KR102298983B1 - Element, insulating film, method for producing same, and radiation sensitive resin composition - Google Patents

Abstract

[식 (C1) 중, A는 페놀성 수산기를 갖는 2가의 방향족기이고, L은 특정의 식으로 나타나는 1가의 기이고, 식 (C2) 중, A'는 페놀성 수산기를 갖는 k＋m＋n가의 방향족기이고, L은 특정의 식으로 나타나는 1가의 기이고, 복수 있는 L은 각각 동일해도 상이해도 좋고, *는 다른 A'와의 결합손이고, k는 0∼9의 정수이고, m은 0∼9의 정수이고, n은 0∼9의 정수이고, k＋m＋n은 1∼9의 정수임]An element for a display or lighting device having a small amount of outgas generated and an insulating film having light-shielding properties in the vicinity of an ultraviolet region is provided.
(B) a photosensitizer, (C) 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) formed from a radiation-sensitive resin composition containing An element for a display or lighting device having an insulating film.

[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 a k+m+n aromatic group having a phenolic hydroxyl group , L is a monovalent group represented by a specific formula, a plurality of L may be the same or different, * is a bond with another A', k is an integer from 0 to 9, m is from 0 to 9 an integer, n is an integer from 0 to 9, and k+m+n is an integer from 1 to 9]

Description

An element, an insulating film, its manufacturing method, and a radiation-sensitive resin composition TECHNICAL FIELD

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

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

For example, an organic EL display or lighting device has an insulating film, such as a planarization film and a partition which partitions a pixel. Such an insulating film is generally formed using a radiation-sensitive resin composition (refer patent documents 1 and 2, for example).

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

Japanese Laid-Open Patent Publication No. 2011-107476 Japanese Laid-Open Patent Publication No. 2010-237310 Japanese Laid-Open Patent Publication No. 2004-103957 International Publication No. 2005/088726 Pamphlet

In IGZO, light deterioration by natural light, lighting, a manufacturing process, etc. is known. For this reason, when using TFT containing the semiconductor layer which consists of a material with large light deterioration, such as IGZO, as an element for a drive of a display or lighting apparatus, especially, as an element for a drive of an organic EL element, from a viewpoint of the prevention of light deterioration of IGZO , As a characteristic of the above-described insulating film, light-shielding properties from ultraviolet to visible light are required. However, many insulating films currently used are transparent, for example in the vicinity of an ultraviolet region.

Moreover, it is necessary for the radiation-sensitive resin composition to be able to form the insulating film with little generation amount of outgas from a viewpoint of manufacturing the element excellent in light emitting characteristic.

The present invention provides a radiation-sensitive resin composition capable of forming an insulating film having a small amount of outgas generated and having light-shielding properties in the vicinity of an ultraviolet region, an insulating film formed of the composition and a method for manufacturing the same, and an element having the insulating film make it a task

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. As a result, it discovered that the said subject could be solved by employ|adopting the following structures, and came to complete this invention. The present invention relates to, for example, the following [1] to [15].

[1] (B) a photosensitizer, and (C) at least one resin selected from a resin having a structural unit represented by formula (C1) to be described later, and a resin having a structure represented by formula (C2) to be described later. An element for a display or lighting device having an insulating film formed of a radiation-sensitive resin composition.

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

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

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

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

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

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

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

[9] The indication according to any one of [3] to [7] above, wherein in the radiation-sensitive resin composition, the content of the resin (C) is 5 to 200 parts by mass based on 100 parts by mass of the resin (A), or Elements for lighting devices.

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

[11] (B) a photosensitizer, and (C) at least one resin selected from a resin having a structural unit represented by formula (C1) to be described later, and a resin having a structure represented by formula (C2) to be described later. A radiation-sensitive resin composition.

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

[13] (B) a photosensitizer, and (C) at least one resin selected from a resin having a structural unit represented by formula (C1) to be described later, and a resin having a structure represented by formula (C2) to be described later. An insulating film formed of a radiation-sensitive resin composition.

[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 with radiation, and developing the radiation-irradiated coating film and heating the developed coating film.

According to the present invention, there is provided a radiation-sensitive resin composition capable of forming an insulating film having a small amount of outgas generated and having light-shielding properties in the vicinity of an ultraviolet region, an insulating film formed of the composition and a method for manufacturing the same, and an element having the insulating film can provide For this reason, for example, in an organic EL element having a thin film transistor including a semiconductor layer made of a material with high light deterioration such as IGZO as a driving element, light deterioration of the material accompanying the use of the element can be suppressed. can For this reason, it is possible to obtain an organic EL device having improved reliability and light emission characteristics.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the outline of the structure of the principal part of an organic electroluminescent device.

(Form for implementing the invention)

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

[ radiation sensitive resin composition]

The radiation-sensitive resin composition of the present invention is at least one selected from a photosensitive agent (B), a resin having a structural unit represented by Formula (C1) to be described later, and a resin having a structure represented by Formula (C2) to be described later. It contains resin (C). It is preferable that the said composition contains the alkali-soluble resin (A) mentioned later further.

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

Hereinafter, each component is described in detail.

[Alkali-soluble resin (A)]

Resin (A) is alkali-soluble resin except resin (C).

Examples of the resin (A) include polyimide (A1), the polyimide precursor (A2), acrylic resin (A3), polysiloxane (A4), polybenzoxazole (A5), and polybenzoxazole. At least 1 sort(s) chosen from a precursor (A6) is mentioned. An insulating film formed from the resin (A), particularly an insulating film formed from at least one selected from polyimide (A1), polyimide precursor (A2), and polysiloxane (A4), is excellent in heat resistance.

The weight average molecular weight (Mw) in terms of polystyrene of the resin (A) is a value measured by a gel permeation chromatography (GPC) method, usually 2,000 to 500,000, preferably 3,000 to 100,000, more preferably 4,000 50,000. When Mw is equal to or more than the lower limit of the above range, an insulating film having sufficient mechanical properties tends to be obtained. When Mw is below the upper limit of the said range, there exists a tendency excellent in the solubility of resin (A) with respect to a solvent or a developing solution.

Alkali solubility in resin (A) means that it can swell or melt|dissolve in an alkali solution, for example, 2.38 mass % tetramethylammonium hydroxide aqueous solution.

10-90 mass % is preferable with respect to 100 mass % of total solids in the composition of this invention, as for content of resin (A), 20-80 mass % is more preferable, 30-75 mass % is still more preferable.

<< polyimide (A1) >>

It is preferable that polyimide (A1) has a structural unit represented by Formula (A1).

In formula (A1), R<^1> is a divalent group which has a hydroxyl group, and X is a tetravalent organic group.

As R<^1> , the divalent group represented by Formula (a1) is mentioned, for example.

In formula (a1), R ² is a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group, or a bis(trifluoromethyl)methylene group;

R ³ is each independently a hydrogen atom, a formyl group, an acyl group, or an alkyl group. However, ^{at least 1 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 sum total of n1 and n2 is 2 or more, some R<^3> may be same or different.

Examples of the acyl group for R ³ 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, etc. and a group having 1 to 20 carbon atoms.

As divalent group represented by Formula (a1), the divalent group which has 1-4 hydroxyl groups is preferable, and the divalent group which has two hydroxyl groups is more preferable. Examples of the divalent group represented by the formula (a1) and having 1 to 4 hydroxyl groups include a divalent group represented by the following formula. In addition, in the following formula, * represents a bond.

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). It is preferable that X is a tetravalent organic group derived from tetracarboxylic dianhydride. Among these, the group represented by following formula (1) is preferable.

In the 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.

The number of carbon atoms of the tetravalent aliphatic hydrocarbon group is usually 4 to 30, preferably 8 to 24. Carbon number of the 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 having an aromatic ring in at least a part of its 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.

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[3.1.1]heptane, bicyclo[3.1.1]hepto-2-ene, bicyclo[2.2.2]octane, bicyclo[2.2.2]octa-5 -bicyclic hydrocarbons, such as ene;

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} ]dodecane, etc. and a tetravalent group derived from a tricyclic or higher hydrocarbon of

As an aliphatic hydrocarbon group which contains an aromatic ring in at least one part of molecular structure, it is preferable that the number of benzene nuclei contained in the said group is three or less, and it is especially preferable that it is one. More specifically, a tetravalent group derived from 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene, and the like is exemplified.

In the above description, the tetravalent group derived from the above-mentioned hydrocarbon is a tetravalent group formed by excluding four hydrogen atoms from the above-mentioned hydrocarbon. The excluded location of four hydrogen atoms is a location which can form a tetracarboxylic dianhydride structure, when the said four hydrogen atoms are substituted by four carboxyl groups.

As the tetravalent aliphatic hydrocarbon group, a tetravalent group represented by the following formula is preferable. In addition, in the following formula, * represents a bond.

As a tetravalent aromatic hydrocarbon group and group represented by said Formula (1), the tetravalent group represented by a following formula is mentioned, for example. In addition, in the following formula, * represents a bond.

A polyimide (A1) can be obtained by imidation of the polyimide precursor (A2) demonstrated below. Imidization here may proceed completely or may proceed partially. That is, the imidation ratio may not be 100%. For this reason, the polyimide (A1) may further have at least 1 sort(s) chosen from the structural unit represented by Formula (A2-1) and the structural unit represented by Formula (A2-2) which are demonstrated below.

In polyimide (A1), the imidation ratio becomes like this. Preferably it is 5 % or more, More preferably, it is 7.5 % or more, More preferably, it is 10 % or more. The upper limit of the imidation ratio is preferably 50%, more preferably 30%. When the imidation rate exists in the said range, it is preferable at the point of heat resistance and the solubility with respect to the developing solution of an exposed part. The imidation ratio can be measured according to the conditions described in Examples.

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

<< polyimide precursor (A2) >>

A polyimide precursor (A2) is a polyimide (A1), It is a compound which can produce|generate the polyimide (A1) which preferably has a structural unit represented by Formula (A1) by dehydration and cyclization (imidization). Examples of the polyimide precursor (A2) include polyamic acid and polyamic acid derivatives.

( polyamic acid )

Polyamic acid has a structural unit represented by Formula (A2-1).

In formula (A2-1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. As a divalent group which has a hydroxyl group represented by R<^1> , and a tetravalent organic group represented by X, the thing similar to the group illustrated as ^{R<1> and X in Formula (A1), respectively is mentioned.}

Polyamic acid WHEREIN: Content of the structural unit represented by Formula (A2-1) is 50 mass % or more normally, Preferably it is 60 mass % or more, More preferably, it is 70 mass % or more, Especially preferably, it is 80 mass % or more. am.

( polyamic acid derivative)

A polyamic acid derivative is a derivative synthesize|combined by esterification of polyamic acid etc. As a polyamic acid derivative, the polymer which substituted the hydrogen atom of the carboxyl group in the structural unit represented by Formula (A2-1) which polyamic acid has is mentioned, for example, Polyamic acid ester is preferable.

Polyamic acid ester is a polymer by which at least one part of the carboxyl group which polyamic acid has was esterified. As polyamic acid ester, the polymer which has a structural unit represented by Formula (A2-2) which can produce|generate the polyimide (A1) which has a structural unit represented by Formula (A1) is mentioned.

In formula (A2-2), R ¹ is a divalent group having a hydroxyl group, X is a tetravalent organic group, and R ⁴ is each independently an alkyl group having 1 to 5 carbon atoms. As a divalent group which has a hydroxyl group represented by R<^1> , and a tetravalent organic group represented by X, the thing similar to the group illustrated as ^{R<1> and X in Formula (A1), respectively is mentioned.} As a C1-C5 alkyl group represented by R<^4> , a methyl group, an ethyl group, and a propyl group are mentioned, for example.

Polyamic acid ester WHEREIN: Content of the structural unit represented by Formula (A2-2) is 50 mass % or more normally, Preferably it is 60 mass % or more, More preferably, it is 70 mass % or more, Especially preferably, 80 mass %. More than that.

<<The synthesis method of a polyimide (A1) and a polyimide precursor (A2)>>

The polyamic acid which is a polyimide precursor (A2) can be obtained by combining and superposing|polymerizing tetracarboxylic dianhydride, the diamine which has a hydroxyl group, and other diamine as needed, for example. Their usage ratio is, for example, 0.3 to 4 moles, preferably approximately equimolar, of all the diamines described above with respect to 1 mole of the tetracarboxylic acid dianhydride. The polymerization WHEREIN: It is preferable to heat the mixed solution of the said tetracarboxylic dianhydride and the said all diamines at 50 degreeC - 200 degreeC, 1 hour - 24 hours.

