JP2014029766A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element which includes an organic insulating film having high exposure sensitivity and excellent heat-resistant shape-retaining properties and has excellent reliability.SOLUTION: There is provided the organic electroluminescent element characterized by including the organic insulating film comprising a radiation-sensitive resin composition which contains: a polymer (A) containing a polymer (A1) having a structural unit represented by general formula (1) and a structural unit represented by general formula (2); a radiation-sensitive compound (B); and a crosslinking agent (C).

Description

  The present invention relates to an organic electroluminescence element, and relates to an organic electroluminescence element having an organic insulating film having high exposure sensitivity and excellent heat-resistant shape retention, and having excellent reliability.

  An organic electroluminescent element as an example of an electronic component includes a protective film for preventing deterioration and damage, a planarizing film for planarizing the element surface and wiring, an electrical insulating film for maintaining electrical insulation, Various resin films such as a pixel separation film for separating the light-emitting portion are provided.

  Conventionally, thermosetting resin materials such as epoxy resins have been widely used as resin materials for forming these resin films. On the other hand, with recent increases in the density of wiring and devices, new resin materials having excellent transparency, high electrical insulation and excellent heat resistance have been demanded for these resin materials.

  In order to meet such various requirements, radiation-sensitive compositions using various resin materials have been proposed. For example, Patent Document 1 discloses a radiation-sensitive resin composition comprising an alicyclic olefin resin, an acid generator, a crosslinking agent, a specific phenol anti-aging agent, and a solvent. However, in order to maintain the transparency of the resin after the heating step in the atmosphere using this radiation-sensitive resin composition, a large amount of a phenolic anti-aging agent must be added, and thus the sensitivity to radiation is low. In some cases, it did not function sufficiently as a radiation sensitive composition.

  Patent Document 2 proposes a radiation-sensitive resin composition using an acrylic photosensitive resin as a resin material. However, according to Patent Document 2, although the acrylic resin can be used to improve the electrical characteristics of the resulting resin film, the heat resistance is not sufficient, and a current is applied for a long time. There was a problem that the reliability when doing so was not sufficient.

  Furthermore, in the case of using the resin film for constituting the organic electroluminescence element described above, when the pattern is used, the pattern shape is not melted or deformed before and after the heating step, and the shape can be maintained (heat resistant shape). However, in the techniques of Patent Documents 1 and 2 described above, such heat resistant shape retainability is not sufficient.

International Publication No. 03/100524 JP 9-152625 A

  An object of the present invention is to provide an organic electroluminescent element having an organic insulating film having high exposure sensitivity and excellent heat-resistant shape retention, and excellent in reliability.

  As a result of diligent research to achieve the above object, the present inventors, as a resin composition for forming an organic insulating film for constituting an organic electroluminescence device, a structural unit comprising a specific (meth) acrylate And a polymer comprising a specific ethylenically unsaturated bond group-containing phenol compound, a radiation-sensitive compound, and a radiation-sensitive resin composition containing a crosslinking agent to achieve the above object. The present inventors have found that the present invention can be accomplished and have completed the present invention.

（上記一般式（１）中、Ｒ^１、Ｒ^２は、それぞれ独立して、水素原子、又は置換基を有していてもよい炭素数１〜６の１価の炭化水素基である。）

（上記一般式（２）中、Ｒ^３は、化学的な単結合、又は置換基を有していてもよい炭素数１〜６の２価の炭化水素基であり、Ｒ^４は、水素原子、又は置換基を有していてもよい炭素数１〜６の１価の炭化水素基である。） That is, according to the present invention, a polymer (A) containing a polymer (A1) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2): An organic electroluminescence device comprising an organic insulating film comprising a radiation-sensitive resin composition containing a radiation-sensitive compound (B) and a crosslinking agent (C) is provided.

(In the general formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.)

(In the general formula (2), R ³ is a chemical single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and R ⁴ is a hydrogen atom. Or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.)

In this invention, it is preferable that the said organic insulating film is a pixel separation film for isolate | separating the organic light emitting layer from which the light emission wavelength which comprises the said organic electroluminescent element mutually differs.
Or in this invention, it is preferable that the said organic insulating film is a planarization film | membrane for planarizing the said organic electroluminescent element surface.
Moreover, in this invention, it is preferable that the said polymer (A) further contains the polymer (A2) which consists only of a structural unit represented by the said General formula (2).
Moreover, in this invention, it is preferable that the said crosslinking agent (C) contains 2 or more types of different compounds.
Furthermore, in this invention, it is preferable that the said radiation sensitive resin composition further contains the compound (D) which has an acidic group or a heat | fever latent acidic group.

  The present invention includes a plurality of semiconductor layers formed on a substrate, a planarization film provided on each semiconductor layer, and a plurality of electrodes that penetrate through the planarization film in the thickness direction and are electrically connected to each semiconductor layer ( Anode), a plurality of light emitting layers provided on each electrode (on the side opposite to the semiconductor layer) corresponding to each electrode, and conductively connected to each electrode, and pixel separation for separating adjacent light emitting layers An organic electroluminescence element including the film, wherein the pixel separation film and / or the planarization film is formed of the radiation-sensitive resin composition. Further, the organic electroluminescence element further includes a counter electrode (cathode) on the pixel separation film and the light emitting layer (a surface opposite to the electrode). Under the present circumstances, it is preferable that the said polymer (A) used for the said radiation sensitive resin composition further contains the polymer (A2) which consists only of a structural unit represented by the said General formula (2). Moreover, it is preferable that the said crosslinking agent (C) used for the said radiation sensitive resin composition contains a 2 or more types of different compound. Furthermore, it is preferable that the said radiation sensitive resin composition further contains the compound (D) which has an acidic group or a heat | fever latent acidic group.

  According to the present invention, it is possible to provide an organic electroluminescence element having an organic insulating film having high exposure sensitivity and excellent heat-resistant shape retention, and excellent in reliability.

FIG. 1 is a cross-sectional view showing an example of an organic electroluminescence element according to the present invention.

The organic electroluminescent device according to the present invention includes a polymer (A1) containing a polymer (A1) having a structural unit represented by the general formula (1) described later and a structural unit represented by the general formula (2) described later. An organic insulating film comprising a radiation-sensitive resin composition containing the coalescence (A), the radiation-sensitive compound (B), and the crosslinking agent (C) is provided.
In the following, first, the radiation-sensitive resin composition used in the present invention will be described.

(Radiation sensitive resin composition)
The radiation sensitive resin composition used by this invention contains a polymer (A), a radiation sensitive compound (B), and a crosslinking agent (C).

(Polymer (A))
The polymer (A) used in the present invention is a polymer (A1) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) (hereinafter, appropriately, (Abbreviated as “polymer (A1)”).

