KR102173287B1 - Radiation-sensitive resin composition, insulation film and method for forming the same, and organic el element - Google Patents

Abstract

(Task) A radiation-sensitive resin that satisfies the properties required for a radiation-sensitive resin composition such as radiation sensitivity and patterning properties, and can form an insulating film having excellent heat resistance and absorption properties without reducing productivity. It is an object to provide a composition.
(Solution means) The present invention is a radiation-sensitive resin composition used for forming an insulating film, comprising a polyimide having a structural unit of formula (1) or a precursor of the polyimide, a radiation-sensitive acid generator, and a phenolic hydroxyl group. It contains a condensed cyclic compound and the content of the condensed cyclic compound is 5 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the polymer. As the condensed cyclic compound, a phenol resin having a structural unit of formula (2-1) or formula (2-2) is preferable. In the following formulae, R ¹ is a divalent group having a hydroxyl group, X is a tetravalent organic group, and R ² is a methylene group, an alkylene group, a divalent alicyclic hydrocarbon group or an aralkylene group. a to e are integers of 0 to 2.

Description

A radiation-sensitive resin composition, an insulating film, and a method of forming the same, and an organic EL element {RADIATION-SENSITIVE RESIN COMPOSITION, INSULATION FILM AND METHOD FOR FORMING THE SAME, AND ORGANIC EL ELEMENT}

The present invention relates to a radiation-sensitive resin composition, an insulating film, a method for forming the same, and an organic EL (Electro Luminescence) device.

Organic EL devices using electroluminescence by organic compounds are expected as next-generation lighting devices in addition to displays and the like. Since the organic EL display element using the organic EL element is of a self-luminous type, it does not require a light source for illumination such as a backlight, and can realize an image display capable of high-speed response at a wide angle. Further, the organic EL display device has excellent advantages such as low power consumption, thinness and weight reduction. Therefore, organic EL display devices have been actively developed in recent years.

Such an organic EL element has an insulating film such as a planarization film and a partition wall for partitioning a pixel (light emitting element). Such an insulating film is generally formed using a radiation-sensitive resin composition (Japanese Laid-Open Patent Publication No. 2011-107476 and Japanese Laid-Open Patent Publication No. 2010-237310).

Such a radiation-sensitive resin composition is required to have high radiation sensitivity and easy patterning into a desired pattern. In addition, in order to meet the demand for higher image quality, it is necessary to cope with the fine pitch of the pattern, and therefore it is desired that the pattern shape is excellent. Further, the insulating film formed of the radiation-sensitive resin composition is required to have excellent heat resistance and the like.

In order to meet these demands, it has been proposed to use polyimide for the insulating film of an organic EL device (Japanese Laid-Open Patent Publication No. Hei 10-186658, Japanese Laid-Open Patent Publication No. 2005-352004 and Japanese Laid-Open Patent Publication No. 2009-9934. ).

The insulating film of polyimide is excellent in heat resistance and can be formed using a radiation-sensitive resin composition. In this case, as the resin component of the resin composition, in addition to polyimide, a polyimide precursor such as polyamic acid may be used.

On the other hand, in recent years, studies on thin film transistors using oxide semiconductor films have been actively conducted. As such an oxide semiconductor film, a polycrystalline thin film of an oxide (abbreviated as ``IGZO'') made of In, Ga, and Zn is used for the semiconductor film of a thin film transistor (Japanese Patent Laid-Open No. 2005-352004), and IGZO ) It has been proposed to use a crystalline thin film for a semiconductor film of a thin film transistor (Japanese Laid-Open Patent Publication No. 2005-352004 and Japanese Laid-Open Patent Publication No. 2009-9934). As a characteristic of an insulating film for a thin film transistor using IGZO as these semiconductor films, in recent years, from the viewpoint of preventing deterioration of IGZO, it is required to impart light blocking properties from ultraviolet to visible light. Insulation films currently used are often transparent, and it is required to impart a light-shielding function.

Japanese Unexamined Patent Publication No. 2011-107476 Japanese Unexamined Patent Publication No. 2010-237310 Japanese Unexamined Patent Publication No. Hei 10-186658 Japanese Patent Publication No. 2005-352004 Japanese Patent Publication No. 2009-9934 Japanese Laid-Open Patent Publication No. 2004-103957 Japanese Patent Publication No. 2005-88726

The present invention has been made in view of the above problems, satisfies the properties required for a radiation-sensitive resin composition such as radiation sensitivity and patterning property, and at the same time satisfies the excellent IGZO element light-shielding property and low (低) An object of the present invention is to provide a radiation-sensitive resin composition capable of forming an insulating film having water absorption properties and the like.

The invention made to solve the above problems is a radiation-sensitive resin composition used for forming an insulating film, at least one selected from the group consisting of a polyimide having a structural unit represented by the following formula (1) and a precursor of this polyimide A type of polymer, a radiation-sensitive acid generator, and a condensed cyclic compound having a phenolic hydroxyl group, and the content of the condensed cyclic compound is 5 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the polymer:

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

Another invention made in order to solve the said subject is an insulating film of an organic EL element formed using the said radiation-sensitive resin composition, and an organic EL element provided with the said insulating film.

The method of forming an insulating film of the present invention comprises: forming a coating film on a substrate, irradiating at least a portion of the coating film with radiation, developing the coating film irradiated with the radiation, and heating the developed coating film As a method of forming an insulating film for an organic EL device having, the coating film is formed of the radiation-sensitive resin composition.

According to the radiation-sensitive resin composition of the present invention, an insulating film having excellent heat resistance or absorption properties, etc., without reducing productivity, while satisfying properties required for a radiation-sensitive resin composition such as radiation sensitivity and patterning property Can be formed. Therefore, the radiation-sensitive resin composition can be suitably used for an insulating film of an organic EL device.

1 is a cross-sectional view schematically showing a structure of a main part of an organic EL display device according to an embodiment of the present invention.

(Form for carrying out the invention)

<Radiation-sensitive resin composition>

The radiation-sensitive resin composition of the present invention is used for forming an insulating film of an organic EL device. The radiation-sensitive resin composition contains a polymer [A], a radiation-sensitive acid generator [B], and a condensed cyclic compound [C], and a compound having a cationic polymerizable group as a suitable component (hereinafter, “[D] cationic polymerization (Also referred to as "sex compound") and a solvent (hereinafter also referred to as "[E] solvent") may be contained. Further, the radiation-sensitive resin composition may contain other optional components within a range that does not impair the effects of the present invention. Hereinafter, each component is described in detail.

<[A] Polymer>

[A] The polymer is selected from the group consisting of a polyimide having a specific structure (hereinafter referred to as "(A1) polyimide") and its polyimide precursor (hereinafter referred to as "(A2) polyimide precursor"). At least one.

The polymer [A] contains the (A1) polyimide and (A2) polyimide precursor having a specific structure, and thus has excellent low water absorption and solubility due to the specific structure. Therefore, the polymer [A] is also dissolved in a low hygroscopic solvent other than NMP, for example, a solvent [E] described later. As a result, the radiation-sensitive resin composition can reduce moisture absorption of the insulating film by using a solvent other than NMP as a polymerization solvent for obtaining the [A] polymer.

[(A1) Polyimide]

(A1) Polyimide contains the structural unit represented by following formula (1).

In the formula (1), R ¹ is a divalent group having a hydroxyl group. X is a tetravalent organic group. Here, "organic device" refers to a group containing at least one carbon atom. In addition, the same applies to the case of "organic device" below.

Examples of R ¹ include a divalent group represented by the following formula (3), and among them, a divalent group having 1 to 4 hydroxyl groups is preferable, and a divalent group having two hydroxyl groups is more preferable. .

In the formula (3), R ³ is a single bond, an oxygen atom, a sulfur atom, a sulfone group, a carbonyl group, a methylene group, a dimethylmethylene group, or a bis(trifluoromethyl)methylene group. Each of R ⁴ is independently a hydrogen atom, an acyl group, or an alkyl group. However, at least one of R ⁴ 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 of n1 and n2 is 2 or more, a plurality of R ⁴ may be the same or different.

Examples of the acyl group represented by R ⁴ include formyl group, acetyl group, propionyl group, butyryl group and isobutyryl group.

Examples of the alkyl group represented by R ⁴ 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. are mentioned.

Examples of the divalent group having one hydroxyl group represented by the above formula (3) include a divalent group represented by the following formula.

Examples of the divalent group having two hydroxyl groups represented by the formula (3) include a divalent group represented by the following formula.

Examples of the divalent group having three hydroxyl groups represented by the above formula (3) include a divalent group represented by the following formula.

Examples of the divalent group having four hydroxyl groups represented by the above formula (3) include a divalent group represented by the following formula.

Examples of the tetravalent organic group represented by X include a tetravalent aliphatic hydrocarbon group and a tetravalent aromatic hydrocarbon group. Among them, a tetravalent aliphatic hydrocarbon group is preferable.

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

As a chain hydrocarbon of the parent skeleton of a tetravalent chain hydrocarbon group, for example, ethane, n-propane, n-butane, n-pentane, n-hexane, n-octane, n-decane, n-dodecane And the like.

Examples of the alicyclic hydrocarbons of the parent skeleton of the tetravalent alicyclic hydrocarbon group include monocyclic hydrocarbons, bicyclic hydrocarbons, and tricyclic or higher hydrocarbons.

Examples of the monocyclic hydrocarbon include cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, and cyclooctane.

Examples of bicyclic hydrocarbons include bicyclo[2.2.1]heptane, bicyclo[3.1.1]heptane, bicyclo[3.1.1]hepto-2-ene, bicyclo[2.2.2]octane, and the like. Can be lifted.

As a tricyclic or higher hydrocarbon, for example, tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[5.2.1.0 ^2,6 ]decane-4-ene, adamantane, tetracyclo[6.2.1.1 ^{3, 6} .0 ^2,7 ]Dodecane and the like.

As the aliphatic hydrocarbon group containing an aromatic ring in at least a part of the molecular structure, for example, the number of aromatic rings contained in one molecule is preferably 3 or less, and particularly preferably one. More specifically, 1-ethyl-6-methyl-1,2,3,4-tetrahydronaphthalene, 1-ethyl-1,2,3,4-tetrahydronaphthalene, etc. are mentioned.

As the tetravalent aliphatic hydrocarbon group, a tetravalent group represented by the following formula is preferable.

Examples of the tetravalent aromatic hydrocarbon group include a tetravalent group represented by the following formula.

　

　

[(A1) Synthesis method of polyimide]

(A1) Polyimide is, for example, tetracarboxylic dianhydride having a specific group (hereinafter, also referred to as ``(A1-1) acid dianhydride'') and diamine having a specific group (hereinafter, ``(A1-2) diamine''). It can be synthesized by polymerizing the polyamic acid in approximately equal moles to produce a polyamic acid, and then dehydrating and cyclizing (imidizing) the polyamic acid. (A1) Polyimide can also be synthesized by synthesizing a polyamic acid derivative by esterifying a polyamic acid instead of imidating the polyamic acid, and imidizing the polyamic acid derivative.

Synthesis of polyamic acid may be performed by dissolving (A1-2) diamine and, if necessary, other diamines in a polymerization solvent, and then reacting with (A1-1) acid dianhydride, and (A1-1) acid dianhydride After dissolving in a polymerization solvent, it may be carried out by reacting with (A1-2) diamine and other diamines as necessary.

In either method, a polyamic acid derivative may be formed by esterifying a carboxyl group of the polyamic acid after generation of the polyamic acid, and then imidization may be performed.

(A1-1) An acid dianhydride is an acid dianhydride represented by the following formula (4).

X ¹ in the above formula (4) is a tetravalent organic group. Examples of the tetravalent organic group represented by X ¹ include the same groups as those illustrated as X.

(A1-2) Diamine is a diamine represented by following formula (5).

In the formula (5), R ⁵ is a divalent group having a hydroxyl group. Examples of the divalent group having a hydroxyl group represented by R ⁵ include the same groups as those illustrated by R ¹ .

As the diamine, in addition to the diamine (A1-2), an aromatic diamine and an aliphatic diamine may be used in combination.

As the aromatic diamine, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodi Phenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodi Phenyl ether, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane , 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'- Diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl ]Hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]sulfone, 1,4-bis(4-amino Phenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene, 4,4'-methylene-bis(2-chloroaniline), 2,2',5,5'-tetrachloro -4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-dia Minobiphenyl, 1,4,4'-(p-phenyleneisopropylidene)bisaniline, 4,4'-(m-phenyleneisopropylidene)bisaniline, 2,2'-bis[4-( 4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[ (4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, and the like.

