TWI789776B - 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. The positive photosensitive resin composition contains the following resin blend (A2), at least one colorant (B) and photoacid generator (C) selected from the group consisting of black dye and black pigment; The above-mentioned resin blend (A2) is a resin containing multiple phenolic hydroxyl groups, and X mole % (however, X is a real number greater than 0) of the multiple phenolic hydroxyl groups is protected by an acid-decomposable group (4). (a2-1), having multiple phenolic hydroxyl groups, Y mole % of the multiple phenolic hydroxyl groups (however, Y is a real number greater than 0) is the same acid decomposable group as that of the acid decomposable group (4). Resin for protection (a2-2); where Y-X≧10.

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

[Problems 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. .

(式(6)中，R¹² 為氫原子或甲基，R¹³ 為選自由以下所成群的酸分解性基(4)。 群I：tert-丁氧基羰基及1,1-二甲基-丙氧基羰基； 群II：式(7)所示基

(式(7)中，R¹⁴ 為碳原子數1～10的飽和或不飽和的直鏈狀或支鏈狀烴基，R¹⁵ 及R¹⁶ 各獨立為碳原子數1～10的飽和或者不飽和的直鏈狀或者支鏈狀烴基或碳原子數3～20的脂環式烴基，或R¹⁵ 及R¹⁶ 可共同形成環員數3～20的脂環結構)； 群III：2-四氫吡喃基； 群IV：2-四氫呋喃基； 群V：式(8)所示基

(式(8)中，R¹⁷ 為碳原子數1～4的直鏈狀或者支鏈狀的烷基，R¹⁸ 為碳原子數1～12的直鏈狀、支鏈狀或者環狀烷基、碳原子數7～12的芳烷基或碳原子數2～12的烯基)；r為0～5的整數，s為0～5的整數，但r+s為1～5的整數)。 [3] 前述樹脂(a2-1)相對於該全單體單位而言含有60莫耳%～100莫耳%的式(6)所示前述單體單位，前述樹脂(a2-2)相對於該全單體單位而言含有60莫耳%～100莫耳%的式(6)所示前述單體單位之[2]所記載的正型感光性樹脂組成物。 [4] 前述樹脂(a2-1)及(a2-2)各酚性羥基之5莫耳%～95莫耳%以前述酸分解性基(4)進行保護之[1]～[3]中任一所記載的正型感光性樹脂組成物。 [5] 前述樹脂(a2-2)與前述樹脂(a2-1)之質量比(樹脂(a2-2)之質量/樹脂(a2-1)之質量)為5/95～95/5之[1]～[4]中任一所記載的正型感光性樹脂組成物。 [6] Y-X≧20之[1]～[5]中任一所記載的正型感光性樹脂組成物。 [7] 前述樹脂(a2-1)及(a2-2)為具有式(12)所示單體單位之共聚物的[1]～[6]中任一所記載的正型感光性樹脂組成物

(對於式(12)，R²¹ 及R²² 各獨立為氫原子、碳原子數1～3的烷基、完全或者部分被氟化的碳原子數1～3的烷基，或鹵素原子，R²³ 為氫原子、碳原子數1～6的直鏈或者碳原子數4～12的環狀烷基、苯基，或由選自由羥基、碳原子數1～6的烷基及碳原子數1～6的烷氧基所成群的至少1種所取代的苯基)。 [8] 前述光酸產生劑(C)為式(13)所示化合物之[1]～[7]中任一所記載的正型感光性樹脂組成物。

(對於式(13)，R²⁴ 為取代或非取代的烷基、取代或非取代的烷氧基、取代或非取代的芳基，或鹵素原子，R²⁵ 及R²⁶ 各獨立為取代或者非取代的芳基、取代或者非取代的雜環基、氰基、乙醯氧基、羧基，或烷氧基羰基，R²⁵ 與R²⁶ 經鍵結可形成環員數3～10的環結構，該環結構可具有取代基)。 [9] 將樹脂成分的合計質量作為基準，含有30質量%～90質量%的前述樹脂摻合物(A2)之[1]～[8]中任一所記載的正型感光性樹脂組成物。 [10] 將樹脂成分的合計100質量份作為基準，含有10質量份～150質量份之前述著色劑(B)之[1]～[9]中任一所記載的正型感光性樹脂組成物。 [11] 作為樹脂成分之合計100質量份，含有0.1質量份～85質量份之前述光酸產生劑(C)之[1]～[10]中任一所記載的正型感光性樹脂組成物。 [12] 前述正型感光性樹脂組成物的硬化被膜之光學濃度(OD值)在每膜厚1μm中為0.5以上之[1]～[11]中任一所記載的正型感光性樹脂組成物。 [13] 進一步含有具有環氧基及酚性羥基之樹脂(D)的[1]～[12]中任一所記載的正型感光性樹脂組成物。 [14] 含有[1]～[13]中任一所記載的正型感光性樹脂組成物之硬化物的有機EL元件隔膜。 [15] 含有[1]～[13]中任一所記載的正型感光性樹脂組成物之硬化物的有機EL元件絕緣膜。 [16] 含有[1]～[13]中任一所記載的正型感光性樹脂組成物之硬化物的有機EL元件。 [發明之效果]That is, the present invention includes the following aspects. [1] A positive photosensitive resin composition comprising a resin blend (A2), at least one colorant (B) selected from the group consisting of black dyes and black pigments, and a photoacid generator (C); the The resin blend (A2) contains: a resin having a plurality of phenolic hydroxyl groups, X mole % of the aforementioned plurality of phenolic hydroxyl groups (however, X is a real number greater than 0) is protected with an acid-decomposable group (4) (a2-1) has a plurality of phenolic hydroxyl groups, and Y mole % of the aforementioned plurality of phenolic hydroxyl groups (however, Y is a real number greater than 0) has the same acid-decomposable properties as the aforementioned acid-decomposable group (4). Resin (a2-2) protected by group; wherein YX≧10. [2] The aforementioned resins (a2-1) and (a2-2) each independently have a monomer unit represented by formula (6), and each of the aforementioned resins (a2-1) and (a2-2) has at least one s that is 1 The positive photosensitive resin described in [1] in which the plurality of R ¹³ present in the aforementioned resins (a2-1) and (a2-2) are the same acid-decomposable group for the above-mentioned monomer units composition,

