TWI775466B - Positive photosensitive resin composition and organic EL element separator - Google Patents

Abstract

The present invention provides a high-sensitivity photosensitive resin composition containing a black colorant with improved process stability. It is a bond containing two or more resins (a3) having a plurality of phenolic hydroxyl groups, at least a part of which is protected by an acid-decomposable group, and the acid-decomposable group of each resin (a3). Resin blend (A3) having different dissociation energies, at least one colorant (B) selected from the group consisting of black dyes and black pigments, and a positive photosensitive resin composition of a photoacid generator (C).

Description

Positive 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 same. 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.

In a display device such as an organic EL display (OLED), in order to improve the display characteristics, a diaphragm material is used for the color pattern spacer in the display area or the edge of the peripheral part of the display area. In the manufacture of the organic EL display device, to prevent the pixels of the organic material from contacting each other, a diaphragm is formed first, and the pixels of the organic material are formed between the diaphragms. This separator 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 mask. In the case of the second negative type, the unexposed part is placed in the positive type. In this case, image development is performed by removing the exposed portion with a developing solution such as an alkaline aqueous solution, and the obtained pattern is subjected to heat treatment to form a separator (insulating film). Next, by an inkjet method or the like, an organic substance emitting red, green, and blue light is formed into a film between the diaphragms to form the pixels of the organic EL display device.

In this area, in recent years, due to the miniaturization of display devices and the diversification of display contents, high-performance and high-definition pixels are required. For the purpose of improving the contrast in the display device and improving the visibility, an attempt has been made to use a colorant to impart light-shielding properties to the diaphragm. However, when a separator is made to have light-shielding properties, the photosensitive resin composition tends to have low sensitivity, and as a result, there is a fear that the exposure time becomes longer and the productivity decreases. Therefore, the photosensitive resin composition used for the formation of the membrane material containing a colorant is required to have higher sensitivity.

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

Patent Document 2 (Japanese Patent Laid-Open No. 2002-116536) describes a radiation-sensitive resin composition containing [A] an alkali-soluble resin, [B] a 1,2-quinonediazide compound, and [C] a colorant , The method of using carbon black to blacken the diaphragm material.

Patent Document 3 (Japanese Patent Laid-Open No. 2010-237310 ) describes a positive radiation-sensitive resin composition containing an alkali-soluble resin and a quinonediazide compound as a radiation-sensitive resin composition exhibiting light-shielding properties by heat treatment after exposure. A composition in which a thermosensitive dye is added to the resin composition. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open 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 properties of the cured film for the photosensitive resin composition used for the formation of the colored separator, it is necessary to use a considerable amount of coloring agent. 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 decrease, and the photosensitive resin composition cannot be sufficiently exposed. As a result, the pattern Reduced formability.

For the formation of the separator in the organic EL element, it is important that the material forming the separator has a high sensitivity from the viewpoint of productivity and the like. However, when a black photosensitive resin composition containing a colorant is used, poor exposure occurs under normally used exposure conditions, and therefore, for example, it is necessary to lengthen the exposure time, which is a factor that reduces productivity. Therefore, it is strongly desired to reduce the exposure amount of the photosensitive resin composition, reduce energy costs, and improve throughput.

As a method of increasing the sensitivity of the photosensitive resin composition, one that makes the resin composition chemically amplified can be mentioned. However, in general, the chemical amplification system has high sensitivity but lacks process stability.

An 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 inventors of the present invention found that when the positive-type photosensitive resin composition is a chemically amplified system containing a plurality of resins with different acid-decomposable properties, even if a black colorant is contained, the sensitivity is high, and it is possible to provide improved process stability. .

所示化合物中之O-R¹⁹ 間的鍵結解離能量作為Δ1，將式(10)

所示化合物中之(酚氧)-(2-四氫呋喃基的第2位碳)間之鍵結解離能量作為Δ2時，滿足Δ1/Δ2＞1之基； 具有複數酚性羥基，前述複數酚性羥基的至少一部分以2-四氫呋喃基保護的樹脂(a3-2)；及 具有複數酚性羥基，前述複數酚性羥基的至少一部分以R²⁰ 所示酸分解性基(6)保護的樹脂(a3-3)，但前述R²⁰ 為，將式(11)

所示化合物中之O-R²⁰ 間的鍵結解離能量作為Δ3時，滿足Δ3/Δ2＜1之基。 [2] Δ1/Δ2超過1.10，Δ3/Δ2未達0.990之[1]所記載的正型感光性樹脂組成物。 [3] Δ1-Δ2為1~10kcal/mol，Δ2-Δ3為0.1~10kcal/mol之[1]或[2]所記載的正型感光性樹脂組成物。 [4] 前述酸分解性基(5)為選自由tert-丁氧基羰基、1,1-二甲基-丙氧基羰基及2-四氫吡喃基所成群的[1]~[3]中任一所記載的正型感光性樹脂組成物。 [5] 前述酸分解性基(6)係式(16)所示基， -CHR²⁸ -O-R²⁹ (16) (式(16)中，R²⁸ 為碳原子數1~4的直鏈狀或者支鏈狀之烷基，R²⁹ 為碳原子數1~12之直鏈狀、支鏈狀或者環狀之烷基、碳原子數7~12的芳烷基或碳原子數2~12的烯基)之[1]~[4]中任一所記載的正型感光性樹脂組成物。 [6] 前述樹脂(a3-1)係具有式(18)所示單體單位者，前述樹脂(a3-1)具有至少1個u為1以上的整數之上述單體單位；

(式(18)中，R³¹ 為氫原子或甲基，R³² 為酸分解性基(5)，t為0~5的整數，u為0~5的整數，但t+u為1~5的整數)，前述樹脂(a3-2)係具有式(19)所示單體單位者，前述樹脂(a3-2)具有至少一個w為1以上的整數之上述單體單位；

(式(19)中，R³³ 為氫原子或甲基，R³⁴ 為2-四氫呋喃基，v為0~5的整數，w為0~5的整數，但v+w為1~5的整數) 前述樹脂(a3-3)係具有式(20)所示單體單位者，前述樹脂(a3-3)具有至少1個y為1以上的整數之上述單體單位；

(式(20)中，R³⁵ 為氫原子或甲基，R³⁶ 為酸分解性基(6)，x為0~5的整數，y為0~5的整數，但x+y為1~5的整數)。 [7] 前述樹脂(a3-1)相對於該全單體單位而言，含有式(18)所示前述單體單位60莫耳%~100莫耳%，前述樹脂(a3-2)相對於該全單體單位而言，含有式(19)所示前述單體單位60莫耳%~100莫耳%，前述樹脂(a3-3)相對於該全單體單位而言，含有式(20)所示前述單體單位60莫耳%~100莫耳%之[6]所記載的正型感光性樹脂組成物。 [8] 以式(18)表示，且u為1以上的整數之單體單位的數目為前述樹脂(a3-1)之全單體單位數的5%~95%，以式(19)表示且w為1以上的整數之單體單位的數目為前述樹脂(a3-2)之全單體單位數的5%~95%，以式(20)表示且y為1以上之整數的單體單位之數目為前述樹脂(a3-3)之全單體單位數的5%~95%之[6]或[7]中任一所記載的正型感光性樹脂組成物。 [9] 前述樹脂(a3-1)、(a3-2)及(a3-3)係具有式(12)所示單體單位之共聚物，

(式(12)中，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、苯基或以選自由羥基、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種進行取代的苯基)之[1]~[8]中任一所記載的正型感光性樹脂組成物。 [10] 前述光酸產生劑(C)為式(13)所示化合物，

(式(13)中，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 鍵結可形成環員數3~10的環結構，該環結構可具有取代基)之[1]~[9]中任一所記載的正型感光性樹脂組成物。 [11] 將樹脂成分之合計質量作為基準，含有30質量%~90質量%之前述樹脂摻合物(A3)之[1]~[10]中任一所記載的正型感光性樹脂組成物。 [12] 將樹脂成分之合計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]~[11]中任一所記載的正型感光性樹脂組成物。 [13] 將樹脂成分的合計100質量份作為基準，含有0.1質量份~85質量份之前述光酸產生劑(C)的[1]~[12]中任一所記載的正型感光性樹脂組成物。 [14] 前述正型感光性樹脂組成物的硬化被膜之光學濃度(OD值)為每膜厚1μm係0.5以上之[1]~[13]中任一所記載的正型感光性樹脂組成物。 [15] 進一步含有具有環氧基及酚性羥基之樹脂(D)之[1]~[14]中任一所記載的正型感光性樹脂組成物。 [16] 含有[1]~[15]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。 [17] 含有[1]~[15]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。 [18] 含有[1]~[15]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 (A3), at least one colorant (B) selected from the group consisting of black dyes and black pigments, and a photoacid generator (C); wherein the resin blend (A3) contains at least two kinds selected from the group consisting of resin (a3-1), resin (a3-2) and resin (a3-3); the resin (a3-1) has plural phenols Resin (a3-1) in which at least a part of the above-mentioned plural phenolic hydroxyl groups is protected by an acid-decomposable group (5) represented by R ¹⁹ , but the above-mentioned R ¹⁹ is, formula (9)

The bond dissociation energy between OR ¹⁹ in the shown compound is taken as Δ1, and formula (10)

When the bond dissociation energy between (phenol oxygen)-(2-position carbon of 2-tetrahydrofuranyl) in the compound shown is Δ2, the group satisfies Δ1/Δ2>1; it has plural phenolic hydroxyl groups, and the above plural phenolic Resin ( ^a3-2 ) in which at least a part of hydroxyl groups is protected by 2-tetrahydrofuran group; -3), but the aforementioned R ²⁰ is, formula (11)

