TWI810578B - Positive photosensitive resin composition, and organic EL element separator - Google Patents

Abstract

The present invention provides a high-sensitivity photosensitive resin composition containing a black colorant with improved process stability. It comprises a resin (a1-1) having multiple phenolic hydroxyl groups, at least a part of which is protected by an acid-decomposable group (1), and having multiple phenolic hydroxyl groups, at least a part of which is protected by an acid decomposable group (1). Resin blend (A1) of resin (a1-2) protected by acid decomposable group (2) different from acid decomposable group (1), at least one selected from the group consisting of black dye and black pigment A positive-type photosensitive resin composition of a colorant (B) and a photoacid generator (C).

Description

Positive type photosensitive resin composition, and organic EL element separator

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

For display devices such as organic EL displays (OLED), in order to improve the display characteristics, a separator material is used for the color pattern spacer in the display area or the edge of the surrounding part of the display area. In the manufacture of an organic EL display device, in order to prevent pixels of organic substances from contacting each other, diaphragms are formed first, and pixels of organic substances are formed between the diaphragms. The diaphragm is generally formed by photolithography using a photosensitive resin composition, and has insulating properties. In detail, the photosensitive resin composition is coated on the substrate using a coating device, and the volatile components are removed by means of heating, etc., and then exposed through a photomask. Next, in the case of negative type, the unexposed part is exposed in the case of positive type. When developing, the exposed part is removed with a developing solution such as an aqueous alkali solution to develop, and the obtained pattern is heat-treated to form a separator (insulating film). Next, organic substances emitting red, green, and blue light are deposited between the separators by inkjet method to form the pixels of the organic EL display device.

In this area, due to miniaturization of display devices and diversification of display contents in recent years, higher performance and higher definition of pixels are required. In order to improve contrast in display devices and improve visibility, attempts have been made to impart light-shielding properties to separator materials using colorants. However, when the separator material has light-shielding properties, the photosensitive resin composition tends to have low sensitivity, and as a result, the exposure time may become longer and the productivity may be lowered. Therefore, higher sensitivity is required for the photosensitive resin composition used for forming the separator material containing the coloring agent.

Patent Document 1 (Japanese Unexamined Patent Application Publication No. 2001-281440) describes that, as a radiation-sensitive resin composition that exhibits higher light-shielding properties by heat treatment after exposure, an alkali-soluble resin and a quinonediazide compound are used. A composition in which titanium black is added to a positive radiation-sensitive resin composition.

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

Patent Document 3 (Japanese Unexamined Patent Application Publication No. 2010-237310) describes a positive-type 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. A composition in which a thermosensitive pigment is added to a permanent resin composition. [Prior Art Literature] [Patent Document]

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

[Problem solved by the invention]

In order to sufficiently improve the light-shielding property of the cured film of the photosensitive resin composition used for forming the colored separator, a considerable amount of coloring agent must be used. When such a large amount of colorant is used, the radiation irradiated on the film of the photosensitive resin composition will be absorbed by the colorant, so the effective intensity of the radiation in the film will be reduced, and the photosensitive resin composition will not be fully exposed. As a result, the pattern Formative reduction.

In the formation of the diaphragm in the organic EL element, it is important that the material forming the diaphragm has high sensitivity from the viewpoint of productivity and the like. However, when a black photosensitive resin composition containing a colorant is used, exposure failure usually occurs under the exposure conditions used, and therefore, for example, the exposure time must be prolonged, which is a cause of lowering productivity. 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 of increasing the sensitivity of the photosensitive resin composition, one that makes the resin composition a chemically amplified system is mentioned. However, there is generally a problem that although the chemical amplification system has high sensitivity, it lacks process stability.

The object of the present invention is to provide a high-sensitivity photosensitive resin composition containing a black colorant with improved process stability. [means to solve the problem]

The present inventors found that when the positive-type photosensitive resin composition is a chemically amplified system containing multiple resins with different acid decomposability, even if it contains a black colorant, it is possible to provide high sensitivity and improved process stability. .

That is, the present invention includes the following aspects. [1] A positive-type photosensitive resin composition comprising: a resin (a1-1) having a plurality of phenolic hydroxyl groups, at least a part of which is protected by an acid-decomposable group (1); A phenolic hydroxyl group, a resin (a1-2) in which at least a part of the plurality of phenolic hydroxyl groups is protected by an acid-decomposable group (2) different from the aforementioned acid-decomposable group (1), and a resin (a1-2) optionally having 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 by an acid-decomposable group (3) different from the acid-decomposable groups (1) and (2), and the acid-decomposable group (1) )~(3) are each independently selected from Group I: tert-butoxycarbonyl and 1,1-dimethyl-propoxycarbonyl; Group II: the group represented by formula (1) -CR ¹ R ² R ³ ( 1) (In formula (1), R ¹ is a saturated or unsaturated linear or branched hydrocarbon group with 1 to 10 carbon atoms, and R ² and R ³ are each independently a saturated hydrocarbon group with 1 to 10 carbon atoms. or an unsaturated straight-chain or branched hydrocarbon group or an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or R ² and R ³ together can form an alicyclic structure with 3 to 20 ring members); Group III: 2-tetrahydropyranyl; Group IV: 2-tetrahydrofuranyl; Group V: the group represented by the formula (2) -CHR ⁴ -OR ⁵ (2) (in the formula (2), R ⁴ is the number of carbon atoms 1~ 4 is a straight-chain or branched-chain alkyl group, ^R5 is a straight-chain, branched-chain or cyclic alkyl group with 1 to 12 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or carbon alkenyl group with 2-12 atoms); the grouped resin blend (A1), at least one colorant (B) and photoacid generator (C) selected from the grouped group of black dyes and black pigments. [2] The aforementioned acid-decomposable groups (1) to (3) are each selected from the positive photosensitive resin composition described in [1] of the different groups of Groups I to IV, V-1 and V-2. Group I: tert-butoxycarbonyl and 1,1-dimethyl-propoxycarbonyl; Group II: the group represented by the aforementioned formula (1); Group III: 2-tetrahydropyranyl; Group IV: 2 -Tetrahydrofuryl; Group V-1: group represented by formula (2-1) -CHR ⁴ -OR ⁵ (2-1) (in formula (2-1), R ⁴ is a straight chain with 1 to 4 carbon atoms A straight-chain or branched-chain alkyl group, ^R5 is a straight-chain or branched-chain alkyl group with 1 to 12 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or an alkene group with 2 to 12 carbon atoms group); Group V-2: 1-cyclohexyloxyethyl[3] The aforementioned resin (a1-1) has the formula (3) (In formula (3), ^R6 is a hydrogen atom or a methyl group, ^R7 is the aforementioned acid decomposable group (1), l is an integer of 0~5, m is an integer of 0~5, but l+m is 1 Integers of ~5)) monomer units, the resin (a1-1) has at least one monomer unit in which m is an integer greater than 1, and the resin (a1-2) has the formula (4) (In formula (4), R ⁸ is a hydrogen atom or a methyl group, R ⁹ is the aforementioned acid decomposable group (2), n is an integer of 0 to 5, o is an integer of 0 to 5, but n+o is 1 ~5 integers), the above-mentioned resin (a1-2) has at least one of the above-mentioned monomer units where o is an integer of 1 or more, and the above-mentioned resin (a1-3) has the formula (5) (In formula (5), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is the aforementioned acid decomposable group (3), p is an integer of 0 to 5, q is an integer of 0 to 5, but p+q is 1 The positive photosensitive resin described in [1] or [2] of the above-mentioned monomer unit represented by an integer of ~5), the above-mentioned resin (a1-3) having at least one monomer unit whose q is an integer of 1 or more Composition. [4] The aforementioned resin (a1-1) contains 60 mol % to 100 mol % of the aforementioned monomer unit represented by formula (3) relative to the total monomer units, and the aforementioned resin (a1-2) contains For the full monomer unit, it contains 60 mol % to 100 mol % of the aforementioned monomer unit shown in formula (4), and the aforementioned resin (a1-3) contains the formula (5 ) The positive-type photosensitive resin composition described in [3] with 60 mol% to 100 mol% of the aforementioned monomer units. [5] The positive-type photosensitive resin composition described in any one of [1] to [4] in which the acid-decomposable group (1) is a 2-tetrahydrofuryl group. [6] The acid-decomposable group (2) is selected from the positive-type photosensitive resin composition described in [5] of the aforementioned group V-1 or V-2. [7] The positive-type photosensitive resin composition described in [6] containing the above-mentioned acid-decomposable group (3) containing the above-mentioned resin (a1-3) selected from the group I, II or III. [8] 5 mol% to 95 mol% of the phenolic hydroxyl groups of the aforementioned resin (a1-1) are protected by the aforementioned acid decomposable group (1), and 5 mol% of the phenolic hydroxyl groups of the aforementioned resin (a1-2) Mole%~95 mole% is protected by the aforementioned acid decomposable group (2), and 5 mole%~95 mole% of the phenolic hydroxyl group of the aforementioned resin (a1-3) is protected by the aforementioned acid decomposable group (3) The positive-type photosensitive resin composition described in any one of [1] to [7] is claimed. [9] The mass ratio of the aforementioned resin (a1-2) to the aforementioned resin (a1-1) (mass of resin (a1-2)/mass of resin (a1-1)) is [ The positive-type photosensitive resin composition described in any one of 1] to [8]. [10] The aforementioned resins (a1-1), (a1-2) and (a1-3) have the formula (12) (In formula (12), R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group with 1 to 3 carbon atoms, or a halogen atom, R ²³ is a hydrogen atom, a straight chain with 1 to 6 carbon atoms or a cyclic alkyl group with 4 to 12 carbon atoms, or a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms, and a group with 1 to 2 carbon atoms The positive-type photosensitive resin composition described in any one of [1] to [9] of a copolymer of monomer units represented by at least one substituted phenyl group represented by ~6 alkoxy groups. [11] The aforementioned 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, R ²⁵ and R ²⁶ are each independently substituted or unsubstituted Substituted aryl, substituted or unsubstituted heterocyclic group, cyano group, acetyloxy group, carboxyl group, or alkoxycarbonyl group, R ²⁵ and R ²⁶ are bonded to form a ring structure with 3 to 10 ring members, the The ring structure may have a substituent) The positive-type photosensitive resin composition described in any one of [1] to [10] of the compound shown. [12] The positive photosensitive resin composition described in any one of [1] to [11] of the above-mentioned resin blend (A1) containing 30% by mass to 90% by mass based on the total mass of the resin components . [13] The positive-type photosensitive resin composition described in any one of [1] to [12] of the above-mentioned colorant (B) containing 10 to 150 parts by mass based on a total of 100 parts by mass of the resin components . [14] The positive-type photosensitive resin described in any one of [1] to [13] of the photoacid generator (C) containing 0.1 to 85 parts by mass based on 100 parts by mass of the resin components in total Composition. [15] The positive photosensitive resin composition described in any one of [1] to [14] in which the optical density (OD value) of the cured film of the aforementioned positive photosensitive resin composition is 0.5 or more per film thickness of 1 μm . [16] The positive-type photosensitive resin composition described in any one of [1] to [15] that further contains a resin (D) having an epoxy group and a phenolic hydroxyl group. [17] An organic EL element separator comprising a cured product of the positive photosensitive resin composition described in any one of [1] to [16]. [18] An organic EL device insulating film comprising a cured product of the positive photosensitive resin composition described in any one of [1] to [16]. [19] An organic EL device comprising a cured product of the positive photosensitive resin composition described in any one of [1] to [16]. [Effect of Invention]

According to the present invention, a high-sensitivity photosensitive resin composition containing a black colorant with improved process stability can be provided.