As the aliphatic diamine, for example, metaxylylenediamine, paraxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, deca Methylenediamine, dodecamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, 1,4-bis(aminomethyl)cyclohexane, isophoronediamine, tetrahydrodicyclopentadienylene Diamine, hexahydro-4,7-methanoindanilylenedimethylenediamine, tricyclo[6.2.1.0 ^2,7 ]-undecylenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine), and the like.

As the polymerization solvent used for the synthesis of polyamic acid, (A1) a raw material for synthesis of polyimide and (A1) polyimide can be dissolved, and those having low water absorption are selected. As the polymerization solvent, the same solvent as exemplified as the [E] solvent described later can be used.

By using the same solvent as the solvent [E] as the polymerization solvent, the step of isolating the polymer [A] after synthesizing the polymer [A] and the step of re-dissolving in another solvent after isolation can be made unnecessary. Accordingly, the productivity of the organic EL device can be improved.

As the imidation reaction of the polyamic acid and the polyamic acid derivative, a known method such as a heat imidation reaction or a chemical imidation reaction can be applied. In the case of a heating imidation reaction, it is preferable to heat the synthesis solution of polyamic acid at 120°C to 210°C for 1 hour to 16 hours. If necessary, the imidation reaction may be performed while removing water in the system using an azeotropic solvent such as toluene, xylene, mesitylene, or the like.

[(A2) Polyimide precursor]

(A2) The polyimide precursor can produce a polyimide having a structural unit represented by the formula (1) by dehydration and cyclization (imidization). This polyimide precursor contains a polyamic acid and a polyamic acid derivative.

(Polyamic acid)

As the polyamic acid, it is preferable that a polyimide having a hydroxyl group in the structural unit can be produced as if it has a structural unit represented by the following formula (6).

In the formula (6), R ⁶ is a divalent group having a hydroxyl group. X ² is a tetravalent organic group.

Examples of the divalent group having a hydroxyl group represented by R ⁶ include the same groups as those exemplified as R ¹ .

Examples of the tetravalent organic group represented by X ² include the same groups as those illustrated as X.

[Polyamic acid derivatives]

The polyamic acid derivative is a derivative synthesized by esterification of polyamic acid or the like. Examples of the polyamic acid derivative include those obtained by substituting hydrogen of a carboxyl group in the structural unit of a polyamic acid, and a polyamic acid ester is preferable.

The polyamic acid ester is one in which at least a part of the carboxyl groups of the polyamic acid is esterified. As this polyamic acid ester, it has the structural unit represented by following formula (7) which can produce the polyimide which has the structural unit represented by said formula (1). The polyamic acid ester represented by the following formula (7) is esterified with a carboxyl group of the polyamic acid having the structural unit represented by the formula (6).

In the formula (7), R ⁷ is a divalent group having a hydroxyl group. Each of R ⁸ is independently an alkyl group having 1 to 5 carbon atoms. X ³ is a tetravalent organic group.

Examples of the divalent group having a hydroxyl group represented by R ⁷ include the same groups as those exemplified as R ¹ .

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ⁸ include a methyl group, an ethyl group, and a propyl group.

Examples of the tetravalent organic group represented by X ³ include the same groups as those illustrated as X.

[(A2) Synthesis of polyimide precursor]

(A2) The polyamic acid as a polyimide precursor can be obtained as a compound before imidization in the process of synthesizing a polyimide.

(A2) The polyamic acid ester as a polyimide precursor can be obtained by esterifying a polyamic acid. There is no restriction|limiting in particular as a method of esterification, A well-known method can be applied.

[A] The weight average molecular weight in terms of polystyrene (hereinafter, also referred to as "Mw") of the polymer is preferably 2,000 to 500,000, and more preferably 3,000 to 300,000 in a value measured by gel permeation chromatography (GPC). . When Mw is less than 2,000, there is a tendency that sufficient mechanical properties as an insulating film cannot be obtained. On the other hand, when Mw exceeds 500,000, the solubility of the polymer [A] in a solvent or developer tends to decrease.

As the content of the [A] polymer, 10 parts by mass or more and 80 parts by mass or less are preferable, more preferably 20 parts by mass or more and 70 parts by mass or less, and 30 parts by mass based on 100 parts by mass of all solid components in the radiation-sensitive resin composition. More preferably, parts by weight or more and 60 parts by mass or less.

[[B] Radiation-sensitive acid generator]

[B] The radiation-sensitive acid generator is a compound that generates an acid by irradiation with radiation. As the radiation, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X rays, and the like can be used. By containing the radiation-sensitive acid generator [B], the radiation-sensitive resin composition can exhibit radiation-sensitive properties and have good radiation sensitivity. [B] As a form of containing the radiation-sensitive acid generator in the radiation-sensitive resin composition, even in the form of the compound described later (hereinafter, appropriately referred to as "[B] radiation-sensitive acid generator"), [ A] The form of a radiation-sensitive acid generator incorporated as part of a polymer or the like, or both of these forms may be sufficient. These [B] radioactive acid generators may be used alone or in combination of two or more.

[B] Examples of the radiation-sensitive acid generator include oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid esters. A compound, a quinone diazide compound, etc. are mentioned. These [B] radiation-sensitive acid generators may be used alone or in combination of two or more.

[Oxime Sulfonate Compound]

As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (8) is preferable.

In formula (8), R ⁹ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group or a group in which some or all of the hydrogen atoms of the alkyl group, monovalent alicyclic hydrocarbon group, or aryl group are substituted with a substituent.

As the alkyl group represented by R ⁹ , a linear or branched alkyl group having 1 to 12 carbon atoms is preferable.

The alicyclic hydrocarbon group represented by R ⁹ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms.

As the aryl group represented by R ⁹ , an aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group, a naphthyl group, a tolyl group, and a xylyl group are more preferable.

Examples of the compound containing an oxime sulfonate group represented by the above formula (8) include an oxime sulfonate compound represented by the following formulas (8-1) to (8-3).

In the above formulas (8-1), (8-2) and (8-3), R ⁹ has the same meaning as in the above formula (8).

In the formulas (8-1) and (8-2), R ¹⁰ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms.

In formula (8-3), X ⁴ is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. However, when m is 2 or 3, a plurality of X ⁴ may be the same or different.

As the alkyl group represented by X ⁴ , a linear or branched alkyl group having 1 to 4 carbon atoms is preferable. As the alkoxy group represented by X ⁴ , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferable. As the halogen atom represented by X ⁴ , a chlorine atom and a fluorine atom are preferable.

Examples of the oxime sulfonate compound represented by the above formula (8-3) include compounds represented by the following formulas (8-3-1) to (8-3-5).

The compounds represented by the above formulas (8-3-1) to (8-3-5) are each (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile , (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2- Methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4- It is methoxyphenyl)acetonitrile and can be obtained as a commercial item.

[Onium salt]

As the onium salt, for example, diphenyliodonium salt, triphenylsulfonium salt, alkylsulfonium salt, benzylsulfonium salt, dibenzylsulfonium salt, substituted benzylsulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, etc. I can.

As the diphenyliodonium salt, for example, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodo Nium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium butyl tris(2,6-difluorophenyl)borate, 4 -Methoxyphenylphenyliodoniumtetrafluoroborate, bis(4-t-butylphenyl)iodoniumtetrafluoroborate, bis(4-t-butylphenyl)iodoniumhexafluoroarsenate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p- Toluenesulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonic acid, etc. are mentioned.

As the triphenylsulfonium salt, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium Phonium-p-toluenesulfonate, triphenylsulfonium butyltris(2,6-difluorophenyl)borate, etc. are mentioned.

Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfoniumhexafluoroantimonate, 4-acetoxyphenyldimethylsulfoniumhexafluoroarsenate, and dimethyl-4-(benzyloxycarbonyloxy ) Phenylsulfoniumhexafluoroantimonate, dimethyl-4-(benzoyloxy)phenylsulfoniumhexafluoroantimonate, dimethyl-4-(benzoyloxy)phenylsulfoniumhexafluoroarsenate, dimethyl-3 -Chloro-4-acetoxyphenylsulfoniumhexafluoroantimonate, etc. are mentioned.

Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, and 4-acetoxyphenylbenzylmethylsulfonium Phonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfoniumhexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3- Chloro-4-hydroxyphenylmethylsulfoniumhexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfoniumhexafluorophosphate, and the like.

Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfoniumhexafluorophosphate, and 4-acetoxyphenyldibenzyl Sulfoniumhexafluoroantimonate, dibenzyl-4-methoxyphenylsulfoniumhexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfoniumhexafluoro arsenate, dibenzyl- 3-methyl-4-hydroxy-5-t-butylphenylsulfoniumhexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfoniumhexafluorophosphate, etc. are mentioned.

As the substituted benzylsulfonium salt, for example, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfoniumhexafluoroantimonate , p-chlorobenzyl-4-hydroxyphenylmethylsulfoniumhexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfoniumhexafluoroantimonate, 3,5-dichlorobenzyl- 4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3-(p -Methoxybenzyl)benzothiazoniumhexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazoniumhexafluoroantimonate, 3-benzyl-5-chlorobenzothiazoniumhexafluoroantimonate, etc. Can be mentioned.

As the tetrahydrothiophenium salt, for example, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalene- 1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1-(4 -n-butoxynaphthalen-1-yl)tetrahydrothiophenium-1,1,2,2-tetrafluoro-2-(norbornan-2-yl)ethanesulfonate, 1-(4-n -Butoxynaphthalen-1-yl)tetrahydrothiophenium-2-(5-t-butoxycarbonyloxybicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetra Fluoroethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium-2-(6-t-butoxycarbonyloxybicyclo[2.2.1]heptane-2- 1)-1,1,2,2-tetrafluoroethanesulfonate, etc. are mentioned.

[N-sulfonyloxyimide compound]

Examples of the N-sulfonyloxyimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(4-methylphenylsulfonyloxy) Succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthali Mid, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-( Trifluoromethylsulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenyl Sulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy) )Bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicar Boximide, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(nonafluorobutanesulfonyloxy)bicyclo[2.2 .1]Hepto-5-ene-2,3-dicarboximide, N-(camphorsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(camphor Sulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1 ]Hepto-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(4 -Methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1 ]Hepto-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dica Boximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N- (4-Fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2 .1]heptane-5,6-oxy-2,3-dicarboximide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2 .1]heptane-5,6-oxy-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3- Dicarboximide, N-(trifluoromethylsulfonyloxy)naphthyldicarboximide, N-(camphorsulfonyloxy)naphthyldicarboximide, N-(4-methylphenylsulfonyloxy)naphthyldicarboximide , N-(phenylsulfonyloxy)naphthyldicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboximide, N-(4-fluorophenylsulfonyloxy)naphthyldicarboxyi Mid, N-(pentafluoroethylsulfonyloxy)naphthyldicarboximide, N-(heptyl propylsulfonyloxy)naphthyldicarboximide, N-(nonafluorobutylsulfonyloxy)naphthyldicar Boximide, N-(ethylsulfonyloxy)naphthyldicarboximide, N-(propylsulfonyloxy)naphthyldicarboximide, N-(butylsulfonyloxy)naphthyldicarboximide, N-(pentylsulfonyl) Phonyloxy)naphthyldicarboximide, N-(hexylsulfonyloxy)naphthyldicarboximide, N-(heptylsulfonyloxy)naphthyldicarboximide, N-(octylsulfonyloxy)naphthyldicarboximide , N-(nonylsulfonyloxy)naphthyldicarboximide, etc. are mentioned.

[Halogen-containing compound]

As a halogen-containing compound, a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, etc. are mentioned, for example.

[Diazomethane compound]

As a diazomethane compound, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-tolylsulfonyl) Phonyl) diazomethane, bis(2,4-xylylsulfonyl)diazomethane, bis(p-chlorophenylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonyl (benzoyl)diazomethane, and the like.

[Sulfone compound]

As a sulfone compound, a β-ketosulfone compound, a β-sulfonylsulfone compound, a diaryldisulfone compound, etc. are mentioned, for example.

[Sulfonic acid ester compound]

As a sulfonic acid ester compound, an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester, an imino sulfonate, etc. are mentioned, for example.

[Carbon acid ester compound]

As a carboxylic acid ester compound, o-nitrobenzyl carboxylic acid etc. are mentioned, for example.

[B] As the radiation-sensitive acid generator, an oxime sulfonate compound, an onium salt, and a sulfonic acid ester compound are preferable, and an oxime sulfonate compound is more preferable. As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the above formula (8) is preferable, and a compound represented by the above formulas (8-3-1) to (8-3-5) is more preferable. Do.

Further, as the onium salt, a tetrahydrothiophenium salt and a benzylsulfonium salt are preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, benzyl-4 -Hydroxyphenylmethylsulfoniumhexafluorophosphate is more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate is more preferable. As said sulfonic acid ester compound, haloalkylsulfonic acid ester is preferable, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is more preferable.