When the bond dissociation energy between OR ²⁰ in the compounds shown is Δ3, the group of Δ3/Δ2<1 is satisfied. [2] The positive-type photosensitive resin composition described in [1] where Δ1/Δ2 exceeds 1.10 and Δ3/Δ2 is less than 0.990. [3] The positive photosensitive resin composition according to [1] or [2], where Δ1-Δ2 is 1 to 10 kcal/mol, and Δ2-Δ3 is 0.1 to 10 kcal/mol. [4] The acid-decomposable group (5) is [1] to [[1]~[ 3] The positive photosensitive resin composition according to any one of the above. [5] The acid-decomposable group (6) is a group represented by the formula (16), -CHR ²⁸ -OR ²⁹ (16) (in the formula (16), R ²⁸ is a straight chain having 1 to 4 carbon atoms or A branched alkyl group, R ²⁹ 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 alkene with 2 to 12 carbon atoms The positive photosensitive resin composition according to any one of [1] to [4] of base). [6] The above-mentioned resin (a3-1) has a monomer unit represented by the formula (18), and the above-mentioned resin (a3-1) has at least one of the above-mentioned monomer units in which u is an integer of 1 or more;

(In formula (18), R ³¹ is a hydrogen atom or a methyl group, R ³² is an acid-decomposable group (5), t is an integer of 0 to 5, u is an integer of 0 to 5, but t+u is 1 to 1 an integer of 5), the aforementioned resin (a3-2) is a monomer unit represented by the formula (19), and the aforementioned resin (a3-2) has at least one of the aforementioned monomer units whose w is an integer of 1 or more;

(In formula (19), R ³³ is a hydrogen atom or a methyl group, R ³⁴ is a 2-tetrahydrofuranyl group, v is an integer of 0 to 5, w is an integer of 0 to 5, but v+w is an integer of 1 to 5 ) The above-mentioned resin (a3-3) has a monomer unit represented by the formula (20), and the above-mentioned resin (a3-3) has at least one of the above-mentioned monomer units whose y is an integer of 1 or more;

(In formula (20), R ³⁵ is a hydrogen atom or a methyl group, R ³⁶ is an acid-decomposable group (6), x is an integer of 0 to 5, y is an integer of 0 to 5, but x+y is 1 to 1 an integer of 5). [7] The above-mentioned resin (a3-1) contains 60 mol% to 100 mol% of the above-mentioned monomer unit represented by the formula (18) relative to the total monomer unit, and the above-mentioned resin (a3-2) relative to the The total monomer unit contains 60 mol % to 100 mol % of the aforementioned monomer unit represented by the formula (19), and the aforementioned resin (a3-3) contains the formula (20 mol %) relative to the total monomer unit. ) The positive photosensitive resin composition described in [6] of the aforementioned monomer unit 60 mol % to 100 mol %. [8] Represented by formula (18), and the number of monomer units in which u is an integer of 1 or more is 5% to 95% of the total number of monomer units of the aforementioned resin (a3-1), represented by formula (19) The number of monomeric units in which w is an integer of 1 or more is 5% to 95% of the total number of monomeric units of the aforementioned resin (a3-2), and the monomer represented by formula (20) and y is an integer of 1 or more The number of units is the positive photosensitive resin composition described in any one of [6] or [7] of 5% to 95% of the total monomer unit number of the resin (a3-3). [9] The aforementioned resins (a3-1), (a3-2) and (a3-3) are copolymers having a monomer unit represented by the formula (12),

(In formula (12), R ²¹ and R ²² are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group having 1 to 3 carbon atoms, or a halogen atom, R ²³ is a hydrogen atom, a straight chain with 1 to 6 carbon atoms or a cyclic alkyl group with 4 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group with 1 to 6 carbon atoms, and 1 to 12 carbon atoms. The positive photosensitive resin composition according to any one of [1] to [8] in which at least one of the alkoxy groups of 6 is substituted with a phenyl group. [10] The aforementioned photoacid generator (C) is a compound represented by the formula (13),

(In formula (13), R ²⁴ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a halogen atom, and R ²⁵ and R ²⁶ are each independently substituted or unsubstituted Substituted aryl group, substituted or unsubstituted heterocyclic group, cyano group, acetyloxy group, carboxyl group or alkoxycarbonyl group, R ²⁵ and R ²⁶ are bonded to form a ring structure with 3 to 10 ring members. The positive photosensitive resin composition according to any one of [1] to [9] in which the structure may have a substituent). [11] The positive photosensitive resin composition according to any one of [1] to [10] of the aforementioned resin blend (A3) containing 30% by mass to 90% by mass based on the total mass of the resin components . [12] The positive-type photosensitive resin composition according to any one of [1] to [11] of the colorant (B) described above in an amount of 10 to 150 parts by mass based on 100 parts by mass of the total of the resin components . [13] The positive photosensitive resin according to any one of [1] to [12] containing 0.1 to 85 parts by mass of the photoacid generator (C) based on 100 parts by mass of the total of the resin components composition. [14] The positive-type photosensitive resin composition according to any one of [1] to [13] wherein the optical density (OD value) of the cured film of the positive-type photosensitive resin composition is 0.5 or more per film thickness of 1 μm . [15] The positive photosensitive resin composition according to any one of [1] to [14] of the resin (D) having an epoxy group and a phenolic hydroxyl group. [16] An organic EL element separator containing the cured product of the positive-type photosensitive resin composition according to any one of [1] to [15]. [17] An organic EL element insulating film containing the cured product of the positive-type photosensitive resin composition according to any one of [1] to [15]. [18] An organic EL device comprising the cured product of the positive-type photosensitive resin composition according to any one of [1] to [15]. [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.

[Type of carrying out the invention]

The present invention will be described in detail below.

The term "alkali-soluble" and "alkali-aqueous-soluble" disclosed in the present invention means that the positive-type photosensitive resin composition or the component thereof, or the film or cured film of the positive-type photosensitive resin composition can be dissolved in the alkali aqueous solution, for example, The meaning of being dissolved in a 2.38 mass % tetramethylammonium hydroxide aqueous solution. The "alkali-soluble functional group" means a group that imparts this alkali solubility to the positive-type photosensitive resin composition or the component, or the film or cured film of the positive-type 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 being decomposed (deprotected) by heating as necessary in the presence of an acid.

The "radical polymerizable functional group" disclosed in the present invention means one or a plurality of ethylenically unsaturated groups.

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

The term "(meth)acrylic acid" disclosed in the present invention refers to acrylic acid or methacrylic acid, the term "(meth)acrylate" refers to acrylate or methacrylate, and the term "(meth)acryloyl" refers to propylene Acryloyl or methacryloyl.

For the present disclosure, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of a resin or polymer represent the difference between the standard polystyrene conversion values determined by gel permeation chromatography (GPC, gel permeation chromatography). mean.

The "resin component" disclosed in the present invention means a resin blend (A3), a resin (D) having an epoxy group and a phenolic hydroxyl group, and a third resin (E).

The positive photosensitive resin composition of one embodiment is a resin (a3) containing two or more resins having plural phenolic hydroxyl groups, and at least a part of the plural phenolic hydroxyl groups are protected by acid-decomposable groups. Resin blend (A3) having different bond dissociation energies of acid-decomposable groups of resin (a3), at least one coloring agent (B) selected from the group consisting of black dyes and black pigments, and a photoacid generator ( C).

所示化合物中之O-R¹⁹ 間之鍵結解離能量作為Δ1，將式(10)

所示化合物中之(酚氧)-(2-四氫呋喃基的第2位碳)間之鍵結解離能量作為Δ2時，滿足Δ1/Δ2＞1之基； 具有複數酚性羥基，前述複數酚性羥基的至少一部分以2-四氫呋喃基保護的樹脂(a3-2)；及具有複數酚性羥基，前述複數酚性羥基的至少一部分以R²⁰ 所示酸分解性基(6)保護的樹脂(a3-3)，但前述R²⁰ 為將式(11)

所示化合物中之O-R²⁰ 間之鍵結解離能量作為Δ3時，滿足Δ3/Δ2＜1之基。[Resin Blend (A3)] The resin blend (A3) contains at least two kinds selected from the group consisting of the following. Resin (a3-1) having plural phenolic hydroxyl groups, wherein at least a part of the plural phenolic hydroxyl groups is protected by an acid-decomposable group (5) represented by R ¹⁹ , but the above R ¹⁹ is a combination of formula (9)

The bond dissociation energy between OR ¹⁹ in the shown compound is taken as Δ1, and formula (10)

When the bond dissociation energy between (phenol oxygen)-(2-position carbon of 2-tetrahydrofuranyl) in the compound shown is Δ2, the group satisfies Δ1/Δ2>1; it has plural phenolic hydroxyl groups, and the above plural phenolic Resin ( ^a3-2 ) in which at least a part of hydroxyl groups is protected by 2-tetrahydrofuran group; -3), but the aforementioned R ²⁰ is the formula (11)

When the bond dissociation energy between OR ²⁰ in the compounds shown is Δ3, the group of Δ3/Δ2<1 is satisfied.

Δ1/Δ2 is preferably more than 1.10, more preferably more than 1.15, more preferably more than 1.25. Δ3/Δ2 is preferably less than 0.990, preferably less than 0.985, more preferably less than 0.980.

In one embodiment, Δ1-Δ2 is 1-10 kcal/mol, preferably 2-9 kcal/mol, more preferably 3-8 kcal/mol. Δ2-Δ3 is preferably 0.1-10kcal/mol, preferably 0.2-5kcal/mol, more preferably 0.3-3kcal/mol.