[Types of implementing the invention]

The present invention will be described in detail below.

The so-called "alkali solubility" and "solubility in aqueous alkali solution" disclosed in the present invention mean that the positive photosensitive resin composition or its components, or the film or cured film of the positive photosensitive resin composition can be dissolved in an aqueous alkali solution, such as It means to dissolve in 2.38% by mass of tetramethylammonium hydroxide aqueous solution. The "alkali-soluble functional group" means a group that imparts alkali solubility to the positive photosensitive resin composition or its component, or the coating or cured coating of the positive photosensitive resin composition. As an alkali-soluble functional group, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group, a mercapto group etc. are mentioned, for example.

The "acid-decomposable group" disclosed in the present invention means a group that generates an alkali-soluble functional group after decomposition (deprotection) by heating if necessary in the presence of an acid.

The "radically polymerizable functional group" disclosed in the present invention means one or plural ethylenically unsaturated groups.

The "monomer unit" disclosed in the present invention means a unit derived from a radically polymerizable monomer.

The so-called "(meth)acrylic acid" disclosed in the present invention means acrylic acid or methacrylic acid, the so-called "(meth)acrylate" means acrylate or methacrylate, and the so-called "(meth)acryl" means acrylic acid. acyl or methacryl.

For the disclosure of the present invention, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin or polymer represent the standard polystyrene conversion value measured by gel permeation chromatography (GPC, gel permeation chromatography). mean.

The "resin component" disclosed in the present invention means a resin blend (A1), a resin (D) having an epoxy group and a phenolic hydroxyl group, and a third resin (E).

The positive-type photosensitive resin composition according to one embodiment includes: a resin (a1-1) having multiple phenolic hydroxyl groups, at least a part of which is protected by an acid-decomposable group (1), and Resin blend (A1) of a resin (a1-2) having a plurality of phenolic hydroxyl groups, at least a part of which is protected by an acid-decomposable group (2) different from the aforementioned acid-decomposable group (1) ), at least one colorant (B) and photoacid generator (C) selected from the group consisting of black dye and black pigment.

[Resin blend (A1)] The resin blend (A1) contains two or more resins having multiple phenolic hydroxyl groups, at least a part of which is protected by different acid-decomposable groups selected from specific acid-decomposable groups. When the resin blend (A1) contains two resins having multiple phenolic hydroxyl groups, at least a part of which are protected by different acid-decomposable groups selected from specific acid-decomposable groups, for For convenience, the respective resins are simply 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 to the case of containing 4 or more types. For example, when 4 types are contained, it is called resin (a1-1), (a1-2), (a1-3) and (a1-4), and when 5 types are contained, it is called resin (a1-1). -1), (a1-2), (a1-3), (a1-4) and (a1-5) are different from each other in acid decomposable groups. These resins are collectively referred to as resin (a1). The phenolic hydroxyl group is an alkali-soluble functional group, and by protecting this part with an acid-decomposable group, the alkali solubility of the resin (a1) before exposure can be suppressed. The resin (a1) may have an alkali-soluble functional group other than the phenolic hydroxyl group, and these alkali-soluble functional groups may be protected by an acid-decomposable group similarly to the phenolic hydroxyl group. In the presence of acid generated during exposure, if necessary, post-exposure bake (PEB, post exposure bake) can be used to promote the decomposition (deprotection) of acid-decomposable groups and regenerate phenolic hydroxyl groups. Thereby, the alkali dissolution of resin (a1) can be accelerated|stimulated in the exposure part at the time of image development. The resin (a1) may have, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group, a mercapto group, etc. in addition to an alkali-soluble functional group other than a phenolic hydroxyl group.

<Protection of phenolic hydroxyl groups by acid-decomposable groups> Various resins (a1) contained in the resin blend (A1) (for example, resins (a1-1), (a1-2)) can be obtained by having A part of the phenolic hydroxyl groups of the base resin (a _b 1) having plural phenolic hydroxyl groups is protected with an acid-decomposable group, and the acid-decomposable groups of each resin (a1) are different. The resin (a1) having a phenolic hydroxyl group protected with an acid-decomposable group has a partial structure of Ar-OR, where Ar represents an aromatic ring derived from phenol, and R represents an acid-decomposable group.

The acid-decomposable group is a group that can generate an alkali-soluble functional group after decomposition (deprotection) by heating if necessary in the presence of an acid. The acid-decomposable group is selected from the groups described in the following groups I to V. Group I: tert-butoxycarbonyl and 1,1-dimethyl-propoxycarbonyl; Group II: the group represented by formula (1) -CR ¹ R ² R ³ (1) (in formula (1), ^R1 is a saturated or unsaturated linear or branched hydrocarbon group with 1 to 10 carbon atoms, ^R2 and ^R3 are each independently a saturated or unsaturated linear or branched hydrocarbon group with 1 to 10 carbon atoms A chain hydrocarbon group or an alicyclic hydrocarbon group with 3 to 20 carbon atoms, or R ² and R ³ together can form an alicyclic structure with 3 to 20 ring members); Group III: 2-tetrahydropyranyl; Group IV: 2-tetrahydrofuryl; group V: group represented by formula (2) -CHR ⁴ -OR ⁵ (2) (in formula (2), R ⁴ is a straight chain or branched chain with 1 to 4 carbon atoms ^R5 is a linear, branched or cyclic alkyl group with 1 to 12 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or an alkenyl group with 2 to 12 carbon atoms) Therefore, the easiness of deprotection of acid-decomposable groups by acid is different, so by combining resins protected with different acid-decomposable groups, it is possible to coexist with the exposed part as the center to rapidly increase the alkali solubility. And ease the performance of the solubility part. Therefore, the process window of PEB conditions can be broadened. These acid-decomposable groups can be used individually or in combination of 2 or more types. When various resins (for example, resins (a1-1) and (a1-2)) each have a plurality of acid-decomposable groups, at least one acid-decomposable group may be different from each other. In one embodiment, each resin (a1) has a single acid-decomposable group. The 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group and the group represented by the formula (2) can form an acetal structure together with the oxygen atom from the phenolic hydroxyl group.

In formula (1), as R ¹ , R ² and R ³ , saturated or unsaturated linear or branched hydrocarbon groups with 1 to 10 carbon atoms include methyl, ethyl, n- Saturated hydrocarbon groups such as propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, and unsaturated hydrocarbon groups such as vinyl, propenyl, butenyl, ethynyl, and propynyl. The alicyclic hydrocarbon group having 3 to ²⁰ carbon atoms represented by R ^and R includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, Saturated monocyclic hydrocarbon groups such as cyclododecyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, cyclodecenyl and other unsaturated monocyclic hydrocarbon groups, bicyclic [2.2 .1] heptenyl, bicyclic [2.2.2] octenyl, tricyclo [3.3.1.1 ^3,7 ] decyl and other saturated polycyclic hydrocarbon groups, bicyclic [2.2.1] heptenyl, bicyclic [ 2.2.2] Unsaturated polycyclic hydrocarbon groups such as octenyl. As the alicyclic structure with 3 to 20 ring members formed jointly by R ^{and R} , monocyclic cycloalkane structures such as cyclopropane structure, cyclobutane structure, cyclopentane structure and cyclohexane structure, Polycyclic cycloalkane structures such as norbornane structure and adamantane structure. As a group represented by formula (2), 1-alkoxyalkyl group is mentioned, for example. Examples of 1-alkoxyalkyl include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1- n-butoxyethyl, 1-isobutoxyethyl, 1-(2-ethylhexyloxy)ethyl and 1-cyclohexyloxyethyl, with 1-n-propoxyethyl better.

The acid-decomposable groups of the plurality of resins (a1) contained in the resin blend (A1) are preferably selected from the aforementioned groups I~IV, and different groups selected from the following groups V-1 and V-2. Group V-1: the 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 chain with 1 to 4 carbon atoms R ^is a linear or branched alkyl group with 1 to 12 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or an alkenyl group with 2 to 12 carbon atoms); Group V -2: 1-cyclohexyloxyethyl

Groups I and II are groups that are empirically difficult to deprotect compared to groups in which oxygen atoms derived from phenolic hydroxyl groups jointly form an acetal structure. The inventors of the present invention calculated the activation energy of deacetalization of phenol protected with an acid-decomposable group when examining the ease of deprotection of a group that forms an acetal structure together with an oxygen atom derived from a phenolic hydroxyl group , and the simulation results obtained from the bond dissociation energy between (phenolic oxygen)-(acid decomposable carbon), it is found that the activation energy of deacetalization is related to the above bond dissociation energy, and the ease of deprotection is not The steric effect is controlled by the acid-decomposing group, which is controlled by the electronic effect on the reaction center. Groups III, IV, V-1 and V-2 are classified according to the easiness of deprotection of acid decomposable groups based on this knowledge. The larger the group number, the easier it is to deprotect.

