KR102373855B1 - Radiation-sensitive resin composition, insulating film and manufacturing method therefor, and organic el element - Google Patents

Abstract

[식 (A1) 중, R¹은 수산기를 갖는 2가의 기이고, X는 4가의 유기기임];

[식 (G1-1) 중, R^G1은 각각 독립적으로 수소 원자, 탄화수소기 등이고, R^G2는 카보닐기 등이고, R^G3은 수소 원자, 탄화수소기이고, R^G4는 알킬기, 알콕시알킬기이고; 식 (G1-2) 중, X^G1은 C-H, 질소 원자이고, 적어도 1개의 X^G1은 질소 원자이고, X^G2는 수소 원자, 탄화수소기, 알콕시알킬기임].(Project) To provide a radiation-sensitive resin composition containing a polyimide-based polymer, wherein a solvent other than N-methyl-2-pyrrolidone is used as the solvent.
(Solution means) (A) Polyimide having a structural unit represented by Formula (A1), and at least one polymer selected from precursors of the polyimide, (B) a radiation-sensitive acid generator, (G1) The radiation-sensitive resin composition containing the compound represented by Formula (G1-1), and the at least 1 sort(s) of solvent chosen from the compound represented by Formula (G1-2):

[in formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group];

[In formula (G1-1), R ^G1 is each independently a hydrogen atom, a hydrocarbon group, etc., R ^G2 is a carbonyl group or the like, R ^G3 is a hydrogen atom or a hydrocarbon group, R ^G4 is an alkyl group or an alkoxyalkyl group; In formula (G1-2), X ^G1 is CH, a nitrogen atom, at least one X ^G1 is a nitrogen atom, and X ^G2 is a hydrogen atom, a hydrocarbon group, or an alkoxyalkyl group].

Description

Radiation-sensitive resin composition, insulating film, manufacturing method thereof, and organic EL element

The present invention relates to a radiation-sensitive resin composition, an insulating film, a method for manufacturing the same, and an organic EL device. In more detail, it is related with the radiation-sensitive resin composition used suitably when forming the insulating film for organic electroluminescent elements.

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, organic electroluminescence (EL) elements using electroluminescence with organic compounds are expected not only as light-emitting elements provided in displays, but also light-emitting elements provided in next-generation lighting devices.

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

Japanese Laid-Open Patent Publication No. 2011-107476 Japanese Laid-Open Patent Publication No. 2010-237310

In the conventional radiation-sensitive resin composition used for forming an insulating film for organic EL, when a polyimide-based polymer is used as a polymer, from the viewpoint of solubility of the polyimide-based polymer, N-methyl-2-pyrrolidone as a solvent (NMP) is often used. However, the radiation-sensitive resin composition using another solvent is preferable at the point that NMP is concerned about the influence on a living body.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. However, when solvents other than NMP, such as γ-butyrolactone and propylene glycol monomethyl ether acetate, are used, striped coating unevenness occurs on the coating film, or foreign substances formed by precipitation of a polyimide-based polymer on the coating film It became clear that problems, such as this generation|occurrence|production, a sensitivity, a resolution, etc. falling, arise. As a result of further examining this point, 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 [12].

[1] (A) at least one polymer selected from a polyimide having a structural unit represented by formula (A1) to be described later and a precursor of the polyimide, (B) a radiation-sensitive acid generator, (G1 ) The radiation-sensitive resin composition containing the at least 1 sort(s) of solvent chosen from the compound represented by Formula (G1-1) mentioned later, and the compound represented by Formula (G1-2) mentioned later.

[2] The radiation-sensitive resin composition according to [1], wherein R ¹ in the formula (A1) is a divalent group represented by the formula (a1) described later.

[3] The solvent (G1) is N,N,2-trimethylpropionamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-hexylox Cy-N,N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide, 1,3-dimethyl-2-imidazolidinone, N- Ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-( t-Butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone and N The radiation-sensitive resin composition according to the above [1] or [2], comprising at least one solvent selected from -methoxybutyl-2-pyrrolidone.

[4] (G2) The radiation-sensitive resin composition according to any one of [1] to [3], further comprising a glycol solvent.

[5] The glycol-based solvent (G2) is diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl According to any one of [1] to [4] above, comprising at least one solvent selected from ether acetate, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether propionate, and triethylene glycol dialkyl ether. A radiation-sensitive resin composition.

[6] The radiation-sensitive resin composition according to any one of [1] to [5], further comprising (C) a novolak resin.

[7] The radiation-sensitive resin composition according to any one of [1] to [6], wherein the novolak resin (C) is a resin comprising a structural unit having a condensed polycyclic aromatic group having a phenolic hydroxyl group.

[8] The above [1] wherein the novolak resin (C) is a resin having at least one selected from a structural unit represented by the formula (C2-1) to be described later and a structural unit represented by the formula (C2-2) to be described later. The radiation-sensitive resin composition according to any one of to [7].

[9] The radiation-sensitive resin composition according to any one of the above [1] to [8], further comprising (D) a crosslinking agent.

[10] An insulating film for an organic EL device formed from the radiation-sensitive resin composition according to any one of [1] to [9].

[11] A step of forming a coating film on a substrate using the radiation-sensitive resin composition according to any one of [1] to [9] above, a step of irradiating at least a part of the coating film with radiation, and the irradiation of the radiation A method for manufacturing an insulating film for an organic EL device, comprising a step of developing the developed coating film and a step of heating the developed coating film.

[12] An organic EL device comprising the insulating film according to [10] above.

ADVANTAGE OF THE INVENTION According to this invention, it is a resin composition excellent in sensitivity and resolution, and it can provide the radiation-sensitive resin composition which can form the insulating film with small application|coating nonuniformity and the foreign material content reduced without using NMP.

(Form for implementing the invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.

[Radiation-sensitive resin composition]

The radiation-sensitive resin composition of the present invention contains (A) a polyimide-based polymer, (B) a radiation-sensitive acid generator, and a specific solvent (G1) described later. By using the solvent (G1), a resin composition excellent in radiation sensitivity can be obtained, and an insulating film having a small coating unevenness and a reduced foreign matter content can be formed.

Hereinafter, each component is described in detail.

[Polymer (A)]

A polymer (A) is at least 1 sort(s) chosen from the polyimide (A1) which has a structural unit represented by Formula (A1), and the precursor (A2) of the said polyimide. Hereinafter, the said polyimide is also called "polyimide (A1)", and the said precursor is also called "polyimide precursor (A2)." The insulating film formed from polyimide (A1) and/or its precursor (A2) is excellent in heat resistance.

The weight average molecular weight (Mw) in terms of polystyrene of the polymer (A) is a value measured by a gel permeation chromatography (GPC) method. WHEREIN: 2,000-500,000 are preferable, 3,000-100,000 are more preferable, 4,000-50,000 This is more preferable. 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. If Mw is below the upper limit of the said range, there exists a tendency excellent in the solubility of the polymer (A) with respect to a solvent or a developing solution.

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

《Polyimide (A1)》

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, two "-" extended from an aromatic ring 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.

