JP2015215397A - Radiation-sensitive resin composition, insulating film, method of producing the same, and organic el element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition capable of forming an insulating film having a light-shielding property at a wavelength of 400 nm and low water absorptivity.SOLUTION: The radiation-sensitive resin composition contains: (A) at least one polymer selected from a polyimide having a structural unit represented by formula (A1), a precursor (A2) of the polyimide, and a specific alkali-soluble polymer (A3); (B) a radiation-sensitive acid generator; (C) a novolac resin; (D) a compound having an isocyanate group blocked with a protecting group; and (E) a solvent. [In the formula (A1), Ris a divalent group having a hydroxyl group, and X is a tetravalent organic group.]

Description

  The present invention relates to a radiation-sensitive resin composition, an insulating film, a method for producing the same, and an organic EL element. More specifically, the present invention relates to a radiation-sensitive resin composition that is suitably used when forming an insulating film for an organic EL element.

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

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

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

  However, IGZO is known to suffer light degradation due to natural light, lighting, manufacturing processes, and the like. For this reason, when a TFT including a semiconductor layer made of a material having a large light deterioration such as IGZO is used as a driving element for a display or lighting device, particularly a driving element for an organic EL element, from the viewpoint of preventing light deterioration of IGZO, As a characteristic of the above-described insulating film, it is required to impart light shielding properties from ultraviolet to visible light. However, many insulating films that are currently used are transparent at a wavelength of, for example, 400 nm, and a light blocking function is required.

  Moreover, in an organic EL element, it is known that when an organic light emitting layer comes into contact with moisture, the organic light emitting layer quickly deteriorates and luminance decreases. It is conceivable that the moisture is derived from a small amount of moisture contained in the insulating film forming material in the form of adsorbed water or the like. For this reason, low water absorption is also required for the insulating film forming material.

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

  An object of the present invention is to provide a radiation-sensitive resin composition capable of forming an insulating film having light shielding properties at a wavelength of 400 nm and having low water absorption.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by adopting the following configuration, and have completed the present invention. The present invention relates to the following [1] to [11], for example.

  [1] A polyimide (A1) having a structural unit represented by the formula (A1), a precursor (A2) of the polyimide, a radical polymerizable monomer (a3-1) having an epoxy group or an oxetanyl group, and a carboxyl group. At least selected from an alkali-soluble polymer (A3) obtained by polymerizing a radical polymerizable monomer (a3-2) having, and another radical polymerizable monomer (a3-3) copolymerizable with the polymerizable monomer 1 type of polymer, (B) a radiation sensitive acid generator, (C) a novolak resin, (D) a compound having a group in which an isocyanate group is blocked by a protective group, and (E) a solvent A radiation-sensitive resin composition.

［式（Ａ１）中、Ｒ¹は水酸基を有する２価の基であり、Ｘは４価の有機基である。］

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

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

［式（ａ１）中、Ｒ²は、単結合、酸素原子、硫黄原子、スルホニル基、カルボニル基、メチレン基、ジメチルメチレン基またはビス（トリフルオロメチル）メチレン基であり；Ｒ³は、それぞれ独立に水素原子、ホルミル基、アシル基またはアルキル基であり、ただし、Ｒ³の少なくとも１つは水素原子であり；ｎ１およびｎ２は、それぞれ独立に０〜２の整数であり、ただし、ｎ１およびｎ２の少なくとも一方は１または２である。］

Wherein (a1), R ² represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group or a bis (trifluoromethyl) methylene group; R ³ are each independently Are a hydrogen atom, a formyl group, an acyl group or an alkyl group, provided that at least one of R ³ is a hydrogen atom; n1 and n2 are each independently an integer of 0 to 2, provided that n1 and n2 At least one of is 1 or 2. ]

  [3] The radiation sensitive property according to any one of [1] to [2], wherein the novolak resin (C) is a resin containing a structural unit having a condensed polycyclic aromatic group having a phenolic hydroxyl group. Resin composition.

  [4] The above-mentioned [1], wherein the novolak resin (C) is a resin having at least one selected from the structural unit represented by the formula (C2-1) and the structural unit represented by the formula (C2-2). ] The radiation sensitive resin composition of any one of [3].

［式（Ｃ２−１）〜式（Ｃ２−２）中、Ｒ²は、メチレン基、炭素数２〜３０のアルキレン基、炭素数４〜３０の２価の脂環式炭化水素基，炭素数７〜３０のアラルキレン基または−Ｒ³−Ａｒ−Ｒ³−で表される基（Ａｒは２価の芳香族基であり、Ｒ³はそれぞれ独立にメチレン基または炭素数２〜２０のアルキレン基である）であり；ａ、ｂ、ｃおよびｅはそれぞれ独立に０〜３の整数であり、ｄは０〜２の整数であり、但し、ａおよびｂが共に０である場合はなく、ｃ〜ｅの全てが０である場合はない。］

[In Formula (C2-1) to Formula (C2-2), R ² represents a methylene group, an alkylene group having 2 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, or a carbon number. A group represented by 7 to 30 aralkylene group or —R ³ —Ar—R ³ — (Ar is a divalent aromatic group, R ³ is independently a methylene group or an alkylene group having 2 to 20 carbon atoms; A, b, c and e are each independently an integer of 0 to 3, d is an integer of 0 to 2, provided that a and b are not both 0 and c There is no case where all of ~ e are 0. ]

[5] The radiation sensitive property according to any one of [1] to [4], wherein the content of the novolak resin (C) is 5 to 200 parts by mass with respect to 100 parts by mass of the polymer (A). Resin composition.
[6] The compound (D) is at least one selected from a compound having one group represented by the formula (D-1) and a compound having one group represented by the formula (D-2) The radiation-sensitive resin composition according to any one of [1] to [5], which is a seed.

［式（Ｄ−１）中、Ｒ^D1は、炭素数１〜２０のアルコキシ基もしくはその誘導体基、炭素数３〜２０のシクロアルコキシ基、炭素数６〜３０のアリーロキシ基、炭素数１〜１５のチオアルコキシ基、炭素数３〜１５のチオシクロアルコキシ基または炭素数３〜２０の複素環式基である。式（Ｄ−２）中、Ｒ^D2およびＲ^D3はそれぞれ独立にアルキル基またはアリール基であり、Ｒ^D2およびＲ^D3は相互に結合して各々が結合している炭素原子とともに環を形成してもよい。］

[In formula (D-1), R ^D1 represents an alkoxy group having 1 to 20 carbon atoms or a derivative group thereof, a cycloalkoxy group having 3 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or 1 to 15 carbon atoms. A thioalkoxy group having 3 to 15 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms. In formula (D-2), R ^D2 and R ^D3 are each independently an alkyl group or an aryl group, and R ^D2 and R ^D3 are bonded to each other to form a ring together with the carbon atom to which each is bonded. Also good. ]

  [7] The above-mentioned [6], wherein the compound (D) is at least one selected from a compound represented by the formula (D-11) and a compound represented by the formula (D-21). Radiation sensitive resin composition.

［式（Ｄ−１１）および（Ｄ−２１）中、Ｒ^D1、Ｒ^D2およびＲ^D3はそれぞれ式（Ｄ−１）および（Ｄ−２）中の同一記号と同義であり；Ｒ^D4は水素原子またはメチル基であり；Ａはメチレン基またはアルキレン基である。］

Wherein (D-11) and ^{(D-21), R D1} , R D2 and R ^D3 are identical symbols synonymous with each formula (D1) and (D2) in; R ^D4 are hydrogen An atom or a methyl group; A is a methylene group or an alkylene group; ]

  [8] The solvent (E) is diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, The radiation-sensitive resin composition according to any one of [1] to [7], comprising at least one selected from propylene glycol monoalkyl ether propionate and triethylene glycol dialkyl ether.

  [9] An insulating film for organic EL elements, formed from the radiation-sensitive resin composition according to any one of [1] to [8].

[10] A step of forming a coating film on the substrate using the radiation-sensitive resin composition according to any one of [1] to [8], wherein at least a part of the coating film is irradiated with radiation. The manufacturing method of the insulating film for organic EL elements which has a process, the process of developing the coating film irradiated with the said radiation, and the process of heating the developed said coating film.
[11] An organic EL device having the insulating film according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the radiation sensitive resin composition which can form the insulating film which has light-shielding property in wavelength 400nm, and has low water absorption can be provided. Therefore, for example, in an organic EL element having, as a driving element, a thin film transistor including a semiconductor layer made of a material with high photodegradation, such as IGZO, the photodegradation of the substance associated with the use of these devices can be suppressed, and an organic light emitting layer It is possible to suppress deterioration due to moisture. For this reason, the organic EL element with improved reliability can be obtained.