In view of the fact that a high-sensitivity positive-type photosensitive resin composition can be obtained even at a low exposure dose, at least one of the acid-decomposable groups of the resin (a1) is selected from the group that forms an acetal together with an oxygen atom derived from a phenolic hydroxyl group. Group III, IV or V of the structure is preferred. The acetal structure is a carboxyl group protected by an alkyl group, that is, it is easier to deprotect than the ester structure, and can be deprotected by a weak photoacid generator, so it is easier to control the deprotection of the positive photosensitive resin composition reaction. In addition, since the alkali solubility of the deprotected carboxyl group is too high, the alkali dissolution retarding effect of the blended other resin cannot be sufficiently exhibited. Among them, the 2-tetrahydrofuryl group is also excellent in pattern formation, and the acid-decomposable group (1) of the resin (a1-1) is used as the 2-tetrahydrofuryl group, and the acid-decomposable group of the other resin (a1) is selected from Group III. Or V, even if it contains a black colorant, it is possible to obtain a positive-type photosensitive resin composition that provides excellent pattern forming properties and improved PEB process stability.

From the viewpoint of the process stability of PEB, the resin blend (A1) preferably contains the resin (a1-1) protected with 2-tetrahydrofuryl and the acid selected from group V-1 or V-2 A resin (a1-2) protected by a decomposable group (2), more preferably a resin (a1-1) protected by a 2-tetrahydrofuryl group and an acid decomposable group selected from group V-1 or V-2 (2) A protected resin (a1-2) and a resin (a1-3) protected with an acid-decomposable group (3) selected from Group I, II or III.

The protection reaction of the phenolic hydroxyl group can be carried out under known conditions using a general protecting agent. For example, in solvents such as no solvent or toluene, hexane, etc., the base resin (a _b 1) of the resin (a1) and the protective agent are reacted in the presence of acid or alkali at a reaction temperature of -20~50°C, Resin (a1) can be obtained.

As a protecting agent, a known protecting agent capable of protecting a phenolic hydroxyl group can be used. As the protecting agent, for example, isobutylene can be used when the acid-decomposable group is tert-butyl, and di-tert-butyl dicarbonate can be used when tert-butoxycarbonyl is used. When the acid-decomposable group is 1-ethoxyethyl, ethyl vinyl ether can be used, when 1-n-propoxyethyl can be used, n-propyl vinyl ether can be used, and when 2-tetrahydrofuryl can be used When 2,3-dihydrofuran and 2-tetrahydropyranyl are used, 3,4-dihydro-2H-pyran and 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. A salt of an organic acid, for example, a pyridinium salt of p-toluenesulfonic acid, etc. can also be used as an acid supply source. Examples of the base include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate, pyridine, and N,N-dimethyl-4-amine. Amine compounds such as pyridine, triethylamine, and diisopropylethylamine.

In another embodiment, after protecting the phenolic hydroxyl group of the radically polymerizable monomer having a phenolic hydroxyl group with an acid-decomposable group, the free radical having a phenolic hydroxyl group protected with an acid-decomposable The resin (a1) can be obtained by polymerizing or copolymerizing a polymerizable monomer and optionally other radical polymerizable monomers. The protection of the phenolic hydroxyl group of the radically polymerizable monomer which has a phenolic hydroxyl group can be performed by the same method as the protection of the phenolic hydroxyl group of base resin (a _b1 ).

<Base resin (a _b 1)> As the base resin (a _b 1) of the resin (a1), a homopolymer or a copolymer of a radically polymerizable monomer having a phenolic hydroxyl group can be used. These base resins (a _b 1) can be used alone or in combination of two or more. The base resin (a _b 1) may further have a radical polymerizable functional group. As a radical polymerizable functional group, a (meth)acryloxy group, an allyl group, and a methallyl group are mentioned.

<Alkaline aqueous solution soluble copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer: base resin (a _b 1-1)> The base of the resin (a1) in one embodiment Resin (a _b 1) is an alkali aqueous solution soluble copolymer of free radical polymerizable monomers having phenolic hydroxyl groups and other free radical polymerizable monomers: in base resin (a _b 1-1) (a _b 1-1 ) has a plurality of phenolic hydroxyl groups. In this embodiment, the resin (a1) is one in which at least a part of the plurality of phenolic hydroxyl groups of the base resin ( _ab 1-1) is protected by an acid-decomposable group. The base resin (a _b 1-1) may further have alkali-soluble functional groups other than phenolic hydroxyl groups, such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, acid anhydride groups or mercapto groups. At least one of the radical polymerizable monomer having a phenolic hydroxyl group and other radical polymerizable monomers preferably has CH ₂ =CHCO- or CH ₂ =C(CH ₃ )CO- as a polymerizable functional group. The other radical polymerizable monomer may have as a polymerizable functional group, for example, CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CHCO-, CH ₂ =C(CH ₃ )CO Radical polymerizable functional groups such as -, -OC-CH=CH-CO- are preferred.

The base resin (a _b 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, the phenolic hydroxyl group can be added to the above-mentioned copolymer. Examples of the radically polymerizable monomer having a phenolic hydroxyl group include 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzyl acrylamide, 4-hydroxyphenyl Acrylamide, 4-hydroxystyrene and 4-hydroxyphenylmaleimide, etc. Examples of other radically polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene, propylene Ether compounds of vinyl alcohol such as amide, acrylonitrile, vinyl-n-butyl ether, alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl ( Meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2 N -Substituted maleimide, maleic anhydride, maleic acid monoester, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-fluoro(meth)acrylic acid , β-styrene (meth)acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid , itaconic acid, crotonic acid, propiolic acid, 3-maleimide propionic acid, 4-maleimide butyric acid, 6-maleimide hexane acid, etc. From the standpoint of heat resistance, etc., the base resin (a _b 1-1) has one or more rings such as alicyclic structure, aromatic structure, polycyclic structure, inorganic ring structure, and heterocyclic structure. The formula structure is better.

The radically polymerizable monomer having a phenolic hydroxyl group used as a raw material of the base resin ( _ab 1-1) preferably forms a monomer unit represented by formula (14). (In the formula (14), R ²⁷ is a hydrogen atom or a methyl group, and a is an integer of 1 to 5) a is preferably an integer of 1 to 3, and 1 is more preferred. As a radically polymerizable monomer having such a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is particularly preferable.

As other radically polymerizable monomers, those forming monomer units represented by formula (12) are preferable. (In formula (12), R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group with 1 to 3 carbon atoms, or a halogen atom, R ²³ is a hydrogen atom, a straight chain with 1 to 6 carbon atoms or a cyclic alkyl group with 4 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms, and an alkyl group with 1 to 6 carbon atoms. A phenyl group substituted by at least one kind of alkoxy group consisting of 6) In formula (12), R ²¹ and R ²² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ^R23 is a cyclic alkyl group with 4 to 12 carbon atoms, a phenyl group, or at least one group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms, and an alkoxy group with 1 to 6 carbon atoms. A substituted phenyl group is preferred. As such other radically polymerizable monomers, phenylmaleimide and cyclohexylmaleimide are particularly preferable.

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

For the base resin (a _b 1-1), 4-hydroxyphenyl methacrylate was used as a radically polymerizable monomer having a phenolic hydroxyl group, and phenylmaleimide was used as another radically polymerizable monomer. Amines or cyclohexylmaleimide are particularly preferred. By radically polymerizing resins using such radically polymerizable monomers, shape retention and developability can be improved, and outgassing can also be reduced.

As the polymerization initiator when the base resin ( _ab 1-1) is produced by radical polymerization, it is not limited to the following, but 2,2'-azobisisobutyronitrile, 2,2 '-Azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid ), 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN), 1,1'-azobis(1-acetyloxy-1-phenylethane), di Azo polymerization such as methyl-2,2'-azobis(2-methylbutyrate), dimethyl-2,2'-azobis(2,4-dimethylvalerate) Initiator, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, tert-butyl cumene peroxide, di-tert-butyl Peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and other peroxide polymerization initiators with a 10-hour half-life temperature of 100~170°C, or benzene peroxide Peroxide polymerization initiators such as formyl, lauryl peroxide, 1,1'-bis(tert-butylperoxy)cyclohexane, tert-butylperoxypivalate, etc. The amount of the polymerization initiator used is generally 0.01 mass part or more, 0.05 mass part or more, 0.5 mass part or more, 40 mass parts or less, 20 mass parts or less or 15 mass parts relative to the total amount of 100 mass parts of the radical polymerizable monomer. Parts by mass or less are preferred.

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

The weight average molecular weight (Mw) of the base resin (a _b 1-1) may be 3000-80000, preferably 4000-70000, more preferably 5000-60000. When the number average molecular weight (Mn) is 1,000 to 30,000, preferably 1,500 to 25,000, more preferably 2,000 to 20,000. The polydispersity (Mw/Mn) can be 1.0~3.5, preferably 1.1~3.0, more preferably 1.2~2.8. When the weight average molecular weight, the number average molecular weight, and the degree of polydispersity are set within the above-mentioned ranges, a positive-type photosensitive resin composition excellent in alkali solubility and developability can be obtained.

In one embodiment, the 5 mol % to 95 mol % of each phenolic hydroxyl group contained in the various resins (resin (a1-1), (a1-2), etc.) of the resin blend (A1), Preferably it is 10 mol%~80 mol%, more preferably 25 mol%~70 mol% is protected by an acid decomposable group. When the proportion of phenolic hydroxyl groups protected by acid-decomposable groups is set at 5 mol % or more, the chemical amplification function can be imparted to the photosensitive resin composition to achieve high sensitivity. When the proportion of phenolic hydroxyl groups protected by acid-decomposable groups is set below 95 mol%, the remaining amount of unreacted acid-decomposable groups can be reduced, and high sensitivity can be achieved to improve the solubility of the exposed part. The proportion of phenolic hydroxyl groups protected by acid-decomposable groups was calculated from the weight loss (%) of resins (a1-1) and (a1-2) in thermogravimetric differential thermal analysis (TG/DTA).

In one embodiment, the resin (a1) is an alkali aqueous solution-soluble homopolymer of a radically polymerizable monomer having a plurality of phenolic hydroxyl groups, wherein at least a part of the plurality of phenolic hydroxyl groups is protected with an acid-decomposable group. , or have multiple phenolic hydroxyl groups, at least a part of the multiple phenolic hydroxyl groups is protected by an acid-decomposable group, and an alkali aqueous solution soluble copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and other radically polymerizable monomers. The latter resin is a copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and other radically polymerizable monomers as the base resin (a _b 1-1), and the base resin (a _b 1-1) has a plurality of phenols Hydroxyl groups, at least a part of these phenolic hydroxyl groups are protected by acid decomposable groups.