Carbon number of a tetravalent aliphatic hydrocarbon group is 4-30 normally, Preferably it is 8-24. 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-heptane, n-octane, n-decane and n-dodecane. can

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 with 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, four "-" extended from a chain hydrocarbon group and an alicyclic group represent 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, four "-" extended from an aromatic ring 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, 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 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 exposure 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 compound which can produce|generate the polyimide (A1) which 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 which has 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 by another group, Polyamic acid ester is preferable.

Polyamic acid ester is a polymer in which at least a 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 polyimide (A1) and polyimide precursor (A2)>>

The polyamic acid which is a polyimide precursor (A2) can be obtained by polymerizing the diamine containing 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 the total diamine relative 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 diamine at 50 degreeC - 200 degreeC, 1 hour - 24 hours.

Hereinafter, the tetracarboxylic dianhydride and the diamine having a hydroxyl group are also referred to as "acid dianhydride (A1-1)" and "diamine (A1-2)", respectively, and the other diamines are referred to as "other diamines (A1-2)" Also called ')'.

The synthesis of polyamic acid may be performed by dissolving diamine (A1-2) in a polymerization solvent, then reacting diamine (A1-2) with acid dianhydride (A1-1), or acid dianhydride (A1-1) After dissolving in the polymerization solvent, you may carry out by making acid dianhydride (A1-1) and diamine (A1-2) react.

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; In addition, after synthesizing the polyamic acid derivative by the above method, it can also be synthesized by imidizing the polyamic acid derivative.

As the imidation reaction of polyamic acid and polyamic acid derivative, well-known methods, such as heating imidation reaction and chemical imidation reaction, can be applied. In the case of heating imidization reaction, it is preferable to heat the solution containing polyamic acid and/or polyamic acid derivative at 120 degreeC - 210 degreeC, 1 hour - 16 hours. The imidation reaction may be performed, if necessary, using an azeotropic solvent such as toluene, xylene, or mesitylene, while removing water in the system.

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

Acid dianhydride (A1-1) is an acid dianhydride represented by Formula (a2).

In formula (a2), X is a tetravalent organic group. As a tetravalent organic group represented by X, the thing similar to the group illustrated as X in Formula (A1) is mentioned.

Diamine (A1-2) is a diamine represented by Formula (a3).

In formula (a3), R< ¹ > is a divalent group which has a hydroxyl group. As a divalent group which has a hydroxyl group represented by R< ¹ >, the thing similar to the group illustrated as R< ¹ > in Formula (A1) is mentioned.

You may use other diamines (A1-2') other than the said diamine (A1-2) with diamine (A1-2). As another diamine (A1-2'), the at least 1 sort(s) of diamine chosen from aromatic diamine and aliphatic diamine which does not have a hydroxyl group is mentioned, for example.

The polyimide (A1) may further have a structural unit in which R ¹ in formulas (A1), (A2-1), and (A2-2) is replaced with a residue of the other diamine (A1-2'). Similarly, the polyimide precursor (A2) may further have the structural unit which replaced R< ¹ > in Formula (A2-1) and (A2-2) with the residue of the said other diamine (A1-2').

As the polymerization solvent used for synthesis of the polyimide (A1) and the polyimide precursor (A2), a solvent capable of dissolving the raw material for their synthesis and the polyimide (A1) and the polyimide precursor (A2) is preferable. . As a polymerization solvent, the solvent similar to the solvent illustrated as a solvent (G) mentioned later can be used.

By using the same solvent as the solvent (G) as the polymerization solvent, a step of isolating these polymers after synthesizing the polyimide (A1) or the polyimide precursor (A2), and re-dissolving in another solvent after isolation is not required. it may not be Thereby, the productivity of the resin composition of this invention can be improved.

Polyimide (A1) and polyimide precursor (A2) have the outstanding solubility to the solvent (G) mentioned later by the said specific structure which has a hydroxyl group. For this reason, these polymers are also soluble in solvents other than N-methyl-2-pyrrolidone (NMP), for example, the solvent (G1) mentioned later. As a result, even if it uses solvents other than NMP as a polymerization solvent for obtaining a polymer (A), it becomes possible to prepare a radiation-sensitive resin composition easily. In particular, by using the solvent (G1), a resin composition excellent in radiation sensitivity can be prepared, and an insulating film having a small coating unevenness and a reduced foreign matter content can be formed.

[Radiation-sensitive acid generator (B)]

The radiation-sensitive acid generator (B) is a compound that generates an acid by treatment including irradiation with 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 radiation-sensitive acid generator (B), the radiation-sensitive resin composition can exhibit positive radiation-sensitive characteristics and can have favorable radiation sensitivity.

Content of the radiation-sensitive acid generator (B) in the radiation-sensitive resin composition of this invention is 5-100 mass parts normally with respect to 100 mass parts of polymer (A), Preferably it is 10-70 mass parts. , More preferably, it is 15-60 mass parts. By making the content of the radiation-sensitive acid generator (B) into the above range, the difference in solubility between the radiation-irradiated portion and the non-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.

Examples of the radiation-sensitive acid generator (B) include a quinonediazide compound, an oximesulfonate compound, an onium salt, an N-sulfonyloxyimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, and a sulfonic acid. An ester compound and a carbonic acid ester compound are mentioned.

As a radiation-sensitive acid generator (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, Quinonediazide Compounds are particularly preferred.

A radiation-sensitive acid generator (B) may be used independently or may use 2 or more types together.

<< quinonediazide compound >>

A quinonediazide compound generate|occur|produces a carbonic 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 (hereinafter also referred to as a "parent nucleus") and a 1,2-naphthoquinonediazidesulfonic acid halide.

Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, poly(hydroxyphenyl)alkane, and other mother nucleus.

Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.

Examples of tetrahydroxybenzophenone include 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4' -tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone there is.

As pentahydroxybenzophenone, 2,3,4,2',6'-pentahydroxybenzophenone is mentioned, for example.

As hexahydroxybenzophenone, for example, 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxy Benzophenone is mentioned.

Examples of the poly(hydroxyphenyl)alkane include bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1, 1-tris(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1, 3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-{4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl }ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobindene- 5,6,7,5',6',7'-hexanol and 2,2,4-trimethyl-7,2',4'-trihydroxyflavan are mentioned.

As other parental nuclei, for example, 2-methyl-2-(2,4-dihydroxyphenyl)-4-(4-hydroxyphenyl)-7-hydroxychroman, 1-[1-{3 -(1-[4-hydroxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]-3-[1-{3-(1-[4-hydroxyl phenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]benzene, 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1, 3-dihydroxybenzene is mentioned.

Among these parent nuclei, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl)ethane, 4,4'-[1-{4-(1-[ 4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene]bisphenol is preferred.

As 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable. Examples of the 1,2-naphthoquinonediazidesulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride, , 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferred.

In the condensation reaction of a phenolic compound or alcoholic compound (parent nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 mol% with respect to the number of OH groups in the phenolic compound or alcoholic compound. , More preferably, 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out according to a known method.

Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the parent nucleus is replaced with an amide bond, for example, 2,3,4-triaminobenzophenone-1,2- Naphthoquinonediazide-4-sulfonic acid amide and the like are also suitably used.

《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. 4924256, 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.

[Other ingredients]

The radiation-sensitive resin composition, in addition to the above components, is a novolak resin (C), a cross-linking agent (D), an adhesion aid (E) and a surfactant (F), if necessary, within a range that does not impair the effects of the present invention It may contain at least 1 sort(s) of other component selected from. Other components may be used individually by 1 type, and may use 2 or more types together.