The polyamic acid derivative which is a polyimide precursor (A2) can be synthesize|combined by esterifying the carboxyl group of the said polyamic acid, etc. 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 polyamic acid by the above method and then dehydrating and cyclizing (imidating) the polyamic acid;

Moreover, after synthesizing a polyamic acid derivative by the above method, it can also be synthesized by imidizing the polyamic acid derivative.

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

Further, when diamine is used excessively with respect to tetracarboxylic dianhydride, for example, dicarboxylic anhydride such as maleic anhydride is used as a terminal blocker for sealing the terminal groups of polyimide, polyamic acid and polyamic acid derivatives. You can use it.

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

It is preferable that a polyimide (A1) and a polyimide precursor (A2) have the said specific structure which has a hydroxyl group, and, by this, has the outstanding solubility to the solvent (E) mentioned later.

<< acrylic resin (A3) >>

As an acrylic resin (A3), resin obtained by superposing|polymerizing at least the radically polymerizable monomer which has a carboxyl group, for example is mentioned. For example, a radically polymerizable monomer having a crosslinkable group (a3-1), a radically polymerizable monomer having a carboxyl group (a3-2), and other radically polymerizable monomers copolymerizable with the polymerizable monomer (a3-3) and resins obtained by polymerizing them.

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 herein ) and component (a3-3) will be sequentially described.

(ingredient ( a3 -One))

The crosslinkable group in a component (a3-1) is crosslinkable groups other than a carboxyl group, For example, an epoxy group and oxetanyl group are mentioned.

As the component (a3-1), for example, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3 -(meth)acryloxymethyloxetane, 3-ethyl-3-(meth)acryloxymethyloxetane, 3-methyl-3-(meth)acryloxyethyloxetane, 3-ethyl-3-(meth)acryl oxyethyloxetane, p-vinylbenzoic acid 3-ethyloxetan-3-ylmethyl ester, and p-vinylphenyl-3-ethyloxetan-3-ylmethyl ether are mentioned. When the acrylic resin (A3) obtained using the component (a3-1) is used, heat resistance and chemical resistance are high, and a small pattern can be formed.

Component (a3-1) can be used individually or in mixture of 2 or more types.

At the time of the synthesis|combination of an acrylic resin (A3), Preferably, 1-70 mass % of component (a3-1) is used with respect to the total mass of all the monomers. If it is such a range, since the size of the pattern obtained from the composition of this invention becomes close to a mask dimension, and chemical-resistance of a coating film becomes high, it is preferable. Heat resistance becomes it high that the said range of a component (a3-1) is 10-65 mass %, and it is more preferable. Since developability becomes more favorable that the said range of a component (a3-1) is 15-50 mass %, it is still more preferable.

(ingredient ( a3 -2))

As the component (a3-2), for example, (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, ω-carboxypolycaprolactone mono (meth)acrylate, succinic acid mono[2-(meth)acryloyloxyethyl], maleic acid mono[2-(meth)acryloyloxyethyl], cyclohexene-3,4-dicarboxylic acid mono[2- (meth)acryloyloxyethyl]. Among these, (meth)acrylic acid and mono(2-methacryloyloxyethyl) succinate are preferable. In particular, when (meth)acrylic acid is used, the pattern size of the composition approaches the mask size, and the transparency is high, A composition having few image development residues and excellent storage stability is obtained.

Component (a3-2) can be used individually or in mixture of 2 or more types.

At the time of the synthesis|combination of an acrylic resin (A3), Preferably, 5-50 mass % of component (a3-2) is used with respect to the total mass of all the monomers. If it is such a range, the developability in aqueous alkali solution of the composition of this invention becomes favorable, and it is preferable. Since the pattern size approaches the mask dimension that the said range of a component (a3-2) is 6-40 mass %, it is more preferable. Since the composition becomes highly sensitive that the said range of a component (a3-2) is 7-32 mass %, it is more preferable.

(ingredient ( a3 -3))

The component (a3-3) will not be specifically limited as long as it is a radically 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, Dicyclopentenyloxyethyl (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 is mentioned, Furthermore, (meth)acrylic acid ester of the compound obtained by modifying|denaturing tetrahydrofurfuryl alcohol, such as 5-tetrahydrofurfuryloxy carbonyl pentyl acrylate with (epsilon)-caprolactone, is mentioned.

When component (a3-3) is used in the range of 15-85 mass % with respect to the total mass of all the monomers used for the synthesis|combination of an acrylic resin (A3), when the composition of this invention is apply|coated, exposed, and developed, the pattern size This is preferable because it approximates the mask dimension, and a desired pattern can be obtained with a low exposure dose. When the balance between image development time and adhesiveness is considered, 20-78 mass % of the said range of a component (a3-3) is preferable.

(Polymerization method of acrylic resin (A3))

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

As a polymerization initiator used when synthesize|combining an acrylic resin (A3), the compound which generate|occur|produces a radical by heat is mentioned, For example, azobisisobutyronitrile, dimethyl-2,2'- azobis (2-methyl) propionate) and the like, and peroxide initiators such as benzoyl peroxide can be used. In order to control the molecular weight, an appropriate amount of a chain transfer agent such as thioglycolic acid may be added.

<< polysiloxane (A4) >>

As polysiloxane (A4), the polysiloxane obtained by making the organosilane represented, for example by Formula (a4) react is mentioned.

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, an epoxy ring-containing group having 2 to 15 carbon atoms, or the above alkyl group. It is a group (substituent) formed by substituting one or two or more hydrogen atoms contained in a substituent, and ^{when there are two or more R<1>} , respectively, they may be same or different;

R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group, or a 6 to 15 carbon atoms having 1 to 6 carbon atoms in the aryl group, if there are plural R ² may be the phase may be the same, respectively;

n is an integer from 0 to 3.

As said substituent, it is at least 1 sort(s) chosen from a halogen atom, an amino group, a hydroxyl group, a mercapto group, and a (meth)acryloyloxy group, for example.

As an alkyl group and its substituent in R<^1> and R<^2> , For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group , trifluoromethyl group, 2,2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-(meth)acryloyl and an oxypropyl group.

As an alkenyl group in R<^1> , a vinyl group is mentioned, for example.

As an aryl group containing group in R<^1> , For example, Aryl groups, such as a phenyl group, a tolyl group, and a naphthyl group;

hydroxyaryl groups such as p-hydroxyphenyl group;

Aralkyl groups, such as a benzyl group and a phenethyl group;

hydroxyaralkyl groups such as 1-(p-hydroxyphenyl)ethyl group and 2-(p-hydroxyphenyl)ethyl group;

and 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl group.

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

As an acyl group in R<^2> , an acetyl group is mentioned, for example.

As an aryl group in R<^2> , a phenyl group is mentioned, for example.

n in Formula (a4) is an integer of 0-3. When n=0, it is a tetrafunctional silane, when n=1, it is a trifunctional silane, when n=2, it is a bifunctional silane, and when n=3, it is a monofunctional silane.

Examples of the organosilane include tetrafunctional silanes such as tetramethoxysilane and tetraphenoxysilane;

Methyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyl Trimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycy trifunctional silanes such as doxypropyltriethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane;

bifunctional silanes such as dimethyldimethoxysilane and diphenyldimethoxysilane;

Monofunctional silanes, such as trimethylmethoxysilane, are mentioned. Among these organosilanes, trifunctional silanes are preferable from the viewpoints of crack resistance and hardness of the insulating film.

As organosilane, the compound described in publications, such as Unexamined-Japanese-Patent No. 2013-210558, Unexamined-Japanese-Patent No. 2014-106250, and Unexamined-Japanese-Patent No. 2014-149330, is also mentioned, for example.

Organosilane may be used individually by 1 type, or may be used in combination of 2 or more type.

20 to 70 mol is preferable with respect to 100 mol of Si atoms, and, as for content of the phenyl group contained in polysiloxane (A4) at the point which makes the crack resistance and hardness of an insulating film compatible, More preferably, it is 35-55 mol. When the content of the phenyl group is equal to or less than the upper limit, an insulating film having high hardness tends to be obtained, and when the content of the phenyl group is equal to or higher than the lower limit, an insulating film having high crack resistance tends to be obtained. The content of the phenyl group, for example, ^{by measuring the 29} Si- nuclear magnetic resonance spectrum of polysiloxane (A4), 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 .

Polysiloxane (A4) is obtained by hydrolyzing and partial condensation of the organosilane mentioned above, for example. General methods can be used for hydrolysis and partial condensation. For example, a solvent, water, and a catalyst are added to organosilane as needed, and heat-stirred. During stirring, if necessary, hydrolysis by-products, such as alcohol, and condensation by-products, such as water, may be distilled off by distillation. Although the reaction temperature is not specifically limited, Usually, it is the range of 0 degreeC - 200 degreeC. Although reaction time is not specifically limited, either, Usually, it is the range of 1 to 48 hours.

As for the addition amount of a solvent, 10-1000 mass parts is preferable with respect to 100 mass parts of organosilanes. Moreover, as for the addition amount of the water used for a hydrolysis reaction, 0.5-2 mol is preferable with respect to 1 mol of hydrolysable groups.

As a catalyst, an acid catalyst and a base catalyst are mentioned, for example. Examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyhydric 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. As for the addition amount of a catalyst, 0.01-10 mass parts is preferable with respect to 100 mass parts of organosilanes.

<< polybenzoxazole (A5) >>

It is preferable that polybenzoxazole (A5) has a structural unit represented by Formula (A5).

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. 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 the 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 a group having 1 to 4 aromatic rings is preferable. , a group having two aromatic rings is more preferable. Thereby, polybenzoxazole (A5) can be made into the thing excellent in rigidity. In addition, ^{the aromatic ring contained in X<1>} may be either a substituted or unsubstituted ring.

As a structure of X<^1> , group represented by a following formula is mentioned, for example. In addition, in the following formula, * represents a bond.

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

When ^{two or more aromatic rings are contained in X 1} , the plurality of aromatic rings may have any structure of a linked polycyclic system or a condensed polycyclic system, but it is preferable that the plurality of aromatic rings have a structure of a linked polycyclic system. Thereby, polybenzoxazole (A5) can be made into the thing excellent in both light-shielding property and rigidity.

It is preferable that it is 6-24, as for total carbon number of X<^1> , it is more preferable that it is 6-18, It is still more preferable that it is 6-14. Thereby, the said effect can be exhibited more notably.

In consideration of these factors, as X ¹ , a biphenylene group or a derivative thereof is particularly preferable. Thereby, it can be set as polybenzoxazole (A5) which is especially excellent in rigidity.

In the formula (A5), Y ¹ may be a group containing at least one ring selected from an alicyclic hydrocarbon ring and an aromatic hydrocarbon ring, and is not particularly limited, but a group having 1 to 4 alicyclic hydrocarbon rings is preferable. and a group having one alicyclic hydrocarbon ring is more preferable. Thereby, polybenzoxazole (A5) can be made into the thing excellent in rigidity and light resistance. In addition, any substituted or unsubstituted ring may be sufficient as the alicyclic hydrocarbon ring and aromatic hydrocarbon ring contained in ^Y<1>.

As a structure of Y<^1> , group represented by a following formula is mentioned, for example. In addition, in the following formula, * represents a bond.

It is preferable that it is 4-24, as for the total carbon number of Y<^1> , it is more preferable that it is 4-15, It is still more preferable that it is 6-9. Thereby, the said effect can be exhibited more notably.

In consideration of these points, 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 in its three-dimensional structure. Thereby, compared with the case where a boat-type structure is selected, when it is set as polybenzoxazole (A5), the improvement of an elasticity modulus can be aimed at.

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

In polybenzoxazole (A5), a cyclization ratio becomes like this. Preferably it is 5 % or more, More preferably, it is 7.5 % or more, More preferably, it is 10 % or more. The upper limit of the cyclization rate is preferably 50%, more preferably 30%. When a cyclization ratio exists in the said range, it is preferable at the point of heat resistance and the solubility with respect to the developing solution of an exposed part. The cyclization rate can be measured in the same manner as the imidization rate described in Examples. However, in the case of polybenzoxazole (A5), it is possible to measure the exchange rate based on the absorption peak of the benzoxazole of jolhwan derived 1557㎝ vicinity ^{-1, -1} 1574㎝ vicinity.

In polybenzoxazole (A5), total content of the structural unit represented by Formula (A5) and Formula (A6) is 50 mass % or more normally, Preferably it is 60 mass % or more, More preferably, it is 70 mass % or more. , Especially preferably, it is 80 mass % or more.