For this embodiment, the resin (a1-1) has monomer units represented by formula (3), (In formula (3), ^R6 is a hydrogen atom or a methyl group, ^R7 is an acid decomposable group (1), l is an integer of 0~5, m is an integer of 0~5, but l+m is 1~5 Integer of 5), the resin (a1-1) preferably has at least one of the above-mentioned monomer units in which m is an integer of 1 or more. The acid decomposable group (1) of ^R7 is preferably selected from the acid decomposable groups contained in the aforementioned acid decomposable groups I~V.

For this embodiment, resin (a1-2) has a monomer unit shown in formula (4), (In formula (4), R ⁸ is a hydrogen atom or a methyl group, R ⁹ is an acid decomposable group (2), n is an integer of 0 to 5, o is an integer of 0 to 5, but n+o is 1 to 5 Integer of 5) The resin (a1-2) preferably has at least one monomer unit in which o is an integer of 1 or more. The acid decomposable group (2) of ^R9 is preferably selected from the acid decomposable groups contained in the aforementioned acid decomposable groups I~V. However, the acid-decomposable group (2) of ^R9 is different from the acid-decomposable group (1) of ^R7 .

For this embodiment, any resin (a1-3) has a monomer unit represented by formula (5), (In formula (5), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is an acid decomposable group (3), p is an integer of 0 to 5, and q is an integer of 0 to 5, but p+q is 1 to 5 Integer of 5), resin (a1-3) preferably has at least one monomer unit whose 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 aforementioned acid-decomposable groups I to V. However, the acid-decomposable group (3) of R ¹¹ is different from the acid-decomposable group (1) of R ⁷ and the acid-decomposable group (2) of R ⁸ .

The resin (a1) preferably has a monomer unit represented by formula (12), (In formula (12), R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group with 1 to 3 carbon atoms, or a halogen atom, R ²³ is a hydrogen atom, a straight chain with 1 to 6 carbon atoms or a cyclic alkyl group with 4 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms, and an alkyl group with 1 to 6 carbon atoms. A phenyl group substituted with at least one kind of alkoxy group consisting of 6). Preferred examples of R ²¹ , R ²² and R ²³ are the same as above.

In one embodiment, the resin (a1-1) contains 60 mol% to 100 mol% of the monomer units shown in formula (3) relative to the total monomer units of the resin (a1-1), and 70 mol% mol%~100 mol%, preferably 80 mol%~100 mol%. When the monomer unit represented by the formula (3) is set at 60 mole % or more, the alkali solubility difference between the exposed part and the unexposed part is increased, and the sensitivity can be increased. When the monomer unit represented by the formula (3) is set at 100 mole % or less, the balance between heat resistance and alkali solubility can be maintained. Under the same viewpoint, in one embodiment, the resin (a1-2) contains 60 mol% to 100 mol% of the monomer unit represented by formula (4) relative to the total monomer units of the resin (a1-2) , preferably 70 mol % to 100 mol %, more preferably 80 mol % to 100 mol %. Under the same viewpoint, in one of the embodiments, the resin (a1-3) contains 60 mol % to 100 mol of the monomer unit represented by formula (5) relative to the total monomer units of the resin (a1-3) %, preferably 70 mol % to 100 mol %, more preferably 80 mol % to 100 mol %.

In one embodiment, a monomer unit represented by formula (3) and m is an integer greater than or equal to 1, that is, a monomer unit represented by formula (3) in which at least one phenolic hydroxyl group is protected by an acid decomposable group (1). The number of monomer units is 5%~95% of the number of all monomer units of the resin (a1-1), preferably 15%~70%, more preferably 25%~60%. If the ratio of the above-mentioned monomer units is set at 5% or more, a chemical amplification function can be imparted to the photosensitive resin composition to achieve high sensitivity. If the proportion of the above-mentioned monomer units is set below 95%, the residual amount of unreacted acid-decomposable groups can be reduced, and high sensitivity can be achieved to improve the solubility of the exposed part. Under the same viewpoint, in one embodiment, the monomer unit represented by formula (4) and o is an integer greater than 1, that is, the formula ( 4) The number of monomer units shown is 5%~95% of the total number of monomer units in the resin (a1-2), preferably 15%~70%, more preferably 25%~60%. Under the same viewpoint, in one embodiment, the monomer unit represented by formula (5) and q is an integer greater than 1, that is, the formula ( 5) The number of monomer units shown is 5%~95% of the total number of monomer units in the resin (a1-3), preferably 15%~70%, more preferably 25%~60%.

In one embodiment, the resin blend (A1) is used as a reference, preferably containing 33-95% by mass of the resin (a1-1). Preferably it is 40-90 mass %, More preferably, it is 50-85 mass %. Taking the resin blend (A1) as a standard, when the resin (a1-1) is contained in an amount of 33-95% by mass, the process stability of PEB can be improved.

In one embodiment, the resin blend (A1) is used as a reference, preferably containing 5-50% by mass of the resin (a1-2). Preferably it is 10-40 mass %, More preferably, it is 15-35 mass %. Taking the resin blend (A1) as a standard, when the resin (a1-2) is contained in an amount of 5-50% by mass, the process stability of PEB can be improved.

In one embodiment, the resin blend (A1) is used as a reference, preferably containing 0-32% by mass of the resin (a1-3). Preferably it is 5-30 mass %, More preferably, it is 10-25 mass %. Using the resin blend (A1) as a standard, the process stability of PEB can be improved by containing the resin (a1-3) at 32% by mass or less.

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

In one embodiment, the mass ratio of resin (a1-3) to resin (a1-1) (mass of resin (a1-3)/mass of resin (a1-1)) is 0/100~32/33 5/95~30/40 is better, and 10/90~25/50 is better. When the mass ratio of resin (a1-3) to resin (a1-1) is set below 32/33, the process stability of PEB can be improved.

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

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

In one embodiment, the positive-type photosensitive resin composition contains 10-80 parts by mass of the resin blend (A1) based on 100 parts by mass of the solid content, preferably 15-60 parts by mass. , preferably 20 parts by mass 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 provided to the photosensitive resin composition to achieve high sensitivity. When the content of the resin blend (A1) is set at 80 parts by mass or less based on 100 parts by mass of the solid content, the remaining amount of unreacted acid-decomposable groups can be reduced and the solubility of the exposed part can be improved. Sensitivity. The so-called "solid content" of the embodiment containing the resin blend (A1) means that the resin blend (A1), the colorant (B), the photoacid generator (C) and any epoxy group and Resin (D) with phenolic hydroxyl group, third resin (E), dissolution accelerator (F) and optional component (G), the total mass of components other than the solvent (H).

In one embodiment, the positive-type photosensitive resin composition contains 30% to 90% by mass of the resin blend (A1) based on the total mass of the resin components, with a range of 40% to 80% by mass. Better, preferably 45% by mass to 65% by mass. When the content of the resin blend (A1) is set to 30% by mass or more, a chemical amplification function can be imparted to the photosensitive resin composition to achieve high sensitivity. When the content of the resin blend (A1) is set to 90% by mass or less, high sensitivity that improves the solubility of the exposed portion can be realized.

[Color (B)] The coloring agent (B) is at least 1 sort(s) chosen from the group which consists of a black dye and a black pigment. A black dye and a black pigment can also be used together. For example, the visibility of display devices, such as an organic EL display, can be improved by forming a black spacer in an organic EL element using the positive photosensitive resin composition containing a coloring agent (B).

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

A black pigment can be used as the colorant (B). Examples of the black pigment include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene-based pigments, lactam-based pigments, and the like. These black pigments can be used for surface treatment. Examples of commercially available perylene-based pigments include K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34 manufactured by BASF Corporation. Irgaphor (registered trademark) black S0100CF manufactured by BASF Corporation is mentioned as an example of a lactamide pigment on the market. 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 because of its high light-shielding properties.

In one embodiment, the positive-type photosensitive resin composition contains 10 to 150 parts by mass of the colorant (B), preferably 30 to 100 parts by mass, based on a total of 100 parts by mass of the resin components. , preferably 40 parts by mass to 70 parts by mass. When the content of the coloring agent (B) is set to 10 parts by mass or more based on the above-mentioned total of 100 parts by mass, the light-shielding properties of the film after firing can be maintained. When the content of the coloring agent (B) is set to 150 parts by mass or less based on the above-mentioned total of 100 parts by mass, the film can be colored without impairing 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-ray, and electron beam. The photoacid generator (C) can accelerate the decomposition of the acid-decomposable groups of the resin (a1) to regenerate the phenolic hydroxyl groups, and increase the alkali solubility of the resin (a1). Moreover, when the acid generated by the photo-acid generator (C) exists in the part irradiated with radiation, the resin of this part can be easily dissolved in aqueous alkali solution together with an acid. As a result, patterns with high resolution can be formed at high sensitivity even at low exposure. A photoacid generator (C) can be used individually or in combination of 2 or more types.

The photoacid generator (C) is preferably one capable of generating an acid with a pKa of 4 or less by irradiation with radiation, more preferably an acid with a pKa of 3 or less. In this way, the photoacid generator (C) can produce|generate the acid which has the decomposing ability of an acid-decomposable group.

The photoacid generator (C) is preferably one capable of generating an acid having a pKa of -15 or higher by irradiation with radiation, more preferably an acid having a pKa of -5 or higher. Such a photoacid generator (C) does not undergo excessive ring-opening polymerization of the epoxy group of the resin (D) having an epoxy group and a phenolic hydroxyl group described later during exposure and post-exposure heat treatment (PEB), and It can maintain the alkali solubility of the resin (D) during image development.

Examples of the photoacid generator (C) include onium salts such as trichloromethyl-s-triazine compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, quaternary ammonium salts, Azomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound in terms of high sensitivity and high insulation. The acid generated from the oxime sulfonate compound has the appropriate decomposing ability to the acid-decomposable group forming an acetal structure together with the oxygen atom derived from the phenolic hydroxyl group, so when these are used in combination, a more excellent Process stability of PEB.

As an oxime sulfonate compound, the compound represented by formula (13) is mentioned, for example.

For 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 each independently substituted or unsubstituted Aryl, substituted or unsubstituted heterocyclic, cyano, acetyloxy, carboxyl or alkoxycarbonyl. R ²⁵ and R ²⁶ can be bonded to form a ring structure with 3-10 ring members, and the ring structure may also have a substituent.