In the general formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, preferably , An alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms.

In the general formula (2), R ³ is a chemical single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent. It is a bond or an alkylene group having 1 to 4 carbon atoms (branched or straight chain type), and more preferably a chemical single bond or an alkylene group having 1 to 2 carbon atoms. In the general formula (2), R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and preferably 1 to 4 carbon atoms. More preferably an alkyl group having 1 to 2 carbon atoms.

  Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro group; cyano group; phenyl group , A phenyl group which may have a substituent such as a 4-methylphenyl group and a 2-chlorophenyl group, a hydroxyl group; and the like.

  The polymer (A1) having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is, for example, the structural unit represented by the general formula (1). Can be obtained by copolymerizing a monomer that will form a structural unit represented by the general formula (2).

  As monomers that form the structural unit represented by the general formula (1), methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, I-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-acrylate Dodecyl; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, n-methacrylate Hexyl, n-octyl methacrylate, 2-ethylhexyl methacrylate Le, methacrylic acid n- decyl, and the like methacrylic acid n- dodecyl. These may be used alone or in combination of two or more. Among these, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate are preferable from the viewpoint that the effect of improving the reliability of the obtained organic electroluminescence element is high.

  Examples of the monomer that forms the structural unit represented by the general formula (2) include 4-hydroxystyrene (p-vinylphenol), 3-hydroxystyrene (m-vinylphenol), 2- Hydroxystyrene (o-vinylphenol), α-methyl-4-hydroxystyrene, α-methyl-3-hydroxystyrene, α-methyl-2-hydroxystyrene, 4-hydroxyallylbenzene, 3-hydroxyallylbenzene, 2- Examples include hydroxyallylbenzene. These may be used alone or in combination of two or more. Among these, 4-hydroxystyrene (p-vinylphenol) is preferable because the effect of improving the reliability of the obtained organic electroluminescence device is high.

  The content ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the polymer (A1) used in the present invention is “the above general formula (1). The weight ratio of the “structural unit represented by the general formula (2)” is preferably 10:90 to 90:10, and more preferably 20:80 to 40:60. By setting these weight ratios in the above range, the exposure sensitivity when forming a pattern by lithography and the life characteristics of the organic electroluminescence element when used as an insulating film can be improved.

  In addition to the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), the polymer (A1) used in the present invention is copolymerizable with these. What copolymerized the monomer may be used. Examples of such other copolymerizable monomers include vinyl ester compounds, (meth) acrylic acid [acrylic acid and / or methacrylic acid, hereinafter (meth) acrylic acid ester and the like. ), Aromatic vinyl compounds (excluding compounds having a phenol group), vinyl cyanide compounds, unsaturated dibasic acids, and anhydrides thereof.

Specific examples of the vinyl ester compound include vinyl acetate and vinyl propionate.
Specific examples of the aromatic vinyl include styrene, α-methylstyrene, vinyl pyridine and the like.
Specific examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, vinylidene cyanide and the like.
Specific examples of the unsaturated dibasic acid and its anhydride include maleic acid, fumaric acid, itaconic acid, maleic anhydride and the like.

  The content of other copolymerizable monomer units in the polymer (A1) used in the present invention is preferably 30% by weight or less, more preferably 15% by weight or less.

  Although it does not specifically limit as a manufacturing method of the polymer (A1) used by this invention, Any methods, such as solution polymerization method, suspension polymerization method, block polymerization method, and emulsion polymerization method, can be used. Moreover, when manufacturing a polymer (A1), it replaces with the ethylenically unsaturated bond group containing phenol compound mentioned above as a monomer which will form the structural unit represented by the said General formula (2). In addition, a method in which the phenolic hydroxyl group of the compound is copolymerized using a previously alkoxylated monomer, and the alkoxy group of the obtained copolymer is hydrolyzed to form a phenolic hydroxyl group is obtained. It may be adopted.

  The average molecular weight of the polymer (A1) used in the present invention is a weight average molecular weight (Mw) in terms of monodisperse polystyrene measured by gel permeation chromatography (GPC), preferably 3,000 to 20,000, more preferably It is 4,000 to 15,000, more preferably 4,500 to 12,000.

  Moreover, as a polymer (A) used by this invention, in addition to the polymer (A1) mentioned above, it further contains the polymer (A2) which consists only of the structural unit represented by the said General formula (2). Is preferred. By further containing the polymer (A2), it is possible to further improve the exposure sensitivity and heat-resistant shape retention in the case of an organic insulating film, and to further improve the reliability of the obtained organic electroluminescence element. Can do.

  The polymer (A2) consisting only of the structural unit represented by the general formula (2) (hereinafter abbreviated as “polymer (A2)” as appropriate) is represented by the general formula (2). For example, it may be a copolymer obtained by copolymerizing two or more monomers that give the structural unit represented by the general formula (2). Alternatively, it may be a homopolymer obtained by homopolymerizing a single monomer that gives the structural unit represented by the general formula (2), but is preferably a homopolymer. In the present invention, the polymer (A2) may be any polymer that can be determined to be substantially composed of only the structural unit represented by the general formula (2). If so, it may be one containing other monomer units.

  As the monomer that forms the structural unit represented by the general formula (2), the same monomers as the polymer (A1) described above can be used.

  Although it does not specifically limit as a manufacturing method of the polymer (A2) used by this invention, Any methods, such as a solution polymerization method, suspension polymerization method, block polymerization method, and emulsion polymerization method, can be used. Moreover, when manufacturing a polymer (A2), it replaces with the ethylenically unsaturated bond group containing phenolic compound mentioned above as a monomer which will form the structural unit represented by the said General formula (2). In addition, a method in which a phenolic hydroxyl group of the compound is polymerized using a monomer alkoxylated in advance and the alkoxy group of the obtained polymer is hydrolyzed to obtain a phenolic hydroxyl group is adopted. May be.

  The average molecular weight of the polymer (A2) used in the present invention is a weight average molecular weight (Mw) in terms of monodisperse polystyrene measured by gel permeation chromatography (GPC), preferably 3,000 to 20,000, more preferably It is 4,000 to 15,000, more preferably 4,500 to 12,000.

  When the polymer (A) is added to the polymer (A1) and contains the polymer (A2), the ratio of the polymer (A1) to the polymer (A2) is “polymer The weight ratio of (A1): polymer (A2) ”is preferably 90:10 to 50:50, more preferably 80:20 to 60:40. By making the ratio of the polymer (A1) and the polymer (A2) in the above-mentioned range, the effect of improving the exposure sensitivity and heat-resistant shape retention in the case of an organic insulating film, and the organic electroluminescence device to be obtained The reliability improvement effect can be further increased.

