TWI802156B - Photosensitive resin composition and organic EL element partition wall - Google Patents

Abstract

The present invention provides a high-sensitivity photosensitive resin composition containing a black agent that can form a thick film pattern with high optical density (OD value) and suppressed surface roughness. The photosensitive resin composition includes (A) a first resin, (B) a second resin having a phenolic hydroxyl group different from the first resin, (C) a second resin having a phenolic hydroxyl group different from both the first resin and the second resin The third resin, (D) radiation-sensitive compound and (E) black agent, the optical density (OD value) of the cured film of the photosensitive resin composition is 0.5 or more per 1 μm of film thickness, and the phenolic hydroxyl equivalent of the second resin It is 1.1~5.0 times of the phenolic hydroxyl equivalent of the third resin.

Description

Photosensitive resin composition and organic EL element partition wall

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

In a display device such as an organic EL display (OLED), in order to improve the display characteristics, a partition wall material is used in the space between the colored patterns in the display area or the edge of the peripheral part of the display area. In the manufacture of an organic EL display device, partition walls are first formed so that pixels of organic substances do not contact each other, and pixels of organic substances are formed between the partition walls. The partition walls are generally formed by photolithography using a photosensitive resin composition, and have insulating properties. Specifically, use a coating device to coat a photosensitive resin composition on a substrate, remove volatile components by means of heating, etc., and then expose through a mask. In this case, the exposed part is removed by a developer such as an aqueous alkali solution to develop the image, and the obtained pattern is subjected to heat treatment to form a partition wall (insulating film). Next, an organic material emitting red, green, and blue light is formed into a film between the partition walls by an inkjet method to form a pixel of an organic EL display device.

In this field, in recent years, due to the miniaturization of display devices and the diversification of displayed content, higher performance and higher definition of pixels are required. For the purpose of improving the contrast of the display device and enhancing the visibility, attempts have been made to use colorants to make the partition material have light-shielding properties. However, when a partition wall material has light-shielding property, there exists a tendency for a photosensitive resin composition to become a low sensitivity, and as a result, exposure time may become long and productivity may fall. Therefore, higher sensitivity is required for the photosensitive resin composition used for forming the partition wall material containing a coloring agent.

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

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

Patent Document 3 (Japanese Unexamined Patent Publication No. 2010-237310 ) describes a positive-type resin composition containing an alkali-soluble resin and a quinonediazo compound as a radiation-sensitive resin composition that exhibits light-shielding properties by heat treatment after exposure. A composition in which a thermosensitive pigment is added to a radiation-sensitive resin composition.

In Patent Document 4 (International Publication No. 2017/069172), a positive photosensitive resin composition is described, which contains (A) a binder resin, (B) a quinone diazo compound, and (C) a solvent black 27-47 At least one black dye among the black dyes specified by the color index. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2001-281440 [Patent Document 2] Japanese Patent Laid-Open No. 2002-116536 [Patent Document 3] Japanese Patent Laid-Open No. 2010-237310 [Patent Document 4] International Publication No. 2017/069172

[Problem to be solved by the invention]

In the photosensitive resin composition used for forming the colored partition wall material, a considerable amount of coloring agent must be used in order to sufficiently improve the light-shielding properties of the cured film. In the case of using such a large amount of colorant, since the radiation irradiated on the film of the photosensitive resin composition is absorbed by the colorant, the effective intensity of the radiation in the film is reduced, and the photosensitive resin composition cannot be fully exposed. reduce.

In particular, when a photosensitive resin composition containing a black agent is used to form a thick film, for example, a film with a thickness of 2 to 3 μm, since the radiation-sensitive compound also absorbs radiation in addition to the black agent, the radiation that reaches the bottom of the film at the exposed portion volume was significantly reduced. Therefore, in the positive type, the alkali solubility of the film bottom of the exposed part is insufficient, and resin residues are generated during development, or a large amount of photosensitive resin composition is consumed in order to obtain a film with a desired thickness, that is, the remaining film rate decreases. On the other hand, in the negative type, the film bottom of the exposed part is not sufficiently insoluble, and the film may be peeled off during image development. Therefore, among photosensitive resin compositions containing a black agent, a photosensitive resin composition capable of imparting a high optical density (OD value) to a cured film and increasing the thickness of the cured film is eagerly desired.

If microscopically uneven resin dissolution occurs during the developing step, the surface area of the resin at that portion, that is, the contact area with the developing solution increases, and the dissolution rate of the resin is locally increased. As a result, the coating film is not uniformly dissolved in the developing step, and the surface of the coating film after development may become rough and the pattern shape may deteriorate. This is more noticeable in thick-film developing steps that generally require a long developing time or use a high-concentration developing solution.

The object of the present invention is to provide a high-sensitivity photosensitive resin composition containing a black agent that can form a thick film pattern with high optical density (OD value) and suppressed surface roughness. [Means to solve the problem]

The inventors of the present invention have found that by using in combination at least two resins having phenolic hydroxyl groups, and the equivalent ratio of the phenolic hydroxyl groups of these resins is within a specific range, it is also possible to form a photosensitive resin composition containing a black agent. Thick film pattern with suppressed surface roughness.

(式(17)中，R ³⁸為氫原子或碳原子數1~5之烷基，R ³⁹為選自由碳原子數1~20之直鏈烷基、碳原子數3~20之分支烷基、碳原子數3~12之環狀烷基、碳原子數6~20之芳基、經酸性官能基以外之基取代之碳原子數1~20之直鏈烷基、經酸性官能基以外之基取代之碳原子數3~20之分支烷基、經酸性官能基以外之基取代之碳原子數3~12之環狀烷基、及經酸性官能基以外之基取代之碳原子數6~20之芳基所成之群之基)。 [6] 如[1]至[5]中任一項之感光性樹脂組成物，其中前述第2樹脂具有以式(10)表示之構造單位：

(式(10)中，R ¹⁵為氫原子或碳原子數1~5之烷基，e為1~5之整數)。 [7] 如[1]至[6]中任一項之感光性樹脂組成物，其中前述第2樹脂具有以式(11)表示之構造單位：

(式(11)中，R ¹⁶及R ¹⁷分別獨立為氫原子、碳原子數1~3之烷基、完全或部分經氟化之碳原子數1~3之氟烷基或鹵原子，R ¹⁸為氫原子、碳原子數1~6之直鏈烷基、碳原子數3~12之環狀烷基、苯基或經選自由羥基、碳原子數1~6之烷基及碳原子數1~6之烷氧基所成之群中之至少1種取代之苯基)。 [8] 如[1]至[7]中任一項之感光性樹脂組成物，其中前述第1樹脂係具有環氧基及酚性羥基之樹脂。 [9] 如[1]至[8]中任一項之感光性樹脂組成物，其中前述第1樹脂係1分子中具有至少2個環氧基之化合物與羥基苯甲酸化合物之反應物，且係具有式(9)之構造的化合物，

(式(9)中，d為1~5之整數，✽表示與1分子中具有至少2個環氧基之化合物之進行反應之環氧基除外之殘基之鍵結部)。 [10] 如[9]之感光性樹脂組成物，其中前述1分子中具有至少2個環氧基之化合物係酚醛清漆型環氧樹脂。 [11] 如[1]至[10]中任一項之感光性樹脂組成物，其中前述黑色劑係溶劑黑27~47之以色彩指數(C.I.)規定之染料。 [12] 如[1]至[11]中任一項之感光性樹脂組成物，其中前述感放射線化合物係光酸產生劑。 [13] 如[1]至[12]中任一項之感光性樹脂組成物，其中以樹脂成分之合計質量為基準，前述第1樹脂包含20質量%~90質量%。 [14] 如[1]至[13]中任一項之感光性樹脂組成物，其中以樹脂成分之合計質量為基準，前述第2樹脂包含5質量%~50質量%。 [15] 如[1]至[14]中任一項之感光性樹脂組成物，其中以樹脂成分之合計質量為基準，前述第3樹脂包含5質量%~50質量%。 [16] 如[1]至[15]中任一項之感光性樹脂組成物，其中以樹脂成分之合計100質量份為基準，前述感放射線化合物包含1質量份~40質量份。 [17] 如[1]至[16]中任一項之感光性樹脂組成物，其中以樹脂成分之合計100質量份為基準，前述黑色劑包含10質量份~150質量份。 [18] 一種有機EL元件隔壁，其包含如[1]至[17]中任一項之感光性樹脂組成物的硬化物。 [19] 一種有機EL元件絕緣膜，其包含如[1]至[17]中任一項之感光性樹脂組成物的硬化物。 [20] 一種有機EL元件，其包含如[1]至[17]中任一項之感光性樹脂組成物的硬化物。 [發明效果] That is, the present invention includes the following aspects. [1] A photosensitive resin composition comprising (A) a first resin, (B) a second resin having a phenolic hydroxyl group different from the first resin, (C) the first resin and the second resin A third resin having a phenolic hydroxyl group, (D) a radiation-sensitive compound, and (E) a black agent, the optical density (OD value) of the cured film of the above-mentioned photosensitive resin composition is 0.5 per 1 μm of film thickness. As mentioned above, the phenolic hydroxyl equivalent of the said 2nd resin is 1.1-5.0 times of the phenolic hydroxyl equivalent of the said 3rd resin. [2] The photosensitive resin composition according to [1], wherein the second resin contains the same structural unit as at least one of the structural units of the third resin and other structural units, and has a structure common to the third resin The units contain 30 mol% to 95 mol% in total, and the alkali dissolution rate of the aforementioned second resin is lower than that of the aforementioned third resin. [3] The photosensitive resin composition according to [1] or [2], wherein the second resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the third resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the aforementioned second resin has a structural unit represented by formula (17):

(In formula (17), R ³⁸ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ³⁹ is a branched alkyl group selected from a straight-chain alkyl group with 1 to 20 carbon atoms and a branched alkyl group with 3 to 20 carbon atoms , cyclic alkyl groups with 3 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, linear alkyl groups with 1 to 20 carbon atoms substituted by groups other than acidic functional groups, and substituted by groups other than acidic functional groups A branched alkyl group with 3 to 20 carbon atoms substituted by a radical, a cyclic alkyl group with 3 to 12 carbon atoms substituted by a group other than an acidic functional group, and a branched alkyl group with 6 to 2 carbon atoms substituted by a group other than an acidic functional group The base of the group formed by the aryl group of 20). [6] The photosensitive resin composition according to any one of [1] to [5], wherein the aforementioned second resin has a structural unit represented by formula (10):

(In formula (10), R ¹⁵ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and e is an integer of 1 to 5). [7] The photosensitive resin composition according to any one of [1] to [6], wherein the second resin has a structural unit represented by formula (11):

(In formula (11), R ¹⁶ and R ¹⁷ are independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms or a halogen atom, R ¹⁸ is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and the number of carbon atoms A phenyl group substituted with at least one of alkoxy groups of 1 to 6). [8] The photosensitive resin composition according to any one of [1] to [7], wherein the first resin is a resin having an epoxy group and a phenolic hydroxyl group. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the first resin is a reactant of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, and It is a compound having the structure of formula (9),

(In formula (9), d is an integer of 1 to 5, and ✽ represents a bonding portion of a residue other than an epoxy group that reacts with a compound having at least two epoxy groups in one molecule). [10] The photosensitive resin composition according to [9], wherein the compound having at least two epoxy groups in one molecule is a novolak-type epoxy resin. [11] The photosensitive resin composition according to any one of [1] to [10], wherein the aforementioned black agent is a dye specified by the color index (CI) of solvent black 27-47. [12] The photosensitive resin composition according to any one of [1] to [11], wherein the radiation-sensitive compound is a photoacid generator. [13] The photosensitive resin composition according to any one of [1] to [12], wherein the first resin contains 20% by mass to 90% by mass based on the total mass of the resin components. [14] The photosensitive resin composition according to any one of [1] to [13], wherein the second resin contains 5% by mass to 50% by mass based on the total mass of the resin components. [15] The photosensitive resin composition according to any one of [1] to [14], wherein the third resin contains 5% by mass to 50% by mass based on the total mass of the resin components. [16] The photosensitive resin composition according to any one of [1] to [15], wherein the radiation-sensitive compound contains 1 to 40 parts by mass based on 100 parts by mass of the total resin components. [17] The photosensitive resin composition according to any one of [1] to [16], wherein the black agent contains 10 to 150 parts by mass based on a total of 100 parts by mass of the resin components. [18] A barrier rib for an organic EL element comprising a cured product of the photosensitive resin composition according to any one of [1] to [17]. [19] An organic EL element insulating film comprising a cured product of the photosensitive resin composition according to any one of [1] to [17]. [20] An organic EL device comprising a cured product of the photosensitive resin composition according to any one of [1] to [17]. [Invention effect]

According to the present invention, it is possible to provide a high-sensitivity photosensitive resin composition containing a black agent that can form a thick film pattern with a high optical density (OD value) and suppressed surface roughness.

The present invention will be described in detail below.

In this disclosure, "alkali-soluble" means that the photosensitive resin composition or its components, or the film or cured film of the photosensitive resin composition is soluble in a 2.38% by mass tetramethylammonium hydroxide aqueous solution. The term "alkali-soluble functional group" means a group that can impart alkali solubility to the photosensitive resin composition or its components, or the coating or cured coating of the photosensitive resin composition. Examples of the alkali-soluble functional group include, for example, a phenolic hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, an acid anhydride group, and a mercapto group.

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

In this disclosure, the so-called "structural unit" means an atomic group constituting a part of the basic structure of a polymer, and the atomic group may have a pendant atom or a pendant atomic group. For example, in the case of a radical (co)polymer, it means _a unit derived from a radically polymerizable compound used as a monomer, and in the case of a phenol novolak resin, it means ₅ OH) and 1 molecule of formaldehyde (HCHO) are formed by the condensation reaction of the following units. With regard to structural units having pendant groups (side groups), structural units having pendant groups used in or derived from the formation of cross-linked sites and structural units having free pendant groups that do not participate in the formation of cross-linked sites are considered to be different from each other. Regarding a polymer having a branched molecular chain (branch chain), the structural unit (branch unit) including a branch point and the structural unit contained in a linear molecular chain are considered to be different from each other.

In this disclosure, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryl" means acrylic acid. acyl or methacryl.

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

式中，單體i(i=1~n)之共聚合比(莫耳基準)之合計為1。 In this disclosure, the phenolic hydroxyl equivalent is a theoretical value calculated from the molecular weight and composition ratio of the structural units constituting the resin. Specifically, the phenolic hydroxyl equivalent means the value calculated by the following formula when the resin is a (co)polymer of n monomers i (i=1 to n natural numbers):

In the formula, the total of the copolymerization ratios (molar basis) of monomer i (i=1~n) is 1.

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

The "resin component" in this disclosure means the 1st resin (A), the 2nd resin (B), and the 3rd resin (C).

The so-called "solid content" in this disclosure includes any components such as resin components, radiation-sensitive compounds (D), black agents (E) and dissolution accelerators (F), which means liquid basic compounds (G) and solvents (H ) total mass of ingredients other than ).