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

  The present invention will be described below.

[Radiation sensitive resin composition]
The radiation-sensitive resin composition of the present invention comprises (A) a polymer, (B) a radiation-sensitive acid generator, (C) a novolak resin, and (D) a group in which an isocyanate group is blocked by a protective group. And (E) a solvent. The compound (D) is also referred to as “block isocyanate compound (D)”.

Since the composition contains the polymer (A), the novolak resin (C), and the blocked isocyanate compound (D), an insulating film excellent in heat resistance, light shielding property at a wavelength of 400 nm and low water absorption is formed. be able to. Moreover, since the said composition has high radiation sensitivity, it can form the insulating film excellent in pattern shape and resolution, and can respond to a request for the narrow pitch of a pattern.
Hereinafter, each component will be described in detail.

[Polymer (A)]
The polymer (A) is at least one polymer selected from a polyimide having a structural unit represented by the formula (A1), a precursor of the polyimide, and the following alkali-soluble polymer.
The alkali-soluble polymer includes a radical polymerizable monomer (a3-1) having an epoxy group or an oxetanyl group, a radical polymerizable monomer (a3-2) having a carboxyl group, and other copolymerizable monomers with the polymerizable monomer. It is obtained by polymerizing the radical polymerizable monomer (a3-3).
Hereinafter, the polyimide is also referred to as “polyimide (A1)”, the precursor is also referred to as “polyimide precursor (A2)”, and the alkali-soluble polymer is also referred to as “alkali-soluble polymer (A3)”. The insulating film formed from the polymer (A), in particular, the insulating film formed from the polyimide (A1) and / or the polyimide precursor (A2) is excellent in heat resistance.

  The weight average molecular weight (Mw) in terms of polystyrene of the polymer (A) is preferably 2,000 to 500,000, preferably 3,000 to 100,000, as measured by gel permeation chromatography (GPC). More preferred is 4,000 to 5,000. When Mw is not less than the lower limit of the above range, an insulating film having sufficient mechanical properties tends to be obtained. When the Mw is not more than the upper limit of the above range, the solubility of the polymer (A) in the solvent or developer tends to be excellent.

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

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

In formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group.
Examples of R ¹ include a divalent group represented by the formula (a1).

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

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

  The divalent group represented by the formula (a1) is preferably a divalent group having 1 to 4 hydroxyl groups, and more preferably a divalent group having 2 hydroxyl groups. Examples of the divalent group having 1 to 4 hydroxyl groups represented by the formula (a1) include a divalent group represented by the following formula. In the following formula, two “-” extending from the aromatic ring represent a bond.

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

In the above formula (1), Ar is each independently a trivalent aromatic hydrocarbon group, and A is a direct bond or a divalent group. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group, and a bis (trifluoromethyl) methylene group.
Carbon number of a tetravalent aliphatic hydrocarbon group is 4-30 normally, Preferably it is 8-24. Carbon number of a tetravalent aromatic hydrocarbon group and the trivalent aromatic hydrocarbon group in said formula (1) is 6-30 normally, Preferably it is 6-24.

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

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

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

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

  The tetravalent aliphatic hydrocarbon group is preferably a tetravalent group represented by the following formula. In the following formula, four “-” extending from the chain hydrocarbon group and the alicyclic ring represent a bond.

  Examples of the tetravalent aromatic hydrocarbon group and the group represented by the above formula (1) include a tetravalent group represented by the following formula. In the following formula, four “-” extending from the aromatic ring represent a bond.

A polyimide (A1) can be obtained by imidation of the polyimide precursor (A2) demonstrated below. The imidization here may proceed completely or partially. In other words, the imidation ratio may not be 100%. Therefore, the polyimide (A1) further has at least one selected from the structural unit represented by the formula (A2-1) and the structural unit represented by the formula (A2-2), which will be described below. May be.
In the polyimide (A1), the imidation ratio is preferably 5% or more, more preferably 7.5% or more, and further preferably 10% or more. The upper limit value of the imidization rate is preferably 50%, more preferably 30%. When the imidation ratio is in the above range, it is preferable from the viewpoint of heat resistance and solubility of the exposed portion in the developer. The imidization rate can be measured under the conditions described in the examples.
In the polyimide (A1), the total content of the structural units represented by the formula (A1), formula (A2-1), and formula (A2-2) is usually 50% by mass or more, preferably 60% by mass or more. Preferably it is 70 mass% or more, Most preferably, it is 80 mass% or more.

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

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

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

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

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

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

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

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

<< Synthesis Method of Polyimide (A1) and Polyimide Precursor (A2) >>
The polyamic acid which is a polyimide precursor (A2) can be obtained, for example, by polymerizing a tetracarboxylic dianhydride, a diamine having a hydroxyl group and a diamine containing another diamine as required. The proportion of these used is, for example, 0.3 to 4 mol, preferably approximately equimolar, with respect to 1 mol of the tetracarboxylic dianhydride. In the polymerization, the mixed solution of the tetracarboxylic dianhydride and the total diamine is preferably heated at 50 ° C. to 200 ° C. for 1 hour to 24 hours.
Hereinafter, the tetracarboxylic dianhydride and the diamine having a hydroxyl group are also referred to as “acid dianhydride (A1-1) and“ diamine (A1-2) ”, respectively, and the other diamine is referred to as“ diamine (A1- 2 ') ".

  The synthesis of polyamic acid may be carried out by dissolving diamine (A1-2) in a polymerization solvent and then reacting diamine (A1-2) with acid dianhydride (A1-1). You may carry out by making an acid dianhydride (A1-1) and diamine (A1-2) react after melt | dissolving an anhydride (A1-1) in a polymerization solvent.

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

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

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

Moreover, when diamine is used excessively with respect to tetracarboxylic dianhydride, for example, dicarboxylic acid such as maleic anhydride is used as an end-capping agent for sealing the end groups of polyimide, polyamic acid and polyamic acid derivatives. Anhydrides may be used.
Acid dianhydride (A1-1) is an acid dianhydride represented by the formula (a2).

In the formula (a2), X is a tetravalent organic group. Examples of the tetravalent organic group represented by X include the same groups as those exemplified as X in formula (A1).
Diamine (A1-2) is a diamine represented by formula (a3).

In the formula (a3), R ¹ is a divalent group having a hydroxyl group. The divalent group having a hydroxyl group represented by R ^1, include those similar to the groups exemplified as R ¹ in the formula (A1).

  In addition to the diamine (A1-2), another diamine (A1-2 ') other than the (A1-2) may be used. Examples of the other diamine (A1-2 ′) include at least one diamine selected from an aromatic diamine and an aliphatic diamine having no hydroxyl group.

The polyimide (A1) further has a structural unit in which R ¹ in the formulas (A1), (A2-1) and (A2-2) is replaced with the residue of the other diamine (A1-2 ′). It may be. Similarly, the polyimide precursor (A2) further has a structural unit in which R ¹ in the formulas (A2-1) and (A2-2) is changed to the residue of the other diamine (A1-2 ′). You may do it.

  As a polymerization solvent used for the synthesis of the polyimide (A1) and the polyimide precursor (A2), these synthesis raw materials and the above (A1) and (A2) can be dissolved, and a low water-absorbing solvent is preferable. . As a polymerization solvent, the solvent similar to the solvent illustrated as the solvent (E) mentioned later can be used.

  By using the same solvent as the solvent (E) as the polymerization solvent, the step of isolating these polymers after synthesizing the polyimide (A1) or the polyimide precursor (A2), and reusing the solvent again after the isolation. The step of dissolving can be eliminated. Thereby, the productivity of the resin composition of the present invention can be improved.

  The polyimide (A1) and the polyimide precursor (A2) have excellent solubility in the solvent (E) described later due to the specific structure having a hydroxyl group. For this reason, these polymers are also soluble in a low water-absorbing solvent other than N-methylpyrrolidone (NMP), for example, the solvent (E) described later. As a result, for example, by using a solvent other than NMP as a polymerization solvent for obtaining the polymer (A), the insulating film formed from the radiation-sensitive resin composition can have a lower water absorption.

<< Alkali-soluble polymer (A3) >>
The alkali-soluble polymer (A3) is copolymerizable with a radical polymerizable monomer (a3-1) having an epoxy group or an oxetanyl group, a radical polymerizable monomer (a3-2) having a carboxyl group, and the polymerizable monomer. It is a copolymer obtained by polymerizing other radical polymerizable monomers (a3-3).
Hereinafter, the monomers (a3-1) to (a3-3) are also referred to as “components (a3-1) to (a3-3)”, respectively, and the components (a3-1) and (a3-2) used here. ) And component (a3-3) will be sequentially described.