(Radiation sensitive compound (B))
The radiation-sensitive compound (B) used in the present invention is a compound that can cause a chemical reaction upon irradiation with radiation such as ultraviolet rays or electron beams. In the present invention, the radiation sensitive compound (B) is preferably one that can control the alkali solubility of the organic insulating film formed by the radiation sensitive resin composition, and it is particularly preferable to use a photoacid generator.

  Examples of the photoacid generator used in such a radiation sensitive compound (B) include azide compounds such as acetophenone compounds, triarylsulfonium salts, quinonediazide compounds, and the like, preferably azide compounds, particularly preferably quinonediazide compounds. It is.

As the quinonediazide compound, for example, an ester compound of a quinonediazidesulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinone diazide sulfonic acid halide include 1,2-naphthoquinone diazide-5-sulfonic acid chloride, 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-benzoquinone diazide-5-sulfonic acid chloride, and the like. Can be mentioned. Typical examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1. -[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and the like. Other compounds having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4- Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, novolac resin oligomer, phenolic hydroxyl group Examples thereof include oligomers obtained by copolymerizing one or more compounds and dicyclopentadiene.
Among these, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and a compound having a phenolic hydroxyl group is preferable, and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl]] is preferred. A condensate (ester) of -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) is more preferred.

In addition to quinonediazide compounds, photoacid generators include onium salts, halogenated organic compounds, α, α′-bis (sulfonyl) diazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfone compounds, Known compounds such as organic acid ester compounds, organic acid amide compounds, and organic acid imide compounds can be used.
These radiation-sensitive compounds can be used alone or in combination of two or more. However, two or more of these radiation-sensitive compounds can be used because the exposure sensitivity when forming a pattern by lithography can be improved. Are preferably used in combination.

  The content of the radiation sensitive compound (B) in the radiation sensitive resin composition used in the present invention is preferably 10 to 60 parts by weight, more preferably 15 to 55 parts by weight with respect to 100 parts by weight of the polymer (A). Parts, more preferably 20 to 50 parts by weight, most preferably 25 to 45 parts by weight. If the content of the radiation-sensitive compound (B) is within this range, the solubility difference in the developer between the radiation-irradiated part and the radiation-unirradiated part when patterning the organic insulating film made of the radiation-sensitive resin composition. Is increased, radiation sensitivity is increased, and patterning by development is easy.

(Crosslinking agent (C))
The radiation sensitive resin composition used in the present invention further contains a crosslinking agent (C) in addition to the polymer (A) and the radiation sensitive compound (B) described above. Examples of the crosslinking agent (C) include those that form a crosslinked structure between the crosslinking agent molecules by heating, and those that react with the polymer (A) to form a crosslinked structure between the resin molecules. A compound having two or more reactive groups.

  Examples of such a reactive group include an amino group, a carboxyl group, a hydroxyl group, an epoxy group, and an isocyanate group. Among these, an amino group, an epoxy group, and an isocyanate group are preferable, and an amino group and an epoxy group are preferable. Is more preferable. The epoxy group is preferably a terminal epoxy group or an alicyclic epoxy group, and more preferably an alicyclic epoxy group.

  Although the molecular weight of a crosslinking agent (C) is not specifically limited, Preferably it is 100-100,000, More preferably, it is 300-50,000, More preferably, it is 500-10,000. The cross-linking agents can be used alone or in combination of two or more. However, when the organic insulating film is used, the exposure sensitivity and heat-resistant shape retention can be further improved. It is preferable to use a combination of two or more types from the viewpoint that the reliability of the luminescence element can be further improved.

  Specific examples of the crosslinking agent (C) include aliphatic polyamines such as hexamethylenediamine; aromatic polyamines such as 4,4′-diaminodiphenyl ether and diaminodiphenylsulfone; 2,6-bis (4′-azidobenzal) Azides such as cyclohexanone and 4,4′-diazidodiphenylsulfone; polyamides such as nylon, polyhexamethylenediamineterephthalamide and polyhexamethyleneisophthalamide; N, N, N ′, N ′, N ′ ′, Melamines which may have a methylol group such as N ′ ′-(hexaalkoxyalkyl) melamine or an imino group (trade names “Cymel 303, Cymel 325, Cymel 370, Cymel 235, Cymel 272, Cymel 232, Cymel 212, My Court 506 "{End Cymel series such as INDUSTRIES}, My Coat series); N, N ′, N ″, N ′ ″-(tetraalkoxyalkyl) glycoluril and other methylol groups and imino groups Good glycolurils (Cymel series such as “Cymel 1170” {manufactured by Cytec Industries, Inc.}); acrylate compounds such as ethylene glycol di (meth) acrylate; hexamethylene diisocyanate polyisocyanate, isophorone diisocyanate polyisocyanate, tri Isocyanate compounds such as diisocyanate polyisocyanate and hydrogenated diphenylmethane diisocyanate; 1,4-di- (hydroxymethyl) cyclohexane, 1,4-di- (hydroxymethyl) norbornane; 1,3,4 -Trihydroxycyclohexane; bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, polyphenol type epoxy resin, cyclic aliphatic epoxy resin, aliphatic glycidyl ether, epoxy acrylate polymer, etc. Of epoxy compounds;

  Specific examples of such an epoxy compound include a trifunctional epoxy compound having a dicyclopentadiene skeleton (trade name “XD-1000”, manufactured by Nippon Kayaku Co., Ltd.), 2,2-bis (hydroxymethyl) 1 -1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol (15 functional alicyclic epoxy resin having cyclohexane skeleton and terminal epoxy group, trade name "EHPE3150", manufactured by Daicel Chemical Industries, Ltd.) Epoxidized 3-cyclohexene-1,2-dicarboxylic acid bis (3-cyclohexenylmethyl) modified ε-caprolactone (aliphatic cyclic trifunctional epoxy resin, trade name “Epolide GT301”, manufactured by Daicel Chemical Industries), Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprola Epoxy compounds having an alicyclic structure such as kuton (aliphatic cyclic tetrafunctional epoxy resin, trade name “Epolide GT401”, manufactured by Daicel Chemical Industries);

  Aromatic amine type polyfunctional epoxy compound (trade name “H-434”, manufactured by Tohto Kasei Kogyo Co., Ltd.), cresol novolac type polyfunctional epoxy compound (trade name “EOCN-1020”, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type Polyfunctional epoxy compounds (Epicoat 152, 154, manufactured by Japan Epoxy Resin Co., Ltd.), polyfunctional epoxy compounds having a naphthalene skeleton (trade name EXA-4700, manufactured by Dainippon Ink & Chemicals, Inc.), chain alkyl polyfunctional epoxy compounds (products) Name “SR-TMP”, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., multifunctional epoxy polybutadiene (trade name “Epolide PB3600”, manufactured by Daicel Chemical Industries, Ltd.), glycerin glycidyl polyether compound (trade name “SR-GLG”, Sakamoto Yakuhin) Kogyo Co., Ltd.), diglycerin polyglycidyl ether compound ( Product name “SR-DGE”, Sakamoto Yakuhin Kogyo Co., Ltd., polyglycerol polyglycidyl ether compound (trade name “SR-4GL”, Sakamoto Yakuhin Kogyo Co., Ltd.) and other epoxy compounds having no alicyclic structure; be able to.