As the substituted or unsubstituted alkyl group of ^R24 , for example, straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms can be mentioned, preferably methyl, ethyl or n-propyl. As the substituted or unsubstituted alkoxy group of ^R24 , for example, straight-chain or branched-chain alkoxy groups having 1 to 5 carbon atoms can be mentioned, preferably methoxy or ethoxy. Examples of substituents for the alkyl and alkoxy groups of ^R24 include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), cyano groups, nitro groups, aryl groups with 6 to 20 carbon atoms, Alkoxy with 1 to 10 carbon atoms and cycloalkyl with 3 to 10 carbon atoms. As the substituted or unsubstituted aryl group of ^R24 , for example, an aryl group having 6 to 20 carbon atoms can be mentioned, preferably phenyl, 4-methylphenyl or naphthyl. As the substituent of the aryl group of ^R24 , 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) . Examples of the halogen atom for ^R24 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As the unsubstituted aryl group of ^R25 and ^R26 , for example, an aryl group having 6 to 20 carbon atoms can be mentioned, preferably a phenyl group or a naphthyl group. Examples of unsubstituted heterocyclic groups for R ²⁵ and R ²⁶ include 2-benzimidazolyl, 2-benzoxazolyl, 2-benzothiazolyl and 2-indolyl. As the substituents of the aryl and heterocyclic groups of ^R25 and ^R26 , for example, alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, and halogen atoms (fluorine atom, chlorine atom, etc.) , bromine atom and iodine atom). Examples of the alkoxycarbonyl group for R ²⁵ and R ²⁶ include ethoxycarbonyl. R ²⁵ is cyano, carboxyl or alkoxycarbonyl, especially cyano, and R ²⁶ is substituted aryl, especially 4-methoxyphenyl.

Examples of the oxime sulfonate compound having a ring structure in which R ²⁵ and R ²⁶ are bonded include an oxime sulfonate compound represented by formula (13a).

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

As the alkyl group of ^R37 , for example, a linear or branched chain alkyl group having 1 to 10 carbon atoms can be mentioned, preferably a methyl group, an ethyl group or an n-propyl group. The alkoxy group of ^R37 includes, for example, straight-chain or branched-chain alkoxy groups having 1 to 5 carbon atoms, preferably methoxy or ethoxy. Examples of the halogen atom for ^R37 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a fluorine atom. d is preferably 0 or 1.

Examples of oxime sulfonate compounds include (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imine)acetonitrile , 2-[2-(propylsulfonyloxyimine)thiophene-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, 2-[2-(4-methylbenzene Sulfonyloxyimine)thiophene-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile and the like.

In one embodiment, the positive-type photosensitive resin composition contains 0.1 to 85 parts by mass of the photoacid generator (C) based on a total of 100 parts by mass of the resin components, and 5 to 40 parts by mass Parts are better, preferably 10 parts by mass to 30 parts by mass. When the content of the photoacid generator (C) is set to 0.1 parts by mass or more based on the above-mentioned total of 100 parts by mass, high sensitivity can be realized. When the content of the photoacid generator (C) is set to 85 parts by mass or less based on 100 parts by mass of the above-mentioned total, alkali developability can be made favorable.

[Resin (D) having epoxy group and 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 alkali aqueous solution soluble resin. The resin (D) which has an epoxy group and a phenolic hydroxyl group may have alkali-soluble functional groups other than a phenolic hydroxyl group. Phenolic hydroxyl groups and other alkali-soluble functional groups can be protected by acid-decomposable groups. A resin (D) having an epoxy group and a phenolic hydroxyl group, for example, a compound having at least two epoxy groups in one molecule (hereinafter also referred to as an "epoxy compound") and a hydroxybenzoic acid compound The carboxyl group is reacted. The epoxy group of the resin (D) having an epoxy group and a phenolic hydroxyl group forms a crosslink by reacting with a phenolic hydroxyl group during heat treatment (post-baking) after image development, thereby improving the film Chemical resistance, heat resistance, etc. Since the phenolic hydroxyl group can impart solubility to the alkaline aqueous solution during development, the resin (D) having epoxy groups and phenolic hydroxyl groups may not be fully decomposed as an acid-decomposable group when exposed at a low exposure dose. (Deprotection) of the dissolution accelerator of the resin blend (A1) to exert its function, thereby making the photosensitive resin composition highly sensitive.

An example of the reaction in which one epoxy group of the epoxy compound reacts with the carboxyl group of the hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group is shown in Reaction Formula 1 below.

Examples of compounds having at least two epoxy groups in one molecule include phenol novolac epoxy resins, cresol novolak epoxy resins, bisphenol epoxy resins, bisphenol epoxy resins, Naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, etc. These epoxy compounds should just have two or more epoxy groups in 1 molecule, and may use only 1 type, and may use it in combination of 2 or more types. Since these compounds are thermosetting types, as the common knowledge of the industry, it is impossible to clearly describe the structure based on the presence or absence of epoxy groups, the type of functional groups, the degree of polymerization, and the like. An example of the structure of a novolac type epoxy resin is represented by formula (21). For formula (21), for example, ^R38 is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 2 carbon atoms, or a hydroxyl group, and e is an integer of 1 to 50.

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

The compound having at least two epoxy groups in one molecule is preferably a novolac epoxy resin, at least one selected from the group consisting of phenol novolak epoxy resins and cresol novolak epoxy resins Whichever is better. The positive-type photosensitive resin composition containing the resin (D) having an epoxy group and a phenolic hydroxyl group derived from a novolac-type epoxy resin has excellent pattern formation properties, easy adjustment of alkali solubility, and less outgassing.

The hydroxybenzoic acid compound is a compound in which at least one of the 2nd to 6th 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-nitro Among benzoic acid, 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, etc., dihydroxybenzoic acid compound is preferable from the viewpoint of improving alkali developability. The hydroxybenzoic acid compound can be used alone or in combination of two or more kinds.

In one embodiment, the resin (D) having an epoxy group and a phenolic hydroxyl group is a reactant of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and has the formula (22) The structure. For formula (22), f is an integer of 1 to 5, and * represents the bonding site of the residue except the epoxy group that participates in the reaction of a compound having at least 2 epoxy groups in one molecule By.

In the method of obtaining the resin (D) having epoxy groups and phenolic hydroxyl groups from epoxy compounds and hydroxybenzoic acid compounds, 0.2 to 0.95 equivalents of hydroxybenzoic acid compounds can be used for 1 equivalent of epoxy groups in epoxy compounds, It is preferable to use 0.3-0.9 equivalent, more preferably to use 0.4-0.8 equivalent. If the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and if it is 0.95 equivalent or less, the increase in molecular weight by side reactions can be suppressed.

A catalyst can be used to accelerate the reaction between the epoxy compound and the hydroxybenzoic acid compound. The usage-amount of a catalyst can be set as 0.1-10 mass parts based on 100 mass parts of reaction raw material mixtures which consist of an epoxy compound and a hydroxybenzoic acid compound. The reaction temperature can be set at 60-150°C, and the reaction time can be set at 3-30 hours. Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium Iodide, triphenylphosphine, chromium octoate, zirconium octoate, etc.

The number average molecular weight (Mn) of the resin (D) having an epoxy group and a phenolic hydroxyl group is preferably 500-8000, more preferably 800-6000, and more preferably 1000-5000. When the number average molecular weight is 500 or more, a resin using a photosensitive material with appropriate alkali solubility is good, and when it is 8000 or less, coating property and developability are good.

In one embodiment, the positive-type photosensitive resin composition contains 5% to 50% by mass of the resin (D) having epoxy groups and phenolic hydroxyl groups based on 100% by mass of the solid content, and 10% by mass ~40% by mass is preferred, 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, a high sensitivity to promote the dissolution of the exposed part can be realized, and it can ensure The stability and durability of the film. When the content of 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 part can be suppressed to a lower level and a high residual film rate can be maintained .

[the third resin (E)] The positive photosensitive resin composition may contain the 3rd resin (E) other than resin (D) which has resin (a1), epoxy group, and phenolic hydroxyl group further. The 3rd resin (E) can be used individually or in combination of 2 or more types.

Examples of the third resin (E) include acrylic resins other than the resin (a1), polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, and polyamic acid resins. , polybenzoxazole resin, polybenzoxazole resin precursor, silicone resin, cyclic olefin polymer, cardo resin (Cardo resin) and derivatives of these resins. And, the general acrylic resin refers to the (co)polymer of α-alkyl acrylate, but for the disclosure of the present invention, the acrylic resin includes the (co)polymer of acrylate and the (co)polymer of α-alkyl acrylate . For example, derivatives of phenol resins include polyalkenylphenol resins in which alkenyl groups are bonded to benzene rings, and derivatives of polystyrene resins include bonds between phenolic hydroxyl groups and hydroxyalkyl groups or alkoxy groups. Hydroxypolystyrene resin derivatives bound to benzene rings, etc. 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, and the plurality of phenolic hydroxyl groups are not protected by acid decomposable groups, that is, all acid decomposable groups of the resin (a1) undergo unprotected. Such a resin has excellent compatibility with the resin blend (A1) and has high alkali solubility, so it is suitable for adjusting the alkali solubility of the film.

In one embodiment, the positive-type photosensitive resin composition contains 1 to 30 parts by mass of the third resin (E) based on 100 parts by mass of the solid content, preferably 1 to 20 parts by mass , preferably 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, provision 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 on the basis of 100 parts by mass of the solid content, the above-mentioned expected performance can be imparted without hindering the patterning property and surface quality of the film.

[Dissolution Accelerator (F)] In the positive-type photosensitive resin composition, a dissolution accelerator (F) may be further contained when the solubility of the alkali-soluble part to the developing solution is to be improved at the time of image development. Examples of the dissolution accelerator (F) include organic low molecular weight compounds selected from the group consisting of compounds having a carboxyl group and compounds having a phenolic hydroxyl group. A dissolution accelerator (F) can be used individually or in combination of 2 or more types.

The "low molecular compound" disclosed in the present invention means a compound having a molecular weight of 1000 or less. The organic low molecular weight compound mentioned above has a carboxyl group or a plurality of phenolic hydroxyl groups and is alkali-soluble.

Examples of such organic low-molecular compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, pivalic acid, hexanoic acid, diethylacetic acid, heptanoic acid, and octanoic acid; Diacid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylate, methylmalonic acid, ethylmalonic acid, di Aliphatic dicarboxylic acids such as methylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarbaryl acid, aconitic acid, and canphoronic acid ; Aromatic monocarboxylic acids such as benzoic acid, benzoic acid, ciminic acid, semiimidic acid, trimethylbenzoic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic acid , 1,2,3,4-Melofanoic acid, pyromellitic acid and other aromatic polycarboxylic acids; dihydroxybenzoic acid, trihydroxybenzoic acid, gallic acid and other aromatic hydroxycarboxylic acids; phenyl Acetic acid, Hydroatropic acid, Cinnamic acid, Mandelic acid, Phenylsuccinic acid, Atropaic acid, Cinnamic acid, Methyl cinnamate, Benzyl cinnamate, Phenylallylidene Cinnamylidene acetic acid, coumaric acid, succinic acid (Umber acid) and other carboxylic acids; catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol , Phloroglucinol, bisphenol and other aromatic polyols.