(Component (a3-1))
Examples of the component (a3-1) include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-ethyl-3- (meth) acryloxyethyl oxetane, 3-ethyl p-vinylbenzoate Examples include oxetane-3-ylmethyl ester and p-vinylphenyl-3-ethyloxet-3-ylmethyl ether. Use of an alkali-soluble polymer (A3) obtained by using at least one selected from the component (a3-1) is preferable because it has high heat resistance and chemical resistance and can form a small pattern. .
The component (a3-1) can be used alone or in combination of two or more.

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

(Component (a3-2))
Examples of the component (a3-2) include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and ω-carboxypolycaprolactone. Mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], maleic acid mono [2- (meth) acryloyloxyethyl], cyclohexene-3,4-dicarboxylic acid mono [2- (meta ) Acryloyloxyethyl]. Among these, (meth) acrylic acid and mono (2-methacryloyloxyethyl) succinate are preferable. When (meth) acrylic acid is used, the pattern size of the resin composition is close to the mask dimension, and the transparency is high. Since a resin composition having little residue and excellent storage stability is obtained, it is more preferable.
The component (a3-2) can be used alone or in combination of two or more.

  In synthesizing the alkali-soluble polymer (A3), the component (a3-2) is preferably used in an amount of 5 to 50% by mass based on the total mass of all monomers. Within such a range, the developability of the resin composition of the present invention with an alkaline aqueous solution is good, which is preferable. The range of the monomer is preferably 6 to 40% by mass because the pattern size is close to the mask dimension, and the range of 7 to 30% by mass is more preferable because of high sensitivity.

(Component (a3-3))
The component (a3-3) is not particularly limited as long as it is a radical polymerizable monomer copolymerizable with the components (a3-1) and (a3-2). For example, styrene, methylstyrene, vinyltoluene, chloromethylstyrene, (meth) acrylamide, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxy Ethyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer, polymethyl methacrylate Macromonomer, N- acryloyl morpholine, indene, 5, such as tetrahydrofurfuryl oxycarbonyl pentyl acrylate, (meth) acrylic acid ester of the compound obtained by modifying tetrahydrofurfuryl alcohol ε- caprolactone. A commercial item can also be used, for example, Nippon Kayaku Co., Ltd. KAYARAD (trademark) TC110S is mentioned preferably.
When the component (a3-3) is used in a range of 15 to 85% by mass with respect to the total mass of all monomers used for the synthesis of the alkali-soluble polymer (A3), the resin composition of the present invention is applied, exposed, When developed, the pattern size is close to the mask dimension, and a desired pattern can be obtained with a low exposure amount, which is preferable. Considering the balance between development time and adhesion, the range of the monomer is preferably 20 to 78% by mass.

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

  The solvent used for the polymerization reaction is preferably a solvent that dissolves the components (a3-1) to (a3-3) and the alkali-soluble polymer (A3) to be produced. Specific examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, acetone, 2-butanone, ethyl acetate, propyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, ethylene glycol monoethyl ether, propylene. Glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N, N-dimethylformamide, acetic acid, water, etc. A mixture thereof may be used.

  Moreover, the process similar to the solvent (E) mentioned later as a polymerization solvent can be made unnecessary by the process of isolating a polymer and the process of re-dissolving in another solvent after isolation. Thereby, the productivity of the resin composition of the present invention can be improved.

  The polymerization initiator used when synthesizing the alkali-soluble polymer (A3) is a compound that generates radicals by heat, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate), or the like. Azo initiators and peroxide initiators such as benzoyl peroxide can be used. In order to adjust the molecular weight, a suitable amount of a chain transfer agent such as thioglycolic acid may be added.

[Radiosensitive acid generator (B)]
The radiation sensitive acid generator (B) is a compound that generates an acid by a treatment including irradiation of radiation. Examples of radiation include visible light, ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. By containing the radiation sensitive acid generator (B), the radiation sensitive resin composition can exhibit positive radiation sensitive characteristics and can have good radiation sensitivity.

  Content of the radiation sensitive acid generator (B) in a radiation sensitive resin composition is 5-100 mass parts normally with respect to 100 mass parts of polymers (A), Preferably it is 10-60 mass parts, More preferably, it is 15-50 mass parts. By setting the content of the radiation-sensitive acid generator (B) within the above range, the difference in solubility between the irradiated portion and the unirradiated portion with respect to an alkaline aqueous solution or the like serving as a developer is increased, and the patterning performance is improved. be able to.

  Examples of the radiation sensitive acid generator (B) include quinonediazide compounds, oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, and carboxylic acid ester compounds. Is mentioned.

As the radiation sensitive acid generator (B), a quinonediazide compound, an oxime sulfonate compound, an onium salt, and a sulfonate compound are preferable, a quinonediazide compound and an oxime sulfonate compound are more preferable, and a quinonediazide compound is particularly preferable.
The radiation sensitive acid generator (B) may be used alone or in combination of two or more.

<Quinonediazide compound>
The quinonediazide compound generates carboxylic acid by processing including irradiation with radiation and development using an aqueous alkali solution. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “host nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide.

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

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

  Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2, Examples include 3,4,2′-tetrahydroxy-4′-methylbenzophenone and 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone.

Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone.
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone and 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone.

  Examples of the poly (hydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p- Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol, bis (2,5- Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobi Nden -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', include 4'-trihydroxy flavan.

  Examples of other mother nuclei include 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-hydroxyphenyl] -1-methylethyl)- 4,6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

  Among these mother 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-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and 1,2-naphthoquinonediazide- 5-sulfonic acid chloride is preferred.

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

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the exemplified ester bond of the mother nucleus is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4- Sulfonamide and the like are also preferably used.

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

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

[Novolac resin (C)]
Examples of the novolak resin (C) include novolak resins including a structural unit having at least one selected from a benzene ring having a phenolic hydroxyl group and a condensed polycyclic aromatic group having a phenolic hydroxyl group. . Among these, a novolak resin containing a structural unit having a condensed polycyclic aromatic group having a phenolic hydroxyl group is preferable from the viewpoint of imparting light shielding properties and heat resistance and alkali developability.

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

  The novolac resin (C) is a substance that develops color when heated. In the method for forming an insulating film described later, the coating film itself formed from the radiation-sensitive resin composition containing the novolak resin (C) before exposure does not have a light-shielding property at a wavelength of 400 nm, but is heated after exposure and development. As a result, the novolak resin (C) is ketoized, and the obtained insulating film is presumed to have a light shielding property at the wavelength. By using such a novolak resin (C), it is possible to achieve both light shielding properties and good alkali developability.

  For example, when the heating temperature is about 60 to 130 ° C., which is the heating temperature during pre-baking, the above light-shielding property is not imparted, and the heating temperature during post-baking. A novolac resin capable of imparting the above-described light shielding property at a temperature exceeding 130 ° C. and not higher than 300 ° C. is preferred.

  Examples of the novolak resin (C) include a structural unit represented by the formula (C1), a structural unit represented by the formula (C2-1), a structural unit represented by the formula (C2-2), and a formula ( And a resin having at least one selected from structural units represented by C3).

In formulas (C1) to (C3), R ¹ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms; R ² is a methylene group or an alkylene group having 2 to 30 carbon atoms. , A divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, an aralkylene group having 7 to 30 carbon atoms or a group represented by —R ³ —Ar—R ³ — (Ar is a divalent aromatic group). Each of R ³ is independently a methylene group or an alkylene group having 2 to 20 carbon atoms; n1 is an integer of 1 to 4, n2 is an integer of 0 to 3, and n1 + n2 ≦ 4 , A to c, e, g and h are each independently an integer of 0 to 3, and d and f are each independently an integer of 0 to 2, provided that a and b are both 0. There is no case where all of c to e are 0, and there is no case where all of f to h are 0. a + b, c + d + e, and f + g + h are each preferably an integer of 1 to 3.

In Formula (C1) to Formula (C3), the bonding position of —OH, —R ¹ and —R ² — is not particularly limited. R ² constituting the above repeating structure may be bonded to different benzene nuclei (for example, (1) below), or may be bonded to the same benzene nuclei (for example, (2) below). In the formula, * is a bond. The following formulas (1) and (2) are specific examples of formula (C2-1), but the same applies to formulas (C2-2) and (C3).

Examples of the alkylene group having 2 to 30 carbon atoms in 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, hexacosylene group, heptacosylene group, octacosylene group, nonacosylene group, triaconylene group.

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

Examples of the aralkylene group having 7 to 30 carbon atoms in R ² include a benzylene group, a phenethylene group, a benzylpropylene group, and a naphthylene methylene group.
Examples of the group represented by —R ³ —Ar—R ³ — in R ² include a group represented by —CH ₂ —Ph—CH ₂ — (Ph is a phenylene group).