The present inventors calculated the activation energy of the deprotection reaction of a phenol protected with an acid-decomposable group and the dissociation energy of the bond between (phenol oxygen)-(acid-decomposable group carbon) and simulated the results, and found that the deprotection reaction The activation energy is related to the above-mentioned bond dissociation energy, and the ease of deprotection is not controlled by the steric effect of the acid-decomposable group, but by the electronic effect on the reaction center. Therefore, the acid-decomposable group (5), the 2-tetrahydrofuranyl group, and the acid-decomposable group (6) having different bond dissociation energies have different easiness of deprotection by acid, and by combining these acid-decomposable groups In the resin protected by the free radicals, a part that can rapidly improve the alkali solubility and a part that eases the solubility expression can coexist with the exposed part as the center. Therefore, the process window of PEB conditions can be expanded. The resins (a3-1), (a3-2) and (a3-3) are collectively referred to as resin (a3). The phenolic hydroxyl group is an alkali-soluble functional group, and by protecting this part with an acid-decomposable group, the alkali-solubility of the resin (a3) before exposure to light is suppressed. Resin (a3) may have alkali-soluble functional groups other than the phenolic hydroxyl group, and these alkali-soluble functional groups may be protected by the same acid-decomposable group as the phenolic hydroxyl group. In the presence of the acid generated during exposure, the decomposition (deprotection) of the acid-decomposable group can be accelerated by performing post-exposure bake (PEB, post exposure bake) as necessary, and the phenolic hydroxyl group can be regenerated. Thereby, at the time of image development, the alkali dissolution of resin (a3) can be accelerated|stimulated in an exposure part. The resin (a3) may have an alkali-soluble functional group other than a phenolic hydroxyl group, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group, a mercapto group, and the like.

<Protection of phenolic hydroxyl groups by acid-decomposable groups> Various resins (a3) contained in the resin blend (A3) can be prepared by combining the phenolic properties of the base resin (a _b 3) having plural phenolic hydroxyl groups A part of the hydroxyl group is protected with an acid-decomposable group. The resin (a3) having a phenolic hydroxyl group protected by an acid-decomposable group has a partial structure of Ar-OR, where Ar represents an aromatic ring derived from a phenol, and R represents an acid-decomposable group.

The acid-decomposable group is a group that can generate an alkali-soluble functional group after being decomposed (deprotected) by heating as necessary in the presence of an acid. Regarding the phenolic oxygen, examples of the acid-decomposable group (5) having a bond dissociation energy larger than that of the second carbon of the 2-tetrahydrofuran group include tert-butoxycarbonyl, 1,1-dimethyl group -Propoxycarbonyl and 2-tetrahydropyranyl. For the phenolic oxygen, the acid-decomposable group (6) having a bond dissociation energy smaller than that of the carbon at the 2nd position of the 2-tetrahydrofuran group includes the formula (16)-CHR ²⁸ -OR ²⁹ (16) ( In formula (16), R ²⁸ is a linear or branched alkyl group with 1 to 4 carbon atoms, and R ²⁹ 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). The 2-tetrahydropyranyl group, the 2-tetrahydrofuranyl group, and the group represented by the formula (16) together with an oxygen atom derived from a phenolic hydroxyl group form an acetal structure.

For the present disclosure, the bond dissociation energy is calculated by the following procedure. Using the quantum chemical calculation software Gaussian16, using the density functional function wB97XD/6-31+G(d) method, the structure (α) of the phenolic hydroxyl group protected by an acid-decomposable group may be converted into a phenol by a deprotection reaction A total of three structures of acid-decomposable radical (β) and phenoxy radical (γ) generated by dissociation of the σ bond of the ether bond (O-R) of the hydroxyl group were optimized. Explore stable structures in a doublet state in structure (α) and a doublet state in structures (β) and (γ). In the above calculation, in order to obtain the solvation effect, the continuum dielectric model (PCM) is used, and the dielectric constant and solvation radius of nitromethane, which is close to the dielectric constant, are input in the actual solvent used for calculation. The vibration analysis calculation was performed for each structure, and the zero-corrected Gibbs energy was calculated. Confirm that there is no virtual vibration generated by the reference vibration calculated by the vibration analysis, and confirm that it has converged to a stable structure. Then, the sum of the Gibbs energies of structures (β) and (γ) G(β)+G(γ) is subtracted from the Gibbs energy G(α) of structure (α), which is defined as bond dissociation as follows energy Δ. Δ=G(α)-(G(β)+G(γ))

From the viewpoint of process stability of PEB, the resin blend (A3) preferably contains the aforementioned resin (a3-1) and resin (a3-2), or contains resin (a3-2) and resin (a3- 3), or containing resin (a3-1) and resin (a3-3), more preferably containing three kinds of resin (a3-1), resin (a3-2) and resin (a3-3).

In one embodiment of the resin blend (A3) containing the resin (a3-1) and the resin (a3-2), the resin blend (A3) contains 5 to 95% of the resin (a3-1) as a reference Quality % is better. Preferably it is 10-90 mass %, More preferably, it is 15-85 mass %. When the resin blend (A3) is used as a reference, the process stability of PEB can be improved by containing the resin (a3-1) in 5 to 95 mass %. In this embodiment, when the resin blend (A3) is used as a reference, it is preferable that the resin (a3-2) is contained in 5 to 95 mass %. Preferably it is 10-90 mass %, More preferably, it is 15-85 mass %. When the resin blend (A3) is used as a reference, the process stability of PEB can be improved by containing the resin (a3-2) in 5 to 95 mass %.

In this embodiment, the mass ratio of resin (a3-2) to resin (a3-1) (mass of resin (a3-2)/mass of resin (a3-1)) is 5/95~95/5 Better, preferably 10/90~90/10, more preferably 15/85~85/15. By setting the mass ratio of resin (a3-2) to resin (a3-1) at 5/95~95/5, the process stability of PEB can be improved.

In one of the embodiments in which the resin blend (A3) contains the resin (a3-2) and the resin (a3-3), the resin blend (A3) is used as a reference to contain the resin (a3-2) 5~ 95% by mass is better. Preferably it is 10-90 mass %, More preferably, it is 15-85 mass %. The process stability of PEB can be improved by containing 5-95 mass % of resin (a3-2) by using resin blend (A3) as a reference|standard. In this embodiment, what contains 5-95 mass % of resin (a3-3) is preferable based on resin blend (A3) as a reference. Preferably it is 10-90 mass %, More preferably, it is 15-85 mass %. When the resin blend (A3) is used as a reference, the process stability of PEB can be improved by containing the resin (a3-3) in 5 to 95 mass %.

In this embodiment, the mass ratio of resin (a3-3) to resin (a3-2) (mass of resin (a3-3)/mass of resin (a3-2)) is 5/95~95/5 Whichever is better, 10/90~90/10 is better, 15/85~85/15 is better. By setting the mass ratio of resin (a3-3) to resin (a3-2) at 5/95~95/5, the process stability of PEB can be improved.

In one embodiment in which the resin blend (A3) contains the resin (a3-1) and the resin (a3-3), when the resin blend (A3) is used as a reference, the resin (a3-1) 5~ 95% by mass is better. Preferably it is 10-90 mass %, More preferably, it is 15-85 mass %. When the resin blend (A3) is used as a reference, when the resin (a3-1) is contained in 5 to 95 mass %, the process stability of PEB can be improved. In this embodiment, what contains 5-95 mass % of resin (a3-3) is preferable based on resin blend (A3) as a reference. Preferably it is 10-90 mass %, More preferably, it is 15-85 mass %. When the resin blend (A3) contains 5 to 95% by mass of the resin (a3-3), the process stability of PEB can be improved.

In this embodiment, the mass ratio of resin (a3-3) to resin (a3-1) (mass of resin (a3-3)/mass of resin (a3-1)) is 5/95~95/5 Better, preferably 10/90~90/10, more preferably 15/85~85/15. The process stability of PEB can be improved by setting the mass ratio of resin (a3-3) to resin (a3-1) at 5/95~95/5.

In one embodiment in which the resin blend (A3) contains three types of resin (a3-1), resin (a3-2), and resin (a3-3), the resin blend (A3) contains as a reference Resin (a3-1) 5-90 mass % is preferable. Preferably it is 7-80 mass %, More preferably, it is 10-60 mass %. When the resin blend (A3) contains 5 to 90 mass % of the resin (a3-1) based on the resin blend (A3), the process stability of PEB can be improved. In this embodiment, what contains 5-90 mass % of resin (a3-2) is preferable based on resin blend (A3). Preferably it is 7-80 mass %, More preferably, it is 10-60 mass %. The process stability of PEB can be improved by containing 5-90 mass % of resin (a3-2) based on resin blend (A3). In this embodiment, what contains 5-90 mass % of resin (a3-3) is preferable based on resin blend (A3). Preferably it is 7-80 mass %, More preferably, it is 10-60 mass %. When 5-90 mass % of resin (a3-3) is contained based on resin blend (A3), the process stability of PEB can be improved.

In this embodiment, the mass ratio of resin (a3-1) to resin (a3-2) to resin (a3-3) (mass of resin (a3-1): mass of resin (a3-2): resin ( a3-3) quality) 5:90:5~25:25:50 is better, 5:85:10~25:35:40 is better, 5:75:20~25:40 : 35 is better. By setting the mass ratio of resin (a3-1) to resin (a3-2) to resin (a3-3) at 5:90:5~25:25:50, the process stability of PEB can be improved.

The protection reaction of the phenolic hydroxyl group can be carried out under known conditions using a general protecting agent. For example, in a solvent-free or toluene, hexane and other solvents, the base resin (a _b 3) of the resin (a3) is reacted with a protective agent in the presence of an acid or a base at a reaction temperature of -20 to 50 °C, and then the Resin (a3) can be obtained.

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

In another embodiment, after protecting the phenolic hydroxyl group of the radically polymerizable monomer having a phenolic hydroxyl group with an acid-decomposable group, the radical having a phenolic hydroxyl group protected with an acid-decomposable group Resin (a3) can be obtained by polymerizing or copolymerizing a polymerizable monomer and other radically polymerizable monomers as needed. Protection of the phenolic hydroxyl group of the radically polymerizable monomer having a phenolic hydroxyl group can be performed by the same method as the protection of the phenolic hydroxyl group of the base resin (a _b 3).

<Base resin (a _b 3)> As the base resin (a _b 3) of the resin (a3), a homopolymer or a copolymer of a radically polymerizable monomer having a phenolic hydroxyl group can be used. These base resins (a _b 3) may be used alone or in combination of two or more. The base resin (a _b 3) may further have a radically polymerizable functional group. As a radical polymerizable functional group, a (meth)acryloyloxy group, an allyl group, and a methallyl group are mentioned.

