JPWO2016024425A1 - Element, insulating film, method for producing the same, and radiation-sensitive resin composition - Google Patents

Abstract

[PROBLEMS] To provide an element for a display or lighting device having an insulating film having a small amount of outgas generation and having a light shielding property in the vicinity of an ultraviolet region. [Solution] (B) a photosensitive agent, (C) at least one resin selected from a resin having a structural unit represented by formula (C1), and a resin having a structure represented by formula (C2); A display or lighting device element having an insulating film formed from a radiation-sensitive resin composition containing the same. [In Formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, L is a monovalent group represented by a specific formula, and in Formula (C2), A ′ is phenolic. A k + m + n-valent aromatic group having a hydroxyl group, L is a monovalent group represented by a specific formula, a plurality of Ls may be the same or different, and * is another A ′ And k is an integer of 0 to 9, m is an integer of 0 to 9, n is an integer of 0 to 9, and k + m + n is an integer of 1 to 9. ]

Description

  The present invention relates to an element, an insulating film, a manufacturing method thereof, and a radiation-sensitive resin composition.

  As a flat panel display, a liquid crystal display (LCD) which is a non-light-emitting type is widespread. In recent years, an electroluminescent display (ELD) which is a self-luminous display is known. In particular, an organic electroluminescence (EL) element using electroluminescence by an organic compound is expected as a light emitting element provided in a next-generation lighting device in addition to a light emitting element provided in a display.

  For example, an organic EL display or lighting device has an insulating film such as a planarization film and a partition wall that partitions pixels. Such an insulating film is generally formed using a radiation sensitive resin composition (see, for example, Patent Documents 1 and 2).

  In recent years, research on thin film transistors (TFTs) using an oxide semiconductor layer has been actively conducted. Patent Document 3 proposes an example in which a polycrystalline thin film of an oxide made of In, Ga, Zn (hereinafter also abbreviated as “IGZO”) is used as a semiconductor layer of a TFT, and Patent Documents 3 and 4 describe an amorphous IGZO film. An example in which a thin film is used for a semiconductor layer of a TFT has been proposed.

JP 2011-107476 A JP 2010-237310 A JP 2004-103957 A International Publication No. 2005/088726 Pamphlet

  In IGZO, light degradation due to natural light, lighting, manufacturing processes, and the like is known. For this reason, when a TFT including a semiconductor layer made of a material having a large light deterioration such as IGZO is used as a driving element for a display or lighting device, particularly a driving element for an organic EL element, from the viewpoint of preventing light deterioration of IGZO, As a characteristic of the above-described insulating film, a light shielding property from ultraviolet to visible light is necessary. However, many insulating films currently used are transparent, for example, in the vicinity of the ultraviolet region.

  In addition, the radiation-sensitive resin composition needs to be able to form an insulating film with a small amount of outgas generation from the viewpoint of manufacturing an element having excellent light emission characteristics.

  The present invention provides a radiation-sensitive resin composition capable of forming an insulating film having a small amount of outgassing and having a light-shielding property in the vicinity of the ultraviolet region, an insulating film formed from the composition, a method for producing the same, and It is an object to provide an element having the insulating film.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by adopting the following configuration, and have completed the present invention. The present invention relates to the following [1] to [15], for example.

  [1] At least one selected from (B) a photosensitive agent, (C) a resin having a structural unit represented by formula (C1) described later, and a resin having a structure represented by formula (C2) described later A display or lighting device element having an insulating film formed from a radiation-sensitive resin composition containing the above resin.

  [2] The above [1], wherein A in the formula (C1) is a divalent group represented by the formula (c1-1), the formula (c1-2), or the formula (c1-3) described later. The element for a display or illumination device described in 1.

  [3] The display or lighting device element according to [1] or [2], wherein the radiation-sensitive resin composition further contains (A) an alkali-soluble resin excluding the resin (C).

  [4] Alkali-soluble resin (A) is polyimide (A1), polyimide precursor (A2), acrylic resin (A3), polysiloxane (A4), polybenzoxazole (A5), and precursor of polybenzoxazole. The display or lighting device element according to [3], which is at least one selected from the body (A6).

  [5] The display or lighting device element according to [4], wherein the polyimide (A1) is a polyimide having a structural unit represented by the formula (A1) described later.

  [6] The display or lighting device element according to [4], wherein the acrylic resin (A3) is a resin obtained by polymerizing at least a radical polymerizable monomer having a carboxyl group.

  [7] The display or lighting device element according to [4], wherein the polysiloxane (A4) is a polysiloxane obtained by reacting an organosilane represented by the formula (a4) described later.

  [8] The photosensitive agent (B) according to any one of [1] to [7], wherein the photosensitive agent (B) is at least one selected from a photoacid generator, a photoradical polymerization initiator, and a photocationic polymerization initiator. Element for display or lighting device.

  [9] In any one of the above [3] to [7], in the radiation sensitive resin composition, the content of the resin (C) is 5 to 200 parts by mass with respect to 100 parts by mass of the resin (A). The display or lighting device element according to Item.

  [10] The display or lighting device element according to any one of [1] to [9], which is an organic electroluminescence element.

  [11] At least one selected from (B) a photosensitive agent, (C) a resin having a structural unit represented by formula (C1) described later, and a resin having a structure represented by formula (C2) described later A radiation sensitive resin composition containing the resin.

  [12] (A) The radiation sensitive resin composition according to [11], further including an alkali-soluble resin excluding the resin (C).

  [13] At least one selected from (B) a photosensitive agent, (C) a resin having a structural unit represented by formula (C1) described later, and a resin having a structure represented by formula (C2) described later An insulating film formed from a radiation-sensitive resin composition containing a resin.

  [14] The insulating film according to [13], wherein the radiation-sensitive resin composition further contains (A) an alkali-soluble resin excluding the resin (C).

  [15] A step of forming a coating film on a substrate using the radiation-sensitive resin composition according to [11] or [12], a step of irradiating at least a part of the coating film, and the radiation The manufacturing method of an insulating film which has the process of developing the irradiated coating film, and the process of heating the developed said coating film.

  According to the present invention, a radiation-sensitive resin composition capable of forming an insulating film having a small amount of outgassing and having a light-shielding property near the ultraviolet region, an insulating film formed from the composition, and a method for manufacturing the same In addition, an element having the insulating film can be provided. For this reason, for example, in an organic EL element having, as a driving element, a thin film transistor including a semiconductor layer made of a material having a large light deterioration such as IGZO, the light deterioration of the substance due to the use of the element can be suppressed. Therefore, an organic EL element with improved reliability and light emission characteristics can be obtained.

FIG. 1 is a cross-sectional view schematically showing the structure of the main part of the organic EL device.

  Hereinafter, the radiation-sensitive resin composition of the present invention, an insulating film formed from the composition, a manufacturing method thereof, and an element having the insulating film will be described.

[Radiation sensitive resin composition]
The radiation-sensitive resin composition of the present invention includes a photosensitive agent (B), a resin having a structural unit represented by the formula (C1) described later, and a resin having a structure represented by the formula (C2) described later. Containing at least one selected resin (C). It is preferable that the composition further contains an alkali-soluble resin (A) described later.

  Since the said composition contains specific resin (C), it can form the insulating film excellent in the light-shielding property in the ultraviolet region vicinity, for example, the light-shielding property in wavelength 400nm. For this reason, in this invention, the optical deterioration of TFT, for example can be prevented. Moreover, since the said composition is excellent in patterning property and radiation sensitivity, it can respond to the request | requirement of the pitch narrowing of a pattern.

  Hereinafter, each component will be described in detail.

[Alkali-soluble resin (A)]
Resin (A) is an alkali-soluble resin excluding resin (C).

  Examples of the resin (A) include polyimide (A1), polyimide precursor (A2), acrylic resin (A3), polysiloxane (A4), polybenzoxazole (A5), and polybenzoxazole precursor ( And at least one selected from A6). The insulating film formed from the resin (A), particularly the insulating film formed from at least one selected from the polyimide (A1), the polyimide precursor (A2), and the polysiloxane (A4) is excellent in heat resistance.

  The weight average molecular weight (Mw) in terms of polystyrene of the resin (A) is usually 2,000 to 500,000, preferably 3,000 to 100,000, as measured by gel permeation chromatography (GPC). 000, more preferably 4,000 to 50,000. When Mw is not less than the lower limit of the above range, an insulating film having sufficient mechanical properties tends to be obtained. When the Mw is not more than the upper limit of the above range, the solubility of the resin (A) in the solvent or developer tends to be excellent.

  In the resin (A), alkali-soluble means that the resin (A) can swell or dissolve in an alkali solution, for example, an aqueous 2.38 mass% tetramethylammonium hydroxide solution.

  The content of the resin (A) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 30 to 75% by mass with respect to 100% by mass of the total solid content in the composition of the present invention. preferable.

<< Polyimide (A1) >>
The polyimide (A1) preferably has a structural unit represented by the formula (A1).

式（Ａ１）中、Ｒ¹は水酸基を有する２価の基であり、Ｘは４価の有機基である。

In formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group.

Examples of R ¹ include a divalent group represented by the formula (a1).

式（ａ１）中、Ｒ²は、単結合、酸素原子、硫黄原子、スルホニル基、カルボニル基、メチレン基、ジメチルメチレン基またはビス（トリフルオロメチル）メチレン基であり；Ｒ³は、それぞれ独立に水素原子、ホルミル基、アシル基またはアルキル基である。ただし、Ｒ³の少なくとも１つは水素原子である。ｎ１およびｎ２は、それぞれ独立に０〜２の整数である。ただし、ｎ１およびｎ２の少なくとも一方は１または２である。ｎ１とｎ２との合計が２以上の場合、複数のＲ³は同一でも異なっていてもよい。

In formula (a1), R ² is a single bond, oxygen atom, sulfur atom, sulfonyl group, carbonyl group, methylene group, dimethylmethylene group or bis (trifluoromethyl) methylene group; R ³ is independently A hydrogen atom, a formyl group, an acyl group or an alkyl group; However, at least one of R ³ is a hydrogen atom. n1 and n2 are each independently an integer of 0-2. However, at least one of n1 and n2 is 1 or 2. When the total of n1 and n2 is 2 or more, the plurality of R ³ may be the same or different.

In R ³ , examples of the acyl group include groups having 2 to 20 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, and an isobutyryl group; examples of the alkyl group include a methyl group, an ethyl group, and n- C1-C20 groups, such as a propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, are mentioned.

  The divalent group represented by the formula (a1) is preferably a divalent group having 1 to 4 hydroxyl groups, and more preferably a divalent group having 2 hydroxyl groups. Examples of the divalent group having 1 to 4 hydroxyl groups represented by the formula (a1) include a divalent group represented by the following formula. In the following formula, * indicates a bond.

Ｘで表される４価の有機基としては、例えば、４価の脂肪族炭化水素基、４価の芳香族炭化水素基、下記式（１）で表される基が挙げられる。Ｘは、テトラカルボン酸二無水物に由来する４価の有機基であることが好ましい。これらの中でも下記式（１）で表される基が好ましい。

Examples of the tetravalent organic group represented by X include a tetravalent aliphatic hydrocarbon group, a tetravalent aromatic hydrocarbon group, and a group represented by the following formula (1). X is preferably a tetravalent organic group derived from tetracarboxylic dianhydride. Among these, a group represented by the following formula (1) is preferable.

上記式（１）中、Ａｒはそれぞれ独立に３価の芳香族炭化水素基であり、Ａは直接結合または２価の基である。前記２価の基としては、例えば、酸素原子、硫黄原子、スルホニル基、カルボニル基、メチレン基、ジメチルメチレン基、ビス（トリフルオロメチル）メチレン基が挙げられる。

In the above formula (1), Ar is each independently a trivalent aromatic hydrocarbon group, and A is a direct bond or a divalent group. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group, and a bis (trifluoromethyl) methylene group.

  Carbon number of a tetravalent aliphatic hydrocarbon group is 4-30 normally, Preferably it is 8-24. Carbon number of a tetravalent aromatic hydrocarbon group and the trivalent aromatic hydrocarbon group in said formula (1) is 6-30 normally, Preferably it is 6-24.

  Examples of the tetravalent aliphatic hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aliphatic hydrocarbon group containing an aromatic ring in at least a part of the molecular structure.

  Examples of the tetravalent chain hydrocarbon group include tetravalent groups derived from chain hydrocarbons such as n-butane, n-pentane, n-hexane, n-octane, n-decane, and n-dodecane. Can be mentioned.

Examples of the tetravalent alicyclic hydrocarbon group include monocyclic hydrocarbons such as cyclobutane, cyclopentane, cyclopentene, methylcyclopentane, cyclohexane, cyclohexene, and cyclooctane; bicyclo [2.2.1] heptane, bicyclo Bicycles such as [3.1.1] heptane, bicyclo [3.1.1] hept-2-ene, bicyclo [2.2.2] octane, bicyclo [2.2.2] oct-5-ene formula hydrocarbons; tricyclo [5.2.1.0 ^2,6] decane, tricyclo [5.2.1.0 ^{2, 6]} deca-4-ene, adamantane, tetracyclo [6.2.1.1 ^{3 , 6} . 0 ^2,7 ] tetravalent groups derived from tricyclic or higher hydrocarbons such as dodecane.

  As the aliphatic hydrocarbon group containing an aromatic ring in at least a part of the molecular structure, for example, those having 3 or less benzene nuclei in the group are preferable, and one is particularly preferable. More specifically, tetravalent groups derived from 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene and the like can be mentioned. .

  In the above description, the tetravalent group derived from the above-described hydrocarbon is a tetravalent group formed by removing four hydrogen atoms from the above-mentioned hydrocarbon. The excluded portion of the four hydrogen atoms is a portion where a tetracarboxylic dianhydride structure can be formed when the four hydrogen atoms are substituted with four carboxyl groups.

  The tetravalent aliphatic hydrocarbon group is preferably a tetravalent group represented by the following formula. In the following formula, * indicates a bond.

４価の芳香族炭化水素基および上記式（１）で表される基としては、例えば、下記式で表される４価の基が挙げられる。なお、下記式において、＊は結合手を示す。

Examples of the tetravalent aromatic hydrocarbon group and the group represented by the above formula (1) include a tetravalent group represented by the following formula. In the following formula, * indicates a bond.

ポリイミド（Ａ１）は、以下に説明するポリイミド前駆体（Ａ２）のイミド化によって得ることができる。ここでのイミド化は完全に進めてもよく、部分的に進めてもよい。すなわちイミド化率は１００％でなくともよい。このため、ポリイミド（Ａ１）は、以下に説明する、式（Ａ２−１）で表される構造単位および式（Ａ２−２）で表される構造単位から選択される少なくとも１種をさらに有してもよい。

A polyimide (A1) can be obtained by imidation of the polyimide precursor (A2) demonstrated below. The imidization here may proceed completely or partially. In other words, the imidation ratio may not be 100%. Therefore, the polyimide (A1) further has at least one selected from the structural unit represented by the formula (A2-1) and the structural unit represented by the formula (A2-2), which will be described below. May be.

  In the polyimide (A1), the imidation ratio is preferably 5% or more, more preferably 7.5% or more, and further preferably 10% or more. The upper limit value of the imidization rate is preferably 50%, more preferably 30%. When the imidation ratio is in the above range, it is preferable from the viewpoint of heat resistance and solubility of the exposed portion in the developer. The imidization rate can be measured under the conditions described in the examples.