《Novolac resin (C)》

Examples of the novolak resin (C) include a novolak resin comprising a structural unit having at least one selected from a benzene ring having a phenolic hydroxyl group and a condensed polycyclic aromatic group having a phenolic hydroxyl group. there is. Among these, from a viewpoint of developability and heat resistance, the novolak resin containing the structural unit which has a condensed polycyclic aromatic group which has a phenolic hydroxyl group is preferable.

The condensed polycyclic aromatic group having a phenolic hydroxyl group is, for example, a group in which some or all of the hydrogen atoms bonded to aromatic ring carbon contained in the condensed polycyclic aromatic hydrocarbon group are substituted with hydroxyl groups. Examples of the condensed polycyclic aromatic hydrocarbon group include a naphthalene ring, an anthracene ring, and a phenanthrene ring.

As the novolak resin (C), for example, a structural unit represented by the formula (C1), a structural unit represented by the formula (C2-1), a structural unit represented by the formula (C2-2), and a structural unit represented by the formula (C3) Resin which has at least 1 sort(s) chosen from structural unit is mentioned.

In formulas (C1) to (C3), R ¹ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms; R ² is a methylene group, an alkylene group having 2 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, an aralkylene group having 7 to 30 carbon atoms, or a group represented by -R ³ -Ar-R ³ - (Ar is a divalent aromatic group, and R ³ is each independently a methylene group or an alkylene group having 2 to 20 carbon atoms); n1 is an integer from 1 to 4, n2 is an integer from 0 to 3, n1+n2≤4, a to c, e, g and h are each independently an integer from 0 to 3, d and f are each It is an integer of 0 to 2 independently, provided that a and b are not both 0, c to e are not both 0, and f to h are not all 0. a+b, c+d+e, and f+g+h are each preferably an integer of 1-3.

In formulas (C1) to (C3), the bonding positions of -OH, -R ¹ and -R ² - are not particularly limited. Further, R ² constituting the repeating structure may be bonded to different benzene nuclei (for example, (1) below) or may be bonded to the same benzene nucleus (eg (2) below). In the formula, * is a bond. Although the following formulas (1) and (2) are specific examples about Formula (C2-1), it is the same also in Formula (C2-2) and Formula (C3).

Examples of the alkylene group having 2 to 30 carbon atoms for R ² include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group. , tetradecylene group, hexadecylene group, octadecylene group, nonadecylene group, eicosylene group, heneicoxylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexaco and a silene group, a heptacosylene group, an octacosylene group, a nonacosylene group, and a triacontylene group.

Examples of the divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms for R ² include a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group.

Examples of the aralkylene group having 7 to 30 carbon atoms for R ² include a benzylene group, a phenethylene group, a benzylpropylene group, and a naphthylenemethylene group.

Examples of the group represented by -R ³ -Ar-R ³ - for R ² include a group represented by —CH ₂ -Ph-CH ₂ — (Ph is a phenylene group).

The novolak resin (C) of the said example is preferable at the point which has favorable alkali solubility. By containing the alkali-soluble novolak resin (C) in the radiation-sensitive resin composition, a radiation-sensitive resin composition with good resolution can be obtained.

The novolak resin (C) can be obtained by condensing, for example, phenols or condensed polycyclic aromatic compounds having a phenolic hydroxyl group and aldehydes in the presence of an acid catalyst, and optionally distilling off unreacted components. can For example, the method described in Japanese Patent Application Laid-Open No. 47-15111, Japanese Unexamined Patent Publication No. 63-238129, etc. can be referred to.

Examples of phenols include 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-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, and isothymol are mentioned.

Examples of the condensed polycyclic aromatic compounds having a phenolic hydroxyl group include compounds having 1 to 6 hydroxyl groups, preferably 1 to 3, and 2 to 3 rings, specifically 1-naphthol. , monohydroxynaphthalene such as 2-naphthol; 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-di dihydroxynaphthalenes such as hydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene; monohydroxyanthracene such as 1-hydroxyanthracene, 2-hydroxyanthracene and 9-hydroxyanthracene; dihydroxyanthracene such as 1,4-dihydroxyanthracene and 9,10-dihydroxyanthracene; trihydroxyanthracene such as 1,2,10-trihydroxyanthracene, 1,8,9-trihydroxyanthracene, and 1,2,7-trihydroxyanthracene; Hydroxyphenanthrene, such as 1-hydroxyphenanthrene, is mentioned.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and terephthalaldehyde.

In the synthesis of the novolac resin (C), the amount of phenols or condensed polycyclic aromatic compounds having a phenolic hydroxyl group to be used is usually 0.5 mol or more, preferably 0.8 to 3.0 mol, with respect to 1 mol of the aldehydes. Examples of the acid catalyst include hydrochloric acid, para-toluenesulfonic acid, and trifluoromethanesulfonic acid.

The weight average molecular weight (Mw) of the novolak resin (C) in terms of polystyrene by gel permeation chromatography (GPC) is usually 500 to 50000, preferably 700 to 5000, and more preferably 800 to 3000. The novolac resin (C) whose Mw is in the said range is preferable at the point of resolution.

In the radiation-sensitive resin composition of the present invention, the content of the novolac resin (C) is usually 100 parts by mass or less, preferably 5 to 95 parts by mass, more preferably based on 100 parts by mass of the polymer (A). is 10-90 parts by mass, more preferably 20-90 parts by mass. When the content of the novolac resin (C) is at least the lower limit of the above range, the developability based on the novolac resin (C) is likely to be exhibited. When the content of the novolac resin (C) is equal to or less than the upper limit of the above range, there is little possibility that the absorbency of the insulating film increases or the heat resistance decreases.

《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 an organic EL element, since the organic light emitting layer deteriorates when it comes into contact with moisture, it is preferable to use a crosslinking agent (D) to reduce the absorbency of the insulating film.

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; and groups having a polymerizable carbon-carbon double bond, such as a vinyl group, a vinylidene group, and a (meth)acryloyl group.

The radiation-sensitive resin composition of this invention WHEREIN: Content of a crosslinking agent (D) is 1-210 mass parts normally with respect to 100 mass parts of polymer (A), Preferably it is 10-150 mass parts, More preferably It is 15-100 mass parts. When content of a crosslinking agent (D) is more than the lower limit of the said range, there exists a tendency for the low water absorption of an insulating film to improve. There exists a tendency for the heat resistance of an insulating film to improve that content of a crosslinking agent (D) is below the upper limit of the said range.

<Blocked isocyanate compound (D1)>

As a crosslinking agent (D), it is preferable to use the compound (D1) which has the group in which the isocyanate group was blocked by the protecting group. The said compound (D1) is also called "block isocyanate compound (D1)." The group in which the isocyanate group was blocked by the protecting group is also called a "blocked isocyanate group."

In the component (D1), blocked isocyanate groups are deblocked (protective groups are dropped) by high-temperature treatment during thermosetting, thereby regenerating active isocyanate groups. An example of the regeneration reaction is shown below. For this reason, prebaking is performed at a temperature at which deblocking of component (D1) does not occur, and post-baking is performed at a temperature at which deblocking occurs. The reaction proceeds between the phenolic hydroxyl groups contained in the rock resin (C) or the like, and an insulating film excellent in low water absorption and heat resistance can be obtained.