<Alkali aqueous solution-soluble copolymer of radical polymerizable monomer having phenolic hydroxyl group and other radical polymerizable monomer: base resin (a _b 3-1)> The base of resin (a3) in one embodiment Resin (a _b 3) is an alkali aqueous solution-soluble copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and other radically polymerizable monomers: in the base resin (a _b 3-1) (a _b 3-1 ) has a plurality of phenolic hydroxyl groups. In this embodiment, at least a part of the plural phenolic hydroxyl groups of the base resin (a _b 3-1) of the resin (a3) is protected by an acid-decomposable group. The base resin (a _b 3-1) may further have an alkali-soluble functional group other than a phenolic hydroxyl group, such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group, or a mercapto group. At least one of the radically polymerizable monomer having a phenolic hydroxyl group and the other radically polymerizable monomer preferably has CH ₂ =CHCO- or CH ₂ =C(CH ₃ )CO- as a polymerizable functional group. The other radically polymerizable monomer may have 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 radically polymerizable functional groups are preferred.

The base resin (a _b 3-1) can be produced by radically polymerizing, for example, a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer. After the copolymer is synthesized 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, and 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, Acrylamide, acrylonitrile, vinyl-n-butyl ether and other vinyl alcohol ether compounds, alkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2, 2,3,3-Tetrafluoropropyl (meth)acrylate, (meth)acrylate such as isobornyl (meth)acrylate, phenylmaleimide, cyclohexylmaleimide, etc. 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 Acrylic acid, β-styrene (meth)acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamon acid, itaconic acid, crotonic acid, propynoic acid, 3-maleiminopropionic acid, 4-maleiminobutyric acid, 6-maleiminohexanoic acid, etc. From the viewpoint of heat resistance, etc., the base resin (a _b 3-1) is composed of one or more rings having an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic cyclic structure, and a heterocyclic structure. The structure is better.

(式(17)中，R³⁰ 為氫原子或甲基，c為1~5的整數) c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。The radically polymerizable monomer having a phenolic hydroxyl group used as a raw material of the base resin (a _b 3-1) is preferably one that forms a monomer unit represented by the formula (17).

(In formula (17), R ³⁰ is a hydrogen atom or a methyl group, and c is an integer of 1 to 5) c is preferably an integer of 1 to 3, more preferably 1. As a radical polymerizable monomer which has such a phenolic hydroxyl group, 4-hydroxyphenyl methacrylate is especially preferable.

(式(12)中，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、苯基或以選自由羥基、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種進行取代的苯基) 式(12)中，R²¹ 及R²² 各獨立以氫原子或碳原子數1~3的烷基者為佳。R²³ 以碳原子數4~12的環狀烷基、苯基或以選自由羥基、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 another radically polymerizable monomer, those which form a monomer unit represented by formula (12) are preferable.

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

In one embodiment, the base resin (a _b 3-1) preferably has the monomer unit represented by the formula (17) and the monomer unit represented by the formula (12).

For the base resin (a _b 3-1), 4-hydroxyphenyl methacrylate was used as the radically polymerizable monomer having a phenolic hydroxyl group, and phenylmaleimide was used as the other radically polymerizable monomer Amines or cyclohexylmaleimide are particularly preferred. Shape maintainability and developability can be improved, and outgassing can also be reduced by using these radically polymerizable resins which are radically polymerized.

Although not limited to the following as a polymerization initiator when the base resin (a _b 3-1) is produced by radical polymerization, 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-acetoxy-1-phenylethane), two Methyl-2,2'-azobis(2-methylbutyrate), dimethyl-2,2'-azobis(2,4-dimethylvalerate) etc. Starter, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumene peroxide, di-tert-butyl Peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and other peroxide polymerization initiators with a half-life temperature of 100~170℃ for 10 hours, or benzene peroxide Peroxide polymerization initiators such as carboxyl, lauryl peroxide, 1,1'-bis(tert-butylperoxy)cyclohexane, and tert-butylperoxypivalate. The amount of the polymerization initiator used is generally 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass relative to 100 parts by mass of the total amount of radically polymerizable monomers. Parts by mass or less are preferred.

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

The weight-average molecular weight (Mw) of the base resin (a _b 3-1) may be 3,000-80,000, preferably 4,000-70,000, and more preferably 5,000-60,000. When the number average molecular weight (Mn) is 1,000 to 30,000, it is preferably 1,500 to 25,000, and more preferably 2,000 to 20,000. The polydispersity (Mw/Mn) may be 1.0-3.5, preferably 1.1-3.0, and preferably 1.2-2.8. When the weight average molecular weight, the number average molecular weight, and the polydispersity are within the above ranges, a positive-type photosensitive resin composition excellent in alkali solubility and developability can be obtained.

In one embodiment, the phenolic hydroxyl group contained in the resin blend (A3) contains 5 mol% to 95 mol% of each phenolic hydroxyl group in various resins (resins (a3-1), (a3-2), etc.), It is preferably 10 mol % to 80 mol %, more preferably 25 mol % to 70 mol %, protected by an acid-decomposable group. When the ratio of the phenolic hydroxyl group protected by the acid-decomposable group is set to 5 mol % or more, a chemical amplification function can be imparted to the photosensitive resin composition and high sensitivity can be realized. When the ratio of the phenolic hydroxyl group protected by the acid-decomposable group is set to 95 mol % or less, the residual amount of the unreacted acid-decomposable group can be reduced, and high sensitivity can be achieved to improve the solubility of the exposed part. The ratio of the phenolic hydroxyl group protected with an acid-decomposable group was calculated from the weight reduction rate (%) of resins (a3-1) and (a3-2) in a thermogravimetric differential thermal analyzer (TG/DTA).

In one embodiment, the resin (a3) is an alkaline aqueous solution-soluble homopolymer of a radically polymerizable monomer having a phenolic hydroxyl group, which has a plurality of phenolic hydroxyl groups, and at least a part of the plurality of phenolic hydroxyl groups is protected by an acid-decomposable group. , or an alkaline aqueous solution-soluble copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and other radically polymerizable monomers having a plurality of phenolic hydroxyl groups, at least a part of which is protected by an acid-decomposable group. The latter resin is a base resin (a _{b 3-1) having a copolymer of a radically polymerizable monomer having a phenolic hydroxyl group and another radically polymerizable monomer, and the base resin (a b 3-1} ) has a plurality of phenols At least a part of these phenolic hydroxyl groups are protected with acid-decomposable groups.

(式(18)中，R³¹ 為氫原子或甲基，R³² 為酸分解性基(5)，t為0~5的整數，u為0~5的整數，但t+u為1~5的整數)所示單體單位，樹脂(a3-1)具有至少1個u為1以上之整數的上述單體單位者為佳。For this embodiment, resin (a3-1) has formula (18)

(In formula (18), R ³¹ is a hydrogen atom or a methyl group, R ³² is an acid-decomposable group (5), t is an integer of 0 to 5, u is an integer of 0 to 5, but t+u is 1 to 1 The monomer unit represented by an integer of 5), the resin (a3-1) preferably has at least one of the above monomer units in which u is an integer of 1 or more.

(式(19)中，R³³ 為氫原子或甲基，R³⁴ 為2-四氫呋喃基，v為0~5的整數，w為0~5的整數，但v+w為1~5的整數)所示單體單位，樹脂(a3-2)具有至少1個w為1以上之整數的上述單體單位者為佳。For this embodiment, resin (a3-2) has formula (19)

(In formula (19), R ³³ is a hydrogen atom or a methyl group, R ³⁴ is a 2-tetrahydrofuranyl group, v is an integer of 0 to 5, w is an integer of 0 to 5, but v+w is an integer of 1 to 5 ), the resin (a3-2) preferably has at least one of the above-mentioned monomer units in which w is an integer of 1 or more.

(式(20)中，R³⁵ 為氫原子或甲基，R³⁶ 為酸分解性基(6)，x為0~5的整數，y為0~5的整數，但x+y為1~5的整數)所示單體單位，樹脂(a3-3)具有至少1個y為1以上之整數的上述單體單位者為佳。For this embodiment, resin (a3-3) has formula (20)

(In formula (20), R ³⁵ is a hydrogen atom or a methyl group, R ³⁶ is an acid-decomposable group (6), x is an integer of 0 to 5, y is an integer of 0 to 5, but x+y is 1 to 1 The monomer unit represented by an integer of 5), the resin (a3-3) preferably has at least one of the above monomer units in which y is an integer of 1 or more.

(式(12)中，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、或以選自由羥基、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種進行取代的苯基)所示單體單位者為佳。R²¹ 、R²² 及R²³ 的較佳例子與前述相同。Resin (a3) to have formula (12)

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

In one embodiment, the resin (a3-1) contains 60 mol % to 100 mol % of the monomer unit represented by the formula (18) relative to the total monomer unit of the resin (a3-1), Preferably, it contains 70 mol % to 100 mol %, and more preferably contains 80 mol % to 100 mol %. When the monomer unit represented by the formula (18) is set to 60 mol % or more, the difference in alkali solubility between the exposed part and the unexposed part is enlarged, and the sensitivity can be increased. By setting the monomer unit represented by the formula (18) to 100 mol % or less, the balance between heat resistance and alkali solubility can be maintained. From the same viewpoint, in one of the embodiments, the resin (a3-2) contains 60 mol % to 100 mol % of the monomer unit represented by the formula (19) relative to the total monomer unit of the resin (a3-2). %, preferably 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol%. From the same viewpoint, in one embodiment, the resin (a3-3) contains 60 mol% to 100 mol% of the monomer unit represented by the formula (20) relative to the total monomer unit of the resin (a3-3). %, preferably 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol%.