[Quinone diazide compound]

The quinone diazide compound generates carboxylic acid by irradiation with radiation. As the quinone diazide compound, a condensation product of a phenolic compound or an alcoholic compound (hereinafter also referred to as "mother core") and a 1,2-naphthoquinone diazide sulfonic acid halide can be mentioned, for example.

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

As trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc. are mentioned, for example.

As tetrahydroxybenzophenone, for example, 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, etc. I can.

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

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

Examples of (polyhydroxyphenyl) alkanes 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'-spirobiindene- 5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, and the like.

Other parent nuclei include, 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-hydro Roxyphenyl]-1-methylethyl)-4,6-dihydroxyphenyl}-1-methylethyl]benzene, 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1 ,3-dihydroxybenzene, etc. are mentioned.

Among these parental 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 the 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazidesulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, etc. 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferred.

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

As the quinone diazide compound, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the exemplified parent nucleus is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2- Naphthoquinone diazide-4-sulfonic acid amide and the like are also suitably used.

The radiation sensitive resin composition can improve the radiation sensitivity and solvent solubility by using the compound illustrated above as the radiation sensitive acid generator [B].

[B] The content of the radiation-sensitive acid generator is 5 parts by mass or more and 100 parts by mass or less, preferably 10 parts by mass or more and 50 parts by mass or less, and 15 parts by mass or more and 40 parts by mass based on 100 parts by mass of the polymer [A]. Partial or less is more preferable. [B] By setting the content of the radiation-sensitive acid generator in the above range, the difference in solubility between the irradiated portion and the non-irradiated portion in an alkaline aqueous solution or the like used as a developer can be increased, and patterning performance can be improved.

[[C] Condensed cyclic compound]

[C] The condensed cyclic compound is a condensed cyclic compound having a phenolic hydroxyl group. This [C] condensed cyclic compound is a polymer containing, for example, a condensed ring as a part of the structural unit. The radiation-sensitive resin composition can impart light-shielding property and developability by containing the [C] condensed cyclic compound.

As a condensed ring, for example, phenylene, pentalene, indene, naphthalene, azulene, heptalene, biphenylene, s-indacene, as-indacene, acenaphthylene, fluorene, phenalene, phenanthrene , Anthracene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, tetracene (naphthacene), pleiaden, picene, perylene, pentafen, pentacene, tetraphenylene, Hexafen and the like. Among these, as a condensed ring, naphthalene and anthracene are preferable. Further, the number of phenolic hydroxyl groups bonded to one condensed ring may be 1 or more, and may be appropriately set according to the type of the condensed ring and the degree of alkali solubility to be achieved.

[C] As a condensed cyclic compound, it is preferable that it is alkali-soluble. The radiation-sensitive resin composition can have good resolution by containing an alkali-soluble [C] condensed cyclic compound.

[C] As the condensed cyclic compound, a phenol resin having a structural unit represented by the following formula (2-1) (hereinafter, also referred to as "[C1] naphthalene-type phenol resin") and a structural unit represented by the following formula (2-2) At least one selected from the group consisting of phenol resins (hereinafter also referred to as "[C2] anthracene phenol resin") is preferred.

　

　

In the formulas (2-1) and (2-2), 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 an aralkyl having 4 to 30 carbon atoms. It's Rengi. a to e are each independently an integer of 0 to 2. However, there is no case where both a and b are 0, and there is no case where all of c to e are 0.

Examples of the alkylene group having ² to 30 carbon atoms represented by R ² include ethylene group, propylene group, butylene group, pentylene group, hexylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene Group, tetradecylene group, hexadecylene group, octadecylene group, nonadecylene group, icosylene group, henicosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexa And a kosylene 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 represented by R ² include a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group.

As an aralkylene group having ⁴ to 30 carbon atoms represented by the above R ² , for example,

Allylene groups such as benzyylene group, phenylene group, and naphthylene group;

Allylene alkylene groups such as a phenylene methylene group, a phenylene ethylene group, a benzyl propylene group, a naphthylene methylene group, and a naphthylene ethylene group;

Allylene dialkylene groups, such as a phenylene dimethylene group and a phenylene diethylene group, etc. are mentioned.

As R ² , a methylene group, an alkylene group having 2 to 30 carbon atoms, and an aralkylene group having 4 to 30 carbon atoms are preferable, and a methylene group and a phenylene dimethylene group are more preferable.

As a in the formula (2-1) and c in the formula (2-2), 1 or 2 is preferable. 0 is preferable as b in the above formula (2-1) and d and e in the formula (2-2).

[C1] Naphthalene-type phenolic resin and [C2] anthracene-type phenolic resin can be obtained as a novolak type by condensing naphthols or anthrols and aldehydes in the presence of a catalyst, for example.

[C1] naphthalene-type phenol resin and [C2] anthracene-type phenol resin are produced by the methods described in Japanese Patent Application Publication No. 47-15111, Japanese Patent Application No. 62-70282, and the like. That is, it can be obtained by reacting an aralkyl halide or an aralkyl alcohol derivative with 1.1 times more moles of phenols or anthrols in the presence of an acid catalyst, and distilling off unreacted naphthols or anthrols if necessary.

As naphthols, for example, 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7 -Dihydroxy naphthalene, etc. are mentioned.

Examples of anthracenes include monohydroxyanthracene such as 1-monohydroxyanthracene, dihydroxyanthracene such as 1,4-dihydroxyanthracene, and 9,10-dihydroxyanthracene, 1,2,10 -Trihydroxyanthracene, such as trihydroxyanthracene, etc. are mentioned.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetoaldehyde, and benzaldehyde.

[C1] As commercially available naphthalene-type phenolic resins, for example, "Phenolite PR-15", "Phenolite ZF101", "Phenolite ZF201", "Phenolite ZF315" (above, DIC), " SN-100", "SN-485" (above, Shinnittetsu Sumikin Chemical Co., Ltd.), and the like.

The content of the [C] condensed cyclic compound is 5 parts by mass or more and 90 parts by mass or less, preferably 8 parts by mass or more and 75 parts by mass or less, and 10 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the polymer [A]. Is more preferable. When the content of the [C] condensed cyclic compound is less than 5 parts by mass, there is a fear that the effect of imparting light-shielding property by containing this [C] condensed cyclic compound is difficult to exhibit. On the other hand, when the content of the [C] condensed cyclic compound exceeds 90 parts by mass, there is a concern that the water absorbency of the insulating film or heat resistance may decrease.

[[D] Cationic polymerizable compound]

[D] The cationic polymerizable compound is a compound having a cationic polymerizable group. As this cationic polymerizable compound [D], a compound having two or more oxetanyl groups in one molecule is mentioned, for example.

Examples of the compound having an oxetanyl group include 4,4-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl, 3,7-bis(3-oxetanyl)-5- Oxanonane, 3,3'-[1,3-(2-methylenyl)propanediylbis(oxymethylene)]bis(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxygen) Cetanyl)methoxymethyl]benzene, 1,2-bis[(3-ethyl-3-oxetanyl)methoxymethyl]ethane, 1,3-bis[(3-ethyl-3-oxetanyl)me Toxymethyl]propane, ethylene glycolbis[(3-ethyl-3-oxetanyl)methyl]ether, dicyclopentenylbis[(3-ethyl-3-oxetanyl)methyl]ether, triethyleneglycolbis[ (3-ethyl-3-oxetanyl)methyl] ether, tetraethylene glycolbis[(3-ethyl-3-oxetanyl)methyl] ether, tricyclodecanediyldimethylenebis[(3-ethyl-3- Oxetanyl)methyl]ether, trimethylolpropanetris[(3-ethyl-3-oxetanyl)methyl]ether, 1,4-bis[(3-ethyl-3-oxetanyl)methoxy]butane, 1,6-bis[(3-ethyl-3-oxetanyl)methoxy]hexane, pentaerythritoltris[(3-ethyl-3-oxetanyl)methyl]ether, pentaerythritol tetrakis[(3 -Ethyl-3-oxetanyl)methyl]ether, polyethylene glycolbis[(3-ethyl-3-oxetanyl)methyl]ether, dipentaerythritol hexakis[(3-ethyl-3-oxetanyl) Methyl] ether, dipentaerythritol pentakis[(3-ethyl-3-oxetanyl)methyl]ether, dipentaerythritol tetrakis[(3-ethyl-3-oxetanyl)methyl]ether, etc. I can.

As a compound having an oxetanyl group, a reaction product of dipentaerythritol hexakis[(3-ethyl-3-oxetanyl)methyl]ether and caprolactone, dipentaerythritolpentakis[(3-ethyl) Reaction product of -3-oxetanyl)methyl]ether and caprolactone, ditrimethylolpropanetetrakis[(3-ethyl-3-oxetanyl)methyl]ether, bisphenol A bis[(3-ethyl-3) -Oxetanyl)methyl] ether and reaction product of ethylene oxide, bisphenol A bis[(3-ethyl-3-oxetanyl) methyl] ether and propylene oxide reaction product, hydrogenated bisphenol A bis[(3 Reaction product of -ethyl-3-oxetanyl)methyl]ether and ethylene oxide, hydrogenated bisphenol A reaction product of bis[(3-ethyl-3-oxetanyl)methyl]ether and propylene oxide, bisphenol F The reaction product of bis[(3-ethyl-3-oxetanyl)methyl] ether and ethylene oxide, etc. are mentioned.

The content of the [D] cationic polymerizable compound is usually 1 part by mass or more and 70 parts by mass or less, preferably 3 parts by mass or more and 50 parts by mass or less, and 5 parts by mass or more and 40 parts by mass based on 100 parts by mass of the polymer [A]. Partial or less is more preferable. When the content of the [D] cationic polymerizable compound is less than 1 part by mass, there is a fear that the effect of improving the water absorption by containing this [D] cationic polymerizable compound is difficult to exhibit. On the other hand, when the content of the [D] cationic polymerizable compound exceeds 100 parts by mass, there is a concern that the heat resistance of the insulating film may decrease.

[[E] Solvent]

[E] The solvent is for making the said radiation-sensitive resin composition liquid. [E] Solvents may be used alone or in combination of two or more.

[E] As the solvent, diethylene glycol dialkyl 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 desirable.

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

As ethylene glycol monoalkyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, etc. are mentioned, for example.

As diethylene glycol monoalkyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. are mentioned, for example.

As propylene glycol monoalkyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc. are mentioned, for example.

As propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. are mentioned, for example.

As propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, etc. Can be mentioned.

[E] As a solvent, N,N,2-trimethylpropionamide, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-dimethylpropanamide, 3-hexyloxy- N,N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide, etc. are also mentioned.

[E] As the solvent, 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") Is preferred.

[E] As the solvent, it is preferable to mix γ-butyrolactone (hereinafter also referred to as "BL"). BL is preferably used in combination with at least one selected from the group consisting of PGMEA, PGME, and EDM.

As the content of BL, in 100 parts by mass of the total amount of the solvent [E], 50 parts by mass or less are preferable, and 20 parts by mass or more and 40 parts by mass or less are more preferable. By making the content of BL into the above range, the dissolved state of the polymer [A] in the radiation-sensitive resin composition can be suitably maintained.

[E] As the solvent, in addition to the exemplified solvent, as necessary, methanol, ethanol, propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-( Alcohol solvents such as 2-ethoxyethoxy)ethanol; Ether solvents such as propylene glycol methyl ether, diglyme, and triglyme; Aromatic hydrocarbon solvents, such as toluene and xylene, etc. can also be used together.

[E] What was illustrated above as a solvent is less hygroscopic than NMP. Therefore, the radiation-sensitive resin composition can be prepared using a low hygroscopic solvent without using NMP having high hygroscopicity. As a result, the radiation-sensitive resin composition can exhibit low hygroscopicity. In addition, since the thing exemplified as the solvent [E] has high safety, the safety of the radiation-sensitive resin composition can be improved.

[E] The solvent can be used for preparation of the radiation-sensitive resin composition. That is, when using the thing illustrated above as the [E] solvent, the insulating film formed from the said radiation-sensitive resin composition can be made into low water absorption. Therefore, the said radiation-sensitive resin composition can be used suitably for formation of the insulating film of an organic EL element.

The content of the [E] solvent is usually 200 parts by mass or less, and preferably 50 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polymer [A]. By setting the content of the [E] solvent in the above range, it is possible to achieve low absorption of the insulating film formed of the ring-radiation resin composition without impairing developability.

[Other optional ingredients]

The radiation-sensitive resin composition, in addition to the essential components and suitable components, as required, [F] adhesion aid, [G] surfactant, [H] crosslinking agent, [I], as long as the effect of the present invention is not impaired. ] You may contain other optional components, such as a heat-sensitive acid generator or a heat-sensitive base generator. Other optional components may be used alone or in combination of two or more. Hereinafter, each component is described in detail.

