epoxy group and a phenolic hydroxyl group, and the third resin (E) are prepared using a polystyrene standard substance under the following measurement conditions. It was calculated using the calibration curve.
Device name: Shodex® GPC-101
Column: Leftox® LF-804
Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: Shodex® RI-71
Temperature: 40 ° C

The ratio of phenolic hydroxyl groups protected by acid-degradable groups is determined by using a thermogravimetric differential thermal analyzer (TG / DTA6200, manufactured by Hitachi High-Tech Science Co., Ltd.) in a nitrogen gas stream at a heating rate of 10 ° C./min. The phenolic hydroxyl group at 260 ° C. is protected by an acid-degradable group when the temperature is raised from room temperature to 250 ° C. under the conditions, held for 10 minutes, and further raised to 400 ° C. under the condition of a temperature rise rate of 10 ° C./min. It was calculated from the weight reduction rate (%) of the resin.

[Production Example 1] Production of an alkaline aqueous solution-soluble copolymer (PCX-02e) (third resin (E)) of a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer 4-hydroxy 25.5 g of phenyl methacrylate ("PQMA" manufactured by Showa Denko Co., Ltd.) and 4.50 g of N-cyclohexyl maleimide (manufactured by Nippon Catalyst Co., Ltd.) as a solvent, 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.) In 77.1 g, 3.66 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 14.6 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Co., Ltd.). rice field. 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 PCX-02e had a number average molecular weight of 3100 and a weight average molecular weight of 6600.

[Production Example 2] Production of a resin (PCX-02e-THF40) in which a phenolic hydroxyl group is protected by a 2-tetrahydrofuranyl group A radically polymerizable monomer having a phenolic hydroxyl group in a 100 mL three-mouthed flask. 10.0 g of an alkaline aqueous solution-soluble copolymer (PCX-02e) of other radically polymerizable monomers and 0.60 g of a pyridinium salt of p-toluenesulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an acid catalyst are added in tetrahydrofuran. (Manufactured by Fuji Film Wako Junyaku Co., Ltd.) Dissolved in 50.0 g. Then, it was ice-cooled in a nitrogen gas atmosphere, and 6.69 g of 2,3-dihydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. Then, the mixture was stirred at room temperature for 16 hours. After neutralizing the acid catalyst with saturated aqueous sodium hydrogen carbonate solution, the aqueous layer was removed. Further, the organic layer was washed twice with water. Then, tetrahydrofuran was distilled off. The obtained solid was dissolved in 50.0 g of ethyl acetate and added dropwise to 200 g of toluene to precipitate the product. The precipitate was collected by filtration and vacuum dried at 80 ° C. for 4 hours to recover 11.0 g of white powder. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a 20% by mass solid content solution of a resin (PCX-02e-THF40) in which the phenolic hydroxyl group was protected by a 2-tetrahydrofuranyl group. The obtained PCX-02e-THF40 has a number average molecular weight of 3716, a weight average molecular weight of 6806, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 40 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 55% of the total number of monomeric units of PCX-02e-THF40.

[Production Example 3] Production of a resin (PCX-02e-nPOE60) in which a phenolic hydroxyl group is protected with a 1-n-propoxyethyl group n-propyl vinyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) instead of 2,3-dihydrofuran. A 20% by mass solution of a resin (PCX-02e-nPOE60) having a phenolic hydroxyl group protected with a 1-n-propoxyethyl group was obtained in the same manner as in Production Example 2 except that 8.23 g was used. .. The obtained PCX-02enPOE60 has a number average molecular weight of 4550, a weight average molecular weight of 8054, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 60 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 55% of the total number of monomeric units of PCX-02enPOE60.

[Production Example 4] Production of a resin (PCX-02e-THP30) in which a phenolic hydroxyl group is protected by a 2-tetrahydropyranyl group 3,4-dihydro-2H-pyran (Tokyo Chemical Industry) instead of 2,3-dihydrofuran A 20% by mass solution of a resin (PCX-02e-THP30) in which a phenolic hydroxyl group is protected by a 2-tetrahydropyranyl group in the same manner as in Production Example 2 except that 6.69 g is used. Got The obtained PCX-02e-THP30 has a number average molecular weight of 3716, a weight average molecular weight of 6806, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 30 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 55% of the total number of monomeric units of PCX-02e-THP30.