In one embodiment, the monomer unit represented by the formula (18) and u is an integer of 1 or more, that is, the monomer unit represented by the formula (18) in which at least one phenolic hydroxyl group is protected by an acid-decomposable group (5). The number of monomer units is 5% to 95% of the total monomer units of the resin (a3-1), preferably 15% to 70%, more preferably 25% to 60%. When the ratio of the above-mentioned monomer unit is set to 5% or more, a chemical amplification function can be imparted to the photosensitive resin composition, and high sensitivity can be realized. When the ratio of the above-mentioned monomer unit is set to 95% or less, the residual amount of unreacted acid-decomposable groups is reduced, the solubility of the exposed part is improved, and high sensitivity can be realized. From the same viewpoint, in one embodiment, it is represented by formula (19), and w is a monomer unit of an integer of 1 or more, that is, at least one phenolic hydroxyl group is represented by formula (19) protected by a 2-tetrahydrofuranyl group The number of monomer units is 5% to 95% of the total number of monomer units of the resin (a3-2), preferably 15% to 70%, more preferably 25% to 60%. From the same viewpoint, in one embodiment, the monomer unit represented by the formula (20) and y is an integer of 1 or more, that is, the formula (20) in which at least one phenolic hydroxyl group is protected by an acid-decomposable group (6). The number of monomer units shown in ) is 5% to 95% of the total monomer units of the resin (a3-3), preferably 15% to 70%, more preferably 25% to 60%.

In one embodiment, the positive photosensitive resin composition contains 10 to 80 parts by mass, preferably 15 to 60 parts by mass, of the resin blend (A3) based on 100 parts by mass of the solid content. , preferably 20 to 40 parts by mass. When the content of the resin blend (A3) is 10 parts by mass or more on the basis of 100 parts by mass of the solid content, a high sensitivity for imparting a chemical amplification function to the photosensitive resin composition can be realized. When the content of the resin blend (A3) is set to 80 parts by mass or less based on 100 parts by mass of solid content, it is possible to reduce the residual amount of unreacted acid-decomposable groups and improve the solubility of the exposed part. Sensitivity. The "solid content" of the embodiment containing the resin admixture (A3) means that the resin admixture (A3), the colorant (B), the photoacid generator (C), and any epoxy group and The phenolic hydroxyl resin (D), the third resin (E), the dissolution accelerator (F), and the optional component (G) are in terms of the total mass of the components other than the solvent (H).

In one embodiment, the positive photosensitive resin composition contains 30% by mass to 90% by mass of the resin blend (A3) based on the total mass of the resin components, and 40% by mass to 80% by mass is Preferably, it is 45 mass % - 65 mass %. When the content of the resin blend (A3) 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 (A3) is set to be 90% by mass or less, high sensitivity that improves the solubility of the exposed portion can be achieved.

[Colorant (B)] The colorant (B) is at least one selected from the group consisting of black dyes and black pigments. Black dye and black pigment can also be used together. For example, the visibility of display apparatuses, such as an organic EL display, can be improved by using the positive photosensitive resin composition containing a colorant (B) to form a black separator in an organic EL element.

In one embodiment, the colorant (B) contains a black dye. As a black dye, the dye prescribed|regulated by the color rendering index (C.I.) of solvent black 27-47 can be used. Preferred black dyes are those specified by C.I. of Solvent Black 27, 29 or 34. When at least one of the dyes specified by C.I. of Solvent Black 27 to 47 can be used as a black dye, the light-shielding property of the film of the positive photosensitive resin composition after firing can be maintained. Compared with the positive photosensitive resin composition containing a black pigment, the positive photosensitive resin composition containing a black dye has less residue of the colorant (B) during development, and can form a high-definition pattern on the film .

Black pigments can be used as colorants (B). Examples of the black pigment include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene-based pigments, lactamide-based pigments, and the like. These black pigments can be used for surface treatments. Examples of perylene-based pigments sold include K0084, K0086, pigment black 21, 30, 31, 32, 33, and 34 manufactured by BASF Corporation. As an example of a commercially available lactamide-based pigment, Irgaphor (registered trademark) black S0100CF manufactured by BASF Corporation is mentioned. The black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene-based pigments, and lactamide-based pigments because of high light-shielding properties.

In one embodiment, the positive photosensitive resin composition contains 10 parts by mass to 150 parts by mass of the colorant (B), preferably 30 parts by mass to 100 parts by mass, based on 100 parts by mass of the total resin components. , preferably 40 to 70 parts by mass. When the content of the colorant (B) is set to 10 parts by mass or more on the basis of 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 colorant (B) is set to 150 parts by mass or less based on the above-mentioned total of 100 parts by mass, the coating film can be colored without impairing the alkali developability.

[Photoacid generator (C)] The positive photosensitive resin composition contains a photoacid generator (C). The photoacid generator (C) is a compound which can generate an acid by irradiation with radiation such as visible light, ultraviolet light, γ-ray, and electron beam. The photoacid generator (C) promotes the decomposition of the acid-decomposable group of the resin (a3) to regenerate the phenolic hydroxyl group, and increases the alkali solubility of the resin (a3). In addition, when the acid generated by the photoacid generator (C) exists in the part irradiated with radiation, the resin and the acid in this part can be easily dissolved in the alkaline aqueous solution. As a result, high-resolution patterns 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 that can generate an acid with a pKa of 4 or less by irradiation with radiation, and preferably one that can generate an acid with a pKa of 3 or less. In this way, the photoacid generator (C) can generate an acid having the ability to decompose an acid-decomposable group.

The photoacid generator (C) is preferably one that can generate an acid having a pKa of -15 or more by irradiation with radiation, and preferably one that can generate an acid whose pKa is -5 or more. In this way, the photoacid generator (C) can prevent the ring-opening polymerization of the epoxy group of the resin (D) having an epoxy group and a phenolic hydroxyl group, which will be described later, from proceeding excessively during exposure and heat treatment (PEB) after exposure, and The alkali solubility of the resin (D) can be maintained during development.

Examples of the photoacid generator (C) include onium salts such as trichloromethyl-s-triazine compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts, quaternary ammonium salts, and diazonium salts. Azomethane compounds, imide sulfonate compounds and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity and high insulating properties. The acid generated from the oxime sulfonate compound has an appropriate decomposition ability to the acid-decomposable group that forms an acetal structure together with an oxygen atom derived from a phenolic hydroxyl group. Therefore, when these are used in combination, 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 heterocyclyl, 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, a linear or branched alkyl group having 1 to 10 carbon atoms, and a methyl group, an ethyl group, or an n-propyl group is preferred. Examples of the substituted or unsubstituted alkoxy group for R ²⁴ include a linear or branched alkoxy group having 1 to 5 carbon atoms, and a methoxy group or an ethoxy group is preferred. Examples of substituents for the alkyl group and alkoxy group of R ²⁴ include halogen atoms (fluorine atom, chlorine atom, bromine atom and iodine atom), cyano group, nitro group, aryl group having 6 to 20 carbon atoms, An alkoxy group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. Examples of the substituted or unsubstituted aryl group for R ²⁴ include aryl groups having 6 to 20 carbon atoms, and preferably phenyl, 4-methylphenyl, or naphthyl. Examples of the substituent of the aryl group for R ²⁴ include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom (fluorine atom, chlorine atom, bromine atom, and iodine atom) . As a halogen atom of R ^<24 >, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

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

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

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

As an alkyl group of R ^<37 >, a C1-C10 linear or branched alkyl group is mentioned, for example, A methyl group, an ethyl group, or an n-propyl group is preferable. Examples of the alkoxy group for R ³⁷ include a linear or branched alkoxy group having 1 to 5 carbon atoms, and a methoxy group or an ethoxy group is preferred. Examples of the halogen atom of R ³⁷ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a fluorine atom is preferred. d is preferably 0 or 1.

Examples of the oxime sulfonate compound include (Z,E)-2-(4-methoxyphenyl)([((4-methylphenyl)sulfonyl)oxy]imine)acetonitrile , 2-[2-(propylsulfonyloxyimide)thiophene-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, 2-[2-(4-methylbenzene sulfonyloxyimide)thiophene-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, etc.

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

[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) having an epoxy group and a phenolic hydroxyl group may have an alkali-soluble functional group other than the phenolic hydroxyl group. Phenolic hydroxyl groups and other alkali-soluble functional groups can be protected by acid-decomposable groups. Resin (D) having an epoxy group and a phenolic hydroxyl group, for example, a part of the epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter also referred to as "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 the reaction with the phenolic hydroxyl group at the time of heat treatment (post-baking) after the development, thereby improving the coating film. chemical resistance, heat resistance, etc. Since the phenolic hydroxyl group imparts solubility to an aqueous alkali solution during development, the resin (D) having an epoxy group and a phenolic hydroxyl group is not sufficiently decomposed as an acid-decomposable group when exposed to a low exposure amount. The (deprotected) resin blend (A3) functions as a dissolution accelerator, whereby the photosensitive resin composition can be highly sensitive.

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

As a compound having at least two epoxy groups in one molecule, for example, novolak-type epoxy resins, cresol novolak-type epoxy resins, bisphenol-type epoxy resins, bisphenol-type epoxy resins, Epoxy resin containing naphthalene skeleton, alicyclic epoxy resin, heterocyclic epoxy resin, etc. These epoxy compounds may only have two or more epoxy groups in one molecule, and only one type may be used, or two or more types may be used in combination. Since these compounds are thermosetting types, it is not possible to clearly describe the structure based on differences in the presence or absence of epoxy groups, the type of functional groups, and the degree of polymerization, as common knowledge of the industry. An example of the structure of the novolak-type epoxy resin is shown in formula (21). In 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 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 Co., Ltd.), 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 Co., Ltd.), and 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 (trade name; manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (trade name; manufactured by DIC Corporation), etc. are mentioned, for example. As an alicyclic epoxy resin, EHPE (registered trademark)-3150 (made by Daicel Chemical Industry Co., Ltd.) etc. are mentioned, for example. As a heterocyclic epoxy resin, TEPIC (registered trademark), TEPIC-L, TEPIC-H, TEPIC-S (made by Nissan Chemical Industries, Ltd.) etc. are mentioned, for example.