  The above exemplified novolak resin (C) is preferable because it has good alkali solubility. By containing the alkali-soluble novolak resin (C) in the radiation-sensitive resin composition, a radiation-sensitive resin composition having good resolution can be obtained.

  The novolak resin (C) is, for example, a condensed polycyclic aromatic compound having phenols or a phenolic hydroxyl group and an aldehyde are condensed in the presence of an acid catalyst, and unreacted components are distilled off if necessary. Can be obtained. For example, methods described in JP-B-47-15111 and JP-A-63-238129 can be referred to.

  Examples of phenols include phenol, orthocresol, metacresol, paracresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4- Dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol, 2-methylresorcinol 4-methylresorcinol, 5-methylresorcinol, 4-t-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 2- Meto Shi-5-methylphenol, 2-t-butyl-5-methylphenol, thymol, include Isochimoru.

  Examples of condensed polycyclic aromatic compounds having a phenolic hydroxyl group include compounds having 1 to 6 hydroxyl groups, preferably 1 to 3 and 2 to 3 rings. Is monohydroxynaphthalene such as 1-naphthol and 2-naphthol; 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1 , 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like; 1-hydroxyanthracene, 2-hydroxyanthracene, 9- Monohydroxy such as hydroxyanthracene 1,4-dihydroxyanthracene, dihydroxyanthracene such as 9,10-dihydroxyanthracene; 1,2,10-trihydroxyanthracene, 1,8,9-trihydroxyanthracene, 1,2,7-trihydroxyanthracene, etc. Trihydroxyanthracene; and hydroxyphenanthrenes such as 1-hydroxyphenanthrene.

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

  In the synthesis of the novolak resin (C), the amount of the phenols or condensed polycyclic aromatic compounds having a phenolic hydroxyl group is usually 0.5 mol or more, preferably 0, per 1 mol of aldehydes. .8 to 3.0 moles. Examples of the acid catalyst include hydrochloric acid, paratoluenesulfonic acid, and trifluoromethanesulfonic acid.

  The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the novolak resin (C) is usually 500 to 50,000, preferably 700 to 5,000, more preferably 800 to 3,000. The novolak resin (C) having Mw in the above range is preferable in terms of resolution.

  In the radiation sensitive resin composition, the content of the novolak resin (C) is usually 5 to 200 parts by weight, preferably 10 to 100 parts by weight, more preferably 100 parts by weight of the polymer (A). It is 15-90 mass parts, Most preferably, it is 18-80 mass parts. When the content of the novolak resin (C) is not less than the lower limit of the above range, the effect of imparting light shielding properties and developability based on the novolak resin (C) is easily exhibited. When the content of the novolak resin (C) is not more than the upper limit of the above range, there is little possibility that the low water absorption and the heat resistance of the insulating film are deteriorated.

[Blocked isocyanate compound (D)]
The blocked isocyanate compound (D) is a compound having a group in which an isocyanate group is blocked by a protective group. Hereinafter, a group in which an isocyanate group is blocked with a protective group is also referred to as a “blocked isocyanate group”.

  In the component (D), the blocked isocyanate group is deblocked (the protecting group is removed) by the high temperature treatment during thermosetting, and the active isocyanate group is regenerated. An example of the regeneration reaction is shown below. For this reason, pre-baking is performed at a temperature at which the deblocking of the component (D) does not occur, and post-baking is performed at a temperature at which the deblocking occurs, so that, for example, the isocyanate group, the polyimide (A1) and its The reaction proceeds with the phenolic hydroxyl group contained in the precursor (A2), the novolak resin (C), etc., and a cured film excellent in low water absorption and heat resistance can be obtained.

Block in the above formula represents a protecting group.
In component (D), the number of blocked isocyanate groups is usually 1 or more, preferably 1 to 2, more preferably 1. Use of the component (D) having the number of blocked isocyanate groups within the above range is preferable in terms of storage stability.

  The component (D) is preferably at least one selected from a compound having a group represented by the formula (D-1) and a compound having a group represented by the formula (D-2). More preferably, it is at least one selected from a compound having one group represented by (D-1) and a compound having one group represented by formula (D-2).

In formula (D-1), R ^D1 represents an alkoxy group having 1 to 20 carbon atoms or a derivative group thereof, a cycloalkoxy group having 3 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or an alkyl group having 1 to 15 carbon atoms. A thioalkoxy group, a thiocycloalkoxy group having 3 to 15 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms. R ^D1 is preferably a 5- or more-membered heterocyclic group, and more preferably a 5- to 18-membered heterocyclic group. The number of carbon atoms in R ^D1 is more preferably 3-15.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a 2-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, and a 2-methylbutoxy group. , 3-methylbutoxy group, 2,2-dimethylpropoxy group, n-hexyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 5-methylpentyloxy group . Examples of the cycloalkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. Examples of the derivative group of the alkoxy group include a group in which one or more hydrogen atoms of a methoxy group are substituted with at least one selected from a cycloalkyl group and an aryl group. Specifically, a dicyclopentylmethoxy group , Dicyclohexylmethoxy group, tricyclopentylmethoxy group, tricyclohexylmethoxy group, phenylmethoxy group, diphenylmethoxy group, and triphenylmethoxy group. Examples of the aryloxy group include a phenoxy group and a naphthyloxy group. Examples of the thioalkoxy group include a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thiobutoxy group, and a thiopentoxy group. Examples of the thiocycloalkoxy group include a thiocyclopentyloxy group and a thiocyclohexyloxy group. Examples of the heterocyclic group include 1-pyrazolyl group, 3-methyl-1-pyrazolyl group, 3,5-dimethyl-1-pyrazolyl group, N-ε-caprolactam group, pyridinyl group, triadylyl group, pyrrolyl group, Examples include imidazolyl, indolyl, thiadiazolyl, oxadiazolyl, and pyrimidinyl groups.

In formula (D-2), R ^D2 and R ^D3 are each independently an alkyl group or an aryl group, and R ^D2 and R ^D3 are bonded to each other to form a ring together with the carbon atom to which each is bonded. Also good. In the formula (D-2), —O—N═C (R ^D2 ) (R ^D3 ) is a group derived from oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime and the like. It is preferable that

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

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

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

Specific examples of component (D) include 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate, (meth) acrylic acid 2- (0- [1′-methylpropylideneamino] carboxyl Amino) ethyl.
A component (D) may be used individually by 1 type, and may use 2 or more types.

  In the radiation sensitive resin composition, the content of the component (D) is usually 10 to 95 parts by weight, preferably 15 to 90 parts by weight, more preferably 20 to 100 parts by weight of the polymer (A). It is -85 mass parts. Moreover, content ratio (C) / (D) of a component (C) and a component (D) is mass ratio, and is 0.05-20 normally, Preferably it is 0.1-10, More preferably, it is 0.1. ~ 5. It is preferable at the point of low water absorption that content of a component (D) is more than the lower limit of the said range. It is preferable at the point of resolution that content of a component (D) is below the upper limit of the said range.

[Solvent (E)]
A solvent (E) can be used in order to make a radiation sensitive resin composition liquid.
As the solvent (E), diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol Monoalkyl ether propionate and triethylene glycol dialkyl ether are preferred.

Examples of the diethylene glycol monoalkyl ether include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether.
Examples of the diethylene glycol dialkyl ether include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

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

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

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

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

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

  Examples of the triethylene glycol dialkyl ether include triethylene glycol dimethyl ether.

  As the solvent (E), amide solvents such as N, N, 2-trimethylpropionamide, 3-butoxy-N, N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3- Examples also include hexyloxy-N, N-dimethylpropanamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like.

  As the solvent (E), propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMEA”), propylene glycol monomethyl ether (hereinafter also referred to as “PGME”), and diethylene glycol ethyl methyl ether (hereinafter also referred to as “EDM”) are particularly preferable.

  In one embodiment, γ-butyrolactone (hereinafter also referred to as “BL”) is preferably used as the solvent (E), and a mixed solvent containing BL is preferable. As content of BL, 70 mass% or less is preferable in the total amount of 100 mass% of a solvent (E), and 20-60 mass% is more preferable. BL is preferably used in combination with at least one selected from PGMEA, PGME and EDM. By setting the BL content in the above range, the dissolved state of the polymer (A) in the radiation-sensitive resin composition tends to be favorably maintained.

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

  The solvent exemplified above as the solvent (E) has a low water absorption compared to NMP. Therefore, the radiation sensitive resin composition can be prepared using a low water absorption solvent without using NMP having high water absorption. As a result, the radiation sensitive resin composition can exhibit low water absorption. Moreover, since the solvent illustrated above as a solvent (E) has high safety | security, it can improve the safety | security of a radiation sensitive resin composition.