(In formula (6), R ¹² is a hydrogen atom or a methyl group, and R ¹³ is an acid-decomposable group (4) selected from the following groups. Group I: tert-butoxycarbonyl and 1,1-dimethyl Base-propoxycarbonyl; Group II: the base shown in formula (7)

(In formula (7), R ¹⁴ is a saturated or unsaturated linear or branched chain hydrocarbon group with 1 to 10 carbon atoms, R ¹⁵ and R ¹⁶ are each independently a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms straight-chain or branched-chain hydrocarbon groups or alicyclic hydrocarbon groups with 3 to 20 carbon atoms, or R ¹⁵ and R ¹⁶ can jointly form an alicyclic structure with 3 to 20 ring members); Group III: 2-tetrahydro Pyranyl; Group IV: 2-tetrahydrofuryl; Group V: group represented by formula (8)

(In formula (8), R ¹⁷ is a linear or branched alkyl group with 1 to 4 carbon atoms, and R ¹⁸ 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); r is an integer of 0 to 5, s is an integer of 0 to 5, but r+s is an integer of 1 to 5) . [3] The above-mentioned resin (a2-1) contains 60 mol% to 100 mol% of the above-mentioned monomer unit represented by the formula (6) with respect to the total monomer units, and the above-mentioned resin (a2-2) is The positive photosensitive resin composition described in [2] of the aforementioned monomer units represented by the formula (6) contains 60 mol% to 100 mol% of the total monomer units. [4] In [1] to [3], 5 mol % to 95 mol % of each phenolic hydroxyl group of the aforementioned resins (a2-1) and (a2-2) are protected with the aforementioned acid decomposable group (4) Any of the positive photosensitive resin compositions described above. [5] The mass ratio of the aforementioned resin (a2-2) to the aforementioned resin (a2-1) (mass of resin (a2-2)/mass of resin (a2-1)) is 5/95 to 95/5 [ The positive-type photosensitive resin composition described in any one of 1] to [4]. [6] The positive photosensitive resin composition described in any one of [1] to [5] where YX≧20. [7] The above-mentioned resins (a2-1) and (a2-2) are copolymers having a monomer unit represented by formula (12) and the composition of the positive-type photosensitive resin described in any one of [1] to [6] thing

(For 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 1 to 2 carbon atoms. A phenyl group substituted by at least one kind of alkoxy group of ~6). [8] The aforementioned photoacid generator (C) is the positive photosensitive resin composition described in any one of [1] to [7] of the compound represented by formula (13).

(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, R ²⁵ and R ²⁶ are each independently substituted or unsubstituted Substituted 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 to 10 ring members, This ring structure may have a substituent). [9] The positive photosensitive resin composition described in any one of [1] to [8] of the aforementioned resin blend (A2) containing 30% by mass to 90% by mass based on the total mass of the resin components . [10] A positive-type photosensitive resin composition containing 10 to 150 parts by mass of the positive-type photosensitive resin composition described in any one of [1] to [9] of the aforementioned colorant (B) based on 100 parts by mass of the resin components in total . [11] The positive-type photosensitive resin composition described in any one of [1] to [10] of the photoacid generator (C) containing 0.1 to 85 parts by mass as a total of 100 parts by mass of resin components . [12] The positive-type photosensitive resin composition described in any one of [1] to [11] in which the optical density (OD value) of the cured film of the above-mentioned positive-type photosensitive resin composition is 0.5 or more per 1 μm of film thickness things. [13] The positive-type photosensitive resin composition described in any one of [1] to [12] that further contains a resin (D) having an epoxy group and a phenolic hydroxyl group. [14] An organic EL element separator comprising a cured product of the positive photosensitive resin composition described in any one of [1] to [13]. [15] An organic EL device insulating film comprising a cured product of the positive-type photosensitive resin composition described in any one of [1] to [13]. [16] An organic EL device comprising a cured product of the positive photosensitive resin composition described in any one of [1] to [13]. [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 a resin or polymer are standard polystyrene conversion values measured by gel permeation chromatography (GPC, gel permeation chromatography).

The "resin component" disclosed in the present invention means a resin (D) having a resin blend (A2), an epoxy group, and a phenolic hydroxyl group, and a third resin (E).

The positive-type photosensitive resin composition of one embodiment comprises the following resin blend (A2), at least one colorant (B) selected from the group consisting of black dyes and black pigments, and a photoacid generator (C ), the resin blend (A2) contains: having a plurality of phenolic hydroxyl groups, X mole % of the aforementioned plurality of phenolic hydroxyl groups (however, X is a real number greater than 0) is protected by an acid decomposable group (4) The resin (a2-1) has multiple phenolic hydroxyl groups, and Y mole % of the above-mentioned multiple phenolic hydroxyl groups (however, Y is a real number greater than 0) is the same acid as the above-mentioned acid decomposable group (4). A resin (a2-2) protected by a decomposable group, wherein Y-X≧10. Y-X is preferably 20 or more, more preferably 25 or more. If Y-X is more than 10, the process stability of PEB can be improved.