Block in the above formula represents a protecting group.

Component (D1) WHEREIN: The number of blocked isocyanate groups is 1 or more normally, Preferably it is 1-2, More preferably, it is 1. When the number of blocked isocyanate groups uses the component (D1) in the said range, it is preferable at the point of storage stability.

It is preferable that component (D1) is at least 1 sort(s) chosen from the compound which has group represented by Formula (D-1), and the compound which has group represented by Formula (D-2), Group represented by Formula (D-1) is 1 It is more preferable that it is at least 1 sort(s) chosen from the compound which has one, and the compound which has one group represented by Formula (D-2).

In the formula (D-1), R ^D1 is an alkoxy group having 1 to 20 carbon atoms or a derivative thereof, a cycloalkoxy group having 3 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or a thioalkoxy group having 1 to 15 carbon atoms. , a thiocycloalkoxy group having 3 to 15 carbon atoms or a heterocyclic group having 3 to 20 carbon atoms. R ^D1 is preferably a 5-membered ring or more heterocyclic group, more preferably a 5- to 18-membered ring heterocyclic group. As for carbon number in R ^D1 , it is more preferable that it is 3-15.

Examples of the alkoxy group include a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, 2-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, 2-methylbutoxy group, 3-methylbutoxy group, 2,2-dimethylpropoxy group, n-hexyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 5- A methylpentyloxy group is mentioned. As a cycloalkoxy group, a cyclopentyloxy group and a cyclohexyloxy group are mentioned, for example. Examples of the derivative group of the alkoxy group include a group in which one or more of the hydrogen atoms of the methoxy group are substituted with at least one selected from a cycloalkyl group and an aryl group, and specifically, a dicyclopentylmethoxy group , a dicyclohexyl methoxy group, a tricyclopentyl methoxy group, a tricyclohexyl methoxy group, a phenyl methoxy group, a diphenyl methoxy group, and a triphenyl methoxy group. As an aryloxy group, a phenoxy group and a naphthyloxy group are mentioned, for example. Examples of the thioalkoxy group include a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thiobutoxy group, and a thiopentyloxy group. Examples of the thiocycloalkoxy group include thiocyclophene. A tyloxy group and a thiocyclohexyloxy group are mentioned. As the heterocyclic group, for example, 1-pyrazolyl group, 3-methyl-1-pyrazolyl group, 3,5-dimethyl-1-pyrazolyl group, N-ε-caprolactam group, pyridinyl group, tria and zylyl group, pyrrolyl group, imidazolyl group, indolyl group, thiadiazolyl group, oxadiazolyl group and pyrimidinyl group.

In the formula (D-2), R ^D2 and R ^D3 are each independently an alkyl group or an aryl group, and R ^D2 and R ^D3 may be bonded to each other to form a ring together with the carbon atom to which they are each bonded. In formula (D-2), -ON=C(R ^D2 )(R ^D3 ) is acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, etc. It is preferably a group derived from oximes of

As an alkyl group, C1-C18 alkyl groups, such as a methyl group, an ethyl group, a propyl group, and a butyl group, are mentioned, for example. As an aryl group, C6-C18 aryl groups, such as a phenyl group, are mentioned, for example. Examples of the ring formed by bonding R ^D2 and R ^D3 to each other include an aliphatic ring having 6 to 18 carbon atoms, such as a cyclohexane ring.

As a component (D1), the compound which has one polymerizable carbon-carbon double bond from a heat resistant viewpoint is preferable. Examples of the group having a polymerizable carbon-carbon double bond include a vinyl group, a vinylidene group, and a (meth)acryloyl group. In particular, at least one selected from the compound represented by the formula (D-11) and the compound represented by the formula (D-21) is preferable.

In formulas (D-11) and (D-21), R ^D1 , R ^D2 and R ^D3 have the same meaning as the same symbol in formulas (D-1) and (D-2), respectively; R ^D4 is a hydrogen atom or a methyl group; A is a methylene group or an alkylene group having 2 to 12 carbon atoms.

Specific examples of component (D1) include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl(meth)acrylate, (meth)acrylic acid 2-(0-[1'-methylpropylideneamino]carboxy amino) ethyl.

A component (D1) may be used individually by 1 type, and may use 2 or more types.

The radiation-sensitive resin composition of the present invention WHEREIN: When using component (D1) as a crosslinking agent (D), content of component (D1) is 10-90 mass parts normally with respect to 100 mass parts of polymer (A), Preferably it is 15-80 mass parts, More preferably, it is 20-70 mass parts. When content of component (D1) is more than the lower limit of the said range, it is preferable at the point of low water absorption and sclerosis|hardenability. It is preferable from a point of resolution that content of a component (D1) is below the upper limit of the said range.

<Other crosslinking agents (D2)>

Examples of the crosslinking agent (D) include an oxetanyl group-containing compound, a bisphenol A-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolac resin-based epoxy compound, a resol resin-based epoxy compound, and a poly(hydroxystyrene). )-based epoxy compound, methoxymethyl group-containing phenolic compound, methylol group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenolic compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine A compound, an alkoxyalkyl group-containing urea compound, an alkoxyalkyl group-containing phenol compound, a carboxymethyl group-containing melamine resin, a carboxymethyl group-containing benzoguanamine resin, a carboxymethyl group-containing urea resin, a carboxymethyl group-containing phenol resin, a carboxymethyl group-containing melamine compound, a carboxymethyl group-containing benzo Other crosslinking agents (D2), such as a guanamine compound, a carboxymethyl group containing urea compound, and a carboxymethyl group containing phenol compound, can also be mentioned.

《Adhesive Aid (E)》

The adhesion aid (E) is a component which improves the adhesiveness between the film-forming object, such as a board|substrate, and an insulating film. The adhesion aid (E) is particularly useful in order to improve the adhesion between the inorganic substrate and the insulating film. Examples of the inorganic material include silicon compounds such as silicon, silicon oxide, and silicon nitride; Metals, such as gold|metal|money, copper, and aluminum, are mentioned.

As the adhesion aid (E), 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 carboxy 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. there is.

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.

To [ content of the adhesion aid (E) in the radiation-sensitive resin composition of this invention / 100 mass parts of polymers (A)), Preferably it is 20 mass parts or less. By setting the content of the adhesion aid (E) in the above range, the adhesion between the formed insulating film and the substrate is further improved.

《Surfactant (F)》

Surfactant (F) 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 (F), 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 (F), a fluorochemical surfactant and silicone type surfactant are mentioned, for example.

As surfactant (F), the specific example of Unexamined-Japanese-Patent No. 2003-015278 and Unexamined-Japanese-Patent No. 2013-231869 is mentioned, for example.

To [ content of surfactant (F) in the radiation-sensitive resin composition of this invention / 100 mass parts of polymer (A)), Preferably it is 10 mass parts or less, More preferably, it is 0.01-7.5 mass parts, More preferably Preferably it is 0.05-5 mass parts. By making content of surfactant (F) into the said range, the film-thickness uniformity of the coating film formed can be improved more.

