Positive photosensitive resin composition, organic el element barrier rib, organic el element insulating film, and organic el element

Abstract

Provided are: a positive photosensitive resin composition which contains a hydrophobic resin (A), a colorant (E) that contains a black dye, and a surfactant (D), wherein the hydrophobic resin (A) includes a specific structure; and an organic EL element barrier rib, an organic EL element insulating film and an organic EL element, each of which comprises the positive photosensitive resin composition.

Description

Positive-type photosensitive resin composition, organic EL element partition, organic EL element insulating film, and organic EL element

[0001] Cross-reference to Related Applications This application claims priority to Japanese Patent Application No. 2024-182238, filed with the Japan Patent Office on 17 October 2024, which is incorporated herein by reference in its entirety.

[0002] The present invention relates to a positive-type photosensitive resin composition, an organic EL element partition, an organic EL element insulating film, and an organic EL element.

[0003] Positive-type photosensitive resin compositions are widely used as partition materials, insulating films, and planarization films in display devices such as organic EL displays (OLEDs) and liquid crystal displays, as well as as interlayer insulating films, planarization films, and protective films in semiconductor devices.

[0004] For example, in display devices such as organic EL displays, partition materials are used in the gaps between color patterns within the display area or at the edges of the peripheral areas of the display area to improve display characteristics. In the manufacture of organic EL display devices, partitions are first formed to prevent organic material pixels from coming into contact with each other, and organic material pixels are formed between these partitions. These partitions are generally formed by photolithography using a photosensitive resin composition and are insulating. Specifically, a photosensitive resin composition is applied to a substrate using a coating apparatus, volatile components are removed by means of heating or other means, and then the image is exposed through a mask. Next, in the case of a negative type, the unexposed areas are removed with a developer such as an alkaline aqueous solution, and in the case of a positive type, the exposed areas are removed with a developer such as an alkaline aqueous solution. The resulting pattern is then heat-treated to form partitions (insulating films). Then, organic materials that emit red, green, and blue light are deposited between the partitions using an inkjet method or the like to form the pixels of the organic EL display device.

[0005] In recent years, the miniaturization of display devices and the diversification of displayed content have led to a demand for higher performance and resolution of pixels. Therefore, attempts have been made to enhance contrast and improve visibility in display devices by using colorants to give partition materials light-shielding properties.

[0006] Regarding such technologies, for example, Patent Document 1 discloses a radiation-sensitive resin composition that exhibits high light-shielding properties after heat treatment following exposure, which is a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound, to which titanium black is added.

[0007] Patent Document 2 discloses a method for blackening a partition material using carbon black in a radiation-sensitive resin composition containing (A) an alkali-soluble resin, (B) a 1,2-quinone diazide compound, and (C) a coloring agent.

[0008] Patent Document 3 discloses a radiation-sensitive resin composition that exhibits light-shielding properties upon heat treatment after exposure, including a composition obtained by adding a heat-sensitive dye to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a quinone diazide compound.

[0009] Patent Document 4 discloses a positive-type photosensitive resin composition containing (A) a binder resin, (B) a quinone diazide compound, and (C) at least one black dye selected from black dyes defined by the color index of Solvent Black 27 to 47.

[0010] On the other hand, one method for increasing the sensitivity of positive-type photosensitive resin compositions is to use a chemical amplification system for the photosensitive resin composition. A chemical amplification system photosensitive resin composition generally contains a resin in which alkali-soluble functional groups are protected by acid-degradable groups, and a photoacid generator. The acid generated from the photoacid generator during exposure promotes the decomposition (deprotection) of acid-degradable groups and regenerates alkali-soluble functional groups. This promotes the alkali dissolution of the resin in the exposed area during development. The acid derived from the photoacid generator decomposes one acid-degradable group, then regenerates it, and participates in the decomposition of another acid-degradable group. Since the apparent quantum efficiency of a chemical amplification system based on the above reaction mechanism is expressed as the product of the quantum efficiency of acid generation and the reaction chain, it is expected that high sensitivity can be achieved by using a chemical amplification system for the photosensitive resin composition.

[0011] Japanese Patent Publication No. 2001-281440, Japanese Patent Publication No. 2002-116536, Japanese Patent Publication No. 2010-237310, International Publication No. 2017 / 069172

[0012] However, when the partition material is given light-shielding properties, the photosensitive resin composition tends to become less sensitive, which can result in longer exposure times and reduced productivity. Therefore, photosensitive resin compositions used to form partition materials, especially those containing colorants, are required to be more sensitive.

[0013] For example, in photosensitive resin compositions used to form colored partition materials, a coloring agent is used to sufficiently enhance the light-shielding properties of the cured film. However, when a coloring agent is used, the radiation irradiated onto the film of the photosensitive resin composition is absorbed by the coloring agent, reducing the effective intensity of the radiation in the film. As a result, the photosensitive resin composition is not sufficiently exposed, and consequently, the ability to form holes and other properties decreases. This is particularly noticeable when a black coloring agent is incorporated into a photosensitive resin composition for the purpose of improving the image quality, making it more flexible, or saving power in a display device, for example, when forming a black partition material.

[0014] For these reasons, positive-type photosensitive resin compositions are desired to be highly sensitive, have excellent residue removal properties, exhibit minimal film loss, and enable the formation of fine patterns. However, currently, no positive-type photosensitive resin composition has been developed that can fully meet these requirements.

[0015] The present invention has been made in view of these circumstances, and aims to provide a positive-type photosensitive resin composition, an organic EL element partition, an organic EL element insulating film, and an organic EL element that are highly sensitive, have excellent residue removal properties, exhibit low film loss, and enable the formation of fine patterns.

[0016] As a result of diligent research to achieve the above-mentioned objectives, the present inventors have found that a positive-type photosensitive resin composition containing a hydrophobic resin (A), a colorant (E) containing a black dye, and a surfactant (D), wherein the hydrophobic resin (A) has a specific structure, has been created, and thus the present invention has been completed.

[0017] That is, the present invention includes the following aspects. <1> A positive photosensitive resin composition containing a hydrophobic resin (A), a colorant (E) containing a black dye, and a surfactant (D), wherein the hydrophobic resin (A) contains a structure (X) represented by the following formula (X) and / or a structure (Y) represented by the following formula (Y).

[0018]

[0019] (In formula (X), * represents a bonding portion with other elements.)

[0020]

[0021] (In formula (Y), * represents a bonding portion with other elements.)

[0022] <2> The positive photosensitive resin composition according to <1>, wherein the component (A) contains a structural unit (1) represented by the following formula (1) and / or a structural unit (1') represented by the following formula (1').

[0023]

[0024] (In formula (1), R １ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ２ represents SiR ３ R ４ R ５ represents, R ３ 、R ４ and R ５ each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, and r + s is an integer of 1 to 5.)

[0025]

[0026] (In formula (1'), R １ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ２ represents SiR ３ R ４ R ５Represents R ３ , R ４ and R ５ Each independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, where t is an integer from 0 to 5, u is an integer from 0 to 5, and t+u is an integer from 1 to 5.) <3> The positive-type photosensitive resin composition according to <1> or <2>, wherein the component (A) comprises a resin having a silicon atom-containing group. <4> The positive-type photosensitive resin composition according to any one of <1> to <3>, wherein the component (A) comprises a structural unit (1a) represented by the following formula (1a), and / or a structural unit (1b) represented by the following formula (1b).

[0027]

[0028] (In formula (1a), R １ａ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ａ , R ３ａ , and R ４ａ Each of these independently represents an alkyl group having 1 to 7 carbon atoms. In formula (1b), R １ｂ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １ａ and R １ｂ These may be the same or different.) <5> The component (A) is a positive-type photosensitive resin composition according to any one of <1> to <4>, comprising a structural unit (1a') represented by the following formula (1a') and / or a structural unit (1b') represented by the following formula (1b').

[0029]

[0030] (In formula (1a'), R １ａ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ａ , R ３ａ , and R ４ａ Each of these independently represents an alkyl group having 1 to 7 carbon atoms. In formula (1b'), R １ｂ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １ａ and R １ｂ ​​These may be the same or different.) <6> The component (A) is a positive-type photosensitive resin composition according to any one of <1> to <5>, wherein the component (A) contains a structural unit (Y1) represented by the following formula (Y1).

[0031]

[0032] <7> The component (A) is a positive-type photosensitive resin composition according to any one of <1> to <6>, comprising a structural unit (Y1') represented by the following formula (Y1').

[0033]

[0034] <8> The positive-type photosensitive resin composition according to any one of <1> to <7>, wherein the proportion of the structural unit (Y1) in the total amount of structural units of component (A) is 10 mol% or more and 50 mol% or less. <9> The positive-type photosensitive resin composition according to any one of <1> to <8>, wherein the proportion of the structural unit (Y1') in the total amount of structural units of component (A) is 10 mol% or more and 50 mol% or less. <10> The positive-type photosensitive resin composition according to any one of <1> to <9>, wherein the content of component (A) in the positive-type photosensitive resin composition is 5% by mass or more and 60% by mass or less, based on the total mass of the resin components. <11> The positive-type photosensitive resin composition according to any one of <1> to <10>, wherein the optical density (OD value) of the cured film of the positive-type photosensitive resin composition is 0.5 or more per 1 μm of film thickness. <12> An organic EL element partition containing a cured product of the positive-type photosensitive resin composition described in any of <1> to <10>. <13> An organic EL element insulating film containing a cured product of the positive-type photosensitive resin composition described in any of <1> to <10>. <14> An organic EL element containing a cured product of the positive-type photosensitive resin composition described in any of <1> to <10>.

[0035] According to the present invention, it is possible to provide a positive-type photosensitive resin composition, an organic EL element partition, an organic EL element insulating film, and an organic EL element that are highly sensitive, have excellent residue removal properties, exhibit minimal film loss, and enable the formation of fine patterns.​​

[0036] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). This embodiment is illustrative for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0037] Furthermore, unless otherwise specified, each configuration and parameter disclosed herein may be in any combination. In addition, unless otherwise specified, the upper and lower limits of the values ​​disclosed herein may be in any combination. Moreover, in this specification, "comprise" may be replaced with "consist essentially of" and "consist of" as needed.

[0038] Furthermore, in this specification, "doing or to do" such as "...to do" may be replaced with "process" or "step," and "process" may be replaced with "doing or to do" or "step," and "step" may be replaced with "doing" or "process." Also, in this specification, "process" such as "process" may be, for example, "an apparatus or part configured to perform a process," and "apparatus" may be, for example, "a mechanism or part."

[0039] In this specification, "alkali-soluble" means that a positive-type photosensitive resin composition or its components, or a coating or cured coating of a positive-type photosensitive resin composition, is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. "Alkali-soluble resin" means a resin that is soluble in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, either on its own or contained in an unexposed or exposed positive-type photosensitive resin composition. Resins that are not alkali-soluble when the positive-type photosensitive resin composition is unexposed but become alkali-soluble upon exposure are also included in alkali-soluble resins. "Alkali-soluble functional group" means a group that has the ability to impart such alkali solubility to a positive-type photosensitive resin composition or its components, or a coating or cured coating of a positive-type photosensitive resin composition. Examples of alkali-soluble functional groups include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphate groups, acid anhydride groups, and mercapto groups.

[0040] In this specification, "acid-degradable group" means a group that decomposes (deprotects) in the presence of an acid, and optionally by heating, to generate an alkali-soluble functional group.

[0041] In this specification, "radical polymerizable functional group" means an ethylenically unsaturated group, and "radical polymerizable compound" means a compound having one or more ethylenically unsaturated groups.

[0042] In this specification, "structural unit" and "unit" (hereinafter sometimes collectively referred to as "structural unit") mean an atomic group that constitutes a part of the basic structure of a polymer, and this 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 radical polymerizable compound used as a monomer, and in the case of a phenol novolac resin, it means one molecule of phenol (C ６ H ５ This refers to the following units formed by the condensation reaction of OH) and one molecule of formaldehyde (HClO).

[0043] ​

[0044] For structural units having pendant groups (side groups), structural units having pendant groups used in the formation of crosslinking sites or groups derived therefrom are considered different from structural units having free pendant groups that are not involved in the formation of crosslinking sites. For polymers having branched molecular chains, structural units containing branching points (branched units) are considered different from structural units included in linear molecular chains.

[0045] In this specification, unless otherwise specified, "and / or" means either one or both. For example, "A and / or B" means A, B, or both.

[0046] In this specification, unless otherwise specified, "(meth)acrylic" means acrylic, methacrylic, or both; "(meth)acrylate" means acrylate, methacrylate, or both; and "(meth)acryloyl" means acryloyl, methacryloyl, or both.

[0047] In this specification, unless otherwise specified, the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of resins, polymers, or copolymers refer to values ​​on a standard polystyrene basis, measured by gel permeation chromatography (GPC).

[0048] In this specification, unless otherwise specified, the phenolic hydroxyl group equivalent is a theoretical value calculated from the molecular weight and composition ratio of the structural units constituting the resin. Specifically, the phenolic hydroxyl group equivalent refers to the value calculated by the following formula when the resin is a (co)polymer of n types of monomers i (i = natural numbers from 1 to n). In the formula, the sum of the copolymerization ratios (on a molar basis) of monomers i (i = 1 to n) is 1.

[0049]

[0050] ​In the case of resins having epoxy groups and phenolic hydroxyl groups, as described later, unless otherwise specified, the phenolic hydroxyl group equivalent refers to the value calculated by the following formula: Phenolic hydroxyl group equivalent = (Epoxy equivalent of raw material + Molecular weight of carboxylic acid to be added) / (Number of phenolic hydroxyl groups of carboxylic acid)

[0051] Unless otherwise specified herein, "resin component" means hydrophobic resin (A) and alkali-soluble resin (B). Component corresponding to surfactant (D) is not included in hydrophobic resin (A) and alkali-soluble resin (B).

[0052] Unless otherwise specified herein, "solids" means the total mass of components excluding the liquid solvent (G), including resin components, quinone diazide compounds (C), surfactants (D), and optional components such as colorants (E) and dissolution accelerators (F).

[0053] <<Positive-type photosensitive resin composition>>

[0054] The positive-type photosensitive resin composition according to this embodiment contains a hydrophobic resin (A), a colorant (E) containing a black dye, and a surfactant (D), wherein the hydrophobic resin (A) includes a structure (X) represented by the following formula (X), and / or a structure (Y) represented by the following formula (Y).

[0055]

[0056] (In equation (X), * represents a bond with another element.)

[0057]

[0058] (In equation (Y), * represents a bond with another element.)

[0059] The positive-type photosensitive resin composition according to this embodiment forms a coating that is highly sensitive, has minimal film loss, and allows for the formation of fine patterns. The reason for this is not entirely clear, but it is presumed to be due to the following reasons.

[0060] ​​First, regarding the low film loss and the ability to form fine patterns, at least the following can be considered: The hydrophobic resin (A) tends to move toward the film surface in association with the surfactant (D) that moves toward the film surface during the film formation process of the positive-type photosensitive resin composition. Therefore, after film formation, the hydrophobic resin (A) is present at a higher concentration on the film surface compared to the inside of the film, reducing the alkali solubility of the film surface. This is thought to lead to a reduction in film loss during development. In addition, since the hydrophobic resin (A) and the alkali-soluble resin (B) tend to have low compatibility, it tends to be easy to create a concentration gradient during curing. Therefore, during development, the hydrophobic resin (A) suppresses the dissolution of the film surface in unexposed areas as an alkali-low soluble resin component (i.e., film loss is small), while in exposed areas, it is released from the film into the developer solution along with the dissolution of carboxylic acid compounds derived from the hydrophobic resin (A), other alkali-soluble resin components, and any dissolution accelerators. Once the film surface dissolves in the exposed area, the dissolution of the interior of the film, which has higher alkali solubility than the film surface, proceeds rapidly due to the relatively low concentration of hydrophobic resin (A). This increases the contrast between the exposed and unexposed areas, and as a result, the pattern-forming properties (e.g., hole-forming properties) of the positive-type photosensitive resin composition can be improved (however, the effects and benefits of this embodiment are not limited to these).

[0061] Furthermore, regarding high sensitivity, at least the following can be considered. For example, in the conventional technology in which a photosensitive resin composition contains a colorant and a photosensitive agent (e.g., a quinone diazide compound), radiation irradiated onto the film is absorbed by the colorant in the film, reducing the radiation intensity inside the film, and resulting in the problem that the photosensitive agent contained in the photosensitive resin composition is not sufficiently exposed. On the other hand, the hydrophobic resin (A) of this embodiment contains functional groups (e.g., structure (X) and / or structure (Y)) that have properties that allow them to act as a photosensitive agent (photosensitivity). Furthermore, since the hydrophobic resin (A) is present in a higher concentration on the film surface than inside the film during the film formation process of the positive-type photosensitive resin composition, the photosensitive functional groups contained in the hydrophobic resin (A) are also present in a higher concentration on the film surface than inside the film. As a result, it is considered that the photosensitivity of the film surface is improved, and high sensitivity can be obtained. Furthermore, to give an example in this regard, compared to conventional techniques that include a photosensitive agent (e.g., a quinone diazide compound, etc.) in the coating separately from the resin, the technique using the positive-type photosensitive resin composition according to this embodiment can be expected to effectively utilize the amount of light irradiation energy irradiated near the surface of the coating without loss (however, the effects and benefits of this embodiment are not limited to these).

[0062] The following describes each component that can be used in the positive-type photosensitive resin composition according to this embodiment.