  Among these epoxy compounds, a polyfunctional epoxy compound having two or more epoxy groups is preferable, and since the organic insulating film obtained using the radiation-sensitive resin composition is excellent in heat-resistant shape retention, it has an alicyclic structure. A polyfunctional epoxy compound having 3 or more epoxy groups is particularly preferable. Moreover, when using 2 or more types of epoxy compounds as a crosslinking agent (C) in combination, it is preferable to use 2 or more types of polyfunctional epoxy compounds having 3 or more epoxy groups, and 3 epoxy groups. More preferably, two or more polyfunctional epoxy compounds having different epoxy groups from each other are used in combination. By using two or more types of such epoxy compounds in combination, it is possible to further enhance the effect of improving exposure sensitivity and heat-resistant shape retention, and the reliability of the obtained organic electroluminescence element.

  The content of the crosslinking agent (C) in the radiation-sensitive resin composition is not particularly limited, and the degree of heat resistance required when a pattern is provided on an organic insulating film obtained using the radiation-sensitive resin composition. Although it may be arbitrarily set in consideration, it is preferably 20 to 100 parts by weight, more preferably 25 to 90 parts by weight, still more preferably 30 to 80 parts by weight, particularly 100 parts by weight of the polymer (A). Preferably it is 30-70 weight part. If the crosslinking agent (C) is too much or too little, the heat resistance tends to decrease.

(Compound (D) having an acidic group or a thermal latent acidic group)
In addition to the polymer (A), the radiation sensitive compound (B) and the crosslinking agent (C), the radiation sensitive resin composition used in the present invention is a compound having an acidic group or a heat latent acidic group ( It is preferable to contain D). The compound (D) having an acidic group or a thermal latent acidic group is not particularly limited as long as it has an acidic group or a thermal latent acidic group that generates an acidic group by heating, but is preferably an aliphatic compound, aromatic Group compounds and heterocyclic compounds, more preferably aromatic compounds and heterocyclic compounds.
These compounds having an acidic group or a heat-latent acidic group can be used alone or in combination of two or more.

The number of acidic groups and thermal latent acidic groups of the compound (D) having an acidic group or thermal latent acidic group is not particularly limited, but it has a total of two or more acidic groups and / or thermal latent acidic groups. Those are preferred. The acidic group or the heat latent acidic group may be the same as or different from each other.
The acidic group may be an acidic functional group, and specific examples thereof include strong acidic groups such as sulfonic acid group and phosphoric acid group; weak acidic groups such as carboxy group, thiol group and carboxymethylenethio group; Can be mentioned. Among these, a carboxy group, a thiol group or a carboxymethylenethio group is preferable, and a carboxy group is particularly preferable. Among these acidic groups, those having an acid dissociation constant pKa in the range of 3.5 to 5.0 are preferred. When there are two or more acidic groups, it is preferable that the first dissociation constant pKa1 is an acid dissociation constant and the first dissociation constant pKa1 is in the above range. The pKa is determined according to pKa = −logKa by measuring the acid dissociation constant Ka = [H ₃ O ⁺ ] [B ⁻ ] / [BH] under dilute aqueous solution conditions. Here, BH represents an organic acid, and B ⁻ represents a conjugate base of the organic acid.
In addition, the measuring method of pKa can calculate hydrogen ion concentration, for example using a pH meter, and can calculate from the density | concentration of a relevant substance, and hydrogen ion concentration.

  The heat-latent acidic group may be any group that generates an acidic functional group upon heating. Specific examples thereof include a sulfonium base, a benzothiazolium base, an ammonium base, a phosphonium base, a block carboxylic acid group, and the like. (Trade names “Nofcure TN-1”, “Nofcure TN-2”, manufactured by NOF Corporation). Among these, from the viewpoints of improving the dimensional stability of the pattern and maintaining the properties such as viscosity and exposure sensitivity during storage of the radiation-sensitive resin composition, that is, having excellent storage stability, the block carboxylic acid. Groups are preferred. The carboxy group blocking agent used to obtain the blocked carboxylic acid group is not particularly limited, but is preferably a vinyl ether compound.

Moreover, the compound (D) which has an acidic group or a heat | fever latent acidic group may have substituents other than an acidic group and a heat | fever latent acidic group.
As such substituents, in addition to hydrocarbon groups such as alkyl groups and aryl groups, halogen atoms; alkoxy groups, aryloxy groups, acyloxy groups, heterocyclic oxy groups; substituted with alkyl groups, aryl groups, or heterocyclic groups Polar groups having no proton such as amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group; alkylthio group, arylthio group, heterocyclic thio group; Examples thereof include a hydrocarbon group substituted with a polar group having no proton.

  Among the compounds (D) having such an acidic group or thermal latent acidic group, specific examples of the compound having an acidic group include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, butanoic acid, and pentanoic acid. , Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, glycolic acid, glyceric acid, ethanedioic acid (also referred to as “oxalic acid”), propanedioic acid (also referred to as “malonic acid”), butane diacid. Acid (also referred to as “succinic acid”), pentanedioic acid, hexanedioic acid (also referred to as “adipic acid”), 1,2-cyclohexanedicarboxylic acid, 2-oxopropanoic acid, 2-hydroxybutanedioic acid, 2 -Hydroxypropanetricarboxylic acid, mercaptosuccinic acid, dimercaptosuccinic acid, 2,3-dimercapto-1-propanol, 1,2,3-trimercaptopropa 2,3,4-trimercapto-1-butanol, 2,4-dimercapto-1,3-butanediol, 1,3,4-trimercapto-2-butanol, 3,4-dimercapto-1,2- Aliphatic compounds such as butanediol and 1,5-dimercapto-3-thiapentane;