A photosensitive resin composition according to an embodiment includes: a first resin (A), a second resin (B) having a phenolic hydroxyl group different from the first resin (A), and the first resin (A) and the second resin (A). The third resin (C) having a phenolic hydroxyl group, the radiation-sensitive compound (D) and the black agent (E) in which the resins (B) are all different.

[the first resin (A)] The first resin (A) is not particularly limited, but preferably has an alkali-soluble functional group and is alkali-soluble. Although it does not specifically limit as an alkali-soluble functional group, A carboxyl group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, a mercapto group etc. are mentioned, for example. The first resin (A) may be resins having two or more types of alkali-soluble functional groups. In the present disclosure, the first resin (A) is a resin different from the second resin (B) and the third resin (C) described later in terms of the resin skeleton, the alkali-soluble function, or both. In one embodiment, the first resin (A) is a resin that is the main component in the resin component, that is, it is contained in the resin component in an amount greater than that of the second resin (B) and the third resin (C).

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

In one embodiment, the first resin (A) includes at least one resin selected from the following (a) to (l). (a) Polyalkenylphenol resin with specific structure (b) Hydroxypolystyrene resin derivatives with specific structure (c) Resin with epoxy group and phenolic hydroxyl group (d) Copolymers of polymerizable monomers with alkali-soluble functional groups and other polymerizable monomers (e) Polyimide resin (f) Polyamide resin (g) polybenzoxazole resin (h) Polybenzoxazole resin precursor (i) Silicone resin (j) Cyclic olefin polymer (k) Cardo resin (l) Phenolic resin

藉由含有此等樹脂，可提高所得感光性樹脂組成物之顯像特性同時可以減低釋氣。 (a) Polyalkenylphenol Resin The polyalkenylphenol resin (a) can be obtained by etherifying the hydroxyl group of a conventional phenolic resin, and then subjecting the ether group to Clausen rearrangement. Among them, polyalkenylphenol resins having a structural unit of formula (1) are preferable.

By containing these resins, the imaging properties of the resulting photosensitive resin composition can be improved and outgassing can be reduced.

(式(2)中，R ⁶、R ⁷、R ⁸、R ⁹及R ¹⁰分別獨立為氫原子、碳原子數1~5之烷基、碳原子數5~10之環烷基或碳原子數6~12之芳基，式(2)之*表示與構成芳香環之碳原子的鍵結部)、碳原子數1~2之烷氧基或羥基，且R ¹、R ²及R ³中之至少1者為式(2)表示之烯基，Q為以式-CR ⁴R ⁵-表示之伸烷基、碳原子數5~10之伸環烷基、具有芳香環之2價有機基、具有脂環式縮合環之2價有機基或該等組合而成之2價基，R ⁴及R ⁵分別獨立為氫原子、碳原子數1~5之烷基、碳原子數2~6之烯基、碳原子數5~10之環狀烷基或碳原子數6~12之芳基。式(1)之構造單位於1分子存在2個以上時，各該式(1)之構造單位可相同亦可不同。 In formula (1), R ¹ , R ² and R ³ are independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group represented by formula (2),

(In formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, a cycloalkyl group with 5 to 10 carbon atoms, or a carbon atom An aryl group with a number of 6 to 12, * in formula (2) represents a bond with a carbon atom constituting an aromatic ring), an alkoxy group or a hydroxyl group with a carbon number of 1 to 2, and R ¹ , R ² and R ³ At least one of them is an alkenyl group represented by formula (2), Q is an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group with 5 to 10 carbon atoms, a divalent organic group having an aromatic ring group, a divalent organic group with an alicyclic condensed ring or a divalent group formed by these combinations, R ⁴ and R ⁵ are independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, and an alkyl group with 2 to 5 carbon atoms. 6-alkenyl group, cyclic alkyl group with 5-10 carbon atoms or aryl group with 6-12 carbon atoms. When two or more structural units of the formula (1) exist in one molecule, the respective structural units of the formula (1) may be the same or different.

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

In the alkenyl represented by formula (2), R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a ring having 5 to 10 carbon atoms An alkyl group or an aryl group with 6 to 12 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, third butyl group, n-pentyl group and the like. The cyclic alkyl group having 5 to 10 carbon atoms may, for example, be cyclopentyl, cyclohexyl, methylcyclohexyl or cycloheptyl. Specific examples of the aryl group having 6 to 12 carbon atoms include phenyl, methylphenyl, ethylphenyl, biphenyl, naphthyl and the like. R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are preferably each independently a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Preferable alkenyl represented by formula (2) may be allyl or methacryl, more preferably allyl, from the viewpoint of reactivity.

Among R ¹ , R ² and R ³ , preferably one of them is allyl or methacryl, and the other two are hydrogen atoms.

Q in formula (1) is an alkylene group represented by the formula -CR ⁴ R ⁵ -, a cycloalkylene group with 5 to 10 carbon atoms, a divalent organic group with an aromatic ring, or a 2-valent organic group with an alicyclic condensed ring. A valent organic group or a divalent group formed by combining them. ^R4 and ^R5 are independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, a cyclic alkyl group with 5 to 10 carbon atoms, or an alkyl group with 6 to 12 carbon atoms. Aryl. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, third butyl group, n-pentyl group and the like. Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl, allyl, butenyl, pentenyl, hexenyl and the like. The cyclic alkyl group having 5 to 10 carbon atoms may, for example, be cyclopentyl, cyclohexyl, methylcyclohexyl or cycloheptyl. Specific examples of the aryl group having 6 to 12 carbon atoms include phenyl, methylphenyl, ethylphenyl, biphenyl, naphthyl and the like. R ⁴ and R ⁵ are preferably independently hydrogen atoms or alkyl groups with 1 to 3 carbon atoms, most preferably both are hydrogen atoms.

作為具有脂環式縮合環之2價有機基的具體例，可舉例伸二環戊二烯基等。 Specific examples of the cycloalkylene group having 5 to 10 carbon atoms include cyclopentylene group, cyclohexylene group, methylcyclohexylene group, cycloheptylene group and the like. Specific examples of divalent organic groups having an aromatic ring include phenylene, cresyl, naphthylene, biphenylene, fenylene, anthracenyl, xylylene, 4,4-methylene A biphenyl group, a group represented by the formula (3), and the like.

As a specific example of the divalent organic group which has an alicyclic condensed ring, a dicyclopentadienyl group etc. are mentioned.

式(4)中，R ¹、R ²及R ³與式(1)相同。較佳的R ¹、R ²及R ³與式(1)中之較佳的R ¹、R ²及R ³相同。 When polyalkenylphenol resin (a) is used as the first resin (A), based on the viewpoint of alkali developability, outgassing, etc., as an especially preferable fatty polyalkenylphenol resin (a), for example, the resin of formula (1) Q is -CH ₂ -, that is, it has a structural unit represented by formula (4).

In formula (4), R ¹ , R ² and R ³ are the same as formula (1). Preferred R ¹ , R ² and R ³ are the same as preferred R ¹ , R ² and R ³ in formula (1).

式(5)中，R ^1a、R ^2a及R ^3a分別獨立為氫原子或碳原子數1~5之烷基。較佳的R ^1a、R ^2a及R ^3a與式(1)中之較佳的R ¹、R ²及R ³相同。 The structural unit represented by formula (1) or formula (4) is preferably 50-100 mole % in polyalkenylphenol resin (a), more preferably 70-100 mole %, and more preferably 80-100 mole % 100 mole %. The structural unit represented by formula (1) or formula (4) is preferably 50 mol% or more in the polyalkenylphenol resin (a), since it improves heat resistance. Since the phenolic hydroxyl group in the polyalkenylphenol resin (a) is ionized in the presence of a basic compound and becomes soluble in water, it is necessary to have a certain amount or more of the phenolic hydroxyl group from the viewpoint of alkali developability. Therefore, the polyalkenylphenol resin (a) comprising the structural unit of formula (4) is particularly preferably a polyalkenylphenol resin having a structural unit represented by formula (4) and a structural unit represented by formula (5) .

In formula (5), R ^1a , R ^2a and R ^3a are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Preferred R ^1a , R ^2a and R ^3a are the same as preferred R ¹ , R ² and R ³ in formula (1).

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

The number average molecular weight of the polyalkenylphenol resin (a) is preferably from 500 to 5000, more preferably from 800 to 3000, and even more preferably from 900 to 2000. The weight average molecular weight of the polyalkenylphenol resin (a) is preferably from 500 to 30,000, more preferably from 3,000 to 25,000, and still more preferably from 5,000 to 20,000. If the number average molecular weight is 500 or more, or the weight average molecular weight is 500 or more, the alkali development speed is appropriate and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good. If the number average molecular weight is 5000 or less, or the weight average molecular weight is 30000 or less, applicability and alkali developability will be favorable.

The phenolic hydroxyl equivalent of the polyalkenylphenol resin (a) is preferably 60-400, more preferably 80-350, and still more preferably 100-300. When the phenolic hydroxyl equivalent of polyalkenylphenol resin (a) is 60 or more, the film thickness of an unexposed part can fully be maintained in alkali image development. When the phenolic hydroxyl equivalent of polyalkenylphenol resin (a) is 400 or less, desired alkali solubility can be acquired.

藉由含有此等樹脂，可提高所得感光性樹脂組成物之顯像特性，同時亦有助於減低釋氣。 (b) Hydroxypolystyrene resin derivative As the first resin (A), a hydroxypolystyrene resin derivative (b) having a structural unit of formula (6) can also be used.

By containing these resins, the imaging characteristics of the obtained photosensitive resin composition can be improved, and at the same time, it can help to reduce outgassing.

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

As the first resin (A), when using a hydroxy polystyrene resin derivative (b), it is preferable to have a structural unit represented by the formula (6) and a formula ( 7) A copolymer of the structural units represented.

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

A hydroxypolystyrene resin derivative (b) having a structural unit represented by formula (6), and a hydroxypolystyrene resin derivative having a structural unit represented by formula (6) and a structural unit represented by formula (7) The substance (b) can be obtained by, for example, having the properties of p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol, etc. Among the aromatic vinyl compounds with phenolic hydroxyl groups, one or more than two kinds of polymers or copolymers obtained by polymerization by conventional methods are reacted with formaldehyde by conventional methods such as the method described in Japanese Patent Application Laid-Open No. 2013-151705 , or further obtained by reacting with alcohol.

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

The number average molecular weight of the hydroxypolystyrene resin derivative (b) is preferably from 1,000 to 20,000, more preferably from 3,000 to 10,000, and still more preferably from 4,000 to 9,000. The weight average molecular weight of the hydroxy polystyrene resin derivative (b) is preferably from 1,000 to 100,000, more preferably from 5,000 to 75,000, and still more preferably from 10,000 to 50,000. If the number average molecular weight is 1000 or more or the weight average molecular weight is 1000 or more, the alkali development rate is appropriate and the difference in dissolution rate between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good. When the number average molecular weight is 20,000 or less or the weight average molecular weight is 100,000 or less, applicability and alkali developability are favorable.

The phenolic hydroxyl equivalent of the hydroxy polystyrene resin derivative (b) is preferably 60-400, more preferably 80-350, and still more preferably 100-300. When the phenolic hydroxyl equivalent of a hydroxy polystyrene resin derivative (b) is 60 or more, the film thickness of an unexposed part can be fully maintained at the time of alkali development. When the phenolic hydroxyl equivalent of the hydroxypolystyrene resin derivative (b) is 400 or less, desired alkali solubility can be obtained.

(c) Resin with epoxy group and phenolic hydroxyl group Resin (c) which has an epoxy group and a phenolic hydroxyl group can also be used as 1st resin (A). These resins (c) can be obtained, for example, by reacting an epoxy group of a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as "epoxy compound") and a carboxyl group of a hydroxybenzoic acid compound. Since the resin (c) having epoxy groups and phenolic hydroxyl groups has epoxy groups, it reacts with phenolic hydroxyl groups to form crosslinks when heated, which can improve the chemical resistance and heat resistance of the film. The phenolic hydroxyl group can impart alkali solubility to the resin during image development.

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

Examples of compounds having at least two epoxy groups in one molecule include novolak epoxy resins such as phenol novolak epoxy resins and cresol novolak epoxy resins, bisphenol epoxy resins, Biphenol type epoxy resin, epoxy resin containing naphthalene skeleton, alicyclic epoxy resin, heterocyclic epoxy resin, etc. As long as these epoxy compounds have two or more epoxy groups in one molecule, only one type may be used, or two or more types may be used in combination. Since these compounds are thermosetting types, their structures cannot be fully described due to differences in the presence or absence of epoxy groups, types of functional groups, degree of polymerization, etc., as common knowledge of those skilled in the art. One example of the structure of the novolac epoxy resin is represented by formula (8). In formula (8), for example, R ¹⁴ is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 2 carbon atoms, or a hydroxyl group, and m is an integer of 1 to 50.

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

The compound having at least two epoxy groups in one molecule is preferably a novolak-type epoxy resin, more preferably a cresol novolak-type epoxy resin. A photosensitive resin composition comprising a resin (c) having an epoxy group and a phenolic hydroxyl group derived from a novolak-type epoxy resin, particularly a cresol novolac-type epoxy resin, is excellent in pattern formation, and alkali-soluble Sexual adjustment is easy, and there is less outgassing.

Hydroxybenzoic acid compounds are compounds in which at least one of the 2-6 positions of benzoic acid is substituted with a hydroxyl group, such as salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, Hydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid , 3-hydroxy-4-nitrobenzoic acid, 4-hydroxy-3-nitrobenzoic acid, etc., from the viewpoint of improving the alkali developing property, dihydroxybenzoic acid compounds are preferred. These hydroxybenzoic acid compounds may be used alone or in combination of two or more.

式(9)中，d為1~5之整數，*表示與1分子中具有至少2個環氧基之化合物之進行反應之環氧基除外的殘基之鍵結部。 In one embodiment, the resin (c) 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 a structure of formula (9),

In formula (9), d is an integer of 1 to 5, and * represents the bonding part of the residue except the epoxy group which reacts with the compound which has at least 2 epoxy groups in 1 molecule.

The method for obtaining the resin (c) having epoxy groups and phenolic hydroxyl groups from epoxy compounds and hydroxybenzoic acid compounds is to use 0.2-1.0 equivalents of hydroxybenzoic acid compounds with respect to 1 equivalent of epoxy groups of epoxy compounds, Preferably use 0.3~0.9 equivalent, more preferably use 0.4~0.8 equivalent. If the hydroxybenzoic acid compound is 0.2 equivalent or more, sufficient alkali solubility can be obtained, and if it is 1.0 equivalent or less, the molecular weight increase by a side reaction can be suppressed.

In order to accelerate the reaction of the epoxy compound and the hydroxybenzoic acid compound, a catalyst may also be used. The usage amount of the catalyst may be 0.1-10 parts by mass based on 100 parts by mass of the reaction raw material mixture formed by the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature may be 60-150° C., and the reaction time is 3-30 hours. Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenyltrimethylammonium Phosphine, chromium octoate, zirconium octoate, etc.