[Production Example 5] Production of a resin (PCX-02e-iBOE60) in which a phenolic hydroxyl group is protected with an isobutoxyethyl group 6.69 g of isobutyl vinyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is used instead of 2,3-dihydrofuran. A solution having a solid content of 20% by mass of a resin (PCX-02e-iBOE60) in which a phenolic hydroxyl group was protected with an isobutoxyethyl group was obtained in the same manner as in Production Example 2 except that it was used. The obtained PCX-02e-iBOE60 has a number average molecular weight of 3716, a weight average molecular weight of 6806, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 60 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 55% of the total number of monomeric units of PCX-02e-iBOE60.

[Production Example 6] Production of a resin (PCX-02e-EOE60) in which a phenolic hydroxyl group is protected with a 1-ethoxyethyl group Ethyl vinyl ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 6.88 g instead of 2,3-dihydrofuran A 20% by mass solution of a resin (PCX-02e-EOE60) in which the phenolic hydroxyl group was protected with a 1-ethoxyethyl group was obtained in the same manner as in Production Example 2 except that the above was used. The obtained PCX-02e-EOE60 has a number average molecular weight of 4300, a weight average molecular weight of 7900, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 60 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 55% of the total number of monomeric units of PCX-02e-EOE60.

[Production Example 7] Production of a resin (PCX-02e-CHOE70) in which a phenolic hydroxyl group is protected by a cyclohexyloxyethyl group 6.88 g of cyclohexyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) is used instead of 2,3-dihydrofuran. A solution having a solid content of 20% by mass of a resin (PCX-02e-CHOE70) in which a phenolic hydroxyl group was protected with a cyclohexyloxyethyl group was obtained in the same manner as in Production Example 2 except that it was used. The obtained PCX-02e-CHOE70 has a number average molecular weight of 4300, a weight average molecular weight of 7900, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 70 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 55% of the total number of monomeric units of PCX-02e-CHOE70.

[Production Example 8] Production of a resin (PCX-02e-Boc5) in which a phenolic hydroxyl group is protected by a tert-butoxycarbonyl group In a 100 mL three-mouthed flask, with a radically polymerizable monomer having a phenolic hydroxyl group. 10.0 g of an alkaline aqueous solution-soluble copolymer (PCX-02e) of other radically polymerizable monomers and 1.74 g of triethylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a base are added in tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.). (Manufactured by Co., Ltd.) Dissolved in 50.0 g. Then, it was ice-cooled in a nitrogen gas atmosphere, and 3.47 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour. Then, the mixture was stirred at room temperature for 16 hours. Then, tetrahydrofuran was distilled off, the obtained solid was dissolved in 50.0 g of ethyl acetate, and the mixture was added dropwise to 200 g of hexane to precipitate the product. The precipitate was collected by filtration and vacuum dried at 80 ° C. for 4 hours to recover 10.3 g of white powder. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a 20% by mass solid content solution of a resin (PCX-02e-Boc5) in which the phenolic hydroxyl group was protected by a tert-butoxycarbonyl group. The obtained PCX-02e-Boc5 has a number average molecular weight of 4400, a weight average molecular weight of 7800, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 5 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 26% of the total number of monomeric units of PCX-02e-Boc5.

[Production Example 9] Production of a resin (PCX-02e-THF70) in which a phenolic hydroxyl group is protected by a 2-tetrahydrofuranyl group Except for using 11.71 g of 2,3-dihydrofuran (manufactured by Tokyo Kasei Kogyo Co., Ltd.). In the same manner as in Production Example 2, a solution having a solid content of 20% by mass of a resin (PCX-02e-THF70) in which a phenolic hydroxyl group was protected with a 2-tetrahydrofuranyl group was obtained. The obtained PCX-02e-THF70 has a number average molecular weight of 3716, a weight average molecular weight of 6806, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 70 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 55% of the total number of monomeric units of PCX-02e-THF70.