《 polybenzoxazole Precursor (A6) >>

The polybenzoxazole precursor (A6) is a compound capable of producing polybenzoxazole (A5), preferably polybenzoxazole (A5) having a structural unit represented by formula (A5) by dehydration and cyclization am. A precursor (A6) has a structural unit represented by Formula (A6), for example.

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. As the divalent group represented by Y ¹ and a tetravalent group represented by X ^1, a group illustrated as X ¹ and Y ¹ in each of formula (A5) it is the same.

In polybenzoxazole precursor (A6), content of the structural unit represented by Formula (A6) is 50 mass % or more normally, Preferably it is 60 mass % or more, More preferably, it is 70 mass % or more, Especially preferably It is 80 mass % or more.

《 polybenzoxazole (A5) and its precursor (A6) synthesis method>>

The polybenzoxazole precursor (A6) contains, for example, at least one selected from dicarboxylic acid containing at least one alicyclic hydrocarbon ring, a diester thereof and a dihalide thereof, and at least one aromatic ring. It can be obtained by superposing|polymerizing diamine which contains and has two hydroxyl groups. The use ratio of these is, for example, 0.5-4 mol of the said diamine with respect to a 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° C. to 200° C. for 1 hour to 72 hours.

Polybenzoxazole (A5) can be synthesize|combined by dehydrating and cyclizing this polybenzoxazole precursor (A6), after synthesizing a polybenzoxazole precursor (A6) by the said method, for example.

As a cyclization reaction of a polybenzoxazole precursor (A6), application of a well-known method is possible. In the case of heating cyclization reaction, it is preferable to heat the solution containing a polybenzoxazole precursor (A6) for 150 degreeC - 400 degreeC, 1 hour - 16 hours. If necessary, you may carry out, removing water in a system using azeotropic solvents, such as toluene, xylene, and mesitylene.

[Photosensitizer (B)]

A photosensitizer (B) is a compound which generate|occur|produces an acid, a compound which generate|occur|produces a radical, and a compound which generate|occur|produces a cation by the process including irradiation of a radiation. As a radiation, a visible light ray, an ultraviolet-ray, a deep ultraviolet ray, X-ray, and a charged particle beam are mentioned, for example. By containing the photosensitive agent (B), the radiation-sensitive resin composition can exhibit radiation-sensitive characteristics and can have favorable radiation sensitivity. As the photosensitizer (B), a photoacid generator is preferable.

Content of the photosensitizer (B) in the composition of this invention is 1-80 mass parts normally with respect to a total of 100 mass parts of resin (C) and resin (A), Preferably it is 5-60 mass parts, 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 mass is wealth

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

<Compound that generates acid>

A photoacid generator is mentioned as a compound which generate|occur|produces an acid, For example, a quinonediazide compound, an oxime sulfonate compound, an onium salt, N-sulfonyloxyimide compound, a halogen-containing compound, a diazomethane compound , a sulfone compound, a sulfonic acid ester compound, and a carbonic acid ester compound. By using a photoacid generator, the composition which exhibits a positive radiation-sensitive characteristic can be obtained.

As a photosensitizer (B), a quinonediazide compound, an oxime sulfonate compound, an onium salt, and a sulfonic acid ester compound are preferable, A quinonediazide compound and an oxime sulfonate compound are more preferable, A quinonediazide compound is especially preferable. .

《 quinonediazide compound"

A quinonediazide compound generate|occur|produces a carboxylic acid by the process including irradiation of a radiation and image development using aqueous alkali solution. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound and a 1,2-naphthoquinonediazidesulfonic acid halide.

As a quinonediazide compound, Unexamined-Japanese-Patent No. 2014-111723, Unexamined-Japanese-Patent No. 2014-149330, Unexamined-Japanese-Patent No. 2014-170080, Unexamined-Japanese-Patent No. 2015-4000, etc. are described, for example. compounds can be mentioned.

As a commercial item of a quinonediazide compound, brand name "MG-300", "NT-200", "NT-300P", and "TS-200" (all are Toyo Gosei Kogyo Co., Ltd. product) are mentioned, for example. .

《Other examples》

As a specific example of an oxime sulfonate compound, the compound described in publications, such as Unexamined-Japanese-Patent No. 2011-227106, Unexamined-Japanese-Patent No. 2012-234148, and Unexamined-Japanese-Patent No. 2013-054125, is mentioned, for example. As a specific example of an onium salt, Unexamined-Japanese-Patent No. 5208573, Unexamined-Japanese-Patent No. 5397152, Unexamined-Japanese-Patent No. 5413124, Unexamined-Japanese-Patent No. 2004-2110525, Unexamined-Japanese-Patent No. 2008-129423, Unexamined-Japanese-Patent No. The compound described in publications, such as Patent Publication 2010-215616 and Unexamined-Japanese-Patent No. 2013-228526, is mentioned.

As a specific example of another acid generator, Unexamined-Japanese-Patent No. 49242256, Unexamined-Japanese-Patent No. 2011-064770, Unexamined-Japanese-Patent No. 2011-232648, Unexamined-Japanese-Patent No. 2012-185430, Unexamined-Japanese-Patent No. The compound described in publications, such as publication 2013-242540, is mentioned.

< radicals Compounds that occur>

A radical photopolymerization initiator is mentioned as a compound which generate|occur|produces a radical, For example, an alkylphenone compound, an acylphosphine oxide compound, an oxime ester compound, a benzoin compound, a benzophenone compound, anthraquinones, thioxanthones can be heard By using a radical photopolymerization initiator, the composition which exhibits a negative radiation-sensitive characteristic can be obtained.

As said compound, Unexamined-Japanese-Patent No. 11-060995, Unexamined-Japanese-Patent No. 2005-202387, Unexamined-Japanese-Patent No. 2006-285226, Unexamined-Japanese-Patent No. 2007-102070, Unexamined-Japanese-Patent No. 2010, for example. -049262, Unexamined-Japanese-Patent No. 2010-083970, Unexamined-Japanese-Patent No. 2012-241127, Unexamined-Japanese-Patent No. 2014-186342, The compound described in publications, such as Unexamined-Japanese-Patent No. 2015-050269, is mentioned.

As a commercial item of a radical photopolymerization initiator, "IRGACURE 127", "IRGACURE 651", "IRGACURE 369", "IRGACURE 379EG", "IRGACURE OXE01", "IRGACURE OXE02" (all are BASF Japan Co., Ltd. product), for example, are can be heard

<Compounds that generate cations>

As a compound which generate|occur|produces a cation, a photocationic polymerization initiator is mentioned, For example, a sulfonium salt, an iodonium salt, and a diazonium salt are mentioned. By using a photocationic polymerization initiator, the composition which exhibits a negative radiation-sensitive characteristic can be obtained.

As a sulfonium salt type|system|group, an iodonium salt type|system|group, or a diazonium salt type|system|group photocationic polymerization initiator, For example, Unexamined-Japanese-Patent No. 11-060995, Unexamined-Japanese-Patent No. 2008-088253, Unexamined-Japanese-Patent No. 2010-074250, The compound described in publications, such as Unexamined-Japanese-Patent No. 2011-238307, Unexamined-Japanese-Patent No. 2012-157996, and Unexamined-Japanese-Patent No. 2015-001667, is mentioned.

As a commercial item of a photocationic polymerization initiator, For example, a sulfonium salt-type cationic polymerization initiator, such as a brand name "UVACURE1590" (made by Daicel Cytech Co., Ltd.), "CPI-110P" (manufactured by San Apro Co., Ltd.); Cationic polymerization of iodonium salts such as "IRGACURE 250" (manufactured by BASF Japan Co., Ltd.), "WPI-113" (manufactured by Wako Pure Chemical Industries, Ltd.), and "Rp-2074" (manufactured by Rhodia Japan Co., Ltd.) an initiator.

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

[Resin (C)]

Resin (C) is at least 1 sort(s) of resin chosen from resin which has a structural unit represented by Formula (C1), and resin which has a structure represented by Formula (C2). Hereinafter, resin which has a structural unit represented by said formula (C1) is also called "resin (C1)", and resin which has a structure represented by said formula (C2) is also called "resin (C2)."

In formula (C1), A is a divalent aromatic group which has a phenolic hydroxyl group, L is a monovalent group represented by Formula (c2-1), Formula (c2-2), or Formula (c2-3) mentioned later.

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

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

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

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

《Double Family A》

A is a divalent aromatic group which has a phenolic hydroxyl group, and it is preferable that it is a divalent group represented by a formula (c1-1), a formula (c1-2), or a formula (c1-3).

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

a1 is an integer of 1-4. b1 is an integer of 0 to 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.

provided that a2+a3 is an integer of 1 or more and 6 or less, b2+b3 is an integer of 0 or more and 5 or less, and a2+a3+b2+b3 is an integer of 1 or more and 6 or less;

a4+a5+a6 is an integer of 1 or more and 8 or less, b4+b5+b6 is an integer of 0 or more and 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 1-3.

R is a C1-C10 hydrocarbon group or a C1-C10 alkoxy group, and when there is two or more R, respectively, they may be same or different. As a hydrocarbon group, alkyl groups, such as a methyl group, a propyl group, an isopropyl group, and t-butyl group, are mentioned, for example. As an alkoxy group, a methoxy group is mentioned, for example.

In formulas (c1-1) to (c1-3), the bonding position of -OH and -R is not particularly limited, and the bonding position of two -CH(L)- is not particularly limited. For example, two -CH(L)- may couple|bond with the different benzene nucleus (for example, following (1)), and may couple|bond with the same benzene nucleus (for example, following (2)). In the formula, * is a bond. Although the following formulas (1) and (2) are specific examples about Formula (c1-2), it is the same also in Formula (c1-3). In addition, the substituent on a benzene nucleus was abbreviate|omitted for convenience.

In said A, it is preferable that the bonding position with -CH(L)- is, for example, o-position and/or p-position with respect to the hydroxyl group contained in said A.

As said A, group represented by Formula (c1-2) or Formula (c1-3) from a viewpoint of provision of light-shielding property, heat resistance, and alkali developability is preferable, and group represented by Formula (c1-2) is more preferable.

<< k+m+n-valued flag A' >>

A' is a k+m+n-valent aromatic group having a phenolic hydroxyl group, for example, a divalent group represented by a formula (c1-1), a formula (c1-2) or a formula (c1-3) is changed to a k+m+n-valent group can be lifted However, -CH(L)OCH(L)-, -CH(L)- and -CH(L)OH shall couple|bond with 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. provided that a2+a3 is an integer of 1 or more and "8-(k+m+n)" or less, b2+b3 is an integer of 0 or more and "7-(m+n)" or less, a2+a3+b2+b3 is an integer of 1 or more and "8-(k+m+n)" or less;

a4+a5+a6 is an integer of 1 or more and "10-(k+m+n)" or less, b4+b5+b6 is an integer of 0 or more and "9-(k+m+n)" or less, and a4+a5+a6+b4+b5+b6 is an integer of 1 or more and "10-(k+m+n)" or less. Further, 1≤a1+b1≤“6-(k+m+n)”, a2+b2≤4, a3+b3≤4, a4+b4≤4, a5+b5≤4, and a6+b6≤2.

《One family flag L》

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

In formula (c2-1), X is an oxygen atom, a sulfur atom, -CH ₂ -, or -NH-, Preferably it is 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 hetero atom-containing group having 1 or more carbon atoms. m is an integer of 0-3, Preferably it is 0 or 1. However, in the case of formula (C1), when m=0, X is not an oxygen atom. When two or more R<^1> exists, each may be same or different, and R<^1> couple|bonded with adjacent ring carbon may mutually couple|bond, and may form the ring, for example, a benzene ring.

In the formula (c2-2), Y is a nitrogen atom, CH or CR ^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 formula (C1), when n = d = 0, Y is not CH, and when n = d = 0 and Y is CR ² , or when n = 1, d = 0 and Y is CH when R ² is —NO ₂ , but not —OH. ^{When two or more} R<2> exists, each may be same or different, and R<^2> couple|bonded with adjacent ring carbon may mutually couple|bond and may form the ring.

Examples of the ring formed by bonding R ² to each other include condensed carbocyclic rings and condensed heterocycles when represented together with the benzene nucleus or pyridine nucleus to which ^{R 2 is bonded, and specifically, the following ring structures are exemplified.} These rings may further have the group enumerated by ^R<1>. * in the formula is a bond. From a light-shielding viewpoint of an insulating film, it is preferable that L has condensed carbocyclic rings, such as a naphthalene ring and an anthracene ring.