When using the solvent illustrated above as a solvent (E), the insulating film formed from a radiation sensitive resin composition can be made into a low water absorption. Therefore, this radiation sensitive resin composition can be used suitably for formation of the insulating film which an organic EL element has.
A solvent (E) may be used individually by 1 type, or may use 2 or more types together.

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

[Other optional ingredients]
The radiation-sensitive resin composition contains, in addition to the above essential components, other optional components such as an adhesion assistant (F) and a surfactant (G) as necessary within the range not impairing the effects of the present invention. May be. Other optional components may be used alone or in combination of two or more.

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

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

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

  The content of the adhesion assistant (F) in the radiation-sensitive resin composition is preferably 20 parts by mass or less with respect to 100 parts by mass of the polymer (A). By setting the content of the adhesion assistant (F) in the above range, the adhesion between the formed insulating film and the substrate is further improved.

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

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

  The content of the surfactant (G) in the radiation-sensitive resin composition is preferably 20 parts by mass or less, more preferably 0.01 to 15 parts by mass, further preferably 100 parts by mass of the polymer (A). Is 0.05 to 10 parts by mass. By making content of surfactant (F) into the said range, the film thickness uniformity of the coating film formed can be improved more.

[Method for preparing radiation-sensitive resin composition]
The radiation sensitive resin composition includes, for example, essential components such as a solvent (E), a polymer (A), a radiation sensitive acid generator (B), a novolak resin (C) and a blocked isocyanate compound (D), It can be prepared by mixing optional ingredients. Moreover, in order to remove dust, after mixing each component uniformly, you may filter the obtained mixture with a filter.

[Method of forming insulating film using radiation-sensitive resin composition]
The insulating film is formed by the steps 1 of forming a coating film on a substrate using the above-described radiation-sensitive resin composition, the step 2 of irradiating at least a part of the coating film, and the irradiation of the radiation. It has the process 3 which develops a coating film, and the process 4 which heats the said developed coating film.

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

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

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

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

  Prebaking conditions vary depending on the composition of the radiation-sensitive resin composition, but for example, the heating temperature is 60 to 130 ° C., and the heating time is about 30 seconds to 15 minutes. The prebaking is preferably performed at a temperature at which the light-shielding property based on the novolak resin (C) is not imparted to the coating film and the thermal dissociation of the protective group does not proceed in the blocked isocyanate compound (D).

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

Among these radiations, visible light and ultraviolet light are preferable, and among visible light and ultraviolet light, radiation containing g-line and / or i-line is particularly preferable. As an exposure amount, 6000 mJ / cm < ² > or less is preferable and 20-2000 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 model 356” manufactured by OAI Optical Associates).

<< Process 3 >>
In step 3, the coating film irradiated with radiation in step 2 is developed. Thereby, the irradiation part of a radiation can be removed and a desired pattern can be formed. As the developer used for the development treatment, an alkaline aqueous solution is preferable.

  Examples of the alkaline compound contained in the aqueous alkaline solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, and di-n-propyl. Amine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5 -Diazabicyclo [4,3,0] -5-nonane. The concentration of the alkaline compound in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability.

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

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

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

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

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

  The insulating film thus obtained is light-absorbing with respect to light having a wavelength of 400 nm, has low water absorption because the constituent material has a low water absorption structure, and has low water absorption even in the production process. Can be processed. In addition, the insulating film exhibits good characteristics in terms of heat resistance, patterning properties, radiation sensitivity, resolution, and the like. For this reason, the said insulating film can be used suitably as an insulating film as a protective film or a planarization film | membrane other than the insulating film as a partition which an organic EL element etc. have, for example.

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

[Organic EL element: Organic EL display device and organic EL lighting device]
Hereinafter, usage examples of the insulating film of the present invention will be described.

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

Hereinafter, the display or lighting device is also collectively referred to as “device”.
An embodiment of the device having an insulating film of the present invention includes a TFT substrate, a first electrode provided on the TFT substrate and connected to the TFT, and a first electrode so as to partially expose the first electrode. The insulating film of the present invention formed on the electrode and the second electrode provided to face the first electrode. In the apparatus of the present invention, examples of the TFT substrate, the first electrode, and the second electrode include a support substrate, TFT, anode, and cathode, respectively.

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

The thickness of the insulating film is not particularly limited, but is preferably 0.3 to 25 μm, more preferably 0.5 to 20 μm, considering the ease of film formation and patterning.
The insulating film is formed so as to straddle adjacent first electrodes, for example. For this reason, the insulating film is required to have good electrical insulation. The volume resistivity of the insulating film is preferably 10 ¹⁰ μΩ · cm or more, more preferably 10 ¹² μΩ · cm or more.

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

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

  For example, the semiconductor layer constituting the TFT may be a layer containing an oxide semiconductor containing one or more elements selected from In, Ga, Sn, and Zn. As an oxide semiconductor containing one or more elements selected from In, Ga, Sn, and Zn, for example, a quaternary metal oxide such as an In—Sn—Ga—Zn—O-based oxide semiconductor; In— Ga-Zn-O-based oxide semiconductor, In-Sn-Zn-O-based oxide semiconductor, In-Al-Zn-O-based oxide semiconductor, Sn-Ga-Zn-O-based oxide semiconductor, Al-Ga- Ternary metal oxides such as Zn-O-based oxide semiconductor and Sn-Al-Zn-O-based oxide semiconductor; In-Zn-O-based oxide semiconductor, Sn-Zn-O-based oxide semiconductor, Al- 2 such as a Zn-O-based oxide semiconductor, a Zn-Mg-O-based oxide semiconductor, a Sn-Mg-O-based oxide semiconductor, an In-Mg-O-based oxide semiconductor, an In-Ga-O-based material, etc. Binary metal oxides: In-O oxide semiconductors, Sn-O oxide semiconductors, Zn O-based oxide 1-component metal oxide such as a semiconductor and the like.

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

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

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

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

  The organic EL device 1 in FIG. 1 is an active matrix organic EL device having a plurality of pixels formed in a matrix. The organic EL device 1 may be either a top emission type or a bottom emission type. The property of the material constituting each member, such as transparency, is appropriately selected according to the top emission type and the bottom emission type. The organic EL device 1 includes a support substrate 2, a thin film transistor (hereinafter also referred to as "TFT") 3, an inorganic insulating film 4, a first insulating film 5, an anode 6 as a first electrode, a through hole 7, and a second insulating film. 8, an organic light emitting layer 9, a cathode 10 as a second electrode, a passivation film 11, and a sealing substrate 12. As the second insulating film 8, the insulating film of the present invention is used.

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

The present invention is not limited to the bottom gate type in which the gate insulating film and the semiconductor layer are sequentially provided on the gate electrode, and may be the top gate type in which the gate insulating film and the gate electrode are sequentially provided on the semiconductor layer.
The gate electrode 30 forms part of a scanning signal line (not shown). The thickness of the gate electrode 30 is preferably 10 to 1000 nm. The gate insulating film 31 covers the gate electrode 30. The film thickness of the gate insulating film 31 is preferably 10 nm to 10 μm. The source electrode 33 is an electrode serving as a carrier generation source. The source electrode 33 forms part of a video signal line (not shown) and is connected to the semiconductor layer 32. The drain electrode 34 is a part that receives carriers moving through the semiconductor layer 32 (channel layer), and is connected to the semiconductor layer 32 in the same manner as the source electrode 33. The thickness of the source electrode 33 and the drain electrode 34 is preferably 10 nm to 1000 nm.

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

  The semiconductor layer 32 can be formed using the above-described oxide semiconductor containing one or more elements selected from In, Ga, Sn, and Zn. Examples of the oxide in this case include a single crystal oxide, a polycrystalline oxide, an amorphous oxide, and a mixture thereof.

  For the semiconductor layer 32 made of amorphous oxide using IGZO, for example, a semiconductor layer is formed by sputtering or vapor deposition using an IGZO target, and patterning is performed by a resist process and an etching process using a photolithography method or the like. Is formed. In this case, the thickness of the semiconductor layer 32 is preferably 1 nm to 1000 nm.

  In the organic EL device 1, since the second insulating film 8 (partition wall) has a light shielding property, the light generated from the organic light emitting layer 9 can be prevented or reduced from reaching the semiconductor layer 32. Therefore, it is possible to use a semiconductor layer made of IGZO or the like that is easily photodegraded.

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

  The first insulating film 5 is a planarizing film that plays a role of planarizing the surface irregularities of the TFT 3. The first insulating film 5 is formed on the inorganic insulating film 4 so as to cover the entire TFT 3.