[Production Example 10] Production of resin (D) (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 in one molecule. 37.6 g of EPICLON (registered trademark) N-770 (phenol novolac type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 188) was charged as a compound having at least two epoxy groups and dissolved at 60 ° C. in a nitrogen gas atmosphere. .. There, 20.1 g (0.65 equivalent to 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Industry Co., Ltd.) as a hydroxybenzoic acid compound, and triphenylphosphine (Tokyo Chemical Industry) 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 second resin (N770OH70) having an epoxy group and a phenolic hydroxyl group. The obtained reactants had a number average molecular weight of 2400 and a weight average molecular weight of 8300.

[Production Example 11] Production of a resin (PCX-02e-THF55) in which a phenolic hydroxyl group is protected by a 2-tetrahydrofuranyl group, except that 9.20 g of 2,3-dihydrofuran (manufactured by Tokyo Kasei Kogyo Co., Ltd.) is used. In the same manner as in Production Example 2, a solution having a solid content of 20% by mass of a resin (PCX-02e-THF55) in which a phenolic hydroxyl group was protected with a 2-tetrahydrofuranyl group was obtained. The obtained PCX-02e-THF55 has a number average molecular weight of 3555, a weight average molecular weight of 6718, a proportion of phenolic hydroxyl groups protected by acid-degradable groups of 55 mol%, and at least one phenolic hydroxyl group is acid-degradable. The number of monomeric units protected by the group was 55% of the total number of monomeric units of PCX-02e-THF55.

Resin blend (A)
As the resin blend (A), PCX-02e-THF40, PCX-02e-nPOE60, PCX-02e-THP30, PCX-02e-iBOE60, PCX-02e-EOE60, PCX-02e-CHOE70, PCX-02e-Boc5, PCX -02e-THF70 and PCX-02e-THF55 were used in the compositions shown in Table 2. The bond-dissociation energy of the acid-decomposable group of the resin calculated by using the quantum chemistry calculation software Gaussian 16 is as follows.

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

Photoacid generator (C)
As the photoacid generator (C), PAG-103 (2- [2- (propylsulfonyloxyimino) thiophene-3 (2H) -iriden] -2- (2-methylphenyl), which is an oxime-based photoacid generator, Acetonitrile, manufactured by BASF, CAS No. 852246-55-0) was used. PAG-103 generates 1-propanesulfonic acid (pKa = -2.8) by light irradiation. The structure of PAG-103 is shown below.

N770OH70 was used as the resin (D) having an epoxy group and a phenolic hydroxyl group.

PCX-02e was used as the third resin (E).

Phloroglucinol was used as the dissolution accelerator (F).

Megafuck (registered trademark) F-559 (fluorine-based surfactant, manufactured by DIC Corporation) was used as a surfactant (leveling agent) (arbitrary component (G)).

A mixed solvent (GBL: PGMEA = 40: 60 (mass ratio)) of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) was used as the solvent (H).

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

[OD value after heating]
A positive 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 80 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.).

[Hole diameter]
A positive photosensitive resin composition was bar-coated on a glass substrate (size 100 mm × 100 mm × 1 mm) so that the dry film thickness was 2.0 μm, and prebaked by heating on a hot plate at 100 ° C. for 1 minute. .. ^{Then, after irradiating ultraviolet rays having an exposure amount of 100 mJ / cm 2} through a photomask having a hole pattern of 10 μm, PEB was performed on a hot plate under the conditions (condition 1) shown in Table 2. Then, an alkaline development treatment was carried out with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds to remove the water adhering with an airbrush, and then the hole diameter was observed with a microscope.
Further, the hole diameter was also observed in the sample in which the PEB condition was changed from the condition 1 as follows.
Condition 2: Temperature of Condition 1 + 5 ° C
Condition 3: Temperature of condition 1 + 10 ° C
Condition 4: Time of Condition 1-30 seconds Condition 5: Time of Condition 1 + 30 seconds 9.5 μm ≤ hole diameter ≤ 10.5 μm was accepted.
[Process stability]
Of the five PEB conditions, the number of conditions that passed the hole diameter evaluation was used as an index of process stability.