In formula (c2-3), R ⁵ has the same meaning as ^{R 1} in formula (c2-1). l is an integer of 0-5 each independently, Preferably it is 0. When two or more R ⁵ are present, each may be the same or different, and R ⁵ bonded to adjacent ring carbon may be bonded to each other to form a ring, for example, a benzene ring.

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

Examples of the hetero atom-containing group having 1 or more carbon atoms in R ¹ to ^{R 2} and R ⁵ include a halogenated hydrocarbon group such as a halogenated alkyl group having 1 to 18 carbon atoms such as a carboxyl group and a trifluoromethyl group, a hydroxymethyl group, and the like. A hydroxyalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms such as a methoxy group and an ethoxy group, an aryloxy group having 6 to 30 carbon atoms such as a phenoxy group and tolyloxy group, 1 to carbon atoms such as a methylthio group An aralkyloxy group having 7 to 30 carbon atoms such as an 18 thioalkoxy group and a benzyloxy group, an acyloxyalkyl group having 2 to 20 carbon atoms such as an acetoxymethyl group, a substituted amino group such as a dimethylamino group and a diphenylamino group, a furanyl group, a thi and heterocyclic rings such as nyl group, pyrrolyl group, imidazolyl group, pyridinyl group, pyrimidinyl group, pyradinyl group, pyrrolyldinyl group, piperidinyl group, piperadinyl group and morpholinyl group.

R ¹ is preferably an alkyl group, an aryl group, a hydroxy group, an acyloxy group or -NO _2. It is preferable that R<^2> is a halogen atom, a halogenated alkyl group, a carboxyl group, an alkoxy group, a thioalkoxy group, an aralkyloxy group, a substituted amino group, and a heterocyclic ring. Moreover, the aspect in which two R<^2> couple|bonded with adjacent ring carbon couple|bonded with each other to form a ring is also preferable.

Resin (C) is a substance which develops color by applying heat. In the method of forming an insulating film to be described later, the coating film itself formed of the composition containing the silver resin (C) before exposure does not have light-shielding properties in the vicinity of ultraviolet light, for example, light-shielding properties at a wavelength of 400 nm, but exposure and It is estimated that the insulating film obtained by ketoizing the resin (C) by heating after development has light-shielding properties at the above wavelengths. By using such a resin (C), in the composition of this invention, light-shielding property provision and alkali developability are compatible.

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

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

Resin (C1) can be obtained, for example by condensing phenols and aldehydes in presence of an acid catalyst, and distilling off unreacted components as needed. As reaction conditions, phenols and aldehydes are made to react in a solvent at 60-200 degreeC normally for about 1 to 20 hours. For example, it can synthesize|combine by the method described in publications, such as Unexamined-Japanese-Patent No. 47-15111 and Unexamined-Japanese-Patent No. 63-238129.

As the resin (C2), a resol resin can be used (when m=n=0 in the formula (C2)), and the resin (C2) can also be obtained from a resol resin (in the formula (C2) , when m+n is an integer greater than or equal to 1).

The resol resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a base catalyst, and distilling off unreacted components as needed. As reaction conditions, phenols and aldehydes are made to react in a solvent at 40-120 degreeC normally for about 1 to 20 hours. In this way, for example, a resol resin in which -CH(L)OH is bonded to an aromatic ring contained in phenols can be obtained. The condensate of the resol resin can be obtained by advancing a dehydration condensation reaction by applying heat or an acid to the resol resin. This reaction proceeds by dehydration condensation of -CH(L)OH contained in the resol resin. When advancing the said reaction by heating, the resol resin or its solution is normally made to react at 60-200 degreeC for about 1 to 20 hours. For example, it can synthesize|combine by the method described in patents, such as Unexamined-Japanese-Patent No. 3889274, Unexamined-Japanese-Patent No. 4013111, and Unexamined-Japanese-Patent No. 2010-111013.

As phenols, for example,

A compound having 1 to 4 hydroxyl groups, preferably 1 to 3, and 1 benzene nucleus, specifically phenol, orthocresol, methacresol, 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-methyl Toxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 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 cores (naphthalene compound), specifically monohydroxynaphthalene such as 1-naphthol and 2-naphthol, 1,2-di Hydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1 dihydroxynaphthalene, such as 8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;

Compounds (anthracene-type compounds) having 1 to 8 hydroxyl groups, preferably 1 to 3, and 3 benzene nuclei, specifically 1-hydroxyanthracene, 2-hydroxyanthracene, 9-hydroxyanthracene, etc. Dihydroxyanthracene, 1,2,10-trihydroxyanthracene, 1,8,9-trihydroxyanthracene, such as monohydroxyanthracene, 1,4-dihydroxyanthracene, and 9,10-dihydroxyanthracene trihydroxyanthracene such as , 1,2,7-trihydroxyanthracene;

can be heard

Examples of the aldehydes include compounds represented by LC(=O)-H (where L in the formula has the same meaning as L in the formula (C1)), and specific examples include the following compounds. have.

In the synthesis|combination of resin (C), the usage-amount of aldehydes is 0.3 mol or more normally with respect to 1 mol of phenols, Preferably it is 0.4-3 mol, More preferably, it is 0.5-2 mol.

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

The weight average molecular weight (Mw) in terms of polystyrene of the resin (C) is a value measured by a gel permeation chromatography (GPC) method, usually 100 to 50,000, preferably 150 to 10,000, more preferably 500 -6,000. Resin (C) in which Mw exists in the said range is preferable from a point of resolution.

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

5-85 mass % is preferable with respect to 100 mass % of total solids in the composition of this invention, as for content of resin (C), 10-75 mass % is more preferable, 10-70 mass % is still more preferable.

The composition of this invention WHEREIN: Content of resin (C) is 5-200 mass parts normally with respect to 100 mass parts of resin (A), Preferably it is 10-100 mass parts, More preferably, 15-90 mass parts, particularly preferably 18 to 80 parts by mass.

The effect of light-shielding property and developability provision based on resin (C) as content of resin (C) being more than the lower limit of the said range is exhibited easily. When the content of the resin (C) is equal to or less than the upper limit of the above range, there is little risk of deterioration of the low water absorption of the insulating film, an increase in the amount of outgas, and a decrease in heat resistance.

《Crosslinking agent (D)》

A crosslinking agent (D) is a compound which has a crosslinkable functional group. As a crosslinking agent (D), the compound which has two or more crosslinkable functional groups in 1 molecule is mentioned, for example.

In addition, the compound corresponding to either of the acrylic resin (A3) and the crosslinking agent (D) is classified into the acrylic resin (A3), and the compound corresponding to any of the resin (C) and the crosslinking agent (D) is a resin Classified as (C).

When the insulating film made of the composition of the present invention is used as a component of an organic EL device, the organic EL device deteriorates when the organic light emitting layer comes into contact with moisture. do.

Examples of the crosslinkable functional group include an isocyanate group, a blocked isocyanate group, an oxetanyl group, a glycidyl ether group, a glycidyl ester group, a glycidylamino group, a methoxymethyl group, an ethoxymethyl group, a benzyloxymethyl group, and an acetonitrile group. oxymethyl group, benzoyloxymethyl group, formyl group, acetyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group;

Group which has ethylenically unsaturated bonds, such as a vinyl group, a vinylidene group, and a (meth)acryloyl group, is mentioned.

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

The composition of this invention WHEREIN: Content of a crosslinking agent (D) is 1-210 mass parts normally with respect to a total of 100 mass parts of resin (C) and resin (A), Preferably it is 10-150 mass parts, More Preferably it is 15-100 mass parts. When the content of the crosslinking agent (D) is equal to or more than the lower limit of the above range, the low water absorption of the insulating film tends to be improved. When content of a crosslinking agent (D) is below the upper limit of the said range, there exists a tendency for the heat resistance of an insulating film to improve.

Examples of the crosslinking agent (D) include a compound having two or more glycidyl groups in one molecule, a compound having two or more oxetanyl groups in one molecule, a compound having two or more ethylenically unsaturated bonds in one molecule, 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 resin, carboxymethyl group-containing melamine compound, carboxymethyl group-containing benzoguanamine compound, carboxy A methyl group-containing urea compound and a carboxymethyl group-containing phenol compound are mentioned.

As a compound which has two or more glycidyl groups in 1 molecule, ethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and trimethylol propane triglycidyl ether are mentioned, for example.

As a compound which has two or more glycidyl groups in 1 molecule, Unexamined-Japanese-Patent No. 2014-170949, Unexamined-Japanese-Patent No. 2014-189616, Unexamined-Japanese-Patent No. 2014-205838, Unexamined-Japanese-Patent No. 2014, for example. -229496 and the compound of Unexamined-Japanese-Patent No. 2015-27665, etc. are mentioned.

Examples of the compound having two or more oxetanyl groups in one molecule include 4,4-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl and 3,7-bis(3-oxeta). nyl)-5-oxanonane, 3,3'-[1,3-(2-methyleneyl)propanediylbis(oxymethylene)]bis(3-ethyloxetane), ethylene glycolbis[(3-ethyl- 3-oxetanyl)methyl]ether, dicyclopentenylbis[(3-ethyl-3-oxetanyl)methyl]ether, triethyleneglycolbis[(3-ethyl-3-oxetanyl)methyl]ether can be heard

As a compound which has two or more oxetanyl groups in 1 molecule, Unexamined-Japanese-Patent No. 2013-234230, Unexamined-Japanese-Patent No. 2014-149330, Unexamined-Japanese-Patent No. 2014-186300, Unexamined-Japanese-Patent No. 2015, for example. -38182 and the compound of Unexamined-Japanese-Patent No. 2015-42713, etc. are mentioned.

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, and trimethylol. Propane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa Polyfunctional (meth)acrylates, such as (meth)acrylate and dipentaerythritol penta (meth)acrylate, are mentioned.

As a compound which has two or more ethylenically unsaturated bonds in 1 molecule, Unexamined-Japanese-Patent No. 2001-104878, Unexamined-Japanese-Patent No. 2013-029780, Unexamined-Japanese-Patent No. 2013-41225, Unexamined-Japanese-Patent No. The compound described in publications, such as 2013-57755 and JP 4400926 A, is mentioned.

As a crosslinking agent (D), the compound which has the group in which the isocyanate group was blocked by the protecting group can also be mentioned, for example. The said compound is also called a "block isocyanate compound." The group in which the isocyanate group was blocked by a protecting group is also called a "block isocyanate group."

As a block isocyanate compound, For example, Unexamined-Japanese-Patent No. 2013-225031, Unexamined-Japanese-Patent No. 5132096, Unexamined-Japanese-Patent No. 5071686, Unexamined-Japanese-Patent No. 2013-223859, Unexamined-Japanese-Patent No. 5199752, Unexamined-Japanese-Patent No. The compound described in publications, such as Unexamined-Japanese-Patent No. 2003-41185, Unexamined-Japanese-Patent No. 4879557, and Unexamined-Japanese-Patent No. 2006-119441, is mentioned.

[Solvent (E)]

The solvent (E) can be used in order to make a radiation-sensitive resin composition liquid.

As the solvent (E), for example, 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 (gamma)-butyrolactone are mentioned.

As a solvent (E), Unexamined-Japanese-Patent No. 2012-12472, Unexamined-Japanese-Patent No. 2013-54376, Unexamined-Japanese-Patent No. 2014-115438, Unexamined-Japanese-Patent No. 2014-197171, Unexamined-Japanese-Patent No. The solvent described in publications, such as 2014-189561, is also mentioned.

As a solvent (E), an amide type solvent can also be mentioned further, For example, the compound described in patents, such as Unexamined-Japanese-Patent No. 4861832 and Unexamined-Japanese-Patent No. 5613851 is mentioned.

As the solvent (E), 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, as the solvent (E), γ-butyrolactone (hereinafter also referred to as “BL”) is preferably used, and a mixed solvent containing BL is preferable. As content of BL, in 100 mass % of total amounts of a solvent (E), 70 mass % or less is preferable and 20-60 mass % is more preferable. It is preferable to use BL together with at least 1 sort(s) chosen from PGMEA, PGME, and EDM. By making content of BL into the said range, there exists a tendency which the melt|dissolution state of resin (A) in a radiation-sensitive resin composition can be maintained suitably.

As a solvent (E), in addition to the solvent illustrated above, alcohol solvents, such as a propanol and a butanol, as needed;

Aromatic hydrocarbon solvents, such as toluene and xylene, etc. can also be used together.

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

The composition of this invention WHEREIN: Content of the solvent (E) is 5-60 mass % normally of the solid content concentration of the said composition, Preferably it is 10-55 mass %, More preferably, it is an amount used as 15-50 mass %. . Here, solid content means all components other than a solvent (E). By making content of the solvent (E) into the said range, there exists a 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 above essential components, the radiation-sensitive resin composition contains, as needed, other optional components such as adhesion aid (F), surfactant (G), dye (H), within a range that does not impair the effects of the present invention. good to do Other optional components may be used independently or may use 2 or more types together.