  In the polyimide (A1), the total content of the structural units represented by the formula (A1), formula (A2-1), and formula (A2-2) is usually 50% by mass or more, preferably 60% by mass or more. Preferably it is 70 mass% or more, Most preferably, it is 80 mass% or more.

<< Polyimide precursor (A2) >>
The polyimide precursor (A2) is a compound that can generate a polyimide (A1), preferably a polyimide (A1) having a structural unit represented by the formula (A1), by dehydration and cyclization (imidization). . Examples of the polyimide precursor (A2) include polyamic acid and polyamic acid derivatives.

(Polyamic acid)
The polyamic acid has a structural unit represented by the formula (A2-1).

式（Ａ２−１）中、Ｒ¹は水酸基を有する２価の基であり、Ｘは４価の有機基である。Ｒ¹で表される水酸基を有する２価の基およびＸで表される４価の有機基としては、各々式（Ａ１）中のＲ¹およびＸとして例示した基と同様なものが挙げられる。

In formula (A2-1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. Examples of the divalent group having a hydroxyl group represented by R ¹ and the tetravalent organic group represented by X include the same groups as those exemplified as R ¹ and X in the formula (A1).

  In the polyamic acid, the content of the structural unit represented by the formula (A2-1) is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. is there.

(Polyamic acid derivative)
The polyamic acid derivative is a derivative synthesized by esterification of polyamic acid or the like. As a polyamic acid derivative, the polymer which substituted the hydrogen atom of the carboxyl group in the structural unit represented by the formula (A2-1) which a polyamic acid has with another group is mentioned, for example, A polyamic acid ester is preferable.

  The polyamic acid ester is a polymer in which at least a part of the carboxyl group of the polyamic acid is esterified. Examples of the polyamic acid ester include a polymer having a structural unit represented by the formula (A2-2) that can produce a polyimide (A1) having the structural unit represented by the formula (A1).

式（Ａ２−２）中、Ｒ¹は水酸基を有する２価の基であり、Ｘは４価の有機基であり、Ｒ⁴はそれぞれ独立に炭素数１〜５のアルキル基である。Ｒ¹で表される水酸基を有する２価の基およびＸで表される４価の有機基としては、各々式（Ａ１）中のＲ¹およびＸとして例示した基と同様なものが挙げられる。Ｒ⁴で表される炭素数１〜５のアルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられる。

In formula (A2-2), R ¹ is a divalent group having a hydroxyl group, X is a tetravalent organic group, and R ⁴ is independently an alkyl group having 1 to 5 carbon atoms. Examples of the divalent group having a hydroxyl group represented by R ¹ and the tetravalent organic group represented by X include the same groups as those exemplified as R ¹ and X in the formula (A1). Examples of the alkyl group having 1 to 5 carbon atoms represented by R ⁴ include a methyl group, an ethyl group, and a propyl group.

  In the polyamic acid ester, the content of the structural unit represented by the formula (A2-2) is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. It is.

<< Synthesis Method of Polyimide (A1) and Polyimide Precursor (A2) >>
The polyamic acid which is a polyimide precursor (A2) can be obtained, for example, by polymerizing a tetracarboxylic dianhydride, a diamine having a hydroxyl group and, if necessary, another diamine in combination. The proportion of these used is, for example, 0.3 to 4 mol, preferably approximately equimolar, with respect to 1 mol of the tetracarboxylic dianhydride. In the polymerization, the mixed solution of the tetracarboxylic dianhydride and the total diamine is preferably heated at 50 ° C. to 200 ° C. for 1 hour to 24 hours.

  The polyamic acid derivative which is the polyimide precursor (A2) can be synthesized by esterifying the carboxyl group of the polyamic acid. There is no limitation in particular as a method of esterification, A well-known method is applicable.

  The polyimide (A1) can be synthesized, for example, by synthesizing a polyamic acid by the above method and then dehydrating and cyclizing (imidizing) the polyamic acid; and a polyamic acid derivative is synthesized by the above method. Then, it can also synthesize | combine by imidating this polyamic acid derivative.

  As the imidization reaction of the polyamic acid and the polyamic acid derivative, known methods such as a heat imidization reaction and a chemical imidation reaction can be applied. In the case of the heating imidization reaction, it is preferable to heat a solution containing a polyamic acid and / or a polyamic acid derivative at 120 ° C. to 210 ° C. for 1 hour to 16 hours.

  Moreover, when diamine is used excessively with respect to tetracarboxylic dianhydride, for example, dicarboxylic acid such as maleic anhydride is used as an end-capping agent for sealing the end groups of polyimide, polyamic acid and polyamic acid derivatives. Anhydrides may be used.

  As a polymerization solvent used for the synthesis of the resin (A) such as the polyimide (A1) and the polyimide precursor (A2), a raw material for synthesis and a solvent capable of dissolving the resin (A) are preferable. As a polymerization solvent, the solvent similar to the solvent illustrated as the solvent (E) mentioned later can be used. The same applies to the synthesis of other resins (A3) to (A6) described later.

  The polyimide (A1) and the polyimide precursor (A2) preferably have the specific structure having a hydroxyl group, and thereby have excellent solubility in the solvent (E) described later.

<< Acrylic resin (A3) >>
The acrylic resin (A3) is, for example, a resin obtained by polymerizing at least a radical polymerizable monomer having a carboxyl group. For example, a radical polymerizable monomer (a3-1) having a crosslinkable group, a radical polymerizable monomer (a3-2) having a carboxyl group, and other radical polymerizable monomers (a3- Examples thereof include resins obtained by polymerizing 3).

  Hereinafter, the monomers (a3-1) to (a3-3) are also referred to as “components (a3-1) to (a3-3)”, respectively, and the components (a3-1) and (a3-2) used here. ) And component (a3-3) will be sequentially described.

(Component (a3-1))
The crosslinkable group in the component (a3-1) is a crosslinkable group other than a carboxyl group, and examples thereof include an epoxy group and an oxetanyl group.

  Examples of the component (a3-1) include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 3-ethyl p-vinylbenzoate Examples include oxetane-3-ylmethyl ester and p-vinylphenyl-3-ethyloxet-3-ylmethyl ether. When the acrylic resin (A3) obtained by using the component (a3-1) is used, heat resistance and chemical resistance are high, and a small pattern can be formed.

  The component (a3-1) can be used alone or in combination of two or more.

  In synthesizing the acrylic resin (A3), the component (a3-1) is preferably used in an amount of 1 to 70% by mass based on the total mass of all monomers. Such a range is preferable because the size of the pattern obtained from the composition of the present invention is close to the mask dimension and the chemical resistance of the coating film is increased. When the said range of a component (a3-1) is 10-65 mass%, heat resistance becomes high and is more preferable. It is further preferable that the range of the component (a3-1) is 15 to 50% by mass because the developability becomes better.

(Component (a3-2))
Examples of the component (a3-2) include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and ω-carboxypolycaprolactone. Mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl], cyclohexene-3,4-dicarboxylic acid mono [2- (meta ) Acryloyloxyethyl]. Among these, (meth) acrylic acid and succinic acid mono (2-methacryloyloxyethyl) are preferable. Particularly, when (meth) acrylic acid is used, the pattern size of the composition is close to the mask dimension, and transparency. Is high, there are few development residues, and the composition excellent in storage stability is obtained.

  The component (a3-2) can be used alone or in combination of two or more.

  In synthesizing the acrylic resin (A3), the component (a3-2) is preferably used in an amount of 5 to 50% by mass based on the total mass of all monomers. Within such a range, the developability of the composition of the present invention with an alkaline aqueous solution is improved, which is preferable. It is more preferable that the range of the component (a3-2) is 6 to 40% by mass because the pattern size is close to the mask dimension. It is more preferable that the range of the component (a3-2) is 7 to 32% by mass because the composition becomes highly sensitive.

(Component (a3-3))
The component (a3-3) is not particularly limited as long as it is a radical polymerizable monomer copolymerizable with the components (a3-1) and (a3-2). For example, styrene, methylstyrene, vinyltoluene, chloromethylstyrene, (meth) acrylamide, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy Ethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, N-acryloylmorpholine, indene, and 5-tetrahydrofurfurylo Such as aryloxycarbonyl pentyl acrylate, (meth) acrylic acid ester of the compound obtained by modifying tetrahydrofurfuryl alcohol ε- caprolactone.

  When the component (a3-3) is used in a range of 15 to 85% by mass with respect to the total mass of all monomers used for the synthesis of the acrylic resin (A3), the composition of the present invention is applied, exposed and developed. Furthermore, the pattern size is close to the mask dimension, and a desired pattern can be obtained with a low exposure amount, which is preferable. Considering the balance between development time and adhesion, the range of the component (a3-3) is preferably 20 to 78% by mass.

(Acrylic resin (A3) polymerization method)
The acrylic resin (A3) can be obtained, for example, by polymerizing a mixture of radically polymerizable monomers containing the component (a3-1), the component (a3-2) and the component (a3-3). The method for polymerizing the monomer is not particularly limited, but radical polymerization in a solution using a solvent is preferable. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 3 to 24 hours. In addition, the polymerization can be performed under any pressure of pressure, reduced pressure, or atmospheric pressure.

  Examples of the polymerization initiator used when synthesizing the acrylic resin (A3) include compounds that generate radicals by heat, and examples thereof include azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropyl). An azo initiator such as Pionate) or a peroxide initiator such as benzoyl peroxide can be used. In order to adjust the molecular weight, a suitable amount of a chain transfer agent such as thioglycolic acid may be added.

<< Polysiloxane (A4) >>
Examples of the polysiloxane (A4) include polysiloxane obtained by reacting an organosilane represented by the formula (a4).

式（ａ４）中、Ｒ¹は水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数６〜１５のアリール基含有基、炭素数２〜１５のエポキシ環含有基、または前記アルキル基に含まれる１または２以上の水素原子を置換基に置き換えてなる基（置換体）であり、Ｒ¹が複数ある場合はそれぞれ同一でも異なっていてもよく；Ｒ²は水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアシル基、または炭素数６〜１５のアリール基であり、Ｒ²が複数ある場合はそれぞれ同一でも異なっていてもよく；ｎは０〜３の整数である。

In formula (a4), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group-containing group having 6 to 15 carbon atoms, or an epoxy ring having 2 to 15 carbon atoms. group, or the alkyl group formed by substituting a substituent one or more hydrogen atoms contained in the group (substituents) may be the same or different each when R ¹ is more; R ² is A hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and when there are a plurality of R ^{2 s} , they may be the same or different; n Is an integer from 0 to 3.

  Examples of the substituent include at least one selected from a halogen atom, an amino group, a hydroxyl group, a mercapto group, and a (meth) acryloyloxy group.

Examples of the alkyl group and its substituent in R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and an n-decyl group. , Trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3- (meth) acryloyloxypropyl group Can be mentioned.

Examples of the alkenyl group for R ¹ include a vinyl group.

Examples of the aryl group-containing group in R ¹ include an aryl group such as a phenyl group, a tolyl group, and a naphthyl group; a hydroxyaryl group such as a p-hydroxyphenyl group; an aralkyl group such as a benzyl group and a phenethyl group; -Hydroxyphenyl) ethyl group, hydroxy (aralkyl group) such as 2- (p-hydroxyphenyl) ethyl group; 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl group.

Examples of the epoxy ring-containing group in R ¹ include a 3-glycidoxypropyl group and a 2- (3,4-epoxycyclohexyl) ethyl group.

Examples of the acyl group for R ² include an acetyl group.

Examples of the aryl group for R ² include a phenyl group.

  N in the formula (a4) is an integer of 0 to 3. A tetrafunctional silane when n = 0, a trifunctional silane when n = 1, a bifunctional silane when n = 2, and a monofunctional silane when n = 3.

  Examples of the organosilane include tetrafunctional silanes such as tetramethoxysilane and tetraphenoxysilane; methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 3-glycidoxypropyltri Trifunctional silanes such as methoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; dimethyldimethoxysilane, diphenyldimethoxysilane Bifunctional silane such emissions; include monofunctional silanes such as trimethyl methoxy silane. Among these organosilanes, trifunctional silanes are preferable from the viewpoint of crack resistance and hardness of the insulating film.

  Examples of the organosilane include compounds described in JP 2013-210558 A, JP 2014-106250 A, JP 2014-149330 A, and the like.

  Organosilanes may be used singly or in combination of two or more.

From the viewpoint of achieving both crack resistance and hardness of the insulating film, the content of the phenyl group contained in the polysiloxane (A4) is preferably 20 to 70 mol, more preferably 35 to 100 mol of Si atoms. 55 moles. When the phenyl group content is less than or equal to the above upper limit value, an insulating film having a high hardness tends to be obtained, and when the phenyl group content is greater than or equal to the lower limit value, an insulating film having a high crack resistance tends to be obtained. It is in. The content of the phenyl group is measured, for example, by measuring the ²⁹ Si-nuclear magnetic resonance spectrum of polysiloxane (A4), and the peak area of Si to which the phenyl group is bonded and the peak area of Si to which the phenyl group is not bonded. It can be obtained from the ratio.

  The polysiloxane (A4) can be obtained, for example, by hydrolyzing and partially condensing the above organosilane. A general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to organosilane, and the mixture is heated and stirred. During the stirring, hydrolysis by-products such as alcohol and condensation by-products such as water may be distilled off as necessary. Although reaction temperature is not specifically limited, Usually, it is the range of 0 to 200 degreeC. The reaction time is not particularly limited, but is usually in the range of 1 to 48 hours.

  The addition amount of the solvent is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the organosilane. Moreover, the addition amount of water used for the hydrolysis reaction is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group.

  Examples of the catalyst include an acid catalyst and a base catalyst. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid, and anhydrides thereof. Examples of the base catalyst include triethylamine, tripropylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, and alkoxysilane having an amino group. The addition amount of the catalyst is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the organosilane.

<< Polybenzoxazole (A5) >>
The polybenzoxazole (A5) preferably has a structural unit represented by the formula (A5).

式（Ａ５）中、Ｘ¹は芳香族環を少なくとも１つ含む４価の基であり、Ｙ¹は脂環式炭化水素環および芳香族炭化水素環から選ばれる環を少なくとも１つ含む２価の基である。Ｘ¹に結合するＮとＯは、Ｘ¹中の同一芳香族環上の隣り合った炭素原子に結合し、ベンゾオキサゾール環を形成している。

In formula (A5), X ¹ is a tetravalent group containing at least one aromatic ring, and Y ¹ is a divalent group containing at least one ring selected from an alicyclic hydrocarbon ring and an aromatic hydrocarbon ring. It is the basis of. N and O bonded to X ¹ are bonded to adjacent carbon atoms on the same aromatic ring in X ¹ to form a benzoxazole ring.

In formula (A5), X ¹ may be a group containing at least one aromatic ring, and is not particularly limited, but a group having a linear structure is preferably used, and 1 to 4 aromatic rings are used. A group having an aromatic ring is preferred, and a group having two aromatic rings is more preferred. Thereby, polybenzoxazole (A5) can be made excellent in rigidity. The aromatic ring contained in X ¹ may be either a substituted or unsubstituted ring.

Examples of the structure of X ¹ include a group represented by the following formula. In the following formula, * indicates a bond.

式（Ａ５）中、Ｘ¹は、炭素原子と水素原子とからなる芳香族炭化水素環で構成されている基が好ましい。

In formula (A5), X ¹ is preferably a group composed of an aromatic hydrocarbon ring composed of a carbon atom and a hydrogen atom.

When X ¹ contains two or more aromatic rings, the plurality of aromatic rings may have either a linked polycyclic system or a condensed polycyclic structure, but have a linked polycyclic structure. It is preferable. Thereby, polybenzoxazole (A5) can be made excellent in both light-shielding property and rigidity.