  Benzoic acid, p-hydroxybenzenecarboxylic acid, o-hydroxybenzenecarboxylic acid, 2-naphthalenecarboxylic acid, methylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, 3-phenylpropanoic acid, dihydroxybenzoic acid, dimethoxybenzoic acid, benzene -1,2-dicarboxylic acid (also referred to as “phthalic acid”), benzene-1,3-dicarboxylic acid (also referred to as “isophthalic acid”), benzene-1,4-dicarboxylic acid (also referred to as “terephthalic acid”) ), Benzene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, benzenehexacarboxylic acid, biphenyl-2,2′-dicarboxylic acid 2- (carboxymethyl) benzoic acid, 3- (carboxymethyl) benzoic acid, 4- (carboxymethyl) benzoic acid Benzoic acid, 2- (carboxycarbonyl) benzoic acid, 3- (carboxycarbonyl) benzoic acid, 4- (carboxycarbonyl) benzoic acid, 2-mercaptobenzoic acid, 4-mercaptobenzoic acid, diphenolic acid, 2-mercapto -6-naphthalenecarboxylic acid, 2-mercapto-7-naphthalenecarboxylic acid, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,4-naphthalenedithiol, 1, 5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1 , 2,3-Tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercapto) Aromatic compounds such as ethyl) benzene;

  Nicotinic acid, isonicotinic acid, 2-furoic acid, pyrrole-2,3-dicarboxylic acid, pyrrole-2,4-dicarboxylic acid, pyrrole-2,5-dicarboxylic acid, pyrrole-3,4-dicarboxylic acid, imidazole Five-membered nitrogen atoms such as 2,4-dicarboxylic acid, imidazole-2,5-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, pyrazole-3,5-dicarboxylic acid Heterocyclic compounds; thiophene-2,3-dicarboxylic acid, thiophene-2,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiazole-2,4-dicarboxylic acid, thiazole -2,5-dicarboxylic acid, thiazole-4,5-dicarboxylic acid, isothiazole-3,4-dicarboxylic acid, isothiazole -3,5-dicarboxylic acid, 1,2,4-thiadiazole-2,5-dicarboxylic acid, 1,3,4-thiadiazole-2,5-dicarboxylic acid, 3-amino-5-mercapto-1,2, 4-thiadiazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3,5-dimercapto-1,2,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole, 3- (5-mercapto-1,2,4-thiadiazol-3-ylsulfanyl) succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylsulfanyl) succinic acid, (5-mercapto-1 , 2,4-thiadiazol-3-ylthio) acetic acid, (5-mercapto-1,3,4-thiadiazol-2-ylthio) acetic acid, 3- (5-mercapto-1,2,4) Thiadiazol-3-ylthio) propionic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) propionic acid, 3- (5-mercapto-1,2,4-thiadiazol-3-ylthio) Succinic acid, 2- (5-mercapto-1,3,4-thiadiazol-2-ylthio) succinic acid, 4- (3-mercapto-1,2,4-thiadiazol-5-yl) thiobutanesulfonic acid, 4 -5-membered heterocyclic compound containing a nitrogen atom and a sulfur atom such as (2-mercapto-1,3,4-thiadiazol-5-yl) thiobutanesulfonic acid;

Pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5 -Dicarboxylic acid, pyridazine-3,4-dicarboxylic acid, pyridazine-3,5-dicarboxylic acid, pyridazine-3,6-dicarboxylic acid, pyridazine-4,5-dicarboxylic acid, pyrimidine-2,4-dicarboxylic acid, pyrimidine -2,5-dicarboxylic acid, pyrimidine-4,5-dicarboxylic acid, pyrimidine-4,6-dicarboxylic acid, pyrazine-2,3-dicarboxylic acid, pyrazine-2,5-dicarboxylic acid, pyridine-2,6- Dicarboxylic acid, triazine-2,4-dicarboxylic acid, 2-diethylamino-4,6-dimercapto-s-triazine, 2-dipropyl Mino-4,6-dimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, 2,4,6-trimercapto- 6-membered heterocyclic compounds containing a nitrogen atom such as s-triazine.
Among these, it is preferable that the number of acidic groups in the compound having an acidic group is 2 or more from the viewpoint that the adhesion of the obtained organic insulating film can be improved.

  Moreover, as a specific example of the compound having a thermal latent acidic group among the compounds (D) having an acidic group or a thermal latent acidic group, the acidic group of the compound having the acidic group is converted into a thermal latent acidic group. Compound. For example, 1,2,4-benzenetricarboxylic acid tris (1-propoxyethyl) obtained by converting a carboxy group of 1,2,4-benzenetricarboxylic acid into a block carboxylic acid group has a heat latent acidic group. It can be used as a compound. From the viewpoint that the adhesiveness of the resulting resin film can be further improved, the number of heat latent acidic groups in the compound having a heat latent acidic group is preferably 2 or more.

  The content of the compound (D) having an acidic group or a heat-latent acidic group in the radiation-sensitive resin composition is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the polymer (A). Preferably it is 1-45 weight part, More preferably, it is 2-40 weight part, More preferably, it is the range of 3-30 weight part. By making the usage-amount of the compound (D) which has an acidic group or a heat | fever latent acidic group into the said range, a radiation sensitive resin composition can be made excellent in liquid stability.

  Moreover, the radiation sensitive resin composition may contain the solvent. The solvent is not particularly limited, and is known as a solvent for the radiation sensitive resin composition, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone. Linear ketones such as 2-octanone, 3-octanone and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and other alcohol ethers; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, propio Esters such as ethyl acid, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, Propylene glycols such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Diethylene glycols; saturated γ-lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-caprolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; Examples include polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide. These solvents may be used alone or in combination of two or more. The content of the solvent is preferably 400 to 2,000 parts by weight, more preferably 450 to 1,600 parts by weight, and even more preferably 500 to 1,200 parts by weight with respect to 100 parts by weight of the polymer (A). It is a range.

  In addition, the radiation-sensitive resin composition used in the present invention is a surfactant, an acidic compound, a coupling agent or a derivative thereof, a sensitizer, a latent acid, if desired, as long as the effects of the present invention are not inhibited. Other compounding agents such as a generator, an antioxidant, a light stabilizer, an antifoaming agent, a pigment, a dye, and a filler; Among these, for example, surfactants, coupling agents or derivatives thereof, sensitizers, antioxidants, and light stabilizers, for example, those described in JP 2011-75609 A can be used. .

The preparation method of the radiation sensitive resin composition used by this invention is not specifically limited, What is necessary is just to mix each component mentioned above by a well-known method.
The mixing method is not particularly limited, but it is preferable to mix a solution or dispersion obtained by dissolving or dispersing the above-described components in a solvent. Thereby, a radiation sensitive resin composition is obtained with the form of a solution or a dispersion liquid.

  A method for dissolving or dispersing each of the above-described components in a solvent may follow a conventional method. Specifically, stirring using a stirrer and a magnetic stirrer, a high-speed homogenizer, a disper, a planetary stirrer, a twin-screw stirrer, a ball mill, a three-roll, etc. can be used. Further, after each component is dissolved or dispersed in a solvent, it may be filtered using, for example, a filter having a pore size of about 0.5 μm.

  The solid content concentration of the radiation-sensitive resin composition is usually 1 to 70% by weight, preferably 5 to 60% by weight, and more preferably 10 to 50% by weight. If the solid content concentration is within this range, dissolution stability, coating properties, film thickness uniformity of the formed resin film, flatness, and the like can be highly balanced.