[Resin blend (A2)] The resin blend (A2) contains: having multiple phenolic hydroxyl groups, at least a part of the multiple phenolic hydroxyl groups being protected by acid-decomposable groups having the same acid-decomposable groups as the phenolic hydroxyl groups with different protection ratios of 2 one or more resins. By combining resins with different protection ratios of phenolic hydroxyl groups, the coexistence of the exposed part as the center to rapidly increase the alkali solubility part and the part to ease the solubility can reduce the response to deprotection by acid diffusion sex. Therefore, the process window of PEB conditions can be widened. The resin blend (A2) contains two kinds of resins with multiple phenolic hydroxyl groups, at least a part of which is protected by acid decomposable groups and the phenolic hydroxyl groups have different protection ratios. The resins are called resins (a2-1) and (a2-2), and when three types are contained, they are called resins (a2-1), (a2-2) and (a2-3). The same applies to the case of containing four or more types. For example, when containing four types, it is called resin (a2-1), (a2-2), (a2-3) and (a2-4), and when containing five types, it is called resin ( a2-1), (a2-2), (a2-3), (a2-4) and (a2-5) have different protection ratios from each other. These resins are collectively referred to as resin (a2). The phenolic hydroxyl group is an alkali-soluble functional group, and the alkali solubility before exposure of resin (a2) is suppressed by protecting this part with an acid-decomposable group. The resin (a2) may have an alkali-soluble functional group other than the phenolic hydroxyl group, and these alkali-soluble functional groups may also be protected with an acid-decomposable group in the same manner as the phenolic hydroxyl group. In the presence of acid generated during exposure, it is necessary to perform post exposure bake (PEB, post exposure bake) to promote the decomposition (deprotection) of acid decomposable groups and regenerate phenolic hydroxyl groups. Thereby, alkali dissolution of the resin (a2) in the exposed part is accelerated at the time of image development. The resin (a2) may have alkali-soluble functional groups other than phenolic hydroxyl groups, such as carboxyl groups, sulfonic acid groups, phosphoric acid groups, acid anhydride groups, mercapto groups, and the like.

<Protection of phenolic hydroxyl groups by acid-decomposable groups> Various resins (a2) contained in the resin blend (A2) (such as resins (a2-1), (a2-2)) can be protected by having multiple phenols A part of the phenolic hydroxyl group of the basic resin (a _b 2) is obtained by protecting a part of the phenolic hydroxyl group with an acid-decomposable group, and the protection ratio of the phenolic hydroxyl group of each resin (a2) is different. The resin (a2) 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.

(式(7)中，R¹⁴ 為碳原子數1～10的飽和或不飽和的直鏈狀或支鏈狀烴基，R¹⁵ 及R¹⁶ 各獨立為碳原子數1～10的飽和或者不飽和的直鏈狀或者支鏈狀烴基或碳原子數3～20的脂環式烴基，或R¹⁵ 及R¹⁶ 可共同形成環員數3～20的脂環結構)； 群III：2-四氫吡喃基； 群IV：2-四氫呋喃基； 群V：式(8)所示基

(式(8)中，R¹⁷ 為碳原子數1～4的直鏈狀或者支鏈狀的烷基，R¹⁸ 為碳原子數1～12的直鏈狀、支鏈狀或者環狀烷基、碳原子數7～12的芳烷基或碳原子數2～12的烯基) 此等酸分解性基可單獨使用，或組合2種類以上而使用。各種樹脂(例如樹脂(a2-1)、(a2-2))各具有複數種酸分解性基時，藉由1個相同酸分解性基之保護率若相異即可。在一實施態樣中，各種樹脂(a2)各具有單一酸分解性基。2-四氫吡喃基、2-四氫呋喃基及式(8)所示基與來自酚性羥基的氧原子共同形成縮醛結構。The acid-decomposable group is bound to be decomposed (deprotected) by heating in the presence of an acid to form an alkali-soluble functional group. The acid-decomposable group is preferably selected from the groups described in the following groups I to V. Group I: tert-butoxycarbonyl and 1,1-dimethyl-propoxycarbonyl; Group II: group represented by formula (7)

(In formula (7), R ¹⁴ is a saturated or unsaturated linear or branched chain hydrocarbon group with 1 to 10 carbon atoms, R ¹⁵ and R ¹⁶ are each independently a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms straight-chain or branched-chain hydrocarbon groups or alicyclic hydrocarbon groups with 3 to 20 carbon atoms, or R ¹⁵ and R ¹⁶ can jointly form an alicyclic structure with 3 to 20 ring members); Group III: 2-tetrahydro Pyranyl; Group IV: 2-tetrahydrofuryl; Group V: group represented by formula (8)

(In formula (8), R ¹⁷ is a linear or branched alkyl group with 1 to 4 carbon atoms, and R ¹⁸ is a linear, branched or cyclic alkyl group with 1 to 12 carbon atoms , an aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms) These acid-decomposable groups may be used alone or in combination of two or more kinds. When various resins (for example, resins (a2-1) and (a2-2)) each have a plurality of acid-decomposable groups, the protection ratios by one same acid-decomposable group may be different. In one embodiment, each resin (a2) has a single acid-decomposable group. The 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group and the group represented by the formula (8) together with the oxygen atom from the phenolic hydroxyl group form an acetal structure.