The compound having at least 2 epoxy groups in one molecule is preferably a novolac epoxy resin, and at least one selected from the group consisting of a novolac epoxy resin and a cresol novolac epoxy resin is better. The positive-type photosensitive resin composition containing the resin (D) having epoxy groups and phenolic hydroxyl groups derived from novolak-type epoxy resins is excellent in patterning properties, easy to adjust the alkali solubility, and less air leakage.

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, and examples thereof include 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 Benzoic acid, 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, etc., are preferably dihydroxybenzoic acid compounds from the viewpoint of improving alkali developability. The hydroxybenzoic acid compound may be used alone or in combination of two or more.

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 formula (22)

the structure. In formula (22), f is an integer of 1 to 5, and * represents a bond site of a residue excluding the following epoxy group which participates in the reaction of a compound having at least two epoxy groups in one molecule By.

In the method of obtaining 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 of the epoxy compound, It is preferable to use 0.3-0.9 equivalent, and it is more preferable to use 0.4-0.8 equivalent. When the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and when it is 0.95 equivalent or less, the increase in molecular weight due to side reactions can be suppressed.

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

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

In one embodiment, the positive photosensitive resin composition contains 5 to 50 mass % of resin (D) having epoxy groups and phenolic hydroxyl groups on the basis of 100 mass % of solid content, and 10 mass % -40 mass % is preferable, and 15 mass % - 30 mass % are preferable. 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 that promotes the dissolution of the exposed portion can be achieved, and it is possible to ensure a high degree of sensitivity after thermal curing. The stability and durability of the film. When the content of the resin (D) having an epoxy group and a phenolic hydroxyl group is 50% by mass or less based on 100% by mass of solid content, the solubility of the unexposed portion 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 a third resin (E) other than the resin (a3) and the resin (D) having an epoxy group and a phenolic hydroxyl group. The third resin (E) may be used alone or in combination of two or more.

Examples of the third resin (E) include acrylic resins other than resin (a3), polystyrene resins, epoxy resins, polyamide resins, phenol resins, polyimide resins, and polyamide resins. , Polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, Cardo resins and derivatives of these resins. Also, generally acrylic resins refer to (co)polymers of α-alkyl acrylates, but for the present disclosure, acrylic resins include (co)polymers of acrylates and (co)polymers of α-alkyl acrylates . For example, examples of derivatives of phenol resins include polyalkenylphenol resins in which alkenyl groups are bonded to benzene rings, and examples of derivatives of polystyrene resins include phenolic hydroxyl groups bonded to hydroxyalkyl groups or alkoxy groups. Hydroxy polystyrene resin derivatives bound to the benzene ring, etc. These resins may or may not have alkali-soluble functional groups.

In one embodiment, the third resin (E) is a resin having plural phenolic hydroxyl groups, and the plural phenolic hydroxyl groups are not protected by acid-decomposable groups, that is, for resin (a3), all acid-decomposable groups are Unprotected. As described above, the resin and the resin blend (A3) are excellent in compatibility and have high alkali solubility, so that they can be suitably used for the adjustment of the alkali solubility of the film.

In one embodiment, the positive photosensitive resin composition contains 1 to 30 parts by mass, preferably 1 to 20 parts by mass, of the third resin (E) based on 100 parts by mass of solid content. , preferably 1 to 10 parts by mass. When the content of the third resin (E) is 1 part by mass or more based on 100 parts by mass of solid content, it can be expected to effectively promote the dissolution of the resin component, impart heat resistance, and improve crosslinking properties. When the content of the third resin (E) is 30 parts by mass or less based on 100 parts by mass of solid content, the above-mentioned expected performance can be imparted without hindering the patterning properties and surface quality of the film.

[Dissolution accelerator (F)] In the positive-type photosensitive resin composition, a dissolution accelerator (F) may be further contained in order to improve the solubility of the alkali-soluble portion in the developing solution during image development. As the dissolution accelerator (F), an organic low-molecular-weight compound selected from the group consisting of a compound having a carboxyl group and a compound having a phenolic hydroxyl group can be mentioned. The dissolution accelerator (F) may be used alone or in combination of two or more.

The "low-molecular compound" disclosed in the present invention means a compound having a molecular weight of 1,000 or less. The said organic low molecular compound has a carboxyl group or a plurality of phenolic hydroxyl groups, and is alkali-soluble.

Examples of such organic low molecular weight compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, 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, diacid 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, cumin acid, hemiimidic acid, trimesic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid , 1,2,3,4-Melofanoic acid (Melofanoic acid), pyromellitic acid and other aromatic polycarboxylic acids; dihydroxybenzoic acid, trihydroxybenzoic acid, gallic acid and other aromatic hydroxycarboxylic acids; phenyl Acetic acid, Hydroatropic acid, Hydrocinnamic acid, Mandelic acid, Phenylsuccinic acid, Atropaic acid, Cinnamic acid, Methyl cinnamate, Benzyl cinnamate, phenylallylidene Cinnamylidene acetic acid, coumaric acid, succinic acid (Umber acid) and other carboxylic acids; catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol , phloroglucinol, bisphenol and other aromatic polyols.

The content of the dissolution accelerator (F) in the positive photosensitive resin composition can be set to 0.1 to 50 parts by mass, 1 to 35 parts by mass, based on 100 parts by mass of the total of the resin components Preferably, it is preferably 2 parts by mass to 20 parts by mass. When the content of the dissolution accelerator (F) is based on 100 parts by mass in total, if it is 0.1 part by mass or more, the dissolution of the resin component can be effectively accelerated, and if it is 50 parts by mass or less, excessive dissolution of the resin component is suppressed , and can improve the patterning and surface quality of the film.

[optional ingredient (G)] In the positive-type photosensitive resin composition, a thermosetting agent, a surfactant, a coloring agent other than (B), etc. may be contained as an optional component (G). For the purposes of this disclosure, arbitrary component (G) is defined as not any of (A3) to (F).

As the thermal hardener, a thermal radical generator can be used. Preferred examples of thermal radical generators include organic peroxides, and specific examples include dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane 10-hour half-life temperature It is an organic peroxide at 100~170℃.

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

In the positive-type 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 octyl phenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as ethylene nonyl phenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dibutyl dilaurate and polyoxyethylene distearate; Megafac (registered trademark) F-251, Same as F-281, Same as F-430, Same as F-444, Same as R-40, Same as F-553, Same as F-554, Same as F-555, Same as F-556, Same as F-556 F-557, same as F-558, same as F-559 (the above are trade names; manufactured by DIC Corporation), Surflon (registered trademark) S-242, same as S-243, same as S-386, same as S-420, Same as S-611 (trade name above; manufactured by ACGSeimi Chemical Co., Ltd.) and other fluorine-based surfactants; organosiloxane polymers KP323, KP326, KP341 (trade name above; manufactured by Shin-Etsu Chemical Co., Ltd.), etc. . These surfactants may be used alone or in combination of two or more.

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

The positive photosensitive resin composition may contain a second colorant other than the colorant (B). As a 2nd coloring agent, a dye, an organic pigment, an inorganic pigment, etc. are mentioned, It can be used according to the objective. The content of the second colorant is used so as not to impair the effects disclosed in the present invention.

Examples of dyes include azo-based dyes, benzoquinone-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, cyanine-based dyes, squaraine-based dyes, croconium-based dyes, and merocyanine dyes. (Merocyanine) dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, halothane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, Frugid dyes system dyes, nickel zirconium system dyes and azulene dyes, etc. Among the dyes, red dyes are preferred. Examples of the red dye include VALIFAST (registered trademark) RED 3312 (a red dye specified by C.I. of Solvent Red 122, manufactured by Dongfang Chemical Industry Co., Ltd.), and VALIFAST (registered trademark) RED 3311 (Solvent Red 8 The red dye specified by the C.I., Dongfang 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 Violet 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 photosensitive resin composition can be used in a solution state (however, when a black pigment is contained, the pigment is in a dispersed state) dissolved in the solvent (H). For example, the colorant ( B) and photoacid generator (C), and optional components (G) such as dissolution accelerator (F), thermosetting agent, surfactant, etc. as necessary, are mixed in a predetermined ratio, and a positive solution state can be prepared. type photosensitive resin composition. The positive photosensitive resin composition can be adjusted to the viscosity suitable for the coating method to be 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 glycol ethers, and the like. Ethylene glycol alkyl ether acetate, such as cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether base ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other diethylene glycol compounds, propylene glycol methyl ether acetate, propylene glycol ethyl ether ethyl Propylene glycol alkyl ether acetate compounds such as esters, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentane Ketones, cyclohexanone and other ketones, 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 propionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, γ-butyrolactone and other esters, N-methyl-2-pyrrolidone, N,N-dimethyl Carboxamide, N,N-dimethylacetamide and other amide compounds. These solvents can be used alone or in combination of two or more.

[Positive photosensitive resin composition] The positive photosensitive resin composition can be prepared by combining a resin blend (A3), a colorant (B), a photoacid generator (C), and optionally a resin (D) having an epoxy group and a phenolic hydroxyl group, and a third The resin (E), the dissolution accelerator (F), or the optional component (G) are dissolved or dispersed in the solvent (H) and mixed to prepare. The solid content concentration of the positive-type photosensitive resin composition can be appropriately determined according to the purpose of use. For example, the solid content concentration of the positive photosensitive resin composition may be set to 1 to 60 mass %, or may be set to 3 to 50 mass % or 5 to 40 mass %.

A known method can be used for the dispersion mixing method when using the pigment. For example, ball mills such as ball mills, sand mills, bead mills, paint shakers, shake mills, etc., kneaders, paddle mixers, planetary mixers, Henschel mixers, etc. can be used. Machines and other drum types can be used as other types of laser machines, colloid mills, ultrasonics, homogenizers, and rotary/revolution mixers. It is preferable to use a bead mill from the viewpoint of dispersion efficiency and microdispersion.