  The 1st insulating film 5 may be formed using the radiation sensitive resin composition mentioned above, and may be formed using a conventionally well-known radiation sensitive resin composition. These materials may be selected depending on whether the organic EL device 1 is a top emission type or a bottom emission type. The first insulating film 5 is formed as an organic insulating film because these materials are organic materials. The first insulating film 5 can be formed by the method described in [Method of forming insulating film] described above.

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

  The through hole 7 is formed to connect the anode 6 and the drain electrode 34. In addition to the first insulating film 5, the through hole 7 is formed so as to penetrate the inorganic insulating film 4 under the first insulating film 5.

  The through hole 7 can be formed by dry etching the inorganic insulating film 4 after forming the first insulating film 5 having a through hole having a desired shape. Here, the first insulating film 5 is formed using the above-described radiation-sensitive resin composition or a conventionally known radiation-sensitive resin composition, and a method similar to the method described in [Method of forming insulating film] described above. Can be formed. Therefore, the through-hole which comprises the through hole 7 can be formed by irradiation and development with respect to the coating film which consists of these materials. Dry etching on the inorganic insulating film 4 can be performed using the first insulating film 5 as a mask. As a result, a through hole communicating with the through hole of the first insulating film 5 is formed in the inorganic insulating film 4, and as a result, a through hole 7 penetrating the first insulating film 5 and the inorganic insulating film 4 is formed.

  Note that, when the inorganic insulating film 4 is not disposed on the TFT 3, the through hole formed by the irradiation and development of radiation to the first insulating film 5 constitutes the through hole 7. As a result, the anode 6 covers a part of the first insulating film 5 and the drain electrode 34 through the through hole 7 provided in the first insulating film 5 so as to penetrate the first insulating film 5. Can be connected with.

  The second insulating film 8 serves as a partition (bank) having a recess 80 that defines the arrangement region of the organic light emitting layer 9. The second insulating film 8 is formed so as to cover a part of the anode 6 and to expose a part of the anode 6.

  The second insulating film 8 is preferably formed on the first insulating film 5 so as to be disposed at least above the semiconductor layer 32 of the TFT 3. Here, “upward” is a direction from the support substrate 2 toward the sealing substrate 12. Since the second insulating film 8 has a light shielding property, light generated from the organic light emitting layer 9 can be prevented or reduced from reaching the semiconductor layer 32.

  Such a second insulating film 8 can be formed using the above-described radiation-sensitive resin composition by the method described in [Method of forming insulating film]. The second insulating film 8 can be formed as a plurality of concave portions 80 in which the organic light emitting layer 9 is formed arranged in a matrix in a plan view by patterning by exposing and developing the coating film. .

  The second insulating film 8 is preferably formed so as to fill the through hole 7. By adopting such a configuration, the insulating film formed on the first insulating film 5 and the insulating film formed in the through hole 7 cause the light generated from the organic light emitting layer 9 to be emitted from the semiconductor layer 32 of the TFT 3. It becomes a defensive wall that prevents or reduces reaching.

  The thickness T1 of the second insulating film 8 (distance between the uppermost surface of the second insulating film 8 and the lowermost surface of the organic light emitting layer 9) is preferably 0.3 μm or more and 25 μm or less, and preferably 0.5 μm or more and 20 μm or less. Is more preferable. If the thickness of the second insulating film 8 exceeds 25 μm, the second insulating film 8 may come into contact with the sealing substrate 12. On the other hand, if the thickness of the second insulating film 8 is less than 0.3 μm, the light shielding property may not be sufficiently provided, or the concave portion of the second insulating film 8 is formed when the organic light emitting layer 9 described later is formed. When the light emitting material composition is applied to 80, the light emitting material composition may leak from the recess 80.

  The organic light emitting layer 9 emits light when an electric field is applied. The organic light emitting layer 9 is a layer containing an organic light emitting material that emits electroluminescence. The organic light emitting layer 9 is formed in a region defined by the second insulating film 8, that is, a recess 80. In this manner, by forming the organic light emitting layer 9 in the recess 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 in contact with the anode 6 at the recess 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 top surface of the organic light emitting layer 9 on the anode 6.

  The anode 6 forms a pixel electrode. The anode 6 is formed on the first insulating film 5 with a conductive material. The cathode 10 is formed so as to cover a plurality of pixels in common, and serves as a common electrode of the organic EL device 1. The passivation film 11 suppresses entry of moisture and oxygen into the organic EL element. The passivation film 11 is provided on the cathode 11.

  The sealing substrate 12 seals the main surface (the side opposite to the support substrate 2) on which the organic light emitting layer 9 is disposed. The main surface on which the organic light emitting layer 9 is disposed can be sealed with the sealing substrate 12 through the sealing layer 13 using a sealing agent (not shown) applied in the vicinity of the outer peripheral edge of the TFT substrate. preferable. The sealing layer 13 can be a layer of an inert gas such as a dried nitrogen gas or a layer of a filling material such as an adhesive.

  In the organic EL device 1 of the present embodiment, since the second insulating film 8 has a light shielding property with respect to light having a wavelength of 400 nm, it is possible to suppress light degradation of the semiconductor layer 32 due to use of the device or the like. . Further, the first insulating film 5 and the second insulating film 8 can be formed using a radiation-sensitive resin composition having low water absorption, and in the process of forming these insulating films 5 and 8, Processing such as cleaning using a low water-absorbing material is possible. Therefore, it is possible to reduce a slight amount of moisture contained in the insulating film forming material in the form of adsorbed water from gradually entering the organic light emitting layer 9, and to reduce deterioration of the organic light emitting layer 9 and deterioration of the light emitting state. .

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

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

・ Measuring method: Gel permeation chromatography (GPC) method ・ Standard material: polystyrene conversion ・ Device: manufactured by Tosoh Corporation, trade name: HLC-8020
Column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL , TSK gel G2000H _XL sequentially connected Solvent: Tetrahydrofuran Sample concentration: 0.7% by mass
・ Injection volume: 70 μL
・ Flow rate: 1mL / min
[Imidation rate of polyimide]
First, the infrared absorption spectrum of the polyimide: measured (device name Thermo Electron Ltd. NICOLET6700FT-IR), an absorption peak (1780 cm around ^-1, 1377 cm around ^-1) of an imide structure caused by a polyimide was confirmed the presence of. Next, after heat-treating the polyimide at 350 ° C. for 1 hour, the infrared absorption spectrum was measured again, and the peak intensities near 1377 cm ⁻¹ before and after the heat treatment were compared. The imidation ratio of polyimide after heat treatment is taken as 100%, and the imidization ratio of polyimide before heat treatment = {peak intensity around 1377 cm ⁻¹ before heat treatment / peak intensity around 1377 cm ⁻¹ after heat treatment} × 100 (%) Sought.

<Synthesis of polymer (A)>
[Synthesis Example A1] Synthesis of Polymer (A-1) After adding 340 g of γ-butyrolactone as a polymerization solvent to a three-necked flask, 50 g of propylene glycol monomethyl ether acetate was added, and a diamine compound with respect to a total of 390 g of the polymerization solvent. 120 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane as was added to the polymerization solvent. After the diamine compound was dissolved in the polymerization solvent, 71 g of 4,4′-oxydiphthalic dianhydride as an acid dianhydride was added. Then, after making it react at 60 degreeC for 1 hour, 19 g of maleic anhydride as a terminal blocker was added, and after making it react at 60 degreeC for further 1 hour, it heated up and made it react at 140 degreeC for 4 hours. During the reaction, the low boiling point solvent PGMEA was distilled off using a Dean-Stark tube under N ₂ flow conditions. As a result, about 550 g of a solution containing the polymer (A-1) was obtained. Mw of the obtained polymer (A-1) was 9500. The imidation ratio of the obtained polymer (A-1) was 10%.

[Synthesis Example A2] Synthesis of Polymer (A-2) In a 3-neck flask with a stirrer, 20 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate as component (a3-1) and methacryl as component (a3-2) 10 parts by weight of acid, 70 parts by weight of benzyl methacrylate as component (a3-3), 150 parts by weight of propylene glycol monomethyl ether acetate as solvent, dimethyl-2,2′-azobis (2-methylpropionate) 3 as a polymerization initiator 1 part by weight of thioglycolic acid as a part by weight and a chain transfer agent was charged and heated at 65 ° C. for 6 hours to obtain a solution containing the polymer (A-2). The weight average molecular weight (Mw) of the obtained polymer (A-2) was 10,000.