<[F] Adhesion aid>

[F] The adhesion aid is a component that improves the adhesion between a film-forming object such as a substrate and a cured film. [F] The adhesion aid is particularly useful because it improves the adhesion between the inorganic substrate and the cured film. Examples of the inorganic material include silicon compounds such as silicon, silicon oxide, and silicon nitride, and metals such as gold, copper, and aluminum.

[F] As the adhesion aid, a functional silane coupling agent is preferable. As this functional silane coupling agent, a silane coupling agent which has reactive substituents, such as a carboxy group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), a thiol group, etc. are mentioned, for example.

As the functional silane coupling agent, for example, N-phenyl-3-aminopropyltrimethoxysilane, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane Toxoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Among these, examples of the functional silane coupling agent include N-phenyl-3-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane are preferred.

The content of the [F] adhesion aid is more preferably 10 parts by mass or less based on 100 parts by mass of the polymer [A]. By setting the content of the [F] adhesion aid in the above range, the adhesion between the insulating film formed from the radiation-sensitive resin composition and the substrate is further improved.

<[G] Surfactant>

[G] Surfactant is a component which improves the coating film formation property of the said radiation-sensitive resin composition. When the radiation-sensitive resin composition contains the [G] surfactant, the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the cured film can be further improved.

As [G] surfactant, a fluorine-type surfactant, a silicone-type surfactant, etc. are mentioned, for example.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and/or a fluoroalkylene group at at least any portion of the terminal, the main chain and the side chain is preferable. For example, 1,1,2,2-tetrafluoro-n- Octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1 ,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1 ,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecane Sodium sulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro-n-dode Cane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarbonyl, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, Fluoroalkylpolyoxyethylene ether, perfluoroalkylpolyoxyethanol, perfluoroalkylalkoxylate, carbonic acid fluoroalkylester, etc. are mentioned.

As a commercial product of a fluorine-based surfactant, for example,

"BM-1000", "BM-1100" (above, BM CHEMIE), "MEGAFACE F142D", "Megapack F172", "Megapack F173", "Megapack F183", "Megapack F178 ", "Megapack F191", "Megapack F471", "Megapack F476" (above, Dai-Nippon Ink Co., Ltd.);

"Fluorad FC-170C", "Fluorad FC-171", "Fluorad FC-430", "Fluorad FC-431" (above, Sumitomo 3M), "Surflon S- 112", "Suplon S-113", "Suplon S-131", "Suplon S-141", "Suplon S-145", "Suplon S-382", "Suplon SC-101" , "Suplon SC-102", "Suplon SC-103", "Suplon SC-104", "Suplon SC-105", "Suplon SC-106" (above, Asahi Glass Company);

"EFTOP EF301", "Ftop EF303", "Ftop EF352" (above, Shin Akita Kasei Co., Ltd.);

``FTERGENT FT-100'', ``Ftergent FT-110'', ``Ftergent FT-140A'', ``Ftergent FT-150'', ``FTERGENT FT-250'', ``Ftergent FT-251'' , ``Ftergent FT-300'', ``Ftergent FT-310'', ``Ftergent FT-400S'', ``Ftergent FTX-218'', ``Ftergent FT-251'' (above, Neos), etc. have.

As a commercial product of a silicone-based surfactant, for example,

``Toray Silicon DC3PA'', ``Tore Silicon DC7PA'', ``Tore Silicon SH11PA'', ``Tore Silicon SH21PA'', ``Tore Silicon SH28PA'', ``Tore Silicon SH29PA'', ``Tore Silicon SH30PA'', ``Tore Silicon SH -190'', ``TORESilicon SH-193'', ``TORESilicon SZ-6032'', ``TORESilicon SF-8428'', ``TORESilicon DC-57'', ``TORESilicon DC-190'', ``SH 8400 FLUID'' ( Above, Torre Downing Silicone Co.);

"TSF-4440", "TSF-4300", "TSF-4445", "TSF-4446", "TSF-4460", "TSF-4452" (above, GE Toshiba Silicon Corporation);

"Organosiloxane polymer KP341" (Shin-Etsu Chemical Co., Ltd.), and the like.

As the content of the [G] surfactant, based on 100 parts by mass of the polymer [A], it is usually 3 parts by mass or less, preferably 0.01 parts by mass or more and 2 parts by mass or less, and more preferably 0.05 parts by mass or more and 1 part by mass or less. . By setting the content of the [G] surfactant within the above range, the uniformity of the film thickness of the formed coating film can be further improved.

<[H] crosslinking agent>

[H] The crosslinking agent can form a cured film of the radiation-sensitive resin composition. The radiation-sensitive resin composition can improve the surface hardness and heat resistance of the cured film by containing the [H] crosslinking agent. [H] The crosslinking agent is a compound having one or more types of crosslinkable functional groups (hereinafter, also referred to as "crosslinkable functional groups"). Examples of the crosslinkable functional group include glycidyl ether group, glycidyl ester group, glycidylamino group, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, acetoxymethyl group, benzoyloxymethyl group, formyl group, acetyl Group, vinyl group, isopropenyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group, and the like.

[H] As a crosslinking agent, for example, a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a novolac resin epoxy compound, a resol resin epoxy compound, a poly(hydroxysterene) epoxy compound, 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 And a methyl group-containing urea compound, a carboxymethyl group-containing phenol compound, and the like.

As the content of the [H] crosslinking agent, 30 parts by mass or less and 20 parts by mass or less are preferable, and more preferably 10 parts by mass or less based on 100 parts by mass of the polymer [A].

<[I] A thermosensitive acid generator or a thermosensitive base generator>

[I] A heat-sensitive acid generator or a heat-sensitive base generator (hereinafter, also referred to as "component [I]") releases an acidic active substance or a basic active substance acting as a catalyst for curing reaction by heating. It is defined as a compound capable of. By using the compound of the component [I], the condensation reaction of the condensed cyclic compound [C] in the heating step after development of the positive radiation-sensitive composition is accelerated, thereby forming a cured film having more excellent surface hardness and heat resistance. can do. In addition, as the heat-sensitive acid generator or the heat-sensitive base generator of the component [I], during prebaking at a relatively low temperature (for example, 70°C to 120°C) in the coating film forming step of the positive radiation-sensitive composition It does not release an acidic active substance or a basic active substance, and has a property of releasing an acidic active substance or a basic active substance during post-baking at a relatively high temperature (for example, 120°C to 250°C) in a heating process after development. It is desirable.

The heat-sensitive acid generator of the component [I] includes an ionic heat-sensitive acid generator and a nonionic heat-sensitive acid generator.

It is preferable that the ionic compound does not contain heavy metals or halogen ions.

Examples of the ionic heat-sensitive acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, and 4 -Hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl Methanesulfonates such as -4-benzoyloxyphenylmethylsulfonium, trifluoromethanesulfonates, camphorsulfonates, p-toluenesulfonates, and hexafluorophosphonates. In addition, as a commercial item of a benzylsulfonium salt, for example, "SI-60", "SI-80", "SI-100", "SI-110", "SI-145", "SI-150", "SI -80L", "SI-100L", "SI-110L", "SI-145L", "SI-150L", "SI-160L", "SI-180L" (above, Sanshin Chemical Co., Ltd.) Can be lifted.

As a nonionic heat-sensitive acid generator, for example, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, a phosphoric acid ester compound, a sulfonimide compound, a sulfone benzotriazole compound, etc. Can be mentioned.

As said halogen-containing compound, a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, etc. are mentioned, for example. Among these, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl- 4,6-bis(trichloromethyl)-s-triazine is preferred.

Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-tol Rilsulfonyl)diazomethane, bis(2,4-xylylsulfonyl)diazomethane, bis(p-chlorophenylsulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfur Fonyl(1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, phenylsulfonyl(benzoyl)diazomethane, etc. are mentioned.

Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, and diaryldisulfone compounds. Among these, 4-trisphenacylsulfone, mesitylphenacylsulfone, bis(phenylsulfonyl)methane, and 4-chlorophenyl-4-methylphenyldisulfone compounds are preferable.

Examples of the sulfonic acid ester compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, iminosulfonate, and the like. Among these, benzointosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and 2,6-dinitrobenzylbenzenesulfonate are preferable. As a commercial item of iminosulfonate, "PAI-101", "PAI-106" (above, Midori Chemical Co., Ltd.), CGI-1311 (Chiba Specialty Chemicals Co., Ltd.), etc. are mentioned, for example.

Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide ("SI-105" manufactured by Midori Chemical), and N-(camphorsulfonyloxy)succinimide (" SI-106"), N-(4-methylphenylsulfonyloxy)succinimide ("SI-101" of Midori Chemical Co., Ltd.), N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N- (4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenyl Sulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide ("PI-105" by Midori Chemical) , N-(camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-( 4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hepto-5- N-2,3-dicarboxylimide ("NDI-100" of Midori Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyl is Mid ("NDI-101" from Midori Chemical), N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide (" NDI-105"), N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide ("NDI-109" manufactured by Midori Chemical), N -(Camphorsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide ("NDI-106" manufactured by Midori Chemical Co.), N-(camphorsulfonyloxy)-7- Oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene- 2,3-dicarboxylimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide, N-(4-methylphenylsulfonyloxy)- 7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide , N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide, N-(2-trifluoromethylphenylsulfonyloxy)-7 -Oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hepto-5-ene-2, 3-dicarboxylimide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hepto-5-ene-2,3-dicarboxylimide, N-(trifluoromethyl Sulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy- 2,3-dicarboxylimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-(2-trifluoromethylphenyl Sulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxylimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5, 6-oxy-2,3-dicarboxylimide, N-(trifluoromethylsulfonyloxy)naphthyldicarboxylimide ("NAI-105" manufactured by Midori Chemical), N-(campersulfonyloxy)naphthyl Dicarboxylimide ("NAI-106" manufactured by Midori Chemical), N-(4-methylphenylsulfonyloxy)naphthyldicarboxylimide ("NAI-101" manufactured by Midori Chemical), N-(phenylsulfonyloxy) Naphthyldicarboxylimide (Midori Chemical Co., Ltd. NAI-100"), N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboxylimide, N-(4-fluorophenylsulfonyloxy)naphthyldicar Boxylimide, N-(pentafluoroethylsulfonyloxy)naphthyldicarboxylimide, N-(heptyldicarboxylimide)naphthyldicarboxylimide, N-(nonafluorobutylsulfonyloxy)naphthyl Dicarboxylimide ("NAI-109" of Midori Chemical Co., Ltd.), N-(ethylsulfonyloxy)naphthyldicarboxylimide, N-(propylsulfonyloxy)naphthyldicarboxylimide, N-(butylsulfonyloxy) ) Naphthyldicarboxylimide ("NAI-1004" of Midori Chemical Co., Ltd.), N-(pentylsulfonyloxy)naphthyldicarboxylimide, N-(hexylsulfonyloxy)naphthyldicarboxylimide, N-(hep Tylsulfonyloxy)naphthyldicarboxylimide, N-(octylsulfonyl Oxy)naphthyldicarboxylimide, N-(nonylsulfonyloxy)naphthyldicarboxylimide, and the like.

Other examples of the heat-sensitive acid generator include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, 1-(4,7-dibutoxy-1-naph) And tetrahydrothiophenium salts such as thalenyl) tetrahydrothiophenium trifluoromethanesulfonate.

Examples of the thermosensitive base generator for the component [I] include transition metal complexes such as cobalt; Orthonitrobenzylcarbamates; α,α-dimethyl-3,5-dimethoxybenzylcarbamates; Acyloxyiminos, etc. are mentioned.

Examples of the transition metal complex include bromopentammonia cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonium cobalt perchlorate, hexamethylamine cobalt perchlorate, hexa And propylamine cobalt perchlorate.

Examples of the orthonitrobenzyl carbamates include [[(2-nitrobenzyl)oxy]carbonyl]methylamine, [[(2-nitrobenzyl)oxy]carbonyl]propylamine, and [[(2 -Nitrobenzyl)oxy]carbonyl]hexylamine, [[(2-nitrobenzyl)oxy]carbonyl]cyclohexylamine, [[(2-nitrobenzyl)oxy]carbonyl]aniline, [[(2-nitro Benzyl)oxy]carbonyl] piperizine, bis[[(2-nitrobenzyl)oxy]carbonyl]hexamethylenediamine, bis[[(2-nitrobenzyl)oxy]carbonyl]phenylenediamine, bis[[( 2-nitrobenzyl)oxy]carbonyl]toluenediamine, bis[[(2-nitrobenzyl)oxy]carbonyl]diaminodiphenylmethane, bis[[(2-nitrobenzyl)oxy]carbonyl]piperazine, [[(2,6-dinitrobenzyl)oxy]carbonyl]methylamine, [[(2,6-dinitrobenzyl)oxy]carbonyl]propylamine, [[(2,6-dinitrobenzyl)oxy ]Carbonyl]hexylamine, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, [[(2,6-dinitrobenzyl)oxy]carbonyl]aniline, [[(2, 6-dinitrobenzyl)oxy]carbonyl]piperizine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]hexamethylenediamine, bis[[(2,6-dinitrobenzyl)oxy]carbo Nyl]phenylenediamine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]toluenediamine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl)oxy]carbonyl]piperazine, etc. are mentioned.