The content of the dissolution accelerator (F) in the positive-type photosensitive resin composition can be set to 0.1 to 50 parts by mass, or 1 to 35 parts by mass based on 100 parts by mass of the total resin components. More preferably, preferably 2 to 20 parts by mass. When the content of the dissolution accelerator (F) is based on the above-mentioned total of 100 parts by mass, if it is at least 0.1 parts by mass, the dissolution of the resin component can be effectively promoted, and if it is at most 50 parts by mass, excessive dissolution of the resin component can be suppressed , and can improve the pattern formation and surface quality of the film.

[optional ingredient (G)] The positive photosensitive resin composition may contain a thermosetting agent, a surfactant, a colorant other than (B), and the like as an optional component (G). For the disclosure of the present invention, any component (G) is defined as any one of (A1)-(F).

As the thermosetting agent, a thermal radical generator can be used. As a preferred thermal free radical generator, organic peroxides can be mentioned, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane Alkanes, tert-butyl cumene peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc. 10-hour half-life temperature It is an organic peroxide at 100~170℃.

The content of the thermosetting agent is preferably not more than 5 parts by mass, preferably not more than 4 parts by mass, more preferably not more than 3 parts by mass, based on 100 parts by mass of the total solid content other than the thermosetting agent.

In the positive photosensitive resin composition, for example, when it is desired to improve the coatability, the smoothness of the film, or the developability of the film, a surfactant may be contained. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as ethylene nonylphenyl ether; non-ionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dibutyl dilaurate and polyoxyethylene distearate; Megafac (registered trademark) F-251, same F-281, same F-430, same F-444, same R-40, same F-553, same F-554, same F-555, same F-556, same F-557, same as F-558, same as F-559 (the above are product names; manufactured by DIC Co., Ltd.), Surflon (registered trademark) S-242, same as S-243, same as S-386, same as S-420, Fluorine-based surfactants such as S-611 (the above are trade names; manufactured by ACGSeimi Chemical Co., Ltd.); organosiloxane polymers KP323, KP326, KP341 (the above are trade names; manufactured by Shin-Etsu Chemical Co., Ltd.), etc. . These surfactants can be used individually or in combination of 2 or more types.

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

The positive photosensitive resin composition may contain a second colorant other than the colorant (B). As a 2nd coloring agent, dye, an organic pigment, an inorganic pigment etc. are mentioned, It can use according to the objective. The content of the second coloring agent used is such that the effect disclosed by the present invention is not impaired.

Examples of dyes include azo-based dyes, benzoquinone-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, cyanine-based dyes, squarylium-based dyes, croconium-based dyes, and merocyanines. (Merocyanine)-based dyes, stilbene-based dyes, diphenylmethane-based dyes, triphenylmethane-based dyes, halothane-based dyes, spiropyran-based dyes, phthalocyanine-based dyes, indigo-based dyes, Frugid dye series dyes, nickel zirconium system dyes and azulene series dyes, etc. Among the dyes, red dye is preferred. As a red dye, for example, VALIFAST (registered trademark) RED 3312 (a red dye specified by the C.I. of solvent red 122, manufactured by Oriental Chemical Industry Co., Ltd.), and VALIFAST (registered trademark) RED 3311 (a solvent red 8 Red dye specified by C.I., manufactured by Oriental Chemical Industry Co., Ltd.).

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

[Solvent (H)] The positive-type photosensitive resin composition can be used in a solution state dissolved in a solvent (H) (however, when a black pigment is contained, the pigment is in a dispersed state). For example, the coloring agent ( B) and photoacid generator (C), and optional ingredients (G) such as dissolution accelerator (F), thermosetting agent, surfactant, etc. if necessary, are mixed in a predetermined ratio, and the correct solution state can be prepared. type photosensitive resin composition. 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, methyl Cellosolve acetate, ethyl cellosolve acetate, etc. Ethylene glycol alkyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl Diethylene glycol compounds such as diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether Propylene glycol alkyl ether acetate compounds such as acid esters, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentane Ketones, ketones such as cyclohexanone, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyl Ethyl acetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethoxy ethyl propionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, gamma-butyrolactone and other esters, N-methyl-2-pyrrolidone, N,N-dimethyl Amide compounds such as formamide and N,N-dimethylacetamide. These solvents can be used individually or in combination of 2 or more types.

[Positive Photosensitive Resin Composition] The positive photosensitive resin composition system can be composed of resin blend (A1), colorant (B), photoacid generator (C) and resin (D) with epoxy group and phenolic hydroxyl group as necessary, third A resin (E), a dissolution accelerator (F), or an optional component (G) is dissolved or dispersed in a solvent (H) and mixed to prepare it. 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-type photosensitive resin composition can be set at 1-60 mass %, or can be set at 3-50 mass % or 5-40 mass %.

For the method of dispersion mixing when using a pigment, a known method can be used. For example, spherical type such as ball mill, sand mill, bead mill, paint vibrator, shaking mill, etc., blending type such as kneader, paddle mixer, planetary mixer, Henschel mixer, etc., and 3-roll mixing can be used. Roller type such as machine, as others can use thunder machine, colloid mill, ultrasonic wave, homogenizer, rotation・revolution mixer, etc. From the viewpoint of dispersion efficiency and fine dispersion, it is better to use a bead mill.

The prepared positive photosensitive resin composition is usually filtered before use. As a filtration means, the Millipore filter etc. which have a pore diameter of 0.05-1.0 micrometer are mentioned, for example.

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

[How to use the positive photosensitive resin composition] When using the positive photosensitive resin composition 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 is coated on the surface of the substrate, and the solvent is removed by means such as heating to form a film. The coating method of the coating composition on the surface of the substrate is not particularly limited, and for example, a spray method, a roll coating method, a slit method, a spin coating method, etc. can be used.

After coating the coating composition on the surface of the substrate, the solvent is usually removed by heating to form a film (pre-baking). Although the heating conditions vary depending on the type and proportion of each component, it is usually 70~130°C. For example, it can be heated on a heating plate for 30 seconds to 20 minutes, and in an oven for 1~60°C. Minute heat treatment to obtain a film.

Next, the prebaked film is irradiated with radiation (such as visible light, ultraviolet rays, far ultraviolet light, X-rays, electron rays, gamma rays, synchrotron radiation, etc.) etc. through a mask with a predetermined pattern (exposure step). Preferable radiation is ultraviolet light or visible light having a wavelength of 250 to 450 nm. In one embodiment, the radiation is i-line. In other implementation aspects, the radiation is ghi rays.

After the exposure step, heat treatment (PEB) to promote the decomposition of acid-decomposable groups may be performed. The alkali solubility of the resin blend (A1) in the exposed portion through PEB can be further improved. The heating conditions vary depending on the type and proportion of each component, but usually at 70~140°C, for example, by heating on a heating plate for 30 seconds to 20 minutes, and in an oven for 1~60 minutes PEB is performed by heat treatment.

After the exposure step or the PEB step, the film is developed by contacting the film with a developing solution, and unnecessary parts are removed to form a pattern on the film (development step). As the developer, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water; primary amines such as ethylamine and n-propylamine can be used; Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and triethanolamine; hydrogen Tetramethylammonium oxide, tetraethylammonium hydroxide, Colin and other quaternary ammonium salts; pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene Aqueous solutions of alkali compounds such as cyclic amines such as 1,5-diazabicyclo[4.3.0]-5-nonane, etc. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like is added to an aqueous alkali solution can be used as a developing solution. The imaging time is usually 30-180 seconds. The developing method is any one of liquid filling method, spray method, dipping method and the like. After developing, wash with running water for 30-90 seconds to remove unnecessary parts, and then air-dry with compressed air or compressed nitrogen to form patterns on the film.

Afterwards, the patterned film is heat-treated at 100-350° C. for 20-200 minutes by a heating device such as a hot plate or an oven to obtain a hardened film (post-baking, heat treatment step). For the heat treatment, the temperature may be maintained constant, or the temperature may be raised continuously or stepwise. The heat treatment is preferably carried out under a nitrogen environment.

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

A method for manufacturing an organic EL element separator or insulating film according to one embodiment includes: dissolving or dispersing a positive-type photosensitive resin composition in a solvent to prepare a coating composition; coating the coating composition on a substrate to form a film , removing the solvent contained in the film and drying the film, exposing the film by irradiating the dried film with radiation so as to pass through a photomask, and decomposing at least a part of the acid-decomposable groups of the resin blend (A1) , By contacting the exposed coating with a developing solution to develop the image, forming a pattern on the coating, and heating the patterned coating at a temperature of 100 ° C to 350 ° C to form an organic EL element diaphragm or insulating film. The PEB described above can be performed after exposure and before development.

One embodiment is an organic EL element separator 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 including a cured product of a positive photosensitive resin composition. [Example]

The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.

(1) Raw material Raw materials used in Examples, Reference Examples, and Comparative Examples were produced or obtained as follows.

The weight average molecular weight and number average molecular weight of the resin (D) having resin (a1), epoxy group and phenolic hydroxyl group and the third resin (E) are determined by using polystyrene standard material under the following measurement conditions Calculated using the prepared standard curve. Device name: Shodex (registered trademark) GPC-101 Column: Shodex (registered trademark) LF-804 Mobile Phase: Tetrahydrofuran Flow rate: 1.0mL/min Detector: Shodex (registered trademark) RI-71 Temperature: 40°C

The ratio of the phenolic hydroxyl group protected with an acid-decomposable group is calculated using a thermogravimetric differential thermal analysis device (TG/DTA6200, manufactured by Hitachi High-Tech Science Co., Ltd.) in a nitrogen stream at a temperature increase rate of 10°C/min. Under the conditions, the temperature is raised from room temperature to 250°C and kept for 10 minutes, and the phenolic hydroxyl group at 260°C is protected by an acid-decomposable group when the temperature is further raised to 400°C at a temperature increase rate of 10°C/min. Calculated from the weight loss rate (%).