[0063] <Hydrophobic resin (A)>

[0064] The type of hydrophobic resin (A) is not particularly limited, but examples include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenolic resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins. Derivatives of these resins preferably have hydrophobic groups. A suitable example of a hydrophobic group is a silicon atom-containing group. As the hydrophobic resin (A), a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group can be used as the base resin, and some or all of the alkali-soluble functional groups can be converted into groups having the above-mentioned hydrophobic groups. The hydrophobic resin (A) may be used alone or in combination of two or more types.

[0065] The hydrophobic resin (A) includes a structure (X) represented by the following formula (X), and / or a structure (Y) represented by the following formula (Y).

[0066]

[0067] (In equation (X), * represents a bond with another element.)

[0068]

[0069] (In equation (Y), * represents a bond with another element.)

[0070] ​​Structures (X) and (Y) contained in the hydrophobic resin (A) may be bonded to the main chain or to the side chains of the hydrophobic resin (A), but it is preferable that they are bonded to the side chains. When the hydrophobic resin (A) contains both structures (X) and (Y), either structure (X) or structure (Y) may be bonded to the side chains of the hydrophobic resin (A), or both structures (X) and (Y) may be bonded to the side chains of the hydrophobic resin (A), but it is preferable that both structures (X) and (Y) are bonded to the side chains of the hydrophobic resin (A). By adopting such a structure, it is possible to easily introduce structures (X) and (Y) into the hydrophobic resin (A) (however, the effects and benefits of this embodiment are not limited to these).

[0071] Structures (X) and (Y) contained in the hydrophobic resin (A) may be contained in a polymerizable monomer having hydrophobic groups that constitutes the hydrophobic resin (A), or they may be contained in another monomer other than a polymerizable monomer having hydrophobic groups.

[0072] A hydrophobic resin (A) containing structure (X) can be produced, for example, by subjecting a polymerizable monomer having structure (X) to a polymerization reaction. Alternatively, a polymerizable monomer without structure (X) can be subjected to a polymerization reaction to prepare a polymer (or copolymer) without structure (X), and then a reaction is carried out to introduce structure (X) into the polymer (or copolymer) to produce a hydrophobic resin (A) containing structure (X).

[0073] A hydrophobic resin (A) containing structure (Y) can be produced, for example, by subjecting a polymerizable monomer having structure (Y) to a polymerization reaction. Alternatively, a polymerizable monomer without structure (Y) can be subjected to a polymerization reaction to prepare a polymer (or copolymer) without structure (Y), and then a reaction to introduce structure (Y) into the polymer (or copolymer) can be carried out to produce a hydrophobic resin (A) containing structure (Y).

[0074] A hydrophobic resin (A) containing structures (X) and (Y) can be produced, for example, by subjecting a polymerizable monomer having structure (X) and a polymerizable monomer having structure (Y) to a polymerization reaction. Alternatively, a polymer (or copolymer) containing structures (X) and (Y) can be produced by subjecting only a polymerizable monomer that does not have either structure (X) or structure (Y) to a polymerization reaction to prepare a polymer (or copolymer) that does not have either structure (X) or structure (Y), and then performing a reaction to introduce structure (X) and a reaction to introduce structure (Y) into the polymer (or copolymer).

[0075] When the hydrophobic resin (A) containing the above structure (X) is irradiated with visible light, ultraviolet light, or radiation (gamma rays, electron beams, etc.), it produces an alkali-soluble carboxylic acid compound via the reaction shown in the following reaction formula 1X. Furthermore, when the hydrophobic resin (A) containing the above structure (Y) is irradiated with visible light, ultraviolet light, or radiation (gamma rays, electron beams, etc.), it produces an alkali-soluble carboxylic acid compound via the reaction shown in the following reaction formula 1Y.

[0076]

[0077] ​Before photosensitivity, the hydrophobic resin (A) interacts with the alkali-soluble functional groups of the alkali-soluble resin (B), described later, such as phenolic hydroxyl groups (e.g., by hydrogen bonding), rendering the alkali-soluble resin (B) insoluble in an alkaline aqueous solution. On the other hand, the presence of an alkali-soluble carboxylic acid compound in the irradiated area makes the resin in that area more easily soluble in the alkaline aqueous solution together with the carboxylic acid compound. Furthermore, the generated carboxylic acid compound promotes the decomposition of the acid-degradable groups of the protective resin (B3), which is optionally included in the positive-type photosensitive resin composition, described later, regenerating its alkali-soluble functional groups and increasing the alkali solubility of the protective resin (B3). Moreover, the carboxylic acid compound has a relatively larger molecular structure than acids produced from photoacid generators commonly used in chemically amplified resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is less likely to diffuse in the film. As a result of these synergistic effects, the difference in alkali solubility between the unexposed and exposed areas can be greatly increased, thereby enabling the formation of highly sensitive and high-resolution patterns even with low exposure levels (however, the effects and benefits of this embodiment are not limited to these).

[0078] The hydrophobic resin (A) preferably contains structural unit (1) represented by the following formula (1), and / or structural unit (1') represented by the following formula (1'). For example, it is preferable that the polymerizable monomer having the hydrophobic group described above forms structural unit (1) represented by formula (1) and / or structural unit (1') represented by formula (1') after polymerization.

[0079]

[0080] (In equation (1), R １ R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２ SiR ３ R ４ R ５ Represents R ３ , R ４ and R ５ ​Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, where r is an integer from 0 to 5, s is an integer from 0 to 5, and r+s is an integer from 1 to 5.

[0081]

[0082] (In equation (1'), R １ R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２ SiR ３ R ４ R ５ Represents R ３ , R ４ and R ５ Each of these independently represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, where t is an integer from 0 to 5, u is an integer from 0 to 5, and t+u is an integer from 1 to 5.

[0083] In formula (1), R １ R is preferably a hydrogen atom or a methyl group. ３ , R ４ , and R ５ Each of these groups is preferably independently a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group. r is preferably an integer from 0 to 3, and more preferably an integer from 0 to 1. s is preferably an integer from 0 to 3, and more preferably an integer from 0 to 1. As polymerizable monomers having such hydrophobic groups, 4-triethylsilyloxyphenyl methacrylate, 4-tert-butyldimethylsilyloxyphenyl (meth)acrylate, and PQMA (4-hydroxyphenyl methacrylate) are preferred. For example, when using PQMA (4-hydroxyphenyl methacrylate) as the polymerizable monomer, a tert-butyldimethylsilyl group can be introduced by reacting it with tert-butyldimethylchlorosilane or the like after polymerization.

[0084] In formula (1'), R １ R is preferably a hydrogen atom or a methyl group. ３ , R ４ , and R​５ Each of these groups is preferably independently a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group. t is preferably an integer from 0 to 3, and more preferably an integer from 0 to 1. u is preferably an integer from 0 to 3, and more preferably an integer from 0 to 1. Hydroxystyrene (e.g., 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene) is preferred as such a polymerizable monomer having hydrophobic groups. For example, when using such hydroxystyrene as the polymerizable monomer, a tert-butyldimethylsilyl group can be introduced by reacting it with tert-butyldimethylchlorosilane or the like after polymerization.

[0085] A preferred example of formula (1) is the structural unit (1a) represented by the following formula (1a).

[0086]

[0087] (In formula (1a), R １ａ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ａ , R ３ａ , and R ４ａ Each of these independently represents an alkyl group having 1 to 7 carbon atoms.

[0088] In equation (1a), R １ａ R is preferably a hydrogen atom or a methyl group. ２ａ , R ３ａ , and R ４ａ Each of these is preferably independently a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group. For example, when a homopolymer of 4-hydroxyphenyl methacrylate (p-hydroxyphenyl methacrylate, PHMA) reacts with tert-butyldimethylchlorosilane, R ２ａ and R ３ａ R becomes a methyl group, ４ａ This becomes a tert-butyl group.

[0089] ​The hydrophobic resin (A) may have structural units represented by formula (2) below if necessary, but sufficient effects can be obtained even without them. For example, other polymerizable monomers that form structural units represented by formula (2) after polymerization can be used.

[0090]

[0091] (In formula (2), R ６ and R ７ Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ８ This refers to a phenyl group substituted with a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0092] R ６ and R ７ Each of these independently includes a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ８ Examples of such polymerizable monomers include cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, or hydroxyl groups, and phenyl groups substituted with at least one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms. Examples of other polymerizable monomers include phenylmaleimide and N-cyclohexylmaleimide.

[0093] However, the positive-type photosensitive resin composition according to this embodiment can achieve sufficient effects even if the hydrophobic resin (A) does not have the structural unit represented by formula (2) described above. Furthermore, sufficient effects can be achieved even if the hydrophobic resin (A) does not have a maleimide structure in its structural unit. Also, from the viewpoint of achieving sufficient effects, the hydrophobic resin (A) does not need to have an imide skeleton in its structural unit. Furthermore, the hydrophobic resin (A) does not need to have a nitrogen atom.

[0094] ​The hydrophobic resin (A) preferably has a structural unit represented by the following formula (3) as one embodiment of formula (1). For example, it is preferable that it is another polymerizable monomer having an alkali-soluble functional group that forms the structural unit represented by formula (3) after polymerization.

[0095]

[0096] (In formula (3), R ９ (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0097] In formula (3), R ９ is preferably a hydrogen atom or a methyl group. a is preferably an integer from 1 to 3, and more preferably 1. Another polymerizable monomer having such an alkali-soluble functional group is 4-hydroxyphenyl (meth)acrylate (p-hydroxyphenyl (meth)acrylate, PHMA).

[0098] An example of a preferred structural unit of formula (3) is the structural unit (1b) represented by the following formula (1b).

[0099]

[0100] (In formula (1b), R １ｂ (This represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

[0101] In equation (1b), R １ｂ The atom is preferably a hydrogen atom or a methyl group. A specific example of a compound that gives the structural unit of formula (1b) is, for example, 4-hydroxyphenyl (meth)acrylate.

[0102] A preferred example of formula (1') is the structural unit (1a') represented by the following formula (1a').

[0103]

[0104] (In formula (1a'), R １ａ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.​​​２ａ , R ３ａ , and R ４ａ each independently represents an alkyl group having 1 to 7 carbon atoms.)

[0105] In formula (1a'), R １ａ is preferably a hydrogen atom or a methyl group. R ２ａ , R ３ａ , and R ４ａ are each independently preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or a phenyl group. For example, when a homopolymer of 4-hydroxystyrene (p-hydroxystyrene) reacts with tert-butyldimethylchlorosilane, R ２ａ and R ３ａ become methyl groups, and R ４ａ becomes a tert-butyl group.

[0106] The hydrophobic resin (A) may have a structural unit represented by the following formula (2) if necessary, but sufficient effects can be obtained even without it. For example, as other polymerizable monomers, those that form a structural unit represented by formula (2) after polymerization can be used.

[0107]

[0108] (In formula (2), R ６ and R ７ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ８ is a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or a phenyl group substituted with at least one selected from the group consisting of a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.)

[0109] R ６ and R ７ are each independently exemplified by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ８Examples of such polymerizable monomers include cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, or hydroxyl groups, and phenyl groups substituted with at least one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms. Examples of other polymerizable monomers include phenylmaleimide and N-cyclohexylmaleimide.

[0110] However, the positive-type photosensitive resin composition according to this embodiment can achieve sufficient effects even if the hydrophobic resin (A) does not have the structural unit represented by formula (2) described above. Furthermore, sufficient effects can be achieved even if the hydrophobic resin (A) does not have a maleimide structure in its structural unit. Moreover, from the viewpoint of achieving sufficient effects, it is preferable that the hydrophobic resin (A) does not have an imide skeleton in its structural unit. Furthermore, it is even more preferable that the hydrophobic resin (A) does not have a nitrogen atom.

[0111] The hydrophobic resin (A) preferably has a structural unit represented by the following formula (3') as one embodiment of formula (1'). For example, it is preferable that it is another polymerizable monomer having an alkali-soluble functional group that forms the structural unit represented by formula (3') after polymerization.

[0112]

[0113] (In formula (3'), R ９ (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0114] In formula (3'), R ９ is preferably a hydrogen atom or a methyl group. a is preferably an integer from 1 to 3, and more preferably 1. Other polymerizable monomers having such alkali-soluble functional groups include hydroxystyrene (e.g., 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene).

[0115] An example of a preferred structural unit of formula (3') is the structural unit (1b') represented by the following formula (1b').

[0116] ​

[0117] (In formula (1b'), R １ｂ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

[0118] In formula (1b'), R １ｂ is preferably a hydrogen atom or a methyl group. Specific examples of the compound that provides the structural unit of formula (1b') include, for example, 4-hydroxystyrene (p-hydroxystyrene).

[0119] The hydrophobic resin (A) preferably contains a structural unit (Y1) represented by the following formula (Y1).

[0120]

[0121] When the hydrophobic resin (A) contains the structural unit (Y1), the proportion of the structural unit (Y1) in the total amount of the structural units of the hydrophobic resin (A) is preferably 10 mol% or more and 50 mol% or less. This lower limit is more preferably 15 mol% or more, still more preferably 20 mol% or more, and even more preferably 25 mol% or more. Also, this upper limit is more preferably 45 mol% or less, still more preferably 40 mol% or less, and even more preferably 35 mol% or less. When this content is at least the above lower limit, the sensitivity, residual film rate, residue removability, etc. can be further improved. Also, when this content is at most the above upper limit, the accuracy of fine pattern formation can be further improved.

[0122] The hydrophobic resin (A) preferably contains the following structural unit (Y1').

[0123]

[0124] When the hydrophobic resin (A) contains structural units (Y1'), it is preferable that the structural units (Y1') of the hydrophobic resin (A) are present in an amount of 10 mol% to 50 mol%. The lower limit of this content is more preferably 15 mol% or more, even more preferably 20 mol% or more, and even more preferably 25 mol% or more. The upper limit of this content is more preferably 45 mol% or less, even more preferably 40 mol% or less, and even more preferably 35 mol% or less. When this content is above the lower limit, sensitivity, residual film rate, and residue removal performance can be further improved. When this content is below the upper limit, the accuracy of fine pattern formation can be further improved.

[0125] The hydrophobic resin (A) preferably contains the structural unit (3) represented by formula (3) and / or the structural unit (3') represented by formula (3') above; more preferably contains the structural unit (Y1) represented by formula (Y1) and / or the structural unit (Y1') represented by formula (Y1') above, and the structural unit (1b) represented by formula (1b) and / or the structural unit (1b') represented by formula (1b') above. Furthermore, the hydrophobic resin (A) preferably contains the structural unit (3) represented by formula (3) and / or the structural unit represented by formula (3') above, and the structural unit (1a) represented by formula (1a) and / or the structural unit (1a') represented by formula (1a'); more preferably contains the structural unit (Y1) represented by formula (Y1) and / or the structural unit (Y1') represented by formula (Y1') above, the structural unit (1b) represented by formula (1b) and / or the structural unit (1b') represented by formula (1b') above, and the structural unit (1a) represented by formula (1a) and / or the structural unit (1a') represented by formula (1a') above.

[0126] Note that R in equation (1a) １ａ And, R in equation (1b) １ｂ These may be the same or different. Also, R in equation (1a') １ａ And, R in equation (1b') １ｂ They may be the same or they may be different.

[0127] The hydrophobic resin (A) is preferably a resin having silicon atom-containing groups. The silicon atom-containing groups may be present in the main chain of the hydrophobic resin (A) or in the side chains (they may also be pendant groups), but it is preferable that they be present in the side chains.

[0128] Examples of silicon atom-containing groups include silyl groups substituted with aliphatic hydrocarbon groups or aryl groups (silyl groups substituted with aliphatic hydrocarbon groups, or silyl groups substituted with aryl groups); groups having a cyclic siloxane structure; and groups having a silsesquioxane structure.

[0129] A silyl group substituted with an aliphatic hydrocarbon group or an aryl group can be monosubstituted, disubstituted, or trisubstituted. The substituents on a silyl group substituted with an aliphatic hydrocarbon group or an aryl group may be the same or different from each other. It is preferable that the silyl group substituted with an aliphatic hydrocarbon group or an aryl group is trisubstituted. The silyl group substituted with an aliphatic hydrocarbon group or an aryl group may further have substituents other than alkyl or aryl groups, such as a silyloxy group substituted with an aliphatic hydrocarbon group or an aryl group.

[0130] The number of ring members in the cyclic siloxane moiety of the group having a cyclic siloxane structure is preferably 6 to 14. Some or all of the hydrogen atoms on the silicon atom of the group having a cyclic siloxane structure may be independently substituted with an aliphatic hydrocarbon group or an aryl group.

[0131] Some or all of the hydrogen atoms on the silicon atom of the group having a silsesquioxane structure may be independently substituted with an aliphatic hydrocarbon group or an aryl group.

[0132] The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms. Examples of aliphatic hydrocarbon groups having 1 to 20 carbon atoms include saturated hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl; unsaturated hydrocarbon groups such as ethenyl, propenyl, butenyl, ethynyl, and propynyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclohexyl. Examples include saturated monocyclic hydrocarbon groups such as chlordodecyl groups; unsaturated monocyclic hydrocarbon groups such as cyclopropenyl groups, cyclobutenyl groups, cyclopentenyl groups, cyclohexenyl groups, cyclooctenyl groups, and cyclodecenyl groups; saturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptanyl groups, bicyclo[2.2.2]octanyl groups, and adamantyl groups; and unsaturated polycyclic hydrocarbon groups such as bicyclo[2.2.1]heptenyl groups and bicyclo[2.2.2]octenyl groups.