The number average molecular weight of the resin (c) having an epoxy group and a phenolic hydroxyl group is preferably from 500 to 8,000, more preferably from 800 to 6,000, and more preferably from 1,000 to 5,000. The weight average molecular weight of the resin (c) having an epoxy group and a phenolic hydroxyl group is preferably 500-30,000, more preferably 2,000-25,000, and more preferably 3,000-20,000. If the number average molecular weight is 500 or more or the weight average molecular weight is 500 or more, the alkali development speed is appropriate and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good. When the number average molecular weight is 8000 or less or the weight average molecular weight is 30000 or less, applicability and alkali developability are favorable.

The phenolic hydroxyl equivalent of the resin (c) having an epoxy group and a phenolic hydroxyl group is preferably 60-300, more preferably 80-250, and more preferably 100-200. When the phenolic hydroxyl group equivalent of the resin (c) which has an epoxy group and a phenolic hydroxyl group is 60 or more, the film thickness of an unexposed part can be fully maintained at the time of alkali image development. If the phenolic hydroxyl equivalent of the resin (c) which has an epoxy group and a phenolic hydroxyl group is 300 or less, desired alkali solubility can be acquired.

(d) A copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer As the first resin (A), a copolymer of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer can be used (d). Examples of alkali-soluble functional groups include carboxyl groups, alcoholic hydroxyl groups, phenolic hydroxyl groups, sulfo groups, phosphoric acid groups, and acid anhydride groups. The polymerizable functional group possessed as a polymerizable monomer can be exemplified by a radical polymerizable functional group, such as CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CHCO-, CH ₂ =C (CH ₃ )CO-, -OC-CH=CH-CO-, etc.

The copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer can be produced, for example, by radical polymerization of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer. A derivative in which an alkali-soluble functional group is added after synthesizing a copolymer by radical polymerization can also be used. Examples of polymerizable monomers having alkali-soluble functional groups include 4-hydroxystyrene, (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl (meth)acrylic acid, and β-furyl (meth)acrylic acid. base) acrylic acid, β-styryl (meth)acrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α- Cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 4-hydroxyphenyl methacrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide , 4-hydroxyphenylmaleimide, 3-maleimide propionic acid, 4-maleimide butyric acid, 6-maleimide caproic acid, etc. Examples of other polymerizable monomers include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide ; Acrylonitrile; Ether compounds of vinyl alcohol such as vinyl-n-butyl ether; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso(meth)acrylate Propyl ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second-butyl (meth)acrylate, third-butyl (meth)acrylate, phenyl (meth)acrylate, ( Tetrahydrofurfuryl methacrylate, Dimethylaminoethyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, Glycidyl (meth)acrylate, 2,2 (meth)acrylate , 2-trifluoroethyl ester, 2,2,3,3-tetrafluoropropyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, di(meth)acrylate (Meth)acrylic acid esters such as cyclopentenyl ester and dicyclopentanyl (meth)acrylate; maleic acid derivatives such as maleic anhydride and maleic acid monoester; phenylmaleimide, cyclohexyl N-substituted maleimides such as maleimide. From the standpoint of heat resistance, etc., the copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is preferably an alicyclic structure, an aromatic structure, a polycyclic structure, an inorganic ring structure, One or more ring structures such as a heterocyclic structure.

式(10)中，R ¹⁵為氫原子或碳原子數1~5之烷基，e為1~5之整數。作為此等具有鹼可溶性官能基之聚合性單體特佳為甲基丙烯酸4-羥基苯酯。 As a polymerizable monomer having an alkali-soluble functional group, it is preferable to form a structural unit represented by formula (10):

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

式(11)中，R ¹⁶及R ¹⁷分別獨立為氫原子、碳原子數1~3之烷基、完全或部分經氟化之碳原子數1~3之氟烷基、或鹵原子，R ¹⁸為氫原子、碳原子數1~6之直鏈烷基、碳原子數3~12之環狀烷基、苯基或經選自由羥基、碳原子數1~6之烷基及碳原子數1~6之烷氧基所成之群中之至少1種取代之苯基。R ¹⁶及R ¹⁷較佳為氫原子。R ¹⁸較佳為碳原子數3~12之環狀烷基及苯基。作為此等其他聚合性單體特佳為苯基馬來醯亞胺及環己基馬來醯亞胺。 Other polymerizable monomers are preferably polymerizable monomers that form structural units represented by formula (11):

In formula (11), R ¹⁶ and R ¹⁷ are independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms, or a halogen atom, R ¹⁸ is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and the number of carbon atoms A phenyl group substituted by at least one of the group consisting of 1-6 alkoxy groups. R ¹⁶ and R ¹⁷ are preferably hydrogen atoms. R ¹⁸ is preferably a cyclic alkyl group and a phenyl group having 3 to 12 carbon atoms. As such other polymerizable monomers, phenylmaleimide and cyclohexylmaleimide are particularly preferable.

As the polymerizable monomer system having an alkali-soluble functional group, 4-hydroxyphenyl methacrylate is used. As other polymerizable monomers, it is particularly preferable to use a compound selected from phenylmaleimide and cyclohexylmaleimide. At least 1 species in the group. By using a resin obtained by radically polymerizing these polymerizable monomers, shape retention and image development properties can be improved, and outgassing can also be reduced.

As a polymerization initiator when producing a copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers by radical polymerization, it is not limited to the following, but 2,2' can be used -Azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2-methylpropionate) dimethyl ester, 4,4'- Azo polymerization initiators such as azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAN), 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 of 10 hours at a temperature of 100~170°C or benzoyl peroxide and lauryl peroxide Acyl, 1,1'-bis(tert-butylperoxy)cyclohexane, tert-butylperoxypivalate and other peroxide polymerization initiators. The amount of the polymerization initiator used is generally preferably 0.01, 0.05, or 0.5 mass parts, 40 mass parts or less, 20 mass parts or less, or 15 mass parts per 100 mass parts of the mixture of polymerizable monomers. servings or less.

RAFT (Reversible Addition Fragmentation Transfer, Reversible Addition Fragmentation Chain Transfer) agent can also be used together with the polymerization initiator. The RAFT agent is not limited to the following, but thiocarbonylsulfur 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 polymerizable monomers.

(式(10)中，R ¹⁵為氫原子或碳原子數1~5之烷基，e為1~5之整數)

(式(11)中，R ¹⁶及R ¹⁷分別獨立為氫原子、碳原子數1~3之烷基、完全或部分經氟化之碳原子數1~3之氟烷基或鹵素原子，R ¹⁸為氫原子、碳原子數1~6之直鏈烷基、碳原子數3~12之環狀烷基、苯基或經選自由羥基、碳原子數1~6之烷基及碳原子數1~6之烷氧基所成之群之至少1種取代之苯基)。 In one embodiment, the copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers has a structural unit represented by formula (10) and a structural unit represented by formula (11):

(In formula (10), ^R15 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and e is an integer of 1 to 5)

(In formula (11), R ¹⁶ and R ¹⁷ are independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms or a halogen atom, R ¹⁸ is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and the number of carbon atoms At least one substituted phenyl group formed by 1-6 alkoxy groups).

The number average molecular weight of the copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is preferably 1,000-30,000, more preferably 1,500-25,000, and more preferably 2,000-20,000. The weight average molecular weight of the copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is preferably 3,000-80,000, more preferably 4,000-70,000, and more preferably 5,000-60,000. If the number average molecular weight is 1000 or more or the weight average molecular weight is 3000 or more, the alkali development speed is appropriate, and the difference in dissolution speed between the exposed part and the unexposed part is sufficient, so the pattern resolution is good. When the number average molecular weight is 30000 or less or the weight average molecular weight is 80000 or less, applicability and alkali developability are favorable. The polydispersity (Mw/Mn) of the copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is preferably 1.0~3.5, more preferably 1.1~3.0, and more preferably 1.2 ~2.8. By making polydispersity into the said range, the photosensitive resin composition excellent in pattern formation property and alkali developability can be obtained.

When the alkali-soluble functional group of the copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer is a phenolic hydroxyl group, the ratio of the polymerizable monomer having an alkali-soluble functional group to another polymerizable monomer The phenolic hydroxyl equivalent of the copolymer (d) is preferably from 60 to 400, more preferably from 80 to 350, and still more preferably from 100 to 300. If the copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer has a phenolic hydroxyl equivalent of 60 or more, the film thickness of the unexposed portion can be maintained sufficiently during alkali development. If the copolymer (d) of the polymerizable monomer having an alkali-soluble functional group and another polymerizable monomer has a phenolic hydroxyl equivalent weight of 400 or less, desired alkali solubility can be obtained.

In this disclosure, when the copolymer (d) of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers also corresponds to the hydroxy polystyrene resin derivative (b), it should be regarded as a copolymer having an alkali-soluble functional group. A copolymer (d) of a polymerizable monomer and another polymerizable monomer. When the copolymer (d) of a polymerizable monomer with an alkali-soluble functional group and another polymerizable monomer is also equivalent to a resin (c) with an epoxy group and a phenolic hydroxyl group, it should be regarded as a polymerization with an alkali-soluble functional group A copolymer (d) of a polymerizable monomer and another polymerizable monomer. That is, the hydroxyl polystyrene resin derivative (b) and the resin (c) with epoxy and phenolic hydroxyl groups are copolymers (d) of polymerizable monomers with alkali-soluble functional groups and other polymerizable monomers. ) equivalent shall be excluded.

(e) polyimide resin, (f) polyamide resin, (g) polybenzoxazole resin, (h) polybenzoxazole resin precursor In one embodiment, the first resin (A) is selected from polyimide resin (e), polyamic acid resin (f), polybenzoxazole resin (g), polybenzoxazole resin precursor At least one kind of substance (h). The polyamide acid resin (f) is a resin having a polyimide structure through dehydration and ring closure. The polybenzoxazole resin precursor (h) becomes the polybenzoxazole resin (g) through dehydration and ring closure.

The polyimide resin (e) has a structural unit represented by formula (12). The polyamic acid resin (f) and the polybenzoxazole resin precursor (h) have structural units represented by formula (13). The polybenzoxazole resin (g) has a structural unit represented by formula (14). The polyimide resin (e) can have both the structural unit represented by formula (12) and the structural unit represented by formula (13), and the polybenzoxazole resin (g) can have the structural unit represented by formula (14). Both the structural unit and the structural unit represented by formula (13).

In formula (12), R ¹⁹ is a 4-10 valent organic group, R ²⁰ is a 2-8 valent organic group, R ²¹ and R ²² are independently hydroxyl, carboxyl, sulfo or mercapto, f and g are 0-6 Integer of .

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

In formula (14), R ²⁸ is a 2-8 valent organic group, R ²⁹ is a 2-8 valent organic group, R ³⁰ and R ³¹ are independently hydroxyl, carboxyl, sulfo or mercapto, j and k are independently 0 An integer of ~6.

R ¹⁹ ~(R ²¹ ) _f in formula (12) represent residues of acid anhydrides. R ¹⁹ is a 4-10 valent organic group, preferably an organic group with 5-40 carbon atoms including an aromatic ring or a cycloaliphatic group.

As the acid dianhydride, for example, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride , 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-di Benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1 -Bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, bis(3,4-dicarboxyphenyl)methane anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9 -Bis (3,4-dicarboxyphenyl) oxalic dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] oxalic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-bis Aromatic tetracarboxylic dianhydride such as carboxyphenyl) hexafluoropropane dianhydride; Aliphatic tetracarboxylic acid such as butane tetracarboxylic dianhydride and 1,2,3,4-cyclopentane tetracarboxylic dianhydride Dianhydrides, etc., and combinations of two or more of them.

R ²³ -(R ²⁵ ) _h in formula (13) and R ²⁸ -(R ³⁰ ) _j in formula (14) represent acid residues, respectively. R ²³ and R ²⁸ are each independently a 2-8 valent organic group, preferably an organic group with 5-40 carbon atoms including an aromatic ring or a cycloaliphatic group.

As the acid, for example, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl Aromatic dicarboxylic acids such as dicarboxylic acids; aromatic tricarboxylic acids such as trimellitic acid, trimellitic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc.; pyromellitic acid, 3, 3',4,4'-Biphenyltetracarboxylic acid, 2,3,3',4'-Biphenyltetracarboxylic acid, 2,2',3,3'-Biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane , 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxy Phenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5 , 6-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, etc. Tetracarboxylic acids; aliphatic tetracarboxylic acids such as butane tetracarboxylic acid and 1,2,3,4-cyclopentane tetracarboxylic acid, etc., and combinations of two or more thereof. One or two carboxyl groups of the above-mentioned tricarboxylic acid and tetracarboxylic acid correspond to R ²⁵ in formula (13) or R ³⁰ in formula (14). The acids may also be in the form of esters or anhydrides.

R ²⁰ -(R 22 ) _g in formula ( ¹² ), R ²⁴ -(R ²⁶ ) _i in formula (13), and R ²⁹ -(R ³¹ ) _k in formula (14) respectively represent residues of diamines. R ²⁰ , R ²⁴ and R ²⁹ are each independently a 2-8 valent organic group, preferably an organic group with 5-40 carbon atoms including an aromatic ring or a cycloaliphatic group.

Diamines corresponding to R ²⁰ of formula (12) and R ²⁴ of formula (13) of polyamide resin (f), for example, 3,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, Aniline, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalene diamine, 2,6-naphthalene diamine, bis(4-aminophenoxy)biphenyl, bis[4-(4- Aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4' -Diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4' Aromatic biphenyls such as -diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl) Amines, or compounds in which at least one hydrogen atom of the aromatic ring of these aromatic diamines is substituted with an alkyl or halogen atom; aliphatic diamines such as cyclohexyldiamine, methylenebiscyclohexylamine, and the like 2 or more combinations.

As the diamine corresponding to R ²⁴ of the formula (13) and R ²⁹ of the formula (14) of the polybenzoxazole resin precursor (h), for example, a diamine having an aromatic ring corresponding to the above-mentioned aromatic diamine A bisaminophenol compound in which the amine is based on a phenolic hydroxyl group in the ortho position, and a combination of two or more thereof.

Polyimide resin (e), polyamic acid resin (f), polybenzoxazole resin (g) and polybenzoxazole resin precursor (h), these terminals can also be obtained by having an acidic Monoamines, acid anhydrides, acid chlorides, monocarboxylic acids, etc. are end-capped, and there are acidic groups at the end of the main chain.

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

The polybenzoxazole resin precursor (h) can be synthesized, for example, by subjecting a bisaminophenol compound to a condensation reaction of polycarboxylic acids such as dicarboxylic acid, tricarboxylic acid, or tetracarboxylic acid. Specifically, for example, a method of reacting an intermediate obtained by condensing a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) and a polycarboxylic acid with a bisaminophenol compound is added to a mixture of pyridine and the like. A method of dropping a dicarboxylic acid dichloride solution into a solution of a bisaminophenol compound of a tertiary amine, etc.

The polyimide resin (e) can be synthesized by, for example, dehydrating and ring-closing the polyamic acid resin (f) obtained by the above method by heating or chemically treating it with an acid or alkali.

The polybenzoxazole resin (g) can be synthesized by, for example, dehydrating and ring-closing the polybenzoxazole resin precursor (h) obtained by the above method by heating or chemically treating it with acid or alkali.