Examples of the α,α-dimethyl-3,5-dimethoxybenzylcarbamates include [[(α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]methylamine, [[(α ,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]propylamine, [[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]hexylamine, [[(α ,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]cyclohexylamine, [[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]aniline, [[(α ,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]piperidine, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]hexamethylenediamine, bis [[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]phenylenediamine, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]toluene Diamine, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy]carbonyl]diaminophenylmethane, bis[[(α,α-dimethyl-3,5-dimethoxybenzyl)oxy] Carbonyl] piperazine, and the like.

Examples of the acyloxyiminos include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, Adipoyl benzophenone oxime, adipoyl acetone oxime, acroyl acetophenone oxime, acroyl benzophenone oxime, atroyl acetone oxime, and the like.

Other examples of the heat-sensitive base generator include 2-nitrobenzylcyclohexylcarbamate and O-carbamoylhydroxyamide.

Among the heat-sensitive acid generators and heat-sensitive base generators listed so far, from the viewpoint of the catalytic action of the condensation/curing reaction of the [C] condensed cyclic compound, 2-nitrobenzylcyclohexylcarbamate, 1-(4, 7-dibutoxy-1-naphthalenyl)tetrahydrothiopheniumtrifluoromethanesulfonate and N-(trifluoromethylsulfonyloxy)naphthyldicarboxylimide are preferred.

As the component [I], either a heat-sensitive acid generator or a heat-sensitive base generator is used, and one type may be used alone, or two or more types may be used in combination. As the content in the case of using the component [I], 0.01 parts by mass or more and 10 parts by mass or less are preferable, and more preferably 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the polymer [A]. By setting the amount of the component [I] in the above range, a cured film having excellent surface hardness can be formed while optimizing the radiation sensitivity of the positive radiation-sensitive composition and maintaining transparency.

<Preparation method of radiation-sensitive resin composition>

The radiation-sensitive resin composition is dissolved or dispersed by mixing a [A] polymer, [B] a radiation-sensitive acid generator and [C] a condensed cyclic compound, a suitable component, and other optional components as necessary in a solvent [E]. It is prepared in the same state.

<Insulation film of organic EL element>

The insulating film of the organic EL device of the present invention is formed from the radiation-sensitive resin composition. Since the said insulating film is formed from the said radiation-sensitive resin composition, it has low water absorption, heat resistance, etc. Since the cured film has the above properties, it is suitable as, for example, an insulating film such as an interlayer insulating film of an organic EL element, a planarization film, a bank (partition wall) partitioning a pixel (light emitting layer), a spacer, a protective film, and the like. In addition, the method of forming the insulating film is not particularly limited, but it is preferable to use the method of forming the cured film described below.

<Method of forming an insulating film>

The radiation-sensitive resin composition can be suitably used for formation of an insulating film of an organic EL device.

The method of forming an insulating film of the present invention is a step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter, also referred to as ``step (1)''), and irradiating at least a part of the coating film with radiation. A step (hereinafter also referred to as ``step (2)''), a step of developing the radiation-irradiated coating film (hereinafter, also referred to as ``step (3)''), and a step of heating the developed coating film (hereinafter, `` Process (4)") is also provided.

According to the method of forming the insulating film, it is possible to form an insulating film having high stability and resolution of the pattern shape. Therefore, the production process margin can be improved, and the improvement of the yield can be achieved. Further, since the radiation-sensitive resin composition is excellent in radiation-sensitive properties, an insulating film having a fine and precise pattern can be easily formed by forming a pattern by exposure, development, and heating using photosensitivity.

[Step (1)]

In this step (1), a coating film is formed by applying the radiation-sensitive resin composition to the surface of the substrate and preferably prebaking to remove the solvent. As a substrate, a resin substrate, a glass substrate, a silicon wafer, etc. are mentioned, for example. As the substrate, an organic EL display element in the middle of manufacturing, for example, a TFT or a TFT substrate or a wiring substrate on which the wiring is formed may be mentioned.

The method of applying the radiation-sensitive resin composition is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an inkjet method. Among these coating methods, a spin coating method and a slit die coating method are preferable. The conditions for prebaking are also different depending on the composition of the radiation-sensitive resin composition, and the like, but for example, the heating temperature can be 60°C to 110°C, and the heating time can be about 30 seconds to 15 minutes. The film thickness of the coating film can be set to 1 µm to 10 µm as a value after prebaking.

[Step (2)]

In this step, the coating film formed in step (1) is irradiated with radiation through a mask having a predetermined pattern. As the radiation used at this time, for example, ultraviolet rays, far ultraviolet rays, X rays, and charged particle rays.

Examples of ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer lasers. Examples of X-rays include synchrotron radiation. As a charged particle beam, an electron beam etc. are mentioned, for example. Among these radiations, ultraviolet rays are preferable, and among ultraviolet rays, radiation containing g-rays and/or i-rays is particularly preferable. As the exposure amount, 6,000 mJ/cm 2 or less is preferable, and 20 mJ/cm 2 to 2,000 mJ/cm 2 is preferable. This exposure amount is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer ("OAI model356" by OAI Optical Associates).

[Step (3)]

In this step, the coating film irradiated with radiation in step (2) is developed. Accordingly, the irradiated portion of the radiation can be removed to form a desired pattern. As the developer used for the developing treatment, an alkaline aqueous solution is preferable. Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, tri Ethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]- 7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane, etc. are mentioned. As a 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 alkali aqueous solution containing a small amount of various organic solvents that dissolve the radiation-sensitive resin composition can be used. As the organic solvent in this case, the same solvent as the polymer [A] or the solvent for obtaining the radiation-sensitive resin composition can be used. The concentration of alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability.

As a developing method, a puddle method, a dipping method, a swing immersion method, a shower method, etc. are mentioned, for example. The developing time varies depending on the composition of the radiation-sensitive resin composition, but is usually about 10 seconds to 180 seconds. Following such a developing treatment, a desired pattern can be formed by performing, for example, washing with flowing water for 30 seconds to 90 seconds, and then air drying with compressed air or compressed nitrogen, for example.

[Step (4)]

In this step, after the step (3), the insulating film is obtained by performing a curing treatment of the coating film by heat treatment (post-baking treatment) on the coating film using a heating device such as a hot plate or an oven. The heating temperature in this heat treatment is, for example, 120°C to 250°C, and the heating time varies depending on the type of heating device. For example, in the case of heating treatment on a hot plate, it is from 5 minutes to It is 30 minutes to 90 minutes when heat-processing in an oven is performed for 30 minutes. At this time, it is also possible to use a step baking method or the like in which two or more heating steps are performed. In this way, the insulating film of the target pattern can be formed on the substrate.

In this step (4), before heating the coating film, a rinse treatment or decomposition treatment may be performed on the patterned coating film. The rinsing treatment can also perform rinsing treatment for washing the coating film using a low hygroscopic solvent listed as a polymerization solvent for synthesizing the polymer [A]. The decomposition treatment is performed to decompose the 1,2-quinonediazide compound remaining in the coating film by irradiating the entire surface with radiation (post-exposure) from a high-pressure mercury lamp or the like. The exposure amount in this post-exposure is preferably about 1,000 mJ/cm 2 to 5,000 mJ/cm 2.

In this way, the insulating film has a low-absorption structure in which the constituent material has a low-absorption structure, and can be treated with a low-hygroscopic compound even in the manufacturing process, and has desirable moisture absorption properties (low water absorption). In addition, it exhibits good properties in terms of PGMEA cleaning properties, permeability, heat resistance, patterning properties, patterning shape properties, development margin properties, radiation sensitivity, resolution, etc. that enable cleaning using PGMEA solvents, and the partition walls of organic EL devices In addition to the insulating film constituting the structure, it can be suitably used as a protective film or an insulating film having a planarization function.

<Organic EL element>

The organic EL device of the present invention includes the insulating film. Hereinafter, the organic EL device will be described with reference to FIG. 1, taking an organic EL display device as an example.

1 is a cross-sectional view schematically showing a structure of a main part of an organic EL display device according to an embodiment of the present invention.

The organic EL display device 1 of Fig. 1 is an active matrix type organic EL display device having a plurality of pixels formed in a matrix shape. The organic EL display element 1 may be of a top emission type or a bottom emission type. The organic EL display device 1 includes a substrate 2, a thin film transistor (hereinafter, also referred to as "TFT") 3, an inorganic insulating film 4, a first insulating film 5, an anode 6, and through A hole 7, a second insulating film 8, an organic light emitting layer 9, a cathode 10, a passivation film 11, and an encapsulation substrate 12 are provided.

<Substrate>

The substrate 2 is made of an insulating material. The insulating material may be selected depending on whether the organic EL display element 1 is of the top emission type or the bottom emission type, that is, whether or not the substrate 2 is required to be transparent. When the organic EL display element 1 is of the bottom emission type, high transparency is required. Therefore, as the insulating material, transparent resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI) with high transparency, and glass such as alkali-free glass are preferable. On the other hand, when the organic EL display element 1 is of the top emission type, an arbitrary insulator can be used as the insulating material, and as in the case of the bottom emission type, it is also possible to use a glass material such as alkali-free glass. .

<TFT>

The TFT 3 is an active element of each pixel portion, and is formed on the substrate 2. The TFT 3 includes a gate electrode 30, a gate insulating film 31, a semiconductor layer 32, a source electrode 33, and a drain electrode 34.

(Gate electrode)

The gate electrode 30 forms part of a scanning signal line (not shown). This gate electrode 30 may be formed as a single layer film or a multilayer film. The thickness of the gate electrode 30 is preferably 10 nm to 1 μm.

The gate electrode 30 can be formed by forming a metal thin film on the substrate 2 by a vapor deposition method, a sputtering method, or the like, and performing patterning using an etching process.

As the material of the metal thin film, for example, aluminum (Al), copper (Cu), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium (Ti), gold (Au), tungsten (W) And metals such as silver (Ag), alloys of these metals, and alloys such as Al-Nd and APC alloys (alloys of silver, palladium, and copper). In the case where the gate electrode 30 is formed as a multilayer film, it is also possible to form the metal thin film by stacking thin films of different materials, such as a stacked film of an Al thin film and a Mo thin film.

The gate electrode 30 may be formed by patterning a metal oxide conductive film or an organic conductive film in place of the metal thin film.

Examples of the material of the metal oxide conductive film include tin oxide, zinc oxide, indium oxide, ITO (Indium Tin Oxide: indium doped tin oxide), and zinc indium oxide (IZO).

Examples of the material for the organic conductive film include conductive organic compounds such as polyaniline, polythiophene, and polypyrrole, and mixtures thereof.

(Gate insulation film)

The gate insulating film 31 covers the gate electrode 30. The gate insulating film 31 can be formed by forming an oxide film or a nitride film by a sputtering method, a CVD method, a vapor deposition method, or the like.

The gate insulating film 31 is formed of, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN. The gate insulating film 31 may be a single insulating film or a stack of a plurality of insulating films. The gate insulating film 31 can also be formed of an organic material such as a polymer material. The thickness of the gate insulating film 31 is preferably 10 nm to 10 µm. In particular, 10 nm to 1 µm is preferable when an inorganic material such as metal oxide is used, and 50 nm to 10 µm is used when an organic material is used. Μm is preferred.

(Semiconductor layer)

The semiconductor layer 32 is disposed on the gate electrode 30 through the gate insulating film 31. This semiconductor layer 32 is connected to the source electrode 33 and the drain electrode 34 and constitutes a channel layer. This channel layer is a portion through which carriers flow and is controlled by the gate electrode 30.

The semiconductor layer 32 can be formed by using, for example, a silicon (Si) material such as a-Si (amorphous-silicon) or p-Si (polysilicon) in an amorphous state. p-Si (polysilicon) is obtained by crystallizing a-Si by excimer laser irradiation, solid phase growth, or the like.

The semiconductor layer 32 can also be formed using an oxide. Examples of the oxide in this case include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof.

As a polycrystalline oxide, zinc oxide (ZnO) etc. are mentioned, for example.

As an amorphous oxide, an amorphous oxide containing at least 1 type of element among indium (In), zinc (Zn), and tin (Sn), etc. is mentioned, for example.