[0133] The aryl group of a silyl group substituted with an aliphatic hydrocarbon group or an aryl group, the aryl group as a substituent on a group having a cyclic siloxane structure, the aryl group as a substituent on a group having a silsesquioxane structure, and the aryl group as a substituent on a silyloxy group substituted with an aliphatic hydrocarbon group or an aryl group are preferably aryl groups having 6 to 20 carbon atoms, and more preferably aryl groups having 6 to 14 carbon atoms. Examples of aryl groups having 6 to 20 carbon atoms include the phenyl group, naphthyl group, fluorenyl group, anthryl group, and phenantrenyl group.

[0134] Examples of silyl groups substituted with aliphatic hydrocarbon groups or aryl groups include trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, and trimethylsilyloxydimethylsilyl group.

[0135] Examples of groups having a cyclic siloxane structure include the pentamethylcyclotrisilyloxy group, the heptamethylcyclotetrasilyloxy group, and the nonamethylcyclopentasilyloxy group.

[0136] Examples of groups having a silsesquioxane structure include silsesquioxanyl group, heptamethylsilsesquioxanyl group, heptaethylsilsesquioxanyl group, hepta(n-propyl)silsesquioxanyl group, and hepta(n-butyl)silsesquioxanyl group.

[0137] Hydrophobic resin (A) can be produced, for example, by radical polymerization of a polymerizable monomer having a hydrophobic group, or by radical copolymerization of a polymerizable monomer having a hydrophobic group with other polymerizable monomers. Examples of polymerizable functional groups that the polymerizable monomer having a hydrophobic group and other polymerizable monomers possess include CH ２ = CH - ien CH ２ = C(CH ３ ) - CH ２ =CHCO-, CH ２ = C(CH ３ Examples of radical polymerizable functional groups include CO-, -OC-CH=CH-CO-, etc. Hydrophobic resin (A) can also be produced by reacting a resin having functional groups such as hydroxyl groups, carboxyl groups, amino groups, and epoxy groups with a compound having hydrophobic groups to convert the functional groups into groups containing hydrophobic groups.

[0138] In one embodiment of this design, the hydrophobic resin (A) is a copolymer of a polymerizable monomer having a hydrophobic group and another polymerizable monomer. Examples of polymerizable monomers having a hydrophobic group include polymerizable monomers having a silicon atom-containing group.

[0139] (Polymerizable monomers containing silicon atoms) Examples of polymerizable monomers containing silicon atoms include trimethylvinylsilane, trimethylallylsilane, trimethyl(3-butenyl)silane, tert-butyldimethylvinylsilane, (trimethylsilyloxy)dimethylvinylsilane, (trimethylsilyloxy)dimethylallylsilane, triethylvinylsilane, triethylallylsilane, triethyl(3-butenyl)silane, (trimethylsilyl)methyl(meth)acrylate, 2-(trimethylsilyl)ethyl(meth)acrylate, 3-(trimethylsilyl)propyl(meth)acrylate, tert-butyldimethylsilyl(meth)acrylate, triisopropylsilylmethyl(meth)acrylate, bis(trimethylsilyl) Examples include methyl(meth)acrylate, 4-(trimethylsilyl)cyclohexyl(meth)acrylate, 3-(trimethylsilyloxy)dimethylsilyl]propyl(meth)acrylate, 3-(tris(trimethylsilyloxy)silyl)propyl(meth)acrylate, 4-trimethylsilyloxyphenyl(meth)acrylate, 4-triethylsilyloxyphenyl(meth)acrylate, 4-triisopropylsilyloxyphenyl(meth)acrylate, 4-tert-butyldimethylsilyloxyphenyl(meth)acrylate, vinylheptamethylcyclotetrasiloxane, and 3-(heptamethylsilsesquioxanyl)propyl(meth)acrylate.

[0140] Other polymerizable monomers include, for example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; and (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0141] Other polymerizable monomers may be polymerizable monomers having alkali-soluble functional groups. Examples of polymerizable monomers having alkali-soluble functional groups include maleic acid derivatives such as maleic acid, monomethyl maleic acid, monoethyl maleic acid, monoisopropyl maleic acid, and maleic anhydride; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; unsaturated carboxylic acid compounds such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid; polymerizable monomers having phenolic hydroxyl groups such as 4-hydroxystyrene, 4-hydroxyphenyl(meth)acrylate, and 3; polymerizable monomers having sulfo groups such as (meth)allylsulfonic acid and styrenesulfonic acid; polymerizable monomers having phosphate groups such as mono(2-(meth)acryloyloxyethyl) phosphate; and polymerizable monomers having acid anhydride groups such as itaconic acid and citraconic acid anhydride.

[0142] Furthermore, it is preferable to use 4-tert-butyldimethylsilyloxyphenyl (meth)acrylate and / or 4-hydroxyphenyl (meth)acrylate as polymerizable monomers having hydrophobic groups, and it is more preferable to use both. By using resins obtained by radical polymerization of these polymerizable monomers, the sensitivity and pattern-forming properties of the positive-type photosensitive resin composition can be improved, and outgassing can also be reduced.

[0143] Furthermore, the polymerization initiator used when producing hydrophobic resin (A) by radical polymerization is not limited to the following, but includes azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN); dicumyl peroxide, 2,5-dimethyl-2,5-di(tert Peroxide polymerization initiators with a 10-hour half-life temperature of 100 to 170°C, such as 1,1'-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide, can be used. Alternatively, peroxide polymerization initiators such as benzoyl peroxide, lauroyl peroxide, 1,1'-di(tert-butylperoxy)cyclohexane, and tert-butylperoxypivalate can be used. The amount of polymerization initiator used is generally preferably 0.01 parts by mass or more, 0.05 parts by mass or more, or 0.5 parts by mass or more, per 100 parts by mass of the total polymerizable monomers. The upper limit is preferably 40 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less.

[0144] In the polymerization of the hydrophobic resin (A), a RAFT (Reversible Addition Fragmentation Transfer) agent may be used in combination with the polymerization initiator. The RAFT agent is not limited to the following, but thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, and xanthanthates can be used. The RAFT agent can be used in an amount of 0.005 parts by mass or more and 20 parts by mass or less, and preferably in an amount of 0.01 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the total polymerizable monomers.

[0145] When the hydrophobic resin (A) has silicon atom-containing groups, the silicon atom content is preferably 1% by mass or more and 10% by mass or less, based on the mass of the hydrophobic resin (A). The lower limit is more preferably 3% by mass or more. The upper limit is more preferably 8% by mass or less. The hydrophobic resin (A) having silicon atom-containing groups preferably contains structural units having silicon atom-containing groups in an amount of 5 mol% to 70 mol% based on the total structural units of the hydrophobic resin (A). The lower limit is more preferably 10 mol% or more, and even more preferably 12 mol% or more. The upper limit is more preferably 50 mol% or less, and even more preferably 20 mol% or less.

[0146] The hydrophobic resin (A) may or may not have alkali-soluble functional groups. Preferably, the hydrophobic resin (A) contains 20 mol% to 90 mol% of structural units having alkali-soluble functional groups, based on the total structural units of the hydrophobic resin (A). The lower limit is more preferably 30 mol% or more, and even more preferably 40 mol% or more. The upper limit is more preferably 85 mol% or less, and even more preferably 80 mol% or less. In this embodiment, it is preferable that the hydrophobic resin (A) does not have alkali-soluble functional groups.

[0147] The weight-average molecular weight (Mw) of the hydrophobic resin (A) is preferably 5,000 or more and 50,000 or less. The lower limit is more preferably 9,000 or more, even more preferably 10,000 or more, and even more preferably 12,000 or more. The upper limit is more preferably 30,000 or less, even more preferably 20,000 or less, even more preferably 17,000 or less, and even more preferably 14,000 or less. By setting the weight-average molecular weight within the above range, a positive-type photosensitive resin composition with even better sensitivity and pattern-forming properties can be obtained.

[0148] The number-average molecular weight (Mn) of the hydrophobic resin (A) is preferably 2,500 or more and 30,000 or less. The upper limit is more preferably 25,000 or less, even more preferably 20,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and even more preferably 7,000 or less. The lower limit is more preferably 4,000 or more, even more preferably 4,500 or more, even more preferably 5,000 or more, and even more preferably 5,500 or more. By setting the number-average molecular weight within the above range, a positive-type photosensitive resin composition with even better sensitivity and pattern-forming properties can be obtained.

[0149] The polydispersity (Mw / Mn) of the hydrophobic resin (A) is preferably 1.0 or more and 3.5 or less. The lower limit is more preferably 1.3 or more, even more preferably 1.8 or more, and even more preferably 1.9 or more. The upper limit is more preferably 3.0 or less, even more preferably 2.5 or less, and even more preferably 2.3 or less. By setting the polydispersity within the above range, a positive-type photosensitive resin composition with even better sensitivity and pattern-forming properties can be obtained.

[0150] The positive-type photosensitive resin composition according to this embodiment preferably contains 3% to 50% by mass of hydrophobic resin (A) based on 100% by mass of solids. The lower limit is more preferably 4% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 40% by mass or less, and even more preferably 30% by mass or less. If the content of hydrophobic resin (A) is above the lower limit, the surfactant (D) promotes the uneven distribution of hydrophobic resin (A) on the film surface, resulting in a high concentration of hydrophobic resin (A) on the film surface, making the film surface poorly soluble in alkaline aqueous solutions, thus enabling further increased sensitivity. If the content of hydrophobic resin (A) is below the upper limit, the dissolution of the film surface in the exposed area proceeds rapidly due to the dissolution of carboxylic acid compounds derived from hydrophobic resin (A) and quinone diazide compound (C), other highly alkali-soluble resin components, and any dissolution accelerator, thus enabling further increased sensitivity.

[0151] The positive-type photosensitive resin composition according to this embodiment preferably contains 5% to 60% by mass of hydrophobic resin (A) based on the total mass of the resin components. The lower limit is more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 35% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 45% by mass or less. If the content of hydrophobic resin (A) is above the lower limit, the surfactant (D) promotes the uneven distribution of hydrophobic resin (A) on the film surface, resulting in a high concentration of hydrophobic resin (A) on the film surface, and the film surface becomes poorly soluble in alkaline aqueous solutions, thus enabling high sensitivity. If the content of hydrophobic resin (A) is below the above upper limit, the dissolution of the film surface in the exposed area proceeds rapidly due to the dissolution of carboxylic acid compounds derived from hydrophobic resin (A) and quinone diazide compound (C), other highly alkali-soluble resin components, and any dissolution accelerator, thereby enabling high sensitivity.

[0152] <Alkali-soluble resin (B)>

[0153] The positive-type photosensitive resin composition according to this embodiment preferably further contains an alkali-soluble resin (B) as a resin other than the hydrophobic resin (A). The type of alkali-soluble resin is not particularly limited, but it is preferably a resin having alkali-soluble functional groups. Examples of alkali-soluble functional groups are not particularly limited, but include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphate groups, acid anhydride groups, and mercapto groups. An alkali-soluble resin (B) having two or more types of alkali-soluble functional groups may be used. The alkali-soluble resin (B) may have alkali-soluble functional groups protected by acid-degradable groups.

[0154] Specific examples of alkali-soluble resin (B) include, for example, a homopolymer or copolymer of a polymerizable monomer having an alkali-soluble functional group (B1), and a resin having an epoxy group and a phenolic hydroxyl group (B2). Alkali-soluble resin (B) may be used alone or in combination of two or more types.

[0155] The alkali-soluble resin (B) may have radical polymerizable functional groups. Specific examples of radical polymerizable functional groups include (meth)acryloyloxy groups, allyl groups, and methallyl groups.

[0156] When the positive-type photosensitive resin composition according to this embodiment contains an alkali-soluble resin, the content of the alkali-soluble resin (B) is usually preferably 5% by mass or more and 80% by mass or less, based on 100% by mass of solids. The lower limit is more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 35% by mass or more. The upper limit is more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less. If the alkali-soluble resin content is in this amount based on 100% by mass of solids, it is possible to ensure the stability and durability of the film after heat curing while suppressing a decrease in the dissolution of the exposed area and a decrease in sensitivity.

[0157] When the positive-type photosensitive resin composition according to this embodiment contains an alkali-soluble resin, it is generally preferable that the alkali-soluble resin (B) is 0% by mass or more and 90% by mass or less, based on the total mass of the resin components. The lower limit is more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more. The upper limit is more preferably 85% by mass or less, even more preferably 75% by mass or less, and even more preferably 65% ​​by mass or less. If the alkali-soluble resin (B) content is within this range based on the total mass of the resin components, it is possible to maintain a certain effect while ensuring a certain level of alkali solubility.

[0158] (A homopolymer or copolymer (B1) containing a polymerizable monomer having an alkali-soluble functional group)

[0159] Examples of alkali-soluble functional groups in a homopolymer or copolymer (B1) containing a polymerizable monomer having an alkali-soluble functional group include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, acid anhydride groups, and mercapto groups.

[0160] Specific examples of component (B1) include acrylic resins, polystyrene resins, epoxy resins, polyamide resins, phenolic resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polybenzoxazole resin precursors, silicone resins, cyclic olefin polymers, cardo resins, and derivatives of these resins, all of which have alkali-soluble functional groups. For example, a derivative of phenolic resin is polyalkenylphenol resin, in which an alkenyl group is bonded to a benzene ring, and a derivative of polystyrene resin is a hydroxypolystyrene resin derivative, in which a phenolic hydroxyl group and a hydroxyalkyl group or alkoxy group are bonded to a benzene ring.

[0161] The copolymer of component (B1) may have two or more alkali-soluble functional groups. Examples of polymerizable monomers having alkali-soluble functional groups and polymerizable monomers include CH ２= CH - ien CH ２ = C(CH ３ ) - CH ２ =CHCO-, CH ２ = C(CH ３ Examples of radical polymerizable functional groups include CO-, -OC-CH=CH-CO-, etc.

[0162] From the viewpoint of heat resistance, copolymers having alkali-soluble functional groups preferably have one or more cyclic structures selected from the group consisting of alicyclic structures, aromatic structures, polycyclic structures, inorganic cyclic structures, and heterocyclic structures.

[0163] Copolymers having alkali-soluble functional groups can be produced, for example, by radical polymerization of a polymerizable monomer having alkali-soluble functional groups with other polymerizable monomers. After synthesizing the copolymer by radical polymerization, alkali-soluble functional groups may be added to the copolymer as described above.

[0164] Polymerizable monomers having alkali-soluble functional groups include, for example, maleic acid derivatives such as maleic acid, monomethyl maleic acid, monoethyl maleic acid, monoisopropyl maleic acid, and maleic anhydride; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; unsaturated carboxylic acid compounds such as fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, 3-maleimidopropionic acid, 4-maleimidobutyric acid, and 6-maleimidohexanoic acid; and 4-H Examples include polymerizable monomers having phenolic hydroxyl groups such as droxystyrene, 4-hydroxyphenyl (meth)acrylate, 3,5-dimethyl-4-hydroxybenzylacrylamide, 4-hydroxyphenylacrylamide, and 4-hydroxyphenylmaleimide; polymerizable monomers having sulfo groups such as (meth)allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, and styrenesulfonic acid; polymerizable monomers having phosphate groups such as phosphate mono(2-(meth)acryloyloxyethyl); and polymerizable monomers having acid anhydride groups such as itaconic anhydride and citraconic anhydride.

[0165] From the viewpoint of sensitivity, the polymerizable monomer having an alkali-soluble functional group is preferably a (meth)acrylic acid derivative or a polymerizable monomer having a phenolic hydroxyl group, and more preferably a polymerizable monomer having a phenolic hydroxyl group.

[0166] Other polymerizable monomers include, for example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, and p-ethylstyrene; acrylamide; acrylonitrile; vinyl alcohol ether compounds such as vinyl-n-butyl ether; and (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, phenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0167] As a polymerizable monomer having an alkali-soluble functional group, it is preferable that it forms a structural unit represented by formula (3) after polymerization. ９ It is preferable that is a hydrogen atom or a methyl group. a is preferably an integer from 1 to 3, and more preferably 1. As a polymerizable monomer having such an alkali-soluble functional group, 4-hydroxyphenyl (meth)acrylate is particularly preferred.

[0168]

[0169] (In equation (3), R ９ (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0170] ​As a polymerizable monomer having an alkali-soluble functional group, it is preferable that it forms a structural unit (3') represented by formula (3') after polymerization. ９ It is preferable that is a hydrogen atom or a methyl group. a is preferably an integer from 1 to 3, and more preferably 1. Hydroxystyrene (e.g., 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene) is particularly preferred as a polymerizable monomer having such an alkali-soluble functional group.

[0171]

[0172] (In equation (3'), R ９ (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0173] Other polymerizable monomers include those that form structural units represented by formula (2) after polymerization, but they are not required to be included. ６ and R ７ Each of these is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ８ Examples of such polymerizable monomers include phenyl groups substituted with at least one selected from the group consisting of cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, hydroxyl groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. Examples of other polymerizable monomers include phenylmaleimide and N-cyclohexylmaleimide, but the positive-type photosensitive resin composition according to this embodiment can achieve sufficient effects even if the alkali-soluble resin (B) does not contain such a maleimide skeleton. Furthermore, from the viewpoint of achieving sufficient effects, it is preferable that the alkali-soluble resin (B) does not have an imide skeleton in its structural units. Moreover, it is even more preferable that the alkali-soluble resin (B) does not have a nitrogen atom.

[0174]

[0175] (In equation (2), R ６ and R ７ ​​Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ８ This refers to a phenyl group substituted with a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0176] In this embodiment, the copolymer having alkali-soluble functional groups may have structural units represented by formula (3), structural units represented by formula (3'), and structural units represented by formula (2). However, as described above, sufficient effects can be obtained even without having the structural unit represented by formula (2).