The number average molecular weight of polyimide resin (e), polyamide acid resin (f), polybenzoxazole resin (g) and polybenzoxazole resin precursor (h) is preferably 500~8000, More preferably, it is 800~6000, and more preferably, it is 1000~5000. When the number average molecular weight is 500 or more, the alkali solubility is appropriate, so it can be favorably used as a resin for a photosensitive material. When the number average molecular weight is 8000 or less, applicability and developability are favorable.

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

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

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

Examples of the organosilane represented by formula (15) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, etc.; methyltrimethoxy Silane, Methyltriethoxysilane, Methyltriisopropoxysilane, Methyltri-n-Butoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyltriisopropoxysilane Silane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane Silane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methoxysilane Acryloxypropyltriethoxysilane, 3-Acryloxypropyltrimethoxysilane, Phenyltrimethoxysilane, Phenyltriethoxysilane, p-Hydroxyphenyltrimethoxysilane , 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl Trimethoxysilane, Trifluoromethyltrimethoxysilane, Trifluoromethyltriethoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, 3-Aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropyltriethoxysilane, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy] Propyltrimethoxysilane, [(3-Ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilane Propyl succinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethyl Oxysilane, 9-Anthracenyltrimethoxysilane, 9-Phenanthryltrimethoxysilane, 9-Phenanthryltrimethoxysilane, 2-Phenanthryltrimethoxysilane, 1-Perylenetrimethoxysilane, 2 - Trifunctional silanes such as indenyltrimethoxysilane and 5-anthracenyltrimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, Di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidyloxypropyl)methyldimethoxysilane, (3-glycidyloxypropyl)methyldimethoxysilane Bifunctional silanes such as ethoxysilane, bis(1-naphthyl)dimethoxysilane, bis(1-naphthyl)diethoxysilane, etc.; trimethylmethoxysilane, tri-n-butylethyl Monofunctional silanes such as oxysilane, (3-glycidyloxypropyl)dimethylmethoxysilane, (3-glycidyloxypropyl)dimethylethoxysilane, and 2 of these A combination of the above.

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

In formula (16), R ³⁴ ~ R ³⁷ are independently a hydrogen atom, an alkyl group with 1 to 6 carbon atoms, an alkyl group with 2 to 6 carbon atoms, or an aryl group with 6 to 16 carbon atoms, and n is The range of 2~8. When n is 2 or more, a plurality of R ³⁵ and R ³⁶ may be the same or different.

Specific examples of the organosilane represented by formula (16) include methyl silicate 51 manufactured by Fuso Chemical Industry Co., Ltd. (R ³⁴ to R ³⁷ are methyl groups, and the average n is 4), Tama Chemical Industry Co., Ltd. Co., Ltd. M silicate 51 (R ³⁴ ~ R ³⁷ is methyl, n average is 3 ~ 5), silicate 40 (R ³⁴ ~ R ³⁷ is ethyl, n average is 4 ~ 6), silicon Ester 45 (R ³⁴ ~ R ³⁷ is ethyl, n average is 6 ~ 8), methyl silicate 51 (R ³⁴ ~ R ³⁷ is methyl, n average is 4) manufactured by COLCOAT Co., Ltd., silicic acid Methyl ester 53A (R ³⁴ ~ R ³⁷ is methyl, n average is 7), ethyl silicate 40 (R ³⁴ ~ R ³⁷ is ethyl, n average is 5), etc. These can also be used in combination of 2 or more types.

The silicone resin (i) can be synthesized by hydrolyzing and partially condensing organosilanes represented by formula (15) and formula (16). By partial condensation, there are residual silanol groups in the silicone resin (i). Examples of hydrolysis and partial condensation include, for example, adding a solvent, water, catalyst, etc. if necessary, to an organosilane mixture, and heating and stirring at 50°C to 150°C for about 0.5 to 100 hours. Hydrolysis by-products (alcohols such as methanol) or condensation by-products (water) can also be distilled off as needed.

As the catalyst, an acid catalyst or an alkali catalyst is preferably used. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or an anhydride thereof, ion exchange resin, and the like. Examples of alkali catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, hydroxide Potassium, alkoxysilanes with amino groups, ion exchange resins, etc. After hydrolysis and partial condensation, the catalyst is removed by washing with water, treatment with an ion exchange resin, or a combination of these, if necessary. By removing the catalyst, the storage stability of the photosensitive resin composition can be improved.

The weight average molecular weight of the silicone resin (i) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000. When the weight average molecular weight is 1,000 or more, film formability can be improved, and if it is 100,000 or less, alkali developability will be favorable.

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

Examples of monomers constituting the cyclic olefin polymer (j) include cyclic olefin monomers having a protic polar group, cyclic olefin monomers having a non-protic polar group, and cyclic olefin monomers having no polar groups. Monomers and monomers other than cyclic olefins, etc. Monomers other than cyclic olefins may have a protic polar group or other polar groups, or may not have a polar group.

As a cyclic olefin monomer having a protic polar group, for example, 5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2 -ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5-exo-6-endo-dihydroxycarbonylbicyclo[2.2.1]hept- 2-ene, 8-hydroxycarbonyltetracyclo[4.4.0.1 ^{2,5 .1 7,10} ]dodeca-3-ene, 8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-exo-9-endo-dihydroxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene and other carboxyl groups Cyclic alkenes; 5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 5-methyl-5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2- ene, 8-(4-hydroxyphenyl)tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-methyl-8-(4-hydroxyphenyl)tetracyclo[ 4.4.0.1 ^2,5 .1 ^7,10 ] Hydroxyl-containing cyclic olefins such as dodec-3-ene, etc., and combinations of two or more thereof.

As a cyclic olefin monomer having a polar group other than protic, for example, 5-acetyloxybicyclo[2.2.1]hept-2-ene, 5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 2-ene, 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 8-acetyloxytetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca Carb-3-ene, 8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-ethoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-n-propoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-isopropoxy Carbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-n-butoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca- 3-ene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-methyl-8-ethoxycarbonyl tetracyclo Cyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-methyl-8-n-propoxytetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca Carb-3-ene, 8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-methyl-8-n-but Oxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1 ^{2, 5} .1 ^7,10 ]dodeca-3-ene, 8-methyl-8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 cyclic olefins with ester groups such as dodec-3-ene; N-substituted imide groups such as N-phenyl-(5-norbornene-2,3-dicarboximide) Cyclic olefins; 8-cyanotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-methyl-8-cyanotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 5-cyanobicyclo[2.2.1]hept-2-ene and other cyclic alkenes with cyano groups; 8-chlorotetracyclo[4.4.0.1 ^{2, 5} .1 ^7,10 ]dodeca-3-ene, 8-methyl-8-chlorotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, etc. have halogen atoms Cyclic olefins, etc., and combinations of two or more of them.

Cyclic olefin monomers without polar groups include, for example, bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo [2.2.1] Hept-2-ene, 5-ethylene-bicyclo[2.2.1]hept-2-ene, 5-methylene-bicyclo[2.2.1]hept-2-ene, 5-ethylene base-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1 ^2,5 ]dec-3,7-diene, tetracyclo[8.4.0.1 ^11,14 .0 ^3,7 ]pentadeca Carbo-3,5,7,12,11-pentaene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dec-3-ene, 8-methyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-ethyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-methylene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-Ethylene-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-vinyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca Carb-3-ene, pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ]pentadeca-3,10-diene, cyclopentene, cyclopentadiene, 1,4- Methylene-1,4,4a,5,10,10a-hexahydroanthracene, 8-phenyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene, tetracyclo[ 9.2.1.0 ^2,10 .0 ^3,8 ]tetradeca-3,5,7,12-tetraene, pentacyclo[7.4.0.1 ^3,6 .1 ^10,13 .0 ^2,7 ]pentadecene -4,11-diene, pentacyclo[9.2.1.1 ^4,7 .0 ^2,10 .0 ^3,8 ]pentadeca-5,12-diene, etc., and combinations of two or more thereof.

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

The cyclic olefin polymer (j) can be synthesized by polymerizing the above-mentioned monomers through ring-opening polymerization or addition polymerization. As a polymerization catalyst, for example, metal complexes such as molybdenum, ruthenium, and osmium, or combinations of two or more of these are preferably used. Cyclic olefin polymers can also be hydrotreated. As the hydrogenation catalyst, catalysts generally used for the hydrogenation of olefin compounds can be used, for example, Ziegler-type homogeneous catalysts, noble metal complex catalysts, supported noble metal catalysts, and the like.

The weight average molecular weight of the cyclic olefin polymer (j) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000. When the weight average molecular weight is 1,000 or more, film formability can be improved, and if it is 100,000 or less, alkali developability will be favorable.

(k) Cardo resin In one embodiment, the first resin (A) contains cardo resin (k). The cardo resin (k) has a cardo structure, that is, a skeleton structure in which two different cyclic structures are bonded to the quaternary carbon constituting the cyclic structure. Examples of the skeleton structure of two cyclic structures that differ in the bonding of the quaternary carbon constituting the cyclic structure include, for example, a stilbene skeleton, a bisphenol stilbene skeleton, a bisaminophenyl stilbene skeleton, an epoxy group-containing stilbene skeleton, With acrylic acid-based fenugreek skeleton, etc. As an example of the cardo structure, a benzene ring is bonded to the oxene ring.

The cardo resin (k) can be synthesized by reacting functional groups of monomers having a cardo structure to polymerize the monomers. As a polymerization method of the monomer which has a cardo structure, a ring-opening polymerization method, an addition polymerization method, etc. are mentioned, for example. As a monomer having a cardo structure, for example, bis(glycidyloxyphenyl) fluorene type epoxy resin, 9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(4- Bisphenol compounds containing cardo structure such as hydroxy-3-methylphenyl) fluorine; 9,9-bis (cyanoalkyl) fluorine compounds such as 9,9-bis (cyanomethyl) fluorine; 9 , 9,9-bis(aminoalkyl)oxene compounds such as 9-bis(3-aminopropyl)oxene and combinations of two or more thereof. The cardo resin (k) may also be a copolymer of a monomer having a cardo structure and other copolymerizable monomers.

The weight average molecular weight of the cardo resin (k) is preferably 1,000-100,000, more preferably 1,000-50,000. When the weight average molecular weight is 1,000 or more, film formability can be improved, and if it is 100,000 or less, alkali developability will be favorable.

(l) Phenolic resin In one embodiment, the first resin (A) includes phenol novolak resin, methanol novolak resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, phenol-bicyclic Phenol resins (1) such as pentadiene copolymer resins or derivatives thereof. The number average molecular weight of the phenolic resin (l) varies with the resin structure, but is preferably 100-50,000, more preferably 500-30,000, and more preferably 800-10,000. If the number average molecular weight is 100 or more, the alkali development rate is appropriate, and the difference in dissolution rate between the exposed part and the unexposed part is sufficient, so the resolution of the pattern is good. When the number average molecular weight is 50000 or less, alkali developability will be favorable.

The content of the first resin (A) in the photosensitive resin composition is based on the total mass of the resin component, the radiation-sensitive compound (D) and the black agent (E), preferably 5-60% by mass, more preferably 10-55% by mass, more preferably 10-50% by mass. When the content of the first resin (A) is 5% by mass or more based on the above-mentioned total mass, the residual film rate, heat resistance, sensitivity, and the like are appropriate. If the content of the first resin (A) is 60% by mass or less on the basis of the above total mass, the optical density (OD value) of the coating film after curing can be 0.5 or more per 1 μm thickness, and the light-shielding property can be maintained after curing .

The photosensitive resin composition, based on the total mass of the resin components, preferably contains 20% by mass to 90% by mass of the first resin (A), more preferably contains 25% by mass to 70% by mass, and more preferably includes 30% by mass %~55% by mass. When the content of the first resin (A) is 20% by mass or more based on the total mass of the resin components, desired alkali solubility can be obtained. When the content of the first resin (A) is 90% by mass or less based on the total mass of the resin components, high sensitivity can be provided to the photosensitive resin composition.

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

[the second resin (B)] As the second resin (B), a resin having a phenolic hydroxyl group different from the first resin (A) can be used. The second resin (B) is not particularly limited as long as it is a resin having a phenolic hydroxyl group. As such a 2nd resin (B), it is preferable to use (a)-(d) or (l) among the resin demonstrated in the said 1st resin (A). However, the second resin (B) is a different resin from the first resin (A). The so-called "different" here means that the structure of the structural unit of a certain resin is different from that of other resins, or when a certain resin contains one or more common structural units with other resins, it means that the total of the common structural units contains less than 70 mo Only the resins with different molecular weights are regarded as the same resins.

The phenolic hydroxyl equivalent of the 2nd resin (B) is 1.1 to 5.0 times the phenolic hydroxyl equivalent of the 3rd resin (C) mentioned later. The phenolic hydroxyl equivalent of the second resin (B) is 1.2 to 4.0 times the phenolic hydroxyl equivalent of the third resin (C), more preferably 1.3 to 2.5 times. The second resin (B) acts as a low-alkali-soluble resin component during development to suppress excessive dissolution of the unexposed part, and on the other hand, dissolves other resin components with high alkali solubility and any dissolution accelerator in the exposed part And it is released from the film into the developing solution, so the sensitivity and residual film rate of the photosensitive resin composition can be improved. Thereby, content of the radiation-sensitive compound (D) in a photosensitive resin composition can be reduced according to a use, As a result, a photosensitive resin composition can be made suitable for thick film formation. In addition, by using the second resin (B) with low alkali solubility and the third resin (C) with higher alkali solubility than the second resin (B), the phenolic hydroxyl group equivalents of these resins fall into the range of the above-mentioned ratio Combining them can uniformly dissolve the film during image development microscopically, and as a result, the roughness of the film surface can be suppressed.

When the alkali-soluble functional group of the first resin (A) is a phenolic hydroxyl group, the phenolic hydroxyl equivalent of the second resin (B) is preferably 1.3 to 4.5 times the phenolic hydroxyl equivalent of the first resin (A), more preferably 1.4 to 4.0 times, more preferably 1.5 to 3.5 times. By making the phenolic hydroxyl equivalent of the first resin (A) and the phenolic hydroxyl equivalent of the second resin (B) with low alkali solubility into the above-mentioned ratio, the film at the time of image development can be microscopically and uniformly dissolved, and as a result, Can effectively suppress the roughness of the film surface.

In this disclosure, the phenolic hydroxyl equivalents of the first resin (A), the second resin (B) and the third resin (C) mean the value before the image development after exposure of the photosensitive resin composition. Whether there is a change between the original phenolic hydroxyl equivalent value of the resins and the phenolic hydroxyl equivalent value of the photosensitive resin composition after exposure and before development can be judged by the following procedure using NMR. For 100 parts by mass of the resin to be measured, 30 parts by mass of the radiation-sensitive compound used in the photosensitive resin composition and 1 part by mass of methyltriphenylsilane as an internal standard were added and mixed in DMSO-d6 to prepare the test Composition. The ¹ H-NMR of the obtained test composition was measured, and the integral value S1 of the phenolic hydroxyl group when the internal standard integral value was 1.00 was calculated. Furthermore, the test composition was irradiated with ultraviolet rays of 1000 mJ/cm ² with an exposure device equipped with an ultra-high pressure mercury lamp, heated at 120°C for 5 minutes using an oil bath, and then ^{the 1} H-NMR of the test composition was measured to calculate the internal standard The integral value S2 of the phenolic hydroxyl group when the integral value is set to 1.00. The resin whose change ratio (absolute value of (S2-S1)/S1) of these integral values is less than 10% is regarded as having no change in the value of phenolic hydroxyl equivalent.