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

<Synthesis of novolac resin (C)>
[Synthesis Example C1] Synthesis of Novolak Resin (C-1) In a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer, 144.2 g (1.0 mol) of 1-naphthol, 400 g of methyl isobutyl ketone, 96 g of water and 32.6 g of 92 mass% paraformaldehyde (1.0 mol in terms of formaldehyde) were charged. Subsequently, 3.4 g of a methanol solution of 30% by mass paratoluenesulfonic acid was added with stirring. Then, it was made to react at 100 degreeC for 8 hours. After completion of the reaction, 200 g of pure water was added, the solution in the system was transferred to a separating funnel, and the aqueous layer was separated and removed from the organic layer. Subsequently, after washing with water until the washing water became neutral, the solvent was removed from the organic layer under heating and reduced pressure to obtain 140 g of a novolak resin (C-1) composed of a structural unit represented by the following formula. The obtained novolak resin (C-1) had a weight average molecular weight (Mw) of 2000.

From the measurement chart using a Fourier transform infrared spectrophotometer (FT-IR), absorption (2800 to 3000 cm ⁻¹ ) derived from expansion and contraction due to a methylene bond can be confirmed as compared with the raw material, and further, absorption derived from aromatic ether (1000 ˜1200 cm ⁻¹ ) could not be found. Based on these results, it was identified that no dehydration etherification reaction between hydroxyl groups (hydroxyl disappearance) occurred in this synthesis example, and a novolak resin having a methylene bond was obtained. These identifications are the same in the following synthesis example C2.

[Synthesis Example C2] Synthesis of Novolak Resin (C-2) In a flask equipped with a thermometer, a condenser tube, a fractionating tube, and a stirrer, 144.2 g (1.0 mol) of 1-naphthol and 134.1 g of terephthalaldehyde were added. (1.0 mol) and 3.0 g of trifluoromethanesulfonic acid were charged and reacted at 150 to 160 ° C. for 4 hours while stirring. After completion of the reaction, 200 g of pure water was added, the solution in the system was transferred to a separating funnel, 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 a novolak resin (C-2) comprising a structural unit represented by the following formula. The obtained novolak resin (C-2) had a weight average molecular weight (Mw) of 3000.

<Preparation of radiation-sensitive resin composition>
Each component used for preparation of a radiation sensitive resin composition is as follows.

・ Polymer (A)
A-1: Polymer of Synthesis Example A1 A-2: Polymer of Synthesis Example A2 A-3: Polymer of Synthesis Example A3
・ Radiosensitive acid generator (B)
B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product of sulfonic acid chloride (2.0 mol) (manufactured by Toyo Gosei Co., Ltd.)
・ Novolac resin (C)
C-1: Novolak resin of Synthesis Example C1 C-2: Novolak resin of Synthesis Example C2 C-3: “MEHC-7800” manufactured by Meiwa Kasei Co., Ltd.
(Phenol novolac resin of the following formula)

・ Block isocyanate compounds (D)
D-1: “Karenz MOI-BP” manufactured by Showa Denko KK
2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate D-2: “Karenz MOI-BM” manufactured by Showa Denko KK
2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate
・ Solvent (E)
E-1: Mixed solvent of 30:20:50 by mass ratio of γ-butyrolactone (BL), propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) E-2: propylene glycol monomethyl ether acetate (PGMEA )
・ Adhesion aid (F)
F-1: “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.
3-glycidoxypropyltrimethoxysilane
・ Surfactant (G)
G-1: Silicone surfactant “SH8400” manufactured by Toray Dow Corning

[Example 1]
As a radiation-sensitive acid generator (B), a polymer solution containing the polymer (A-1) of Synthesis Example A1 (amount corresponding to 40 parts (solid content) of polymer (A-1)) is used as (B- 1) 16 parts, 25 parts of (C-1) as novolak resin (C), 15 parts of (D-1) as blocked isocyanate compound (D), 174 parts of (E-1) as solvent (E), adhesion aid (F) 3 parts of (F-1) and 1 part of (G-1) as a surfactant (G) are mixed and filtered through a 0.2 μm membrane filter to prepare a radiation sensitive resin composition. did. In addition, the solid content concentration of the said composition was 30 mass%.

[Examples 2 to 12, Comparative Examples 1 to 3]
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that the components of the types and blending amounts shown in Table 1 were used.

[Evaluation]
Using the radiation-sensitive resin compositions obtained in Examples and Comparative Examples, an insulating film and an organic EL element were produced by the method described below. The patterning property, radiation sensitivity and resolution of the composition were evaluated by the following methods, respectively, for the light shielding property, water absorption and heat resistance of the obtained insulating film, and device characteristics of the obtained organic EL device.

<Patternability>
Using a spinner or a slit die coater, the radiation-sensitive resin composition obtained in the above example or the like was applied on a silicon substrate, and then pre-baked on a hot plate at 120 ° C. for 2 minutes to form a coating film did. This coating film was exposed at an exposure amount of 100 mJ / cm ² at a wavelength of 365 nm through a pattern mask using an exposure machine (“MPA-6000” manufactured by Canon Inc.). Thereafter, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds, washed with running ultrapure water for 1 minute, dried, and dried on a silicon substrate having a diameter of 5 μm. A coating film having a pattern in which a plurality of through holes are arranged in a line was formed. 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 3.0 μm.

  At this time, it is confirmed that the exposed portion after development is completely dissolved in the coating film, and a pattern of 5 μm is formed, and the insulating film is peeled off or the insulating film is formed without development residue. Although a pattern was formed and the insulating film was not peeled off, there was a slight development residue, a case where a 5 μm pattern could not be formed, or a case where the insulating film was peeled off was defined as “bad”.

<Radiation sensitivity>
Using a spinner or a slit die coater, the radiation-sensitive resin composition obtained in the above-described Examples and the like was applied on a silicon substrate, and then pre-baked on a hot plate at 120 ° C. for 2 minutes to obtain a film thickness of 3. A 0 μm coating film was formed. The coating film was exposed using an exposure machine (Canon “MPA-6000”) while changing the exposure amount through a pattern mask having a predetermined pattern. Thereafter, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds, washed with running ultrapure water for 1 minute, dried, and dried on a silicon substrate with a diameter of 20.0 μm. A coating film having a plurality of through holes was formed.

At this time, the exposure amount required for the coating film to completely dissolve in accordance with the shape of the mask pattern having a diameter of 20.0 μm was measured, and the exposure amount at this time was defined as radiation sensitivity (exposure sensitivity). The radiation sensitivity was determined to be “good” when it was 100 mJ / cm ² or less, and “bad” when it exceeded 100 mJ / cm ² .

<Resolution>
Using a spinner or a slit die coater, the radiation-sensitive resin composition obtained in the above-described Examples and the like was applied on a silicon substrate, and then pre-baked on a hot plate at 120 ° C. for 2 minutes to obtain a film thickness of 3. A 0 μm coating film was formed. The coating film was exposed at an exposure amount of 100 mJ / cm ² through a pattern mask having a hole pattern diameter width of 5 μm to 50 μm using an exposure machine (“MPA-6000” manufactured by Canon Inc.). Thereafter, development is performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds, followed by washing with running ultrapure water for 1 minute, and perpendicular to the direction of a plurality of through-hole lines. The cross-sectional shape was observed with SEM (“SU3500” manufactured by Hitachi High-Technology Corporation), and the width of the bottom of the cross-section was measured. It can be said that the smaller the base width, the better the resolution.

<Light shielding>
Using a spinner or a slit die coater, the radiation-sensitive resin composition obtained in the above example or the like was applied on a glass substrate (Corning “Corning 7059”), and then on a hot plate at 120 ° C. for 2 minutes. After pre-baking, post-baking was performed at 250 ° C. for 45 minutes in a clean oven to form an insulating film having a thickness of 3.0 μm.

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

<Water absorption>
Using a spinner or a slit die coater, after applying the radiation-sensitive resin composition obtained in the above-mentioned examples etc. on a silicon substrate, pre-baking on a hot plate at 120 ° C. for 2 minutes, and then in a clean oven Post-baking was performed at 250 ° C. for 45 minutes to form an insulating film having a thickness of 3.0 μm. Sample obtained when the insulation film was heated from room temperature to 200 ° C. (30 ° C./min) at a vacuum degree of 1.0 × 10 ⁻⁹ Pa using Thermal Desorption Spectroscopy (“TDS1200” from ESCO). The detection value of the water peak (M / z = 18) was measured for the gas desorbed from the surface and the sample using a mass spectrometer (“5973N” manufactured by Agilent Technologies). The integrated value [A · sec] of the total peak intensity from 60 ° C. to 200 ° C. was taken to evaluate the water absorption. The water absorption is “excellent” when the integrated value [A · sec] of the total peak intensity from 60 ° C. to 200 ° C. is 3.0 × 10 ⁻⁸ or less, exceeding 3.0 × 10 ⁻⁸ . When it was 0 × 10 ⁻⁸ or less, it was ^judged as “good”, and when it exceeded 5.0 × 10 ⁻⁸ , it was ^judged as “bad”.