The prepared positive photosensitive resin composition is usually filtered before use. As a filtering means, a Millipore filter etc. with a pore diameter of 0.05-1.0 micrometers etc. are mentioned, for example.

The positive-type 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-type photosensitive resin composition for radiation lithography, first, the positive-type photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition is applied 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 substrate surface is not particularly limited, and for example, a spray method, a roll coating method, a slit method, a spin coating method, and the like can be used.

After the coating composition is applied to 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 to 130°C. A film was obtained by heat treatment for 1 minute.

Next, the pre-baked film is irradiated with radiation (eg, visible rays, ultraviolet rays, extreme ultraviolet rays, X-rays, electron rays, gamma rays, synchrotron radiation, etc.) through a mask with a predetermined pattern (exposure step). The preferred radiation is ultraviolet light or visible light having a wavelength of 250-450 nm. In one embodiment, the radiation is i-line. In other embodiments, the radiation is a ghi line.

After the exposure step, a heat treatment (PEB) to promote the decomposition of the acid-decomposable group may be performed. The alkali solubility of the resin blend (A3) in the exposed portion by PEB can be further improved. The heating conditions vary depending on the type of each component, the mixing ratio, etc., but usually at 70~140°C, for example, it can be heated on a hot plate for 30 seconds to 20 minutes, and in an oven for 1 to 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 developer, and the unnecessary portion is 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, etc.; 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; alcohol amines 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 basic compounds such as cyclic amines such as 1,5-diazabicyclo[4.3.0]-5-nonane and the like. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, a surfactant, or the like to the aqueous alkali solution can be used as a developer. The imaging time is usually 30 to 180 seconds. The developing method is any of a liquid filling method, a spray method, a dipping method, and the like. After developing, wash under running water for 30 to 90 seconds, remove unnecessary parts, and air-dry with compressed air or compressed nitrogen to form patterns on the film.

After that, the patterned coating is subjected to heat treatment at 100 to 350° C. for 20 to 200 minutes with a heating device such as a hot plate and an oven, for example, to obtain a cured coating (post-baking, heat treatment step). For the heat treatment, the temperature may be maintained constant, the temperature may be continuously raised, or the temperature may be raised stepwise. Preferably, the heat treatment is carried out in a nitrogen atmosphere.

The optical density (OD value) of the cured film of the positive photosensitive resin composition per film thickness 1 μm is preferably 0.5 or more, more preferably 0.7 or more, and more preferably 1.0 or more. When 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.

The method for producing an organic EL element diaphragm or insulating film according to an embodiment includes preparing a coating composition by dissolving or dispersing a positive-type photosensitive resin composition in a solvent, and applying the coating composition on a substrate to form a coating , The solvent contained in the film is removed and the film is dried, and the film is exposed to light by irradiating the dried film with radiation through a mask to decompose at least a part of the acid-decomposable groups of the resin blend (A3) , By contacting the exposed film with a developing solution to develop a pattern, forming a pattern on the film, and heating the patterned film at a temperature of 100°C to 350°C to form an organic EL element diaphragm or insulating film. The PEB described above can be performed after exposure and before development.

One embodiment is an organic EL element separator containing a cured product of a positive-type photosensitive resin composition.

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

One embodiment is an organic EL element containing a cured product of a positive-type 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 The 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) and the third resin (E) having the resin (a3), epoxy group, and phenolic hydroxyl group were determined by using a polystyrene standard under the following measurement conditions. calculated from the standard curve created. 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℃

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

[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 other radically polymerizable monomers 25.5 g of 4-hydroxyphenyl methacrylate (“PQMA” manufactured by Showa Denko Co., Ltd.) and 4.50 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) were completely dissolved in a solvent. In 77.1 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.), 3.66 g of V-601 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved In 14.6 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.). The two solutions obtained were placed in a 300 mL 3-necked flask, in 61.2 g of 1-methoxy-2-propyl acetate (Daicel Co., Ltd.) heated at 85° C. under a nitrogen atmosphere, simultaneously. The dropwise addition was carried out over 2 hours, and then the 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 collected by filtration, and vacuum-dried at 90° C. for 4 hours to collect 32.4 g of white powder. The obtained PCX-02e had a number-average molecular weight of 3,100 and a weight-average molecular weight of 6,600.

[Production Example 2] Production of a resin (PCX-02e-THF40) in which the phenolic hydroxyl group is protected by a 2-tetrahydrofuran 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 p as an acid catalyst -0.60 g of a pyridinium salt of toluenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50.0 g of tetrahydrofuran (manufactured by Fuji Thin Film Wako Pure Chemical Industries, Ltd.). Then, it ice-cooled under nitrogen atmosphere, and 6.69 g of 2, 3- dihydrofuran (made by Tokyo Chemical Industry Co., Ltd.) was dripped over 1 hour. Thereafter, stirring was performed at room temperature for 16 hours. After neutralizing the acid catalyst with a saturated aqueous sodium bicarbonate solution, the aqueous layer was removed. The organic layer was further washed twice with water. Then, tetrahydrofuran was distilled off. The obtained solid was dissolved in 50.0 g of ethyl acetate and dropped into 200 g of toluene to precipitate the product. The precipitate was collected by filtration, and 11.0 g of white powder was collected after vacuum drying at 80° C. for 4 hours. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a 20 mass % solid content solution of a resin (PCX-02e-THF40) in which the phenolic hydroxyl group was protected by a 2-tetrahydrofuran group. The obtained PCX-02e-THF40 has a number-average molecular weight of 3716, a weight-average molecular weight of 6806, the proportion of phenolic hydroxyl groups protected by acid-decomposable groups is 40 mol%, and at least one phenolic hydroxyl group is protected by acid-decomposable groups. The number of monomeric units protected was 55% of the total monomeric units of PCX-02e-THF40.

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

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

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

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

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

[Production Example 8] Production of a resin (PCX-02e-Boc5) in which the phenolic hydroxyl group is protected by a tert-butoxycarbonyl 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 triethyl as an alkali were added Amine (manufactured by Fuji Thin Film Wako Pure Chemical Industries, Ltd.) 1.74 g. It was dissolved in 50.0 g of tetrahydrofuran (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). Then, it ice-cooled under nitrogen atmosphere, and 3.47 g of di-tert-butyl dicarbonate (made by Tokyo Chemical Industry Co., Ltd.) was dripped over 1 hour. Thereafter, stirring was performed at room temperature for 16 hours. Then, tetrahydrofuran was distilled off, the obtained solid was melt|dissolved in 50.0 g of ethyl acetate, it dripped into 200 g of hexane, and the product was precipitated. The precipitate was collected by filtration, and 10.3 g of white powder was collected after vacuum drying at 80° C. for 4 hours. The obtained powder was dissolved in propylene glycol monomethyl acetate to obtain a 20 mass % solution of solid content of a resin (PCX-02e-Boc5) in which the phenolic hydroxyl group was protected by a tert-butoxycarbonyl group. The obtained PCX-02e-Boc5 has a number-average molecular weight of 4400, a weight-average molecular weight of 7800, the proportion of phenolic hydroxyl groups protected by acid-decomposable groups is 5 mol%, and at least one phenolic hydroxyl group is acid-decomposable groups. The number of monomeric units protected was 26% of the total monomeric units of PCX-02e-Boc5.

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

[Production Example 10] Production 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 two epoxy groups in 1 molecule were placed in a 300 mL three-necked flask. -770 (Novolak-type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent: 188) 37.6 g, and dissolved at 60° C. in a nitrogen atmosphere. Then, 20.1 g of 3,5-dihydroxybenzoic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound (0.65 equivalent to 1 equivalent of epoxy), triphenylphosphine ( Tokyo Chemical Industry Co., Ltd. product) 0.173 g (0.660 mmol), and reacted at 110 degreeC 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 obtained reactant had a number average molecular weight of 2400 and a weight average molecular weight of 8300.

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

Resin blend (A) As resin blend (A), PCX-02e-THF40, PCX-02e-nPOE60, PCX-02e-THP30, PCX-02e-iBOE60, PCX-02e-EOE60, PCX-02e were used -CHOE70, PCX-02e-Boc5, PCX-02e-THF70, PCX-02e-THF55 have the compositions shown in Table 2. The bond dissociation energy of the acid-decomposable group of the resin calculated using the quantum chemistry calculation software Gaussian16 is shown below.

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

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

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

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 Co., Ltd.) 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 Evaluation methods used in Examples, Reference Examples, and Comparative Examples are shown below.

[OD value after heating] The positive photosensitive resin composition was spin-coated on a glass substrate (size 100 mm×100 mm×1 mm) to a dry film thickness of 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 under nitrogen atmosphere, and obtained the film. The OD value of the cured film was measured with a permeation densitometer (BMT-1, manufactured by Sakata Inx Engineering Co., Ltd.), corrected only by the OD value of glass, and converted into an OD value per film thickness of 1 μm. The thickness of the film was measured using an optical film thickness measuring apparatus (F20-NIR, manufactured by Film Metrics Co., Ltd.).

[Aperture diameter] The positive photosensitive resin composition was spin-coated on a glass substrate (size 100 mm×100 mm×1 mm) to a dry film thickness of about 2.0 μm, heated at 100° C. for 1 minute on a hot plate, and pre-baked. Then, after irradiating ultraviolet rays with an exposure amount of 100 mJ/cm ² through a mask having a hole pattern of 10 μm, PEB was performed on a hot plate under the conditions described in Table 2 (condition 1). After that, an alkali development treatment was performed for 60 seconds with a 2.38 mass % tetramethylammonium hydroxide aqueous solution, and the adhered water was sprayed with a spray gun, and then the pore diameter was observed with a microscope. The pore diameter was also observed in the same manner for the samples in which the conditions of PEB were changed from Condition 1 to the following. Condition 2: Temperature of Condition 1 + 5℃ Condition 3: Temperature of Condition 1 + 10℃ Condition 4: Time of Condition 1 - 30 seconds Condition 5: Time of Condition 1 + 30 seconds 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 index of process stability for pore size evaluation.