[Solvent (G)]

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

The radiation-sensitive resin composition of this invention WHEREIN: As for content of the solvent (G), solid content concentration in the said composition is 5-60 mass % normally, Preferably it is 10-55 mass %, More preferably, it is 15-50 mass %. is the amount to be Here, solid content means all components other than a solvent (G). By making the content of the solvent (G) within the above range, the coating unevenness of the insulating film formed from the radiation-sensitive resin composition is reduced without impairing developability, and the foreign matter content tends to be reduced.

《Solvent (G1)》

In the present invention, at least one solvent (G1) selected from the compound represented by the formula (G1-1) and the compound represented by the formula (G1-2) is used as the solvent (G) at least.

By using the solvent (G1), the coating unevenness of the insulating film to be formed becomes small, and the content of foreign substances can be reduced. Moreover, by using a solvent (G1), radiation sensitivity, such as a sensitivity and resolution, of the resin composition obtained improves. The reason that the radiation sensitivity is improved is that during heating at the time of pre-baking, a part of the solvent (G1) remains in the coating film, and exposure and development are performed on the coating film in a state in which the solvent (G1) remains, thereby exposure to a developer. It is presumed that this is because the dissolution of wealth is accelerated.

In formula (G1-1), R ^G1 is each independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a group formed by inserting -O- between at least one carbon-carbon bond in the hydrocarbon group, and two R ^G1 may be bonded to each other to form a ring together with a nitrogen atom, R ^G2 is a methylene group or a carbonyl group, R ^G3 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ^G4 is an alkyl group having 1 to 12 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms.

It is preferable that carbon number of the hydrocarbon group in R ^G1 is 1-6. As said hydrocarbon group, a C1-C6 linear or branched hydrocarbon group, a C3-C6 alicyclic hydrocarbon group, and a C6 aromatic hydrocarbon group are mentioned, for example. Specifically, Alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; Alkenyl groups, such as a vinyl group, 1-propenyl group, 2-propenyl group, and 3-butenyl group; alkynyl groups such as an ethynyl group, a 2-propynyl group, and a 2-butynyl group; cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group; Aryl groups, such as a phenyl group, are mentioned.

In R ^G1 , examples of the group formed by inserting -O- between at least one carbon-carbon bond in the hydrocarbon group include an alkoxyalkyl group having 2 to 8 carbon atoms. Specifically, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a hexyloxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, and a methoxybutyl group are mentioned.

Two R ^G1 may be bonded to each other to form a ring together with the nitrogen atom. As said ring, a pyrrolidine ring and a piperidine ring are mentioned, for example. A linear or branched hydrocarbon group, such as an alkyl group, may couple|bond with these rings.

R ^G1 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom or a methyl group.

R ^G2 is preferably a carbonyl group.

Examples of the hydrocarbon group for R ^G3 include the same groups as the hydrocarbon group for R ^G1 . R ^G3 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably a hydrogen atom or a methyl group.

It is preferable that carbon number of the alkyl group in R ^G4 is 1-6, More preferably, it is 1-3, Especially preferably, it is 1. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are mentioned.

Examples of the alkoxyalkyl group for R ^G4 include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a hexyloxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, and a methoxybutyl group. , a methoxyhexyl group, an ethoxyhexyl group, a methoxyoctyl group, and an ethoxyoctyl group.

As the compound represented by formula (G1-1), R ^G1 is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^G2 is a carbonyl group, R ^G3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R A compound in which ^G4 is an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 10 carbon atoms is preferable. For example, N,N,2-trimethylpropionamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-hexyloxy-N,N- dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, and n-butoxy-N-isopropyl-propionamide.

In the formula (G1-2), each X ^G1 is independently CH or a nitrogen atom, provided that at least one X ^G1 is a nitrogen atom, and each X ^G2 is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or 2 carbon atoms. -18 is an alkoxyalkyl group. However, "when two X ^G1 are CH and N atoms, respectively, X ^G2 bonded to an N atom is a methyl group, and X ^G2 bonded to a carbon atom is a hydrogen atom" (N-methyl-2-pyrrolidone) is excluded. .

In addition, when X ^G1 is CH, it is assumed that X ^G2 is bonded to the carbon atom C.

Examples of the hydrocarbon group for X ^G2 include the same groups as the hydrocarbon group for R ^G1 in formula (G1-1). Carbon number of the alkoxyalkyl group in X ^G2 becomes like this. Preferably it is 2-10, More preferably, it is 2-6. Specifically, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a hexyloxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, and a methoxybutyl group are mentioned.

X ^G2 is each independently preferably a hydrogen atom, an alkyl group having 2 to 18 carbon atoms, or an alkoxyalkyl group having 2 to 18 carbon atoms. X ^G2 bonded to a nitrogen atom is preferably an alkyl group having 1 to 5 carbon atoms when both X ^G1 are nitrogen atoms, and when one of the two X ^G1 is a nitrogen atom and the other is CH A C2-C5 alkyl group or a C2-C10 alkoxyalkyl group is preferable.

Examples of the compound represented by the formula (G1-2) include 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, and N-(n-propyl)-2-pyrrolidone. Don, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(t-butyl)-2-pyrrolidone, N-(n-pentyl)-2 -pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, and N-methoxybutyl-2-pyrrolidone are mentioned.

A solvent (G1) may be used individually by 1 type, and may use 2 or more types together.

It is preferable that the quantity of the solvent (G1) in all the solvents (G) is 5 mass % or more, More preferably, it is 10-80 mass %, More preferably, it is 20-70 mass %, Especially preferably, 30-60 mass %. mass%. When the usage-amount of a solvent (G1) exists in the said range, it is preferable at the point of applicability|paintability.

《Glycol solvent (G2)》

As a solvent (G), it is preferable to use the glycol-type solvent (G2) together with a solvent (G1) from a viewpoint of suppressing the splash which generate|occur|produces at the time of coating film formation. The glycol-based solvent (G2) refers to an organic solvent having a structural unit represented by -O-A-O- and not having a nitrogen atom. Said A is a C2-C10 alkylene group.

As a glycol-type solvent (G2), the solvent represented by R-(OA) _n -OR is mentioned, for example. In the formula, A is an alkylene group having 2 to 10 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms, n is an integer of 1 to 4, preferably an integer of 1 to 3, R is each independently a hydrogen atom or a carbon number An alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, or an acyl group having 2 to 4 carbon atoms, preferably having 2 to 3 carbon atoms.

Examples of the glycol-based solvent (G2) include diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, Propylene glycol monoalkyl ether, propylene glycol monoalkyl ether propionate, and triethylene glycol dialkyl ether are preferable.

As diethylene glycol monoalkyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether are mentioned, for example.

As diethylene glycol dialkyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether are mentioned, for example.

As ethylene glycol monoalkyl ether, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether are mentioned, for example.

Examples of the ethylene glycol monoalkyl ether acetate include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate.

Examples of the diethylene glycol monoalkyl ether acetate include diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.

Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, and propylene glycol monobutyl ether propionate. can be heard

As triethylene glycol dialkyl ether, triethylene glycol dimethyl ether is mentioned, for example.

As the glycol-based solvent (G2), propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and propylene glycol monomethyl ether are particularly preferred. desirable.

A glycol-type solvent (G2) may be used individually by 1 type, and may use 2 or more types together.