<Heat resistance>
In the same manner as in the evaluation of <Water Absorption>, an insulating film was formed using the radiation-sensitive resin composition, and this insulating film was measured at 100 ° C. using a thermogravimetric apparatus (“TGA2950” manufactured by TA Instruments). To 500 ° C., 5% weight loss temperature was determined by TGA measurement (in air, temperature rising rate 10 ° C./min). The heat resistance was defined as “excellent” when the 5% weight loss temperature exceeded 350 ° C., “good” when 350 to 330 ° C., and “bad” when less than 330 ° C.

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

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

  After applying the radiation sensitive resin composition obtained in the above-mentioned Examples etc. on the TFT substrate using a spinner or slit die coater, pre-baking on a hot plate at 120 ° C. for 2 minutes, and then in a clean oven An insulating film having a thickness of 3.0 μm was formed by post-baking at 250 ° C. for 45 minutes.

<Element characteristics>
The device characteristics were evaluated as switching response characteristics and device reliability evaluation.

<Switching response characteristics>
The switching response characteristic was evaluated by measuring the ON / OFF ratio. The ON / OFF ratio was calculated by measuring the current flowing between the source electrode and the drain electrode with a voltage applied to the gate electrode using a prober and a semiconductor parameter analyzer. More specifically, the semiconductor layer is irradiated with light (white light having a distribution centering on wavelengths of 450 nm and 500 nm, illuminance of 30000 lx) from above the insulating film formed from the radiation-sensitive resin composition. , The ratio of the current value when the voltage applied to the gate electrode is plus 10 V and minus 10 V when the drain electrode is plus 10 V and the source electrode is 0 V is the ON / OFF ratio. The switching response characteristics, that is, the element characteristics, were “good” when the ON / OFF ratio was 1.0 × 10 ⁵ or more, and “bad” when the ON / OFF ratio was less than 1.0 × 10 ⁵ .

<Element reliability>
The element reliability was evaluated using the variation amount of the TFT threshold voltage before and after stress application. The TFT threshold voltage is calculated by measuring the current flowing between the source electrode and the drain electrode with a voltage applied to the gate electrode using a prober and a semiconductor parameter analyzer. The stress on the element includes temperature stress, voltage Stress and light irradiation stress were applied, and the TFT threshold voltage was calculated again after a certain period of time.

  Specifically, the surface temperature of the TFT substrate is kept at 60 ° C., and light from the upper side of the insulating film formed from the radiation-sensitive resin composition with respect to the semiconductor layer (white having a distribution centering on wavelengths of 450 nm and 500 nm) Under the condition of irradiation with light and illuminance of 30000 lx), an electrical stress of −20 V was applied to the semiconductor film by keeping the drain electrode and the source electrode at 0 V and keeping the gate electrode at −20 V.

  The above conditions were maintained for 12 hours, and the TFT threshold voltage was calculated before and after stress application to determine the amount of variation. The element reliability was defined as “good” when the variation amount of the TFT threshold voltage was within 1V, and “bad” when the variation amount exceeded 1V.

  As shown in Table 2, the radiation sensitive resin compositions and insulating films of Examples 1 to 12 were excellent in patternability, pattern shape, low water absorption and heat resistance. Moreover, the insulating film formed in Examples 1-12 is excellent in light-shielding property, and is highly sensitive. An element using this insulating film and a semiconductor layer that is easily deteriorated in light was excellent in element characteristics (switching response characteristics and TFT reliability) even in a light irradiation environment. On the other hand, the insulating film formed in Comparative Examples 1 to 3 is inferior in light-shielding property, is not highly sensitive, or is not low in water absorption, and an element using this insulating film and a semiconductor layer that is easily deteriorated by light, In the light irradiation environment, the device characteristics (switching response or TFT reliability) were inferior.

  DESCRIPTION OF SYMBOLS 1 ... Organic EL device, 2 ... Support substrate, 3 ... TFT, 30 ... Gate electrode, 31 ... Gate insulating film, 32 ... Semiconductor layer, 33 ... Source electrode, 34 ... Drain electrode, 4 ... Inorganic insulating film, 5 ... 1st DESCRIPTION OF SYMBOLS 1 insulating film (flattening film), 6 ... anode, 7 ... through hole, 8 ... 2nd insulating film (partition), 80 ... recessed part, 9 ... organic light emitting layer, 10 ... cathode, 11 ... passivation film, 12 ... Sealing substrate, 13 ... Sealing layer

Claims (11)

(A) polyimide (A1) having a structural unit represented by the formula (A1),
The polyimide precursor (A2), a radical polymerizable monomer (a3-1) having an epoxy group or an oxetanyl group, a radical polymerizable monomer (a3-2) having a carboxyl group, and copolymerizable with the polymerizable monomer Alkali-soluble polymer (A3) obtained by polymerizing other radical polymerizable monomer (a3-3)
At least one polymer selected from:
(B) a radiation sensitive acid generator;
(C) a novolac resin;
(D) a compound having a group in which an isocyanate group is blocked by a protective group;
(E) A radiation sensitive resin composition containing a solvent.

[In Formula (A1), R ¹ is a divalent group having a hydroxyl group, and X is a tetravalent organic group. ] The radiation sensitive resin composition according to claim 1, wherein R ¹ in the formula (A1) is a divalent group represented by the formula (a1).

Wherein (a1), R ² represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a methylene group, a dimethylmethylene group or a bis (trifluoromethyl) methylene group; R ³ are each independently Are a hydrogen atom, a formyl group, an acyl group or an alkyl group, provided that at least one of R ³ is a hydrogen atom; n1 and n2 are each independently an integer of 0 to 2, provided that n1 and n2 At least one of is 1 or 2. ]   The radiation sensitive resin composition according to claim 1, wherein the novolak resin (C) is a resin containing a structural unit having a condensed polycyclic aromatic group having a phenolic hydroxyl group. The novolak resin (C) is a resin having at least one selected from the structural unit represented by the formula (C2-1) and the structural unit represented by the formula (C2-2). The radiation sensitive resin composition of any one.

[In Formula (C2-1) to Formula (C2-2), R ² represents a methylene group, an alkylene group having 2 to 30 carbon atoms, a divalent alicyclic hydrocarbon group having 4 to 30 carbon atoms, or a carbon number. A group represented by 7 to 30 aralkylene group or —R ³ —Ar—R ³ — (Ar is a divalent aromatic group, R ³ is independently a methylene group or an alkylene group having 2 to 20 carbon atoms; A, b, c and e are each independently an integer of 0 to 3, d is an integer of 0 to 2, provided that a and b are not both 0 and c There is no case where all of ~ e are 0. ]   The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the content of the novolak resin (C) is 5 to 200 parts by mass with respect to 100 parts by mass of the polymer (A). The compound (D) is at least one selected from a compound having one group represented by the formula (D-1) and a compound having one group represented by the formula (D-2) The radiation sensitive resin composition of any one of Claims 1-5.

[In formula (D-1), R ^D1 represents an alkoxy group having 1 to 20 carbon atoms or a derivative group thereof, a cycloalkoxy group having 3 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, or 1 to 15 carbon atoms. A thioalkoxy group having 3 to 15 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms. In formula (D-2), R ^D2 and R ^D3 are each independently an alkyl group or an aryl group, and R ^D2 and R ^D3 are bonded to each other to form a ring together with the carbon atom to which each is bonded. Also good. ] The radiation sensitivity according to claim 6, wherein the compound (D) is at least one selected from a compound represented by the formula (D-11) and a compound represented by the formula (D-21). Resin composition.

Wherein (D-11) and ^{(D-21), R D1} , R D2 and R ^D3 are identical symbols synonymous with each formula (D1) and (D2) in; R ^D4 are hydrogen An atom or a methyl group; A is a methylene group or an alkylene group; ] Solvent (E) is
Diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, ethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether propionate, The radiation sensitive resin composition of any one of Claims 1-7 containing at least 1 sort (s) selected from triethylene glycol dialkyl ether.   The insulating film for organic EL elements formed from the radiation sensitive resin composition of any one of Claims 1-8.   The process of forming a coating film on a board | substrate using the radiation sensitive resin composition of any one of Claims 1-8, the process of irradiating at least one part of the said coating film, and the said radiation are irradiated The manufacturing method of the insulating film for organic EL elements which has the process of developing the developed coating film, and the process of heating the developed said coating film.   An organic EL device having the insulating film according to claim 9.

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