The phenolic hydroxyl equivalent of the second resin (B) is preferably 250-700, more preferably 260-600, and still more preferably 270-550. When the phenolic hydroxyl equivalent of the 2nd resin (B) is 250 or more, the film thickness of the unexposed part can be fully maintained at the time of alkali image development. If the phenolic hydroxyl group equivalent of the 2nd resin (B) is 700 or less, desired alkali solubility will be acquired.

The second resin (B) contains the same structural unit as at least one of the structural units of the third resin (C) described later and other structural units, and the total structural unit common to the third resin (C) contains 30 mole% to 95% Mole%, the alkali dissolution rate of the second resin (B) is preferably lower than the alkali dissolution rate of the third resin (C). In this embodiment, since part of the structural unit of the second resin (B) and the third resin (C) are common, the compatibility between the second resin (B) and the third resin (C) is high. Therefore, the dissolution of the film can be microscopically uniform during image development, and as a result, the roughness of the film surface can be effectively suppressed. In this embodiment, the second resin (B) preferably contains a total of 40 mol% to 90 mol% of the common structural unit with the third resin (C), more preferably 50 mol% to 85 mol% %. When the plurality of structural units between the second resin (B) and the third resin (C) are the same, the value of the mole % above represents the sum of the mole % of the plurality of structural units. In this disclosure, the alkali dissolution rate of the resin or photosensitive resin composition is determined by the following procedure. In the 20% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of the resin or photosensitive resin composition, MEGAFAC (registered trademark) as a leveling agent is added in an amount of 0.1 mass parts per 100 mass parts of the resin solid content F-559 (a fluorine-based surfactant, manufactured by DIC Corporation). The obtained mixture was coated on a glass substrate (70 mm×70 mm×0.7 mm) so that the dry film thickness was 5.0 μm, and after vacuum drying for 30 seconds, the film was dried at 120° C. for 120 seconds. After drying, alkali development was performed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. The imaging time ranges from 8 to 400 seconds, and is adjusted to the time when the coating is insoluble. The value obtained by dividing the film reduction amount (nm) after development by the development time (second) was defined as the alkali dissolution rate (nm/second). By making the alkali dissolution rate of the second resin (B) lower than that of the third resin (C), it can be ensured that the solubility of the second resin (B) to alkali is lower than that of the third resin (C).

The second resin (B) is preferably a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. A copolymer of a polymerizable monomer having a phenolic hydroxyl group and other polymerizable monomers is a copolymer of a polymerizable monomer having an alkali-soluble functional group and other polymerizable monomers described for the first resin (A) ( At least a part, preferably all, of the alkali-soluble functional groups in d) are copolymers of phenolic hydroxyl groups. Alkaline solubility lower than that of the third resin (C) is imparted to the second resin (B) by at least a part of the structural units derived from other polymerizable monomers. The second resin (B) of this embodiment can be obtained by having It is produced by free-radical polymerization of phenolic hydroxyl polymerizable monomers and other polymerizable monomers.

(式(17)中，R ³⁸為氫原子或碳原子數1~5之烷基，R ³⁹為選自碳原子數1~20之直鏈烷基、碳原子數3~20之分支烷基、碳原子數3~12之環狀烷基、碳原子數6~20之芳基、經酸性官能基以外之基取代之碳原子數1~20之直鏈烷基、經酸性官能基以外之基取代之碳原子數3~20之分支烷基、經酸性官能基以外之基取代之碳原子數3~12之環狀烷基、及經酸性官能基以外之基取代之碳原子數6~20之芳基所成之群中之基)。本揭示中，所謂酸性官能基表示與2.38質量%之氫氧化四甲基銨水溶液進行酸鹼反應的基，具體而言，舉例為酚性羥基、羧基、磺基、磷酸基、酸酐基及巰基。 In one embodiment, the second resin (B) has a structural unit represented by formula (17),

(In formula (17), R ³⁸ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ³⁹ is a straight chain alkyl group with 1 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms , cyclic alkyl groups with 3 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, linear alkyl groups with 1 to 20 carbon atoms substituted by groups other than acidic functional groups, and substituted by groups other than acidic functional groups A branched alkyl group with 3 to 20 carbon atoms substituted by a radical, a cyclic alkyl group with 3 to 12 carbon atoms substituted by a group other than an acidic functional group, and a branched alkyl group with 6 to 2 carbon atoms substituted by a group other than an acidic functional group The base of the group formed by the aryl group of 20). In this disclosure, the so-called acidic functional group means a group that undergoes an acid-base reaction with a 2.38 mass % tetramethylammonium hydroxide aqueous solution, specifically, phenolic hydroxyl group, carboxyl group, sulfo group, phosphoric acid group, acid anhydride group, and mercapto group .

In ^R38 of the formula (17), specific examples of an alkyl group with 1 to 5 carbon atoms can be methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl base, n-pentyl, etc. R ³⁸ is preferably methyl.

In ^R39 of the formula (17), as a straight-chain alkyl group with 1 to 20 carbon atoms and a branched alkyl group with 3 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n- Hexadecyl, etc. Examples of cyclic alkyl groups having 3 to 12 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, isobornyl, adamantyl, and dicyclopentyl wait. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, 4-(benzyloxymethoxy)phenyl, biphenyl, naphthyl, fenyl, anthracenyl, and phenanthrenyl. R ³⁹ is preferably tert-butyl, cyclohexyl, isobornyl, dicyclopentyl, phenyl or 4-(benzyloxymethoxy)phenyl.

(式(10)中，R ¹⁵為氫原子或碳原子數1~5之烷基，e為1~5之整數)。R ¹⁵較佳為甲基。e較佳為1。e為1時，OH較佳位於4位。 In one embodiment, the second resin (B) has a structural unit represented by formula (10),

(In formula (10), R ¹⁵ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and e is an integer of 1 to 5). R ¹⁵ is preferably methyl. e is preferably 1. When e is 1, OH is preferably located at the 4th position.

(式(11)中，R ¹⁶及R ¹⁷分別獨立為氫原子、碳原子數1~3之烷基、完全或部分經氟化之碳原子數1~3之氟烷基或鹵原子，R ¹⁸為氫原子、碳原子數1~6之直鏈烷基、碳原子數3~12之環狀烷基、苯基或經選自由羥基、碳原子數1~6之烷基及碳原子數1~6之烷氧基所成之群中之至少1種取代之苯基)。R ¹⁶及R ¹⁷較佳為氫原子。R ¹⁸較佳為苯基或環己基。 In one embodiment, the second resin (B) has a structural unit represented by formula (11):

(In formula (11), R ¹⁶ and R ¹⁷ are independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms or a halogen atom, R ¹⁸ is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and the number of carbon atoms A phenyl group substituted with at least one of alkoxy groups of 1 to 6). R ¹⁶ and R ¹⁷ are preferably hydrogen atoms. R ¹⁸ is preferably phenyl or cyclohexyl.

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

The number average molecular weight of the second resin (B) is preferably from 1,000 to 30,000, more preferably from 1,500 to 25,000, and even more preferably from 2,000 to 20,000. The weight average molecular weight of the second resin (B) is preferably from 3,000 to 80,000, more preferably from 4,000 to 70,000, and still more preferably from 5,000 to 60,000. If the number average molecular weight is 1000 or more or the weight average molecular weight is 3000 or more, the alkali development rate is appropriate and the difference in dissolution rate between the exposed part and the unexposed part is sufficient, so the pattern resolution is good. When the number average molecular weight is 30000 or less or the weight average molecular weight is 80000 or less, applicability and alkali developability are favorable. The polydispersity (Mw/Mn) of the second resin (B) is preferably from 1.0 to 3.5, more preferably from 1.1 to 3.0, and still more preferably from 1.2 to 2.8. By making polydispersity into the said range, the photosensitive resin composition excellent in pattern formation property and alkali developability can be obtained.

In the photosensitive resin composition, based on the total mass of the resin components, the second resin (B) preferably contains 5 mass % to 50 mass %, more preferably contains 8 mass % to 45 mass %, and more preferably contains 10 mass % %~40% by mass. If the content of the second resin (B) is 5% by mass or more based on the total mass of the resin components, the contrast due to the difference in dissolution rate from the first resin (A) can be sufficiently obtained. When the content of the second resin (B) is 50% by mass or less based on the total mass of the resin components, the film can be microscopically and uniformly dissolved during image development, and as a result, the surface roughness of the film can be effectively suppressed.

[the third resin (C)] As the third resin (C), among the resins described for the first resin (A), a resin having a phenolic hydroxyl group different from both the first resin (A) and the second resin (B) can be used.

The phenolic hydroxyl equivalent of the third resin (C) is preferably 107-240, more preferably 140-235, and still more preferably 170-230. When the phenolic hydroxyl equivalent of the 3rd resin (C) is 107 or more, the film thickness of the unexposed part at the time of alkali image development can be fully maintained. When the phenolic hydroxyl equivalent of the 3rd resin (C) is 240 or less, desired alkali solubility can be acquired.

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

The number average molecular weight of the third resin (C) is preferably from 1,000 to 30,000, more preferably from 1,500 to 25,000, and still more preferably from 2,000 to 20,000. The weight average molecular weight of the third resin (C) is preferably from 3,000 to 80,000, more preferably from 4,000 to 70,000, and still more preferably from 5,000 to 60,000. If the number average molecular weight is 1000 or more or the weight average molecular weight is 3000 or more, the alkali development rate is appropriate and the difference in dissolution rate between the exposed part and the unexposed part is sufficient, so the pattern resolution is good. When the number average molecular weight is 30000 or less or the weight average molecular weight is 80000 or less, applicability and alkali developability are favorable. The polydispersity (Mw/Mn) of the third resin (C) is preferably from 1.0 to 3.5, more preferably from 1.1 to 3.0, and still more preferably from 1.2 to 2.8. By making polydispersity into the said range, the photosensitive resin composition excellent in pattern formation property and alkali developability can be obtained.

In the photosensitive resin composition, based on the total mass of the resin components, the third resin (C) preferably contains 5 mass % to 50 mass %, more preferably contains 8 mass % to 45 mass %, and more preferably contains 10 mass % %~40% by mass. When the content of the third resin (C) is 5% by mass or more based on the total mass of the resin components, the film can be microscopically and uniformly dissolved during image development, and as a result, the surface roughness of the film can be effectively suppressed. If the content of the third resin (C) is less than 50% by mass based on the total mass of the resin components, a contrast due to the difference in dissolution rate between the first resin (A) and the second resin (B) can be formed A pattern that can be maintained.

[Radiation sensitive compound (D)] As the radiation-sensitive compound (D), a photoacid generator, a photobase generator, or a photopolymerization initiator can be used. A photoacid generator is a compound that generates an acid when irradiated with radiation such as visible light, ultraviolet light, γ-rays, and electron beams. Since the photoacid generator can increase the solubility of the portion irradiated with radiation to an aqueous alkali solution, it can be used in a positive-type photosensitive resin composition that dissolves the portion. A photobase generator is a compound that generates a base when irradiated with radiation. Since the photobase generator can reduce the solubility of the portion to be irradiated with radiation in aqueous alkali solution, it can be used in a negative-type photosensitive resin composition that insolubilizes the portion. Photopolymerization initiators are compounds that generate free radicals when irradiated with radiation. When the photopolymerization initiator contains a binder resin or a radical polymerizable compound having a radically polymerizable functional group in the photosensitive resin composition, it can be used to make the binder resin of the part irradiated with radiation radically polymerizable. The radical polymerization of the functional or radical polymerizable compound proceeds, and a negative photosensitive resin composition of a polymer insoluble in aqueous alkali solution is formed in this part.

＜Photoacid generator＞ The radiation-sensitive compound (D) is preferably a photoacid generator in terms of obtaining a high-sensitivity and high-resolution pattern. As the photoacid generator, at least one selected from the group consisting of quinone diazonium compounds, perium salts, phosphonium salts, diazonium salts, and iodonium salts can be used. In one embodiment, the photoacid generator is a compound or salt with high sensitivity to i-line (365 nm).

A quinonediazo compound is preferably used as the photoacid generator. Examples of quinonediazo compounds include those obtained by sulfonic acid in which quinonediazo is bonded to polyhydroxy compounds through ester bonds, those obtained by sulfonic acids in which quinonediazo is bonded to polyamine compounds by sulfonamide, and those obtained by polyhydroxy compounds. Polyamine-based compound with sulfonic acid of quinonediazo bonded by ester bond or sulfonamide bond, etc. From the viewpoint of the contrast between the exposed part and the unexposed part, it is preferable that 20 mole % or more of the functional groups of the polyhydroxy compound or the polyamine compound are substituted with quinone diazo.

Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP- IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP , DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP- PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are product names, Asahi organic material industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyl Acyloxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Chemical Industry Co., Ltd.), etc., but not limited to these.

Examples of the aforementioned polyamine-based compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylene, 4,4'-diaminodiphenylene, etc., but not limited to these.

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

The quinonediazo compound is preferably 1,2-naphthoquinonediazo-4-sulfonate or 1,2-naphthoquinonediazo-5-sulfonate of a polyhydroxy compound.

When the quinonediazo compound is irradiated with ultraviolet light or the like, it undergoes the reaction shown in the following reaction formula 2 to form a carboxyl group. By generating a carboxyl group, the exposed part (film) becomes soluble in an aqueous alkali solution, and alkali developability is produced in this part.

When the radiation-sensitive compound (D) is a photoacid generator, the content of the photoacid generator in the photosensitive resin composition may be 1 to 40 parts by mass, preferably 5 parts by mass, based on 100 parts by mass of the total resin components. ~35 parts by mass, more preferably 10~30 parts by mass. The content of the photoacid generator is based on the above-mentioned total of 100 parts by mass. If it is more than 1 part by mass, the alkali developability will be good, and if it is less than 40 parts by mass, it will be possible to suppress the alkali developability caused by heating at 300°C or higher. Capsule reduced.

(photobase generator) A photobase generator can also be used as a radiation sensitive compound (D). As a photobase generator, at least 1 sort(s) chosen from the group which consists of an amide compound and an ammonium salt can be used. In one embodiment, the photobase generator is a compound or salt with high sensitivity to i-line (365 nm).