<Adhesive aid (F)>

The adhesion adjuvant (F) is a component which improves the adhesiveness of film formation objects, such as a board|substrate, and an insulating film. The adhesion adjuvant (F) is particularly useful in order to improve the adhesion between the inorganic substrate and the insulating film. As an inorganic substance, For example, silicone compounds, such as silicon, silicon oxide, and silicon nitride;

Metals, such as gold|metal|money, copper, and aluminum, are mentioned.

As the adhesion aid (F), a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxyl group, a halogen atom, a vinyl group, a methacryloyl group, an isocyanate group, an epoxy group, an oxetanyl group, an amino group, and a thiol group. have.

As the functional silane coupling agent, for example, N-phenyl-3-aminopropyltrimethoxysilane, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethyl Toxysilane, γ-isocyanatepropyltriethoxysilane, 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)ethyl Trimethoxysilane and γ-methacryloxypropyltrimethoxysilane are preferable.

Content of the close_contact|adherence adjuvant (F) in the composition of this invention is in 100 mass % of total solids in the composition of this invention, Preferably it is 20 mass % or less, More preferably, it is 0.01-15 mass %. 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 coating-film formation property of a radiation-sensitive resin composition. When the radiation-sensitive resin composition contains the surfactant (G), the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the insulating film can be further improved. As surfactant (G), a fluorochemical surfactant and silicone type surfactant are mentioned, for example.

As surfactant (G), the specific example described in publications, such as Unexamined-Japanese-Patent No. 2003-015278 and Unexamined-Japanese-Patent No. 2013-231869, is mentioned, for example.

Content of surfactant (G) in the composition of this invention is in 100 mass % of total solids in the composition of this invention, Preferably it is 20 mass % or less, More preferably, it is 0.01-15 mass %, More preferably, 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 which improves the light-shielding property of an insulating film. By using the dye (H), it is possible to obtain an element for a display or lighting device with more excellent reliability. The dye (H) may be a component that absorbs light in a wavelength range of 400 nm to 1000 nm, and examples thereof include dyes of anthraquinone-based, methine-based, indigoid-based and azo-based organic compounds. .

As dye (H), Unexamined-Japanese-Patent No. 2003-246840, Unexamined-Japanese-Patent No. 2007-177088, Unexamined-Japanese-Patent No. 2008-255241, Unexamined-Japanese-Patent No. 2012-31218, Unexamined-Japanese-Patent No. The compound described in publications, such as 2013-509988, Unexamined-Japanese-Patent No. 2015-30753, Unexamined-Japanese-Patent No. 2015-32660, and Unexamined-Japanese-Patent No. 2015-43378, is mentioned.

As a commercial item of dye (H), "OilBlue5511", "PlastBlueDB-463", "SDO-11", "SDO-12", "SDO-14", "SDO-C8", "SDO- C12”, “SDO-C33” (all of Arimoto Chemical High School), “NEOSUPERBLACK C-832” (Chuogo Sei Chemicals Ltd.), “Aizen Spilon Red BEH Special” (Hodogaya Chemical High School) (Note) can be mentioned.

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

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

[ radiation sensitive Preparation method of resin composition]

A radiation-sensitive resin composition can be prepared by mixing essential components, such as a photosensitive agent (B) and resin (C), and another component as needed with a solvent (E), for example. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter etc.

[ radiation sensitive Method of forming an insulating film using a resin composition]

In the method for forming an insulating film of the present invention, step 1 of forming a coating film on a substrate using the radiation-sensitive resin composition described above, step 2 of irradiating at least a part of the coating film with radiation, and developing the coating film irradiated with radiation It has a process 3 and process 4 of heating the developed coating film.

According to the method of forming the insulating film, it is possible to form an insulating film having excellent light-shielding properties and a small amount of outgas. In addition, since the radiation-sensitive resin composition described above has excellent radiation sensitivity, it is possible to easily form an insulating film having a fine and elaborate pattern by forming a pattern by exposure, development, and heating using the characteristic.

《Process 1》

At the process 1, a coating film is formed by apply|coating a radiation-sensitive resin composition to the board|substrate surface, and removing a solvent (E) by preferably prebaking. As a film thickness of the said coating film, it is 0.3-25 micrometers normally as a value after prebaking, Preferably it can be set as 0.5-20 micrometers.

As a board|substrate, a resin substrate, a glass substrate, and a silicon wafer are mentioned, for example. As a board|substrate, in organic electroluminescent element in the middle of manufacture, the TFT board|substrate with which TFT or its wiring was formed is mentioned, for example.

As a coating method of a radiation-sensitive resin composition, the spray method, the roll coating method, the spin coating method, the slit-die coating method, the bar coating method, and the inkjet method are mentioned, for example. Among these coating methods, the spin coating method and the slit die coating method are preferable.

Although it changes also with the composition of a radiation-sensitive resin composition etc. as conditions of a prebaking, for example, a heating temperature is 60-130 degreeC, and a heating time becomes about 30 second - about 15 minutes. It is preferable to perform prebaking at the temperature to which light-shielding property based on resin (C) is not provided to a 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 rays, far ultraviolet rays, X-rays, and charged particle beams. Examples of visible light include g-line (wavelength 436 nm) and h-line (wavelength 405 nm). As an ultraviolet-ray, i-line|wire (wavelength 365 nm) is mentioned, for example. As far ultraviolet rays, a laser beam by a KrF excimer laser is mentioned, for example. Examples of X-rays include synchrotron radiation. As a charged particle beam, an electron beam is mentioned, for example.

Among these radiations, visible rays and ultraviolet rays are preferable, and among visible rays and ultraviolet rays, radiation containing g-rays and/or i-rays is particularly preferable. When using the radiation containing i-line|wire, as an exposure amount, 6000 mJ/cm<2> or less is preferable, and 20-2000 mJ/cm<2> is preferable. This exposure amount can measure the intensity|strength in wavelength 365nm of a radiation with an illuminometer ("OAI model356" by OAI Optical Associates).

《Process 3》

In step 3, the coating film irradiated with radiation in step 2 is developed. Accordingly, for example, when a positive composition is used, a portion irradiated with radiation is removed, and when a negative composition is used, a portion not irradiated with radiation is removed to form a desired pattern. . As a developing solution used for a developing process, aqueous alkali solution is preferable.

Examples of the alkaline compound contained in the aqueous alkali solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di- n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperizine, 1,8-diazabicyclo [5.4. 0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonane. As a density|concentration of the alkaline compound in aqueous alkali solution, 0.1 mass % or more and 5 mass % or less are preferable from a viewpoint of obtaining moderate developability.

As the developer, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous alkali solution, or an aqueous solution obtained by adding a small amount of various organic solvents for dissolving the radiation-sensitive resin composition to an aqueous alkali solution may 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.

As a developing method, the puddle method, the dipping method, the rocking|fluctuation immersion method, and the shower method are mentioned, for example. Although development time changes with the composition of the radiation-sensitive resin composition, it is about 10 second - 180 second normally. A desired pattern can be formed by performing, for example, running-water washing|cleaning for 30 second - 90 second following such a developing process, for example, blowing in the wind with compressed air or compressed nitrogen, and drying.

《Process 4》

In process 4, an insulating film is obtained by performing hardening process of a coating film by heat processing (post-baking process) with respect to a coating film using heating apparatuses, such as a hotplate and oven, after process 3. The heating temperature in this heat treatment is, for example, more than 130° C. and 300° C. or less, and the heat time varies depending on the type of heating equipment. For example, when heat treatment is performed on a hot plate, 5 minutes - 30 minutes, when heat-processing in oven, it is 30 minutes - 90 minutes. At this time, the step baking method etc. which perform a heating process twice or more can also be used.

By heat treatment in the above temperature range, the insulating film has 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, and more preferably 5% or less. In this way, the insulating film of the target pattern can be formed on the board|substrate.

In step 4, before heating of the coating film, a rinse treatment or a decomposition treatment may be performed on the patterned coating film. In the rinse process, it is preferable to wash|clean a coating film using the solvent mentioned as 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) such as a high-pressure mercury lamp. The exposure amount in this post-exposure becomes like this. Preferably it is about 1000-5000 mJ/cm<2>.

The composition of the present invention exhibits good characteristics in patterning properties and radiation sensitivity, and the insulating film thus obtained has light-shielding properties in the vicinity of an ultraviolet region, for example, light having a wavelength of 400 nm. In addition, the insulating film has a small amount of outgas generated, and exhibits favorable properties 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 other than the insulating film as a partition which organic electroluminescent element etc. have, for example.

The film thickness of the insulating film of this invention is 0.3-25 micrometers normally from a light-shielding viewpoint, Preferably it is 0.5-20 micrometers. As for the insulating film of this invention, the total light transmittance in wavelength 400nm becomes like this. Preferably it is 0 to 15 %, More preferably, it is 0 to 12 %, More preferably, it is 0 to 5 %. Moreover, as for the insulating film of this invention, the total light transmittance in wavelength 600nm becomes like this. Preferably it is 30 % or less, More preferably, it is 10 % or less. The total light transmittance can be measured, for example, using a spectrophotometer (“150-20 double beam” manufactured by Hitachi Seisakusho Co., Ltd.).

[Element for display or lighting device]

Hereinafter, an element for a display or lighting device having an insulating film of the present invention will be described.

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

Hereinafter, the display or lighting device is collectively referred to as simply "device".

One embodiment of the device of the present invention includes: a first electrode formed on a TFT substrate and connected to the TFT; the insulating film of the present invention formed on the first electrode to partially expose the first electrode; It has a second electrode formed to face the electrode.

One embodiment of a device having a device of the present invention includes a TFT substrate, a first electrode formed on the TFT substrate and connected to the TFT, and a first electrode formed on the first electrode to partially expose the first electrode. It has the insulating film of the said invention, and the 2nd electrode provided opposite the 1st electrode.

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

Although the film thickness of an insulating film is not specifically limited, Considering the easiness of film-forming and patterning, Preferably it is 0.3-25 micrometers, More preferably, it is 0.5-20 micrometers.

The insulating film is formed so as to span the adjacent first electrodes, for example. For this reason, good electrical insulation is calculated|required of an insulating film. 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 barrier rib that divides the TFT substrate into a plurality of regions. It is preferable that the said insulating film (partition wall) is formed on a TFT substrate so that it may arrange|position at least above the said semiconductor layer from a viewpoint of the light-shielding property with respect to the semiconductor layer contained in TFT. Here, "upward" is a direction toward the second electrode from the TFT substrate. As an example, when viewed from above of the TFT substrate, 50% or more of the area of the semiconductor layer overlaps with the insulating film (barrier), and in particular, 80% or more of the area of the semiconductor layer, more The aspect in which 90% or more, especially 100% overlaps with the insulating film (barrier) is mentioned.

In the device of the present invention, the insulating film exposing the first electrode has light-shielding properties in the vicinity of the ultraviolet region, for example, at a wavelength of 400 nm, as described above. By forming 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 light deterioration such as IGZO as a driving element, the insulating film acts as a light shielding film, and the use of the device, etc. Light deterioration of the semiconductor layer can be suppressed.

For example, the semiconductor layer constituting the TFT may be a layer containing an oxide semiconductor containing at least one element 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.

Examples of the oxide semiconductor containing at least one element selected from In, Ga, Sn, Ti, Nb, Sb and Zn include quaternary metal oxides such as In-Sn-Ga-Zn-O-based oxide semiconductors;

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 semiconductor, Al-Ga-Zn- ternary metal oxides such as O-based oxide semiconductors and Sn-Al-Zn-O-based oxide semiconductors;

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 binary metal oxides such as oxide semiconductors and In-Ga-O-based materials;

and single-type metal oxides such as In-O-based oxide semiconductors, Sn-O-based oxide semiconductors, and Zn-O-based oxide semiconductors.

In the present invention, when the semiconductor layer constituting the TFT is the above-mentioned oxide semiconductor layer, in particular, even when it is an oxide semiconductor layer made of an In-Ga-Zn-O-based oxide semiconductor (IGZO semiconductor), the photodegradation thereof can be prevented. have.

The device of the present invention comprises: a first electrode formed 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 barrier rib; It is preferable that it is an organic electroluminescent device which has an organic electroluminescent element containing two electrodes.