In formula (7), examples of saturated or unsaturated linear or branched hydrocarbon groups having 1 to 10 carbon atoms represented by R ¹⁴ , R ¹⁵ and R ¹⁶ include methyl, ethyl, and n-propane. Saturated hydrocarbon groups such as isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc., unsaturated hydrocarbon groups such as vinyl, propenyl, butenyl, ethynyl, propynyl, etc. Examples of alicyclic hydrocarbon groups having 3 to 20 carbon atoms represented by ^R15 and ^R16 include 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. Examples of the alicyclic structure having 3 to 20 ring members formed jointly by ^R15 and ^R16 include monocyclic cycloalkane structures such as cyclopropane structure, cyclobutane structure, cyclopentane structure, and cyclohexane structure, Polycyclic cycloalkane structures such as norbornane structure and adamantane structure. Examples of the group represented by the formula (8) include 1-alkoxyalkyl. 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 Base is better.

Even at a low exposure level, since a high-sensitivity positive-type photosensitive resin composition can be obtained, the acid-decomposable group of the resin (a2) forms an acetal structure with an oxygen atom from a phenolic hydroxyl group and is selected from Group III , IV or V are preferred. The acetal structure and the carboxyl group protected by the alkyl group are 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, the alkali solubility of the deprotected carboxyl group is too high, so the alkali dissolution retardation effect of other resins blended cannot be fully exerted. Among them, 2-tetrahydrofuran is preferable because of its excellent gene patterning properties.

The protection reaction of the phenolic hydroxyl group can be carried out under known conditions using general protecting agents. For example, the base resin (a _b 2) of the resin (a2) and the protective agent are reacted at a reaction temperature of -20 to 50°C in the presence of an acid or a base in a solvent-free or toluene, hexane and other solvents. Resin (a2) was 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 it is tert-butoxycarbonyl. Ethyl vinyl ether can be used when the acid-decomposable group is 1-ethoxyethyl, n-propyl vinyl ether can be used when it is 1-n-propoxyethyl, and 2-tetrahydrofuryl can be used For 2,3-dihydrofuran and 2-tetrahydropyranyl, 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. As a salt of an organic acid, for example, a pyridinium salt of p-toluenesulfonic acid or the like can 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, and pyridine, N,N-dimethyl-4- Amine compounds such as aminopyridine, triethylamine, and diisopropylethylamine.

In other embodiments, after protecting the phenolic hydroxyl group of the radically polymerizable monomer having a phenolic hydroxyl group with an acid decomposable group, by radically polymerizing the phenolic hydroxyl group protected with an acid decomposable group Resin (a2) can be obtained by polymerizing or copolymerizing with other radically polymerizable monomers as necessary. The protection of the phenolic hydroxyl group of the radically polymerizable monomer having a phenolic hydroxyl group can be carried out by the same method as the protection of the phenolic hydroxyl group of the base resin (a _b 2).

<Base resin (a _b 2)> As the base resin (a _b 2) of the resin (a2), a homopolymer or a copolymer of a radically polymerizable monomer having a phenolic hydroxyl group can be used. These base resins (a _b 2) can be used individually or in combination of 2 or more types. The base resin (a _b 2) 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 2-1)> In one embodiment, the base of the resin (a2) Resin (a _b 2) is an alkali aqueous solution soluble copolymer of a free radical polymerizable monomer having a phenolic hydroxyl group and other free radical polymerizable monomers: it is the base resin (a _b 2-1), (a _b 2- 1) It has plural phenolic hydroxyl groups. In this embodiment, the resin (a2) is one in which at least a part of the plurality of phenolic hydroxyl groups of the base resin ( _ab 2-1) is protected with an acid decomposable group. The base resin (a _b 2-1) may further have an alkali-soluble functional group other than a phenolic hydroxyl group, for example, may further have a carboxyl group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group, or a mercapto group. 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- , -OC-CH=CH-CO- and other free radical polymerizable functional groups are preferred.

The base resin (a _b 2-1) can be produced, for example, by radically polymerizing a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer. After synthesizing the copolymer by radical polymerization, a phenolic hydroxyl group can be added to the aforementioned 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 2-1) may have one or more types of alicyclic structure, aromatic structure, polycyclic structure, inorganic ring structure, heterocyclic structure, etc. Structure is better.

(對於式(15)，R³⁹ 為氫原子或甲基，b為1～5的整數) 所示單體單位者為佳。b以1～3的整數者為佳，以1者為較佳。作為具有如此酚性羥基之自由基聚合性單體，以4-羥基苯基甲基丙烯酸酯為特佳。A radically polymerizable monomer having a phenolic hydroxyl group as a raw material of the base resin (a _b 2-1) can form the formula (15)

(For formula (15), R ³⁹ is a hydrogen atom or a methyl group, and b is an integer of 1 to 5). Monomer units are preferably represented. b is preferably an integer of 1 to 3, more preferably 1. As the radically polymerizable monomer having such a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is particularly preferable.