[0177]

[0178] (In equation (3), R ９ (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0179]

[0180] (In equation (3'), R ９ (where a is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a is an integer from 1 to 5.)

[0181]

[0182] (In equation (2), R ６ and R ７ Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ８ This refers to a phenyl group substituted with a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0183] ​​​For example, hydroxyphenyl (meth)acrylate (e.g., 4-hydroxyphenyl (meth)acrylate) or hydroxystyrene (e.g., 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene) may be used as polymerizable monomers having alkali-soluble functional groups, and phenylmaleimide or N-cyclohexylmaleimide may be used as other polymerizable monomers. Alternatively, the other polymerizable monomers mentioned above may not be used.

[0184] The type and amount of polymerization initiator used when producing copolymers having alkali-soluble functional groups by radical polymerization are the same as those described for the polymerization initiator used when producing hydrophobic resin (A) by radical polymerization. The type and amount of RAFT agent that can be used in combination with the polymerization initiator are also the same as those described for the RAFT agent used when producing hydrophobic resin (A) by radical polymerization.

[0185] The weight-average molecular weight (Mw) of the copolymer having alkali-soluble functional groups is preferably 3,000 to 80,000. The lower limit is more preferably 4,000 or more, and even more preferably 5,000 or more. The upper limit is more preferably 30,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and even more preferably 6,000 or less. The number-average molecular weight (Mn) of the copolymer having alkali-soluble functional groups is preferably 1,000 to 30,000. The lower limit is more preferably 1,500 or more, and even more preferably 2,000 or more. The upper limit is preferably 20,000 or less, even more preferably 10,000 or less, even more preferably 5,000 or less, and even more preferably 4,000 or less. The polydispersity (Mw / Mn) of the copolymer having alkali-soluble functional groups is preferably 1.0 to 3.5. This lower limit is more preferably 1.3 or higher, and even more preferably 1.5 or higher. Furthermore, this upper limit is more preferably 2.5 or lower, and even more preferably 2.0 or lower. By setting the weight-average molecular weight, number-average molecular weight, and polydispersity of the copolymer having alkali-soluble functional groups within the above ranges, a positive-type photosensitive resin composition with excellent coating properties, pattern-forming properties, and alkali-developability can be obtained.

[0186] When the alkali-soluble functional group of a copolymer having an alkali-soluble functional group is a phenolic hydroxyl group, the equivalent amount of phenolic hydroxyl groups in the copolymer having an alkali-soluble functional group is preferably 60 or more and 400 or less. The lower limit is more preferably 100 or more, and even more preferably 140 or more. The upper limit is preferably 300 or less, and even more preferably 200 or less. If the equivalent amount of phenolic hydroxyl groups in the copolymer having an alkali-soluble functional group is above the lower limit, the film thickness of the unexposed areas can be sufficiently maintained during alkali development. If the equivalent amount of phenolic hydroxyl groups in the copolymer having an alkali-soluble functional group is below the upper limit, the desired alkali solubility can be obtained.

[0187] In this specification, if a copolymer having an alkali-soluble functional group also falls under the category of a resin having epoxy groups and phenolic hydroxyl groups, as described later, it shall be treated as a copolymer having an alkali-soluble functional group. That is, resins having epoxy groups and phenolic hydroxyl groups do not include those that fall under the category of copolymer having an alkali-soluble functional group.

[0188] (Resin (B2) having epoxy groups and phenolic hydroxyl groups)

[0189] Resins having epoxy groups and phenolic hydroxyl groups are alkaline aqueous solution soluble resins. Resins having epoxy groups and phenolic hydroxyl groups may also have alkali-soluble functional groups other than phenolic hydroxyl groups. Resins having epoxy groups and phenolic hydroxyl groups can be obtained, for example, by reacting some of the epoxy groups of a compound having at least two epoxy groups in one molecule (hereinafter sometimes referred to as "epoxy compound") with the carboxyl group of a hydroxybenzoic acid compound. The epoxy groups of resins having epoxy groups and phenolic hydroxyl groups form crosslinks by reacting with phenolic hydroxyl groups during post-development heat treatment (post-bake), thereby improving the chemical resistance, heat resistance, etc. of the coating. Since phenolic hydroxyl groups contribute to solubility in alkaline aqueous solutions during development, resins having epoxy groups and phenolic hydroxyl groups also function as dissolution accelerators for other resins when exposed at low exposure levels, thereby making the photosensitive resin composition highly sensitive.

[0190] Reaction Equation 2 below shows an example of a reaction in which one of the epoxy groups of an epoxy compound reacts with the carboxyl group of a hydroxybenzoic acid compound to form a compound having a phenolic hydroxyl group.

[0191]

[0192] ​Examples of compounds having at least two epoxy groups in one molecule include novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins, bisphenol-type epoxy resins, biphenol-type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These epoxy compounds only need to have two or more epoxy groups in one molecule and can be used individually or in combination of two or more types. Since these compounds are thermosetting, it is common knowledge to those skilled in the art that their structure cannot be uniquely described based on differences in the presence or absence of epoxy groups, the type of functional group, the degree of polymerization, etc.

[0193] An example of the structure of a novolac-type epoxy resin is shown in formula (4). In formula (4), R １０ m represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a hydroxyl group, and m is an integer from 1 to 50.

[0194]

[0195] ​Examples of phenol novolac type epoxy resins include "EPICLON® N-770", "EPICLON® N730A" (both trade names, DIC Corporation), and "jER®-152" (trade name, Mitsubishi Chemical Corporation). Examples of cresol novolac type epoxy resins include "EPICLON® N-695" (trade name, DIC Corporation) and "EOCN®-102S" (trade name, Nippon Kayaku Co., Ltd.). Examples of bisphenol-type epoxy resins include bisphenol A type epoxy resins such as "jER(registered trademark) 828" and "jER(registered trademark) 1001" (both product names, Mitsubishi Chemical Corporation) and "YD-128" (product name, Nippon Steel Chemical & Material Co., Ltd.), and bisphenol F type epoxy resins such as "jER(registered trademark) 806" (product name, Mitsubishi Chemical Corporation) and "YDF-170" (product name, Nippon Steel Chemical & Material Co., Ltd.). Examples of biphenol-type epoxy resins include "jER(registered trademark) YX-4000" and "jER(registered trademark) YL-6121H" (both product names, Mitsubishi Chemical Corporation). Examples of naphthalene skeleton-containing epoxy resins include "NC-7000" (product name, Nippon Kayaku Co., Ltd.) and "EXA-4750" (product name, DIC Corporation). Examples of alicyclic epoxy resins include "EHPE(registered trademark)-3150" (Daicel Corporation). Examples of heterocyclic epoxy resins include "TEPIC®", "TEPIC®-L", "TEPIC®-H", and "TEPIC®-S" (all product names, Nissan Chemical Corporation).

[0196] (B2) The compound having at least two epoxy groups in one molecule is preferably a novolac-type epoxy resin, more preferably at least one selected from the group consisting of phenol novolac-type epoxy resins and cresol novolac-type epoxy resins, and even more preferably a cresol novolac-type epoxy resin. Positive-type photosensitive resin compositions containing a resin having epoxy groups and phenolic hydroxyl groups derived from a novolac-type epoxy resin, particularly a cresol novolac-type epoxy resin, exhibit excellent pattern-forming properties, easy adjustment of alkali solubility, and low outgassing.

[0197] Hydroxybenzoic acid compounds are compounds in which at least one of the 2-6 positions of benzoic acid is substituted with a hydroxyl group. Examples include salicylic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2-hydroxy-5-nitrobenzoic acid, 3-hydroxy-4-nitrobenzoic acid, and 4-hydroxy-3-nitrobenzoic acid. Dihydroxybenzoic acid compounds are preferred in that they enhance alkali developability. Hydroxybenzoic acid compounds may be used alone or in combination of two or more.

[0198] In this embodiment, a specific example of a resin having epoxy groups and phenolic hydroxyl groups is a reaction product of a compound having at least two epoxy groups in one molecule and a hydroxybenzoic acid compound, having the structure of formula (5).

[0199]

[0200] (In formula (5), b is an integer from 1 to 5, and * represents the binding site with the residue excluding the epoxy group involved in the reaction, in a compound having at least two epoxy groups in one molecule.)

[0201] ​In a method for obtaining a resin having epoxy groups and phenolic hydroxyl groups from an epoxy compound and a hydroxybenzoic acid compound, the hydroxybenzoic acid compound can be used in an amount of 0.2 equivalents to 0.95 equivalents per equivalent of epoxy groups in the epoxy compound. The lower limit is more preferably 0.3 equivalents or more, and even more preferably 0.4 equivalents or more. The upper limit is more preferably 0.9 equivalents or less, and even more preferably 0.8 equivalents or less. If the hydroxybenzoic acid compound is above the lower limit, sufficient alkali solubility can be obtained, and if it is below the upper limit, the increase in molecular weight due to side reactions can be effectively suppressed.

[0202] A catalyst may be used to accelerate the reaction between the epoxy compound and the hydroxybenzoic acid compound. The amount of catalyst used can be 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the reaction material mixture consisting of the epoxy compound and the hydroxybenzoic acid compound. The reaction temperature can be 60°C or more and 150°C or less, and the reaction time can be 3 hours or more and 30 hours or less. Examples of catalysts used in this reaction include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, chromium octanoate, and zirconium octanoate.

[0203] The number-average molecular weight (Mn) of the resin having epoxy groups and phenolic hydroxyl groups is preferably 500 or more and 8000 or less. The lower limit is more preferably 800 or more, and even more preferably 1000 or more. The upper limit is more preferably 6000 or less, and even more preferably 5000 or less. The weight-average molecular weight (Mw) of the resin having epoxy groups and phenolic hydroxyl groups is preferably 500 or more and 30000 or less. The lower limit is more preferably 2000 or more, and even more preferably 3000 or more. The upper limit is preferably 25000 or less, and even more preferably 20000 or less. If the number-average molecular weight is 500 or more, or the weight-average molecular weight is 500 or more, the alkaline development rate is appropriate and the difference in dissolution rate between the exposed and unexposed areas is sufficient, resulting in good pattern resolution. If the number-average molecular weight is 8000 or less, or the weight-average molecular weight is 30000 or less, the coating properties and alkaline developability are good.

[0204] In this embodiment, the epoxy equivalent of the resin having epoxy groups and phenolic hydroxyl groups is preferably 300 or more and 7000 or less. The lower limit is more preferably 400 or more, and even more preferably 500 or more. The upper limit is more preferably 6000 or less, and even more preferably 5000 or less. If the epoxy equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 300 or more, sufficient alkali solubility can be imparted to the resin having epoxy groups and phenolic hydroxyl groups. If the epoxy equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 7000 or less, the strength and heat resistance of the cured film can be increased. The epoxy equivalent is determined according to JIS K 7236:2009.

[0205] In this embodiment, the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is preferably 160 or more and 500 or less. The lower limit is more preferably 170 or more, and even more preferably 180 or more. The upper limit is more preferably 400 or less, and even more preferably 300 or less. If the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 160 or more, the strength and heat resistance of the cured film can be increased. If the hydroxyl equivalent of the resin having epoxy groups and phenolic hydroxyl groups is 500 or less, sufficient alkali solubility can be imparted to the resin having epoxy groups and phenolic hydroxyl groups. The hydroxyl equivalent is determined according to JIS K 0070:1992.

[0206] (Protective resin (B3))

[0207] The alkali-soluble resin (B) may include a resin having alkali-soluble functional groups protected by acid-degradable groups (hereinafter also simply referred to as the "protective resin"). The protective resin (B3) is not particularly limited as long as it has a plurality of alkali-soluble functional groups, and at least a portion of the plurality of alkali-soluble functional groups are protected by acid-degradable groups. Examples of protective resin (B3) include a resin in which the above-mentioned alkali-soluble resin having a plurality of alkali-soluble functional groups is used as a base resin, and at least a portion of the alkali-soluble functional groups are protected by acid-degradable groups. Examples of alkali-soluble functional groups include phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, acid anhydride groups, and mercapto groups. The alkali-soluble functional groups are preferably phenolic hydroxyl groups or carboxyl groups, and more preferably phenolic hydroxyl groups. Because a portion of the alkali-soluble functional groups are protected by acid-degradable groups, the alkali solubility of the protective resin (B3) before exposure is suppressed. The protective resin (B3) may have alkali-soluble functional groups other than alkali-soluble functional groups protected by acid-degradable groups. In the presence of acid generated during exposure, post-exposure bake (PEB) is performed as needed to promote the decomposition (deprotection) of acid-degradable groups and regenerate alkali-soluble functional groups. This promotes the alkali dissolution of the protective resin (B3) in the exposed area during development. The protective resin (B3) may be used alone or in combination of two or more types. For example, the protective resin (B3) may be a combination of two or more resins with different polymer or copolymer structural units, acid-degradable groups, protection rates of alkali-soluble functional groups, or combinations thereof.

[0208] (Protection of alkali-soluble functional groups by acid-degradable groups)

[0209] The protective resin (B3) can be obtained by protecting some of the alkali-soluble functional groups of a base resin having multiple alkali-soluble functional groups with acid-degradable groups. For example, if the alkali-soluble functional group is a phenolic hydroxyl group, the protective resin (B3) having phenolic hydroxyl groups protected by acid-degradable groups is Ar-O-R １１ It has a partial structure where Ar represents an aromatic ring derived from phenol, and R１１ This represents an acid-degradable group.

[0210] Acid-degradable groups are groups that decompose (deprotect) in the presence of an acid, and optionally by heating, to generate alkali-soluble functional groups. Specifically, examples include groups having tertiary alkyl groups such as tert-butyl group, 1,1-dimethyl-propyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-methyladamantyl group, 1-ethyladamantyl group, tert-butoxycarbonyl group, and 1,1-dimethyl-propoxycarbonyl group; and groups represented by formula (6). When the alkali-soluble functional group is a phenolic hydroxyl group, the group represented by formula (6) forms an acetal structure or a ketal structure together with the oxygen atom derived from the alkali-soluble functional group. These acid-degradable groups can be used individually or in combination of two or more types. -CR １２ R １３ -O-R １４ ...(6) (In formula (6), R １２ and R １３ Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R １４ R is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms. １２ or R １３ One of the two and R １４ They may combine to form a ring structure with 3 to 10 members, R １２ , R １３ and R １４ (This may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine.)

[0211] Since a highly sensitive photosensitive resin composition can be obtained even with low exposure, the acid-degradable group is preferably a group represented by formula (6). １２ and R １３Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R １４ It is more preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine. Examples of such acid-degradable groups include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group, with 1-ethoxyethyl group and 1-n-propoxyethyl group being preferred. As an acid-degradable group, there is a group represented by formula (6), where R １２ or R １３ One of the two and R １４ A ring structure with 3 to 10 members formed by the bonding of these elements can also be suitably used. In this case, R, which is not involved in the formation of the ring structure, can also be used. １２ or R １３ It is preferable that the group is a hydrogen atom. Examples of such acid-degradable groups include the 2-tetrahydrofuranyl group and the 2-tetrahydropyranyl group, with the 2-tetrahydrofuranyl group being preferred.

[0212] The protection reaction of alkali-soluble functional groups can be carried out under known conditions using common protective agents. For example, protective resin (B3) can be obtained by reacting the base resin of protective resin (B3) and a protective agent in the presence of an acid or base in a solvent-free environment or in a solvent such as toluene or hexane at a reaction temperature of -20°C to 50°C.

[0213] As a protective agent, known protective agents capable of protecting alkali-soluble functional groups can be used. For example, if the acid-degradable group is a tert-butyl group, isobutene can be used as a protective agent; if it is a tert-butoxycarbonyl group, ditert-butyl dicarbonate can be used. If the acid-degradable group is a methoxymethyl group, chloromethyl methyl ether can be used; if it is a 1-ethoxyethyl group, ethyl vinyl ether can be used; if it is a 1-n-propoxyethyl group, n-propyl vinyl ether can be used; if it is a 2-tetrahydrofuranyl group, 2,3-dihydrofuran can be used; and if it is a 2-tetrahydropyranyl group, 3,4-dihydro-2H-pyran can be used.

[0214] Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and perchloric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid. Salts of organic acids, such as the pyridinium salt of p-toluenesulfonic acid, can also be used as acid sources. Examples of bases include inorganic hydroxides such as sodium hydroxide and potassium hydroxide, inorganic carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate, and cesium carbonate, metal hydrides such as sodium hydride, and amine compounds such as pyridine, N,N-dimethyl-4-aminopyridine, imidazole, triethylamine, and diisopropylethylamine.

[0215] In another embodiment, a protective resin (B3) can be obtained by protecting the alkali-soluble functional groups of a polymerizable monomer having alkali-soluble functional groups with acid-degradable groups, and then polymerizing or copolymerizing the polymerizable monomer having alkali-soluble functional groups protected with acid-degradable groups and, if necessary, other polymerizable monomers. The protection of the alkali-soluble functional groups of the polymerizable monomer having alkali-soluble functional groups can be carried out in the same manner as the protection of the alkali-soluble functional groups of the base resin.

[0216] The protective resin (B3) has structural units represented by formula (7), and preferably has at least one structural unit represented by formula (7) where q is an integer of 1 or more.

[0217]

[0218] (In formula (7), R １５ R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. １６ (where p is an acid-degradable group, p is an integer from 0 to 5, q is an integer from 0 to 5, and p+q is an integer from 1 to 5.)

[0219] Note that in the formula, R １６ The acid-degradable group is preferably a group represented by formula (6). -CR １２ R １３ -O-R １４ ...(6) (In formula (6), R １２ , R １３ and R １４ (As stated above.)