Specific examples of the amorphous oxide include, for example, Sn-In-Zn oxide, In-Ga-Zn oxide (IGZO: indium gallium zinc oxide), In-Zn-Ga-Mg oxide, Zn-Sn oxide (ZTO: zinc oxide Tin), In oxide, Ga oxide, In-Sn oxide, In-Ga oxide, In-Zn oxide (IZO: indium zinc oxide), Zn-Ga oxide, Sn-In-Zn oxide, and the like. In addition, in the amorphous oxide, the composition ratio of the constituent material does not necessarily have to be an equimolar ratio, and it is possible to select a composition ratio that realizes desired characteristics.

For the semiconductor layer 32 of amorphous oxide using IGZO or ZTO, for example, a semiconductor layer is formed by sputtering or evaporation using an IGZO target or a ZTO target, and a resist process and etching using a photolithography method or the like. It is formed by performing patterning by a process. The thickness of the semiconductor layer 32 in this case is preferably 1 nm to 1 μm.

As oxides forming the semiconductor layer 32, zinc oxide (ZnO), indium gallium zinc oxide (IGZO), zinc tin oxide (ZTO), and indium zinc oxide (ZIO) are preferable. By using these oxides, the TFT 3 can have the semiconductor layer 32 excellent in carrier mobility and exhibit a high ON/OFF ratio.

In the case where the semiconductor layer 32 is formed as an oxide layer, in the region of the semiconductor layer 32 where the source electrode 33 and the drain electrode 34 are not formed, for example, a thickness of 5 nm to 80 nm. It is preferable to form a protective layer (not shown) made of SiO ₂ . This protective layer may be referred to as an etching stop layer, a stop layer, or the like.

(Source electrode and drain electrode)

The source electrode 33 is an electrode that serves as a carrier generation source. This source electrode 33 forms a part of a video signal line (not shown) and is connected to the semiconductor layer 32.

The drain electrode 34 receives carriers that move through the semiconductor layer 32 (channel layer), and is connected to the semiconductor layer 32 in the same manner as the source electrode 33.

In addition, whether the source electrode 33 or the drain electrode 34 is determined by, for example, the conductivity type (p-type or n-type) of the semiconductor layer 32, whether it is a high voltage side or a low voltage side when voltage is applied.

The source electrode 33 and the drain electrode 34 may be formed as a single layer film or a multilayer film. The thickness of the gate electrode 30 is preferably 10 nm to 1 μm.

The source electrode 33 and the drain electrode 34 can be formed by forming a conductor film by a method such as a printing method, a coating method, a sputtering method, a CVD method, or a vapor deposition method, and then patterning using a photolithography method or the like. .

As a constituent material of the source electrode 33 and the drain electrode 34, for example, metals such as Al, Cu, Mo, Cr, Ta, Ti, Au, W, and Ag, alloys of these metals, Al-Nd, and Metal materials, such as an alloy, such as APC, are mentioned. When the source electrode 33 and the drain electrode 34 are configured as a multilayer film, it is also possible to form a stack of thin films of different materials, such as a stacked film of a Ti thin film and an Al thin film.

As a constituent material of the source electrode 33 and the drain electrode 34, a conductive metal oxide or a conductive organic compound may be used instead of a metal material. Examples of the conductive metal oxide include tin oxide, zinc oxide, indium oxide, ITO, indium zinc oxide (IZO), AZO (aluminum doped zinc oxide), and GZO (gallium doped zinc oxide). As a conductive organic compound, polyaniline, polythiophene, polypyrrole, etc. are mentioned, for example.

<Inorganic insulation film>

The inorganic insulating film 4 is for protecting the semiconductor layer 32, for example, to prevent the semiconductor layer 32 from being affected by humidity. This inorganic insulating film 4 is formed so as to cover the entire TFT 3.

The inorganic insulating film 4 is formed of, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN. The inorganic insulating film 4 may be a single insulating film or a stack of a plurality of insulating films. The inorganic insulating film 4 may be omitted when forming the first insulating layer 5.

<1st insulating film>

The first insulating film 5 serves to flatten the surface irregularities of the TFT 3. This first insulating film 5 is formed on the inorganic insulating film 4 so as to cover the entire TFT 3.

The first insulating film 5 is a cured film having insulating properties formed using the radiation-sensitive resin composition. This first insulating film 5 is formed as an organic insulating film because the radiation-sensitive resin composition is an organic material. The first insulating film 5 is formed by a method or the like described in <Method of forming an insulating film>.

It is preferable that the thickness of the first insulating film 5 is increased so as to exhibit an excellent function as a planarization film. The thickness of the first insulating film 5 is preferably 1 µm to 6 µm.

<Anode>

The anode 6 constitutes a pixel electrode. This anode 6 is formed on the first insulating film 5 by a conductive material. As the conductive material, it may be selected according to whether the organic EL display element 1 is of the top emission type or the bottom emission type, that is, whether the anode 6 is required to be transparent or light reflectivity is required. In the case of the bottom emission type, the anode 6 is required to be transparent. Therefore, as the material of the anode 6, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and tin oxide having high transparency are preferable. On the other hand, when the organic EL display element 1 is of the top emission type, the anode 6 is required to have light reflectivity. Therefore, as the material of the anode 6, APC alloy (alloy of silver, palladium, copper), ARA (alloy of silver, rubidium, gold), MoCr (alloy of molybdenum and chromium), NiCr (nickel) with high light reflectivity And an alloy of chromium) and the like are preferred. The thickness of the anode 6 is preferably 100 nm to 500 nm.

<Through hole>

The through hole 7 is for connecting the anode 6 and the second source-drain electrode 34. This through hole 7 is formed so as to penetrate the inorganic insulating film 4 under the first insulating film 5 as well.

The through hole 7 can be formed by dry etching the inorganic insulating film 4 after forming the first insulating film 5 having a desired shape through hole. Here, the first insulating film 5 is formed by the same method as the method described in the above-described <Method of Forming an Insulating Film> using the radiation-sensitive resin composition. Therefore, the through hole constituting the through-hole 7 can be formed by irradiating and developing radiation to the coating film of the radiation-sensitive resin composition. Dry etching of the inorganic insulating film 4 can be performed using the first insulating film 5 as a mask. Accordingly, as a result of forming a through hole communicating with the through hole of the first insulating film 5 in the inorganic insulating film 4, a through hole 7 penetrating the first insulating film 5 and the inorganic insulating film 4 is formed. .

Further, in the case of a structure in which the inorganic insulating film 4 is not disposed on the TFT 3, through-holes formed by irradiation and development of radiation to the first insulating film 5 constitute the through hole 7. As a result, the anode 6 covers at least a portion of the first insulating film 5 and at the same time, the through hole 7 formed in the first insulating film 5 is interposed therebetween, 2 Can be connected to the drain electrode 34.

<Second insulating film>

The second insulating film 8 serves as a partition wall having a concave portion 80 that defines an arrangement region of the organic light-emitting layer 9. This second insulating film 8 is formed so as to cover a part of the anode 6 and expose a part of the anode 6. Such a second insulating film 8 is formed by the method described in the above-described <Method of Forming an Insulating Film> using the radiation-sensitive resin composition. The second insulating film 8 can be formed as a matrix in which a plurality of concave portions 80 in which the organic light-emitting layer 9 is formed are arranged in a plan view by patterning the coating film by exposure and development. .

The concave portion 80 is coated with a light emitting material composition in an ink state by, for example, an ink jet method, as described later. In this case, it is desired that at least the inner surface of the concave portion 80 of the second insulating film 8 has low wettability (high water repellency). Methods of improving the wettability of the second insulating film 8 include a method of plasma treating the second insulating film 8 with fluorine gas, and a method of improving the liquid repellency of the radiation-sensitive resin composition. Among these methods, since the plasma treatment may adversely affect other constituent members of the organic EL display element 1, a method of increasing the liquid repellent of the radiation-sensitive resin composition is preferable.

The thickness T1 of the second insulating film 8 (distance between the upper surface of the second insulating film 8 and the upper surface of the organic light emitting layer 9) is preferably 0.1 μm or more and 2 μm or less, and 0.8 μm or more and 1.2 μm or less. desirable. When the thickness of the second insulating film 8 exceeds 2 μm, there is a fear that the second insulating film 8 may come into contact with the encapsulation substrate 12. On the other hand, if the thickness of the second insulating film 8 is less than 0.1 μm, when forming the organic light emitting layer 9 to be described later, when applying the light emitting material composition to the concave portion 80 of the second insulating film 8, light emission There is a fear that the material composition may leak from the concave portion 80.

<Organic light emitting layer>

The organic light-emitting layer 9 emits light by applying an electric field. This organic light-emitting layer 9 is a layer containing an organic light-emitting material that emits light. The organic light-emitting layer 9 is formed in a region defined by the second insulating film 8, that is, in the concave portion 80. In this way, by forming the organic light-emitting layer 9 in the concave portion 80, the periphery of the organic light-emitting layer 9 is surrounded by the second insulating film 8, and a plurality of adjacent pixels can be partitioned.

The organic light-emitting layer 9 is formed by filling the concave portion 80 of the second insulating film 8 with an organic light-emitting material. Although there is no particular limitation as a method of filling the concave portion 80 with the organic light-emitting material, an ink jet method is preferable.

The organic light-emitting material may be a low-molecular organic light-emitting material or a high-molecular organic light-emitting material. For example, a material in which a base material such as Alq ₃ and BeBq ₃ is doped with quinacridone or coumarin may be mentioned. When filling with an organic light-emitting material by an ink jet method, a high-molecular organic light-emitting material is preferable. Examples of the polymer organic light emitting material include polyphenylenevinylene and derivatives thereof, polyacetylene, derivatives thereof, polyphenylene, derivatives thereof, and poly(para-phenylene- ethylene)), derivatives thereof, poly(3-hexylthiophene) (P3HT)), derivatives thereof, polyfluorene (PF), derivatives thereof, and the like.

The organic light-emitting layer 9 is formed in contact with the anode 6 in the concave portion 80 of the second insulating film 8. The thickness T2 of the organic light-emitting layer 9 is preferably 50 nm to 100 nm. Here, the thickness T2 of the organic light-emitting layer 9 means the distance from the bottom surface of the organic light-emitting layer 9 on the anode 6 to the upper surface of the organic light-emitting layer 9 on the anode 6.

Further, a hole injection layer and/or an intermediate layer may be disposed between the anode 6 and the organic light emitting layer 9. When the hole injection layer and the intermediate layer are disposed between the anode 6 and the organic light emitting layer 9, the hole injection layer is disposed on the anode, the intermediate layer is disposed on the hole injection layer, and the organic light-emitting layer is disposed on the intermediate layer. The light-emitting layer 9 is disposed. In addition, as long as holes can be efficiently transported from the anode to the organic light-emitting layer, the hole injection layer and the intermediate layer may be omitted.

<cathode>

The cathode 10 is formed by covering a plurality of pixels in common, and forms a common electrode of the organic EL display element 1. This cathode 10 is made of a conductive member. The material for forming the cathode 10 may be selected according to whether the organic EL display element 1 is of a top emission type or a bottom emission type, that is, whether or not a transparent cathode 10 is obtained. In the case of a top emission type, the cathode 10 is preferably an ITO electrode or an IZO electrode constituting an electrode having visible light transmission. On the other hand, when the organic EL display device 1 is of the bottom emission type, the cathode 10 need not be transparent to visible light. In that case, the constituent material of the cathode 10 is not particularly limited as long as it is conductive, but for example, it is possible to select an alloy containing barium (Ba), barium oxide (BaO), aluminum (Al), and Al. Do.

Further, an electron injection layer made of, for example, barium (Ba) or lithium fluoride (LiF) may be disposed between the cathode 10 and the organic light emitting layer 9.

<passivation film>

The passivation film 11 suppresses intrusion of moisture or oxygen into the organic EL display element 1. This passivation film 11 is formed on the cathode 10. The passivation film 11 is formed using a metal nitride such as SiN or aluminum nitride (AlN). The passivation film 11 may be a single insulating film or a laminate of a plurality of insulating films.

<Encapsulation substrate>

The sealing substrate 12 seals the main surface (the side opposite to the substrate 2) on which the organic light-emitting layer 9 is disposed. As the sealing substrate 12, a glass substrate such as alkali-free glass is used. It is preferable that the sealing substrate 12 be sealed with the sealing substrate 12 through the sealing layer 13 using a sealing agent (not shown) applied to the vicinity of the outer peripheral end. The sealing layer 13 can be a layer of an inert gas such as dried nitrogen gas, or a layer of a filling material such as an adhesive.

In the organic EL display device 1 of the present embodiment, the first insulating film 5 and the second insulating film 8 are formed using the radiation-sensitive resin composition having low hygroscopicity, and these insulating films 5 and 8 In the formation step of ), a treatment such as washing using a material having low hygroscopicity can be performed. Therefore, a small amount of moisture contained in the insulating film-forming material in the form of adsorbed water or the like can be reduced to gradually invade the organic light-emitting layer 9, thereby reducing deterioration of the organic light-emitting layer 9 and deterioration of the light-emitting state.