(對於式(12)，R²¹ 及R²² 各獨立為氫原子、碳原子數1～3的烷基、完全或者部分被氟化的碳原子數1～3的烷基，或鹵素原子，R²³ 為氫原子、碳原子數1～6的直鏈或者碳原子數4～12的環狀烷基、苯基，或由選自由羥基、碳原子數1～6的烷基及碳原子數1～6的烷氧基所成群的至少1種所取代的苯基。)所示單體單位者為佳。對於式(12)，R²¹ 及R²² 各獨立以氫原子或碳原子數1～3的烷基者為佳。R²³ 係以碳原子數4～12的環狀烷酯、苯基或以選自由羥酯、碳原子數1～6的烷基及碳原子數1～6的烷氧基所成群的至少1種進行取代的苯基者為佳。作為如此其他自由基聚合性單體，以苯基馬來醯亞胺及環己基馬來醯亞胺為特佳。As other radically polymerizable monomers to form formula (12)

(For 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 1 to 2 carbon atoms. A phenyl group substituted by at least one kind of alkoxy group consisting of ~6 alkoxy groups.) is preferably a monomer unit. For formula (12), each of R ²¹ and R ²² independently is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ^R23 is at least one group consisting of a cyclic alkyl ester with 4 to 12 carbon atoms, a phenyl group, or a group selected from a hydroxyl ester, an alkyl group with a carbon number of 1 to 6, and an alkoxy group with a carbon number of 1 to 6. One type of 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 2-1) preferably has monomer units represented by formula (15) and monomer units represented by formula (12).

For the base resin (a _b 2-1), 4-hydroxyphenyl methacrylate was used as a radically polymerizable monomer having a phenolic hydroxyl group, and phenylmaleimide was used as another radically polymerizable monomer Or cyclohexylmaleimide is particularly preferred. By using a resin obtained by radically polymerizing these radically polymerizable monomers, shape retention and developability can be improved, and outgassing can be reduced.

As the polymerization initiator when the base resin ( _ab 2-1) 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 not less than 0.01 parts by mass, not less than 0.05 parts by mass, or not less than 0.5 parts by mass, but not more than 40 parts by mass and not more than 20 parts by mass relative to 100 parts by mass of the total amount of radically polymerizable monomers Or less than 15 parts by mass is preferred.

A RAFT (Reversible Addition Fragmentation Transfer, reversible addition fragmentation type chain transfer) agent and a polymerization initiator can be used together. As the RAFT agent, although not limited to the following ones, thiocarbonylthio compounds such as dithioesters, 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 2-1) may be 3000-80000, preferably 4000-70000, more preferably 5000-60000. The number average molecular weight (Mn) may be 1000-30000, preferably 1500-25000, more preferably 2000-20000. The polydispersity (Mw/Mn) may 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 various resins (resins (a2-1), (a2-2), etc.) contained in the resin blend (A2) are each 5 mol% to 95 mol% of the phenolic hydroxyl group, Preferably it is 10 mol % to 80 mol %, more preferably 25 mol % to 70 mol % is protected with an acid decomposable group (4). When the ratio of the phenolic hydroxyl group protected by an acid-decomposable group is set at 5 mol % or more, a 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 at 95 mol% or less, the remaining amount of unreacted acid-decomposable groups can be reduced and the solubility of the exposed part can be improved. The proportion of phenolic hydroxyl groups protected by acid-decomposable groups can be calculated from the weight loss (%) of resins (a2-1) and (a2-2) using a thermogravimetric differential thermal analysis device (TG/DTA).

In one embodiment, the resin (a2) is 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, and is soluble in an aqueous alkali solution. A homopolymer, or a base of a radically polymerizable monomer having a phenolic hydroxyl group and other radically polymerizable monomers having multiple phenolic hydroxyl groups, wherein at least a part of the multiple phenolic hydroxyl groups is protected with an acid-decomposable group Aqueous solution soluble copolymer. 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 2-1), and the base resin (a _b 2-1) has multiple phenols phenolic hydroxyl groups, at least a part of these phenolic hydroxyl groups are protected with acid decomposable groups.

(式(6)中，R¹² 為氫原子或甲基，R¹³ 選自由 群I：tert-丁氧基羰基及1,1-二甲基-丙氧基羰基； 群II：式(7)所示基

(式(7)中，R¹⁴ 為碳原子數1～10的飽和或不飽和的直鏈狀或支鏈狀烴基，R¹⁵ 及R¹⁶ 各獨立為碳原子數1～10的飽和或者不飽和的直鏈狀或者支鏈狀烴基或碳原子數3～20的脂環式烴基，或R¹⁵ 及R¹⁶ 可共同形成環員數3～20的脂環結構)； 群III：2-四氫吡喃基； 群IV：2-四氫呋喃基； 群V：式(8)所示基

(式(8)中，R¹⁷ 為碳原子數1～4的直鏈狀或者支鏈狀的烷基，R¹⁸ 為碳原子數1～12的直鏈狀、支鏈狀或者環狀烷基、碳原子數7～12的芳烷基或碳原子數2～12的烯基)；所成群的酸分解性基(4)，r為0～5的整數，s為0～5的整數，但r+s為1～5的整數。)，前述樹脂(a2-1)及(a2-2)各具有至少1個s為1以上的整數之前述單體單位，存在於前述樹脂(a2-1)及(a2-2)中之複數的R¹³ 皆為相同的酸分解性基者為佳。For this embodiment, each resin (a2) independently has a monomer unit represented by formula (6),

(In formula (6), R ¹² is a hydrogen atom or a methyl group, R ¹³ is selected from group I: tert-butoxycarbonyl and 1,1-dimethyl-propoxycarbonyl; Group II: formula (7) Shown base

(In formula (7), R ¹⁴ is a saturated or unsaturated linear or branched chain hydrocarbon group with 1 to 10 carbon atoms, R ¹⁵ and R ¹⁶ are each independently a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms straight-chain or branched-chain hydrocarbon groups or alicyclic hydrocarbon groups with 3 to 20 carbon atoms, or R ¹⁵ and R ¹⁶ can jointly form an alicyclic structure with 3 to 20 ring members); Group III: 2-tetrahydro Pyranyl; Group IV: 2-tetrahydrofuryl; Group V: group represented by formula (8)

(In formula (8), R ¹⁷ is a linear or branched alkyl group with 1 to 4 carbon atoms, and R ¹⁸ 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); the grouped acid decomposable group (4), r is an integer of 0 to 5, and s is an integer of 0 to 5 , but r+s is an integer from 1 to 5. ), the above-mentioned resins (a2-1) and (a2-2) each have at least one of the above-mentioned monomer units in which s is an integer greater than or equal to 1, and the plural numbers present in the above-mentioned resins (a2-1) and (a2-2) It is preferable that all R ^13s are the same acid-decomposable group.