As the amide compound, for example, 2-nitrophenylmethyl-4-methacryloxypiperidine-1-carboxylate, 9-anthracenemethyl-N,N-dimethylaminomethyl ester, 1-(anthracen-2-yl)ethylimidazole carboxylate, (E)-1-[3-(2-hydroxyphenyl)-2-acryloyl]piperidine, etc. Examples of ammonium salts include 1,2-diisopropyl-3-(bisdimethylamino)methylene)guanidinium 2-(3-benzoylphenyl)propionate, (Z)- [[Bis(dimethylamino)methylene]amino]-N-cyclohexylamino)methylammonium tetrakis(3-fluorophenyl)borate, 1,2-dicyclohexyl-4,4, 5,5-Tetramethylbiguanide n-butyltriphenylborate, etc.

When the radiation-sensitive compound (D) is a photobase generator, the content of the photobase generator in the photosensitive resin composition may be 1 to 40 parts by mass, preferably 5 parts by mass, based on 100 parts by mass of the total resin components. ~35 parts by mass, more preferably 10~30 parts by mass. The content of the photobase generator is based on the above-mentioned total of 100 parts by mass. If it is more than 1 part by mass, the alkali developability will be good, and if it is not more than 40 parts by mass, it will be possible to suppress the development of alkali developability due to heating at 300°C or higher. The capsule is reduced.

＜Photopolymerization Initiator＞ A photopolymerization initiator can be used as the radiation-sensitive compound (D). As the photopolymerization initiator, a group selected from benzyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine oxide compounds, oxime ester compounds, acridine compounds, benzophenone compounds, At least one selected from the group consisting of acetophenone compounds, aromatic ketoester compounds, and benzoate compounds. In one embodiment, the photopolymerization initiator is a compound having high sensitivity to i-line (365 nm). The photopolymerization initiator is preferably an α-hydroxy ketone compound, an α-amino ketone compound, an acyl phosphine oxide compound, an oxime ester compound, an acridine compound or a benzophenone compound based on the sensitivity improvement during exposure, and more preferably It is an α-amino ketone compound, an acyl phosphine oxide compound or an oxime ester compound.

Examples of benzyl ketal compounds include 2,2-dimethoxy-1,2-diphenylethan-1-one. Examples of α-hydroxyketone compounds include, for example, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one or 2-hydroxy-1 -[4-[4-(2-Hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one. As α-amino ketone compounds, for example, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropane -1-one, 2-methyl-2-morpholin-1-phenylpropane-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propane-1 -ketone, 2-dimethylamino-1-(4-ethylphenyl)-2-methylpropane-1-one, 2-dimethylamino-1-(4-isopropylphenyl)- 2-methylpropan-1-one, 1-(4-butylphenyl)-2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1-(4- Methoxyphenyl)-2-methylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylthiophenyl)propan-1-one, 2-methyl -1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane -1-ketone, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butane-1-one, 2-dimethylamino-2-[(4- Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone. As the acylphosphine oxide compound, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide Or bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide. As the oxime ester compound, for example, 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-( O-methoxycarbonyl) oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl) oxime, 1-[4-(phenylthio)benzene Base] octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-di Keto-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O- Acetyl) oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methanol oxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime. The acridine compound is, for example, 1,7-bis(acridin-9-yl)-n-heptane. As the benzophenone compound, for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4 -Phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone, alkylated benzophenone, 3,3',4,4'-tetra(tertiary butyl peroxycarbonyl) benzophenone, 4-methylbenzophenone, dibenzyl ketone or fennelone. As the acetophenone compound, for example, 2,2-dioxyacetophenone, 2,3-diethoxyacetophenone, 4-tert-butyldichloroacetophenone, benzylidene acetophenone Or 4-azidobenzylidene acetophenone, etc. As the aromatic ketoester compound, for example, methyl 2-phenyl-2-oxyacetate is exemplified. As the benzoate compound, for example, ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate or 2 - Methyl benzoylbenzoate.

When the first resin (A), the second resin (B), or the third resin (C) or two or more of them have cationic polymerizable groups such as epoxy groups, they can be used as photopolymerization initiators by A photocationic polymerization initiator that generates cationic species or Lewis acid by light. As photocationic polymerization initiators, for example, triphenyl percolium, diphenyl-4-(phenylthio) phenyl permeate, diphenyl permeate, bis(dodecyl phenyl permeate), etc. ) iodonium, etc., diazonium, such as phenyldiazonium, 1-benzyl-2-cyanopyridinium, 1-(naphthylmethyl)-2-cyanopyridinium, etc., pyridinium, ( Fe cations such as 2,4-cyclopentadien-1-yl)[(1-methylethyl)benzene]-Fe, etc., the anion part is BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , [BX ₄ ] ^- (X is a phenyl group substituted with at least 2 or more fluorine atoms or a trifluoromethyl group), etc. Onium salts.

When the radiation-sensitive compound (D) is a photopolymerization initiator, the content of the photopolymerization initiator in the photosensitive resin composition may be 1 to 40 parts by mass, preferably 1 to 40 parts by mass, based on 100 parts by mass of the total resin components. It is 1.5-35 mass parts, More preferably, it is 2-30 mass parts. The content of the photopolymerization initiator is based on the above-mentioned total of 100 parts by mass. If it is more than 1 part by mass, the alkali developability will be good, and if it is less than 40 parts by mass, it will be possible to suppress the development of the photopolymerization by heating at 300°C or higher. The capsule is reduced.

When the radiation-sensitive compound (D) is a photopolymerization initiator, the photosensitive resin composition may further contain a radically polymerizable compound. Resins and compounds having a plurality of ethylenically unsaturated groups as radical polymerizable compounds can crosslink the film to increase its hardness.

It is preferable to use a compound having a plurality of (meth)acrylic groups as the radical polymerizable compound from the viewpoint of reactivity at the time of exposure, hardness of the film, heat resistance, and the like. Examples of such compounds include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate Acrylates, Trimethylolpropane Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Ethoxylated Trimethylolpropane Di(meth)acrylate, Ethoxylated Trimethylolpropane Propane tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate ) acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9- Nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, Dimethylol-tricyclodecane di(meth)acrylate, Ethoxylated glycerol tri(methyl) ) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta( Meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca( Meth)acrylate, pentaerythritol undeca(meth)acrylate, pentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-( 3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl)isocyanurate, 1, 3-bis((meth)acryloxyethyl)isocyanurate, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl] fluorine, 9 ,9-bis[4-(3-(meth)acryloxypropoxy)phenyl] terpine or 9,9-bis(4-(meth)acryloxyphenyl) terpine or its acid Modifiers, Ethylene Oxide Modifiers or Propylene Oxide Modifiers.

The content of the radically polymerizable compound in the photosensitive resin composition may be 15 parts by mass to 65 parts by mass, preferably 20 parts by mass to 60 parts by mass, more preferably 25 parts by mass to 50 parts by mass. If the content of the radically polymerizable compound is within the above range, the alkali developability will be favorable, and the heat resistance of the cured film can be improved.

[Black agent (E)] The black agent (E) can be selected from the group consisting of black dyes and black pigments. A black dye and a black pigment can also be used together. Visibility of display devices such as an organic EL display can be improved by forming a black partition wall in an organic EL element using a photosensitive resin composition containing a black agent (E).

In one embodiment, the black agent (E) contains a black dye. As the black dye, dyes specified by the color index (C.I.) of solvent black 27~47 can be used. The black dye is preferably solvent black 27, 29 or 34 specified by C.I. When at least one of solvent black 27~47 dyes specified by C.I. is used as the black dye, the light-shielding properties of the cured photosensitive resin composition film can be maintained. Compared with the photosensitive resin composition containing black pigment, the photosensitive resin composition containing black dye has less colorant residue during image development, and can form high-definition patterns on the film.

When the black agent (E) is a black dye, the content of the black dye in the photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass based on 100 parts by mass of the total resin components , and more preferably 20 to 80 parts by mass. When the content of the black dye is 10 parts by mass or more based on the total of 100 parts by mass, the light-shielding properties of the cured film can be maintained. The content of the black dye is 150 parts by mass or less on the basis of 100 parts by mass of the above-mentioned total, so that the residual film rate, heat resistance, sensitivity, etc. are appropriate.

Black pigments can also be used as black agents (E). Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene-based pigments, lactam-based pigments, and the like. What surface-treated these black pigments can also be used. Examples of commercially available perylene-based pigments include K0084, K0086, Pigment Black 21, 30, 32, 33, and 34 manufactured by BASF Corporation. Irgaphor (registered trademark) black S0100CF manufactured by BASF Corporation is exemplified as an example of a commercially available lactamide pigment. The black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene-based pigments, and lactam-based pigments because of its high light-shielding properties. In a negative-type photosensitive resin composition in which the radiation-sensitive compound (D) is a photopolymerization initiator, it is advantageous that the black agent (E) is a black pigment that is difficult to inhibit polymerization.

When the black agent (E) is a black pigment, the content of the black pigment in the photosensitive resin composition is preferably 10 to 150 parts by mass, more preferably 15 to 100 parts by mass, based on 100 parts by mass of the total resin components , and more preferably 20 to 80 parts by mass. When the content of the black pigment is 10 parts by mass or more based on the above-mentioned total of 100 parts by mass, sufficient light-shielding properties can be obtained. The content of the black pigment is 150 parts by mass or less on the basis of the above-mentioned total of 100 parts by mass, so that the remaining film rate, sensitivity, etc. are appropriate.

When the black agent (E) contains both the black dye and the black pigment, the total amount of the black dye and the black pigment in the photosensitive resin composition is preferably 10 to 150 parts by mass based on 100 parts by mass of the total resin components , more preferably 15 to 100 parts by mass, and more preferably 20 to 80 parts by mass. When the total amount of the black dye and the black pigment is 10 parts by mass or more based on 100 parts by mass of the above-mentioned total, sufficient light-shielding properties can be obtained. The total amount of black dye and black pigment is based on the above-mentioned total of 100 parts by mass, and if it is 150 parts by mass or less, the remaining film rate, sensitivity, etc. are appropriate.

[optional ingredient] The photosensitive resin composition may contain a dissolution accelerator (F), a basic compound (G), a solvent (H), a thermosetting agent, a surfactant, a second colorant other than the black agent (E), etc. as optional components . In this disclosure, an optional component is defined as not corresponding to any one of (A) to (E).

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

For example, as a low-molecular compound having a carboxyl group, formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, pivalic acid, hexanoic acid, diethylacetic acid, heptanoic acid, octanoic acid and other aliphatic monocarboxylic acids can be exemplified; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid, ethylmalonic acid Aliphatic dicarboxylic acids such as dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as propanetricarboxylic acid, aconitic acid, and camphoric acid Acids; aromatic monocarboxylic acids such as benzoic acid, toluic acid, humic acid, hemimellitic acid, and mesitylenic acid; phthalic acid, isophthalic acid, terephthalic acid, Aromatic polycarboxylic acids such as trimellitic acid, trimellitic acid, trimellitic acid, and pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; benzene Glycolic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, phenylpentadiene acetic acid, coumarin Other carboxylic acids such as umbellic acid and umbellic acid.

Examples of low-molecular-weight compounds having phenolic hydroxyl groups include catechol, resorcinol, hydroquinone, propyl gallate, dihydroxynaphthalene, leuco isatin, and 1,2,4-glucinol , Anthracenol, Pyrogallol, Phloroglucinol, Tetrahydroxybenzophenone, Phenolphthalein, Phenolphthalic Acid, Tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl) ) ethane, α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, etc.

The content of the dissolution accelerator (F) may be 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass, more preferably 3 to 12 parts by mass, based on 100 parts by mass of the total resin components. The content of the dissolution accelerator (F) is based on the above-mentioned total of 100 parts by mass. If it is 0.1 parts by mass or more, the dissolution of the resin component can be effectively promoted, and if it is 20 parts by mass or less, excessive dissolution of the resin component can be suppressed, and Improve the pattern formation and surface quality of the film.

[Basic compound (G)] The photosensitive resin composition may contain a basic compound (G) in order to secure the long-term reliability of the organic EL device. The basic compound (G) acts as a quencher for acid components or acid sites such as carboxylic acid and phenolic hydroxyl group contained in the photosensitive resin composition, or acid gas generated from a photoacid generator. When using a film as an organic EL element, by using a basic compound (G), reduction of emission luminance, shrinkage of a pixel, and generation|occurrence|production of a black spot can be prevented.

As the basic compound (G), for example, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, 3-(2-ethylhexyloxy)propylamine, di-n-butylamine, di-n- Amylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tricyclohexylamine, triphenylamine, aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine Amine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Benzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-amino Phenyl)propane, 2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 1 ,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene , poly(4-vinylpyridine), poly(2-pyridine), poly(N-2-pyrrolidone), polyethylenimine polyallylamine, poly(dimethylaminoethylacrylamide) , formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide , benzamide, pyrrolidone, N-methylpyrrolidone, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3- Tetramethylurea, 1,3-diphenylurea, tributylthiourea, imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, pyridine, 2-picoline , 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotine acid, nicotine Basic acid amide, quinoline, 8-oxyquinoline, acridine, pyrazine, pyrazole, pyrazine, quinazoline, purine, pyrrolizine, piperidine, morpholine, 4-methylmorpholine, piperidine oxazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8 - Diazabicyclo[5.4.0]-7-undecene and 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine.

The content of the basic compound (G) is preferably not more than 4 parts by mass, more preferably not more than 3 parts by mass, and more preferably not more than 2 parts by mass, based on 100 parts by mass of the total solid content excluding the basic compound (G). servings or less.

[Solvent (H)] The photosensitive resin composition can be used in a solution state dissolved in a solvent (however, when a black pigment is included, the pigment is in a dispersed state). For example, by mixing the radiation-sensitive compound (D) and the black agent ( E) Optional ingredients such as dissolution accelerator (F), basic compound (G), thermosetting agent, surfactant, etc. as needed, can prepare a photosensitive resin composition in a solution state. The photosensitive resin composition can be adjusted to a viscosity suitable for the coating method used by changing the amount of solvent.

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

[Thermohardener] As the thermosetting agent, a thermal radical generating agent can be used. Examples of preferred thermal free radical generators include organic peroxides, specifically dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane Alkanes, tert-butylcumene peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, etc. for 10 hours Organic peroxides with a half-life temperature of 100~170°C, etc.

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

[Surfactant] The photosensitive resin composition may contain a surfactant in order to improve, for example, applicability, smoothness of a film, or image development of a film. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene octyl Polyoxyethylene aryl ethers such as polyoxyethylene phenyl ether, polyoxyethylene nonylphenyl ether, etc.; polyoxyethylene dilaurate, polyoxyethylene distearate, etc. Non-ionic surfactants such as oxyethylene dialkyl esters; MEGFAC (registered trademark) F-251, same F-281, same F-430, same F-444, same R-40, same F- 553, Same as F-554, Same as F-555, Same as F-556, Same as F-557, Same as F-558, Same as F-559 (the above are product names, made by DIC Co., Ltd.), SURFLON (registered trademark) S Fluorinated surfactants such as -242, same as S-243, same as S-386, same as S-420, same as S-611 (the above are trade names, manufactured by ACG Semichemical Co., Ltd.); organosiloxane polymer KP323 , KP326, KP341 (the above are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Surfactants may be used alone or in combination of two or more.