[Production Example 1] Production of an alkali aqueous solution soluble copolymer (PCX-02e) (third resin (E)) of a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer Completely dissolve 25.5 g of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko Co., Ltd.) and 4.50 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) 3.66 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 77.1 g of 1-methoxy-2-propyl acetate (manufactured by Daicel Corporation) In 14.6 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.). The resulting two solutions were placed in 61.2 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.) heated at 85° C. under a nitrogen atmosphere in a 300 mL 3-necked flask. After dripping over 2 hours, reaction was performed at 85° C. for 3 hours. The reaction solution cooled to room temperature was dropped into 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, vacuum-dried at 90° C. for 4 hours, and 32.4 g of a white powder was recovered. The number average molecular weight of the obtained PCX-02e was 3100, and the weight average molecular weight was 6600.

[Production Example 2] Production of resin (PCX-02e-THF40) in which phenolic hydroxyl group is protected with 2-tetrahydrofuryl group In a 100 mL 3-necked flask, 10.0 g of an alkali aqueous solution soluble copolymer (PCX-02e) of a radically polymerizable monomer having a phenolic hydroxyl group and other radically polymerizable monomers, and p - 0.60 g of pyridinium salt of toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), was dissolved in 50.0 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Thereafter, 6.69 g of 2,3-dihydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour under ice-cooling under a nitrogen atmosphere. Stirring was then carried out at room temperature for 16 hours. After neutralizing the acid catalyst with saturated aqueous sodium bicarbonate solution, the aqueous layer was removed. The organic layer was further washed twice with water. Thereafter, tetrahydrofuran was distilled off. The obtained solid was dissolved in 50.0 g of ethyl acetate, and was dropped into 200 g of toluene to precipitate a product. The precipitate was recovered by filtration, and 11.0 g of a white powder was recovered after vacuum-drying at 80° C. for 4 hours. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a solid content 20% by mass solution of a resin (PCX-02e-THF40) whose phenolic hydroxyl group was protected with a 2-tetrahydrofuryl group. The number average molecular weight of the obtained PCX-02e-THF40 is 3716, the weight average molecular weight is 6806, the proportion of phenolic hydroxyl groups protected by acid decomposable groups is 40 mole%, and at least one phenolic hydroxyl group is protected by acid decomposable groups. The number of protected monomer units is 55% of the total number of monomer units in PCX-02e-THF40.

[Production Example 3] Production of resin (PCX-02e-nPOE60) in which phenolic hydroxyl group is protected with 1-n-propoxyethyl group Except that 8.23 g of n-propyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2,3-dihydrofuran, the phenolic hydroxyl group was obtained as 1-n-propoxyethyl in the same manner as in Production Example 2. Solid content 20 mass % solution of the resin (PCX-02e-nPOE60) to protect. The number average molecular weight of the obtained PCX-02e-nPOE60 is 4550, the weight average molecular weight is 8054, the proportion of phenolic hydroxyl groups protected by acid decomposable groups is 60 mole%, and at least one phenolic hydroxyl group is protected by acid decomposable groups. The number of protected monomer units is 55% of the total number of monomer units in PCX-02e-nPOE60.

[Production Example 4] Production of resin (PCX-02e-THP30) with phenolic hydroxyl group protected by 2-tetrahydropyranyl group Except for using 6.69 g of 3,4-dihydro-2H-pyran (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2,3-dihydrofuran, the phenolic hydroxyl group was obtained in the same manner as in Production Example 2. Solid content 20 mass % solution of the resin (PCX-02e-THP30) protected by the pyryl group. The number average molecular weight of the obtained PCX-02e-THP30 is 3716, the weight average molecular weight is 6806, the proportion of phenolic hydroxyl groups protected by acid decomposable groups is 30 mole%, and at least one phenolic hydroxyl group is protected by acid decomposable groups. The number of monomer units to be protected is 55% of the number of all monomer units in PCX-02e-THP30.

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

[Production Example 6] Production of resin (PCX-02e-EOE60) with phenolic hydroxyl group protected with 1-ethoxyethyl group Except for using 6.88 g of ethyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2,3-dihydrofuran, a resin in which the phenolic hydroxyl group was protected with 1-ethoxyethyl was obtained in the same manner as in Production Example 2. (PCX-02e-EOE60) solid content 20% by mass solution. The number average molecular weight of the obtained PCX-02e-EOE60 is 4300, the weight average molecular weight is 7900, the proportion of phenolic hydroxyl groups protected by acid decomposable groups is 60 mole%, and at least one phenolic hydroxyl group is protected by acid decomposable groups. The number of protected monomer units is 55% of the total number of monomer units in PCX-02e-EOE60.

[Production Example 7] Production of resin (PCX-02e-CHOE70) in which phenolic hydroxyl group is protected with cyclohexyloxyethyl group Except for using 6.88 g of cyclohexyl vinyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2,3-dihydrofuran, the resin in which the phenolic hydroxyl group was protected with a cyclohexyloxyethyl group was obtained in the same manner as in Production Example 2 ( PCX-02e-CHOE70) solid content 20% by mass solution. The number average molecular weight of the obtained PCX-02e-CHOE70 is 4300, the weight average molecular weight is 7900, the proportion of phenolic hydroxyl groups protected by acid decomposable groups is 70 mole%, and at least one phenolic hydroxyl group is protected by acid decomposable groups. The number of protected monomer units is 55% of the number of all monomer units in PCX-02e-CHOE70.

[Production Example 8] Production of resin (PCX-02e-Boc5) in which phenolic hydroxyl group is protected with tert-butoxycarbonyl group In a 100 mL 3-necked flask, 10.0 g of an alkali aqueous solution soluble copolymer (PCX-02e) of a radical polymerizable monomer having a phenolic hydroxyl group and other radical polymerizable monomers, and triethyl Amine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 1.74 g. Dissolve in 50.0 g of tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Thereafter, 3.47 g of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour under ice-cooling under a nitrogen atmosphere. Stirring was then carried out at room temperature for 16 hours. Then, tetrahydrofuran was distilled off, the obtained solid was dissolved in 50.0 g of ethyl acetate, and it was dripped in 200 g of hexane, and the product was precipitated. The precipitate was recovered by filtration, and 10.3 g of a white powder was recovered after vacuum-drying at 80° C. for 4 hours. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a solid content 20% by mass solution of a resin (PCX-02e-Boc5) whose phenolic hydroxyl group was protected with a tert-butoxycarbonyl group. The number average molecular weight of the obtained PCX-02e-Boc5 is 4400, the weight average molecular weight is 7800, the proportion of phenolic hydroxyl groups protected by acid decomposable groups is 5 mole%, and at least one phenolic hydroxyl group is protected by acid decomposable groups. The number of protected monomeric units was 26% of the total monomeric units of PCX-02e-Boc5.

[Production Example 9] Production of resin (PCX-02e-THF70) in which phenolic hydroxyl group is protected with 2-tetrahydrofuryl group Except using 11.71 g of 2,3-dihydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.), in the same manner as in Production Example 2, a solid resin (PCX-02e-THF70) in which the phenolic hydroxyl group was protected with a 2-tetrahydrofuryl group was obtained. Component 20% by mass solution. The number average molecular weight of the obtained PCX-02e-THF70 is 3716, the weight average molecular weight is 6806, the proportion of phenolic hydroxyl groups protected by acid decomposable groups is 70 mole%, and at least one phenolic hydroxyl group is protected by acid decomposable groups. The number of protected monomer units is 55% of the total number of monomer units in PCX-02e-THF70.

[Manufacture Example 10] Manufacture of resin (D) (N770OH70) having epoxy group and phenolic hydroxyl group 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as a solvent, and EPICLON (registered trademark) N as a compound having at least 2 epoxy groups in 1 molecule were placed in a 300 mL 3-necked flask. 37.6 g of -770 (phenol novolak type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 188) was dissolved at 60° C. under a nitrogen atmosphere. Then, 20.1 g (0.65 equivalent to 1 equivalent of epoxy) of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound, and triphenylphosphine ( Tokyo Chemical Industry Co., Ltd.) 0.173 g (0.660 mmol), and reacted at 110° C. for 24 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain a solution of the second resin (N770OH70) having 286.5 g of epoxy groups and phenolic hydroxyl groups. The number average molecular weight of the obtained reactant was 2400, and the weight average molecular weight was 8300.

[Production Example 11] Production of resin (PCX-02e-THF55) in which phenolic hydroxyl group is protected with 2-tetrahydrofuryl group Except using 9.20 g of 2,3-dihydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.), in the same manner as in Production Example 2, a solid resin (PCX-02e-THF55) in which the phenolic hydroxyl group was protected with 2-tetrahydrofuran group was obtained. Component 20% by mass solution. The number average molecular weight of the obtained PCX-02e-THF55 is 3555, the weight average molecular weight is 6718, the proportion of phenolic hydroxyl groups protected by acid decomposable groups is 55 mole%, and at least one phenolic hydroxyl group is protected by acid decomposable groups. The number of protected monomer units is 55% of the total number of monomer units in 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 were used - Compositions shown in Table 2 for CHOE70, PCX-02e-Boc5, PCX-02e-THF70, and PCX-02e-THF55. The bond dissociation energy of the acid-decomposable group of the resin calculated using the quantum chemical calculation software Gaussian16 is shown below.

Colorant (B) As the colorant (B), VALIFAST (registered trademark) BLACK 3804 (a black dye specified as C.I. of solvent black 34, manufactured by Oriental Chemical Industry Co., Ltd.) was used as a black dye.

Photoacid Generator (C) As the photoacid generator (C), PAG-103 (2-[2-(propylsulfonyloxyimine)thiophene-3(2H)-ylidene]-2-( 2-methylphenyl)acetonitrile, manufactured by BASF Corporation, CAS No. 852246-55-0). PAG-103 produces 1-propanesulfonic acid (pKa=-2.8) by light irradiation. The structure of PAG-103 is shown below.

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

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

As the dissolution accelerator (F), phloroglucinol was used.

As a surfactant (leveling agent) (optional component (G)), Megafac (registered trademark) F-559 (fluorine-based surfactant, manufactured by DIC Corporation) was used.