(對於式(12)，R²¹ 及R²² 各獨立為氫原子、碳原子數1～3的烷基、完全或者部分被氟化的碳原子數1～3的烷基，或鹵素原子，R²³ 為氫原子、碳原子數1～6的直鏈或者碳原子數4～12的環狀烷基、苯基，或由選自由羥基、碳原子數1～6的烷基及碳原子數1～6的烷氧基所成群的至少1種所取代的苯基。)所示單體單位者為佳。R²¹ 、R²² 及R²³ 的較佳例與前述相同。Resin (a2) has formula (12)

(For 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 1 to 2 carbon atoms. A phenyl group substituted by at least one kind of alkoxy group consisting of ~6 alkoxy groups.) is preferably a monomer unit. Preferred examples of R ²¹ , R ²² and R ²³ are the same as above.

In one embodiment, the resin (a2-1) contains 60 mol% to 100 mol% of the monomer units represented by formula (6) relative to the total monomer units of the resin (a2-1), preferably containing 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol%. When the monomer unit represented by the formula (6) is set at 60 mol % or more, the difference in alkali solubility between the exposed part and the unexposed part can be increased and the sensitivity can be increased. When the monomer unit represented by formula (6) is set below 100 mol %, the balance between heat resistance and alkali solubility can be maintained. From the same point of view, in one embodiment, the resin (a2-2) contains 60 mol% to 100 mol% of the monomer unit represented by the formula (6) relative to the total monomer units of the resin (a2-2) , preferably containing 70 mol% to 100 mol%, more preferably containing 80 mol% to 100 mol%.

In one embodiment, the monomer unit represented by formula (6) and s is an integer greater than or equal to 1, that is, at least one phenolic hydroxyl group is protected by an acid decomposable group (4) represented by formula (6) The number of monomer units is 5% to 95% of the total monomer units of the resin (a2-1), preferably 15% to 70%, more preferably 25% to 60%. When 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. When the ratio of the above-mentioned monomer units is set at 95% or less, the residual amount of unreacted acid-decomposable groups can be reduced, and the high sensitivity of the solubility of the exposed part can be improved. From the same point of view, in one embodiment, a monomer unit represented by formula (6) and s is an integer greater than 1, that is, at least one phenolic hydroxyl group is protected by an acid decomposable group (4). The number of monomer units represented by formula (6) is 5% to 95% of the total monomer units of the resin (a2-2), preferably 15% to 70%, more preferably 25% to 60%.

In one embodiment, based on the resin blend (A2), it is preferable to contain the resin (a2-1) in an amount of 5 to 95% by mass. It is preferably 10 to 90% by mass, more preferably 15 to 85% by mass. Using the resin blend (A2) as a standard, the process stability of PEB can be improved by containing the resin (a2-1) in an amount of 5 to 95% by mass.

In one embodiment, the resin blend (A2) is used as a reference, and it is preferable to contain the resin (a2-2) in an amount of 5 to 95% by mass. Preferably it is 10-90 mass %, More preferably, it is 15-85 mass %. Using the resin blend (A2) as a standard, the process stability of PEB can be improved by containing the resin (a2-2) in an amount of 5-95% by mass.

In one embodiment, the mass ratio of resin (a2-2) to resin (a2-1) (mass of resin (a2-2)/mass of resin (a2-1)) is 5/95 to 95/5 Preferably, 10/90 to 90/10 is more preferred, and 15/85 to 85/15 is more preferred. By setting the mass ratio of resin (a2-2) to resin (a2-1) at 5/95˜95/5, the process stability of PEB can be improved.

In one embodiment, the positive photosensitive resin composition contains 10 to 80 parts by mass of the resin blend (A2) based on 100 parts by mass of the solid content, preferably 15 to 60 parts by mass, Preferably it is 20 to 40 parts by mass. When the content of the resin blend (A2) is 10 parts by mass or more based on 100 parts by mass of the solid content, high sensitivity for imparting a chemical amplification function to the photosensitive resin composition can be realized. When the content of the resin blend (A2) 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 (A2) means that the resin blend (A2), 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 (A2), preferably 40% to 80% by mass, based on the total mass of the resin components. , preferably 45% by mass to 65% by mass. When the content of the resin blend (A2) is set to 30% by mass or more, high sensitivity for imparting a chemical amplification function to the photosensitive resin composition can be achieved. When the content of the resin blend (A2) 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, those 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 to 47 is 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 it is 40 mass parts - 70 mass parts. 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 (a2) to regenerate the phenolic hydroxyl groups, and increase the alkali solubility of the resin (a2). 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 may be bonded to form a ring structure with 3 to 10 ring members, and the ring structure may also have a substituent.