The total carbon number of X ¹ is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 14. Thereby, the said effect can be exhibited more notably.

Considering these, X ¹ is particularly preferably a biphenylene group or a derivative thereof. Thereby, it can be set as polybenzoxazole (A5) excellent in especially rigidity.

In formula (A5), Y ¹ is not particularly limited as long as Y ¹ is a group containing at least one ring selected from an alicyclic hydrocarbon ring and an aromatic hydrocarbon ring, but 1 to 4 alicyclic carbonizations A group having a hydrogen ring is preferable, and a group having one alicyclic hydrocarbon ring is more preferable. Thereby, polybenzoxazole (A5) can be made excellent in rigidity and light resistance. The alicyclic hydrocarbon ring and aromatic hydrocarbon ring contained in Y ¹ may be either substituted or unsubstituted rings.

Examples of the structure of Y ¹ include a group represented by the following formula. In the following formula, * indicates a bond.

Ｙ¹の総炭素数は、４〜２４であることが好ましく、４〜１５であることがより好ましく、６〜９であることがさらに好ましい。これにより、前記効果をより顕著に発揮させることができる。

Y ¹ has preferably 4 to 24 carbon atoms, more preferably 4 to 15 carbon atoms, and still more preferably 6 to 9 carbon atoms. Thereby, the said effect can be exhibited more notably.

Considering these, Y ¹ is particularly preferably a cyclohexylene group or a derivative thereof. When a cyclohexylene group is selected as Y ¹ , the cyclohexylene group preferably has a chair-type trans configuration. Thereby, compared with the case where a boat-type structure is selected, the elastic modulus can be improved when polybenzoxazole (A5) is used.

  The polybenzoxazole (A5) can be obtained by a cyclization reaction of the polybenzoxazole precursor (A6) described below. The cyclization reaction here may proceed completely or partially. That is, the cyclization rate may not be 100%. For this reason, polybenzoxazole (A5) may further have a structural unit represented by the formula (A6) described below.

In the polybenzoxazole (A5), the cyclization rate is preferably 5% or more, more preferably 7.5% or more, and further preferably 10% or more. The upper limit of the cyclization rate is preferably 50%, more preferably 30%. When the cyclization rate is within the above range, it is preferable from the viewpoint of heat resistance and solubility of the exposed portion in the developer. The cyclization rate can be measured in the same manner as the imidation rate described in the Examples. However, in the case of polybenzoxazole (A5), around 1557cm ^-1 from benzoxazole ring, an absorption peak around 1574 ^-1 can be measured cyclization ratio based.

  In polybenzoxazole (A5), the total content of the structural units represented by formula (A5) and formula (A6) is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, Especially preferably, it is 80 mass% or more.

<< Polybenzoxazole precursor (A6) >>
The polybenzoxazole precursor (A6) is a compound capable of generating polybenzoxazole (A5), preferably polybenzoxazole (A5) having a structural unit represented by the formula (A5) by dehydration and cyclization. It is. The precursor (A6) has, for example, a structural unit represented by the formula (A6).

式（Ａ６）中、Ｘ¹は芳香族環を少なくとも１つ含む４価の基であり、Ｙ¹は脂環式炭化水素環を少なくとも１つ含む２価の基である。Ｘ¹に結合するＮとＯＨは、同一芳香族環上の隣り合った炭素に結合している。Ｘ¹で表される４価の基およびＹ¹で表される２価の基としては、各々式（Ａ５）中のＸ¹およびＹ¹として例示した基と同様なものが挙げられる。

In formula (A6), X ¹ is a tetravalent group containing at least one aromatic ring, and Y ¹ is a divalent group containing at least one alicyclic hydrocarbon ring. N and OH bonded to X ¹ are bonded to adjacent carbons on the same aromatic ring. Examples of the divalent group represented by tetravalent group and Y ¹ represented by X ^1, include those similar to the groups exemplified as X ¹ and Y ¹ in each formula (A5).

  In the polybenzoxazole precursor (A6), the content of the structural unit represented by the formula (A6) is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass. It is at least mass%.

<< Method of synthesizing polybenzoxazole (A5) and its precursor (A6) >>
The polybenzoxazole precursor (A6) includes, for example, at least one alicyclic hydrocarbon ring, at least one selected from dicarboxylic acids, diesters thereof, and dihalides thereof, and at least one aromatic ring. It can be obtained by polymerizing a diamine having two hydroxyl groups. These usage ratios are 0.5-4 mol with respect to the sum total of 1 mol of the said dicarboxylic acid, a diester body, and a dihalide body, Preferably it is 1-2 mol. In the polymerization, the mixed solution is preferably heated at 50 to 200 ° C. for 1 to 72 hours.

  The polybenzoxazole (A5) can be synthesized, for example, by synthesizing the polybenzoxazole precursor (A6) by the above method and then dehydrating and cyclizing the polybenzoxazole precursor (A6).

  A known method can be applied as the cyclization reaction of the polybenzoxazole precursor (A6). In the case of the thermal cyclization reaction, it is preferable to heat the solution containing the polybenzoxazole precursor (A6) at 150 to 400 ° C. for 1 to 16 hours. If necessary, it may be carried out while removing water in the system using an azeotropic solvent such as toluene, xylene, mesitylene and the like.

[Photosensitive agent (B)]
The photosensitive agent (B) is a compound that generates an acid, a compound that generates a radical, or a compound that generates a cation by a treatment including irradiation of radiation. Examples of radiation include visible light, ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. By containing the photosensitizer (B), the radiation-sensitive resin composition can exhibit radiation-sensitive characteristics and can have good radiation sensitivity. As the photosensitive agent (B), a photoacid generator is preferred.

  The content of the photosensitive agent (B) in the composition of the present invention is usually 1 to 80 parts by mass, preferably 5 to 60 parts by mass with respect to 100 parts by mass in total of the resin (C) and the resin (A). More preferably, it is 10-55 mass parts. Content of the photosensitive agent (B) in the composition of this invention is 5-100 mass parts normally with respect to 100 mass parts of resin (A), Preferably it is 10-60 mass parts, More preferably, it is 15-55. Part by mass.

  By setting the content of the photosensitive agent (B) in the above range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to an alkaline aqueous solution or the like serving as a developer can be increased, and the patterning performance can be improved.

<Compound that generates acid>
Examples of the acid-generating compound include a photoacid generator, such as a quinonediazide compound, an oxime sulfonate compound, an onium salt, an N-sulfonyloxyimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, and a sulfonic acid ester compound. Examples thereof include carboxylic acid ester compounds. By using a photoacid generator, a composition exhibiting positive radiation sensitive properties can be obtained.

  As a photosensitizer (B), a quinone diazide compound, an oxime sulfonate compound, an onium salt, and a sulfonate compound are preferable, a quinone diazide compound and an oxime sulfonate compound are more preferable, and a quinone diazide compound is particularly preferable.

<Quinonediazide compound>
The quinonediazide compound generates carboxylic acid by processing including irradiation with radiation and development using an aqueous alkali solution. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound and 1,2-naphthoquinonediazidesulfonic acid halide.

  Examples of the quinonediazide compound include compounds described in JP-A No. 2014-111723, JP-A No. 2014-149330, JP-A No. 2014-170080, JP-A No. 2015-4000, and the like.

  Examples of commercially available quinonediazide compounds include trade names “MG-300”, “NT-200”, “NT-300P”, and “TS-200” (all manufactured by Toyo Gosei Co., Ltd.). it can.

《Other examples》
Specific examples of the oxime sulfonate compound include compounds described in JP 2011-227106 A, JP 2012-234148 A, JP 2013-054125 A, and the like. Specific examples of the onium salt include, for example, Japanese Patent No. 5208573, Japanese Patent No. 5397152, Japanese Patent No. 5413124, Japanese Patent Application Laid-Open No. 2004-210525, Japanese Patent Application Laid-Open No. 2008-129623, Japanese Patent Application Laid-Open No. 2010-215616, and Japanese Patent Application Laid-Open No. 2013-2013. And compounds described in publications such as No. 228526.

  Specific examples of other acid generators are described in, for example, Japanese Patent Nos. 49242256, 2011-0664770, 2011-232648, 2012-185430, 2013-242540, and the like. Compounds.

<Compound that generates radicals>
Examples of the compound that generates radicals include photo radical polymerization initiators, and examples thereof include alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzoin compounds, benzophenone compounds, anthraquinones, and thioxanthones. By using a photo radical polymerization initiator, a composition exhibiting negative radiation sensitive properties can be obtained.

  Examples of the above compounds include JP-A-11-060995, JP-A-2005-202387, JP-A-2006-285226, JP-A-2007-102070, JP-A-2010-049262, JP-A-2010-083970, Examples thereof include compounds described in JP 2012-241127 A, JP 2014-186342 A, JP 2015-050269 A, and the like.

  Examples of commercially available radical photopolymerization initiators include “IRACURE 127”, “IRACURE 651”, “IRACURE 369”, “IRACURE 379EG”, “IRACURE OXE01”, “IRACURE OXE02” (all of which are BASF Japan). Manufactured).

<Compounds that generate cations>
Examples of the compound that generates a cation include a photocation polymerization initiator, and examples thereof include a sulfonium salt, an iodonium salt, and a diazonium salt. By using a cationic photopolymerization initiator, a composition exhibiting negative radiation sensitive characteristics can be obtained.

  Examples of the sulfonium salt-based, iodonium salt-based, or diazonium salt-based photocationic polymerization initiator include, for example, JP-A-11-060995, JP-A-2008-088253, JP-A-2010-074250, and JP-A-2011-238307. Examples thereof include compounds described in JP 2012-157996, JP-A 2015-001667, and the like.

  Examples of commercially available photocationic polymerization initiators include sulfonium salt cationic polymerization initiators such as trade names “UVACURE1590” (manufactured by Daicel Cytec Co., Ltd.), “CPI-110P” (manufactured by San Apro Co., Ltd.), Iodonium salt cationic polymerization initiators such as “IRGACURE250” (BASF Japan Ltd.), “WPI-113” (Wako Pure Chemical Industries, Ltd.), “Rp-2074” (Rhodia Japan Ltd.) Is mentioned.

  A photosensitive agent (B) may be used individually by 1 type, or may use 2 or more types together.

[Resin (C)]
The resin (C) is at least one resin selected from a resin having a structural unit represented by the formula (C1) and a resin having a structure represented by the formula (C2). Hereinafter, the resin having the structural unit represented by the formula (C1) is also referred to as “resin (C1)”, and the resin having the structure represented by the formula (C2) is also referred to as “resin (C2)”.

式（Ｃ１）中、Ａはフェノール性水酸基を有する２価の芳香族基であり、Ｌは後述する式（ｃ２−１）、式（ｃ２−２）または式（ｃ２−３）で表される１価の基である。

In Formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, and L is represented by Formula (c2-1), Formula (c2-2), or Formula (c2-3) described later. It is a monovalent group.

式（Ｃ２）中、Ａ’はフェノール性水酸基を有するｋ＋ｍ＋ｎ価の芳香族基であり、Ｌは後述する式（ｃ２−１）、式（ｃ２−２）または式（ｃ２−３）で表される１価の基である。複数あるＬは各々同一であっても異なっていてもよい。＊は他のＡ’との結合手である。

In formula (C2), A ′ is a k + m + n-valent aromatic group having a phenolic hydroxyl group, and L is represented by formula (c2-1), formula (c2-2) or formula (c2-3) described later. A monovalent group. A plurality of L may be the same or different. * Is a bond with another A ′.

k is an integer of 0-9, m is an integer of 0-9, and n is an integer of 0-9. k + m + n is an integer of 1-9, preferably an integer of 2-9, more preferably an integer of 2-5. When m = n = 0, that is, when formula (C2) is represented by A ′-(CH (L) OH) _k , the resin (C2) is, for example, a resole resin, and m + n is an integer of 1 or more Resin (C2) is, for example, a condensate of resole resin.

  In formula (C2), for example, when n is 2, a group represented by -CH (L) -CH (L)-is not bonded to A ', but -CH (L )-Indicates that two groups are directly bonded. The same applies when n is 3 or more and m is 2 or more.

  By using the resin (C) having the substituent L, an insulating film with less outgas generation can be formed, and a composition excellent in patternability and radiation sensitivity can be obtained.

<< Divalent group A >>
A is a divalent aromatic group having a phenolic hydroxyl group, and is preferably a divalent group represented by formula (c1-1), formula (c1-2), or formula (c1-3). .

式（ｃ１−１）〜（ｃ１−３）中の各記号の意味は、以下のとおりである。

The meaning of each symbol in the formulas (c1-1) to (c1-3) is as follows.

  a1 is an integer of 1 to 4. b1 is an integer of 0-3. a2 to a5 and b2 to b5 are each independently an integer of 0 to 4. a6 and b6 are integers of 0-2.

  However, a2 + a3 is an integer from 1 to 6, b2 + b3 is an integer from 0 to 5, a2 + a3 + b2 + b3 is an integer from 1 to 6, a4 + a5 + a6 is an integer from 1 to 8, and b4 + b5 + b6 is 0 or more It is an integer of 7 or less, and a4 + a5 + a6 + b4 + b5 + b6 is an integer of 1 or more and 8 or less. Further, 1 ≦ a1 + b1 ≦ 4, a2 + b2 ≦ 4, a3 + b3 ≦ 4, a4 + b4 ≦ 4, a5 + b5 ≦ 4, and a6 + b6 ≦ 2.

  a1, a2 + a3, and a4 + a5 + a6 are each preferably an integer of 1 to 3.

  R is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and when there are a plurality of R, they may be the same or different. Examples of the hydrocarbon group include alkyl groups such as a methyl group, a propyl group, an isopropyl group, and a t-butyl group. Examples of the alkoxy group include a methoxy group.

  In formula (c1-1) to formula (c1-3), the bonding positions of —OH and —R are not particularly limited, and the bonding positions of two —CH (L) — are not particularly limited. For example, two —CH (L) — may be bonded to different benzene nuclei (for example, (1) below) or may be bonded to the same benzene nuclei (for example, (2) below). In the formula, * is a bond. The following formulas (1) and (2) are specific examples of the formula (c1-2), but the same applies to the formula (c1-3). For convenience, substituents on the benzene nucleus are omitted.

上記Ａにおいて、−ＣＨ（Ｌ）−との結合位置は、例えば、上記Ａに含まれる水酸基に対してｏ位および／またはｐ位であることが好ましい。

In the above A, the bonding position to —CH (L) — is preferably, for example, the o-position and / or the p-position with respect to the hydroxyl group contained in A.

  The group A is preferably a group represented by the formula (c1-2) or the formula (c1-3) from the viewpoints of providing light shielding properties and heat resistance and alkali developability, and represented by the formula (c1-2). Are more preferred.

<< K + m + n-valent group A '>>
A ′ is a k + m + n-valent aromatic group having a phenolic hydroxyl group. For example, a divalent group represented by the formula (c1-1), the formula (c1-2) or the formula (c1-3) The group changed into k + m + n valent group is mentioned. However, -CH (L) OCH (L)-, -CH (L)-, and -CH (L) OH shall be bonded to an aromatic ring.