[0220] In formula (6), R １２ and R １３ Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R １４ It is more preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine. Examples of such acid-degradable groups include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group, with 1-ethoxyethyl group and 1-n-propoxyethyl group being preferred. １２ or R １３ One of the two and R １４ Examples of acid-degradable groups formed by the bonding of these groups to create a ring structure with 3 to 10 members include the 2-tetrahydrofuranyl group and the 2-tetrahydropyranyl group, with the 2-tetrahydrofuranyl group being preferred.​

[0221] The protective resin (B3) has structural units represented by formula (7'), and preferably has at least one structural unit represented by formula (7) where w is an integer of 1 or more.

[0222]

[0223] (In formula (7'), R １５ R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. １６ (where is an acid-degradable group, v is an integer from 0 to 5, w is an integer from 0 to 5, and v + w is an integer from 1 to 5.)

[0224] Note that in the formula, R １６ The acid-degradable group is preferably a group represented by formula (6). -CR １２ R １３ -O-R １４ ...(6) (In formula (6), R １２ , R １３ and R １４ (As stated above.)

[0225] In formula (6), R １２ and R １３ Each of these is independently a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms, or a branched alkyl group having 3 to 4 carbon atoms, and R １４ It is more preferably a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, which may be substituted with a halogen atom selected from the group consisting of chlorine, bromine, and iodine. Examples of such acid-degradable groups include 1-alkoxyalkyl groups. Examples of 1-alkoxyalkyl groups include methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-(2-chloroethoxy)ethyl group, 1-(2-ethylhexyloxy)ethyl group, 1-cyclohexyloxyethyl group, and 1-(2-cyclohexylethoxy)ethyl group, with 1-ethoxyethyl group and 1-n-propoxyethyl group being preferred.​１２ or R １３ One of the two and R １４ Examples of acid-degradable groups formed by the bonding of these groups to create a ring structure with 3 to 10 members include the 2-tetrahydrofuranyl group and the 2-tetrahydropyranyl group, with the 2-tetrahydrofuranyl group being preferred.

[0226] The protective resin (B3) may or may not have the structural unit represented by formula (2). Even if the protective resin (B3) does not have the structural unit represented by formula (2), sufficient effects can be obtained. From the viewpoint of obtaining sufficient effects, it is preferable that the protective resin (B3) does not have an imide skeleton in its structural unit. Furthermore, it is even more preferable that the protective resin (B3) does not have nitrogen atoms.

[0227]

[0228] (In formula (2), R ６ and R ７ Each is independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ８ This refers to a phenyl group substituted with a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, a phenyl group, or at least one selected from the group consisting of a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.

[0229] In formula (2), R ６ and R ７ Each of these can be independently exemplified by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ８ Examples include cyclic alkyl groups having 3 to 12 carbon atoms, phenyl groups, or hydroxyl groups, and phenyl groups substituted with at least one selected from the group consisting of alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms.

[0230] ​In this embodiment, it is preferable that the number of structural units represented by formula (7) where q is an integer of 1 or more, and / or represented by formula (7') where w is an integer of 1 or more, that is, structural units represented by formula (7) and / or formula (7') in which at least one alkali-soluble functional group is protected by an acid-degradable group, is 5% to 95% of the total number of structural units in the protective resin (B3). The lower limit is more preferably 15% or more, and even more preferably 25% or more. The upper limit is more preferably 90% or less, and even more preferably 85% or less. By setting the proportion of the above structural units to 5% or more, the dissolution of the exposed area can be promoted, creating a difference in solubility between the unexposed and exposed areas, thereby achieving high sensitivity and ensuring the stability and durability of the film after heat curing. By setting the proportion of the above structural units to 95% or less, the amount of unreacted acid-degradable groups remaining can be reduced, increasing the solubility of the exposed area and achieving high sensitivity.

[0231] In this embodiment, the positive-type photosensitive resin composition preferably contains 0.5% to 50% by mass of protective resin (B3) based on 100% by mass of solids. The lower limit is more preferably 1% by mass or more, and even more preferably 2% by mass or more. Furthermore, the lower limit is more preferably 40% by mass or even more preferably 30% by mass or less. If the content of protective resin (B3) is above the above lower limit based on 100% by mass of solids, the dissolution of the exposed area can be promoted, creating a difference in solubility between the unexposed and exposed areas, thereby achieving high sensitivity and ensuring the stability and durability of the film after heat curing. If the content of protective resin (B3) is below the above upper limit based on 100% by mass of solids, the amount of unreacted acid-degradable groups remaining can be reduced, increasing the solubility of the exposed area and achieving high sensitivity.

[0232] <Quinone diazide compound (C)>

[0233] The quinone diazide compound (C) is a compound that, when irradiated with visible light, ultraviolet light, or radiation (gamma rays, electron beams, etc.), undergoes the reaction shown in reaction formula 3 below to produce an alkali-soluble carboxylic acid compound, and is not a hydrophobic resin (A).

[0234]

[0235] The quinone diazide compound (C) interacts with the alkali-soluble functional groups of the alkali-soluble resin (B), such as phenolic hydroxyl groups, before photosensitivity (e.g., by hydrogen bonding), rendering the alkali-soluble resin (B) insoluble in an alkaline aqueous solution. On the other hand, the presence of an alkali-soluble carboxylic acid compound in the irradiated area makes the resin in that area more easily soluble in the alkaline aqueous solution together with the carboxylic acid compound. Furthermore, the generated carboxylic acid compound promotes the decomposition of the acid-degradable groups of the protective resin (B3), which is optionally included in the positive-type photosensitive resin composition, regenerating its alkali-soluble functional groups and increasing the alkali solubility of the protective resin (B3). Moreover, the carboxylic acid compound has a relatively larger molecular structure than acids produced from photoacid generators commonly used in chemical amplification resists, such as p-toluenesulfonic acid and 1-propanesulfonic acid, and is less likely to diffuse in the film. As a result of these synergistic effects, the difference in alkali solubility between the unexposed and exposed areas can be increased, thereby enabling the formation of highly sensitive and high-resolution patterns even with low exposure levels. The quinone diazide compound (C) may be used alone or in combination of two or more types.

[0236] ​The positive-type photosensitive resin composition preferably contains substantially no photoacid generators (excluding diazonaphthoquinone derivatives) commonly used in chemically amplified resists, and more preferably substantially no photoacid generators (excluding diazonaphthoquinone derivatives) with a molecular weight of 2000 or less. On the other hand, the positive-type photosensitive resin composition according to this embodiment may contain the above-mentioned diazonaphthoquinone derivatives as a photosensitive agent, to the extent that it does not impair the effects of this embodiment. Among these, for example, it may contain the above-mentioned quinone diazide compound (C). Note that "substantially free of photoacid generators" means that such components are not actively added or mixed, and does not exclude their unavoidable inclusion or mixing. A preferred example of the case where the photoacid generator is "substantially free" is that the amount of the photoacid generator contained in the positive-type photosensitive resin composition is preferably 0.2 parts by mass or less, more preferably 0.1 parts by mass or less, even more preferably 0.05 parts by mass or less, and even more preferably 0 parts by mass (0% by mass) based on 100 parts by mass of the total resin components.

[0237] Furthermore, the positive-type photosensitive resin composition does not need to contain diazonaphthoquinone derivatives with a molecular weight of 2000 or less if it is necessary to suppress the occurrence of defects caused by low molecular weight substances. Specific examples of the diazonaphthoquinone derivatives with a molecular weight of 2000 or less mentioned above include, for example, compounds that correspond to the quinone diazide compound (C) mentioned above and have a molecular weight of 2000 or less. These do not need to be included in one or more types, or even all of them.

[0238] In this embodiment, high-resolution patterns can be formed without the post-exposure heating (PEB) required for typical chemically amplified resists. The hydrophobic resin (A) and the quinone diazide compound (C) have relatively high quantum efficiency, and carboxylic acid compounds are efficiently generated in the exposed areas. By omitting PEB, it is possible to avoid a decrease in pattern formation performance caused by excessive diffusion of acid generated from the photoacid generator into the unexposed areas under the high-temperature environment of the PEB process. Furthermore, if the alkali-soluble resin (B) contains a resin having epoxy groups and phenolic hydroxyl groups, omitting PEB prevents ring-opening polymerization of the epoxy groups of the resin having epoxy groups and phenolic hydroxyl groups from proceeding, thus maintaining the alkali solubility of the resin having epoxy groups and phenolic hydroxyl groups during development.

[0239] Examples of quinone diazide compounds (C) include those in which the sulfonic acid of quinone diazide is esterified to a polyhydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, and those in which the sulfonic acid of quinone diazide is esterified or sulfonamide bonded to a polyhydroxypolyamino compound. From the viewpoint of contrast between the exposed and unexposed areas, it is preferable that 20 mol% or more of the total functional groups of the polyhydroxy compound or polyamino compound are substituted with quinone diazide.

[0240] Examples of polyhydroxy compounds include "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", and "Methylenetris". -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” (all product names, Honshu Chemical Industry Co., Ltd.), “BIR-OC”, “BIP-PC”, “B IR-PC”, “BIR-PTBP”, “BIR-PCHP”, “BIP-BIOC-F”, “4PC”, “BIR-BIPC-F”, “TEP-BIP-A”, “46DMOC”, “46DMOEP”, “TM-BIP-A” Examples include, but are not limited to, the following: (product names, Asahi Organic Chemicals Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, "BisP-AP" (product name, Honshu Chemical Industry Co., Ltd.), etc.

[0241] Examples of polyamino compounds include, but are not limited to, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfide.

[0242] Examples of polyhydroxypolyamino compounds include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

[0243] The quinone diazide compound (C) is preferably 1,2-naphthoquinone diazide-5-sulfonic acid ester of a polyhydroxy compound or 1,2-naphthoquinone diazide-4-sulfonic acid ester of a polyhydroxy compound. Commercially available products such as "TS-150A," "TS-200A," and "TPPA-150DF" (all trade names, manufactured by Toyo Gosei Kogyo Co., Ltd.) can be used.

[0244] In this embodiment, the positive-type photosensitive resin composition may contain 5 to 60 parts by mass of quinone diazide compound (C) based on 100 parts by mass of the total resin components. The lower limit is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more. The upper limit is preferably 50 parts by mass or less, and more preferably 42 parts by mass or less. If the content of quinone diazide compound (C) is above the lower limit based on the total of 100 parts by mass, high sensitivity may be achieved. If the content of quinone diazide compound (C) is below the upper limit based on the total of 100 parts by mass, good alkaline developability may be achieved.

[0245] <Surfactant (D)> The positive-type photosensitive resin composition contains a surfactant. The surfactant promotes the migration of the hydrophobic resin (A) to the film surface of the positive-type photosensitive resin composition, making the film surface more alkali-insoluble. Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and other surfactants. Among these, silicone-based surfactants are preferred from the viewpoint of further enhancing the effects described above.

[0246] Specific examples of fluorine-based surfactants include "Megafac® F-251", "Megafac® F-281", "Megafac® F-430", "Megafac® F-444", "Megafac® R-40", "Megafac® F-553", "Megafac® F-554", "Megafac® F-555", "Megafac® F-556", "Megafac® F-557", and "Megafac® Examples include "F-558", "Megafac® F-559", "Megafac® F-562", and "Megafac® F-563", "Megafac® F-569" (product names, DIC Corporation), as well as "Surflon® S-242", "Surflon® S-243", "Surflon® S-386", "Surflon® S-420", and "Surflon® S-611" (product names, AGC Seimi Chemical Co., Ltd.). The fluorine-based surfactant is preferably "Megafac® F-563", "Megafac® F-569", "Megafac® F-554", "Megafac® R-40", or "Megafac® F-562", and more preferably "Megafac® F-563", "Megafac® F-569", or "Megafac® R-40".

[0247] In recent years, there has been a demand to refrain from using organofluorine compounds such as PFAS, and there is a so-called demand for non-PFAS. From this perspective, the positive-type photosensitive resin composition according to this embodiment has the advantage that the desired effect can be obtained even without containing organofluorine compounds. From this perspective, the positive-type photosensitive resin composition according to this embodiment may contain the above-mentioned fluorine-based surfactant, but it is preferable that it does not contain a fluorine-based surfactant.

[0248] The silicone-based surfactant is not particularly limited, but it is preferably a silicone-based surfactant having silicon atoms in its side chains. For example, a silicone-based surfactant containing a (meth)acrylic copolymer having at least one silicon-containing hydrocarbon group selected from the group consisting of silicon-containing alkyl groups and silicon-containing alkylene groups is preferred. The acrylic copolymer promotes the migration of the hydrophobic resin (A) to the film surface of the positive-type photosensitive resin composition, making the film surface more alkali-insoluble. Furthermore, from the viewpoint of further enhancing this effect, the silicone-based surfactant is preferably one that does not have silicon atoms in its main chain but has silicon atoms in its side chains. The silicone-based surfactant may be used alone or in combination of two or more types.

[0249] Examples of the above-mentioned acrylic copolymer include (D1), a copolymer of a polymerizable monomer represented by formula (8) and a polymerizable monomer having a polyoxyalkylene group represented by formula (9).

[0250]

[0251] (In formula (8), R １７ L is a hydrogen atom or a methyl group. １ Rf is a divalent group with 1 to 30 carbon atoms. １ This is a silicon-containing alkyl group or partially silicate alkyl group having 4 to 6 carbon atoms, which may contain one or more ether bonds in the chain.

[0252]

[0253] (In formula (9), R １８ R is a hydrogen atom or a methyl group, １９ Each of these is independently a linear or branched alkylene group having 2 to 4 carbon atoms, and R ２０ (where c is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and c is an integer from 2 to 50.)

[0254] In formula (8), L １ ​​The divalent group having 1 to 30 carbon atoms represented by may contain at least one heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur atoms, and may also contain a silicon atom-containing alkyl group or a partially silicate alkyl group having 4 to 6 carbon atoms. １ is, -OCH ２ CH ２ -, -OCH ２ CH ２ N(C) ３ H ７ ) SO ２ -, -OCH ２ CH ２ NH(C=O)OCH ２ CH ２ -, -OCH ２ CH(OH)CH ２ O-, or -N(C ４ H ９ )CH ２ CH ２ - is preferable.

[0255] The polymerizable monomer represented by formula (8) may be used alone or in combination of two or more types.

[0256] In formula (9), R １９ Examples of linear or branched alkylene groups having 2 to 4 carbon atoms, represented by R, include ethylene, propylene, tetramethylene, and isobutylene groups. １９ They may be the same or they may be different from each other. From the standpoint of leveling, R １９ The group is preferably a propylene group, a tetramethylene group, or an isobutylene group, and it is more preferable that multiple identical groups are linked together via adjacent oxygen atoms to form a polyoxypropylene chain, a polytetramethylene chain, or a polyisobutylene chain.

[0257] In formula (9), R ２０ Examples of alkyl groups having 1 to 6 carbon atoms represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, and n-hexyl groups.

[0258] The polymerizable monomer having a polyoxyalkylene group represented by formula (9) may be used alone or in combination of two or more types.

[0259] The copolymer (D1) may be a copolymer of a polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), or other polymerizable monomers.

[0260] Other polymerizable monomers include, for example, the polymerizable monomer represented by formula (10).

[0261]

[0262] (In equation (10), R ２１ R is a hydrogen atom or a methyl group, ２２ (A is a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms.)

[0263] In formula (10), R ２２ Examples of linear, branched, or cyclic alkyl groups having 1 to 18 carbon atoms, represented by , include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, stearyl, isopropyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, isobornyl, adamantyl, dicyclopentanyl, and dicyclopentenyl groups.

[0264] Other polymerizable monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0265] Other polymerizable monomers may be used individually or in combination of two or more.

[0266] ​From the viewpoint of leveling properties, the mass ratio of the polymerizable monomer represented by formula (8) to the polymerizable monomer having a polyoxyalkylene group represented by formula (9) in the copolymer (D1) (mass of polymerizable monomer represented by formula (8) / mass of polymerizable monomer having a polyoxyalkylene group represented by formula (9)) is preferably 10 / 90 to 70 / 30, more preferably 15 / 85 to 60 / 40, and even more preferably 25 / 75 to 50 / 50. When other polymerizable monomers are used, it is preferable to use them in an amount such that the other polymerizable monomers constitute 50% by mass or less, based on the mass of the copolymer (D1).

[0267] Copolymer (D1) can be obtained, for example, by radical polymerization of a polymerizable monomer represented by formula (8), a polymerizable monomer having a polyoxyalkylene group represented by formula (9), and other polymerizable monomers as needed, in an organic solvent using a polymerization initiator. Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfoxides such as dimethyl sulfoxide; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and aromatic hydrocarbons such as toluene and xylene. Examples of polymerization initiators include peroxide polymerization initiators such as benzoyl peroxide, and azo polymerization initiators such as 2,2'-azobisisobutyronitrile. If necessary, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, and octylthioglycolic acid may be used.

[0268] Preferred examples of silicone-based surfactants include "MEGAFACE EFS-131," "MEGAFACE EFS-321," "MEGAFACE EFS-521," and "MEGAFACE EFS-801" (product names, all manufactured by DIC Corporation).

[0269] In particular, "MEGAFACE EFS-131," "MEGAFACE EFS-321," and "MEGAFACE EFS-521" are preferred because they are fluorine-free, have silicon atoms in the side chains but not in the main chain, and include both the structure represented by formula (8) and the structure represented by formula (9) described above. All of these are (meth)acrylic copolymers that do not have silicon atoms in the main chain and have at least one silicon atom-containing hydrocarbon group selected from the group consisting of silicon atom-containing alkyl groups and silicon atom-containing alkylene groups.