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

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

[OD value after heating] The positive-type photosensitive resin composition was spin-coated on a glass substrate (100 mm×100 mm×1 mm in size) until the dry film thickness was about 1.5 μm, and the solvent was dried by heating at 120° C. for 80 seconds on a hot plate. Then, it hardened at 250 degreeC for 60 minutes in nitrogen atmosphere, and obtained the film|membrane. The OD value of the hardened coating was measured with a permeation density meter (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.), and only the OD value of the glass was corrected to convert it into the OD value of the coating per thickness of 1 μm. The thickness of the film was measured using an optical film thickness measuring device (F20-NIR, manufactured by Film Metrics Co., Ltd.).

[aperture] The positive-type photosensitive resin composition was spin-coated on a glass substrate (100 mm×100 mm×1 mm in size) until the dry film thickness was about 2.0 μm, heated on a hot plate at 100° C. for 1 minute and pre-baked. Thereafter, after irradiating ultraviolet rays with an exposure dose of 100 mJ/cm2 through a photomask having a hole pattern of 10 μm, PEB was performed under the conditions (condition 1) described in Table 2 on a hot plate. Thereafter, alkali development was performed for 60 seconds with a 2.38% by mass tetramethylammonium hydroxide aqueous solution, and after spraying off the attached moisture with a spray gun, the pore diameter was observed with a microscope. The pore diameter was also observed in the same way for the samples in which the conditions of PEB were further changed from Condition 1 to the following. 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 ≦ pore diameter ≦ 10.5 μm is regarded as a passer. [Process Stability] Among the 5 PEB conditions, the number of qualified conditions is used as an indicator of process stability for the pore size evaluation.

(3) Preparation and evaluation of positive photosensitive resin composition [Examples 1-8, Reference Example 1 and Comparative Examples 1-9] With the composition described in Table 2, mix and dissolve the resin blend (A), the resin (D) having epoxy groups and phenolic hydroxyl groups, and the third resin (E) with a stirring rotor, and dissolve them in the resulting solution , Add the colorant (B), photoacid generator (C), dissolution accelerator (F), surfactant (G) and GBL/PGMEA mixed solvent (H) listed in Table 2, and mix further. After visually confirming whether or not the components were dissolved, it was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a positive-type photosensitive resin composition with a solid content concentration of 12% by mass. The parts by mass of the compositions in Table 2 are solid content conversion values. The evaluation results of the positive photosensitive resin compositions of Examples 1-8, Reference Example 1 and Comparative Examples 1-9 are shown in Table 2.

In Examples 1-8, Reference Example 1, and Comparative Examples 1-9, holes were formed even if a black coloring agent was contained. Examples 1 to 8 and Reference Example 1 contain plural kinds of different acid-decomposable resins having plural phenolic hydroxyl groups, at least a part of which are protected by acid-decomposable groups. Compared with Comparative Examples 1-9, the resins with acid decomposability can improve the process stability of PEB. [industrial availability]

The positive-type photosensitive resin composition according to this embodiment can be suitably used for radiation lithography for forming a separator or an insulating film of an organic EL element. An organic EL element provided with a separator or an insulating film formed of the positive photosensitive resin composition disclosed in the present invention can be suitably used as an electronic component of a display device showing good contrast.

Claims (18)

A positive-type photosensitive resin composition comprising: a resin (a1-1) having a plurality of phenolic hydroxyl groups, at least a part of which is protected by an acid-decomposable group (1), and a plurality of phenolic hydroxyl groups, The resin (a1-2) in which at least a part of the aforementioned plurality of phenolic hydroxyl groups is protected by an acid-decomposable group (2) different from the aforementioned acid-decomposable group (1), and the resin (a1-2) optionally having a plurality of phenolic hydroxyl groups, the aforementioned plurality of phenolic A resin (a1-3) in which at least a part of the active hydroxyl group is protected by an acid-decomposable group (3) different from the aforementioned acid-decomposable groups (1) and (2), wherein the aforementioned acid-decomposable groups (1) to ( 3) each independently selected from the following group of resin blends (A1), at least one colorant (B) selected from the group of black dyes and black pigments, photoacid generators (C), and Oxygen and phenolic hydroxyl resin (D); Group I: tert-butoxycarbonyl and 1,1-dimethyl-propoxycarbonyl; Group II: group represented by formula (1) -CR ¹ R ² R ³ (1) (In formula (1), R ¹ is a saturated or unsaturated linear or branched hydrocarbon group with 1 to 10 carbon atoms, R ² and R ³ are each independently a carbon number of 1 to 10 10 saturated or unsaturated linear or branched hydrocarbon groups or alicyclic hydrocarbon groups with 3 to 20 carbon atoms, or ^R2 and ^R3 together can form an alicyclic structure with 3 to 20 ring members); Group III: 2-tetrahydropyranyl; Group IV: 2-tetrahydrofuranyl; Group V: group represented by formula (2) -CHR ⁴ -OR ⁵ (2) (In formula (2), R ⁴ is a carbon atom A straight-chain or branched-chain alkyl group with a number of 1-4, ^R5 is a straight-chain, branched-chain or cyclic alkyl group with a carbon number of 1-12, an aralkyl group with a carbon number of 7-12 or an alkenyl group with 2 to 12 carbon atoms). Such as the positive-type photosensitive resin composition of claim 1, wherein the aforementioned acid-decomposable groups (1)~(3) are each selected from different groups in Groups I~IV, V-1 and V-2; Group I: tert-butoxycarbonyl and 1,1-dimethyl-propoxycarbonyl; Group II: the group represented by the aforementioned formula (1); Group III: 2-tetrahydropyranyl; Group IV: 2-tetrahydrofuranyl ; Group V-1: group shown in formula (2-1) -CHR ⁴ -OR ⁵ (2-1) (in formula (2-1), R ⁴ is a linear or branched chain with 1 to 4 carbon atoms A chain-like alkyl group, ^R5 is a straight-chain or branched-chain alkyl group with 1 to 12 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or an alkenyl group with 2 to 12 carbon atoms); V-2: 1-cyclohexyloxyethyl. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the aforementioned resin (a1-1) has a monomer unit represented by the following formula (3):

(In formula (3), ^R6 is a hydrogen atom or a methyl group, ^R7 is the aforementioned acid decomposable group (1), l is an integer of 0~5, m is an integer of 0~5, but l+m is 1 Integer of ~5)), the aforementioned resin (a1-1) has at least one aforementioned monomer unit where m is an integer greater than 1, and the aforementioned resin (a1-2) has a monomer unit shown in the following formula (4),

(In formula (4), R ⁸ is a hydrogen atom or a methyl group, R ⁹ is the aforementioned acid decomposable group (2), n is an integer of 0 to 5, o is an integer of 0 to 5, but n+o is 1 ~5 integers), the aforementioned resin (a1-2) has at least one aforementioned monomer unit where o is an integer greater than 1, and the aforementioned resin (a1-3) has a monomer unit shown in the following formula (5),

(In formula (5), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is the aforementioned acid decomposable group (3), p is an integer of 0 to 5, q is an integer of 0 to 5, but p+q is 1 Integer of ~5), said resin (a1-3) has at least 1 said monomer unit whose q is an integer of 1 or more. Such as the positive photosensitive resin composition of claim 3, which The aforementioned resin (a1-1) contains 60 mol % to 100 mol % of the aforementioned monomer unit represented by formula (3) relative to the total monomer unit, and the aforementioned resin (a1-2) contains In terms of monomer units, it contains 60 mol % to 100 mol % of the aforementioned monomer units represented by formula (4), and the aforementioned resin (a1-3) contains 60 mol% to 100 mol % of the aforementioned monomer units represented by formula (5). 60 mol% to 100 mol% of the aforementioned monomer units. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the acid-decomposable group (1) is 2-tetrahydrofuryl. The positive-type photosensitive resin composition according to claim 2, wherein the acid-decomposable group (1) is 2-tetrahydrofuryl, and the acid-decomposable group (2) is selected from the group V-1 or V-2. The positive-type photosensitive resin composition according to claim 6, wherein the acid-decomposable group (3) contains the aforementioned resin (a1-3) selected from the group I, II or III. The positive-type photosensitive resin composition according to claim 1 or 2, wherein 5 mol% to 95 mol% of the phenolic hydroxyl groups of the aforementioned resin (a1-1) are protected by the aforementioned acid-decomposable group (1), and the aforementioned 5 mol% to 95 mol% of the phenolic hydroxyl groups of the resin (a1-2) are protected by the aforementioned acid decomposable group (2), and 5 mol% to 95 mol% of the phenolic hydroxyl groups of the aforementioned resins (a1-3) Mole % is protected by the aforementioned acid decomposable group (3). The positive-type photosensitive resin composition according to claim 1 or 2, wherein the mass ratio of the aforementioned resin (a1-2) to the aforementioned resin (a1-1) (mass of resin (a1-2)/resin (a1-1) The quality) is 5/95~50/33. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the aforementioned resins (a1-1), (a1-2) and (a1-3) are copolymers having monomer units represented by the following formula (12) ,

(In formula (12), R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group with 1 to 3 carbon atoms, or a halogen atom, and R ²³ It is a hydrogen atom, a straight chain with 1 to 6 carbon atoms or a cyclic alkyl group with 4 to 12 carbon atoms, or a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms, and a group with 1 to 6 carbon atoms. A phenyl group substituted with at least one kind of alkoxy group consisting of 6). The positive-type photosensitive resin composition according to claim 1 or 2, wherein the aforementioned photoacid generator (C) is a compound represented by the following 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, R ²⁵ and R ²⁶ are each independently substituted or unsubstituted Substituted aryl, substituted or unsubstituted heterocyclic group, cyano group, acetyloxy group, carboxyl group or alkoxycarbonyl group, R ²⁵ and R ²⁶ are bonded to form a ring structure with ring members 3 to 10, the ring structure may have substituents). The positive-type photosensitive resin composition as claimed in claim 1 or 2, wherein the total mass of the resin components is used as a reference, and contains 30 mass %~90% by mass of the aforementioned resin blend (A1). The positive-type photosensitive resin composition according to claim 1 or 2, wherein the colorant (B) is contained in an amount of 10 to 150 parts by mass based on a total of 100 parts by mass of the resin components. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the photoacid generator (C) is contained in an amount of 0.1 to 85 parts by mass based on 100 parts by mass of the total resin components. The positive photosensitive resin composition according to claim 1 or 2, wherein the optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per film thickness of 1 μm. An organic EL element separator, which is a cured product containing the positive photosensitive resin composition according to any one of claims 1 to 15. An insulating film for an organic EL element, which is a cured product containing the positive photosensitive resin composition according to any one of claims 1 to 15. An organic EL element, which is a hardened product containing the positive photosensitive resin composition according to any one of claims 1 to 15.