  In this case, a1 to a6 and b1 to b6 in the formulas (c1-1) to (c1-3) are as follows. a1 is an integer of 1 or more and “6- (k + m + n)” or less. b1 is an integer of 0 or more and “5- (k + m + n)” or less. a2 to a5 and b2 to b5 are each independently an integer of 0 to 4. a6 and b6 are integers of 0-2. However, a2 + a3 is an integer of 1 to “8− (k + m + n)”, b2 + b3 is an integer of 0 to “7− (m + n)”, and a2 + a3 + b2 + b3 is an integer of 1 to “8− (k + m + n)”. A4 + a5 + a6 is an integer from 1 to “10− (k + m + n)”, b4 + b5 + b6 is an integer from 0 to “9− (k + m + n)”, and a4 + a5 + a6 + b4 + b5 + b6 is from 1 to “10− (k + m + n)” It is an integer. Further, 1 ≦ a1 + b1 ≦ “6- (k + m + n)”, a2 + b2 ≦ 4, a3 + b3 ≦ 4, a4 + b4 ≦ 4, a5 + b5 ≦ 4, and a6 + b6 ≦ 2.

<< monovalent group L >>
L is a monovalent group represented by formula (c2-1), formula (c2-2), or formula (c2-3).

式（ｃ２−１）中、Ｘは酸素原子、硫黄原子、−ＣＨ₂−または−ＮＨ−であり、好ましくは酸素原子または硫黄原子である。Ｒ¹はハロゲン原子、−ＯＨ、−ＳＨ、−ＮＯ₂、−ＮＨ₂、炭化水素基、および炭素数１以上のヘテロ原子含有基から選ばれる１価の基である。ｍは０〜３の整数であり、好ましくは０または１である。ただし、式（Ｃ１）の場合では、ｍ＝０であるときＸは酸素原子ではない。Ｒ¹が複数存在する場合、各々同一であっても異なってもよく、また隣接する環炭素に結合したＲ¹は相互に結合して環、例えばベンゼン環を形成していてもよい。

In formula (c2-1), X represents an oxygen atom, a sulfur atom, —CH ₂ — or —NH—, preferably an oxygen atom or a sulfur atom. R ¹ is a monovalent group selected from a halogen atom, —OH, —SH, —NO ₂ , —NH ₂ , a hydrocarbon group, and a heteroatom-containing group having 1 or more carbon atoms. m is an integer of 0 to 3, preferably 0 or 1. However, in the case of the formula (C1), when m = 0, X is not an oxygen atom. When a plurality of R ¹ are present, they may be the same or different, and R ¹ bonded to adjacent ring carbons may be bonded to each other to form a ring, for example, a benzene ring.

In formula (c2-2), Y represents a nitrogen atom, C—H or C—R ² . R ² has the same meaning as R ¹ in formula (c2-1). R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group. n is an integer of 0 to 4, preferably an integer of 0 to 3, and d is 0 or 1. However, in the case of the formula (C1), when n = d = 0, Y is not CH, and when n = d = 0 and Y is C—R ² , or n = 1, d = When 0 and Y is C—H, R ² is not —NO ₂ or —OH. When a plurality of R ² are present, they may be the same or different, and R ² bonded to adjacent ring carbons may be bonded to each other to form a ring.

Examples of the ring formed by bonding R ² to each other include a condensed carbocyclic ring and a condensed heterocyclic ring when shown together with a benzene nucleus or a pyridine nucleus to which R ² is bonded. Is mentioned. These rings may further have the groups listed for R ¹ . * In the formula is a bond. From the viewpoint of light shielding properties of the insulating film, L preferably has a condensed carbocyclic ring such as a naphthalene ring or an anthracene ring.

式（ｃ２−３）中、Ｒ⁵は式（ｃ２−１）中のＲ¹と同義である。ｌはそれぞれ独立に０〜５の整数であり、好ましくは０である。Ｒ⁵が複数存在する場合、各々同一であっても異なってもよく、また隣接する環炭素に結合したＲ⁵は相互に結合して環、例えばベンゼン環を形成していてもよい。

In formula (c2-3), R ⁵ has the same meaning as R ¹ in formula (c2-1). l is each independently an integer of 0 to 5, preferably 0. When a plurality of R ⁵ are present, they may be the same or different, and R ⁵ bonded to adjacent ring carbons may be bonded to each other to form a ring, for example, a benzene ring.

Examples of the hydrocarbon group in R ^{1 to} R ⁵ include an alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a pentyl group, and an aryl group having 6 to 24 carbon atoms such as a phenyl group. Groups.

Examples of the heteroatom-containing group having 1 or more carbon atoms in R ^{1 to} R ² and R ⁵ include halogenated hydrocarbon groups such as a halogenated alkyl group having 1 to 18 carbon atoms such as a carboxyl group and a trifluoromethyl group, C1-C18 hydroxyalkyl group such as hydroxymethyl group, C1-C18 alkoxy group such as methoxy group and hetoxy group, C6-C30 aryloxy group such as phenoxy group and tolyloxy group, methylthio group C1-C18 thioalkoxy group such as benzyloxy group, C7-C30 aralkyloxy group such as benzyloxy group, C2-C20 acyloxyalkyl group such as acetoxymethyl group, dimethylamino group, diphenylamino group, etc. Substituted amino group, furanyl group, thienyl group, pyrrolyl group, imidazolyl group, pyridinyl group, pyrimidinyl group, pyra Heterocycles such as a dinyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, and a morpholinyl group can be mentioned.

R ¹ is preferably an alkyl group, an aryl group, a hydroxyalkyl group, an acyloxyalkyl group, or —NO ₂ . R ² is preferably a halogen atom, a halogenated alkyl group, a carboxyl group, an alkoxy group, a thioalkoxy group, an aralkyloxy group, a substituted amino group, or a heterocyclic ring. Also preferred is an embodiment in which two R ² bonded to adjacent ring carbons are bonded to each other to form a ring.

  The resin (C) is a substance that develops color when heated. In the method for forming an insulating film described later, the coating film formed from the composition containing the resin (C) before exposure does not have a light shielding property near the ultraviolet region, for example, a light shielding property at a wavelength of 400 nm. The resin (C) is ketoized by heating after exposure and development, and the obtained insulating film is presumed to have a light-shielding property at the wavelength. By using such a resin (C), in the composition of this invention, light-shielding provision and alkali developability can be made compatible.

  For example, the light shielding property is not imparted at about 60 to 130 ° C., which is a heating temperature at the time of pre-baking, and the light shielding property can be imparted at about 300 ° C. or less exceeding the heating temperature at the time of post baking. .

  Among the above exemplified resins (C), a novolac resin having a repeating structural unit represented by the formula (C1) is preferable because it has good alkali solubility (developability). By containing an alkali-soluble novolak resin in the radiation-sensitive resin composition, a radiation-sensitive resin composition with good resolution can be obtained.

  The resin (C1) can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst and distilling off unreacted components as necessary. As reaction conditions, phenols and aldehydes are usually reacted at 60 to 200 ° C. for about 1 to 20 hours in a solvent. For example, it can be synthesized by the method described in JP-B-47-15111, JP-A-63-238129 and the like.

  As the resin (C2), a resole resin can be used (when m = n = 0 in the formula (C2)), and the resin (C2) can also be obtained from the resole resin (formula (C2)). In the case where m + n is an integer of 1 or more).

  The resole resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a base catalyst and distilling off unreacted components as necessary. As reaction conditions, phenols and aldehydes are usually reacted at 40 to 120 ° C. for about 1 to 20 hours in a solvent. In this way, for example, a resole resin in which —CH (L) OH is bonded to an aromatic ring contained in phenols can be obtained. The condensate of the resole resin can be obtained by advancing the dehydration condensation reaction by adding heat or acid to the resole resin. This reaction proceeds by dehydration condensation of —CH (L) OH contained in the resole resin. When the reaction is advanced by heating, the resol resin or a solution thereof is usually reacted at 60 to 200 ° C. for about 1 to 20 hours. For example, it is compoundable by the method as described in gazettes, such as patent 3889274, patent 4013111, and Unexamined-Japanese-Patent No. 2010-1111013.

Examples of phenols include:
Compounds having 1 to 4 hydroxyl groups, preferably 1 to 3 and 1 benzene nucleus, specifically phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2, 5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol , 2-propylphenol, 3-propylphenol, 4 Propyl phenol, 2-isopropyl phenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, 2-isopropyl-5-methylphenol, 5-isopropyl-2-methylphenol;
A compound having 1 to 6 hydroxyl groups, preferably 1 to 3 and 2 benzene nuclei (naphthalene type compound), specifically monohydroxynaphthalene such as 1-naphthol and 2-naphthol, 2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3 -Dihydroxynaphthalene such as dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene;
Compounds having 1 to 8 hydroxyl groups, preferably 1 to 3 and 3 benzene nuclei (anthracene type compounds), specifically 1-hydroxyanthracene, 2-hydroxyanthracene, 9-hydroxyanthracene, etc. Monohydroxyanthracene, 1,4-dihydroxyanthracene, dihydroxyanthracene such as 9,10-dihydroxyanthracene, 1,2,10-trihydroxyanthracene, 1,8,9-trihydroxyanthracene, 1,2,7-tri Trihydroxyanthracene such as hydroxyanthracene;
Is mentioned.

  Examples of aldehydes include compounds represented by L—C (═O) —H (L in the formula has the same meaning as L in formula (C1)), and specifically, The compound of this is mentioned.

樹脂（Ｃ）の合成において、アルデヒド類の使用量は、フェノール類１モルに対して、通常０．３モル以上であり、好ましくは０．４〜３モル、より好ましくは０．５〜２モルである。

In the synthesis of the resin (C), the amount of aldehydes to be used is usually 0.3 mol or more, preferably 0.4 to 3 mol, more preferably 0.5 to 2 mol, relative to 1 mol of phenols. It is.

  Examples of the acid catalyst in the synthesis of the novolak resin include hydrochloric acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. As a base catalyst in the synthesis | combination of a resole resin, ammonia water and a tertiary amine are mentioned, for example.

  The weight average molecular weight (Mw) in terms of polystyrene of the resin (C) is usually 100 to 50,000, preferably 150 to 10,000, more preferably as measured by gel permeation chromatography (GPC). Is 500 to 6,000. Resin (C) having Mw in the above range is preferable in terms of resolution.

  Resin (C) may be used individually by 1 type, or may use 2 or more types together.

  The content of the resin (C) is preferably 5 to 85% by mass, more preferably 10 to 75% by mass, and further more preferably 10 to 70% by mass with respect to 100% by mass of the total solid content in the composition of the present invention. preferable.

  In the composition of the present invention, the content of the resin (C) is usually 5 to 200 parts by weight, preferably 10 to 100 parts by weight, and more preferably 15 to 90 parts by weight with respect to 100 parts by weight of the resin (A). Part by mass, particularly preferably 18 to 80 parts by mass.

  When the content of the resin (C) is not less than the lower limit of the above range, the effect of imparting light-shielding properties and developability based on the resin (C) is easily exhibited. When the content of the resin (C) is not more than the upper limit of the above range, there is little possibility that deterioration of the low water absorption of the insulating film, increase in the outgas amount, and decrease in heat resistance will occur.

<< Crosslinking agent (D) >>
The crosslinking agent (D) is a compound having a crosslinkable functional group. As a crosslinking agent (D), the compound which has a 2 or more crosslinkable functional group in 1 molecule is mentioned, for example.

  In addition, the compound corresponding to both acrylic resin (A3) and a crosslinking agent (D) is classified into acrylic resin (A3), and the compound applicable to both resin (C) and crosslinking agent (D) is And classified into resin (C).

  When the insulating film made of the composition of the present invention is used as a constituent element of an organic EL device, the organic EL device deteriorates when the organic light emitting layer comes into contact with moisture. It is preferable to reduce the property.

  Examples of crosslinkable functional groups include isocyanate groups and blocked isocyanate groups, oxetanyl groups, glycidyl ether groups, glycidyl ester groups, glycidyl amino groups, methoxymethyl groups, ethoxymethyl groups, benzyloxymethyl groups, acetoxymethyl groups, benzoic groups. Roxymethyl group, formyl group, acetyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group; ethylenic group such as vinyl group, vinylidene group, (meth) acryloyl group Examples thereof include a group having an unsaturated bond.

  A crosslinking agent (D) may be used individually by 1 type, or may use 2 or more types together.

  In the composition of the present invention, the content of the crosslinking agent (D) is usually 1 to 210 parts by mass, preferably 10 to 150 parts by mass with respect to 100 parts by mass in total of the resin (C) and the resin (A). Part, more preferably 15 to 100 parts by mass. When the content of the crosslinking agent (D) is not less than the lower limit of the above range, the low water absorption of the insulating film tends to be improved. When the content of the crosslinking agent (D) is not more than the upper limit of the above range, the heat resistance of the insulating film tends to be improved.

  As the crosslinking agent (D), for example, a compound having two or more glycidyl groups in one molecule, a compound having two or more oxetanyl groups in one molecule, and two or more ethylenic unsaturations in one molecule Compound having a bond, methoxymethyl group-containing phenol compound, methylol group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, Alkoxyalkyl group-containing urea compound, alkoxyalkyl group-containing phenol compound, carboxymethyl group-containing melamine resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin, carboxymethyl group-containing phenol Fat, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, and carboxymethyl group-containing phenol compound.

  Examples of the compound having two or more glycidyl groups in one molecule include ethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and trimethylolpropane triglycidyl ether.

  Examples of the compound having two or more glycidyl groups in one molecule include, for example, JP-A No. 2014-170949, JP-A No. 2014-189616, JP-A No. 2014-205838, JP-A No. 2014-229696, JP-A No. 2015-2015. And compounds described in publications such as 27665.

  Examples of the compound having two or more oxetanyl groups in one molecule include 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl, 3,7-bis (3-oxetanyl) -5- Oxanonane, 3,3 ′-[1,3- (2-methylenyl) propanediylbis (oxymethylene)] bis (3-ethyloxetane), ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, And dicyclopentenyl bis [(3-ethyl-3-oxetanyl) methyl] ether and triethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether.

  Examples of the compound having two or more oxetanyl groups in one molecule include JP2013-234230, JP2014149330, JP2014-186300, JP2015-38182, and JP2015. And compounds described in publications such as No. 42713.

  Examples of the compound having two or more ethylenically unsaturated bonds in one molecule include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (Meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Examples include polyfunctional (meth) acrylates such as erythritol penta (meth) acrylate.

  Examples of the compound having two or more ethylenically unsaturated bonds in one molecule include JP 2001-104878, JP 2013-029780, JP 2013-41225, JP 2013-57755, and Patent. And compounds described in publications such as No. 4400936.

  As a crosslinking agent (D), the compound which has the group by which the isocyanate group was blocked by the protective group can also be mentioned, for example. The said compound is also called "block isocyanate compound." A group in which an isocyanate group is blocked with a protective group is also referred to as a “blocked isocyanate group”.

  Examples of the blocked isocyanate compound include JP2013-225031, JP51332096, JP5071686, JP2013-223859, JP51999752, JP200341185, JP4879557, Examples thereof include compounds described in Japanese Unexamined Patent Publication No. 2006-119441.

[Solvent (E)]
A solvent (E) can be used in order to make a radiation sensitive resin composition liquid.

  Examples of the solvent (E) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Methoxypropyl acetate, diethylene glycol ethyl methyl ether, diethyl ketone, methyl butyl ketone, dipropyl ketone, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, n-pentanol, diacetone alcohol, and γ-butyrolactone.

  Examples of the solvent (E) include the solvents described in JP 2012-12472 A, JP 2013-54376 A, JP 2014-115438 A, JP 2014-197171 A, JP 2014-189561 A, and the like. Also mentioned.

  Examples of the solvent (E) may further include amide solvents, and examples thereof include compounds described in Japanese Patent Nos. 461832 and 5613851.