[0270] The amount of surfactant (D) in the positive-type photosensitive resin composition is preferably 0.01 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the total resin components. The lower limit of this amount is more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more. The upper limit of this amount is preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less. If the amount of surfactant (D) is equal to or greater than the lower limit based on 100 parts by mass of the total, the leveling properties of the positive-type photosensitive resin composition are improved, allowing the positive-type photosensitive resin composition to be uniformly applied to the substrate, thereby promoting the uneven distribution of the hydrophobic resin (A). If the amount of surfactant (D) is equal to or less than the upper limit based on 100 parts by mass of the total, the leveling properties of the positive-type photosensitive resin composition can be improved and the uneven distribution of the hydrophobic resin can be promoted without adversely affecting the cured film after post-baking.

[0271] Furthermore, the content of surfactant (D) in the total amount of surfactants is preferably 50% by mass or more. The lower limit of this content is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. The upper limit of this content is more preferably 95% by mass or less, and even more preferably 90% by mass or less. By setting the content of surfactant (D) within the above range, wettability with the substrate can be more effectively ensured, and coating can be performed more uniformly without the occurrence of repelling. In this embodiment, it is preferable that the positive-type photosensitive resin composition does not contain fluorine-based surfactants.

[0272] The positive-type photosensitive resin composition may contain other surfactants besides those mentioned above, for example, to improve coating properties, improve the smoothness of the film, or improve the developability of the film. Other surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and acetylene-based surfactants such as "Orphin® E1004", "Orphin® E1010", "Orphin® E1020", and "Orphin® E1030W" (all product names, Nisshin Chemical Industry Co., Ltd.), and "Acetylenel® E40", "Acetylenel® E60", "Acetylenel® E100", and "Acetylenel® E200" (all product names, Kawaken Fine Chemical Co., Ltd.).

[0273] The content of the other surfactants mentioned above is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less, based on 100 parts by mass of the total other solids. The positive-type photosensitive resin composition according to this embodiment preferably does not contain such other surfactants.

[0274] <Coloring agent (E)>

[0275] The positive-type photosensitive resin composition according to this embodiment contains a colorant (E) containing a black dye. Component (E) may also contain other colorants besides the black dye. By forming a black partition on an organic EL element using a photosensitive resin composition containing a colorant (E) containing a black dye, the visibility of a display device such as an organic EL display can be improved.

[0276] In this embodiment, the inclusion of a colorant (E) causes the amount of radiation transmitted during exposure to decrease sharply from the surface to the interior of the film. Therefore, carboxylic acid compounds derived from the hydrophobic resin (A) and quinone diazide compound (C) are generated relatively frequently near the film surface, but less frequently inside the film. Because the carboxylic acid compounds derived from the hydrophobic resin (A) and quinone diazide compound (C) have low diffusivity within the film, they remain near the film surface, contributing to the dissolution of the film surface in the exposed areas. The interior of the film has a relatively low concentration of hydrophobic resin (A), resulting in relatively high alkali solubility. Therefore, even if radiation does not penetrate sufficiently into the interior of the film, a highly sensitive and high-precision thick film pattern can be formed by using the positive-type photosensitive resin composition of this embodiment (however, the effects and benefits of this embodiment are not limited to these).

[0277] Examples of black dyes include those defined by the color index (C.I.) of Solvent Black 27 to 47. Preferably, the black dye is defined by the C.I. of Solvent Black 27, Solvent Black 29, or Solvent Black 34. When at least one of the dyes defined by the C.I. of Solvent Black 27 to 47 is used as the black dye, the light-shielding properties of the film of the cured positive-type photosensitive resin composition can be maintained. Compared to a positive-type photosensitive resin composition containing a black dye, a positive-type photosensitive resin composition containing a black pigment leaves less colorant residue during development and can form high-definition patterns.

[0278] Examples of black pigments include carbon black, carbon nanotubes, acetylene black, graphite, iron black, aniline black, titanium black, perylene pigments, and lactam pigments. Surface-treated versions of these black pigments can also be used. Examples of commercially available perylene pigments include BASF's K0084, K0086, Pigment Black 21, 30, 31, 32, 33, and 34. An example of a commercially available lactam pigment is BASF's Irgaphor® Black S0100CF. Due to its high light-shielding properties, the black pigment is preferably at least one selected from the group consisting of carbon black, titanium black, perylene pigments, and lactam pigments.

[0279] In addition, other dyes and pigments not mentioned above can also be used in combination. These can be used as needed, within limits that do not impair the function and effects of this embodiment.

[0280] Other dyes include, for example, azo dyes, benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, croconium dyes, merocyanine dyes, stilbene dyes, diphenylmethane dyes, triphenylmethane dyes, fluorane dyes, spiropyran dyes, phthalocyanine dyes, indigo dyes, fulgid dyes, nickel complex dyes, and azulene dyes.

[0281] Other pigments include, for example, 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. Examples include Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. Pigment Green 7, and C.I. Pigment Brown 23, 25, 26.

[0282] However, in this embodiment, it is preferable to increase the content of the black dye and decrease the content of other colorants (e.g., pigments). From this viewpoint, the content of colorants other than the black dye in the total amount of colorant (E) is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably none (0% by mass).

[0283] The content of the colorant (E) in the positive-type photosensitive resin composition is preferably 10 parts by mass or more and 200 parts by mass or less, based on 100 parts by mass of the total resin components. The lower limit is more preferably 25 parts by mass or more, and even more preferably 40 parts by mass or more. The upper limit is more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less. If the content of the colorant (E) is above the lower limit based on the total of 100 parts by mass, sufficient light shielding can be obtained, and in particular, since the colorant (E) contains a black dye, the light shielding of the film after curing can be maintained. If the content of the colorant (E) is below the upper limit based on the total of 100 parts by mass, the residual film rate and sensitivity are appropriate, and in particular, when the colorant (E) contains a black dye, high heat resistance can be imparted to the film.

[0284] <Optional ingredients>

[0285] The positive-type photosensitive resin composition may contain optional components such as a dissolution accelerator (F) and a thermosetting agent. In this specification, optional components are defined as those that do not fall under any of components (A) to (E).

[0286] (Dissolution accelerator (F))

[0287] The positive-type photosensitive resin composition may further contain a dissolution accelerator (F) to improve the solubility of the alkali-soluble portion in the developer during development. Examples of dissolution accelerators (F) include organic low-molecular-weight compounds selected from the group consisting of compounds having a carboxyl group and compounds having a phenolic hydroxyl group. Dissolution accelerators (F) may be used alone or in combination of two or more.

[0288] In this specification, "low molecular weight compound" refers to a compound with a molecular weight of 1000 or less unless otherwise specified. The above organic low molecular weight compounds have a carboxyl group or multiple phenolic hydroxyl groups and are alkali soluble.

[0289] Examples of such low-molecular-weight organic compounds include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, and caprylic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, and citraconic acid; aliphatic tricarboxylic acids such as tricarbaryl acid, aconitic acid, and camphoronic acid; and aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemimelitic acid, and mesitylene acid. Examples include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid; aromatic hydroxycarboxylic acids such as dihydroxybenzoic acid, trihydroxybenzoic acid, and gallic acid; other carboxylic acids such as phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamyridene acetate, coumaric acid, and umbellic acid; and aromatic polyols such as catechol, resorcinol, hydroquinone, 1,2,4-benzenetriol, pyrogallol, phloroglucinol, and bisphenol.

[0290] The content of the dissolution accelerator (F) in the positive-type photosensitive resin composition is preferably 0.1 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the total resin components. The lower limit is more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is more preferably 35 parts by mass or less, and even more preferably 20 parts by mass or less. If the content of the dissolution accelerator (F) is above the lower limit based on 100 parts by mass of the total, the dissolution of the resin components can be effectively promoted, and if it is below the upper limit, excessive dissolution of the resin components can be suppressed, thereby improving the pattern formation properties and surface quality of the coating.

[0291] (Thermosetting agent)

[0292] A thermal radical generator can be used as a thermosetting agent. Preferred thermal radical generators include organic peroxides, specifically organic peroxides with a 10-hour half-life temperature of 100°C to 170°C, such as dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

[0293] The content of the thermosetting agent is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total solid content excluding the thermosetting agent.

[0294] <<Coating composition>>

[0295] <Solvent (G)>

[0296] Positive-type photosensitive resin compositions can be dissolved or dispersed in a solvent (G) and used as coating compositions in solution or dispersion form. For example, a coating composition containing a positive-type photosensitive resin composition can be prepared by dissolving resin components (hydrophobic resin (A), and optionally other resins such as alkali-soluble resin (B)) in a solvent (G), and mixing a surfactant (D), and optionally a quinone diazide compound (C) and optional components (dissolution accelerator (F), thermosetting agent, etc.) in predetermined proportions into a solution obtained by dissolving resin components (hydrophobic resin (A), and optionally other resins such as alkali-soluble resin (B)) in a solvent (G). The viscosity of the coating composition can be adjusted to suit the application method by changing the amount of solvent (G).

[0297] Examples of solvents (G) include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol compounds such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; and propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate. Examples include tate compounds; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and cyclohexanone; esters such as ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyethyl acetate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; and amide compounds such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Solvent (G) may be used alone or in combination of two or more.

[0298] The solid content concentration of the coating composition can be appropriately determined depending on the intended use. For example, the solid content concentration of the coating composition can be 1% by mass or more and 60% by mass or less. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less.

[0299] When using pigments, known methods can be used for dispersion and mixing. For example, ball-type devices such as ball mills, sand mills, bead mills, paint shakers, and rocking mills; blade-type devices such as kneaders, paddle mixers, planetary mixers, and Henschel mixers; roll-type devices such as three-roll mixers; and other devices such as lithographs, colloid mills, ultrasonic devices, homogenizers, and rotational / revolutionary mixers may be used. From the viewpoint of dispersion efficiency and fine dispersion, it is preferable to use a bead mill.

[0300] The prepared coating composition is usually filtered before use. Examples of filtration methods include Millipore filters with pore sizes of 0.05 μm to 1.0 μm.

[0301] The coating composition prepared in this way also exhibits excellent long-term storage stability.

[0302] <<How to use the positive-type photosensitive resin composition>>

[0303] When using a positive-type photosensitive resin composition in radiation lithography, first, the positive-type photosensitive resin composition is dissolved or dispersed in a solvent to prepare a coating composition. Next, the coating composition can be applied to the substrate surface, and the solvent can be removed by means of heating or other means to form a film. The method of applying the coating composition to the substrate surface is not particularly limited, and for example, a spray method, roll coating method, slit method, or spin coating method can be used.

[0304] After applying the coating composition to the substrate surface, the solvent is usually removed by heating to form a film (pre-baking). The heating conditions vary depending on the type and proportion of each component, but typically the film can be obtained by heating at a temperature of 70°C to 130°C, for example, 30 seconds to 20 minutes on a hot plate, or 1 minute to 60 minutes in an oven. In this embodiment, the thickness of the formed film is preferably 2 μm to 3 μm.

[0305] Next, the pre-baked film is irradiated with radiation (e.g., visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, gamma rays, or synchrotron radiation) through a photomask having a predetermined pattern (exposure step). Preferred radiation is ultraviolet to visible light having a wavelength of 250 nm to 450 nm. In this embodiment, the radiation is i-rays. In another embodiment, the radiation is gh-i-rays.

[0306] When a positive-type photosensitive resin composition contains a protective resin (B3) as an alkali-soluble resin (B), a heat treatment (PEB) can be performed after the exposure process to promote the decomposition of acid-degradable groups. PEB promotes the deprotection of protected alkali-soluble functional groups in the protective resin (B3) of the exposed area, thereby further increasing the alkali solubility of the exposed area. Although the heating conditions vary depending on the type and proportion of each component, PEB can usually be performed by heating at a temperature of 70°C to 140°C, for example, for 30 seconds to 20 minutes on a hot plate, or for 1 minute to 60 minutes in an oven.

[0307] In one embodiment of this product, the PEB process may be omitted after the exposure process. This prevents the film from flowing or deforming due to heating, allowing for the formation of a thick film pattern with high precision, and also reduces the number of steps involved in forming partitions or insulating films.

[0308] After the exposure or PEB process, the film is developed by contacting it with a developer (e.g., alkaline development) to remove unwanted parts and form a pattern on the film (development process). As the developer, aqueous solutions of alkaline compounds such as inorganic alkali compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonane can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, etc. to an alkaline aqueous solution can also be used as the developer. The development time is usually between 30 seconds and 180 seconds. The development method can be any of the following: liquid immersion method, shower method, or dipping method. After development, the film can be rinsed with running water for 30 to 90 seconds to remove unwanted parts, and then air-dried with compressed air or compressed nitrogen to form a pattern.

[0309] Subsequently, the patterned coating can be heated using a heating device such as a hot plate or oven at, for example, 100°C to 350°C for 20 minutes to 200 minutes to obtain a cured coating (post-bake, heat treatment step). During the heat treatment, the temperature may be maintained constant, continuously increased, or increased in stages. The heat treatment is preferably carried out under a nitrogen gas atmosphere.

[0310] (Percentage of remaining film)

[0311] In this embodiment, a positive-type photosensitive resin composition is applied to a film thickness of 3 ± 0.3 μm after pre-baking. The film is then formed by pre-baking at 125°C for 120 seconds, followed by alkaline development at 23°C with a 2.38% by mass aqueous tetramethylammonium hydroxide solution for 60 seconds. The residual film rate, defined by the following formula, is 90% or higher, preferably 95% or higher, and more preferably 99% or higher. The residual film rate is an indicator of the solubility of the unexposed areas. A higher residual film rate indicates a greater difference in solubility between the exposed and unexposed areas, allowing for the formation of a thick film pattern with a large height difference with high precision. Residual film rate (%) = Film thickness after development (μm) / Film thickness before development (μm) ... (Formula)

[0312] (optical density)

[0313] In embodiments in which the positive-type photosensitive resin composition contains a colorant (E), the optical density (OD value) of the cured film of the positive-type photosensitive resin composition is preferably 0.5 or more per 1 μm of film thickness, more preferably 0.7 or more, and even more preferably 1.0 or more. If the OD value of the cured film per 1 μm of film thickness is equal to or greater than the above lower limit, sufficient light shielding can be obtained.

[0314] The method for manufacturing an organic EL element partition or organic EL element insulating film according to this embodiment includes: preparing a coating composition by dissolving or dispersing a positive-type photosensitive resin composition in a solvent; applying the coating composition to a substrate to form a film; removing the solvent contained in the film to dry the film; exposing the film by irradiating the dried film with radiation through a photomask; developing the exposed film by contacting it with a developer solution to form a pattern on the film; and heat-treating the patterned film at a temperature of 100°C to 350°C to form an organic EL element partition or organic EL element insulating film. The above PEB can also be performed after exposure and before development. In embodiments in which the positive-type photosensitive resin composition according to this specification includes a colorant (E), it is possible to form a highly sensitive and high-precision thick film pattern.

[0315] <<Organic EL element partition>>

[0316] One of the preferred examples of the present embodiment includes an organic EL element partition wall containing a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition contains a colorant (E). The cured product of the positive photosensitive resin composition according to the present embodiment used for the organic EL element partition wall can be obtained by the curing method described above. The cured product can be said to be a cured product obtained by curing the positive photosensitive resin composition according to the present embodiment. And the process of the manufacturing method of the organic EL element partition wall according to the present embodiment is not particularly limited, and known processes and their conditions can be appropriately adopted. For example, it can be obtained by the manufacturing method including the coating process, the reduced-pressure drying process, the pre-baking process, the exposure process, the alkali development process, and the post-baking process described above. The organic EL element partition wall according to the present embodiment can be preferably used as a black organic EL element partition wall. As described above, in a display device such as an organic EL display, in order to improve the display characteristics, a partition wall (partition wall material) is used in the interval part of the colored pattern in the display area or the edge of the peripheral part of the display area. Among the partition walls, the black partition wall has higher light-shielding properties than other colors. Therefore, during the UV irradiation in the exposure process, (i) problems such as ultraviolet rays being difficult to reach the deep part of the coating film of the positive photosensitive resin composition, and (ii) problems such as the exposure time becoming long and the productivity decreasing tend to occur easily. However, according to the present embodiment, such problems can be particularly effectively prevented, so that the high performance and high definition of pixels can be realized at a higher level than before.

[0317] <<Organic EL element insulating film>>

[0318] One of the preferred examples of the present embodiment includes an organic EL element insulating film containing a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition preferably contains a colorant (E). The cured product of the positive photosensitive resin composition according to the present embodiment used for the organic EL element insulating film can be obtained by the curing method described above. And the steps of the manufacturing method of the organic EL element insulating film according to the present embodiment are not particularly limited, and known steps and their conditions can be appropriately adopted. For example, in the case of an organic EL element used in an organic EL display, since its light-emitting layer and the like are easily affected by moisture and impurity gases and tend to deteriorate, it is meaningful to be able to provide an insulating film with excellent reliability. The organic EL element insulating film according to the present embodiment is expected to be able to meet such requirements.

[0319] <<Organic EL Element>>

[0320] One of the preferred examples of the present embodiment includes an organic EL element containing a cured product of a positive photosensitive resin composition. The positive photosensitive resin composition contains a colorant (E) containing a black dye. The cured product of the positive photosensitive resin composition according to the present embodiment used for the organic EL element can be obtained by the curing method described above. By using this cured product for the partition member, insulating film and other members described above, an excellent organic EL element can be realized. In particular, when applied to a black member, it can exhibit particularly excellent effects compared to the prior art.