[Example]

Hereinafter, embodiments of the present invention will be described in detail based on examples, but the present invention is not limitedly interpreted by these examples.

<Synthesis of polymer [A] (polymer (A-1))>

[Synthesis Example 1]

After 340 g of γ-butyrolactone as a polymerization solvent was added, 50 g of propylene glycol monoethyl ether acetate was added, and 2,2'-bis(3-amino-) as a diamine compound was added so that the solid content concentration was 35% with respect to the total 390 g of the polymerization solvent. 120 g of 4-hydroxyphenyl)hexafluoropropane was added to the polymerization solvent. After dissolving the diamine compound, 71 g of 4,4-oxydiphthalic acid as an acid dianhydride was added. Thereafter, after reacting at 60° C. for 1 hour, 19 g of maleic anhydride was added as an end-sealing agent, followed by further reacting at 60° C. for 1 hour, followed by heating and reacting at 180° C. 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 84 g of a polyimide solution containing the polymer (A-1) was obtained.

For the polyimide solution containing the polymer (A-1) prepared by using a good solvent of the polymer (A-1) to a concentration of 10% by mass, an E-type rotational viscometer ("RE215" by Tokisan Corporation) Using, the solution viscosity was measured as a value after 10 minutes at 25°C. The solution viscosity of the polyimide solution containing the polymer (A-1) was 100 mPa·s as a value at a solid content concentration of 40.0%.

<Synthesis of [C] condensed cyclic compounds (naphthalene type phenol resins (C1-1) to (C1-3), anthracene type phenol resins (C2-1) and (C2-2))>

[Synthesis Example 2] (Synthesis of naphthalene-type phenol resin (C1-1))

Into a flask equipped with a thermometer, a cooling tube, a separator tube, and a stirrer, 144 g (1.0 mol) of 1-naphthol, 400 g of methyl isobutyl ketone, 96 g of water, and 27.7 g (0.85 mol) of 92 mass% paraformaldehyde were placed. Next, 4.8 g of an aqueous solution of paratoluenesulfonic acid adjusted to a concentration of 50% was added while stirring. The amount of water in the reaction system is 62.9 parts by mass per 100 parts by mass of 1-naphthol. Then, it heated up to 80 degreeC, stirring and was made to react for 2 hours. During the reaction, the organic layer and the aqueous layer were not completely compatible with "uniformity", but were "non-uniformity". After completion of the reaction, the solution in the system was transferred to a separation lot, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water exhibits neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 165 g of a naphthalene-type phenol resin (C1-1) having a structural unit derived from 1-naphthol represented by the following formula.

As a result of GPC analysis of the naphthalene-type phenol resin (C1-1), the total content of the product having a number average molecular weight (Mn) of less than 300 in the naphthalene-type phenol resin (C1-1) was 2.5% by mass in total, and The content rate of 1-naphthol) in the reaction was 0.51% by mass. In addition, from the chart of the product by electric field separation mass spectrometry (FD-MS), it was possible to confirm the elongated product by methylene bond compared to the raw material. In addition, from the measurement chart with a Fourier transform infrared spectrophotometer (FT-IR), absorption (1,250 cm ^-1 ) derived from an aromatic ether could not be confirmed. For this reason, in the present synthesis example, it was estimated that a naphthalene-type phenol resin having a methylene bond was obtained without causing a dehydration etherification reaction (a loss of a hydroxyl group) between hydroxyl groups. In addition, the weight average molecular weight (Mw) of the naphthalene type phenol resin (C1-1) was 2,300.

[Synthesis Example 3] (Synthesis of naphthalene-type phenol resin (C1-2))

In a flask equipped with a thermometer, a cooling tube, a separator tube, and a stirrer, 648 g (4.5 mol) of 1-naphthol, 201 g (1.5 mol) of terephthalaldehyde, and 0.45 g of trifluoromethanesulfonic acid were put. Subsequently, the reaction was performed at 150°C to 160°C for 4 hours while stirring. Water produced in this reaction was sequentially trapped and removed out of the system. After completion of the reaction, unreacted 1-naphthol was removed by distillation under reduced pressure to obtain 682 g of naphthalene-type phenol resin (C1-2) represented by the following formula.

As a result of GPC analysis of naphthalene-type phenol resin (C1-2), the total content of the product having a number average molecular weight (Mn) of less than 300 in this naphthalene-type phenol resin (C1-2) was 2.5%, and residual monomers (unreacted The content rate of 1-naphthol) was 0.50%. In addition, from the chart of the product by electric field separation mass spectrometry (FD-MS), it was possible to confirm the elongated product by methylene bond compared to the raw material. In addition, from the measurement chart with a Fourier transform infrared spectrophotometer (FT-IR), absorption (1,250 cm ^-1 ) derived from an aromatic ether could not be confirmed. For this reason, in the present synthesis example, it was estimated that a naphthalene-type phenol resin having a methylene bond was obtained without causing a dehydration etherification reaction (a loss of a hydroxyl group) between hydroxyl groups. In addition, the weight average molecular weight (Mw) of the naphthalene type phenol resin (C1-2) was 2,000.

[Synthesis Example 4] (Synthesis of naphthalene-type phenol resin (C1-3))

In a flask equipped with a thermometer, a cooling tube, a separator tube, and a stirrer, 721 g (4.5 mol) of 1,4-naphthalenediol, 201 g (1.5 mol) of terephthalaldehyde, and 0.45 g of trifluoromethanesulfonic acid were placed. Subsequently, the reaction was performed at 150°C to 160°C for 4 hours while stirring. Water produced in this reaction was sequentially trapped and removed out of the system. After completion of the reaction, unreacted 1,4-naphthalenediol was removed by distillation under reduced pressure to obtain 690 g of naphthalene-type phenol resin (C1-3) represented by the following formula.

As a result of GPC analysis of the naphthalene-type phenol resin (C1-3), the total content of the product having a number average molecular weight (Mn) of less than 300 in this naphthalene-type phenol resin (C1-3) was 2.5%, and the residual monomer (unreacted The content rate of 1,4-naphthalenediol) was 0.50%. In addition, from the chart by the electric field desorption mass spectrometry (FD-MS) of the product, it was possible to confirm the elongated product by methylene bond compared with the raw material. In addition, from the measurement chart with a Fourier transform infrared spectrophotometer (FT-IR), absorption (1,250 cm ^-1 ) derived from an aromatic ether could not be confirmed. For this reason, in this synthesis example, it was estimated that the dehydration etherification reaction (hydroxyl group disappearance) between hydroxyl groups did not occur, and a naphthalene-type phenol resin having a methylene bond was obtained. In addition, the weight average molecular weight (Mw) of the naphthalene-type phenol resin (C1-3) was 1,800.

[Synthesis Example 5] (Synthesis of anthracene type phenol resin (C2-1))

In a flask equipped with a thermometer, a cooling tube, a separator tube, and a stirrer, 194 g (1.0 mol) of 1-antrol, 400 g of methyl isobutyl ketone, 96 g of water and 27.7 g (0.85 mol) of 92% paraformaldehyde were put. Then, 4.8 g of an aqueous solution of paratoluenesulfonic acid adjusted to a concentration of 50% was added while stirring. The amount of water in the reaction system is 62.9 parts by mass per 100 parts by mass of 1-antrol. Then, it heated up to 80 degreeC, stirring and was made to react for 2 hours. During the reaction, the organic layer and the aqueous layer were not completely compatible with "uniformity", but were "non-uniformity". After completion of the reaction, the solution in the system was transferred to a separation lot, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 202 g of an anthracene-type phenol resin (C2-1) having a structural unit derived from 1-anthrol represented by the following formula.

As a result of GPC analysis of anthracene-type phenol resin (C2-1), the total content of the product having a number average molecular weight (Mn) of less than 300 in this anthracene-type phenol resin (C2-1) was 2.5%, and residual monomers (unreacted The content rate of 1-antrol) was 0.50%. In addition, from the chart by the electric field desorption mass spectrometry (FD-MS) of the product, it was possible to confirm the elongated product by methylene bond compared with the raw material. In addition, from the measurement chart with a Fourier transform infrared spectrophotometer (FT-IR), absorption (1,250 cm ^-1 ) derived from an aromatic ether could not be confirmed. For this reason, in this synthesis example, it was estimated that the dehydration-etherification reaction (hydroxyl group disappearance) did not occur between the hydroxyl groups, and an anthracene-type phenol resin having a methylene bond was obtained. Moreover, the weight average molecular weight (Mw) of the anthracene type phenol resin (C2-1) was 2,000.

[Synthesis Example 6] (Synthesis of anthracene-type phenol resin (C2-2))

To a flask equipped with a thermometer, a cooling tube, a separator tube, and a stirrer, 210 g (1.0 mol) of 1,4-anthracenediol, 400 g of methyl isobutyl ketone, 96 g of water and 27.7 g (0.85 mol) of 92% paraformaldehyde were placed. Then, 4.8 g of an aqueous solution of paratoluenesulfonic acid adjusted to a concentration of 50% was added while stirring. The amount of water in the reaction system is 62.9 parts by mass with respect to 100 parts by mass of 1,4-anthracenediol. Then, it heated up to 80 degreeC, stirring and was made to react for 2 hours. During the reaction, the organic layer and the aqueous layer were not completely compatible with "uniform", but were "non-uniform". After completion of the reaction, the solution in the system was transferred to a separation lot, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 220 g of an anthracene-type phenol resin (C2-2) having a structural unit derived from 1,4-anthracenediol represented by the following formula. .

As a result of GPC analysis of the anthracene-type phenol resin (C2-2), the total content of the product having a number average molecular weight (Mn) of less than 300 in this anthracene-type phenol resin (C2-2) was 2.5%, and the residual monomer (unreacted The content rate of 1,4-anthracenediol) was 0.50%. In addition, from the chart by the electric field desorption mass spectrometry (FD-MS) of the product, it was possible to confirm the elongated product by methylene bond compared with the raw material. In addition, from the measurement chart with a Fourier transform infrared spectrophotometer (FT-IR), absorption (1,250 cm ^-1 ) derived from an aromatic ether could not be confirmed. For this reason, in this synthesis example, it was estimated that the dehydration-etherification reaction (hydroxyl group disappearance) did not occur between the hydroxyl groups, and an anthracene-type phenol resin having a methylene bond was obtained. Moreover, the weight average molecular weight (Mw) of the anthracene type phenol resin (C2-2) was 2,000.

<Preparation of radiation-sensitive resin composition>

[A] polymer, [B] radiation-sensitive acid generator, [C] condensed cyclic compound ([C1] naphthalene-type phenol resin and [C2] anthracene-type phenol resin) used to prepare a radiation-sensitive resin composition, [D] The cationic polymerizable compound, [E] solvent, [F] adhesion aid, [G] surfactant, [H] crosslinking agent, and [I] heat-sensitive acid generator are as follows.

<[A] Polymer>

A-1: Polymer of Synthesis Example 1 (A-1)

<[B] Radiation-sensitive acid generator>

B-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonedia Condensation product of gide-5-sulfonic acid chloride (2.0 mol) ("MILNESS-AC" by Toyo Kosei Kogyo)

<[C] Condensed cyclic compound>

[[C1] Naphthalene-type phenolic resin]

C1-1: Phenol resin of Synthesis Example 2 (C1-1)

C1-2: Phenol resin of Synthesis Example 3 (C1-2)

C1-3: Phenol resin of Synthesis Example 4 (C1-3)

[[C2] Anthracene type phenolic resin]

C2-1: Phenol resin of Synthesis Example 5 (C2-1)

C2-2: Phenol resin of Synthesis Example 6 (C2-2)

[D] Cationic polymerizable compound

D-1: 4,4-bis[(3-ethyl-3-oxetanyl)methyl]biphenyl ("OXBP" from Ubekosan)

[E] solvent

E-1: mixed solvent of 30:20:50 by mass ratio of BL, PGMEA and PGME

E-2: mixed solvent of 50:10:40 in mass ratio of BL, PGMEA and PGME

E-3: mixed solvent of 60:10:30 by mass ratio of BL, PGMEA and PGME

[F] Adhesion aid

F-1: N-phenyl-3-aminopropyltrimethoxysilane ("KBM-573" from Shin-Etsu Chemical Co., Ltd.)