(3) Preparation and Evaluation of Positive Photosensitive Resin Compositions [Examples 1 to 8, Reference Examples 1 and Comparative Examples 1 to 9]
The resin blend (A) having the composition shown in Table 2, the resin (D) having an epoxy group and a phenolic hydroxyl group, and the third resin (E) were mixed and dissolved in a mix rotor, and the solution was obtained in Table 2. The colorant (B), the photoacid generator (C), the dissolution accelerator (F), the surfactant (G) and the GBL / PGMEA mixed solvent (H) according to No. 2 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 positive photosensitive resin composition having a solid content concentration of 12% by mass. The mass part of the composition in Table 2 is a solid content conversion value. Table 2 shows the evaluation results of the positive photosensitive resin compositions of Examples 1 to 8, Reference Example 1, and Comparative Examples 1 to 9.

Examples 1 to 8, Reference Examples 1 and Comparative Examples 1 to 9 were able to form holes even though they contained a black colorant. Examples 1 to 8 and Reference Example 1 include a plurality of resins having a plurality of phenolic hydroxyl groups and having at least a part of the plurality of phenolic hydroxyl groups protected by an acid-degradable group and having different acid-degradable properties. , The process stability of PEB could be improved as compared with Comparative Examples 1 to 9 containing a single acid-decomposable resin.

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

Claims

The resin (a1-1) having a plurality of phenolic hydroxyl groups and at least a part of the plurality of phenolic hydroxyl groups being protected by an acid-degradable group (1) and the plurality of phenolic hydroxyl groups. It has a resin (a1-2) in which at least a part of the phenolic hydroxyl groups of the above is protected by an acid-degradable group (2) different from the acid-degradable group (1), and optionally, a plurality of phenolic hydroxyl groups. , A resin (a1-3) in which at least a part of the plurality of phenolic hydroxyl groups is protected with an acid-degradable group (3) different from the acid-degradable groups (1) and (2), and the acid. The degradable groups (1) to (3) are independently group I: tert-butoxycarbonyl group and 1,1-dimethyl-propoxycarbonyl group;
Group II: Group represented by the formula (1) -CR 1 R 2 R 3 (1)
(In the formula (1), R 1 is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R 2 and R 3 are independent of 1 to 10 carbon atoms. A saturated or unsaturated linear or branched hydrocarbon group of 10 or an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or both R 2 and R 3 are alicyclics having 3 to 20 ring members. Structure may be formed);
Group III: 2-tetrahydropyranyl group;
Group IV: 2-tetrahydrofuranyl group;
Group V: Group represented by the formula (2) -CHR 4 - OR 5 (2)
(In the formula (2), R 4 is a linear or branched alkyl group having 1 to 4 carbon atoms, and R 5 is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms);
Resin blend (A1) selected from the group consisting of
At least one colorant (B) selected from the group consisting of black dyes and black pigments, and
A positive photosensitive resin composition containing a photoacid generator (C).
The positive photosensitive resin composition according to claim 1, wherein each of the acid-degradable groups (1) to (3) is selected from a different group from the groups I to IV, V-1 and V-2.
Group I: tert-butoxycarbonyl group and 1,1-dimethyl-propoxycarbonyl group;
Group II: A group represented by the above formula (1);
Group III: 2-tetrahydropyranyl group;
Group IV: 2-tetrahydrofuranyl group;
Group V-1: Group represented by the formula (2-1) -CHR 4 - OR 5 (2-1)
(In the formula (2-1), R 4 is a linear or branched alkyl group having 1 to 4 carbon atoms, and R 5 is a linear or branched alkyl group having 1 to 12 carbon atoms. , An aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms);
Group V-2: 1-cyclohexyloxyethyl group
The resin (a1-1) has the formula (3).

(In the formula (3), R 6 is a hydrogen atom or a methyl group, R 7 is the acid-degradable group (1), l is an integer of 0 to 5, and m is an integer of 0 to 5. Yes, but l + m is an integer from 1 to 5))
The resin (a1-1) has at least one of the monomer units in which m is an integer of 1 or more.
The resin (a1-2) has the formula (4).

(In the formula (4), R 8 is a hydrogen atom or a methyl group, R 9 is the acid-degradable group (2), n is an integer of 0 to 5, and o is an integer of 0 to 5. Yes, where n + o has a monomeric unit represented by an integer of 1 to 5), and the resin (a1-2) has at least the monomeric unit in which o is an integer of 1 or more. Have one
The resin (a1-3) is the formula (5).