The TFT substrate includes, for example, a support substrate, a TFT formed corresponding to the organic EL element on the support substrate, and a planarization layer covering the TFT. For example, the first electrode is formed on the planarization layer and is connected to the TFT through a through hole passing through the planarization layer. In addition, it is preferable that the insulating film (barrier) which has light-shielding property is formed on the 1st electrode and the planarization layer so that the 1st electrode may be partially exposed.

Hereinafter, as a display or lighting device of the present invention, an organic EL display or lighting device will be taken as a specific example, and will be described with reference to FIG. 1 . Fig. 1 is a cross-sectional view schematically showing the structure of a main part of an organic EL display or lighting device (hereinafter, simply referred to as &quot;organic EL device&quot;) according to the present invention.

The organic EL device 1 of Fig. 1 is an active matrix organic EL device having a plurality of pixels formed in a matrix shape. The organic EL device 1 may be either a top emission type or a bottom emission type. The properties of the material constituting each member, for example, transparency, are appropriately selected according to the top emission type and the bottom emission type.

The organic EL device 1 includes a supporting 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 , 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 formed of an insulating material. When the organic EL device 1 is a bottom emission type, high transparency is required for the support substrate 2 . Therefore, as an insulating material, transparent resins, such as high transparency polyethylene terephthalate, polyethylene naphthalate, a polyimide, and an alkali free glass, glass materials, such as, for example, are preferable, for example. 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 it is possible to use the transparent resin and glass material described above.

The TFT 3 is an active element in 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. In the present invention, the present invention is not limited to a bottom gate type in which a gate insulating film and a semiconductor layer are sequentially provided on a gate electrode, but a top gate type in which a gate insulating film and a gate electrode are sequentially provided on a semiconductor layer may be used.

The semiconductor layer may be formed using the oxide semiconductor including at least one element selected from In, Ga, Sn, Ti, Nb, Sb, and Zn as described above.

The first insulating film 4 is a planarization film serving to planarize the surface unevenness of the TFT 3 . The first insulating film 4 is formed so as to cover the entire TFT 3 . The first insulating film 4 may be formed using the above-mentioned radiation-sensitive resin composition, or may be formed using a conventionally known radiation-sensitive resin composition. The first insulating film 4 can be formed by the method or the like described in the above-described method for forming the insulating film.

The anode 5 forms a pixel electrode. The anode 5 is formed on the first insulating film 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, as a material of the anode 5, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and tin oxide with high transparency are preferable. When the organic EL device 1 is of the top emission type, the anode 5 is required to have light reflectivity. Therefore, as the material of the anode 5, Al (aluminum), APC alloy (alloy of silver, palladium, and copper), ARA (alloy of silver, rubidium, gold), MoCr (of molybdenum and chromium) with high light reflectivity alloy) and NiCr (an alloy of nickel and chromium) are preferable, and a laminated film of these metals and an electrode (eg, ITO) having high transparency 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 barrier rib (bank) having a recess 70 defining an 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 while exposing a part of the anode 5 . The second insulating film 7 can be formed by using the above-mentioned radiation-sensitive resin composition, for example, by the method described in the method for forming the insulating film.

The thickness of the second insulating film 7 (the 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 0.5 µm or more 20 ㎛ or less is more preferable.

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 the region defined by the second insulating film 7 , that is, in the recess 70 . In this way, by forming the organic light emitting layer 8 in the concave portion 70 , the periphery of the organic light emitting layer 8 is surrounded by the second insulating film 7 , and a plurality of 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 injection layer between the organic light emitting layer 8 and the cathode 9 . Layers may be arranged.

The cathode 9 is formed to cover a plurality of pixels in common, and constitutes 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, it is preferable that the cathode 9 is a visible light transmissive electrode, and an ITO electrode and an IZO electrode are mentioned. When the organic EL device 1 is a bottom-emission type, the cathode 9 does not need to be a visible light-transmitting electrode. In that case, as a constituent material of the cathode 9, the alloy containing barium (Ba), barium oxide (BaO), aluminum (Al), and Al is mentioned, for example.

The passivation film 10 suppresses penetration of moisture and oxygen into the organic EL element. This passivation film 10 is formed on the cathode 9 .

The sealing substrate 11 seals the main surface (the surface on the side opposite to the support substrate 2 in the TFT substrate) on which the organic light emitting layer 8 is disposed. As the sealing substrate 11, glass substrates, such as an alkali free glass substrate, are mentioned. It is preferable that the main surface on which the organic light emitting layer 8 is arrange|positioned is sealed with the sealing substrate 11 through the sealing layer 12 using the sealing compound apply|coated near the outer peripheral edge part of a TFT board|substrate. . The sealing layer 12 can be made into a layer of inert gas, such as dried nitrogen gas, or a layer of filling materials, such as an adhesive agent, for example.

In the organic EL device 1 of the present embodiment, since the second insulating film 7 has light-shielding properties with respect to light having a wavelength of 400 nm, light deterioration of the semiconductor layer accompanying the use of the device, etc. can be suppressed. Moreover, since the amount of outgassing from the second insulating film 7 is small, the light emitting characteristic is excellent. In addition, the first insulating film 4 and the second insulating film 7 can be formed using a radiation-sensitive resin composition with low water absorption, and in the forming process of these insulating films 4 and 7, It is possible to process such as cleaning using the material. Therefore, it is possible to reduce the intrusion of a small amount of moisture contained in the insulating film forming material in the form of an adsorbate or the like into the organic light emitting layer 8 gradually, thereby reducing deterioration of the organic light emitting layer 8 and deterioration of the light emitting state.

Example

Hereinafter, the present invention will be described more specifically based on Examples, but the present invention is not limited to these Examples. In the following description, unless otherwise indicated, "part" represents "part by mass".

[ GPC analysis]

The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of resin (A) and resin (C) were measured by the gel permeation chromatography (GPC) method under the following conditions.

·Standard material: polystyrene

· Apparatus: manufactured by Tosoh Corporation, product name: HLC-8020

·Column: Tosoh Co., Ltd. guide column H _XL -H, TSK gel G7000H _XL , TSK gel GMH _XL 2ea, TSK gel G2000H _XL sequentially connected

Solvent: tetrahydrofuran (however, in the case of polyimide, N,N-dimethylformamide)

・Sample concentration: 0.7% by mass

・Injection amount: 70μL

Flow rate: 1mL/min

[NMR analysis]

The chemical shift of the resin (A) was measured by a nuclear magnetic resonance (NMR) method under the following conditions.

・Device: manufactured by Nippon Denshi Co., Ltd., brand name: JNM-ECX400

·Solvent: CDCL ₃

[of polyimide imidization rate ]

First, the infrared absorption spectrum of a polyimide was measured, and ^{presence of the absorption peak (1780 cm -1} vicinity, 1377 cm ^-1 vicinity) of the imide structure resulting from a polyimide was confirmed. Next, about this polyimide, after heat-processing at 350 degreeC for 1 hour, the infrared absorption spectrum was measured again. The peak intensity of the vicinity of ^{1377 cm -1} before the heat treatment and after the heat treatment was compared. Assuming that the imidation rate of the polyimide after heat treatment is 100%, the imidization rate of the polyimide before heat treatment = { ^{Peak intensity near 1377 cm -1} before heat treatment / Peak intensity ^{near 1377 cm -1} after heat treatment} x 100 (%) ) was saved. "NICOLET6700FT-IR" (made by Thermo Electron Corporation) was used for the measurement of an infrared absorption spectrum.

<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-neck flask, 50 g of propylene glycol monomethyl ether acetate (PGMEA) was added, and 2,2'-bis (diamine compound) as a diamine compound to a total of 390 g of polymerization solvent 120 g of 3-amino-4-hydroxyphenyl) hexafluoropropane was added to the polymerization solvent. After dissolving the diamine compound in the polymerization solvent, 71 g of 4,4'-oxydiphthalic dianhydride as 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 1 hour, it heated up and made it react at 140 degreeC for 4 hours. During the reaction, PGMEA as a low boiling point solvent was distilled off using a Dean-Stark tube under _{N 2 flow conditions.} Thereby, about 550 g of a solution containing 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 three-necked flask with a stirrer, 20 parts of 3,4-epoxycyclohexylmethyl methacrylate as component (a3-1), 10 parts of methacrylic acid as component (a3-2), and benzylmethacrylate as component (a3-3) 65 parts of acrylate, 150 parts of propylene glycol monomethyl ether acetate as a solvent, 3 parts of dimethyl-2,2'-azobis(2-methylpropionate) as a polymerization initiator, and 2 parts of thioglycolic acid as a chain transfer agent, , heated at 65°C for 6 hours to obtain a solution containing resin (A-2). The weight average molecular weight (Mw) of the obtained resin (A-2) was 10000.

[Synthesis Example A3] Synthesis of Resin (A-3)

In a three-necked flask with a stirrer, 40 parts of 3,4-epoxycyclohexylmethyl methacrylate as component (a3-1), 30 parts of mono(2-methacryloyloxyethyl) succinate as component (a3-2); 25 parts of benzyl methacrylate as component (a3-3), 150 parts of propylene glycol monomethyl ether acetate as a solvent, 3 parts of dimethyl-2,2'-azobis(2-methylpropionate) as a polymerization initiator, and a chain 2 parts of thioglycolic acid as a transfer agent was thrown in, and it heated at 65 degreeC for 6 hours, and obtained the solution containing 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-neck flask, 63.39 g (0.55 mol) of methyltrimethoxysilane, 69.41 g (0.35 mol) of phenyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 24.64 g (0.1 mol) and 150.36 g of diacetone alcohol were charged, and an aqueous solution of phosphoric acid in which 0.338 g of phosphoric acid (0.2 mass % with respect to the charged monomer) was dissolved in 55.8 g of water was added over 10 minutes while stirring at room temperature. Then, after immersing the flask in a 70 degreeC oil bath and stirring for 1 hour, the oil bath was heated up to 115 degreeC over 30 minutes. The internal temperature of the solution reached 100 degreeC 1 hour after the start of temperature increase, and it heat-stirred from there for 2 hours (internal temperature is 100-110 degreeC). A total of 115 g of methanol and water as by-products flowed out during the reaction. Diacetone alcohol was added to the diacetone alcohol solution of obtained resin (A-4) so that resin (A-4) density|concentration might be set to 40 mass %, and the diacetone alcohol solution of resin (A-4) was 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 novolac resin (C-1)

144.2 g (1.0 mol) of 1-naphthol, 400 g of methyl isobutyl ketone, and 102.3 g (0.7 mol) of α-methylcinnamaldehyde were charged to a flask equipped with a thermometer, a cooling tube, a flow dividing tube and a stirrer. Then, stirring, 3.4 g of the methanol solution of 30 mass % density|concentration of para-toluenesulfonic acid was added. 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 separation funnel, and the water layer was separated and removed from the organic layer. Next, the organic layer was washed with water until the washing water became neutral, 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 weight average molecular weight (Mw) of the obtained novolak resin (C-1) was 4500.

From the measurement chart of the infrared absorption spectrum by "NICOLET6700FT-IR" (manufactured by Thermo Electron Corporation), compared with the raw material, absorption (2700 ^{to 3000 cm -1} ) derived from CH stretching due to a substituted methylene bond was confirmed. From these results, it was identified that novolak resin having a substituted methylene bond was obtained without dehydration etherification reaction between hydroxyl groups (disappearance of hydroxyl groups) in this synthesis example. These estimates are the same also in the following synthesis examples C2 to C8.

[Synthesis Examples C2 to C8]

In Synthesis Examples C2 to C8, novolak resins (C-2) to (C-6) and other novolak resins (C-7) to ( C-8) was obtained. A result is shown in Table 1.

< radiation sensitive Preparation of resin composition>

The resin (A) used for the preparation of the radiation-sensitive resin composition is the resins (A-1) to (A-4) of Synthesis Examples A1 to A4, and the Resin (C) is the novolac resin (C) of Synthesis Examples C1 to C6. -1) to (C-6), and the other resin (C') is another novolak resin (C-7) to (C-8) of Synthesis Examples C7 to C8, and a photosensitizer (B) and a crosslinking agent (D) , the solvent (E), the adhesion aid (F), the surfactant (G), and the dye (H) are as follows.

・Photosensitizer (B)

B-1: naphthoquinone diazide sulfonic acid ester (NT-300P, manufactured by Toyo Gosei Kogyo Co., Ltd.)

B-2: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (“IRACURE OXE01” manufactured by BASF Japan Co., Ltd.)

· crosslinking agent (D)

D-1: 4,4-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl ("OXBP" manufactured by Ubegosan Co., 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

・Adhesive aid (F)

F-1: N-phenyl-3-aminopropyltrimethoxysilane

(“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.)