  Examples of the solvent (E) include propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), propylene glycol monomethyl ether (hereinafter also referred to as “PGME”), diethylene glycol ethyl methyl ether (hereinafter also referred to as “EDM”), diacetone alcohol. (Hereinafter also referred to as “DAA”) is particularly preferable.

  In one embodiment, γ-butyrolactone (hereinafter also referred to as “BL”) is preferably used as the solvent (E), and a mixed solvent containing BL is preferable. As content of BL, 70 mass% or less is preferable in the total amount of 100 mass% of a solvent (E), and 20-60 mass% is more preferable. BL is preferably used in combination with at least one selected from PGMEA, PGME and EDM. It exists in the tendency which can maintain suitably the melt | dissolution state of resin (A) in a radiation sensitive resin composition by making content of BL into the said range.

  As the solvent (E), in addition to the solvents exemplified above, alcohol solvents such as propanol and butanol; aromatic hydrocarbon solvents such as toluene and xylene can be used in combination as necessary.

  A solvent (E) may be used individually by 1 type, or may use 2 or more types together.

  In the composition of the present invention, the content of the solvent (E) is such that the solid content concentration of the composition is usually 5 to 60% by mass, preferably 10 to 55% by mass, more preferably 15 to 50% by mass. It is. Here, solid content means all components other than a solvent (E). By making content of a solvent (E) into the said range, it exists in the tendency for the low water absorption of the insulating film formed from the said composition to improve, without impairing developability.

[Other optional ingredients]
In addition to the essential components described above, the radiation-sensitive resin composition is within a range that does not impair the effects of the present invention, and other additives such as an adhesion assistant (F), a surfactant (G), and a dye (H) as necessary. An optional component may be contained. Other optional components may be used alone or in combination of two or more.

<Adhesion aid (F)>
The adhesion aid (F) is a component that improves the adhesion between a film forming object such as a substrate and the insulating film. The adhesion assistant (F) is particularly useful for improving the adhesion between the inorganic substrate and the insulating film. Examples of the inorganic substance include silicon compounds such as silicon, silicon oxide, and silicon nitride; and metals such as gold, copper, and aluminum.

  As the adhesion assistant (F), a functional silane coupling agent is preferable. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, halogen atoms, vinyl groups, methacryloyl groups, isocyanate groups, epoxy groups, oxetanyl groups, amino groups, and thiol groups. Can be mentioned.

  Examples of the functional silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ- Isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4- (Epoxycyclohexyl) ethyltrimethoxysilane. Among these, N-phenyl-3-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane and γ-methacryloxypropyltrimethoxysilane are preferred.

  The content of the adhesion assistant (F) in the composition of the present invention is 100% by mass of the total solid content in the composition of the present invention, preferably 20% by mass or less, more preferably 0.01 to 15% by mass. is there. By setting the content of the adhesion assistant (F) in the above range, the adhesion between the formed insulating film and the substrate is further improved.

<Surfactant (G)>
Surfactant (G) is a component which improves the film-forming property of a radiation sensitive resin composition. By containing the surfactant (G), the radiation-sensitive resin composition can improve the surface smoothness of the coating film, and as a result, the film thickness uniformity of the insulating film can be further improved. Examples of the surfactant (G) include a fluorine-based surfactant and a silicone-based surfactant.

  As surfactant (G), the specific example described in Unexamined-Japanese-Patent No. 2003-015278, Unexamined-Japanese-Patent No. 2013-231869, etc. can be mentioned, for example.

  The surfactant (G) content in the composition of the present invention is 100% by mass of the total solid content in the composition of the present invention, preferably 20% by mass or less, more preferably 0.01 to 15% by mass, More preferably, it is 0.05-10 mass%. By making content of surfactant (G) into the said range, the film thickness uniformity of the coating film formed can be improved more.

<Dye (H)>
The dye (H) is a component that enhances the light shielding property of the insulating film. By using the dye (H), it is possible to obtain a display or lighting device that is more reliable. The dye (H) may be any component that absorbs light in the wavelength range of 400 nm to 1000 nm, and examples thereof include anthraquinone-based, methine-based, indigoid-based, and azo-based organic compound pigments.

  As the dye (H), for example, JP2003-246840, JP2007-177708, JP2008-255241, JP201231218, JP2013-509988, JP2015-30753A, for example. , JP-A-2015-32660, JP-A-2015-43378 and the like.

  Examples of commercially available dyes (H) include trade names “OilBlue 5511”, “PlastBlueDB-463”, “SDO-11”, “SDO-12”, “SDO-14”, “SDO-C8”, and “SDO-C8”. -C12 "," SDO-C33 "(all Arimoto Chemical Co., Ltd.)," NEOSSUPERBLACK C-832 "(Chuo Synthetic Chemical Co., Ltd.)," Aizen Spiron Red BEH Special "(Hodogaya Chemical Co., Ltd.) ).

  In the composition of the present invention, the content of the dye (H) is preferably 1 to 50% by mass, more preferably 3 to 50% by mass, further preferably 100% by mass of the total solid content in the composition of the present invention. Is 5-50 mass%. By making content of dye (H) into the said range, the light-shielding property and sensitivity of the formed insulating film can be made compatible.

  Dye (H) may be used individually by 1 type, or may be used in combination of 2 or more type.

[Method for preparing radiation-sensitive resin composition]
The radiation-sensitive resin composition can be prepared, for example, by mixing the solvent (E) with essential components such as the photosensitizer (B) and the resin (C) and other components as necessary. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.

[Method of forming insulating film using radiation-sensitive resin composition]
The method for forming an insulating film of the present invention includes a step 1 for forming a coating film on a substrate using the above-described radiation-sensitive resin composition, a step 2 for irradiating at least a part of the coating film, and the radiation It has the process 3 which develops the irradiated coating film, and the process 4 which heats the said developed coating film.

  According to the method for forming an insulating film, it is possible to form an insulating film having excellent light shielding properties and a small outgas amount. Moreover, since the above-mentioned radiation sensitive resin composition is excellent in radiation sensitivity, an insulating film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development, and heating utilizing the characteristics. can do.

<< Process 1 >>
In step 1, the radiation-sensitive resin composition is applied to the substrate surface, and preferably the pre-baking is performed to remove the solvent (E) to form a coating film. As a film thickness of the said coating film, it is 0.3-25 micrometers normally as a value after a prebaking, Preferably it can be set as 0.5-20 micrometers.

  Examples of the substrate include a resin substrate, a glass substrate, and a silicon wafer. The substrate further includes, for example, a TFT substrate on which TFTs and wirings thereof are formed in an organic EL element being manufactured.

  Examples of the method for applying the radiation sensitive resin composition include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an ink jet method. Among these coating methods, spin coating and slit die coating are preferable.

  Prebaking conditions vary depending on the composition of the radiation-sensitive resin composition, but for example, the heating temperature is 60 to 130 ° C., and the heating time is about 30 seconds to 15 minutes. The pre-bake is preferably performed at a temperature at which the light shielding property based on the resin (C) is not imparted to the coating film.

<< Process 2 >>
In step 2, the coating film formed in step 1 is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include visible light, ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. Examples of visible light include g-line (wavelength 436 nm) and h-line (wavelength 405 nm). Examples of ultraviolet rays include i-line (wavelength 365 nm). Examples of the far ultraviolet light include laser light from a KrF excimer laser. X-rays include, for example, synchrotron radiation. Examples of the charged particle beam include an electron beam.

Among these radiations, visible light and ultraviolet light are preferable, and among visible light and ultraviolet light, radiation containing g-line and / or i-line is particularly preferable. When using radiation containing i-line, the exposure amount is preferably 6000 mJ / cm ² or less, and preferably 20 to 2000 mJ / cm ² . The amount of exposure can be measured by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (“OAI model 356” from OAI Optical Associates).

<< Process 3 >>
In step 3, the coating film irradiated with radiation in step 2 is developed. Thus, for example, when a positive composition is used, a portion irradiated with radiation is removed, and when a negative composition is used, a non-irradiated portion is removed to form a desired pattern. . As the developer used for the development treatment, an alkaline aqueous solution is preferable.

  Examples of the alkaline compound contained in the aqueous alkaline solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and di-n-propyl. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5 -Diazabicyclo [4.3.0] -5-nonane. The concentration of the alkaline compound in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability.

  As the developer, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to an alkaline aqueous solution, or an aqueous solution obtained by adding a small amount of various organic solvents that dissolve the radiation-sensitive resin composition in an alkaline aqueous solution. It can also be used. As the organic solvent in the latter aqueous solution, the same solvent as the solvent (E) for obtaining the resin (A) or the radiation sensitive resin composition can be used.

  Examples of the developing method include a liquid filling method, a dipping method, a rocking dipping method, and a shower method. The development time varies depending on the composition of the radiation sensitive resin composition, but is usually about 10 seconds to 180 seconds. Following such development processing, for example, washing with running water is performed for 30 seconds to 90 seconds, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

<< Process 4 >>
In step 4, after step 3, using a heating device such as a hot plate or an oven, the coating film is cured by a heat treatment (post-bake treatment) on the coating film to obtain an insulating film. The heating temperature in this heat treatment is, for example, more than 130 ° C. and not more than 300 ° C., and the heating time varies depending on the type of heating equipment, but for example, 5 minutes to 30 when performing the heat treatment on a hot plate. In the case of performing heat treatment in an oven for 30 minutes, it is 30 minutes to 90 minutes. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used.

  By the heat treatment in the above temperature range, the insulating film is provided with a light shielding property such that the total light transmittance at a wavelength of 400 nm is, for example, 15% or less, preferably 12% or less, more preferably 5% or less. In this manner, an insulating film having a target pattern can be formed on the substrate.

In step 4, before the coating film is heated, the patterned coating film may be rinsed or decomposed. In the rinse treatment, it is preferable to wash the coating film using the solvent mentioned as the solvent (E). In the decomposition treatment, the photosensitive agent (B) such as a quinonediazide compound remaining in the coating film can be decomposed by irradiating the entire surface with radiation (post-exposure) from a high-pressure mercury lamp or the like. The exposure amount in this post-exposure is preferably about 1000 to 5000 mJ / cm ² .

  The composition of the present invention exhibits good characteristics in patterning property and radiation sensitivity, and the insulating film thus obtained has a light shielding property to light in the vicinity of the ultraviolet region, for example, at a wavelength of 400 nm. Further, the insulating film generates a small amount of outgas and exhibits good characteristics in heat resistance and low water absorption. For this reason, the said insulating film can be used suitably as an insulating film as a protective film or a planarization film | membrane other than the insulating film as a partition which an organic EL element etc. have, for example.

  The thickness of the insulating film of the present invention is usually 0.3 to 25 μm, preferably 0.5 to 20 μm, from the viewpoint of light shielding properties. In the insulating film of the present invention, the total light transmittance at a wavelength of 400 nm is preferably 0 to 15%, more preferably 0 to 12%, and further preferably 0 to 5%. Further, the insulating film of the present invention has a total light transmittance at a wavelength of 600 nm of preferably 30% or less, more preferably 10% or less. The total light transmittance can be measured using, for example, a spectrophotometer (“150-20 type double beam” manufactured by Hitachi, Ltd.).

[Display or lighting device elements]
Hereinafter, a display or lighting device element having the insulating film of the present invention will be described.

  Examples of the display device having the element of the present invention include a liquid crystal display (LCD), an electrochromic display (ECD), an electroluminescent display (ELD), and particularly an organic EL display. As an illuminating device which has an element of the present invention, organic EL lighting is mentioned, for example.

  Hereinafter, the display or lighting device is also collectively referred to as “device”.

  One embodiment of the element of the present invention includes a first electrode provided on a TFT substrate and connected to the TFT, and the first electrode formed on the first electrode so as to partially expose the first electrode. It has an insulating film and a second electrode provided to face the first electrode.

  An embodiment of the device having the element of the present invention includes a TFT substrate, a first electrode provided on the TFT substrate and connected to the TFT, and a first electrode so as to partially expose the first electrode. The insulating film of the present invention formed above and a second electrode provided to face the first electrode.

  In the element and device of the present invention, the insulating film is formed so as to cover at least part of the first electrode and partially expose the first electrode. In particular, the insulating film is preferably formed so as to cover the edge portion of the first electrode.

  The thickness of the insulating film is not particularly limited, but is preferably 0.3 to 25 μm, more preferably 0.5 to 20 μm, considering the ease of film formation and patterning.

The insulating film is formed so as to straddle adjacent first electrodes, for example. For this reason, the insulating film is required to have good electrical insulation. The volume resistivity of the insulating film is preferably 10 ¹⁰ μΩ · cm or more, more preferably 10 ¹² μΩ · cm or more.

  The insulating film is, for example, a partition that partitions the surface of the TFT substrate into a plurality of regions. The insulating film (partition wall) is preferably formed on the TFT substrate so as to be disposed at least above the semiconductor layer, from the viewpoint of light shielding with respect to the semiconductor layer included in the TFT. Here, “upward” is a direction from the TFT substrate toward the second electrode. As an example, when projected from the top of the TFT substrate, an aspect in which 50% or more of the area of the semiconductor layer overlaps with the insulating film (partition wall), particularly 80% or more of the area of the semiconductor layer, Further, an embodiment in which 90% or more, particularly 100%, overlaps with the insulating film (partition wall) can be mentioned.

  In the apparatus of the present invention, the insulating film exposing the first electrode has a light shielding property near the ultraviolet region, for example, at a wavelength of 400 nm as described above. By providing such an insulating film, for example, even in a device having a thin film transistor including a semiconductor layer made of a material with high photodegradation such as IGZO as a driving element, the insulating film functions as a light-shielding film. Photodegradation of the semiconductor layer due to use or the like can be suppressed.

  For example, the semiconductor layer constituting the TFT may be a layer containing an oxide semiconductor containing one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn. Examples of the oxide in this case include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof.

  As an oxide semiconductor containing one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn, for example, a quaternary system such as an In—Sn—Ga—Zn—O-based oxide semiconductor Metal oxide: In—Ga—Zn—O-based oxide semiconductor, In—Sn—Zn—O-based oxide semiconductor, In—Al—Zn—O-based oxide semiconductor, Sn—Ga—Zn—O-based oxide Ternary metal oxides such as semiconductor, Al—Ga—Zn—O-based oxide semiconductor, Sn—Al—Zn—O-based oxide semiconductor; In—Zn—O-based oxide semiconductor, Sn—Zn—O-based Oxide semiconductor, Al-Zn-O-based oxide semiconductor, Zn-Mg-O-based oxide semiconductor, Sn-Mg-O-based oxide semiconductor, In-Mg-O-based oxide semiconductor, In-Ga-O Binary metal oxides such as In-based materials; In-O-based oxide semiconductors, Sn-O-based materials Compound semiconductor, 1-component metal oxide such as Zn-O-based oxide semiconductor can be mentioned.

  In the present invention, even when the semiconductor layer constituting the TFT is the oxide semiconductor layer, particularly when the semiconductor layer is an oxide semiconductor layer made of an In—Ga—Zn—O-based oxide semiconductor (IGZO semiconductor), Photodegradation can be prevented.

  The apparatus of the present invention includes a first electrode provided on the TFT substrate and connected to the TFT, an organic light emitting layer formed on the first electrode in a region partitioned by the partition, and an organic light emitting layer An organic EL device having an organic EL element including the second electrode provided on the top is preferable.