When using a solvent (G1) and a glycol-type solvent (G2) together, these ratios are as follows. It is preferable that the quantity of the solvent (G1) is 10-80 mass % in a total of 100 mass % of (G1) and (G2), More preferably, it is 20-70 mass %, More preferably, it is 30-60 mass %. am. When the ratio is in the above range, when the resin composition is applied to the substrate, it is preferable at the point that splashing does not occur easily.

《Other solvents (G3)》

As a solvent (G), you may use together other solvents (G3) other than the solvent illustrated above. As a solvent (G3), For example, Alcohol solvents, such as methanol, ethanol, a propanol, and a butanol; Aromatic hydrocarbon solvents, such as toluene and xylene, are mentioned.

Other solvents (G3) may be used individually by 1 type, and may use 2 or more types together.

[Method for preparing radiation-sensitive resin composition]

A radiation-sensitive resin composition is prepared by mixing essential components, such as a polymer (A) and a radiation-sensitive acid generator (B), and other arbitrary components with the solvent (G) containing, for example, a solvent (G1). can do. Moreover, in order to remove a foreign material, after mixing each component uniformly, you may filter the obtained mixture with a filter etc.

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

The method of forming the insulating film includes a step 1 of forming a coating film on a substrate using the radiation-sensitive resin composition described above, a step 2 of irradiating at least a part of the coating film with radiation, and a step 3 of developing the coating film irradiated with the radiation. and step 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 a small coating unevenness and a reduced foreign matter content. 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》

In the process 1, a radiation-sensitive resin composition is apply|coated to the board|substrate surface, Preferably it prebaking is performed and a coating film is formed. 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 the organic electroluminescent element in the middle of manufacture, for example, a TFT board|substrate and a wiring board in which TFT and its wiring were formed are mentioned.

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.

As conditions for prebaking, although it changes also with the composition of a radiation-sensitive resin composition, etc., for example, a heating temperature will be 60-130 degreeC, and a heating time will be about 30 second - 15 minutes. When using a blocked isocyanate compound (D1), it is preferable to perform prebaking at the temperature to which thermal dissociation of a protecting group does not advance.

《Process 2》

In step 2, the coating film formed in step 1 is irradiated with radiation through a mask having a predetermined pattern. As a radiation used at this time, a visible light ray, an ultraviolet-ray, a deep ultraviolet-ray, X-ray, and a charged particle beam is mentioned, for example. 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, for example, a laser beam by a KrF excimer laser is exemplified. 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. As an exposure amount, 6000 mJ/cm<2> or less is preferable, and 20-2000 mJ/cm<2> is preferable. This exposure amount is the value measured by the intensity|strength in wavelength 365nm of radiation by the illuminometer ("OAI model 356" by OAI Optical Associates).

《Process 3》

In step 3, the coating film irradiated with radiation in step 2 is developed. Thereby, the radiation-irradiated portion can be 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, piperidine, 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 that of the solvent (G) 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 by air-drying with compressed air or compressed nitrogen.

《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 Minute - 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.

In this way, the insulating film of the target pattern can be formed on the board|substrate.

In step 4, before heating 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 (G). In the decomposition treatment, the radiation-sensitive acid generator (B) such as a quinonediazide compound remaining in the coating film can be decomposed by irradiating the entire surface with radiation from a high-pressure mercury lamp (post-exposure). The exposure amount in the subsequent exposure is preferably about 1000 to 5000 mJ/cm 2 .

The insulating film thus obtained exhibits favorable characteristics in terms of heat resistance, patternability, radiation sensitivity, resolution, and the like, while exhibiting a small coating unevenness and a reduced foreign matter content. In addition, since the constituent material has a low water absorption structure, it has low water absorption, and also in the manufacturing process, treatment using a low water absorption compound is possible. 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 said insulating film is 0.3-25 micrometers normally, Preferably it is 0.5-20 micrometers.

The insulating film of the present invention can be suitably used as an insulating film of an organic EL element, specifically, a planarization film, an insulating film such as a barrier rib partitioning a pixel (light emitting element). The insulating film is, for example, a barrier rib that divides the surface of the TFT (thin film transistor) substrate into a plurality of regions.

(Example)

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

[GPC analysis]

The weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymer (A) and the novolak resin (C) were gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8020) method. and measured in terms of polystyrene under the conditions of a tetrahydrofuran (THF) solvent.

・Measuring method: gel permeation chromatography (GPC) method

・Standard material: polystyrene equivalent

· Apparatus: manufactured by Toso Co., Ltd., product name: HLC-8020

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

· Solvent: tetrahydrofuran

・Sample concentration: 0.7% by mass

・Injection amount: 70μL

Flow rate: 1 mL/min

<Imidation rate of polymer (A)>

First, the infrared absorption spectrum of the polyimide (device name: NICOLET 6700 FT-IR manufactured by Thermo Electron Corporation) was measured, and the absorption peak of the imide structure resulting from the polyimide (1780 cm ^-1 vicinity, 1377 cm ^-1 ) vicinity) was confirmed. Next, about this polyimide, after heat-processing at 350 degreeC for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity of 1377 cm ^-1 vicinity after heat processing before and after heat processing was compared. Assuming that the imidization 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.

<Synthesis of Polymer (A)>

[Synthesis Example A1] Synthesis of Polymer (A-1)

After adding 340 g of 3-methoxy-N,N-dimethylpropanamide as a polymerization solvent to a three-neck flask, 50 g of propylene glycol monomethyl ether acetate was added, and 2,2'-bis(3-amino-4- as a diamine compound) 120 g of 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 prepared. Then, after making it react at 60 degreeC for 1 hour, 19g of maleic anhydride was added as a terminal blocker, and after making it react at 60 degreeC for 1 hour, it heated up and made it react at 180 degreeC for 4 hours. Thereby, about 600 g of solutions containing a polymer (A-1) with a solid content concentration of 35 mass % were obtained. Mw of the obtained polymer (A-1) was 8000. The imidation rate of the obtained polymer (A-1) was 10 %.

[Synthesis Example A2]

The same procedure as in Synthesis Example A1 was carried out except that 3-methoxy-N,N-dimethylpropanamide was changed to N,N,2-trimethylpropionamide, and the polymer (A-2) was included in the solid content concentration of 35 mass. % polyimide solution was obtained. Mw of the obtained polymer (A-2) was 9200, and the imidation rate was 15 %.

[Synthesis Example A3]

In the same manner as in Synthesis Example A1 except that 3-methoxy-N,N-dimethylpropanamide was changed to 1,3-dimethyl-2-imidazolidinone, the solid content containing the polymer (A-3) The polyimide solution with a density|concentration of 35 mass % was obtained. Mw of the obtained polymer (A-3) was 7500, and the imidation rate was 20 %.

[Synthesis Example A4]

Polyimide having a solid content concentration of 35% by mass containing the polymer (A-4) in the same manner as in Synthesis Example A1 except that 3-methoxy-N,N-dimethylpropanamide was changed to γ-butyrolactone. A solution was obtained. Mw of the obtained polymer (A-4) was 9000, and the imidation rate was 20 %.

[Synthesis Example A5]

The same procedure as in Synthesis Example A1 was carried out except that 3-methoxy-N,N-dimethylpropanamide was changed to N-methyl-2-pyrrolidone, and the polymer (A-5) was included, with a solid content concentration of 35 mass. % polyimide solution was obtained. Mw of the obtained polymer (A-5) was 8500, and the imidation rate was 20 %.