・Surfactant (G)

G-1: Silicone-based surfactant (“SH8400” manufactured by Toray Dow Corning)

・Dye (H)

H-1: C.I.Solvent Blue70

("OilBlue5511" manufactured by Arimoto Chemical)

H-2: C.I.Solvent Blue45

(“PlastBlueDB-463” manufactured by Arimoto Chemical)

H-3: C.I.Solvent Black27

("NEOSUPERBLACK C-832" manufactured by Chugo Sei Chemicals)

H-4: C.I.Solvent Red83 (“Aizen Spilon Red BEH Special” manufactured by Hodogaya Chemical Industry Co., Ltd.)

[Example 1]

To a resin solution (an amount equivalent to 40 parts (solid content) of resin (A-1)) containing the resin (A-1) of Synthesis Example A1, (B-1) 16 parts, (C-1) 25 parts, (D-1) 15 parts, (F-1) 3 parts, (G-1) 1 part and a solvent were mixed, filtered through a membrane filter having a diameter of 0.2 µm, and a radiation-sensitive resin having the composition shown in Table 2 Composition 1 was prepared. In addition, the solid content concentration of the said composition was 30 mass %.

[Examples 2 to 27 and Comparative Examples 1 to 3]

In Examples 2-27 and Comparative Examples 1-3, except having used each component of the kind and compounding quantity shown in Table 2, it carried out similarly to Example 1, and prepared the radiation-sensitive resin compositions 2-30.

[evaluation]

An insulating film and an organic EL element were produced by the method demonstrated below using the radiation-sensitive resin composition obtained by the Example and the comparative example. The patterning property and radiation sensitivity of the composition were evaluated by the following method, respectively, the light-shielding property (transmittance), absorption, heat resistance and outgassing amount of the obtained insulating film, and the device characteristics of the obtained organic EL device. In addition, in the following evaluation, "the said composition" means the radiation-sensitive resin composition obtained by the Example and the comparative example.

< patternability >

After apply|coating the said composition on a silicon substrate using a spinner, it prebaked at 120 degreeC for 2 minute(s) on a hotplate, and formed the coating film. This coating film was exposed using the exposure machine ("MPA-6000" by Canon Corporation) at the exposure amount of 100 mJ/cm<2> in wavelength 365nm through the pattern mask which has a predetermined|prescribed pattern. The exposure amount was measured with an illuminometer ("OAI model356" by OAI Optical Associates). Then, using 2.38 mass % tetramethylammonium hydroxide aqueous solution, it develops by the puddle method at 25 degreeC for 80 second, it washes under running water for 1 minute with ultrapure water, and it dries, and a 5 micrometer diameter plurality of 5 micrometers on a silicon substrate. A coating film having a pattern in which through-holes were arranged in rows was formed. This coating film was post-baked at 250 degreeC for 45 minutes in a clean oven, and the insulating film with a film thickness of 3.0 micrometers was obtained.

At this time, in the said coating film, it was confirmed whether the exposed part after image development completely melt|dissolved in the case of a positive type, and in the case of a negative type, it confirmed whether the unexposed part after image development completely melt|dissolved. A pattern of 5 μm is formed, and a pattern of 5 μm is formed when an insulating film is formed without peeling of the insulation film or development residue, and a pattern of 5 μm when there is little development residue although there is no separation of the insulation film. A case in which it cannot be formed or a case in which peeling of the insulating film occurs was defined as “defective”.

<Radiation sensitivity>

After apply|coating the said composition on a silicon substrate using a spinner, it prebaked at 120 degreeC for 2 minutes on a hotplate, and formed the coating film with a film thickness of 3.0 micrometers. This coating film was exposed by changing the exposure amount through a pattern mask having a predetermined pattern using an exposure machine ("MPA-6000" manufactured by Canon Corporation). Then, using 2.38 mass % tetramethylammonium hydroxide aqueous solution, it develops by the puddle method at 25 degreeC for 80 second, and it washes under running water for 1 minute with ultrapure water, and it dries, and a plurality of 20.0 micrometers in diameter on a silicon substrate. A coating film having a through hole was formed.

At this time, according to the shape of the mask pattern with a diameter of 20.0 micrometers, the exposure amount required for the coating film to melt|dissolve completely was measured, and the exposure amount at this time was made into radiation sensitivity (exposure sensitivity). Radiation sensitivity was set as "favorable" when the exposure amount in wavelength 365nm was 100 mJ/cm<2> or less, and "bad" when it exceeded 100 mJ/cm<2>. The exposure amount was measured with an illuminometer ("OAI model356" by OAI Optical Associates).

<Transmittance>

After applying the composition on a glass substrate (“Corning 7059” by Corning Corporation) using a spinner, pre-baking at 120° C. for 2 minutes on a hot plate, and post-baking at 250° C. for 45 minutes in a clean oven, the film thickness An insulating film having a thickness of 3.0 mu m was formed.

With respect to the glass substrate having this insulating film, the total light transmittance was measured in a wavelength range of 300 nm to 780 nm using a spectrophotometer (“150-20 double beam” manufactured by Hitachi Seisakusho Co., Ltd.), and the wavelength The total light transmittance in 400 nm was calculated|required. This transmittance is "good" when the total light transmittance is 5% or less at a wavelength of 400 nm, "good" when it exceeds 5% and 15% or less, and "bad" when it exceeds 15%. did it with Moreover, the total light transmittance in wavelength 600nm was calculated|required. This transmittance|permeability was set as "good" when the total light transmittance was 10 % or less in wavelength 600 nm, and when it exceeded 10 % and was 30 % or less, it was made into "good|favorableness".

<Absorbency>

After applying the composition on a silicon substrate using a spinner, pre-baking at 120° C. for 2 minutes on a hot plate, followed by post-baking at 250° C. for 45 minutes in a clean oven to form an insulating film having a thickness of 3.0 μm .

This insulating film was heated from room temperature to 200°C (30°C/min) at ^{a vacuum degree of 1.0×10 −9} Pa using Thermal Desorption Spectroscopy (“TDS1200” by ESCO). At that time, the sample surface and the gas released from the sample were measured as a detection value of the water peak (M/z=18) with a mass spectrometer ("5973N" manufactured by Agilent Technologies). The integrated value [A·sec] of the total peak intensity at 60°C to 200°C was taken to evaluate the water absorption. Water absorption is "excellent" when the integral value [A sec] of the total peak intensity of 60°C to 200°C is 3.0×10 ^{-8 or less, and exceeds 3.0×10 -8} and 5.0×10 ^-8 or less When "good" and 5.0x10 ^-8 were exceeded, it was set as "bad".

<Heat resistance>

In the same manner as in the evaluation of <water absorption>, an insulating film is formed using the composition, and the insulating film is TGA at 100°C to 500°C using a thermogravimetric apparatus ("TGA2950" by TA Instruments). The 5% weight loss temperature was calculated|required by performing a measurement (under air, a temperature increase rate of 10 degreeC/min). Heat resistance was made into "good|favorableness" in the case of "excellent" and 350-330 degreeC, when 5% weight loss temperature exceeded 350 degreeC.

<Out gas volume>

In the same manner as in the evaluation of <water absorption>, an insulating film was formed using the above composition, a silicon substrate with an insulating film was cut into 1 cm x 5 cm pieces, and the silicon wafer analyzer (trade name " Heating and desorption apparatus JTD-505" manufactured by Nippon Bunseki Kogyo Co., Ltd., "Gas Chromatography Mass Spectrometer GCMS-QP2010Plus" manufactured by Shimadzu Corporation), maintained at 230°C for 15 minutes (temperature increase rate of 10°C) /min) was calculated|required [microgram/cm<3> of the amount of outgassing].

《Evaluation of device characteristics》

After producing a TFT substrate in which TFT was formed on this glass substrate using a glass substrate ("Corning 7059" by Corning Corporation), an insulating film was formed on this TFT substrate to produce an element for evaluation. About this element for evaluation, element characteristic was evaluated.

The TFT substrate was formed in the following procedure. First, a molybdenum film was formed on a glass substrate by sputtering, and a gate electrode was formed by photolithography and etching using a resist. Next, a silicon oxide film was formed by sputtering on the entire surface of the glass substrate and the upper layer of the gate electrode to obtain 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 upper layer of 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 upper layers of the source electrode and the drain electrode to be a passivation film to obtain a TFT substrate.

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

<Switching response characteristics>

The device characteristics were evaluated as switching response characteristics. The switching response characteristic was evaluated by measuring 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, under the condition that the semiconductor layer was irradiated with white light (illuminance of 30000 lux) centered at a wavelength of 450 nm or 500 nm from above the insulating film formed of the composition, the drain electrode was set to plus 10 V and the source electrode to 0 V. In this case, the ratio of the current value when the voltage applied to the gate electrode was plus 10 V and minus 10 V was defined as the ON/OFF ratio. Switching response characteristic, that is, the device characteristics is, ON / OFF ratio was a "poor" to 1.0 × 10 "good" if less than ^5, less than 1.0 × 10 ^5.

< TFT Reliability>

The TFT reliability is evaluated by comparing the change in the Id-Vg characteristics (the amount of change in the threshold voltage Vth) when an electrical stress is applied between the gate electrode and the source electrode, when irradiated with light and when not irradiated with light. evaluated.

(Id- Vg Characteristics and threshold voltage Vth measurement of)

Application of electrical stress is performed by maintaining the potential of the source electrode of the evaluation element at 0 V and the potential of the drain electrode at +10 V, applying a voltage between the source electrode and the drain electrode, and changing the potential Vg of the gate electrode at -20 V. It carried out by changing it to +20V. Id-Vg characteristics were obtained by plotting the current Id flowing between the drain electrode and the source electrode when the potential Vg of the gate electrode was changed in this way. In this Id-Vg characteristic, the voltage at which the current value turns ON was set as the threshold voltage Vth.

(threshold voltage Vth measurement of the amount of change in

Electrical stress was applied between the gate electrode and the source electrode by applying a positive voltage of +20V and a negative voltage of -20V each for 12 hours. Such electrical stress was applied to each of the conditions under which light was irradiated from above to the semiconductor film of the element for evaluation and under the condition where the semiconductor film was not irradiated with light. The amount of change of the threshold voltage Vth was calculated from the Id-Vg characteristic for each of the light irradiation condition and the light non-irradiation condition. And when the change amount of the threshold voltage Vth at the time of light irradiation is suppressed to less than 1.5 times the change amount of the threshold voltage Vth at the time of light non-irradiation, the TFT reliability is set as "good", and it is suppressed to 1.5 to 2 times. TFT reliability was set as "favorable" when it was, and TFT reliability was set as "poor" when exceeding 2 times.

< EL Evaluating luminescence properties>

Using a glass substrate ("Corning 7059" by Corning Corporation), sputtering an ITO transparent electrode on this glass substrate, and then applying a photosensitive resist ("NN700", manufactured by JSR Co., Ltd.) by spin coating and drying, Exposure was carried out through a predetermined pattern mask. After exposure, it developed and heat-hardened, and the predetermined|prescribed resist pattern was formed. Next, the ITO film was etched using an etchant to form a predetermined pattern of the ITO film, and then the resist pattern was removed with a stripper.

A photosensitive resist (“NN700”, manufactured by JSR Co., Ltd.) was applied to a film thickness of 5 μm by spin coating on a glass substrate on which ITO transparent electrodes were formed in an array shape as described above, and then applied on a hot plate at 80° C. It prebaked for 3 minutes with furnace, and formed the coating film. Next, this coating film was exposed through a predetermined pattern mask. After exposure, it developed and post-baked for 5 minutes at 200 degreeC in clean oven. In this way, the planarization layer which has the contact hole in which only a part of the ITO transparent electrode was exposed was formed on the glass substrate. The film thickness of the planarization layer after post-baking was 3 micrometers. A plurality of glass substrates with a planarization layer were prepared as described above, and used at the following steps.

An Al film having a thickness of 100 nm was formed on the glass substrate on which the planarization layer was formed by DC sputtering using an Al target. Next, a photosensitive resist ("NN700", manufactured by JSR Corporation) was applied by spin coating, dried, and exposed through a predetermined pattern mask. After exposure, it developed and heat-hardened, and the predetermined|prescribed resist pattern was formed. Next, the Al film was etched using a mixed acid etchant to form a predetermined Al film pattern, and then the resist pattern was removed with a stripper. 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 DC magnetron reactive sputtering using an ITO target. Next, a photosensitive resist ("NN700", manufactured by JSR Corporation) was applied by spin coating, dried, and exposed through a predetermined pattern mask. After exposure, it developed and heat-hardened, and the predetermined|prescribed resist pattern was formed. Next, the ITO film was etched using an etchant to form an ITO film pattern identical to the Al film on the Al film, and then the resist pattern was removed with a stripper. In this way, an anode made of an Al film and an ITO film was formed.