  The TFT substrate includes, for example, a support substrate, a TFT provided on the support substrate corresponding to the organic EL element, and a planarization layer that covers the TFT. For example, the first electrode is formed on the planarization layer, and is connected to the TFT through a through hole penetrating the planarization layer. The insulating film (partition wall) having a light shielding property is preferably formed on the first electrode and the planarization layer so as to partially expose the first electrode.

  Hereinafter, an organic EL display or illumination device will be described as a specific example of the display or illumination device of the present invention with reference to FIG. FIG. 1 is a cross-sectional view schematically showing the structure of the main part of an organic EL display or illumination device (hereinafter also simply referred to as “organic EL device”) according to the present invention.

  The organic EL device 1 in FIG. 1 is an active matrix organic EL device having a plurality of pixels formed in a matrix. The organic EL device 1 may be either a top emission type or a bottom emission type. The property of the material constituting each member, such as transparency, is appropriately selected according to the top emission type and the bottom emission type.

  The organic EL device 1 includes a support substrate 2, a thin film transistor (hereinafter also referred to as “TFT”) 3, a first insulating film 4, an anode 5 as a first electrode, a through hole 6, a second insulating film 7, and an organic light emitting layer. 8. A cathode 9 as a second electrode, a passivation film 10 and a sealing substrate 11 are provided. As the second insulating film 7, the insulating film of the present invention is used.

  The support substrate 2 is made of an insulating material. When the organic EL device 1 is a bottom emission type, the support substrate 2 is required to have high transparency. Therefore, as the insulating material, for example, transparent resins such as highly transparent polyethylene terephthalate, polyethylene naphthalate, and polyimide, and glass materials such as alkali-free glass are preferable. On the other hand, when the organic EL device 1 is a top emission type, any insulator can be used as the insulating material, and the above-described transparent resin and glass material can be used.

  The TFT 3 is an active element of each pixel portion, and is formed on the support substrate 2. The TFT 3 includes a gate electrode, a gate insulating film, a semiconductor layer, a source electrode, and a drain electrode. The present invention is not limited to the bottom gate type in which the gate insulating film and the semiconductor layer are sequentially provided on the gate electrode, and may be the top gate type in which the gate insulating film and the gate electrode are sequentially provided on the semiconductor layer.

  The semiconductor layer can be formed using the above-described oxide semiconductor including one or more elements selected from In, Ga, Sn, Ti, Nb, Sb, and Zn.

  The first insulating film 4 is a flattening film that plays a role of flattening surface irregularities due to the TFT 3. The first insulating film 4 is formed so as to cover the entire TFT 3. The 1st insulating film 4 may be formed using the radiation sensitive resin composition mentioned above, and may be formed using a conventionally well-known radiation sensitive resin composition. The first insulating film 4 can be formed by the method described in the above-described insulating film forming method.

  The anode 5 forms a pixel electrode. The anode 5 is formed on the first insulating layer 4 with a conductive material. When the organic EL device 1 is a bottom emission type, the anode 5 is required to be transparent. Therefore, the material of the anode 5 is preferably highly transparent ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), or tin oxide. When the organic EL device 1 is a top emission type, the anode 5 is required to have light reflectivity. Therefore, as the material of the anode 5, Al (aluminum), APC alloy (silver, palladium, copper alloy), ARA (silver, rubidium, gold alloy), MoCr (molybdenum and chromium alloy) having high light reflectivity are used. ), NiCr (nickel and chromium alloy) is preferable, and a laminated film of these metals and a highly transparent electrode (eg, ITO) is preferable.

  The through hole 6 is formed to connect the anode 5 and the drain electrode of the TFT 3.

  The second insulating film 7 serves as a partition (bank) having a recess 70 that defines the arrangement region of the organic light emitting layer 8. The second insulating film 7 is formed so as to cover a part of the anode 5 and to expose a part of the anode 5. The 2nd insulating film 7 can be formed by the method etc. which were demonstrated in the formation method of an insulating film using the radiation sensitive resin composition mentioned above.

  The thickness of the second insulating film 7 (distance between the uppermost surface of the second insulating film 7 and the lowermost surface of the organic light emitting layer 8) is preferably 0.3 μm or more and 25 μm or less, and preferably 0.5 μm or more and 20 μm or less. More preferred.

  The organic light emitting layer 8 emits light when an electric field is applied. The organic light emitting layer 8 is a layer containing an organic light emitting material that emits electroluminescence. The organic light emitting layer 8 is formed on the anode 5 in a region defined by the second insulating film 7, that is, a recess 70. In this way, by forming the organic light emitting layer 8 in the recess 70, the periphery of the organic light emitting layer 8 is surrounded by the second insulating film 7, and adjacent pixels can be partitioned.

  Further, a hole injection layer and / or a hole transport layer may be disposed between the anode 5 and the organic light emitting layer 8, and an electron transport layer and / or an electron between the organic light emitting layer 8 and the cathode 9. An injection layer may be disposed.

  The cathode 9 is formed so as to cover a plurality of pixels in common and serves as a common electrode of the organic EL device 1. The cathode 9 is made of a conductive member. When the organic EL device 1 is a top emission type, the cathode 9 is preferably a visible light transmissive electrode, and examples thereof include an ITO electrode and an IZO electrode. When the organic EL device 1 is a bottom emission type, the cathode 9 does not need to be a visible light transmissive electrode. In that case, examples of the constituent material of the cathode 9 include barium (Ba), barium oxide (BaO), aluminum (Al), and an alloy containing Al.

  The passivation film 10 suppresses the entry of moisture and oxygen into the organic EL element. The passivation film 10 is provided on the cathode 9.

  The sealing substrate 11 seals the main surface (surface opposite to the support substrate 2 in the TFT substrate) on which the organic light emitting layer 8 is disposed. Examples of the sealing substrate 11 include glass substrates such as non-alkali glass substrates. The main surface on which the organic light emitting layer 8 is disposed is preferably sealed with the sealing substrate 11 through the sealing layer 12 using a sealing agent applied in the vicinity of the outer peripheral edge of the TFT substrate. The sealing layer 12 can be, for example, a layer of an inert gas such as dried nitrogen gas or a layer of a filling material such as an adhesive.

  In the organic EL device 1 of the present embodiment, since the second insulating film 7 has a light shielding property with respect to light having a wavelength of 400 nm, it is possible to suppress the photodegradation of the semiconductor layer due to use of the device, etc. Further, since the outgas amount from the second insulating film 7 is small, the light emission characteristics are excellent. In addition, the first insulating film 4 and the second insulating film 7 can be formed using a radiation-sensitive resin composition having low water absorption, and in the process of forming these insulating films 4 and 7, Processing such as cleaning using a low water-absorbing material is possible. Therefore, a slight amount of water contained in the insulating film forming material in the form of adsorbed water or the like can be prevented from gradually entering the organic light emitting layer 8, and deterioration of the organic light emitting layer 8 and deterioration of the light emitting state can be reduced. .

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description, “part” means “part by mass” unless otherwise specified.

[GPC analysis]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the resin (A) and the resin (C) were measured under the following conditions by gel permeation chromatography (GPC).
-Standard material: Polystyrene-Equipment: Tosoh Corporation, trade name: HLC-8020
-Column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL , TSK gel G2000H _XL sequentially connected-Solvent: Tetrahydrofuran (However, in the case of polyimide, N, N -Dimethylformamide)
Sample concentration: 0.7% by mass
・ Injection volume: 70 μL
・ Flow rate: 1mL / min
[NMR analysis]
The chemical shift of the resin (A) was measured by the nuclear magnetic resonance (NMR) method under the following conditions.
・ Device: JEOL Ltd., product name: JNM-ECX400
Solvent: CDCL ₃
[Imidation rate of polyimide]
First, measuring the infrared absorption spectrum of the polyimide, the absorption peak (1780 cm around ^-1, 1377 cm around ^-1) of an imide structure caused by a polyimide was confirmed the presence of. Next, the polyimide was heat-treated at 350 ° C. for 1 hour, and the infrared absorption spectrum was measured again. The peak intensities near 1377 cm ⁻¹ before and after heat treatment were compared. The imidation ratio of polyimide after heat treatment is taken as 100%, and the imidization ratio of polyimide before heat treatment = {peak intensity around 1377 cm ⁻¹ before heat treatment / peak intensity around 1377 cm ⁻¹ after heat treatment} × 100 (%) Asked. For the measurement of the infrared absorption spectrum, “NICOLET6700FT-IR” (manufactured by Thermo Electron) was used.

<Synthesis of Resin (A)>
[Synthesis Example A1] Synthesis of Resin (A-1) After adding 340 g of γ-butyrolactone (BL) as a polymerization solvent to a three-necked flask, 50 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and a total of 390 g of the polymerization solvent. On the other hand, 120 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as a diamine compound was added to the polymerization solvent. After the diamine compound was dissolved in the polymerization solvent, 71 g of 4,4′-oxydiphthalic dianhydride as an acid dianhydride was added. Then, after making it react at 60 degreeC for 1 hour, 19 g of maleic anhydride as a terminal blocker was added, and after making it react at 60 degreeC for further 1 hour, it heated up and made it react at 140 degreeC for 4 hours. During the reaction, the low boiling point solvent PGMEA was distilled off using a Dean-Stark tube under N ₂ flow conditions. As a result, about 550 g of a solution containing the resin (A-1) was obtained. Mw of the obtained resin (A-1) was 7500. The imidation ratio of the obtained resin (A-1) was 10%.

[Synthesis Example A2] Synthesis of Resin (A-2) In a 3-neck flask with a stirrer, 20 parts of 3,4-epoxycyclohexylmethyl methacrylate as component (a3-1) and 10 parts of methacrylic acid as component (a3-2) , 65 parts of benzyl methacrylate as the component (a3-3), 150 parts of propylene glycol monomethyl ether acetate as the solvent, 3 parts of dimethyl-2,2′-azobis (2-methylpropionate) as the polymerization initiator, and a chain transfer agent Was charged with 2 parts of thioglycolic acid and heated at 65 ° C. for 6 hours to obtain a solution containing the resin (A-2). The weight average molecular weight (Mw) of the obtained resin (A-2) was 10,000.

[Synthesis Example A3] Synthesis of Resin (A-3) In a three-necked flask equipped with a stirrer, 40 parts of 3,4-epoxycyclohexylmethyl methacrylate as component (a3-1) and succinic acid mono (as component (a3-2)) 30 parts of 2-methacryloyloxyethyl), 25 parts of benzyl methacrylate as component (a3-3), 150 parts of propylene glycol monomethyl ether acetate as a solvent, dimethyl-2,2′-azobis (2-methylpropio) as a polymerization initiator 3 parts of nate) and 2 parts of thioglycolic acid as a chain transfer agent were heated at 65 ° C. for 6 hours to obtain a solution containing the resin (A-3). The weight average molecular weight (Mw) of the obtained resin (A-3) was 15000.

[Synthesis Example A4] Synthesis of Resin (A-4) In a 500 mL three-necked flask, 63.39 g (0.55 mol) of methyltrimethoxysilane, 69.41 g (0.35 mol) of phenyltrimethoxysilane, 2- ( 3,4-Epoxycyclohexyl) ethyltrimethoxysilane (24.64 g, 0.1 mol) and diacetone alcohol (150.36 g) were charged and stirred at room temperature while water (55.8 g) was charged with phosphoric acid (0.338 g). An aqueous phosphoric acid solution in which 0.2% by mass) was dissolved was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 70 ° C. and stirred for 1 hour, and then the temperature of the oil bath was raised to 115 ° C. over 30 minutes. One hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 2 hours (the internal temperature was 100 to 110 ° C.). During the reaction, a total of 115 g of methanol and water as by-products were distilled out. Diacetone alcohol is added to the obtained resin (A-4) diacetone alcohol solution so that the resin (A-4) concentration is 40% by mass, and the resin (A-4) diacetone alcohol solution is added. Obtained. The weight average molecular weight (Mw) of the obtained resin (A-4) was 5000, and the phenyl group content with respect to 100 mol of Si atoms was 35 mol.

<Synthesis of Resin (C)>
[Synthesis Example C1] Synthesis of Novolak Resin (C-1) In a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer, 144.2 g (1.0 mol) of 1-naphthol, 400 g of methyl isobutyl ketone, 102.3 g (0.7 mol) of α-methylcinnamaldehyde was charged. Subsequently, 3.4 g of a methanol solution of 30% by mass paratoluenesulfonic acid was added with stirring. Then, it was made to react at 100 degreeC for 8 hours. After completion of the reaction, 200 g of pure water was added, the solution in the system was transferred to a separatory funnel, and the aqueous layer was separated and removed from the organic layer. Next, the organic layer was washed with water until the washing water showed neutrality, and then the solvent was removed from the organic layer under heating and reduced pressure to obtain 157 g of novolak resin (C-1). The obtained novolak resin (C-1) had a weight average molecular weight (Mw) of 4,500.

From the measurement chart of the infrared absorption spectrum by “NICOLET6700FT-IR” (manufactured by Thermo Electron), absorption (2700 to 3000 cm ⁻¹ ) derived from C—H stretching due to a substituted methylene bond was confirmed in comparison with the raw material. From these results, it was identified that no dehydration etherification reaction between hydroxyl groups (hydroxyl disappearance) occurred in this synthesis example, and a novolak resin having a substituted methylene bond was obtained. These estimations are the same in the following synthesis examples C2 to C8.

[Synthesis Examples C2 to C8]
Synthesis Examples C2 to C8 were performed in the same manner as Synthesis Example C1 except that the aldehydes listed in Table 1 were used, and novolak resins (C-2) to (C-6) and other novolak resins (C-7) To (C-8). The results are shown in Table 1.