(Organic electroluminescence device)
Next, the organic electroluminescence element of the present invention will be described. FIG. 1 is a cross-sectional view showing an example of an organic electroluminescence element according to the present invention. As shown in FIG. 1, an organic electroluminescent element 1 according to an example of the present invention includes a planarization film 4 formed on a plurality of thin film transistors 3 on a substrate 2 including a plurality of thin film transistors 3, and a planarization film 4. A through-electrode (anode) 5 in a through-hole formed through the thickness direction, and organic light-emitting layers 7, 8, 9 in contact with the through-electrode 5 (surface opposite to the thin-film transistor) The pixel separation film 6 that separates the adjacent organic light emitting layers 7, 8, 9 and the upper surfaces of the pixel separation film 6 and the organic light emitting layers 7, 8, 9 are formed so as to face each other. And an electrode (cathode) 10 functioning as an electrode. In the organic electroluminescence element 1, the thin film transistor 3, the through electrode 5, the organic light emitting layers 7, 8, 9 and the electrode 10 are electrically connected. ON / OFF is switched, whereby various displays are performed. Each of the organic light emitting layers 7, 8, and 9 can correspond to, for example, a red organic light emitting layer, a green organic light emitting layer, and a blue organic light emitting layer, respectively. In this case, the adjacent organic light emitting layers 7, 8, and 9 have different light emission wavelengths.

  The substrate 2 is not particularly limited, and is a flexible plastic substrate such as polycarbonate, polyimide, polyethylene terephthalate, alicyclic olefin polymer, a glass substrate such as quartz, soda glass, inorganic alkali glass, or a silicon substrate such as a silicon wafer. And so on.

  The thin film transistor 3 is not particularly limited, and a known thin film transistor can be used without limitation.

  The through electrode 5 can be made of, for example, a conductive material (transparent conductive material or the like) such as indium tin oxide (ITO).

The organic light emitting layers 7, 8, and 9 are not particularly limited and can be formed using a known organic electroluminescence material.
The electrode 10 can be formed of a conductive material such as aluminum.

  In the organic electroluminescence element 1 of the present invention, at least one of the planarization film 4 and the pixel separation film 6 is formed of an organic insulating film made of the above-described radiation-sensitive resin composition. In the present invention, at least one of the planarization film 4 and the pixel isolation film 6 is formed of the organic insulating film made of the above-described radiation-sensitive resin composition, whereby the reliability of the organic electroluminescence element 1, particularly It is possible to improve the reliability when a current is applied for a long time. In the present invention, at least one of the planarization film 4 and the pixel isolation film 6 may be formed of the organic insulating film made of the above-described radiation-sensitive resin composition. Both of the films 6 may be formed of an organic insulating film made of the radiation sensitive resin composition described above.

  The planarization film 4 is a layer that is usually provided to planarize the surface of the organic electroluminescence element 1, and as shown in FIG. 1, the through electrode 5 is formed in a state of penetrating in the thickness direction. It will be.

  Further, as shown in FIG. 1, the pixel separation film 6 is a layer for separating adjacent organic light emitting layers 7, 8, 9, and surrounds each organic light emitting layer 7, 8, 9. It is formed.

  The formation method in the case where at least one of the planarization film 4 and the pixel isolation film 6 is formed by the organic insulating film made of the above-described radiation-sensitive resin composition is not particularly limited, and for example, a coating method or A method such as a film lamination method can be used.

  For example, after applying the radiation-sensitive resin composition on the substrate 2 (in the case of the planarization film 4) or on the planarization film 4 (in the case of the pixel separation film 6), the solvent is removed by heating and drying. It is a method of removing. Examples of the method for applying the radiation sensitive resin composition include various methods such as a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, and a screen printing method. Can be adopted. The heating and drying conditions vary depending on the type and blending ratio of each component, but are usually 30 to 150 ° C., preferably 60 to 120 ° C., usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more. Preferably it may be performed in 1 to 30 minutes.

  In the film lamination method, the radiation-sensitive resin composition is applied onto a B-stage film-forming substrate such as a resin film or a metal film, and then the solvent is removed by heat drying to obtain a B-stage film. In this method, the stage film is laminated on the substrate 2 (in the case of the planarization film 4) or on the planarization film 4 (in the case of the pixel separation film 6). The heating and drying conditions can be appropriately selected according to the type and mixing ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. . Film lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like.

  The thicknesses of the planarization film 4 and the pixel isolation film 6 are not particularly limited, but are preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and still more preferably 0.5 to 30 μm.

  Moreover, since the radiation sensitive resin composition contains the crosslinking agent (C) as described above, it is formed on the substrate 2 (in the case of the planarizing film 4) or on the planarizing film 4 (in the case of the pixel separation film 6). After that, a crosslinking reaction can be performed. Such crosslinking may be appropriately selected depending on the type of the crosslinking agent (C), but is usually performed by heating. The heating method can be performed using, for example, a hot plate or an oven. The heating temperature is usually 180 to 250 ° C., and the heating time is appropriately selected depending on the area and thickness of the planarization film 4 and the pixel separation film 6, the equipment used, etc. For example, when using a hot plate, When using an oven for 5 to 60 minutes, it is usually in the range of 30 to 90 minutes. Heating may be performed in an inert gas atmosphere as necessary. Any inert gas may be used as long as it does not contain oxygen and does not oxidize the planarization film 4 and the pixel isolation film 6, and examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen is suitable. These inert gases can be used alone or in combination of two or more.

  Further, the planarization film 4 and the pixel isolation film 6 may be patterned. For example, in the case of the planarizing film 4, as shown in FIG. 1, patterning as described later can be used to form a through hole for forming a through electrode 5 that penetrates in the thickness direction. . In the case of the pixel separation film 6, as shown in FIG. 1, patterning as described later can be used to form a light emitting area for forming the organic light emitting layers 7, 8, 9.

  As a method for patterning the planarization film 4 and the pixel separation film 6, for example, a latent image pattern is formed by irradiating the resin film before patterning with actinic radiation, and then the developer is applied to the resin film having the latent image pattern. For example, a method of making a pattern appear by bringing the pattern into contact with each other.