With respect to the obtained anode substrate, the composition was applied using Clean Track (manufactured by Tokyo Electron Corporation: Mark VZ), and then prebaked on a hot plate at 120° C. for 2 minutes, and a 4 μm-thick coating film was applied. formed With respect to this coating film, using the exposure machine (i-line stepper "NSR-2005i10D" by Nikon), it exposed with the exposure amount 100mJ/cm<2> in wavelength 365nm through the pattern mask which has a predetermined|prescribed pattern. Then, using 2.38 mass % tetramethylammonium hydroxide aqueous solution, it develops by the puddle method at 25 degreeC for 80 second, wash|cleaning in running water for 1 minute with ultrapure water, drying, post-baking at 250 degreeC for 45 minutes in a clean oven, , a barrier rib was formed on the anode substrate.

An organic EL element was formed on the anode substrate on which the barrier ribs were formed by vacuum deposition. The organic EL element was created with the following procedure.

With respect to a cathode substrate in which a partition wall subjected to ultrasonic cleaning, followed by transferring the substrate into the N ₂ atmosphere, it was carried out for 3 hours and dried at 200 ℃. Further, the substrate was transferred to an oxygen plasma processing apparatus, evacuated, and RF power of 50 W was applied to a ring-shaped electrode formed in the vicinity of the substrate to perform oxygen plasma cleaning processing. The oxygen pressure was 0.6 Pa, and the treatment time was 40 seconds.

After moving the substrate to the vacuum deposition chamber and evacuating the deposition chamber to 1E ^-4 Pa, molybdenum oxide (MoOx) having hole injection properties is applied to the substrate by resistance heating deposition using a deposition mask of a predetermined pattern. It formed into a film under the conditions of the film-forming rate of 0.004-0.005 nm/sec by this, and formed the hole injection layer with a film thickness of 1 nm.

Resist 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (α-NPD) having hole transport properties on the hole injection layer using a deposition mask of a predetermined pattern It formed into a film under the same exhaust conditions as a hole injection layer by the heat vapor deposition method, and the hole transport layer with a film thickness of 35 nm was formed. The film-forming rate was 0.2-0.3 nm/sec condition.

On the hole transport layer, using a deposition mask of a predetermined pattern, tris(8-quinolinolato)aluminum (Alq ₃ ), which is an alkylate complex as a green light emitting material, was deposited under the same deposition conditions as the hole transport layer by resistance heating deposition. was formed into a film to form a light emitting layer with a film thickness of 35 nm. The film-forming rate was 0.5 nm/sec or less conditions.

On the light emitting layer, lithium fluoride was deposited by resistance heating evaporation 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.

Next, the said board|substrate was transferred to another film-forming chamber (sputtering chamber), and the cathode with a film thickness of 130 nm was formed on the electron injection layer by the RF sputtering method using an ITO target.

The substrate was transferred to a glove box, N ₂ leaked, and a sealing glass having a moisture absorbent attached to the element surface side was adhered to the substrate using a UV curing acrylic adhesive, and sealed.

As described above, an organic EL device for evaluation was obtained.

After storing the organic EL element for evaluation in a constant temperature and humidity chamber with a temperature of 85°C and a humidity of 85% for 500 hours, the organic EL element was activated at room temperature and a dark spot (non-light emitting location) was observed. The case where the area of a dark spot was less than 10 % with respect to the whole was made into "good|favorableness", and the case where it is 10 % or more or extinction was made into "poor".

As shown in Table 3 and Table 4, the insulating films formed in Examples 1-27 were excellent in light-shielding property, and there was also little amount of outgassing. Moreover, the compositions and insulating films of Examples 1-27 were excellent also in patterning property, radiation sensitivity, low water absorption, and heat resistance. The element using this insulating film and the semiconductor layer which is easy to light deterioration was excellent in the switching response characteristic and TFT reliability also in the light irradiation environment. Moreover, the obtained organic electroluminescent element was excellent in EL light emitting characteristic.

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 property and was inferior in element characteristic. In addition, although the compositions of Comparative Examples 1 and 2 contain a novolak resin, the said novolak resin is not a resin which has a structural unit represented by Formula (C1) (corresponding to alkali-soluble resin (A)). For this reason, the insulating film formed from the composition of Comparative Examples 1 and 2 had a large amount of outgassing and was inferior in EL luminescence characteristic, and the composition of Comparative Examples 1-2 was inferior in patternability and radiation sensitivity.

1: organic EL device
2: support substrate
3: TFT
4: first insulating film (planarization film)
5: positive electrode
6: Through hole
7: second insulating film (barrier)
70: recess
8: organic light emitting layer
9: cathode
10: passivation film
11: Encapsulation substrate
12: encapsulation layer

Claims (15)

(B) a photosensitizer;
(C) a resin having a structural unit represented by the formula (C1);
Resin which has a structure represented by Formula (C2)
An insulating film formed of a radiation-sensitive resin composition containing at least one resin selected from
Element for a display or lighting device having:

[in formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, and L is a monovalent group represented by a formula (c2-1), a formula (c2-2), or a formula (c2-3);

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

[In formula (c2-1), X is an oxygen atom, a sulfur atom, -CH ₂ - or -NH-, R ¹ is a halogen atom, -OH, -SH, -NO ₂ , -NH ₂ , a hydrocarbon group, and , a monovalent group selected from hetero atom-containing groups having 1 or more carbon atoms, and m is 1;
In formula (c2-2), Y is a nitrogen atom, CH or CR ² , R ² has the same meaning as ^{R 1} in formula (c2-1) ^{, and R 3} and R ⁴ are each independently a hydrogen atom or a hydrocarbon group. , n is an integer from 0 to 4, d is 1, and ^{when there are two} or more R 2 , each 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 two or more R ⁵ are present, each may be the same or different ^{Alternatively, R 5} bonded to adjacent ring carbon may be bonded to each other to form a ring]. According to claim 1,
In Formula (C1), A is a divalent group represented by Formula (c1-1), Formula (c1-2), or Formula (c1-3), a display or lighting device element:

[In formulas (c1-1) to (c1-3), a1 is an integer of 1 to 4, b1 is an integer of 0 to 3, a2 to a5 and b2 to b5 are each independently an integer of 0 to 4 , a6 and b6 are integers of 0 to 2, provided that a2+a3 is an integer of 1 or more and 6 or less, a2+a3+b2+b3 is an integer of 1 or more and 6 or less, a4+a5+a6 is an integer of 1 or more and 8 or less, and a4+a5+a6+b4+b5+b6 is an integer of 1 or more and 8 or less. is an integer of;
R is a hydrocarbon group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; According to claim 1,
The radiation-sensitive resin composition,
(A) Alkali-soluble resin except for the above resin (C)
A device for a display or lighting device further comprising a. 4. The method of claim 3,
Alkali-soluble resin (A) is polyimide (A1), precursor of said polyimide (A2), acrylic resin (A3), polysiloxane (A4), polybenzoxazole (A5), and precursor of said polybenzoxazole ( A6) The element for display or lighting devices which is at least 1 sort(s) selected from. 5. The method of claim 4,
Element for display or lighting devices in which polyimide (A1) is a polyimide having a structural unit represented by formula (A1):

[In formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group]. 5. The method of claim 4,
The element for display or lighting devices whose acrylic resin (A3) is resin obtained by polymerizing at least the radically polymerizable monomer which has a carboxyl group. 5. The method of claim 4,
Element for display or lighting devices wherein polysiloxane (A4) is polysiloxane obtained by reacting the organosilane represented by formula (a4):

[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, an epoxy ring-containing group having 2 to 15 carbon atoms, or the above It is a group formed by substituting 1 or 2 or more hydrogen atoms contained in an alkyl group with a substituent, and ^{when there are two or more R<1>} , respectively, they may be same or different;
R ² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group, or a 6 to 15 carbon atoms having 1 to 6 carbon atoms in the aryl group, if there are plural R ² may be the phase may be the same, respectively;
n is an integer from 0 to 3]. 8. The method according to any one of claims 1 to 7,
The element for display or lighting devices whose photosensitizer (B) is at least 1 sort(s) chosen from a photoacid generator, a photoradical polymerization initiator, and a photocationic polymerization initiator. 8. The method according to any one of claims 3 to 7,
The said radiation-sensitive resin composition WHEREIN: Content of resin (C) is 5-200 mass parts with respect to 100 mass parts of resin (A) The element for display or lighting devices. 8. The method according to any one of claims 1 to 7,
An element for a display or lighting device, which is an organic electroluminescent element. (B) a photosensitizer;
(C) a resin having a structural unit represented by the formula (C1);
Resin which has a structure represented by Formula (C2)
at least one resin selected from
A radiation-sensitive resin composition containing:

[in formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, and L is a monovalent group represented by a formula (c2-1), a formula (c2-2), or a formula (c2-3);

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

[In formula (c2-1), X is an oxygen atom, a sulfur atom, -CH ₂ - or -NH-, R ¹ is a halogen atom, -OH, -SH, -NO ₂ , -NH ₂ , a hydrocarbon group, and , a monovalent group selected from hetero atom-containing groups having 1 or more carbon atoms, m is an integer of 0 to 3, provided that in the case of formula (C1), when m=0, X is not an oxygen atom, and R ¹ is plural When present, each may be the same or different, and R ¹ bonded to adjacent ring carbons may be bonded to each other to form a ring;
In the formula (c2-2), Y is a nitrogen atom, CH or CR ² , R ² has the same meaning as ^{R 1} in the formula (c2-1) ^{, and R 3} and R ⁴ are each independently a hydrogen atom or a hydrocarbon group , n is an integer of 0 to 4, d is 0 or 1, with the proviso that in the case of formula (C1), when n = d = 0, Y is not CH, and n = d = 0 and Y is When CR ² , or when n=1, d=0 and Y is CH, R ² is not -NO ₂ , -OH, and ^{when there are two} or more R 2 , each may be the same or different, and adjacent rings ^{R 2} bonded to carbon 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 two or more R ⁵ are present, even if they are the same or different ^{Alternatively, R 5} bonded to adjacent ring carbon may be bonded to each other to form a ring]. 12. The method of claim 11,
(A) Alkali-soluble resin except for the above resin (C)
Further containing, the radiation-sensitive resin composition. (B) a photosensitizer;
(C) a resin having a structural unit represented by the formula (C1);
Resin which has a structure represented by Formula (C2)
at least one resin selected from
An insulating film formed of a radiation-sensitive resin composition containing:

[in formula (C1), A is a divalent aromatic group having a phenolic hydroxyl group, and L is a monovalent group represented by a formula (c2-1), a formula (c2-2), or a formula (c2-3);

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

[In formula (c2-1), X is an oxygen atom, a sulfur atom, -CH ₂ - or -NH-, R ¹ is a halogen atom, -OH, -SH, -NO ₂ , -NH ₂ , a hydrocarbon group, and , a monovalent group selected from hetero atom-containing groups having 1 or more carbon atoms, m is an integer of 0 to 3, provided that in the case of formula (C1), when m=0, X is not an oxygen atom, and R ¹ is plural When present, each may be the same or different, and R ¹ bonded to adjacent ring carbons may be bonded to each other to form a ring;
In formula (c2-2), Y is a nitrogen atom, CH or CR ² , R ² has the same meaning as ^{R 1} in formula (c2-1) ^{, and R 3} and R ⁴ are each independently a hydrogen atom or a hydrocarbon group. , n is an integer of 0 to 4, d is 0 or 1, with the proviso that in the case of formula (C1), when n = d = 0, Y is not CH, and n = d = 0 and Y is When CR ² , or when n=1, d=0 and Y is CH, R ² is not -NO ₂ , -OH, and ^{when there are two} or more R 2 , each may be the same or different, and adjacent rings ^{R 2} bonded to carbon 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 two or more R ⁵ are present, each may be the same or different ^{Alternatively, R 5} bonded to adjacent ring carbon may be bonded to each other to form a ring]. 14. The method of claim 13,
The radiation-sensitive resin composition,
(A) Alkali-soluble resin except for the above resin (C)
An insulating film further comprising a. A process of forming a coating film on a substrate using the radiation-sensitive resin composition according to claim 11 or 12, a process of irradiating at least a part of the coating film with radiation, a process of developing the coating film irradiated with the radiation; A method for producing an insulating film, comprising a step of heating the developed coating film.

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