[0321] As described above, the positive-type photosensitive resin composition according to this embodiment can be suitably used in radiation lithography for forming partitions and insulating films of organic EL elements. With respect to partitions of organic EL elements, it can be used in the process as a positive-type photosensitive resin composition for forming partition materials. Furthermore, in the case of a positive-type photosensitive resin composition containing the above-mentioned colorant (E), an organic EL element equipped with a partition or insulating film formed using it can be suitably used as an electronic component of a display device that exhibits good contrast. In particular, when used as a black positive-type resist, a black partition material, etc., it is possible to achieve a good balance of high sensitivity, residue removal, low film loss, and fine pattern formation at a level that was not possible with conventional methods, while maintaining sufficient light shielding properties.

[0322] The present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to these examples.

[0323] <<(1) Raw materials>>

[0324] The raw materials used in the examples and comparative examples were manufactured or obtained as follows.

[0325] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the resin were calculated using a calibration curve created with polystyrene standards under the following measurement conditions: Instrument name: Shodex® GPC-101 Column: Shodex® LF-804 Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: Shodex® RI-71 Temperature: 40°C

[0326] <Hydrophobic resin (A)>

[0327] (Manufacturing Example 1) Hydrophobic Resin (A): Production of PHMA Homopolymer 27.1 g of 4-hydroxyphenyl methacrylate (p-hydroxyphenyl methacrylate, PHMA, Resonaq Corporation "PQMA") was completely dissolved in 44.14 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) as a solvent. 2.86 g of V-601 (Fujifilm Wako Pure Chemical Corporation) was completely dissolved in 4.29 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) as a polymerization initiator. The two resulting solutions were simultaneously added dropwise over 2 hours to 90.5 g of isopropyl acetate (Shinko Organic Chemicals Co., Ltd.) heated to 89°C under a nitrogen gas atmosphere in a 300 mL three-necked flask equipped with a reflux condenser, and then reacted at 90°C for 4 hours. 50 g of the reaction solution, cooled to room temperature, was added dropwise to 250 g of hexane to precipitate the polymer. The precipitated polymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 15.63 g of a white powder (poly(p-hydroxyphenyl methacrylate), PHMA homopolymer). The obtained PHMA homopolymer had a number-average molecular weight of 4418, a weight-average molecular weight of 8870, and a Mw / Mn ratio of 2.01.

[0328] (Production Example 2) Hydrophobic Resin (A): Production of PHMA / DNQ binary copolymer (75 / 25) In a 300 mL three-necked flask equipped with a reflux tubing, 14.74 g of the PHMA homopolymer from Production Example 1 and 5.55 g of 2-diazo-1-naphthol-4-sulfonyl chloride (DNQ, trademark name: SK-30C, Showa Chemical Co., Ltd.) were completely dissolved in 13.75 g of acetone as a solvent. As a reaction catalyst, 1.74 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 15.7 g of acetone. The resulting reaction catalyst solution was added dropwise to the three-necked flask at room temperature under a nitrogen gas atmosphere over 30 minutes, and then reacted at room temperature for 3 hours. 3.0 g of 10% HCl aqueous solution was added to terminate the reaction. 50 g of the reaction solution was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 13.21 g of white powder (a binary copolymer of PHMA and DNQ (PHMA / DNQ = 75 / 25), and a PHMA / DNQ binary copolymer). The obtained PHMA / DNQ binary copolymer (75 / 25) had a number-average molecular weight of 6238, a weight-average molecular weight of 12900, and a Mw / Mn ratio of 2.07.

[0329] The above "PHMA / DNQ binary copolymer (75 / 25)" indicates that the proportion of structural units derived from PHMA (corresponding to formula (1b) above) in the total monomer units of the resin was 75 mol%, and the proportion of structural units derived from 2-diazo-1-naphthol-4-sulfonyl chloride (corresponding to formula (Y1) above) in the total monomer units of the resin was 25 mol%. The same notation will be used hereafter unless otherwise specified.

[0330] (Production Example 3) Hydrophobic Resin (A): Production of PHMA / DNQ binary copolymer (65 / 35) In a 300 mL three-necked flask equipped with a reflux tubing, 14.74 g of the PHMA homopolymer from Production Example 1 and 7.77 g of 2-diazo-1-naphthol-4-sulfonyl chloride (DNQ, trademark name: SK-30C, Showa Chemical Co., Ltd.) were completely dissolved in 13.75 g of acetone as a solvent. 1.74 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 15.7 g of acetone as a reaction catalyst. The resulting reaction catalyst solution was added dropwise to the three-necked flask at room temperature under a nitrogen gas atmosphere over 30 minutes, and then reacted at room temperature for 3 hours. 3.0 g of 10% HCl aqueous solution was added to terminate the reaction. 50 g of the reaction solution was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 14.21 g of a white powder (PHMA / DNQ binary copolymer (65 / 35)). The obtained PHMA / DNQ binary copolymer had a number-average molecular weight of 6128, a weight-average molecular weight of 13100, and a Mw / Mn ratio of 2.14.

[0331] Furthermore, the above "PHMA / DNQ binary copolymer (65 / 35)" indicates that the proportion of PHMA in the total monomer units of the resin was 65 mol%, and the proportion of monomer units containing 2-diazo-1-naphthol-4-sulfonyl chloride in the total monomer units of the resin was 35 mol%.

[0332] (Production Example 4) Hydrophobic resin (A): Production of PHMA / TBDMS / DNQ ternary copolymer In a 300 mL three-necked flask equipped with a reflux tubing, 8.37 g of the PHMA homopolymer from Production Example 1, 2.43 g of tert-butyldimethylchlorosilane (TBDMS, trademark name: TBMS, Shin-Etsu Chemical Co., Ltd.), and 1.62 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) as a reaction catalyst were completely dissolved in 27.70 g of acetone as a solvent, and the mixture was reacted at room temperature for 3 hours. 2.68 g of 2-diazo-1-naphthol-4-sulfonyl chloride (DNQ, trademark name: SK-30C, Showa Chemical Co., Ltd.) was added to the reaction mixture in a three-necked flask. 1.74 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 15.7 g of acetone to form a catalyst solution. This catalyst solution was added dropwise to the three-necked flask at room temperature under a nitrogen atmosphere over 30 minutes, and the reaction was then allowed to proceed at room temperature for 3 hours. 3.0 g of 10% HCl aqueous solution was added to terminate the reaction. 50 g of the reaction solution was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 11.28 g of a white powder (PHMA / TBDMS / DNQ ternary copolymer) (57 / 14 / 29). The obtained PHMA / TBDMS / DNQ ternary copolymer had a number-average molecular weight of 6238, a weight-average molecular weight of 12900, and a Mw / Mn ratio of 2.07.

[0333] The above "PHMA / TBDMS / DNQ ternary copolymer (57 / 14 / 29)" indicates that the proportion of structural units derived from PHMA (corresponding to formula (1b) above) in the total monomer units of the resin was 57 mol%, the proportion of structural units derived from TBDMS (corresponding to formula (1a) above) in the total monomer units of the resin was 14 mol%, and the proportion of structural units derived from 2-diazo-1-naphthol-4-sulfonyl chloride (corresponding to formula (Y1) above) in the total monomer units of the resin was 29 mol%.

[0334] (Production Example 5) Hydrophobic Resin (A): Production of PHS / DNQ Binary Copolymer (75 / 25) 9.94 g of PHS homopolymer (homopolymer of p-hydroxystyrene (PHS), trademark name: Marcalinka S-2P, Maruzen Petrochemical Co., Ltd.) and 5.55 g of 2-diazo-1-naphthol-4-sulfonyl chloride (DNQ, trademark name: SK-30C, Showa Chemical Co., Ltd.) were completely dissolved in 13.75 g of acetone, the solvent, in a 300 mL three-necked flask equipped with a reflux condenser. 1.74 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 15.7 g of acetone as a reaction catalyst. The resulting reaction catalyst solution was added dropwise to a three-necked flask at room temperature under a nitrogen gas atmosphere over 30 minutes, and then reacted at room temperature for 3 hours. 3.0 g of 10% HCl aqueous solution was added to terminate the reaction. 50 g of the reaction solution was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 14.74 g of a white powder (PHS / DNQ binary copolymer (75 / 25)). The obtained PHS / DNQ binary copolymer (75 / 25) had a number-average molecular weight of 6323, a weight-average molecular weight of 12554, and a Mw / Mn ratio of 1.99.

[0335] Furthermore, the above "PHS / DNQ binary copolymer (75 / 25)" indicates that PHS accounts for 75 mol% of the total monomer units of the resin, and monomer units containing 2-diazo-1-naphthol-4-sulfonyl chloride account for 25 mol% of the total monomer units of the resin.

[0336] (Production Example 6) Hydrophobic Resin (A): Production of PHS / DNQ binary copolymer (65 / 35) 9.94 g of PHS homopolymer (trademark: Marukalinka S-2P, Maruzen Petrochemical Co., Ltd.) and 7.77 g of 2-diazo-1-naphthol-4-sulfonyl chloride (DNQ, trademark: SK-30C, Showa Chemical Co., Ltd.) were completely dissolved in 13.75 g of acetone, the solvent, in a 300 mL three-necked flask equipped with a reflux condenser. 1.74 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 15.7 g of acetone as a reaction catalyst. The resulting reaction catalyst solution was added dropwise to a three-necked flask at room temperature under a nitrogen gas atmosphere over 30 minutes, and then reacted at room temperature for 3 hours. 3.0 g of 10% HCl aqueous solution was added to terminate the reaction. 50 g of the reaction solution was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 14.21 g of a white powder (PHS / DNQ binary copolymer (65 / 35)). The obtained PHS / DNQ binary copolymer had a number-average molecular weight of 6422, a weight-average molecular weight of 12980, and a Mw / Mn ratio of 2.02.

[0337] Furthermore, the above-mentioned "PHS / DNQ binary copolymer (65 / 35)" indicates that the proportion of structural units derived from PHS (corresponding to formula (1b') above) in the total monomer units of the resin was 65 mol%, and the proportion of structural units derived from 2-diazo-1-naphthol-4-sulfonyl chloride (corresponding to formula (Y1') above) in the total monomer units of the resin was 35 mol%.

[0338] (Manufacturing Example 7) Hydrophobic Resin (A): Production of PHS / TBDMS / DNQ Ternary Copolymer In a 300 mL three-necked flask equipped with a reflux tubing, 5.64 g of PHS homopolymer (trademark: Marukalinka S-2P, Maruzen Petrochemical Co., Ltd.), 2.43 g of tert-butyldimethylchlorosilane (TBDMS, trademark: TBMS, Shin-Etsu Chemical Co., Ltd.), and 1.62 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) as a reaction catalyst were completely dissolved in 27.70 g of acetone as a solvent and reacted at room temperature for 3 hours. 2.68 g of 2-diazo-1-naphthol-4-sulfonyl chloride (DNQ, trademark name: SK-30C, Showa Chemical Co., Ltd.) was added to the reaction mixture in a three-necked flask. 1.74 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 15.7 g of acetone to form a catalyst solution. This catalyst solution was added dropwise to the three-necked flask at room temperature under a nitrogen atmosphere over 30 minutes, and the reaction was then allowed to proceed at room temperature for 3 hours. 3.0 g of 10% HCl aqueous solution was added to terminate the reaction. 50 g of the reaction solution was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 6.82 g of a white powder (PHS / TBDMS / DNQ terpolymer (57 / 14 / 29)). The obtained PHS / TBDMS / DNQ ternary copolymer had a number-average molecular weight of 6442, a weight-average molecular weight of 13100, and a Mw / Mn ratio of 2.03.

[0339] Furthermore, the above "PHS / TBDMS / DNQ terpolymer (57 / 14 / 29)" indicates that the proportion of structural units derived from PHS (corresponding to formula (1b') above) in the total monomer units of the resin is 57 mol%, the proportion of structural units derived from TBDMS (corresponding to formula (1a') above) in the total monomer units of the resin is 14 mol%, and the proportion of structural units derived from 2-diazo-1-naphthol-4-sulfonyl chloride (corresponding to formula (Y1') above) in the total monomer units of the resin is 29 mol%.

[0340] (Production Example 8) Hydrophobic Resin (A): Production of PHS / DNQ Binary Copolymer (60 / 40) 9.94 g of PHS homopolymer (trademark: Marukalinka S-1P, Maruzen Petrochemical Co., Ltd.) and 8.88 g of 2-diazo-1-naphthol-4-sulfonyl chloride (DNQ, trademark: SK-30C, Showa Chemical Co., Ltd.) were completely dissolved in 13.75 g of acetone, the solvent, in a 300 mL three-necked flask equipped with a reflux condenser. 1.74 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 15.7 g of acetone as a reaction catalyst. The resulting reaction catalyst solution was added dropwise to a three-necked flask at room temperature under a nitrogen gas atmosphere over 30 minutes, and then reacted at room temperature for 3 hours. 3.0 g of 10% HCl aqueous solution was added to terminate the reaction. 50 g of the reaction solution was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 17.53 g of a white powder (PHS / DNQ binary copolymer (60 / 40)). The obtained PHS / DNQ binary copolymer had a number-average molecular weight of 1575, a weight-average molecular weight of 3105, and a Mw / Mn ratio of 1.97.

[0341] (Production Example 9) Hydrophobic Resin (A): Production of PHS / DNQ Binary Copolymer (50 / 50) 9.94 g of PHS homopolymer (trademark: Marukalinka S-1P, Maruzen Petrochemical Co., Ltd.) and 11.1 g of 2-diazo-1-naphthol-4-sulfonyl chloride (DNQ, trademark: SK-30C, Showa Chemical Co., Ltd.) were completely dissolved in 13.75 g of acetone, the solvent, in a 300 mL three-necked flask equipped with a reflux condenser. 1.74 g of triethylammonium (Fujifilm Wako Pure Chemical Industries, Ltd.) was completely dissolved in 15.7 g of acetone as a reaction catalyst. The resulting reaction catalyst solution was added dropwise to a three-necked flask at room temperature under a nitrogen gas atmosphere over 30 minutes, and then reacted at room temperature for 3 hours. 3.0 g of 10% HCl aqueous solution was added to terminate the reaction. 50 g of the reaction solution was added dropwise to 250 g of hexane to precipitate the copolymer. The precipitated copolymer was recovered by filtration and vacuum-dried at 80°C for 5 hours, yielding 19.88 g of a white powder (PHS / DNQ binary copolymer (50 / 50)). The obtained PHS / DNQ binary copolymer had a number-average molecular weight of 1473, a weight-average molecular weight of 2896, and a Mw / Mn ratio of 1.97.

[0342] <Alkali-soluble resin (B)>

[0343] (Manufacturing Example 10) Alkali-soluble resin (B): Production of resin (N695OH) having epoxy groups and phenolic hydroxyl groups 75.2 g of γ-butyrolactone (Mitsubishi Chemical Corporation) as a solvent and 37.8 g of "EPICLON® N-695" (DIC Corporation, cresol novolac type epoxy resin, epoxy equivalent 214) as a compound having at least two epoxy groups in one molecule were charged into a 300 mL three-necked flask and dissolved at 60°C under a nitrogen gas atmosphere. 20.1 g of 3,5-dihydroxybenzoic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydroxybenzoic acid compound (0.65 equivalents per 1 equivalent of epoxy) and 0.166 g (0.660 mmol) of triphenylphosphine (Tokyo Chemical Industries, Ltd.) as a reaction catalyst were added and the mixture was reacted at 110°C for 21 hours. The reaction solution was allowed to return to room temperature, diluted with γ-butyrolactone to a solid content of 20% by mass, and filtered to obtain a solution of 274.2 g of resin (N695OH) having epoxy groups and phenolic hydroxyl groups. The number-average molecular weight of the obtained reactant was 3000, the weight-average molecular weight was 5100, the epoxy equivalent was 2200, and the phenolic hydroxyl group equivalent was 161.

[0344] <Quinone diazide compound (C)>

[0345] As the quinone diazide compound (C), "TS-150A" (trade name, Toyo Gosei Kogyo Co., Ltd.; ester of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) and 6-diazo-5,6-dihydro-5-oxonaphthalene-1-sulfonic acid (1,2-naphthoquinone diazide-5-sulfonic acid)) was used.

[0346] The structure of "TS-150A" is shown below. In the formula below, "TS-150A" has an average of 1.5 Rs out of 3 Rs per molecule having a quinone diazide structure.

[0347]

[0348] <Surfactant (D)>

[0349] ​As the surfactant (D), "MEGAFACE EFS-131" (a (meth)acrylic copolymer having no silicon atom in the main chain and having at least one silicon atom-containing hydrocarbon group selected from the group consisting of a silicon atom-containing alkyl group and a silicon atom-containing alkylene group, manufactured by DIC Corporation) was used.

[0350] <Colorant (E)>

[0351] As the colorant, "VALIFAST (registered trademark) BLACK 3804" ("VB3804"), a black dye (a black dye defined by C.I. of Solvent Black 34) manufactured by Orient Chemical Industries Co., Ltd., was used.

[0352] <Solvent (G)>

[0353] As the solvent (G), a mixed solvent of γ-butyrolactone (GBL) and propylene glycol monomethyl ether acetate (PGMEA) (GBL:PGMEA = 40:60 (mass ratio)) was used.

[0354] <<(2) Evaluation Method>>

[0355] The evaluation methods used in the examples and comparative examples are as follows.