(3) Preparation and evaluation of positive photosensitive resin composition [Examples 1 to 8, Reference Example 1 and Comparative Examples 1 to 9] In the composition described in Table 2, the resin blend (A), the resin (D) having an epoxy group and a phenolic hydroxyl group, and the third resin (E) were mixed and dissolved with a stirring rotor, and were dissolved in the obtained solution. , add the coloring agent (B), photoacid generator (C), dissolution accelerator (F), surfactant (G) and GBL/PGMEA mixed solvent (H) described in Table 2, and further mix. After visually confirming whether or not the components were dissolved, filtration was performed with a Millipore filter having 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 mass parts of the composition in Table 2 are solid content conversion values. Table 2 shows the evaluation results of the positive photosensitive resin compositions of Examples 1 to 8, Reference Example 1, and Comparative Examples 1 to 9.

In Examples 1 to 8, Reference Example 1, and Comparative Examples 1 to 9, pores were formed even when a black colorant was contained. Examples 1 to 8 and Reference Example 1 containing a plurality of resins having different acid-decomposability and having a plurality of phenolic hydroxyl groups and at least a part of the plurality of phenolic hydroxyl groups protected by acid-decomposable groups are different from those containing a single Compared with Comparative Examples 1 to 9 of the acid-decomposable resin, the process stability of PEB can be further improved. [Industrial availability]

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

Claims (18)

A positive photosensitive resin composition, which contains a resin blend (A3), at least one colorant (B) selected from the group consisting of black dyes and black pigments, and a photoacid generator (C); wherein the resin blends The compound (A3) contains at least two kinds selected from the group consisting of resin (a3-1), resin (a3-2) and resin (a3-3); the resin (a3-1) has a plurality of phenolic hydroxyl groups, At least a part of the above-mentioned plural phenolic hydroxyl groups is protected by the acid-decomposable group (5) represented by R ¹⁹ , but the above-mentioned R ¹⁹ is the bond dissociation energy between OR ¹⁹ in the compound represented by the formula (9) as △1;

When the bond dissociation energy between (phenol oxygen)-(2-position carbon of 2-tetrahydrofuranyl) in the compound represented by formula (10) is taken as Δ2, the group satisfying Δ1/Δ2>1;

The resin (a3-2) has plural phenolic hydroxyl groups, and at least a part of the plural phenolic hydroxyl groups is protected by 2-tetrahydrofuran groups; the resin (a3-3) has plural phenolic hydroxyl groups, and the plural phenolic hydroxyl groups are At least a part of R ²⁰ is protected by the acid-decomposable group (6) represented by R 20, but the aforementioned R ²⁰ satisfies △ 3 when the bond dissociation energy between OR ²⁰ in the compound represented by the formula (11) is △ 3 The basis of /△2<1;

The aforementioned resin (a3-1) has a monomer unit represented by the formula (18), and the aforementioned resin (a3-1) has at least one of the aforementioned monomer units in which u is an integer of 1 or more;

(In formula (18), R ³¹ is a hydrogen atom or a methyl group, R ³² is an acid-decomposable group (5), t is an integer of 0 to 5, u is an integer of 0 to 5, but t+u is 1 to 1 Integer of 5) the aforementioned resin (a3-2) has a monomer unit represented by the formula (19), and the aforementioned resin (a3-2) has at least one of the aforementioned monomer units whose w is an integer of 1 or more;

(In formula (19), R ³³ is a hydrogen atom or a methyl group, R ³⁴ is a 2-tetrahydrofuranyl group, v is an integer of 0 to 5, w is an integer of 0 to 5, but v+w is an integer of 1 to 5 ) The aforementioned resin (a3-3) has a monomer unit represented by the formula (20), and the aforementioned resin (a3-3) has at least one of the aforementioned monomer units whose y is an integer of 1 or more;

(In formula (20), R ³⁵ is a hydrogen atom or a methyl group, R ³⁶ is an acid-decomposable group (6), x is an integer of 0 to 5, y is an integer of 0 to 5, but x+y is 1 to 1 an integer of 5). The positive photosensitive resin composition of claim 1, wherein Δ1/Δ2 exceeds 1.10, and Δ3/Δ2 is less than 0.990. The positive photosensitive resin composition of claim 1 or 2, wherein Δ1-Δ2 is 1~10 kcal/mol, and Δ2-Δ3 is 0.1~10 kcal/mol. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the acid-decomposable group (5) is selected from the group consisting of tert-butoxycarbonyl, 1,1-dimethyl-propoxycarbonyl and 2-tetrakis Groups of hydrogen pyranyl groups. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the acid-decomposable group (6) is a group represented by the formula (16), -CHR ²⁸ -OR ²⁹ (16) (in the formula (16), R ²⁸ is a linear or branched alkyl group with 1 to 4 carbon atoms, R ²⁹ is a linear, branched or cyclic alkyl group with 1 to 12 carbon atoms, and 7 to 12 carbon atoms aralkyl or alkenyl with 2 to 12 carbon atoms). The positive-type photosensitive resin composition according to claim 1 or 2, wherein the resin (a3-1) contains 60 mol % to 100 mol % of the monomer unit represented by the formula (18) with respect to the total monomer unit. Molar %, the aforementioned resin (a3-2) contains 60 mol % to 100 mol % of the aforementioned monomer unit represented by the formula (19) relative to the total monomer unit, and the aforementioned resin (a3-3) relative to the total monomer unit Specifically, it contains 60 mol % to 100 mol % of the aforementioned monomer unit represented by the formula (20). The positive photosensitive resin composition according to claim 1 or 2, wherein the number of monomer units represented by formula (18) and where u is an integer of 1 or more is the total number of monomer units of the aforementioned resin (a3-1). 5% to 95%, the number of monomer units represented by formula (19) and w is an integer of 1 or more is 5% to 95% of the total monomer units of the aforementioned resin (a3-2). The number of monomer units represented by 20) where y is an integer of 1 or more is 5% to 95% of the total number of monomer units of the aforementioned resin (a3-3). The positive photosensitive resin composition according to claim 1 or 2, wherein the aforementioned resins (a3-1), (a3-2) and (a3-3) 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 having 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group having 1 to 3 carbon atoms, or a halogen atom, R ²³ is a hydrogen atom, a straight chain with 1 to 6 carbon atoms or a cyclic alkyl group with 4 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group with 1 to 6 carbon atoms, and 1 to 12 carbon atoms. phenyl group substituted with at least one of the alkoxy groups of 6). The positive photosensitive resin composition according to claim 1 or 2, wherein the 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 A substituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, an acetyloxy group, a carboxyl group, or an alkoxycarbonyl group, the bonding of R ²⁵ and R ²⁶ can form a ring structure with 3 to 10 ring members. The ring structure may have substituents). The positive-type photosensitive resin composition according to claim 1 or 2, wherein the resin blend (A3) 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 claim 1 or 2, which contains 10 to 150 parts by mass of the colorant (B) based on 100 parts by mass of the total of the resin components. The positive photosensitive resin composition according to claim 1 or 2, which contains 0.1 to 85 parts by mass of the photoacid generator (C) based on 100 parts by mass of the total of the resin components. The positive photosensitive resin composition according to claim 1 or 2, wherein the optical density (OD value) of the cured film of the positive photosensitive resin composition is 0.5 or more per 1 μm of film thickness. Composition of positive photosensitive resin as claimed in item 1 or 2 The product further contains a resin (D) having an epoxy group and a phenolic hydroxyl group. A positive photosensitive resin composition, which contains a resin blend (A3), at least one colorant (B) selected from the group consisting of black dyes and black pigments, and a photoacid generator (C); wherein the resin blends The compound (A3) contains at least two kinds selected from the group consisting of resin (a3-1), resin (a3-2) and resin (a3-3); the resin (a3-1) has a plurality of phenolic hydroxyl groups, At least a part of the above-mentioned plural phenolic hydroxyl groups is protected by the acid-decomposable group (5) represented by R ¹⁹ , but the above-mentioned R ¹⁹ is the bond dissociation energy between OR ¹⁹ in the compound represented by the formula (9) as △1;

When the bond dissociation energy between (phenol oxygen)-(2-position carbon of 2-tetrahydrofuranyl) in the compound represented by formula (10) is taken as Δ2, the group satisfying Δ1/Δ2>1;

The resin (a3-2) has plural phenolic hydroxyl groups, and at least a part of the plural phenolic hydroxyl groups is protected by 2-tetrahydrofuran groups; the resin (a3-3) has plural phenolic hydroxyl groups, and the plural phenolic hydroxyl groups are At least a part of R ²⁰ is protected by the acid-decomposable group (6) represented by R 20, but the aforementioned R ²⁰ satisfies △ 3 when the bond dissociation energy between OR ²⁰ in the compound represented by the formula (11) is △ 3 The basis of /△2<1;

The aforementioned resins (a3-1), (a3-2) and (a3-3) 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 having 1 to 3 carbon atoms, a fully or partially fluorinated alkyl group having 1 to 3 carbon atoms, or a halogen atom, R ²³ is a hydrogen atom, a straight chain with 1 to 6 carbon atoms or a cyclic alkyl group with 4 to 12 carbon atoms, a phenyl group, or a hydroxy group, an alkyl group with 1 to 6 carbon atoms, and 1 to 12 carbon atoms. phenyl group substituted with at least one of the alkoxy groups of 6). An organic EL element separator containing a cured product of the positive-type photosensitive resin composition according to any one of claims 1 to 15. An organic EL element insulating film containing a cured product of the positive-type photosensitive resin composition according to any one of claims 1 to 15. An organic EL element containing a cured product of the positive-type photosensitive resin composition according to any one of claims 1 to 15.