＜感放射線性樹脂組成物の調製＞
感放射線性樹脂組成物の調製に用いた樹脂（Ａ）は合成例Ａ１〜Ａ４の樹脂（Ａ−１）〜（Ａ−４）であり、樹脂（Ｃ）は合成例Ｃ１〜Ｃ６のノボラック樹脂（Ｃ−１）〜（Ｃ−６）であり、他の樹脂（Ｃ’）は合成例Ｃ７〜Ｃ８の他のノボラック樹脂（Ｃ−７）〜（Ｃ−８）であり、感光剤（Ｂ）、架橋剤（Ｄ）、溶剤（Ｅ）、密着助剤（Ｆ）、界面活性剤（Ｇ）および染料（Ｈ）は、下記の通りである。
・感光剤（Ｂ）
Ｂ−１：ナフトキノンジアジドスルホン酸エステル
（ＮＴ−３００Ｐ、東洋合成工業（株）製）
Ｂ−２：１，２−オクタンジオン−１−［４−（フェニルチオ）−２−（Ｏ−ベンゾイルオキシム）］（ＢＡＳＦジャパン（株）製の「ＩＲＡＣＵＲＥ ＯＸＥ０１」）
・架橋剤（Ｄ）
Ｄ−１：４，４−ビス［（３−エチル−３−オキセタニル）メチル］ビフェニル（宇部興産（株）製の「ＯＸＢＰ」）
Ｄ−２：ジペンタエリスリトールヘキサアクリレート
（東亞合成（株）製の「Ｍ−４０２」）
・溶剤（Ｅ）
ＢＬ：γ−ブチロラクトン
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＤＡＡ：ジアセトンアルコール
・密着助剤（Ｆ）
Ｆ−１：Ｎ−フェニル−３−アミノプロピルトリメトキシシラン
（信越化学工業（株）製の「ＫＢＭ−５７３」）
・界面活性剤（Ｇ）
Ｇ−１：シリコーン系界面活性剤（東レダウコーニング社製の「ＳＨ８４００」）
・染料（Ｈ）
Ｈ−１：Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ７０
（有本化学製の「ＯｉｌＢｌｕｅ５５１１」）
Ｈ−２：Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ４５
（有本化学製の「ＰｌａｓｔＢｌｕｅＤＢ−４６３」）
Ｈ−３：Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌａｃｋ２７
（中央合成化学製の「ＮＥＯＳＵＰＥＲＢＬＡＣＫ Ｃ−８３２」）
Ｈ−４：Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ８３（保土ヶ谷化学工業社製の「Ａｉｚｅｎ Ｓｐｉｌｏｎ Ｒｅｄ ＢＥＨ Ｓｐｅｃｉａｌ」）
［実施例１］
合成例Ａ１の樹脂（Ａ−１）を含む樹脂溶液（樹脂（Ａ−１）４０部（固形分）に相当する量）に、（Ｂ−１）１６部、（Ｃ−１）２５部、（Ｄ−１）１５部、（Ｆ−１）３部、（Ｇ−１）１部、および溶剤を混合し、口径０．２μｍのメンブランフィルタで濾過して、表２に記載の組成を有する感放射線性樹脂組成物１を調製した。なお、前記組成物の固形分濃度は３０質量％であった。

<Preparation of radiation-sensitive resin composition>
Resin (A) used for preparation of the radiation sensitive resin composition is Resin (A-1) to (A-4) of Synthesis Examples A1 to A4, and Resin (C) is a novolak resin of Synthesis Examples C1 to C6. (C-1) to (C-6), and other resins (C ′) are other novolak resins (C-7) to (C-8) of Synthesis Examples C7 to C8. ), Crosslinking agent (D), solvent (E), adhesion aid (F), surfactant (G) and dye (H) are as follows.
・ Sensitive agent (B)
B-1: Naphthoquinone diazide sulfonate ester
(NT-300P, manufactured by Toyo Gosei Co., Ltd.)
B-2: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (“IRACURE OXE01” manufactured by BASF Japan Ltd.)
・ Crosslinking agent (D)
D-1: 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl (“OXBP” manufactured by Ube Industries, Ltd.)
D-2: Dipentaerythritol hexaacrylate
("M-402" manufactured by Toagosei Co., Ltd.)
・ Solvent (E)
BL: γ-butyrolactone PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether DAA: diacetone alcohol
・ Adhesion aid (F)
F-1: N-phenyl-3-aminopropyltrimethoxysilane
("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Surfactant (G)
G-1: Silicone surfactant (“SH8400” manufactured by Toray Dow Corning)
・ Dye (H)
H-1: C.I. I. Solvent Blue 70
("OilBlue 5511" manufactured by Arimoto Chemical)
H-2: C.I. I. Solvent Blue45
("PlastBlueDB-463" manufactured by Arimoto Chemical)
H-3: C.I. I. Solvent Black27
("NEOSUPERBLACK C-832" manufactured by Chuo Synthetic Chemical)
H-4: C.I. I. Solvent Red83 ("Aizen Spiron Red BEH Special" manufactured by Hodogaya Chemical Co., Ltd.)
[Example 1]
In a resin solution containing resin (A-1) of Synthesis Example A1 (amount corresponding to 40 parts (solid content) of resin (A-1)), (B-1) 16 parts, (C-1) 25 parts, (D-1) 15 parts, (F-1) 3 parts, (G-1) 1 part, and a solvent are mixed and filtered through a membrane filter having a diameter of 0.2 μm to have the composition shown in Table 2. Radiation sensitive resin composition 1 was prepared. In addition, the solid content concentration of the said composition was 30 mass%.

[Examples 2-27 and Comparative Examples 1-3]
In Examples 2-27 and Comparative Examples 1-3, radiation-sensitive resin compositions 2-30 were prepared in the same manner as in Example 1 except that the components of the types and blending amounts shown in Table 2 were used. .

［評価］
実施例・比較例で得られた感放射線性樹脂組成物を用いて、以下に説明する方法により絶縁膜および有機ＥＬ素子を作製した。前記組成物のパターニング性および放射線感度を、得られた絶縁膜の遮光性（透過率）、吸水性、耐熱性およびアウトガス量を、また得られた有機ＥＬ素子の素子特性を、それぞれ下記方法で評価した。なお、以下の評価において、「上記組成物」とは、実施例・比較例で得られた感放射線性樹脂組成物を意味する。

[Evaluation]
Using the radiation-sensitive resin compositions obtained in Examples and Comparative Examples, an insulating film and an organic EL element were produced by the method described below. The patterning property and radiation sensitivity of the composition, the light-shielding property (transmittance), water absorption, heat resistance, and outgas amount of the obtained insulating film, and the device characteristics of the obtained organic EL device, were as follows. evaluated. In the following evaluation, the “composition” means a radiation-sensitive resin composition obtained in Examples and Comparative Examples.

<Patternability>
The composition was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 120 ° C. for 2 minutes to form a coating film. This coating film was exposed at an exposure amount of 100 mJ / cm ² at a wavelength of 365 nm through a pattern mask having a predetermined pattern using an exposure machine (“MPA-6000” manufactured by Canon Inc.). The exposure amount was measured with an illuminometer (“OAI model 356” manufactured by OAI Optical Associates). After that, development was performed by using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds, washed with ultrapure water for 1 minute, dried, and dried on a silicon substrate. A coating film having a pattern in which a plurality of through holes of 5 μm were arranged in a line was formed. This coating film was post-baked at 250 ° C. for 45 minutes in a clean oven to obtain an insulating film having a thickness of 3.0 μm.

  At this time, in the coating film, it was confirmed whether the exposed portion after development was completely dissolved in the case of the positive type or whether the non-exposed portion after development was completely dissolved in the case of the negative type. “Good” when a 5 μm pattern is formed and an insulating film is formed without insulating film peeling or development residue 5 μm when a 5 μm pattern is formed and there is no insulating film peeling but there is a slight development residue The case where this pattern cannot be formed, or the case where the insulating film peels off is determined as “defective”.

<Radiation sensitivity>
The composition was applied onto a silicon substrate using a spinner and then pre-baked on a hot plate at 120 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The coating film was exposed using an exposure machine (Canon “MPA-6000”) while changing the exposure amount through a pattern mask having a predetermined pattern. After that, development was performed by using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds, washed with ultrapure water for 1 minute, dried, and dried on a silicon substrate. A coating film having a plurality of through holes of 20.0 μm was formed.

At this time, the exposure amount required for the coating film to completely dissolve in accordance with the shape of the mask pattern having a diameter of 20.0 μm was measured, and the exposure amount at this time was defined as radiation sensitivity (exposure sensitivity). The radiation sensitivity was “good” when the exposure dose at a wavelength of 365 nm was 100 mJ / cm ² or less, and “bad” when the exposure amount exceeded 100 mJ / cm ² . The exposure amount was measured with an illuminometer (“OAI model 356” manufactured by OAI Optical Associates).

<Transmissivity>
After applying the above composition on a glass substrate (Corning “Corning 7059”) using a spinner, prebaking at 120 ° C. for 2 minutes on a hot plate, and then post-baking at 250 ° C. for 45 minutes in a clean oven. Baking was performed to form an insulating film having a thickness of 3.0 μm.

  For the glass substrate having this insulating film, the total light transmittance was measured in the wavelength range of 300 nm to 780 nm using a spectrophotometer (“150-20 type double beam” manufactured by Hitachi, Ltd.), and the wavelength was 400 nm. The total light transmittance was determined. This transmittance is “excellent” when the total light transmittance at a wavelength of 400 nm is 5% or less, “good” when it exceeds 5% and 15% or less, and “bad” when it exceeds 15%. did. Moreover, the total light transmittance in wavelength 600nm was calculated | required. This transmittance was “excellent” when the total light transmittance at a wavelength of 600 nm was 10% or less, and “good” when it exceeded 10% and was 30% or less.

<Water absorption>
After applying the above composition on a silicon substrate using a spinner, pre-baking on a hot plate at 120 ° C. for 2 minutes and then post-baking in a clean oven at 250 ° C. for 45 minutes to obtain a film thickness of 3.0 μm An insulating film having was formed.

This insulating film was heated from normal temperature to 200 ° C. at a vacuum degree of 1.0 × 10 ⁻⁹ Pa using Thermal Desorption Spectroscopy (“TDS1200” from ESCO) (30 ° C./min). At that time, the sample surface and the gas desorbed from the sample were measured as a detected value of the peak of water (M / z = 18) with a mass spectrometer (“5973N” manufactured by Agilent Technologies). The integrated value [A · sec] of the total peak intensity from 60 ° C. to 200 ° C. was taken to evaluate the water absorption. The water absorption is “excellent” when the integrated value [A · sec] of the total peak intensity from 60 ° C. to 200 ° C. is 3.0 × 10 ⁻⁸ or less, exceeding 3.0 × 10 ⁻⁸ . When it was 0 × 10 ⁻⁸ or less, it was ^judged as “good” and when it exceeded 5.0 × 10 ⁻⁸ , it was ^judged as “bad”.

<Heat resistance>
In the same manner as in the evaluation of <Water Absorption>, an insulating film is formed using the above composition, and this insulating film is heated to 100 ° C. to 500 ° C. using a thermogravimetric apparatus (“TGA2950” manufactured by TA Instruments). A 5% weight loss temperature was determined by performing TGA measurement at 10 ° C. (in air, at a rate of temperature increase of 10 ° C./min). The heat resistance was “excellent” when the 5% weight loss temperature exceeded 350 ° C., and “good” when the temperature was 350 to 330 ° C.

<Outgas>
In the same manner as in the evaluation of <water absorption>, an insulating film is formed using the above composition, a silicon substrate with an insulating film is cut into 1 cm × 5 cm pieces, and a silicon wafer analyzer device (product) Name “Heat Desorption Device JTD-505” manufactured by Nippon Analytical Industries, Ltd., “Gas Chromatograph Mass Spectrometer GCMS-QP2010 Plus” manufactured by Shimadzu Corporation), maintained at 230 ° C. for 15 minutes (temperature increase rate 10 ° C. ) / Min), the amount of outgas in μg / cm ³ was determined.

<Evaluation of device characteristics>
Using a glass substrate (Corning “Corning 7059”), a TFT substrate having TFTs formed on the glass substrate was prepared, and then an insulating film was formed on the TFT substrate to prepare an evaluation element. The element characteristics were evaluated for this evaluation element.

The TFT substrate was formed by the following procedure. First, a molybdenum film was formed on a glass substrate by sputtering, and a gate electrode was formed by photolithography using a resist and etching. Next, a silicon oxide film was formed by sputtering on the entire surface of the glass substrate and on the upper layer of the gate electrode to form a gate insulating film. An InGaZnO-based amorphous oxide film (InGaZnO ₄ ) was formed on the gate insulating film by sputtering, and a semiconductor layer was formed by photolithography and etching using a resist. A molybdenum film was formed on the semiconductor layer by sputtering, and a source electrode and a drain electrode were formed by photolithography and etching using a resist. Finally, a silicon oxide film was formed by sputtering on the entire surface of the substrate and on the upper layer of the source electrode and drain electrode to obtain a passivation film, thereby obtaining a TFT substrate.

  After applying the above composition on the TFT substrate using a spinner, pre-baking on a hot plate at 120 ° C. for 2 minutes and then post-baking in a clean oven at 250 ° C. for 45 minutes to obtain a film thickness of 3.0 μm An insulating film having was formed.

<Switching response characteristics>
The device characteristics were evaluated as switching response characteristics. The switching response characteristic was evaluated by measuring the ON / OFF ratio. The ON / OFF ratio was calculated by measuring the current flowing between the source electrode and the drain electrode with a voltage applied to the gate electrode using a prober and a semiconductor parameter analyzer. Specifically, the drain electrode is set to plus 10 V under the condition that the semiconductor layer is irradiated with white light (illuminance 30000 lux) centered on a wavelength of 450 nm or 500 nm from above the insulating film formed from the above composition. The ratio of the current value when the voltage applied to the gate electrode is plus 10 V and minus 10 V when the source electrode is 0 V is defined as the ON / OFF ratio. The switching response characteristics, that is, the element characteristics, were “good” when the ON / OFF ratio was 1.0 × 10 ⁵ or more, and “bad” when the ON / OFF ratio was less than 1.0 × 10 ⁵ .

<TFT reliability>
TFT reliability refers to changes in Id-Vg characteristics (amount of change in threshold voltage Vth) when an electrical stress is applied between the gate electrode and the source electrode, when the evaluation element is irradiated with light and when light is not irradiated. It was evaluated by comparing with.

(Measurement of Id-Vg characteristics and threshold voltage Vth)
The electrical stress is applied by keeping the potential of the source electrode of the evaluation element at 0 V, the potential of the drain electrode at +10 V, and applying the voltage between the source electrode and the drain electrode, and the potential Vg of the gate electrode at −20 V. To + 20V. In this way, when the potential Vg of the gate electrode is changed, the current Id flowing between the drain electrode and the source electrode is plotted to obtain the Id-Vg characteristic. In this Id-Vg characteristic, the voltage at which the current value is ON is set to the threshold voltage Vth.

(Measurement of change in threshold voltage Vth)
Electrical stress was applied by applying a positive voltage of +20 V and a negative voltage of −20 V for 12 hours between the gate electrode and the source electrode. Such electrical stress was performed under the condition where the semiconductor film of the evaluation element was irradiated with light from above and under the condition where the semiconductor film was not irradiated with light. The amount of change in the threshold voltage Vth was calculated from the Id-Vg characteristic for each of the light irradiation condition and the light non-irradiation condition. When the amount of change in the threshold voltage Vth during light irradiation is suppressed to less than 1.5 times the amount of change in the threshold voltage Vth during non-light irradiation, the TFT reliability is assumed to be “excellent”. The TFT reliability is determined to be “good” when it is suppressed to 5 to 2 times, and the TFT reliability is determined to be “bad” when it exceeds 2 times.

<EL emission characteristic evaluation>
Using a glass substrate (Corning “Corning 7059”), an ITO transparent electrode was sputtered on this glass substrate, and then a photosensitive resist (“NN700”, manufactured by JSR Corporation) was applied by spin coating. It dried and exposed through the predetermined pattern mask. After exposure, development and heat curing were performed to form a predetermined resist pattern. Subsequently, the ITO film was etched using an etching solution to form a predetermined ITO film pattern, and then the resist pattern was removed with a stripping solution.

  After applying a photosensitive resist (“NN700”, manufactured by JSR Corporation) to a film thickness of 5 μm by spin coating on the glass substrate on which ITO transparent electrodes are formed in an array as described above, A coating film was formed by pre-baking on a hot plate at 80 ° C. for 3 minutes. Subsequently, this coating film was exposed through a predetermined pattern mask. After exposure, the film was developed and post-baked at 200 ° C. for 5 minutes in a clean oven. In this way, a planarization layer having a contact hole in which only a part of the ITO transparent electrode was exposed was formed on the glass substrate. The thickness of the planarization layer after post-baking was 3 μm. A plurality of glass substrates on which a planarizing layer was formed as described above were prepared and used in the following steps.