[G] surfactant

G-1: Tore Dow Corning's "SH8400"

[H] crosslinking agent

H-1: Gunei Kagaku's "C-357"

[I] Thermal acid generator

I-1: Sanshin Kagaku's "SI-110L"

[Example 1]

To a polymer solution containing the polymer (A-1) of Synthesis Example 1 (amount equivalent to 100 parts by mass (solid content) of the polymer (A-1)), [B] as a radiation-sensitive acid generator (B-1) 20 Parts by mass, [C] 30 parts by mass of a naphthalene-type phenol resin (C1-1) as a condensed cyclic compound, [D] 30 parts by mass as a cationic polymerizable compound, [F] as an adhesive (F-1 ) 5 parts by mass, [G] as surfactant (G-1) 0.1 parts by mass, [H] crosslinking agent as (H-1) 10 parts by mass, [I] heat sensitive acid generator as (I-1) 1 mass (E-1) was mixed as a subsidiary and [E] solvent, and the solid content concentration was set to 28 mass %, and it filtered with a 0.2 micrometers membrane filter, and the radiation-sensitive resin composition was prepared.

[Examples 2 to 13 and Comparative Examples 1 to 6]

A radiation-sensitive resin composition was prepared in the same manner as in Example 1, except that each component of the kind and compounding amount shown in Table 1 was used. In addition, in Table 1, "-" means that the said component is not mixed.

[evaluation]

For the radiation-sensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 6, the composition, insulating film, and device properties were evaluated by the method described below.

[Evaluation of composition]

The composition was evaluated in terms of patterning property, pattern shape, radiation sensitivity, and resolution.

<Patternability>

After coating the radiation-sensitive resin composition on a silicon substrate using a spinner or a slit die coater, it was prebaked on a hot plate at 120° C. for 2 minutes to form a coating film having a thickness of 3 μm. The coating film was exposed at an exposure amount of 100 mJ/cm 2 using an exposure machine ("MPA-6000" manufactured by Canon) through a pattern mask. After that, it was developed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25° C. for 80 seconds by a puddle method, washed with ultrapure water for 1 minute, and dried to open a plurality of through holes having a diameter of 20.0 μm on the wafer. Insulation patterns arranged in shape were formed. At this time, it is confirmed that the pattern of the through-hole completely dissolves, and the development residual film rate is 80% or more, and the pattern formed without peeling off is "good", the residual film rate after development is less than 80%, or the pattern is formed by peeling off. What doesn't work was called "bad".

<Pattern shape>

In the same manner as in the above patterning evaluation, a coating film having a plurality of through holes arranged in a line shape was formed on a silicon substrate. This coating film was cured by heating at 250° C. for 45 minutes in a clean oven to obtain an insulating film having a thickness of 3 μm. In this insulating film, a vertical cross-sectional shape in a direction orthogonal to a line of a plurality of through holes was observed by SEM ("SU3500" by Hitachi High-Technology). In the case where the bottom of the vertical section has the maximum line width, that is, when a forward taper shape is formed, it was said to be "good", and if not, it was said to be "defective".

<Radiation sensitivity>

After coating the radiation-sensitive resin composition on a silicon substrate using a spinner or a slit die coater, it was prebaked on a hot plate at 120° C. for 2 minutes to form a coating film having a thickness of 3 μm. With respect to this coating film, exposure was performed using an exposure machine ("MPA-6000" manufactured by Canon) by changing the exposure amount through a pattern mask having a predetermined pattern. Thereafter, it was developed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25° C. for 80 seconds by a puddle method, washed with ultrapure water for 1 minute, and dried to have a plurality of through holes having a diameter of 20.0 μm on the silicon substrate. Formed an insulating pattern. The exposure amount required to completely dissolve the 20.0 µm through-hole pattern was measured, and the exposure amount at this time was taken as radiation sensitivity (exposure sensitivity). When the radiation sensitivity was 100 mJ/cm 2 or less, it was "good" and when it exceeded 100 mJ/cm 2, it was referred to as "defective".

<Resolution>

After coating the radiation-sensitive resin composition on a silicon substrate using a spinner or a slit die coater, it was prebaked on a hot plate at 120° C. for 2 minutes to form a coating film having a thickness of 3 μm. The coating film was exposed at an exposure amount of 100 mJ/cm 2 using an exposure machine ("MPA-6000" manufactured by Canon) through a pattern mask having a hole pattern diameter of 5 μm to 50 μm. Thereafter, it was developed by a puddle method at 25° C. for 80 seconds in a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with ultrapure water for 1 minute, and a vertical cross-sectional shape in a direction orthogonal to the lines of a plurality of through holes was obtained by SEM ( It observed with "SU3500" of Hitachi High-Technology), and the low width|variety of this cross section was measured. It can be said that the resolution is better as the lower width is smaller.

[Evaluation of insulating film properties]

The insulating film was evaluated as light-shielding property, water absorption, and heat resistance.

<Light-shielding property>

An insulating film was formed in the same manner as in the evaluation of <radiation sensitivity> except for using a glass substrate ("corning 7059" by Corning) instead of the silicon substrate. For the glass substrate having this insulating film, the total light transmittance was measured in a wavelength range of 380 nm to 780 nm using a spectrophotometer ("150-20 double beam" manufactured by Hitachi Corporation). The shading rate was calculated. The light-shielding property was said to be "good" when the light-shielding rate was 50% or less, and "defective" when the light-shielding rate exceeded 50%.

<absorbency>

After coating the radiation-sensitive resin composition on the silicon substrate using a spinner or a slit die coater, pre-baking on a hot plate at 120°C for 2 minutes, and post-baking at 250°C for 45 minutes in a clean oven to a film thickness of 3 μm. Formed a coating film of. Desorption from the sample surface and sample when the cured film was heated from room temperature to 200°C at a vacuum degree of 1.0×10 ^-9 Pa using a thermal desorption spectroscopy (“TDS1200” from ESCO). The measured gas was measured for the detection value of the peak of water (M/z = 18) with a mass spectrometer ("5973N" by Agilent Technologies). The integral value of the total peak intensity of 60°C to 200°C was taken, and the water absorption was evaluated. Absorptivity was referred to as "good" when the integral value of the total peak intensity of 60°C to 200°C was 1.0×10 ⁻⁷ or less, and “bad” when it exceeded 1.0×10 ⁻⁷ .

<Heat resistance>

In the same manner as in the evaluation of water absorption, a cured film was formed using a radiation-sensitive resin composition, and the cured film was measured for TGA at 100°C to 500°C using a thermogravimetric measuring device (“TGA2950” by TA Instruments). Below, the 5% weight loss temperature was calculated|required by performing the temperature rising rate 10 degreeC/min). Heat resistance was said to be "good" when the 5% weight loss temperature was 350°C or higher, and "defective" when it was below 350°C.

[Evaluation of device characteristics]

The element characteristics were evaluated as switching response characteristics and TFT reliability using an evaluation element prepared by the method described below.

<Production of element for evaluation>

The evaluation element was produced by forming a TFT on a glass substrate ("Corning 7059" by Corning) to produce a TFT substrate, and then forming an insulating film on the TFE substrate.

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 on the entire surface of the substrate by sputtering on the upper layer of the gate electrode to obtain a gate insulating film. On this gate insulating film, an InGaZnO-based amorphous oxide film (InGaZnO ₄ ) was formed 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 on the entire surface of the substrate by sputtering on the upper layers of the source electrode and the drain electrode to obtain a passivation film, thereby obtaining a TFT substrate.

On the other hand, the insulating film is pre-baked on a hot plate at 120°C for 2 minutes after coating the radiation-sensitive resin composition on a TFT substrate using a spinner or a slit die coater, and then post-baked at 250°C for 45 minutes in a clean oven. As a result, it was formed to have a thickness of 3.0 µm.

<Switching response characteristics>

The switching response characteristic was evaluated by measuring the ON/OFF ratio. The ON/OFF ratio was calculated by measuring the current flowing between the source electrode and the drain electrode in a state in which a voltage was applied to the gate electrode of the element for evaluation using a prober and a semiconductor parameter analyzer. Specifically, under the condition that the semiconductor film of the evaluation element is irradiated with white light (illuminance 30000 lux) centered at a wavelength of 450 nm or 500 nm from above, the potential of the drain electrode is +10 V and the potential of the source electrode is 0 V. In one case, the ratio of the current value when the voltage applied to the gate electrode is +10V and -10V was taken as the ON/OFF ratio. The switching response characteristic was said to be "good" when the ON/OFF ratio was 1.0 x 10 ⁵ or more, and "defective" when it was less than 1.0 x 10 ⁵ .

<TFT reliability>

TFT reliability is evaluated by comparing the change in 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 between the light irradiation and the light ratio irradiation to the evaluation element. did.

(Measurement of Id-Vg characteristics and threshold voltage Vth)

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

(Measurement of change in threshold voltage Vth)

Electrical stress was applied by applying a positive voltage of +20V and a negative voltage of -20V for 12 hours between the gate electrode and the source electrode, respectively. Such electrical stress was performed for each of the conditions in which the semiconductor film of the evaluation element was irradiated with light from above and the semiconductor film was not irradiated with light. The amount of change in the threshold voltage Vth was calculated from the Id-Vg characteristics for each of the light irradiation condition and the light ratio irradiation condition. In addition, when the amount of change in the threshold voltage Vth during light irradiation is suppressed to less than twice the amount of change in the threshold voltage Vth during light ratio irradiation, the TFT reliability is said to be "good" and exceeds 2 times. The TFT reliability was said to be "poor".

As shown in Table 2, the radiation-sensitive resin compositions of Examples 1 to 13 were excellent in patterning properties, pattern shapes, and radiation sensitivity. In addition, the insulating films formed from the radiation-sensitive resin compositions of Examples 1 to 13 had excellent absorbency, light-shielding properties, and heat resistance, and the device using this insulating film had excellent device characteristics (switching response characteristics and TFT reliability).

On the other hand, the radiation sensitivity of the radiation-sensitive resin compositions of Comparative Examples 1 to 6 was inferior. In addition, the insulating film formed of the radiation-sensitive resin composition of Comparative Examples 1 to 6 is inferior in absorbency and light-shielding property, and at the same time, the device using this insulating film is inferior in device characteristics (switching response characteristics and TFT reliability). Became.

According to the present invention, radiation-sensitive radiation capable of forming an insulating film having excellent heat resistance or absorption characteristics, while satisfying the properties required for a radiation-sensitive resin composition such as radiation sensitivity and patterning property, and not reducing productivity. It is possible to provide a resin composition. Therefore, the radiation-sensitive resin composition can be suitably used for an insulating film of an organic EL device.

1: organic EL display element
2: substrate
3: TFT
30: gate electrode
31: gate insulating film
32: semiconductor layer
33: source electrode
34: drain electrode
4: inorganic insulating film
5: first insulating film (planarization film)
6: anode
7: through hole
8: second insulating film (partition wall)
80: recess
9: organic light emitting layer
10: cathode
11: passivation film
12: encapsulation substrate
13: encapsulation layer

Claims (8)

As a radiation-sensitive resin composition used for forming an insulating film,
At least one polymer selected from the group consisting of a polyimide having a structural unit represented by the following formula (1) and a precursor of this polyimide,
Radiation-sensitive acid generator,
A condensed cyclic compound having a phenolic hydroxyl group, and
It contains a compound containing a cationic polymerizable group,
The content of the condensed cyclic compound is 5 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the polymer,
The compound containing the cationic polymerizable group has two or more oxetanyl groups in one molecule, and the content of the compound containing the cationic polymerizable group is 1 part by mass or more and 70 parts by mass per 100 parts by mass of the polymer. The following radiation-sensitive resin composition:

(In formula (1), R ¹ is a divalent group having a hydroxyl group; X is a tetravalent organic group). The method of claim 1,
The radiation-sensitive resin composition, wherein the condensed cyclic compound is a phenolic resin having at least one selected from the group consisting of a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2):

(In formulas (2-1) and (2-2), 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 an aralkyl having 4 to 30 carbon atoms. Is a ren group; a to e are each independently an integer of 0 to 2; provided, however, that a and b are not all 0, and c to e are not all 0). delete The method of claim 1,
The radiation-sensitive resin composition in which R ¹ is any of a plurality of divalent groups represented by the following formula.

The method of claim 1,
It further contains a solvent, and this solvent,
γ-butyrolactone and,
Diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, and propylene glycol monoalkyl ether propionate selected from the group consisting of A radiation-sensitive resin composition containing at least one type. An insulating film of an organic EL device formed of the radiation-sensitive resin composition according to any one of claims 1, 2, 4, and 5. An insulating film of an organic EL device comprising a step of forming a coating film on a substrate, a step of irradiating at least a portion of the coating film with radiation, a step of developing the radiation-irradiated coating film, and a step of heating the developed coating film. As a method of formation,
A method for forming an insulating film, wherein the coating film is formed of the radiation-sensitive resin composition according to any one of claims 1, 2, 4, and 5. An organic EL device comprising the insulating film according to claim 6.

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