<Synthesis of novolac resin (C)>

[Synthesis Example C1] Synthesis of novolak resin (C-1)

To a flask equipped with a thermometer, a cooling tube, a separator tube, and a stirrer, 144.2 g (1.0 mol) of 1-naphthol, 400 g of methyl isobutyl ketone, 96 g of water, and 32.6 g of 92% by mass paraformaldehyde (1.0 mol in terms of formaldehyde) put in 3.4 g of para-toluenesulfonic acid was added, stirring continuously. 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 aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water became neutral, the solvent was removed from the organic layer under heating and reduced pressure to obtain 140 g of a novolak resin (C-1) composed of a structural unit represented by the following formula. The weight average molecular weight (Mw) of the obtained novolak resin (C-1) was 2000.

From the measurement chart by a Fourier transform infrared spectrophotometer (FT-IR), compared with the raw material, absorption (2800-3000 cm ^-1 ) derived from stretching due to a methylene bond can be confirmed, and also derived from aromatic ether No absorption (1000-1200 cm ^-1 ) was found. From these results, it was identified that in this synthesis example, dehydration etherification reaction (disappearance of hydroxyl groups) between hydroxyl groups did not occur and a novolak resin having a methylene bond was obtained.

<Preparation of radiation-sensitive resin composition>

Each component used for preparation of the radiation-sensitive resin composition is as follows.

・Polymer (A)

A-1: Polymer of Synthesis Example A1

A-2: Polymer of Synthesis Example A2

A-3: Polymer of Synthesis Example A3

A-4: Polymer of Synthesis Example A4

A-5: Polymer of Synthesis Example A5

・Radiation-sensitive acid generator (B)

B-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonedia Condensate of zid-5-sulfonic acid chloride (2.0 mol) (manufactured by Toyogo Seiko Co., Ltd.)

・Novolac resin (C)

C-1: Novolak resin of Synthesis Example C1

Crosslinking agent (D) (block isocyanate compound)

D-1: "Karenz MOI-BP" manufactured by Showa Denko Co., Ltd.

2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate

・Adhesive agent (E)

E-1: "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.

3-Glycidoxypropyltrimethoxysilane

・Surfactant (F)

F-1: Silicone surfactant "SH8400" manufactured by Toledow Corning Silicone

[Example 1]

To 200 parts of a polymer solution containing the polymer (A-1) of Synthesis Example A1 (solid content concentration of 35% by mass; an amount equivalent to 70 parts (solid content) of the polymer (A-1)), a radiation-sensitive acid generator (B) ) as (B-1) 20 parts, as novolak resin (C) (C-1) 30 parts, as a crosslinking agent (D) 20 parts of a block isocyanate compound (D-1), as an adhesion aid (E) (E- 1) 5 parts, 0.2 parts of (F-1) as a surfactant (F), and a mixed solvent consisting of 3-methoxy-N,N-dimethylpropanamide and propylene glycol monomethyl ether acetate as the solvent (G) (mass ratio) 10:25), and while making it so that solid content concentration might be 25 mass %, it filtered with the membrane filter with a diameter of 0.2 micrometer, and the radiation-sensitive resin composition was prepared.

[Examples 2-14, Comparative Examples 1-4]

Except having used each component of the kind and compounding quantity shown in Table 1, it carried out similarly to Example 1, and prepared the radiation-sensitive resin composition. In Table 1, as the amount of the solvent (G), the amount of the solvent derived from the polymer solution and the amount of the solvent added separately were respectively shown.

[evaluation]

An insulating film was produced by the method demonstrated below using the radiation-sensitive resin composition obtained by the Example and the comparative example. The coating properties, radiation sensitivity, resolution and LWR of the composition, and absorption properties were evaluated by the following methods, respectively.

(1) Non-uniformity of application

Using a slit coating device having a slit head having a slit gap of 50 μm and a coating effective width of 200 mm, the gap between the slit and the substrate is adjusted so that the film thickness after drying is 3.0 μm, and the coating speed is 50 mm/sec. The coating liquid of the radiation-sensitive resin composition obtained in each Example and the comparative example was apply|coated on the rectangular glass substrate of width 300mm, length 300mm, and thickness 0.7mm, and the coating surface of length 250mm was obtained. After application|coating, it prebaked with the hotplate for 90 degreeC for 120 second, and obtained the coating film. Then, the coated surface was visually observed, the number of stripe-shaped nonuniformity was counted, and the following reference|standard evaluated. The results are shown in Table 1.

-AA: There is no stripe-shaped nonuniformity at all on the coated surface.

-BB: 1-5 pieces of stripe-shaped nonuniformity are seen.

-CC: Six or more stripe-shaped nonuniformities are seen.

(2) Evaluation of the occurrence of foreign matter on the coating film

The said coating film obtained by evaluation of the said "(1) application|coating nonuniformity" was visually observed, and the following reference|standard evaluated the generation|occurrence|production of a foreign material.

·AA: No foreign matter was observed.

-BB: The generation of a foreign material was confirmed slightly (1-10 pieces).

·CC: Remarkably, foreign matter was observed (11 or more).

(3) radiation sensitivity

Using a spinner or a slit-die coater, the radiation-sensitive resin composition obtained in each Example and Comparative Example was applied on a silicon substrate, and then prebaked on a hot plate at 120° C. for 2 minutes, and a coating film having a thickness of 3.0 μm was applied. formed This coating film was exposed by changing the exposure amount through the pattern mask which has a predetermined|prescribed pattern using the exposure machine ("MPA-6000" by Canon Corporation). Thereafter, development was performed by a puddle method at 25° C. for 80 seconds in a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed in running water for 1 minute with ultrapure water, dried, and a plurality of through-holes having a diameter of 20.0 μm were formed on a silicon substrate. An insulating pattern with The exposure dose required for completely dissolving the 20.0 µm through-hole pattern was measured, and the exposure dose at this time was defined as the radiation sensitivity (exposure sensitivity). Radiation sensitivity was set to "good" when it was 100 mJ/cm<2> or less, and "bad" when it exceeded 100 mJ/cm<2>. An exposure amount is the value measured by the intensity|strength in wavelength 365nm of radiation by the illuminometer ("OAI model 356" by OAI Optical Associates).

(4) Resolution

Using a spinner or a slit-die coater, the radiation-sensitive resin composition obtained in each Example and Comparative Example was applied on a silicon substrate, and then prebaked on a hot plate at 120° C. for 2 minutes, and a coating film having a thickness of 3.0 μm was applied. formed This coating film was exposed using an exposure machine ("MPA-6000" by Canon Corporation) through a pattern mask having a hole pattern diameter of 3 µm to 50 µm and an exposure amount of 100 mJ/cm 2 at a wavelength of 365 nm. The exposure dose is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (“OAI model 356” by OAI Optical Associates). Thereafter, development was performed by the puddle method at 25° C. for 80 seconds in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, washed in running water for 1 minute with ultrapure water, and the vertical cross-sectional shape in the direction orthogonal to the lines of the plurality of through-holes was measured by SEM ( It observed with Hitachi High-Technologies' "SU3500"), and the base width was measured in the said cross section. It can be said that the resolution is so favorable that the base width is small. When a hole pattern was 10 micrometers or less and there was no development residue, it was set as "good", and when a hole pattern exceeded 10 micrometers, it was set as "bad".