  An Al film having a thickness of 100 nm was formed on a glass substrate on which a planarization layer was formed by DC sputtering using an Al target. Subsequently, a photosensitive resist (“NN700”, manufactured by JSR Corporation) was applied by a spin coat method, dried, and exposed through a predetermined pattern mask. After exposure, development and heat curing were performed to form a predetermined resist pattern. Subsequently, the Al film was etched using a mixed acid etching solution to form a predetermined Al film pattern, and then the resist pattern was removed with a stripping solution. Thereafter, the glass substrate was transferred to a sputtering apparatus, and an ITO film having a thickness of 20 nm was formed on the Al pattern by a DC magnetron reactive sputtering method using an ITO target. Subsequently, a photosensitive resist (“NN700”, manufactured by JSR Corporation) was applied by a spin coat method, dried, and exposed through a predetermined pattern mask. After exposure, development and heat curing were performed to form a predetermined resist pattern. Subsequently, the ITO film was etched using an etching solution to form an ITO film pattern similar to the Al film on the Al film, and then the resist pattern was removed with a stripping solution. In this way, an anode composed of an Al film and an ITO film was formed.

After applying the above composition to the obtained anode substrate using a clean track (manufactured by Tokyo Electron Co., Ltd .: Mark VZ), it was pre-baked on a hot plate at 120 ° C. for 2 minutes to form a coating having a thickness of 4 μm. A film was formed. This coating film was exposed using an exposure machine (Nikon i-line stepper “NSR-2005i10D”) through a pattern mask having a predetermined pattern at an exposure amount of 100 mJ / cm ² at a wavelength of 365 nm. Thereafter, development was carried out by using a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds, washing with ultrapure water for 1 minute, drying, and drying in a clean oven at 250 ° C. Was post-baked for 45 minutes to form partition walls on the anode substrate.

  An organic EL element was formed on the anode substrate on which the partition walls were formed by a vacuum deposition method. The organic EL element was prepared by the following procedure.

The anode substrate on which the partition walls were formed was subjected to ultrasonic cleaning, and then the substrate was transferred into an N ₂ atmosphere and dried at 200 ° C. for 3 hours. Further, the substrate was transferred to an oxygen plasma processing apparatus, evacuated, and 50 W RF power was applied to a ring electrode provided in the vicinity of the substrate to perform an oxygen plasma cleaning process. The oxygen pressure was 0.6 Pa and the treatment time was 40 seconds.

After the substrate is moved to the vacuum film formation chamber and the film formation chamber is evacuated to 1E ^-4 Pa, molybdenum oxide (MoOx) having a hole injection property is deposited on the substrate using a vapor deposition mask having a predetermined pattern. A hole-injection layer having a film thickness of 1 nm was formed by resistance heating vapor deposition at a film formation rate of 0.004 to 0.005 nm / sec.

  On the hole injection layer, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) having hole transportability is formed using a deposition mask having a predetermined pattern. A film was formed by resistance heating vapor deposition under the same exhaust conditions as the hole injection layer to form a 35 nm-thick hole transport layer. The film formation rate was 0.2 to 0.3 nm / sec.

On the hole transport layer, tris (8-quinolinolato) aluminum (Alq ₃ ), which is an alkylate complex, is used as a green light emitting material by a resistance heating vapor deposition method in the same manner as the hole transport layer, using a vapor deposition mask having a predetermined pattern. A light emitting layer having a film thickness of 35 nm was formed. The film formation rate was 0.5 nm / sec or less.

  On the light emitting layer, lithium fluoride was deposited by resistance heating vapor deposition under the same exhaust conditions as the hole injection layer to form an electron injection layer having a thickness of 0.8 nm. The film formation rate was 0.004 nm / sec or less.

  Subsequently, the substrate was transferred to another film formation chamber (sputtering chamber), and a cathode having a thickness of 130 nm was formed on the electron injection layer by an RF sputtering method using an ITO target.

The substrate is transferred to the glove box, N ₂ leaks, and the sealing glass with the hygroscopic material attached to the element surface side is bonded to the substrate using a UV curing acrylic adhesive. And sealed.

  The organic EL element for evaluation was obtained as described above.

  The organic EL element for evaluation was stored in a constant temperature and humidity chamber having a temperature of 85 ° C. and a humidity of 85% for 500 hours, and then the organic EL element was started at room temperature to observe a dark spot (non-light emitting portion). The case where the area of the dark spot was less than 10% with respect to the whole was determined as “good”, and the case where it was 10% or more or quenched was determined as “bad”.

表３および表４に示すように、実施例１〜２７で形成した絶縁膜は、遮光性に優れており、またアウトガス量も少なかった。また、実施例１〜２７の組成物および絶縁膜は、パターニング性、放射線感度、低吸水性および耐熱性にも優れていた。この絶縁膜および光劣化しやすい半導体層を使用した素子は、光照射環境下においても、スイッチング応答特性およびＴＦＴ信頼性に優れていた。また、得られた有機ＥＬ素子は、ＥＬ発光特性に優れていた。

As shown in Tables 3 and 4, the insulating films formed in Examples 1 to 27 were excellent in light shielding properties and had a small outgas amount. Moreover, the composition and insulating film of Examples 1-27 were excellent also in patternability, radiation sensitivity, low water absorption, and heat resistance. An element using this insulating film and a semiconductor layer that is easily deteriorated in light was excellent in switching response characteristics and TFT reliability even in a light irradiation environment. Moreover, the obtained organic EL element was excellent in EL light emission characteristics.

  On the other hand, since the composition of Comparative Example 3 did not contain a novolac resin, the formed insulating film was inferior in light shielding properties and inferior in device characteristics. Moreover, although the composition of Comparative Examples 1-2 contains novolak resin, the said novolak resin is not resin which has a structural unit represented by Formula (C1) (it corresponds to alkali-soluble resin (A)). For this reason, the insulating film formed from the composition of Comparative Examples 1 and 2 has a large amount of outgas and is inferior in EL emission characteristics, and the composition of Comparative Examples 1 and 2 is inferior in patternability and radiation sensitivity. It was.

  DESCRIPTION OF SYMBOLS 1 ... Organic EL apparatus, 2 ... Support substrate, 3 ... TFT, 4 ... 1st insulating film (planarization film), 5 ... Anode, 6 ... Through hole, 7 ... 2nd insulating film (partition), 70 ... Concave part, 8 ... organic light emitting layer, 9 ... cathode, 10 ... passivation film, 11 ... sealing substrate, 12 ... sealing layer

Claims (15)

(B) a photosensitive agent;
(C) formed from a radiation-sensitive resin composition containing a resin having a structural unit represented by formula (C1) and at least one resin selected from a resin having a structure represented by formula (C2) A display or lighting device element having the insulating film formed.

[In Formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, and L is represented by Formula (c2-1), Formula (c2-2), or Formula (c2-3). Is a valent group. ]

[In Formula (C2), A ′ is a k + m + n-valent aromatic group having a phenolic hydroxyl group, and L is represented by Formula (c2-1), Formula (c2-2), or Formula (c2-3). A monovalent group, a plurality of Ls may be the same or different, * is a bond to another A ′, k is an integer of 0 to 9, and m is 0 to 0; It is an integer of 9, n is an integer of 0-9, k + m + n is an integer of 1-9. ]

[In the formula (c2-1), X is an oxygen atom, a sulfur atom, —CH ₂ — or —NH—, and R ¹ is a halogen atom, —OH, —SH, —NO ₂ , —NH ₂ , hydrocarbon. A monovalent group selected from a group and a heteroatom-containing group having 1 or more carbon atoms, and m is an integer of 0 to 3, provided that in the case of formula (C1), when m = 0, X is When there are a plurality of R ^{1 s} instead of oxygen atoms, they may be the same or different, and R ¹ bonded to adjacent ring carbons may be bonded to each other to form a ring;
Wherein (c2-2), Y is a nitrogen atom, C-H or C-R ^2, R ² has the same meaning as R ¹ in the formula (c2-1), R ³ and R ⁴ are each independently Is a hydrogen atom or a hydrocarbon group, n is an integer of 0 to 4, and d is 0 or 1, provided that in the case of formula (C1), when n = d = 0, Y is C— R ² is not —NO ₂ , —OH when not H and when n = d = 0 and Y is C—R ² , or when n = 1, d = 0 and Y is C—H In the case where a plurality of R ² are present, they may be the same or different, and R ² bonded to adjacent ring carbons may be bonded to each other to form a ring;
In formula (c2-3), R ⁵ has the same meaning as R ¹ in formula (c2-1), l is each independently an integer of 0 to 5, and when a plurality of R ⁵ are present, they are the same. They may be different from each other, and R ⁵ bonded to adjacent ring carbons may be bonded to each other to form a ring. ] The display or illumination device according to claim 1, wherein A in the formula (C1) is a divalent group represented by the formula (c1-1), the formula (c1-2), or the formula (c1-3). Element.

[In the formulas (c1-1) to (c1-3), a1 is an integer of 1 to 4, b1 is an integer of 0 to 3, and a2 to a5 and b2 to b5 are each independently 0 to 4 A6 and b6 are integers of 0 to 2, provided that a2 + a3 is an integer of 1 to 6, a2 + a3 + b2 + b3 is an integer of 1 to 6, and a4 + a5 + a6 is an integer of 1 to 8 , A4 + a5 + a6 + b4 + b5 + b6 is an integer of 1 to 8, and R is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ] The radiation-sensitive resin composition is
(A) The display or lighting device element according to claim 1, further comprising an alkali-soluble resin excluding the resin (C).   Alkali-soluble resin (A) is polyimide (A1), polyimide precursor (A2), acrylic resin (A3), polysiloxane (A4), polybenzoxazole (A5), and polybenzoxazole precursor (A6). The display or illumination device element according to claim 3, which is at least one selected from the group consisting of: The element for a display or lighting device according to claim 4, wherein the polyimide (A1) is a polyimide having a structural unit represented by the formula (A1).

[In Formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. ]   The display or lighting device element according to claim 4, wherein the acrylic resin (A3) is a resin obtained by polymerizing at least a radical polymerizable monomer having a carboxyl group. The element for a display or lighting device according to claim 4, wherein the polysiloxane (A4) is a polysiloxane obtained by reacting an organosilane represented by the formula (a4).

[In the formula (a4), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group-containing group having 6 to 15 carbon atoms, or an epoxy ring having 2 to 15 carbon atoms. Or a group formed by replacing one or more hydrogen atoms contained in the alkyl group with a substituent, and when there are a plurality of R ^{1 s} , they may be the same or different; R ² is a hydrogen atom, An alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and when there are a plurality of R ^{2 s} , they may be the same or different; It is an integer of 3. ]   The display or illumination device element according to any one of claims 1 to 7, wherein the photosensitive agent (B) is at least one selected from a photoacid generator, a photoradical polymerization initiator, and a photocationic polymerization initiator. .   In the said radiation sensitive resin composition, content of resin (C) is 5-200 mass parts with respect to 100 mass parts of resin (A), The display of any one of Claims 3-7, or Element for lighting device.   The display or lighting device element according to any one of claims 1 to 9, which is an organic electroluminescence element. (B) a photosensitive agent;
(C) A radiation-sensitive resin composition comprising: a resin having a structural unit represented by formula (C1); and at least one resin selected from a resin having a structure represented by formula (C2).

[In Formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, and L is represented by Formula (c2-1), Formula (c2-2), or Formula (c2-3). Is a valent group. ]

[In Formula (C2), A ′ is a k + m + n-valent aromatic group having a phenolic hydroxyl group, and L is represented by Formula (c2-1), Formula (c2-2), or Formula (c2-3). A monovalent group, a plurality of Ls may be the same or different, * is a bond to another A ′, k is an integer of 0 to 9, and m is 0 to 0; It is an integer of 9, n is an integer of 0-9, k + m + n is an integer of 1-9. ]

[In the formula (c2-1), X is an oxygen atom, a sulfur atom, —CH ₂ — or —NH—, and R ¹ is a halogen atom, —OH, —SH, —NO ₂ , —NH ₂ , hydrocarbon. A monovalent group selected from a group and a heteroatom-containing group having 1 or more carbon atoms, and m is an integer of 0 to 3, provided that in the case of formula (C1), when m = 0, X is When there are a plurality of R ^{1 s} instead of oxygen atoms, they may be the same or different, and R ¹ bonded to adjacent ring carbons may be bonded to each other to form a ring;
Wherein (c2-2), Y is a nitrogen atom, C-H or C-R ^2, R ² has the same meaning as R ¹ in the formula (c2-1), R ³ and R ⁴ are each independently Is a hydrogen atom or a hydrocarbon group, n is an integer of 0 to 4, and d is 0 or 1, provided that in the case of formula (C1), when n = d = 0, Y is C— R ² is not —NO ₂ , —OH when not H and when n = d = 0 and Y is C—R ² , or when n = 1, d = 0 and Y is C—H In the case where a plurality of R ² are present, they may be the same or different, and R ² bonded to adjacent ring carbons may be bonded to each other to form a ring;
In formula (c2-3), R ⁵ has the same meaning as R ¹ in formula (c2-1), l is each independently an integer of 0 to 5, and when a plurality of R ⁵ are present, they are the same. They may be different from each other, and R ⁵ bonded to adjacent ring carbons may be bonded to each other to form a ring. ] (A) The radiation sensitive resin composition of Claim 11 which further contains alkali-soluble resin except the said resin (C). (B) a photosensitive agent;
(C) formed from a radiation-sensitive resin composition containing a resin having a structural unit represented by formula (C1) and at least one resin selected from a resin having a structure represented by formula (C2) Insulating film.

[In Formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, and L is represented by Formula (c2-1), Formula (c2-2), or Formula (c2-3). Is a valent group. ]

[In Formula (C2), A ′ is a k + m + n-valent aromatic group having a phenolic hydroxyl group, and L is represented by Formula (c2-1), Formula (c2-2), or Formula (c2-3). A monovalent group, a plurality of Ls may be the same or different, * is a bond to another A ′, k is an integer of 0 to 9, and m is 0 to 0; It is an integer of 9, n is an integer of 0-9, k + m + n is an integer of 1-9. ]

[In the formula (c2-1), X is an oxygen atom, a sulfur atom, —CH ₂ — or —NH—, and R ¹ is a halogen atom, —OH, —SH, —NO ₂ , —NH ₂ , hydrocarbon. A monovalent group selected from a group and a heteroatom-containing group having 1 or more carbon atoms, and m is an integer of 0 to 3, provided that in the case of formula (C1), when m = 0, X is When there are a plurality of R ^{1 s} instead of oxygen atoms, they may be the same or different, and R ¹ bonded to adjacent ring carbons may be bonded to each other to form a ring;
Wherein (c2-2), Y is a nitrogen atom, C-H or C-R ^2, R ² has the same meaning as R ¹ in the formula (c2-1), R ³ and R ⁴ are each independently Is a hydrogen atom or a hydrocarbon group, n is an integer of 0 to 4, and d is 0 or 1, provided that in the case of formula (C1), when n = d = 0, Y is C— R ² is not —NO ₂ , —OH when not H and when n = d = 0 and Y is C—R ² , or when n = 1, d = 0 and Y is C—H In the case where a plurality of R ² are present, they may be the same or different, and R ² bonded to adjacent ring carbons may be bonded to each other to form a ring;
In formula (c2-3), R ⁵ has the same meaning as R ¹ in formula (c2-1), l is each independently an integer of 0 to 5, and when a plurality of R ⁵ are present, they are the same. They may be different from each other, and R ⁵ bonded to adjacent ring carbons may be bonded to each other to form a ring. ] The radiation-sensitive resin composition is
The insulating film according to claim 13, further comprising (A) an alkali-soluble resin excluding the resin (C).   A step of forming a coating film on a substrate using the radiation-sensitive resin composition according to claim 11, a step of irradiating at least a part of the coating film, and a coating film irradiated with the radiation. The manufacturing method of an insulating film which has the process to develop and the process to heat the said developed coating film.

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