The substituted or unsubstituted alkyl group for R ²⁴ includes, for example, straight-chain or branched-chain alkyl groups having 1 to 10 carbon atoms, preferably methyl, ethyl or n-propyl. The substituted or unsubstituted alkoxy group of ^R24 includes, for example, straight-chain or branched-chain alkoxy groups having 1 to 5 carbon atoms, preferably methoxy or ethoxy. Examples of substituents for ^R24 's alkyl and alkoxy groups include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms), cyano groups, nitro groups, aryl groups having 6 to 20 carbon atoms, An alkoxy group with 1 to 10 carbon atoms and a cycloalkyl group with 3 to 10 carbon atoms. The substituted or unsubstituted aryl group for ^R24 includes, for example, an aryl group having 6 to 20 carbon atoms, preferably phenyl, 4-methylphenyl or naphthyl. Examples of substituents for the aryl group of ^R24 include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, and halogen atoms (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.

Examples of unsubstituted aryl groups for R ²⁵ and R ²⁶ include aryl groups having 6 to 20 carbon atoms, preferably phenyl or naphthyl. Examples of unsubstituted heterocyclic groups for R ²⁵ and R ²⁶ include 2-benzimidazolyl, 2-benzoxazolyl, 2-benzothiazolyl and 2-indolyl. As substituents for 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 atoms, chlorine atoms, 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), each R ³⁷ is independently an alkyl group, an alkoxy group or a halogen atom, and d represents an integer of 0-5.

Examples of the alkyl group for ^R37 include linear or branched chain alkyl groups having 1 to 10 carbon atoms, preferably methyl, ethyl or n-propyl. The alkoxy group for R ³⁷ includes, for example, a straight-chain or branched alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group or an ethoxy group. 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 More preferably, preferably 10 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. (Deprotected) the dissolution accelerator of the resin blend (A2) to exert its function, whereby the photosensitive resin composition can be highly sensitized.

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, The naphthalene skeleton includes epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and the like. 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. Because these compounds are thermosetting, as the common knowledge of the industry, it is impossible to uniformly record the structure according to the presence or absence of epoxy groups, the type of functional groups, and the degree of polymerization. An example of the structure of a novolac type epoxy resin is represented by formula (21). For formula (21), for example, R ³⁸ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a hydroxyl group, and e is an integer of 1 to 50.

As a phenol novolak 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.

之結構。對於式(22)，f為1～5的整數，*表示除去以下環氧基的殘基之鍵結部位，該環氧基為參與於1分子中具有至少2個環氧基之化合物的反應者。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 for 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, and it is more preferable to use 0.4-0.8 equivalent. If the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and if it is 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) which has 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% by mass to 50% by mass of the resin (D) having epoxy groups and phenolic hydroxyl groups based on 100% by mass of solid content, and 10% by mass to 40 mass % is preferable, More preferably, it is 15 mass % - 30 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 further contain the third resin (E) other than the resin (D) having the resin (a2), epoxy group, and phenolic hydroxyl group. 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 (a2), 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 multiple phenolic hydroxyl groups, and the multiple phenolic hydroxyl groups are not protected by acid-decomposable groups, that is, all acid-decomposable groups of the resin (a2) are removed. protector. Such a resin has excellent compatibility with the resin blend (A2), 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, it is 1 mass part - 10 mass parts. 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 based on 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; phenylacetic acid, Hydroatropic acid, Cinnamic acid, Mandelic acid, Phenylsuccinic acid, Atropaic acid, Cinnamic acid, Methyl cinnamate, Benzyl cinnamate, Ethylphenylene (Cinnamylidene acetic acid), coumaric acid, succinic acid (Umber acid) and other carboxylic acids; catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, m- Aromatic polyols such as glucinol and bisphenol, etc.

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 not any one of (A2) to (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°C, etc.

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 colorant 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-type photosensitive resin composition system can be composed of resin blend (A2), colorant (B), photoacid generator (C) and resin (D) with epoxy group and phenolic hydroxyl group if 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 may be set at 1 to 60% by mass, or may be set at 3 to 50% by mass or 5 to 40% by 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, a Millipore filter etc. with a pore diameter of 0.05-1.0 micrometers 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 mixing ratio 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 minutes. 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 rays or visible rays 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 (A2) 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, or 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 to 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 seconds to 90 seconds, remove unnecessary parts, and air-dry with compressed air or compressed nitrogen to form a pattern on the film.

Thereafter, the patterned film is heated by a heating device such as a hot plate or an oven, for example, at 100-350° C. for 20-200 minutes to obtain a cured film (post-baking, heat treatment step). For the heat treatment, the temperature may be maintained constant, or the temperature may be raised continuously, or may be raised 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 (A2) , by contacting the exposed film with a developer to develop a pattern, and heat-treating the patterned film at a temperature of 100°C to 350°C to form an organic EL element separator 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 materials 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 the resin (a2), the epoxy group and the phenolic hydroxyl group and the third resin (E) were determined by using polystyrene standard materials 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 Dissolve 25.5 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA") and 4.50 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) in the solvent 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, it was ice-cooled under a nitrogen atmosphere, and 6.69 g of 2,3-dihydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped over 1 hour. 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] Spin-coat the positive-type photosensitive resin composition on a glass substrate (size 100mm×100mm×1mm) to a dry film thickness of about 2.0 μm, heat on a hot plate at 100° C. for 1 minute, and pre-bake it. Thereafter, after irradiating ultraviolet rays with an exposure amount of 100 mJ/cm ² through a photomask having a hole pattern of 10 μm, PEB was performed under the conditions described in Table 2 (condition 1) 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 water 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 If 9.5μm≦pore diameter≦10.5μm is qualified By. [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 1-2, Reference Examples 1-7 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 coloring agent (B), photoacid generator (C), dissolution accelerator (F), surfactant (G) and GBL/PGMEA mixed solvent (H) recorded 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. Table 2 shows the evaluation results of the positive photosensitive resin compositions of Examples 1-2, Reference Examples 1-7 and Comparative Examples 1-9.