(5) LWR

Using a spinner or a slit die coater, the radiation-sensitive resin composition obtained in each Example and Comparative Example was applied on a silicon substrate, and then prebaked on a hot plate at 120° C. for 2 minutes, and a coating film having a thickness of 3.0 μm was applied. formed This coating film was exposed using an exposure machine ("MPA-6000" by Canon Corporation) through a pattern mask having a square pattern with a line width of 5 µm at an exposure amount of 100 mJ/cm 2 at a wavelength of 365 nm. An exposure amount is the value measured by the intensity|strength in wavelength 365nm of radiation by the illuminometer ("OAI　model 356" by OAI　Optical　Associates). Then, it developed by the puddle method for 80 second at 25 degreeC in 2.38 mass % tetramethylammonium hydroxide aqueous solution, running water washing was performed for 1 minute with ultrapure water, and several square patterns were formed. Using a scanning electron microscope ("SU3500" by Hitachi High-Technologies Corporation), it observed from the pattern upper part, and measured the line|wire width in 10 arbitrary points|pieces. The 3-sigma value (deviation) of the measured value of line|wire width was made into LWR (micrometer). When the value of this LWR was 0.5 micrometer or less, it was set as "good", and when it exceeded 0.5 micrometer, it was set as "poor".

(6) absorbency

After applying the radiation-sensitive resin composition obtained in each Example and Comparative Example on a silicon substrate using a spinner or a slit-die coater, pre-baking on a hot plate at 120° C. for 2 minutes, and then in a clean oven at 250° C. 45 Minutes were post-baked to form the insulating film which has a film thickness of 3.0 micrometers. With respect to this insulating film, the sample surface when the temperature was raised from room temperature to 200°C (30°C/min) at a vacuum degree of 1.0×10 ^-9 Pa using thermal desorption spectroscopy (“TDS1200” manufactured by ESCO Corporation) and The detected value of the water peak (M/z=18) was measured for the gas which escaped from a sample with the mass spectrometer ("5973N" by Agilent Technologies). Water absorption was evaluated by taking the integral value [A·sec] of the total peak intensity at 60°C to 200°C. Water absorption was judged to be favorable when the said integral value was 3.0 x 10 ^-8 [A·sec] or less.

Claims (12)

(A) at least 1 sort(s) of polymer chosen from the polyimide which has a structural unit represented by Formula (A1), and the said polyimide precursor;
(B) a radiation-sensitive acid generator;
(G1) at least one solvent selected from the compound represented by the formula (G1-1) and the compound represented by the formula (G1-2);
(G2) glycol-based solvents
A radiation-sensitive resin composition containing:

[in formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group];

[In formula (G1-1), R ^G1 is each independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a group formed by inserting -O- between at least one carbon-carbon bond in the hydrocarbon group, 2 R ^G1 may be bonded to each other to form a ring together with a nitrogen atom, R ^G2 is a methylene group or a carbonyl group, R ^G3 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ^G4 is a ring having 1 to 12 carbon atoms an alkyl group or an alkoxyalkyl group having 2 to 10 carbon atoms;
In the formula (G1-2), each X ^G1 is independently CH or a nitrogen atom, provided that at least one X ^G1 is a nitrogen atom, and each X ^G2 is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or 2 carbon atoms. to 18 alkoxyalkyl group, with the proviso that "when two X ^G1 are CH and N atoms, respectively, X ^G2 bonded to an N atom is a methyl group, and X ^G2 bonded to a carbon atom is a hydrogen atom"]. According to claim 1,
Radiation-sensitive resin composition in which R ¹ in Formula (A1) is a divalent group represented by Formula (a1):

[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, provided that at least one of R ³ is a hydrogen atom; n1 and n2 are each independently an integer of 0 to 2, provided that at least one of n1 and n2 is 1 or 2; When the sum of n1 and n2 is 2 or more, a plurality of R ³ may be the same or different]. According to claim 1,
The solvent (G1) is N,N,2-trimethylpropionamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-hexyloxy-N ,N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2 -pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(t-butyl )-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone and N-methoxy A radiation-sensitive resin composition comprising at least one solvent selected from butyl-2-pyrrolidone. According to claim 1,
The glycol-based solvent (G2) is diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, A radiation-sensitive resin composition comprising at least one solvent selected from propylene glycol monoalkyl ether, propylene glycol monoalkyl ether propionate, and triethylene glycol dialkyl ether. According to claim 1,
(C) radiation-sensitive resin composition further containing novolac resin (A) at least 1 sort(s) of polymer chosen from the polyimide which has a structural unit represented by Formula (A1), and the said polyimide precursor;
(B) a radiation-sensitive acid generator;
(G1) at least one solvent selected from the compound represented by the formula (G1-1) and the compound represented by the formula (G1-2);
(C) novolac resin
A radiation-sensitive resin composition containing:

[in formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group];

[In formula (G1-1), R ^G1 is each independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a group formed by inserting -O- between at least one carbon-carbon bond in the hydrocarbon group, 2 R ^G1 may be bonded to each other to form a ring together with a nitrogen atom, R ^G2 is a methylene group or a carbonyl group, R ^G3 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ^G4 is a ring having 1 to 12 carbon atoms an alkyl group or an alkoxyalkyl group having 2 to 10 carbon atoms;
In the formula (G1-2), each X ^G1 is independently CH or a nitrogen atom, provided that at least one X ^G1 is a nitrogen atom, and each X ^G2 is independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or 2 carbon atoms. to 18 alkoxyalkyl group, with the proviso that "when two X ^G1 are CH and N atoms, respectively, X ^G2 bonded to an N atom is a methyl group, and X ^G2 bonded to a carbon atom is a hydrogen atom"]. 7. The method of claim 6,
The radiation-sensitive resin composition wherein the novolac resin (C) is a resin comprising a structural unit having a condensed polycyclic aromatic group having a phenolic hydroxyl group. 8. The method of claim 7,
A radiation-sensitive resin composition wherein the novolak resin (C) is a resin having at least one selected from the structural unit represented by the formula (C2-1) and the structural unit represented by the formula (C2-2):

[In formulas (C2-1) to (C2-2), R ² is a methylene group, an alkylene group having 2 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, or aralkyl having 7 to 30 carbon atoms. a ene group or a group represented by -R ³ -Ar-R ³ - (Ar is a divalent aromatic group, and R ³ is each independently a methylene group or an alkylene group having 2 to 20 carbon atoms); a, b, c and e are each independently an integer of 0 to 3, d is an integer of 0 to 2, provided that a and b are not both 0, and c to e are not all 0 ]. According to claim 1,
(D) The radiation-sensitive resin composition further containing a crosslinking agent. The insulating film for organic electroluminescent elements formed from the radiation-sensitive resin composition in any one of Claims 1-9. A process of forming a coating film on a substrate using the radiation-sensitive resin composition according to any one of claims 1 to 9, a process of irradiating at least a part of the coating film with radiation, and developing the radiation-irradiated coating film A method for manufacturing an insulating film for an organic EL device, comprising the steps of: and heating the developed coating film. The organic EL element provided with the insulating film of Claim 10.