As the actinic radiation, the radiation-sensitive compound (B) contained in the radiation-sensitive resin composition can be activated to change the alkali solubility of the radiation-sensitive resin composition containing the radiation-sensitive compound (B). If it is, it will not specifically limit. Specifically, ultraviolet rays, ultraviolet rays having a single wavelength such as g-line or i-line, light rays such as KrF excimer laser light and ArF excimer laser light; particle beams such as electron beams; As a method for selectively irradiating these actinic radiations in a pattern to form a latent image pattern, a conventional method may be followed. A method of irradiating a light beam such as a laser beam or an ArF excimer laser beam through a desired mask pattern, a method of drawing with a particle beam such as an electron beam, or the like can be used. When light is used as the active radiation, it may be single wavelength light or mixed wavelength light. Irradiation conditions may be appropriately selected depending on the active radiation to be used, for example, when using a light beam of wavelength 200 to 450 nm, the amount of irradiation is usually 10~1,000mJ / cm ^2, preferably 50 to 500 mJ / It is a range of cm ² and is determined according to irradiation time and illuminance. After irradiation with actinic radiation in this manner, the resin film is heat-treated at a temperature of about 60 to 130 ° C. for about 1 to 2 minutes as necessary.

  Next, the latent image pattern formed on the resin film before patterning is developed and made visible. As the developer, an aqueous solution of an alkaline compound is usually used. As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of these compounds include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate and sodium metasilicate; ammonia water; primary amines such as ethylamine and n-propylamine; diethylamine Secondary amines such as di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline Alcohol alcohols such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 -En, N-Me Cyclic amines such as Rupiroridon; and the like. These alkaline compounds can be used alone or in combination of two or more.

As an aqueous medium of the alkaline aqueous solution, water; water-soluble organic solvents such as methanol and ethanol can be used. The alkaline aqueous solution may have a surfactant added in an appropriate amount.
As a method of bringing the developer into contact with the resin film having the latent image pattern, for example, a paddle method, a spray method, a dipping method, or the like is used. The development is usually appropriately selected in the range of 0 to 100 ° C, preferably 5 to 55 ° C, more preferably 10 to 30 ° C, and usually 30 to 180 seconds.

After the planarization film 4 and the pixel separation film 6 having the target pattern are formed in this manner, rinsing with a rinsing liquid can be performed as necessary in order to remove the development residue. After the rinse treatment, the remaining rinse liquid is removed with compressed air or compressed nitrogen.
Furthermore, in order to deactivate the radiation-sensitive compound (B) as necessary, the entire surface of the substrate 2 on which the organic electroluminescence element 1 is formed can be irradiated with actinic radiation. For irradiation with actinic radiation, the method exemplified in the formation of the latent image pattern can be used. The planarizing film 4 and the pixel isolation film 6 may be heated simultaneously with or after the irradiation. Examples of the heating method include a method of heating the organic electroluminescence element 1 in a hot plate or an oven. The temperature is usually in the range of 100 to 300 ° C, preferably 120 to 200 ° C.

  In the present invention, the planarization film 4 and the pixel isolation film 6 can undergo a crosslinking reaction after patterning. Crosslinking may be performed according to the method described above.

  In the organic electroluminescence device of the present invention, since the planarization film 4 and the pixel separation film 6 are formed of the organic insulating film made of the above-described radiation-sensitive resin composition, such an organic insulating film has an exposure sensitivity. Since it is high, it can be patterned with a relatively small amount of exposure, so that it is excellent in productivity, and the organic insulating film is excellent in heat-resistant shape retention, so that a desired pattern shape can be appropriately formed. it can. In addition, according to the present invention, the planarization film 4 and the pixel isolation film 6 are formed of the organic insulating film made of the above-described radiation-sensitive resin composition, so that the organic electroluminescence element of the present invention is reliable. (In particular, the reliability when a current is applied for a long time) can be excellent.

  In the above, as the organic electroluminescence element of the present invention, the configuration including the pixel separation film 6 as illustrated in FIG. 1 is illustrated, but the configuration is not particularly limited to such a configuration. A configuration in which the film 6 is not provided may be employed. In this case, only the planarizing film 4 may be formed of an organic insulating film made of the above-described radiation sensitive resin composition.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. “Part” and “%” in each example are based on weight unless otherwise specified.
In addition, the definition and evaluation method of each characteristic are as follows.

<Exposure sensitivity>
On a glass substrate (Corning, product name Corning 1737), a radiation sensitive resin composition is applied by spin coating, and is heated and dried (prebaked) at 110 ° C. for 2 minutes using a hot plate. A 5 μm resin film was formed. Then, to pattern the resin film, it is used capable of forming a mask line and space pattern of 10.0 [mu] m, changing the exposure amount for each 25 mJ / cm ² from 50 mJ / cm ² to 200 mJ / cm ² Then, the exposure process was performed. Next, using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, adjusting the time so that the film thickness becomes 1.1 μm at 25 ° C., rinsing with ultrapure water for 30 seconds. Thereby, the laminated body which consists of a resin film which has the line and space from which an exposure amount differs, and a glass substrate was obtained.

  And the formation part of the line and space of the obtained laminated body was observed using the optical microscope, and the length of the line and space of the resin film of the part exposed by each exposure amount was measured, respectively. Then, an approximate curve is created from the relationship between each exposure amount and the length of the line and space of the resin film formed at the corresponding exposure amount, and the exposure amount when the line and space become 10 μm is calculated. The amount was calculated as exposure sensitivity. It is preferable that the exposure amount when the line and space become 10 μm is low, because the pattern can be formed with low energy or in a short time.

<Heat-resistant shape retention (pattern dimension heat resistance)>
Using the radiation-sensitive resin composition, a 10 μm line and space pattern was formed on the substrate in the same manner as the exposure sensitivity measurement described above, and the entire surface of the substrate was irradiated with 1000 mJ / cm ² of exposure light. . Next, the substrate is put into an oven at 230 ° C. in which nitrogen is flowed so that the oxygen concentration becomes 1% or less after 10 minutes, heat treatment is performed for 60 minutes, and the line pattern of the heat-treated substrate is observed with an optical microscope. did. And the absolute value of the difference of the pattern width after a heat processing and the pattern width before a heating (10 micrometers) was computed, and the value was evaluated as pattern dimension heat resistance. The smaller the pattern dimension heat resistance value, the better the heat resistant shape retention, the smaller the amount of pattern deformation caused by heat treatment, and the less the pattern variation within the substrate surface can be determined.

<Reliability evaluation of organic electroluminescence element (lifetime of organic EL element)>
A glass substrate having an ITO transparent electrode film having a film thickness of 50 nm, a sheet resistance of 50 Ω / □, and a surface roughness (Ra) of 1 nm, which has been patterned on the surface, is cleaned with ultraviolet-ozone treatment, and then washed with ultrapure water. Sonication was performed for a minute, and then moisture was removed by blowing nitrogen onto the substrate surface. The radiation-sensitive resin composition obtained in each of the examples and comparative examples was applied onto the ITO film-coated glass substrate with a spin coater, and was heated and dried at 110 ° C. for 120 seconds on a hot plate. Next, exposure is performed through a mask having a predetermined pattern using an exposure machine (“Mask Aligner PLA504F”, manufactured by Canon Inc.), and paddle development is performed with a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds. Processing was carried out. After that, heat treatment is performed at 230 ° C. for 60 minutes while flowing nitrogen in an oven, so that light emitting areas of 10 μm length and 100 μm width are arranged in a 2 mm square area, and the thickness of the light emitting area is 1.5 μm thick. A lattice pattern surrounded by the resin film was formed. Next, 100 mW plasma treatment was performed on the substrate using oxygen gas for 3 minutes.