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

[the second coloring agent] The photosensitive resin composition may contain the 2nd coloring agent other than a black agent (E). Examples of the second coloring agent include dyes, organic pigments, inorganic pigments and the like, which can be used according to the purpose. The 2nd coloring agent can be used in the content which does not impair the effect of this invention.

Examples of dyes include azo-based dyes, benzoquinone-based dyes, naphthoquinone-based dyes, anthraquinone-based dyes, cyanine-based dyes, squalilium-based dyes, crotonium-based dyes, and merocyanine-based dyes. , diphenylethylene dyes, diphenylmethane dyes, triphenylmethane dyes, fluoran dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, alkyd dyes, nickel zirconium Compound-based dyes and azulene-based dyes, etc.

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.

[Manufacturing method of photosensitive resin composition] The photosensitive resin composition can be prepared by mixing the first resin (A), the second resin (B), the third resin (C), the radiation-sensitive compound (D), the black agent (E) and the dissolution accelerator ( F), the above-mentioned arbitrary components, such as a basic compound (G), are prepared by dissolving or dispersing in a solvent (H). Depending on the purpose of use, the solid content concentration of the photosensitive resin composition can be appropriately determined. For example, the solid content concentration of the photosensitive resin composition may be 1-60% by mass, 3-50% by mass, or 5-40% by mass.

A known method can be used for the dispersion mixing method in the case of using a pigment. For example, ball mills, sand mills, bead mills, paint shakers, swing mills, etc., blending types such as kneaders, paddle mixers, planetary mixers, and Henschel mixers, and 3-rollers can be used. The roller type of the mixer, etc., as other crushing machines, colloid mills, ultrasonic waves, homogenizers, rotation/revolution mixers, etc. From the viewpoint of dispersion efficiency and fine dispersion, it is preferable to use a bead mill.

The prepared photosensitive resin composition is usually filtered before use. Examples of filtration means include, for example, a microporous filter having a pore size of 0.05 to 1.0 μm.

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

[Use of photosensitive resin composition] When the photosensitive resin composition is used in radiation lithography, first, the photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition is coated on the surface of the substrate, and the solvent is removed by means such as heating to form a film. The coating method of the coating composition on the surface of the substrate is not particularly limited, and examples thereof include spraying, roll coating, slit coating, and spin coating.

After the coating composition is coated on the surface of the substrate, the solvent is usually removed by heating to form a film (pre-baking). The heating conditions vary depending on the type and blending ratio of each component, but usually heat treatment at 70-130°C for 30 seconds to 20 minutes on a heating plate, and 1 to 60 minutes in an oven to obtain a coating. In one embodiment, the thickness of the formed film is 2-3 μm.

Next, irradiate the pre-baked film with radiation (such as visible light, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, gamma rays, synchrotron radiation, etc.) through a mask with a specific pattern (exposure step). In the case of using a quinonediazo compound as the radiation-sensitive compound, preferred radiation is ultraviolet to visible light having a wavelength of 250-450 nm. In one embodiment, the radiation is i-line. In other implementation aspects, the radiation is ghi rays.

After the exposure step, the film is developed by contacting the film with a developer to remove unnecessary parts and form a pattern on the film (development step). As the developer, inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, etc.; primary amines such as ethylamine and n-propylamine; diethylamine, diethylamine, etc. -Secondary amines such as n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Alcoholamines such as dimethylethanolamine and triethanolamine; Tetramethylammonium hydroxide, tetraethylammonium hydroxide, Quaternary ammonium salts of choline, etc.; pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5 - Aqueous solutions of alkali compounds such as cyclic amines such as nonene. An aqueous solution in which a water-soluble organic solvent such as methanol or ethanol or a surfactant is appropriately added to an alkaline aqueous solution can also be used as a developing solution. The imaging time is usually 30-180 seconds. The imaging method may be any one of the liquid coating method, the rinsing method, and the dipping method. After imaging, wash with running water for 30-90 seconds to remove unnecessary parts, and dry with compressed air or compressed nitrogen to form patterns on the film.

Subsequently, the patterned film is heat-treated at 100-350° C. for 20-200 minutes by a heating device such as a heating plate or an oven to obtain a cured film (post-baking, heat treatment step). During the heat treatment, the temperature may be kept constant, or the temperature may be continuously increased, or may be increased stepwise.

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

[Manufacturing method of organic EL element partition wall or organic EL element insulating film] One embodiment is a method for manufacturing an organic EL element partition wall or an organic EL element insulating film, which includes the following steps: dissolving or dispersing a photosensitive resin composition in a solvent to prepare a coating composition, and coating the coating composition Spread on the substrate to form a coating, remove the solvent contained in the coating and dry the coating, irradiate the dried coating with radiation through a photomask to expose the coating, and make the exposed coating contact with the developing solution to develop the image, on the coating Form a pattern, and heat-treat the patterned film at a temperature of 100°C to 350°C to form an organic EL element partition wall or an organic EL element insulating film.

[next door to organic EL element] One embodiment is an organic EL element partition wall, which includes a cured product of a photosensitive resin composition.

[Organic EL element insulating film] One embodiment is an insulating film for an organic EL element, which includes a cured product of a photosensitive resin composition.

[Organic EL element] One embodiment is an organic EL device including a hardened 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) Evaluation of physical properties The evaluation of the physical properties of the resin or photosensitive resin composition is performed by the following procedures.

[Alkali dissolution rate] Add MAGFAC (registered trademark) as a leveling agent to a 20% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of the resin or photosensitive resin composition at an amount of 0.1 parts by mass per 100 parts by mass of the solid content of the resin F-559 (a fluorine-based surfactant, manufactured by DIC Corporation). The resulting mixture was coated on a glass substrate (70 mm x 70 mm x 0.7 mm) so that the dry film thickness was 5.0 μm, and after vacuum drying for 30 seconds, the film was dried at a temperature of 120° C. for 120 seconds. After drying, alkali development was performed with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution. The imaging time ranges from 8 to 400 seconds, and is adjusted to the time when the coating is insoluble. The amount of film reduction (nm) after development was divided by the development time (seconds) as the alkali dissolution rate (nm/second).

[molecular weight] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the first resin (A), the second resin (B), the third resin (C) and other resins are based on the following measurement conditions using polystyrene Calculated from the calibration line made by the standard substance. Device name: Shodex (registered trademark) GPC-101 Column: Shodex (registered trademark) LF-804 Mobile Phase: Tetrahydrofuran Flow rate: 1.0mL/min Detector: Shodex (registered trademark) RI-71 Temperature: 40°C

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

[Manufacturing example 1] The first resin (A): Manufacture of resin (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- 37.6 g of 770 (phenol novolak type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 188) was dissolved at 60° C. under a nitrogen atmosphere. 20.1 g of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) as a hydroxybenzoic acid compound (0.65 equivalent to 1 equivalent of epoxy group) and triphenyl as a reaction catalyst were added thereto. Phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.173 g (0.660 mmol) was reacted at 110° C. for 24 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain 286.5 g of a solution of a resin (N770OH70) having an epoxy group and a phenolic hydroxyl group. The number average molecular weight of the obtained reactant is 2400, the weight average molecular weight is 5400, the epoxy equivalent is 2000, and the phenolic hydroxyl equivalent is 142.

[Production Example 2] Production of the first resin (A): a resin (N695OH70) having an epoxy group and a phenolic hydroxyl group 75.2 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) as a solvent, and EPICLON (registered trademark) N- 37.8 g of 695 (cresol novolak type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 214) was dissolved at 60° C. under a nitrogen atmosphere. 20.1 g of 3,5-dihydroxybenzoic acid (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) as a hydroxybenzoic acid compound (0.65 equivalent to 1 equivalent of epoxy group) and triphenyl as a reaction catalyst were added thereto. Phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.166 g (0.660 mmol) was reacted at 110° C. for 21 hours. The reaction solution was returned to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and the solution was filtered to obtain 274.2 g of a solution of a resin (N695OH70) having an epoxy group and a phenolic hydroxyl group. The number average molecular weight of the obtained reactant is 3000, the weight average molecular weight is 5100, the epoxy equivalent is 2200, and the phenolic hydroxyl equivalent is 161.

[Production Example 3] Second Resin (B): Production of Second Resin (B-TBMA42.5%) with Phenolic Hydroxyl 17.3 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 6.15 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) and methacrylic acid third 13.8 g of butyl ester (manufactured by Mitsubishi Chemical Co., Ltd. "ACRYL ESTER TB") was completely dissolved in 56.0 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) as a solvent, and 2 , 2.69 g of dimethyl 2'-azobis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd. ) 4.05g. The two solutions obtained were added dropwise to 100 g of isopropyl acetate (manufactured by Shengang Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL 3-necked flask under nitrogen atmosphere at the same time for 2 hours, and then in The reaction was carried out under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was added dropwise to the 80:20 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 36.5 g of white powder. The obtained second resin B-TBMA42.5% having phenolic hydroxyl groups had a number average molecular weight of 4100, a weight average molecular weight of 7600, and a phenolic hydroxyl group equivalent of 384.

[Manufacturing example 4] Second resin (B): Production of second resin (B-PhMA41%) having phenolic hydroxyl groups 17.0 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 5.83 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), and phenyl methacrylate ("ACRYL ESTER PH" manufactured by Mitsubishi Chemical Co., Ltd.) 14.4g was completely dissolved in 60.0g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) in the solvent, and 2,2' as a polymerization initiator - 2.72 g of dimethyl azobis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 4.08 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.) middle. The resulting two solutions were added dropwise to 95.9 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL 3-necked flask under nitrogen atmosphere at the same time for 2 hours, and then React at 89°C for 4 hours under reflux. The reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 36.5 g of white powder. The obtained second resin B-PhMA41% having phenolic hydroxyl groups had a number average molecular weight of 4300, a weight average molecular weight of 7800, and a phenolic hydroxyl group equivalent of 390.

[Manufacturing Example 5] Second Resin (B): Production of Second Resin (B-PhMA20%) Having Phenolic Hydroxyl Group 24.6 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 5.71 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), and phenyl methacrylate ("ACRYL ESTER PH" manufactured by Mitsubishi Chemical Co., Ltd.) 6.89g was completely dissolved in 55.8g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) in the solvent, and 2,2' as a polymerization initiator - 2.83 g of dimethyl azobis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") is completely dissolved in 4.23 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) middle. The two solutions obtained were added dropwise to 100 g of isopropyl acetate (manufactured by Shengang Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL 3-necked flask under nitrogen atmosphere at the same time for 2 hours, and then in The reaction was carried out under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 36.4 g of white powder. The obtained second resin B-PhMA 20% having phenolic hydroxyl groups had a number average molecular weight of 3600, a weight average molecular weight of 7200, and a phenolic hydroxyl group equivalent of 270.

[Production Example 6] The third resin (C): Production of a copolymer (PCX-02e) of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer Acetic acid in which 25.5 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA") and 4.50 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) were completely dissolved in acetic acid In 77.1 g of 1-methoxy-2-propyl ester (manufactured by DAICEL Co., Ltd.), 3.66 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in acetic acid 1- Methoxy-2-propyl ester (manufactured by DAICEL Co., Ltd.) 14.6 g. The two solutions obtained were added dropwise to 1-methoxy-2-propyl acetate (manufactured by DAICEL Co., Ltd.) heated to 85° C. g, and then reacted at 85°C for 3 hours under reflux. The reaction solution cooled to room temperature was added dropwise to 815 g of toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 90° C. for 4 hours to recover 32.4 g of white powder. The obtained copolymer PCX-02e of the polymerizable monomer with phenolic hydroxyl group and other polymerizable monomers had a number average molecular weight of 3100, a weight average molecular weight of 6700, and a phenolic hydroxyl group equivalent of 210.

[Production Example 7] Production of a copolymer of glycidyl methacrylate and methacrylic acid (GMA-MAA) Dissolve 99.5g (0.7 mol) of glycidyl methacrylate (GMA) and 8.6g (0.1 mol) of methacrylic acid (MAA) in 72.1g of propylene glycol monomethyl ether (PGME) respectively, and use it as the polymerization initiator 7.6 g of V-65 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 7.6 g of PGME. The obtained two kinds of solutions were added dropwise to PGME 172.6 g heated to 80° C. in a 500 mL 3-neck flask under a nitrogen atmosphere at the same time over 2 hours, and then stirred for 2 hours to make it react. In this way, a copolymer of glycidyl methacrylate and methacrylic acid (GMA-MAA ). The obtained GMA-MAA has a carboxyl group and an epoxy group in the molecule, so it has high self-reactivity, that is, it is easy to undergo ring-opening polymerization of the epoxy group, so if it is reprecipitated and vacuum-dried, it will become high in molecular weight and cannot be separated. Leave. The PGME solution of GMA-MAA has low stability, and the viscosity of the solution increases due to the progress of high molecular weight over time.

[Production Example 8] Second Resin (B): Production of Second Resin (B-CHMA 20%) Having Phenolic Hydroxyl Group 24.5 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 7.11 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), and cyclohexyl methacrylate 5.68 g of ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 69.3 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2'-azobis 2.72 g of dimethyl (isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 10.87 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.). The resulting two solutions were added dropwise to 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL 3-necked flask under nitrogen atmosphere simultaneously over 2 hours, and then placed in The reaction was carried out under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 39.1 g of white powder. The obtained second resin B-CHMA 20% having phenolic hydroxyl groups had a number average molecular weight of 3,500, a weight average molecular weight of 7,200, and a phenolic hydroxyl equivalent of 271.

[Production Example 9] Second Resin (B): Production of Second Resin (B-CHMA40%) Having Phenolic Hydroxyl Group 17.14 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 14.39 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), and cyclohexyl methacrylate 5.75 g of ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 69.3 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2'-azobis 2.72 g of dimethyl (isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 10.87 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.). The two solutions obtained were added dropwise to 143 g of isopropyl acetate (manufactured by Shengang Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL 3-necked flask under nitrogen atmosphere at the same time for 2 hours. The reaction was carried out under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 39.1 g of white powder. The obtained second resin B-CHMA 40% having phenolic hydroxyl groups had a number average molecular weight of 3900, a weight average molecular weight of 7500, and a phenolic hydroxyl group equivalent of 387.

[Production Example 10] Second Resin (B): Production of Second Resin (B-BOM32%) Having Phenolic Hydroxyl Group 17.3 g of 4-hydroxyphenyl methacrylate ("PQMA" manufactured by Showa Denko Co., Ltd.), 29.0 g of N,N-diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), tetrahydrofuran (dehydrated) (Kanto Chemical Co., Ltd.) 160g in a 500mL 3-necked flask, stirred under nitrogen atmosphere until the solid was completely dissolved. The solution was cooled to 0° C., and 26.4 g of benzyl chloride methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the solution. After the dropwise addition, it was heated to 70° C. for 5 hours to react. After the reaction solution returned to room temperature, unnecessary substances were removed by filtration, 200 mL of ethyl acetate (special grade manufactured by Junzheng Chemical Co., Ltd.) was added, and THF was distilled off. The organic layer was washed once with 300 mL of saturated aqueous sodium bicarbonate solution and twice with 200 mL of pure water. After drying over sodium carbonate, the solvent was distilled off completely. The crude product was purified by silica gel column chromatography using a developing solvent of hexane:ethyl acetate=50:1 to obtain 31.2 g of PQMA-BOM.