In Examples 1-2, Reference Examples 1-7, and Comparative Examples 1-9, holes were formed even if a black coloring agent was contained. Examples 1-2 and Reference Examples 1-7 containing plural kinds of different acid-decomposable resins having plural phenolic hydroxyl groups, at least a part of which are protected by acid-decomposable groups, and containing Compared with Comparative Examples 1-9, which have a single acid-decomposable resin, the process stability of PEB can be improved. [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 (14)

A positive-type photosensitive resin composition, which contains the following resin blend (A2), at least one colorant (B) selected from the group consisting of black dyes and black pigments, and a photoacid generator (C); the above-mentioned resin The blend (A2) is a resin containing: having plural phenolic hydroxyl groups, and X mole % (however, X is a real number greater than 0) of the aforementioned plural phenolic hydroxyl groups are protected with acid decomposable groups (4) (a2-1), having multiple phenolic hydroxyl groups, Y mole % of the above-mentioned multiple phenolic hydroxyl groups (however, Y is a real number greater than 0) is decomposed with the same acid as the above-mentioned acid-decomposable group (4) A resin (a2-2) protected by a sex group, wherein YX≧10; each of the aforementioned resins (a2-1) and (a2-2) independently has a monomer unit represented by formula (6);

In formula (6), R ¹² is a hydrogen atom or a methyl group, R ¹³ is an acid-decomposable group (4) selected from the following group I to group V, r is an integer of 0 to 5, and s is 0 An integer of ~5, but r+s is an integer of 1~5; Group I: tert-butoxycarbonyl and 1,1-dimethyl-propoxycarbonyl; Group II: the group shown in formula (7)- CR ¹⁴ R ¹⁵ R ¹⁶ (7) (In formula (7), R ¹⁴ is a saturated or unsaturated linear or branched hydrocarbon group with 1 to 10 carbon atoms, R ¹⁵ and R ¹⁶ are each independently a carbon atom Saturated or unsaturated linear or branched chain hydrocarbon groups with a number of 1 to 10 or alicyclic hydrocarbon groups with a carbon number of 3 to 20, or R ¹⁵ and R ¹⁶ can jointly form an alicyclic structure with a ring member number of 3 to 20 ); Group III: 2-tetrahydropyranyl; Group IV: 2-tetrahydrofuranyl; Group V: the group shown in formula (8) -CHR ¹⁷ -OR ¹⁸ (8) (in formula (8), R ¹⁷ is A linear or branched alkyl group with 1 to 4 carbon atoms, ^R18 is a linear, branched or cyclic alkyl group with 1 to 12 carbon atoms, an arane with 7 to 12 carbon atoms group or alkenyl group with 2 to 12 carbon atoms); each of the aforementioned resins (a2-1) and (a2-2) has at least one aforementioned monomer unit in which s is an integer greater than or equal to 1, present in the aforementioned resin (a2- 1) and (a2-2) in the plurality of R ¹³ are all the same acid decomposable group; the mass ratio of the aforementioned resin (a2-2) to the aforementioned resin (a2-1) (mass ratio of the resin (a2-2) / quality of resin (a2-1)) is 5/95~95/5. The positive-type photosensitive resin composition according to claim 1, wherein the aforementioned resin (a2-1) contains 60 mol % to 100 mol % of the aforementioned monomer represented by formula (6) relative to the total monomer unit unit, the aforementioned resin (a2-2) contains 60 mol % to 100 mol % of the aforementioned monomer unit represented by the formula (6) relative to the total monomer units. Such as the positive-type photosensitive resin composition of claim 1, wherein the phenolic hydroxyl groups of the above-mentioned resins (a2-1) and (a2-2) are 5 mole % to 95 mole % Protected with the aforementioned acid decomposable group (4). The positive-type photosensitive resin composition according to any one of claims 1-3, wherein Y-X≧20. The positive-type photosensitive resin composition according to any one of claims 1 to 3, wherein the aforementioned resins (a2-1) and (a2-2) are copolymers having monomer units 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, 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, 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. At least one substituted phenyl group consisting of 6 alkoxy groups. The positive-type photosensitive resin composition according to any one of claims 1 to 3, wherein the aforementioned photoacid generator (C) is a compound represented by formula (13),

In formula (13), R ²⁴ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, and R ²⁵ and R ²⁶ are each independently substituted or unsubstituted Aryl, substituted or unsubstituted heterocyclic group, cyano group, acetyloxyl group, carboxyl group, or alkoxycarbonyl group, R ²⁵ and R ²⁶ can be 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 according to any one of Claims 1 to 3, wherein the resin blend (A2) is contained in an amount of 30% by mass to 90% by mass based on the total mass of the resin components. The positive-type photosensitive resin composition according to any one of claims 1 to 3, wherein the colorant (B) is contained in an amount of 10 to 150 parts by mass based on 100 parts by mass of the total resin components. The positive-type photosensitive resin composition according to any one of Claims 1 to 3, 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 any one of claims 1 to 3, wherein the optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness. The positive-type photosensitive resin composition according to any one of claims 1 to 3, further comprising a resin (D) having epoxy groups and phenolic hydroxyl groups. An organic EL element separator, which contains the cured product of the positive photosensitive resin composition according to any one of claims 1 to 11. An insulating film for an organic EL element, which contains a cured product of the positive photosensitive resin composition according to any one of claims 1 to 11. An organic EL element, which contains the cured product of the positive photosensitive resin composition according to any one of claims 1 to 11.