(In the formula (5), R 10 is a hydrogen atom or a methyl group, R 11 is the acid-degradable group (3), p is an integer of 0 to 5, and q is an integer of 0 to 5. However, p + q has a monomer unit represented by an integer of 1 to 5), and the resin (a1-3) has at least the monomer unit in which q is an integer of 1 or more. The positive photosensitive resin composition according to any one of claims 1 or 2, which has one.
The resin (a1-1) contains 60 mol% to 100 mol% of the monomer unit represented by the formula (3) with respect to all the monomer units thereof, and the resin (a1-2) contains 60 mol% to 100 mol% of the monomer unit. The monomer unit represented by the formula (4) is contained in an amount of 60 mol% to 100 mol% with respect to all the monomer units, and the resin (a1-3) is based on the total monomer units. The positive photosensitive resin composition according to claim 3, which contains 60 mol% to 100 mol% of the monomer unit represented by the formula (5).
The positive photosensitive resin composition according to any one of claims 1 to 4, wherein the acid-degradable group (1) is a 2-tetrahydrofuranyl group.
The positive photosensitive resin composition according to claim 5, wherein the acid-degradable group (2) is selected from the group V-1 or V-2.
The positive photosensitive resin composition according to claim 6, wherein the acid-degradable group (3) comprises the resin (a1-3) selected from the group I, II, or III.
5 mol% to 95 mol% of the phenolic hydroxyl group of the resin (a1-1) is protected by the acid-degradable group (1), and 5 mol% to 5 mol% of the phenolic hydroxyl group of the resin (a1-2). 95 mol% is protected by the acid-degradable group (2), and 5 mol% to 95 mol% of the phenolic hydroxyl group of the resin (a1-3) is protected by the acid-degradable group (3). The positive photosensitive resin composition according to any one of claims 1 to 7.
Claimed that the mass ratio of the resin (a1-2) to the resin (a1-1) (mass of resin (a1-2) / mass of resin (a1-1)) is 5/95 to 50/33. Item 2. The positive photosensitive resin composition according to any one of Items 1 to 8.
The resins (a1-1), (a1-2) and (a1-3) are represented by the formula (12).

(In the formula (12), R 21 and R 22 are independently hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, and fully or partially fluorinated alkyl groups having 1 to 3 carbon atoms, respectively. Alternatively, it is a halogen atom, and R 23 is a hydrogen atom, a linear group having 1 to 6 carbon atoms, a cyclic alkyl group having 4 to 12 carbon atoms, a phenyl group, or a hydroxy group, and an alkyl group having 1 to 6 carbon atoms. And a phenyl group substituted with at least one selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms.)
The positive photosensitive resin composition according to any one of claims 1 to 9, which is a copolymer having a monomer unit represented by.
The photoacid generator (C) has the formula (13).

(In formula (13), R 24 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, and R 25 and R 26 are independent of each other. It is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, an acetoxy group, a carboxy group, or an alkoxycarbonyl group, and R 25 and R 26 are bonded to each other to have 3 to 10 ring members. The ring structure may be formed, and the ring structure may have a substituent.)
The positive photosensitive resin composition according to any one of claims 1 to 10, which is a compound represented by.
The positive photosensitive resin composition according to any one of claims 1 to 11, which comprises the resin blend (A1) of 30% by mass to 90% by mass based on the total mass of the resin components.
The positive photosensitive resin composition according to any one of claims 1 to 12, which contains 10 parts by mass to 150 parts by mass of the colorant (B) based on a total of 100 parts by mass of the resin components.
The positive photosensitive resin according to any one of claims 1 to 13, which contains 0.1 part by mass to 85 parts by mass of the photoacid generator (C) based on a total of 100 parts by mass of the resin components. Composition.
The positive photosensitive resin composition according to any one of claims 1 to 14, wherein the optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of the film thickness. ..
The positive photosensitive resin composition according to any one of claims 1 to 15, further comprising a resin (D) having an epoxy group and a phenolic hydroxyl group.
An organic EL device partition wall containing a cured product of the positive photosensitive resin composition according to any one of claims 1 to 16.
An organic EL device insulating film containing a cured product of the positive photosensitive resin composition according to any one of claims 1 to 16.
An organic EL device containing a cured product of the positive photosensitive resin composition according to any one of claims 1 to 16.