12.1 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 3.45 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), and 12.3 g of PQMA-BOM In 41.8 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) completely dissolved in the solvent, 2,2'-azobis(isobutyrate) dimethyl (Fuji Film 2.14 g of "V-601" manufactured by Wako Pure Chemical Industries, Ltd.) was completely dissolved in 8.54 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.). The two solutions obtained were added dropwise to 69.7 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL 3-necked flask under a nitrogen atmosphere at the same time for 2 hours, and then React at 89°C for 4 hours under reflux. The reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 29.3 g of white powder. The obtained second resin B-BOM32% having phenolic hydroxyl groups had a number average molecular weight of 3600, a weight average molecular weight of 6900, and a phenolic hydroxyl equivalent of 431.

[Production Example 11] Second Resin (B): Production of Second Resin (B-IBMA 20%) Having Phenolic Hydroxyl Group 23.1 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 8.86 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), and isobornyl methacrylate 5.35 g of ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 69.2 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2'-azobis 2.72 g of dimethyl (isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 10.83 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.). The resulting two solutions were added dropwise to 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL 3-necked flask under nitrogen atmosphere simultaneously over 2 hours, and then placed in The reaction was carried out under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 39.1 g of white powder. The obtained second resin B-IBMA 20% having phenolic hydroxyl groups had a number average molecular weight of 3,600, a weight average molecular weight of 7,100, and a phenolic hydroxyl equivalent of 288.

[Production Example 12] Second Resin (B): Production of Second Resin (B-TCDMA20%) Having Phenolic Hydroxyl Group 23.1 g of 4-hydroxyphenyl methacrylate (manufactured by Showa Denko Co., Ltd. "PQMA"), 8.79 g of N-cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.), and bicyclomethacrylate 5.37 g of pentyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was completely dissolved in 69.2 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) of the solvent, and 2,2'-azo 2.72 g of dimethyl bis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. "V-601") was completely dissolved in 10.83 g of isopropyl acetate (manufactured by Shinko Organic Chemicals Co., Ltd.). The resulting two solutions were added dropwise to 143 g of isopropyl acetate (manufactured by Shinko Organic Chemical Industry Co., Ltd.) heated to 89° C. in a 300 mL 3-necked flask under nitrogen atmosphere simultaneously over 2 hours, and then placed in The reaction was carried out under reflux at 89°C for 4 hours. The reaction solution cooled to room temperature was added dropwise to a 50:50 mixture of 1000 g of hexane and toluene to precipitate the copolymer. The precipitated copolymer was recovered by filtration, and vacuum-dried at 80° C. for 5 hours to recover 39.1 g of white powder. The obtained second resin B-TCDMA 20% having phenolic hydroxyl groups had a number average molecular weight of 3800, a weight average molecular weight of 8000, and a phenolic hydroxyl group equivalent of 287.

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

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

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

[Other resins] As other resins, SHONOL (registered trademark) BRG-558 (phenol novolac resin manufactured by AICA Industry Co., Ltd., phenolic hydroxyl equivalent 107), EPICLON (registered trademark) N-770 (phenol novolac type manufactured by DIC Co., Ltd.) Epoxy resin, epoxy equivalent 188) and the GMA-MAA of manufacturing example 7.

Table 1 shows the structural unit ratio, phenolic hydroxyl equivalent, alkali dissolution rate and weight average molecular weight (Mw) of the resin. In Table 1, PQMA is a structural unit derived from 4-hydroxyphenyl methacrylate, and CHMI represents a structural unit derived from N-cyclohexylmaleimide.

[Radiation sensitive compound (D)] As the radiation-sensitive compound (D), TS-150A (4,4'-[1-[4-[1-[4-hydroxyphenyl)-1-methylethyl]phenyl] of a quinonediazo compound was used Ethylene]bisphenol (TrisP-PA) and 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-quinonediazo-5-sulfonic acid) ester , Toyo Gosei Kogyo Co., Ltd.). The structure of TS-150A is shown below.

[Black agent (E)] As a black agent, VALIFAST (registered trademark) black 3820 (black dye specified by C.I. of solvent black 27, manufactured by Oriental Chemical Industry Co., Ltd.) was used as a black dye.

[Dissolution Accelerator (F)] As the dissolution accelerator (F), phloroglucinol was used.

[Basic compound (G)] As the basic compound (G), tri-n-octylamine (TOA) was used.

[Solvent (H)] As the solvent (H), a mixed solvent of γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate (PGMEA) and diethyl carbonate (DEC) (GBL:PGMEA:DEC=35:45:20 Mass ratio)), or a mixed solvent of γ-butyrolactone (GBL), propylene glycol monomethyl ether acetate (PGMEA), diethyl carbonate (DEC) and propylene glycol monomethyl ether (PGME) (GBL: PGMEA: DEC : PGME=35:35:20:10 (mass ratio)). The value of the mass ratio of GBL and PGME includes the user in Production Example 1, 2 or 7.

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

[Solubility] <Solubility of exposed part> Bar-coat the photosensitive resin composition on a glass substrate (size 100mm×100mm×1mm) so that the dry film thickness is 2.7 μm, and heat it on a hot plate at 120°C for 120 seconds The solvent is dried (pre-baked). After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, manufactured by FILMETRICS Co., Ltd.), an exposure device equipped with an ultra-high pressure mercury lamp (trade name MULTILIGHT ML-251A/B, manufactured by USHIO Electric Co., Ltd.) , through a band-pass filter for mercury exposure (trade name HB0365, manufactured by Asahi Spectroscopic Co., Ltd.) and a quartz mask (with lines and spaces of 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, and 500 μm (L/S ) pattern) was exposed at 100 mJ/cm ² . Exposure was measured using an ultraviolet integrated light meter (trade name UIT-150, light receiving part UVD-S365, manufactured by Ushio Electric Co., Ltd.). Subsequently, using a rotary developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.), alkali developing was performed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution in the range of 20 seconds to 200 seconds until the film of the exposed part disappeared. Therefore, in Table 2, in accordance with the development time, the solubility of the exposed parts is all shown as 2.70 μm (only Comparative Example 2 exceeds 2.70 μm due to pattern peeling).

＜Solubility of unexposed part＞ The photosensitive resin composition was bar-coated on a glass substrate (size 100mm×100mm×1mm) so that the dry film thickness was 2.7 μm, and the solvent was dried by heating at 120° C. for 120 seconds on a hot plate (pre-baking). After measuring the dry film thickness using an optical film thickness measuring device (F20-NIR, manufactured by FILMETRICS Co., Ltd.), tetramethyl hydroxide was oxidized at 2.38% by mass using a rotary developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). The ammonium aqueous solution is subjected to alkaline development for the same development time as the solubility of the exposed part. The film thickness after alkaline development was measured again using an optical film thickness measuring device (F20-NIR, manufactured by FILMETRICS Co., Ltd.), and the film thickness (μm) dissolved before and after development was calculated as the solubility of the unexposed part.

＜Poor solubility＞ The solubility (µm) of the unexposed portion was subtracted from the solubility (µm) of the exposed portion to obtain a solubility difference (µm). A larger difference in solubility means higher sensitivity and better pattern formation.

[OD value of hardened film] The photosensitive resin composition was spin-coated on a glass substrate (size 100mm×100mm×1mm) so that the dry film thickness was about 1.5 μm, and the solvent was dried by heating at 120° C. for 120 seconds on a hot plate. Subsequently, by curing at 250° C. for 60 minutes under a nitrogen atmosphere, a film was obtained. The OD value of the hardened coating was measured with a transmission densitometer (BMT-1, manufactured by SAKATA INX Engineering Co., Ltd.), and the OD value of the glass alone was used for correction, and converted into the OD value of the coating per 1 μm thickness. The film thickness was measured using an optical film thickness measuring device (F20-NIR, manufactured by FILMETRICS Co., Ltd.).

[Pattern Formability] On a glass substrate (100mm x 100mm x 1mm in size), the photosensitive resin composition was bar-coated so that the dry film thickness was 2.7 μm, and the solvent was dried by heating at 120° C. for 120 seconds on a hot plate ( pre-baked). An exposure device (trade name MULTILIGHT ML-251A/B, manufactured by USHIO Electric Co., Ltd.) equipped with an ultra-high pressure mercury lamp was separated from a mercury exposure band-pass filter (trade name HB0365, manufactured by Asahi Spectral Co., Ltd.) and quartz The photomask (pattern with φ10μm) is exposed at 100mJ/cm ² or less. Exposure was measured using an ultraviolet integrated light meter (trade name UIT-150, light receiving part UVD-S365, manufactured by Ushio Electric Co., Ltd.). After exposure, alkaline development was performed for 60 seconds with a 2.38% by mass tetramethylammonium hydroxide aqueous solution using a rotary developing device (AD-1200, manufactured by Takizawa Sangyo Co., Ltd.). Furthermore, the coating was cured by heating at 250° C. for 60 minutes in an inert oven (DN411I, manufactured by Yamato Science Co., Ltd.). The film thickness of the cured film was measured using an optical film thickness measuring device (F20-NIR, manufactured by FILMETRICS Co., Ltd.), and the formed holes were observed with a microscope (VHX-6000, manufactured by KEYENCE Corporation). A film thickness of 3.0 μm or more and a pore diameter of 10 μm or more was judged to be good, and a film thickness of 2.9 μm or less or a pore diameter of 9 μm or less was judged to be poor.

[rough surface] Visual observation with a microscope, when irregularities of about 0.5 μm were observed on the entire surface of the film, it was judged to be defective, and when unevenness was not seen on the entire surface of the film, it was judged to be good.

(4) Preparation and evaluation of photosensitive resin composition [Examples 1-9, Comparative Examples 1-4] Add the radiation-sensitive compound (D), black agent (E), dissolution accelerator (F), basic compound (G) and solvent listed in Table 2 to the solution obtained by mixing and dissolving the resin components in the composition listed in Table 2 (H) Further mixing. After visually confirming the dissolution of the components, filter through a microporous filter with a pore size of 0.22 μm to prepare a photosensitive resin composition with a solid content concentration of about 12% by mass. The composition mass parts in Table 2 are solid content conversion values. Table 2 also records the alkali dissolution rate of the photosensitive resin composition. Table 2 shows the evaluation results of the photosensitive resin compositions of Examples 1-9 and Comparative Examples 1-4. In Comparative Example 3, pattern peeling occurred during development, and since the exact solubility could not be measured, the values related to the solubility in Table 2 were put in parentheses. The stability of the PGME solution of GMA-MAA in Comparative Example 4 was low and could not be evaluated.

[產業上之可利用性]

[Industrial availability]

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

Claims (18)

A photosensitive resin composition comprising (A) a first resin, (B) a second resin having a phenolic hydroxyl group different from the first resin, and (C) different from both the first resin and the second resin The third resin having a phenolic hydroxyl group, (D) a radiation-sensitive compound, and (E) a black agent, the optical density (OD value) of the cured film of the above-mentioned photosensitive resin composition is 0.5 or more per 1 μm of film thickness, and the above-mentioned The phenolic hydroxyl equivalent of the second resin is 1.1 to 5.0 times the phenolic hydroxyl equivalent of the third resin, and the second resin includes the same structural unit and other structural units as at least one of the structural units of the third resin , and the common structural unit with the aforementioned 3rd resin contains 30 mol%～95 mol% in total, the alkali dissolution rate of the aforementioned 2nd resin is less than the alkali dissolution rate of the aforementioned 3rd resin, and the aforementioned 2nd resin has formula (17 ) represents the structural unit:

(In formula (17), R ³⁸ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ³⁹ is a branched alkyl group selected from a straight-chain alkyl group with 1 to 20 carbon atoms and a branched alkyl group with 3 to 20 carbon atoms , cyclic alkyl groups with 3 to 12 carbon atoms, aryl groups with 6 to 20 carbon atoms, linear alkyl groups with 1 to 20 carbon atoms substituted by groups other than acidic functional groups, and substituted by groups other than acidic functional groups A branched alkyl group with 3 to 20 carbon atoms substituted by an acidic functional group, a cyclic alkyl group with 3 to 12 carbon atoms substituted by a group other than an acidic functional group, and a branched alkyl group with 6 to 6 carbon atoms substituted by a group other than an acidic functional group The base of the group formed by the aryl group of 20). The photosensitive resin composition according to claim 1, wherein the second resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. The photosensitive resin composition according to claim 1 or 2, wherein the third resin is a copolymer of a polymerizable monomer having a phenolic hydroxyl group and another polymerizable monomer. The photosensitive resin composition according to claim 1 or 2, wherein the aforementioned second resin has a structural unit represented by formula (10):

(In formula (10), R ¹⁵ is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and e is an integer of 1 to 5). The photosensitive resin composition according to claim 1 or 2, wherein the aforementioned second resin has a structural unit represented by formula (11):

(In formula (11), R ¹⁶ and R ¹⁷ are independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a fully or partially fluorinated fluoroalkyl group with 1 to 3 carbon atoms or a halogen atom, R ¹⁸ is a hydrogen atom, a straight-chain alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 3 to 12 carbon atoms, a phenyl group, or a group selected from hydroxyl, an alkyl group with 1 to 6 carbon atoms and the number of carbon atoms A phenyl group substituted with at least one of alkoxy groups of 1 to 6). The photosensitive resin composition according to claim 1 or 2, wherein the first resin is a resin having epoxy groups and phenolic hydroxyl groups. The photosensitive resin composition according to claim 1 or 2, wherein the first resin is a reactant of a compound having at least 2 epoxy groups in one molecule and a hydroxybenzoic acid compound, and has a structure of formula (9) compound,

(In the formula (9), d is an integer of 1 to 5, and * represents a bonding portion of a residue other than an epoxy group reacting with a compound having at least two epoxy groups in one molecule). The photosensitive resin composition according to claim 7, wherein the compound having at least 2 epoxy groups in one molecule is a novolak type epoxy resin. Such as the photosensitive resin composition of claim 1 or 2, wherein the aforementioned black agent is a dye specified by the color index (C.I.) of solvent black 27~47 material. The photosensitive resin composition according to claim 1 or 2, wherein the radiation-sensitive compound is a photoacid generator. The photosensitive resin composition according to claim 1 or 2, wherein the first resin contains 20% by mass to 90% by mass based on the total mass of the resin components. The photosensitive resin composition according to claim 1 or 2, wherein the second resin contains 5% by mass to 50% by mass based on the total mass of the resin components. The photosensitive resin composition according to claim 1 or 2, wherein the third resin contains 5% by mass to 50% by mass based on the total mass of the resin components. The photosensitive resin composition according to claim 1 or 2, wherein the radiation-sensitive compound contains 1 to 40 parts by mass based on 100 parts by mass of the total resin components. The photosensitive resin composition according to claim 1 or 2, wherein the black agent contains 10 to 150 parts by mass based on 100 parts by mass of the total resin components. A barrier rib for an organic EL element, comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 15. An insulating film for an organic EL element, comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 15. An organic EL element comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 15.