[0356] (Sensitivity)

[0357] A positive-type photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 μm. After vacuum drying at room temperature for 60 seconds, pre-baking was performed by heating on a covered hot plate at 125°C for 120 seconds. The film was exposed using an exposure apparatus incorporating an ultra-high pressure mercury lamp (product name "Multi-Light ML-251A / B", Ushio Inc.) via a quartz photomask (having a φ10 μm aperture pattern). The exposure amount was measured using an ultraviolet integrated light meter (product name "UIT-150", light receiving unit "UVD-S365", Ushio Inc.). After exposure, alkaline development was performed for 60 seconds using a spin developing apparatus ("AD-1200", Takizawa Sangyo Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Repeat the above procedure while varying the exposure amount to find the minimum exposure amount (mJ / cm²) at which a pattern with a hole diameter of 10 μm that completely reaches the glass substrate after development can be formed. ２ The sensitivity was defined as ). Comparative Examples 1 and 3 were evaluated as having no sensitivity ("-" in the table) because they were not exposed to light using the above method.

[0358] (Dissolvability of unexposed areas)

[0359] A positive-type photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 μm. After vacuum drying at room temperature for 60 seconds, pre-baking was performed by heating on a covered hot plate at 125°C for 120 seconds. The dry film thickness was measured using an optical film thickness measuring device ("F20-NIR", Filmetrics Inc.), and then alkaline development was performed using a spin developer ("AD-1200", Takizawa Sangyo Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. The film thickness after alkaline development was measured again using an optical film thickness measuring device ("F20-NIR", Filmetrics Inc.), and the film thickness dissolved before and after development (μm) was used as an indicator of the solubility of the unexposed area. A solubility of 0 μm in the unexposed area is equivalent to a residual film rate of 100%, as defined by the following formula. Residual film percentage (%) = Film thickness after development (μm) / Film thickness before development (μm) ... (Formula)

[0360] (OD value of the cured film)

[0361] A positive-type photosensitive resin composition was spin-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of approximately 1.5 μm. Pre-baking was performed by heating on a hot plate at 125°C for 120 seconds. Subsequently, a film was obtained by curing at 250°C for 60 minutes under a nitrogen gas atmosphere. The OD value of the cured film was measured using a transmission densitometer ("BMT-1", Sakata Inx Corporation), and corrected with the OD value of the glass alone to convert it to the OD value per 1 μm of film thickness. The film thickness was measured using an optical film thickness measuring device ("F20-NIR", Filmetrix Co., Ltd.).

[0362] (Measuring the hole diameter)

[0363] A positive-type photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 μm. After 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating on a covered hot plate at 125°C for 120 seconds. The film was exposed using an exposure apparatus incorporating a high-pressure mercury lamp (product name "Multi-Light ML-251A / B", Ushio Inc.) via a quartz photomask (with a φ10 μm aperture pattern). The exposure amount was measured using an ultraviolet integrated light meter (product name "UIT-150", light receiving unit "UVD-S365", Ushio Inc.). After exposure, alkaline development was performed for 60 seconds using a spin developing apparatus ("AD-1200", Takizawa Sangyo Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Exposure amount: 50 (mJ / cm²) ２ In the experiment, the hole diameters of the opened hole pattern were measured using a microscope (magnification 2,000x).

[0364] (Substrate interface residue)

[0365] A positive-type photosensitive resin composition was bar-coated onto a glass substrate (100 mm x 100 mm x 1 mm) to a dry film thickness of 3.0 μm. After 60 seconds of vacuum drying at room temperature, the substrate was pre-baked by heating on a covered hot plate at 125°C for 120 seconds. The film was exposed using an exposure apparatus incorporating a high-pressure mercury lamp (product name "Multi-Light ML-251A / B", Ushio Inc.) via a quartz photomask (with a φ10 μm aperture pattern). The exposure amount was measured using an ultraviolet integrated light meter (product name "UIT-150", light receiving unit "UVD-S365", Ushio Inc.). After exposure, alkaline development was performed for 60 seconds using a spin developing apparatus ("AD-1200", Takizawa Sangyo Co., Ltd.) with a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Exposure amount: 50 (mJ / cm²) ２ In the experiment, the surface of the substrate with the opened hole pattern was observed using an electron microscope (magnification 20,000x) and judged according to the following criteria: ◎: No film-like residue was observed on the surface area (φ10 μm), and no dot residues were observed. 〇: No film-like residue was observed on the surface area (φ10 μm), and very few dot residues (less than 5) were observed. △: No film-like residue was observed on the surface area (φ10 μm), but dot residues (5 or more) were observed. ×: Film-like residue was observed across the entire surface area (φ10 μm).

[0366] <<(3) Preparation and evaluation of positive-type photosensitive resin composition>>

[0367] <Examples 1-9, Comparative Examples 1-3>

[0368] Each component was mixed under the conditions described in Table 1. After visually confirming that the components had dissolved, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a positive-type photosensitive resin composition with a solid content concentration of 12% by mass. In Table 1, the composition values ​​for components other than the solvent are in "parts by mass," and these values ​​are converted to solid content. The composition values ​​for the solvent are also in "parts by mass."

[0369] <Example 1> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHMA-based resin (A), an alkali-soluble resin (B), a surfactant (D), a colorant (E), and a solvent (G) to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass. The positive-type photosensitive resin composition of Example 1 contained 30% by mass of hydrophobic resin (A) based on 100% by mass of solid content. The positive-type photosensitive resin composition of Example 1 contained 42.8% by mass of hydrophobic resin (A) based on the total mass of resin components. Furthermore, the positive-type photosensitive resin composition of Example 1 contained 40% by mass of alkali-soluble resin (B) based on 100% by mass of solid content. In addition, the positive-type photosensitive resin composition of Example 1 contained 57% by mass of alkali-soluble resin (B) based on the total mass of resin components. Furthermore, the amount of surfactant (D) in the positive-type photosensitive resin composition of Example 1 was 0.14 parts by mass (= 0.1 ÷ (30 + 40) × 100) based on 100 parts by mass of the total resin components. The amount of colorant (E) in the positive-type photosensitive resin composition of Example 1 was 43 parts by mass (= 30 ÷ (30 + 40) × 100) based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 1 was 12% by mass.

[0370] <Example 2> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHMA-based resin as the hydrophobic resin (A), an epoxy resin as the alkali-soluble resin (B), a surfactant (D), a black dye as the coloring agent (E), and a solvent (G), to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass, but the positive-type photosensitive resin composition of Example 2 contained 30% by mass of the hydrophobic resin (A) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 2 contained 42.8% by mass of the hydrophobic resin (A) based on the total mass of the resin components. In addition, the positive-type photosensitive resin composition of Example 2 contained 40% by mass of the alkali-soluble resin (B) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 2 contained 57% by mass of alkali-soluble resin (B) based on the total mass of the resin components. In addition, the surfactant (D) content in the positive-type photosensitive resin composition of Example 2 was 0.14 parts by mass based on 100 parts by mass of the total resin components. The colorant (E) content in the positive-type photosensitive resin composition of Example 2 was 43 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 2 was 12% by mass.

[0371] <Example 3> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHS-type resin as the hydrophobic resin (A), an epoxy resin as the alkali-soluble resin (B), a surfactant (D), a black dye as the coloring agent (E), and a solvent (G), to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass, but the positive-type photosensitive resin composition of Example 3 contained 30% by mass of the hydrophobic resin (A) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 3 contained 42.8% by mass of the hydrophobic resin (A) based on the total mass of the resin components. In addition, the positive-type photosensitive resin composition of Example 3 contained 40% by mass of the alkali-soluble resin (B) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 3 contained 57% by mass of alkali-soluble resin (B) based on the total mass of the resin components. In addition, the surfactant (D) content in the positive-type photosensitive resin composition of Example 3 was 0.14 parts by mass based on 100 parts by mass of the total resin components. The colorant (E) content in the positive-type photosensitive resin composition of Example 3 was 43 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 3 was 12% by mass.

[0372] <Example 4> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHS-type resin as the hydrophobic resin (A), an epoxy resin as the alkali-soluble resin (B), a surfactant (D), a black dye as the coloring agent (E), and a solvent (G), to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass, but the positive-type photosensitive resin composition of Example 4 contained 30% by mass of the hydrophobic resin (A) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 4 contained 42.8% by mass of the hydrophobic resin (A) based on the total mass of the resin components. In addition, the positive-type photosensitive resin composition of Example 4 contained 40% by mass of the alkali-soluble resin (B) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 4 contained 57% by mass of alkali-soluble resin (B) based on the total mass of the resin components. In addition, the surfactant (D) content in the positive-type photosensitive resin composition of Example 4 was 0.14 parts by mass based on 100 parts by mass of the total resin components. The colorant (E) content in the positive-type photosensitive resin composition of Example 4 was 43 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 4 was 12% by mass.

[0373] <Example 5> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHMA-based resin as the hydrophobic resin (A), an epoxy resin as the alkali-soluble resin (B), a surfactant (D), a black dye as the coloring agent (E), and a solvent (G), to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass, but the positive-type photosensitive resin composition of Example 5 contained 30% by mass of the hydrophobic resin (A) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 5 contained 42.8% by mass of the hydrophobic resin (A) based on the total mass of the resin components. In addition, the positive-type photosensitive resin composition of Example 5 contained 40% by mass of the alkali-soluble resin (B) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 5 contained 57% by mass of alkali-soluble resin (B) based on the total mass of the resin components. In addition, the surfactant (D) content in the positive-type photosensitive resin composition of Example 5 was 0.14 parts by mass based on 100 parts by mass of the total resin components. The colorant (E) content in the positive-type photosensitive resin composition of Example 5 was 43 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 5 was 12% by mass.

[0374] <Example 6> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHS-type resin as the hydrophobic resin (A), an epoxy resin as the alkali-soluble resin (B), a surfactant (D), a black dye as the coloring agent (E), and a solvent (G), to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass, but the positive-type photosensitive resin composition of Example 6 contained 30% by mass of the hydrophobic resin (A) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 6 contained 42.8% by mass of the hydrophobic resin (A) based on the total mass of the resin components. In addition, the positive-type photosensitive resin composition of Example 6 contained 40% by mass of the alkali-soluble resin (B) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 6 contained 57% by mass of alkali-soluble resin (B) based on the total mass of the resin components. In addition, the surfactant (D) content in the positive-type photosensitive resin composition of Example 6 was 0.14 parts by mass based on 100 parts by mass of the total resin components. The colorant (E) content in the positive-type photosensitive resin composition of Example 6 was 43 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 6 was 12% by mass.

[0375] <Example 7> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHS-type resin as the hydrophobic resin (A), an epoxy resin as the alkali-soluble resin (B), a surfactant (D), a black dye as the coloring agent (E), and a solvent (G), to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass, but the positive-type photosensitive resin composition of Example 7 contained 20% by mass of the hydrophobic resin (A) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 7 contained 28.6% by mass of the hydrophobic resin (A) based on the total mass of the resin components. In addition, the positive-type photosensitive resin composition of Example 7 contained 50% by mass of the alkali-soluble resin (B) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 7 contained 71% by mass of alkali-soluble resin (B) based on the total mass of the resin components. In addition, the surfactant (D) content in the positive-type photosensitive resin composition of Example 7 was 0.14 parts by mass based on 100 parts by mass of the total resin components. The colorant (E) content in the positive-type photosensitive resin composition of Example 7 was 43 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 7 was 12% by mass.

[0376] <Example 8> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHS-type resin as the hydrophobic resin (A), an epoxy resin as the alkali-soluble resin (B), a surfactant (D), a black dye as the coloring agent (E), and a solvent (G), to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass, but the positive-type photosensitive resin composition of Example 8 contained 30% by mass of the hydrophobic resin (A) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 8 contained 42.8% by mass of the hydrophobic resin (A) based on the total mass of the resin components. In addition, the positive-type photosensitive resin composition of Example 8 contained 40% by mass of the alkali-soluble resin (B) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 8 contained 57% by mass of alkali-soluble resin (B) based on the total mass of the resin components. In addition, the surfactant (D) content in the positive-type photosensitive resin composition of Example 8 was 0.14 parts by mass based on 100 parts by mass of the total resin components. The colorant (E) content in the positive-type photosensitive resin composition of Example 8 was 43 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 8 was 12% by mass.

[0377] <Example 9> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHS-type resin as the hydrophobic resin (A), an epoxy resin as the alkali-soluble resin (B), a surfactant (D), a black dye as the coloring agent (E), and a solvent (G), to the composition shown in Table 1. As mentioned above, the values ​​in Table 1 are based on parts by mass, but the positive-type photosensitive resin composition of Example 9 contained 15% by mass of the hydrophobic resin (A) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 9 contained 21.4% by mass of the hydrophobic resin (A) based on the total mass of the resin components. In addition, the positive-type photosensitive resin composition of Example 9 contained 55% by mass of the alkali-soluble resin (B) based on 100% by mass of solid content. Furthermore, the positive-type photosensitive resin composition of Example 9 contained 78.6% by mass of alkali-soluble resin (B) based on the total mass of the resin components. In addition, the surfactant (D) content in the positive-type photosensitive resin composition of Example 9 was 0.14 parts by mass based on 100 parts by mass of the total resin components. The colorant (E) content in the positive-type photosensitive resin composition of Example 9 was 43 parts by mass based on 100 parts by mass of the total resin components. The solid content concentration of the coating composition of Example 9 was 12% by mass.

[0378] <Comparative Example 1> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHMA homopolymer, an epoxy resin which is an alkali-soluble resin (B), a surfactant (D), a black dye which is a coloring agent (E), and a solvent (G), to the composition shown in Table 1.

[0379] <Comparative Example 2> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHMA homopolymer, an epoxy resin which is an alkali-soluble resin (B), a quinone diazide compound (DNQ) (C), a surfactant (D), a black dye which is a coloring agent (E), and a solvent (G), to have the composition shown in Table 1.

[0380] <Comparative Example 3> A positive-type photosensitive resin composition with a solid content of 12% by mass was prepared, containing a PHMA homopolymer, an epoxy resin which is an alkali-soluble resin (B), a surfactant (D), a black dye which is a coloring agent (E), and a solvent (G), to have the composition shown in Table 1.

[0381] Table 1 shows the composition and evaluation results of the positive-type photosensitive resin compositions for each example and comparative example.

[0382]

[0383] The positive-type photosensitive resin compositions of each example were able to reduce the solubility of the unexposed areas to about 0 μm, increase the contrast between the exposed and unexposed areas, and at least confirmed that patterns could be formed with high precision. Therefore, it was at least confirmed that this example offers excellent residue removal, low film loss, and the ability to form fine holes.​

Claims

1. A positive-type photosensitive resin composition comprising a hydrophobic resin (A), a colorant (E) containing a black dye, and a surfactant (D), wherein the hydrophobic resin (A) comprises a structure (X) represented by the following formula (X), and / or a structure (Y) represented by the following formula (Y). (In equation (X), * represents a bond with another element.) (In equation (Y), * represents a bond with another element.) 2. The positive photosensitive resin composition according to claim 1, wherein the component (A) contains a structural unit (1) represented by the following formula (1) and / or a structural unit (1') represented by the following formula (1'). (In formula (1), R １ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ２ represents SiR ３ R ４ R ５ represents, R ３ , R ４ and R ５ each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, r is an integer of 0 to 5, s is an integer of 0 to 5, and r + s is an integer of 1 to 5. ) (In formula (1'), R １ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ２ represents SiR ３ R ４ R ５ represents, R ３ , R ４ and R ５ each independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms, t is an integer of 0 to 5, u is an integer of 0 to 5, and t + u is an integer of 1 to 5. ) 3. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the component (A) comprises a resin having a silicon atom-containing group.

4. The positive-type photosensitive resin composition according to claim 1 or 2, wherein component (A) comprises a structural unit (1a) represented by the following formula (1a), and / or a structural unit (1b) represented by the following formula (1b). (In formula (1a), R １ａ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ａ , R ３ａ , and R ４ａ Each of these independently represents an alkyl group having 1 to 7 carbon atoms. In formula (1b), R １ｂ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １ａ and R １ｂ They may be the same or they may be different.

5. The positive-type photosensitive resin composition according to claim 1 or 2, wherein component (A) comprises a structural unit (1a') represented by the following formula (1a') and / or a structural unit (1b') represented by the following formula (1b'). (In formula (1a'), R １ａ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ａ , R ３ａ , and R ４ａ Each of these independently represents an alkyl group having 1 to 7 carbon atoms. In formula (1b'), R １ｂ R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. １ａ and R １ｂ They may be the same or they may be different.

6. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the component (A) comprises a structural unit (Y1) represented by the following formula (Y1).

7. The positive-type photosensitive resin composition according to claim 1 or 2, wherein component (A) comprises a structural unit (Y1') represented by the following formula (Y1').

8. The positive-type photosensitive resin composition according to claim 6, wherein the proportion of the structural unit (Y1) in the total amount of structural units of component (A) is 10 mol% or more and 50 mol% or less.

9. The positive-type photosensitive resin composition according to claim 7, wherein the proportion of the structural unit (Y1') in the total amount of structural units of component (A) is 10 mol% or more and 50 mol% or less.

10. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the content of component (A) in the positive-type photosensitive resin composition is 5% by mass or more and 60% by mass or less, based on the total mass of the resin components.

11. The positive-type photosensitive resin composition according to claim 1 or 2, wherein the optical density (OD value) of the cured film of the positive-type photosensitive resin composition is 0.5 or more per 1 μm of film thickness.

12. An organic EL element partition comprising a cured product of the positive-type photosensitive resin composition according to claim 1 or 2.

13. An insulating film for an organic EL element comprising a cured product of the positive-type photosensitive resin composition according to claim 1 or 2.

14. An organic EL element comprising a cured product of the positive-type photosensitive resin composition according to claim 1 or 2.

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