Next, the substrate on which the lattice pattern was formed was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Nippon Vacuum Engineering Co., Ltd.), and the vacuum layer was depressurized to 1 × 10 ⁻⁴ Pa. Thereafter, a plurality of layers described below were formed on the light emitting area of the substrate on which the lattice pattern was formed by vacuum vapor deposition of the material installed on the heating boat.
That is, first, a molybdenum oxide layer was formed with a thickness of about 0.75 nm. Next, N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is about 90 nm, tris (8-hydroxyquinolinato) aluminum (III) (Alq) is about 70 nm, fluorine. About 0.8 nm of lithium fluoride (LiF) and about 100 nm of aluminum (Al) were formed. And finally, the organic electroluminescent element sample was produced by adhere | attaching the glass cap with a getter agent using a sealing agent.

And about the organic electroluminescent element sample obtained by doing in this way, constant current drive (50 mA) in an 80 degreeC atmosphere using the light emission characteristic time-dependent change evaluation system ("ELS-108", the product made by EA Sea Co., Ltd.). / Cm ² ), the lifetime characteristics when the panel was made to emit light were evaluated. In the evaluation, the driving time until the luminance of the organic light emitting layer reaches 80% of the initial value is defined as the life time.

<< Synthesis Example 1 >>
50 parts of pt-butoxystyrene, 50 parts of methyl methacrylate and 4 parts of azobisisobutyronitrile as a polymerization initiator are dissolved in 150 parts of propylene glycol monomethyl ether as a solvent, and the reaction temperature is adjusted under a nitrogen atmosphere. The polymerization was carried out for 10 hours while maintaining at 70 ° C. Then, sulfuric acid was added to the reaction solution, and the reaction temperature was maintained at 90 ° C. for 10 hours, and the pt-butoxystyrene unit was deprotected and converted to the p-vinylphenol unit. Then, ethyl acetate is added to the obtained copolymer, washing with water is repeated 5 times, the ethyl acetate phase is separated, and the solvent is removed, whereby a copolymer of p-vinylphenol and methyl methacrylate (A1 -1) was obtained. The ratio of each monomer unit in the obtained copolymer (A1-1) was p-vinylphenol unit: methyl methacrylate unit = 50: 50 (weight ratio). The weight average molecular weight (Mw) was 9600.

<< Synthesis Example 2 >>
In the same manner as in Synthesis Example 1, except that the amount of pt-butoxystyrene was changed from 50 parts to 75 parts and the amount of methyl methacrylate was changed from 50 parts to 25 parts, p-vinylphenol and A copolymer (A1-2) with methyl methacrylate was obtained. The ratio of each monomer unit in the obtained copolymer (A1-2) was p-vinylphenol unit: methyl methacrylate unit = 75: 25 (weight ratio). The weight average molecular weight (Mw) was 6480.

<< Synthesis Example 3 >>
The homopolymer of p-vinylphenol (A2-1) was changed in the same manner as in Synthesis Example 1 except that the blending amount of pt-butoxystyrene was changed from 50 parts to 100 parts and methyl methacrylate was not blended. ) The weight average molecular weight (Mw) was 9400.

<< Synthesis Example 4 >>
Copolymer of p-vinylphenol and n-butyl methacrylate (A1-3) in the same manner as in Synthesis Example 1 except that 50 parts of n-butyl methacrylate was used instead of 50 parts of methyl methacrylate. Got. The ratio of each monomer unit in the obtained copolymer (A1-3) was p-vinylphenol unit: n-butyl methacrylate unit = 50: 50 (weight ratio). The weight average molecular weight (Mw) was 11000.

<< Synthesis Example 5 >>
A copolymer (A1-4) of p-vinylphenol and styrene was obtained in the same manner as in Synthesis Example 1 except that 50 parts of styrene was used instead of 50 parts of methyl methacrylate. The ratio of each monomer unit in the obtained copolymer (A1-4) was p-vinylphenol unit: styrene unit = 50: 50 (weight ratio). The weight average molecular weight (Mw) was 4700.

Example 1
100 parts of the copolymer (A1-1) of p-vinylphenol and methyl methacrylate obtained in Synthesis Example 1, and 4,4 ′-[1- [4- [1-] as the radiation-sensitive compound (B). (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid ester (2 mol) (trade name) "TS-200", manufactured by Toyo Gosei Kogyo Co., Ltd.) 15 parts, 2,3,4,4'-tetrahydroxybenzophenone and 6-diazo-5,6-dihydro-5 as radiation sensitive compound (B) 25 parts of an ester form (3-mol form) with oxo-naphthalene-1-sulfonic acid (trade name “4NT-300”, manufactured by Toyo Gosei Co., Ltd.), 2,2-bis (hydroxy) as a crosslinking agent (C) Methyl) 1-pig 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (trade name “EHPE3150”, manufactured by Daicel Chemical Industries, Ltd., 15-functional alicyclic epoxy resin having cyclohexane skeleton and terminal epoxy group) 30 parts, epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd., aliphatic cyclic tetrafunctional A radiation-sensitive resin composition was obtained by mixing 20 parts of epoxy resin)) and 630 parts of diethylene glycol ethyl methyl ether as a solvent. The solid content concentration of the radiation-sensitive resin composition was adjusted to be between 23 and 24% by weight (the same applies to the following examples).

  And according to the above-mentioned method using the obtained radiation sensitive resin composition, each measurement and evaluation of the exposure sensitivity of a resin film, heat-resistant shape retainability, and the reliability of an organic electroluminescent element were performed. The results are shown in Table 1. At this time, the planarization film 4 was formed to have a film thickness of 4.0 μm and the pixel isolation film 6 had a film thickness of 1.5 μm (the same applies to the following examples).

Example 2
Copolymer (A1-2) 100 of p-vinylphenol and methyl methacrylate obtained in Synthesis Example 2 instead of 100 parts of copolymer (A1-1) of p-vinylphenol and methyl methacrylate Except having used the part, it carried out similarly to Example 1, obtained the radiation sensitive resin composition, and evaluated similarly. The results are shown in Table 1.

Example 3
The blending amount of the copolymer (A1-1) of p-vinylphenol and methyl methacrylate was changed from 100 parts to 80 parts, and the homopolymer of p-vinylphenol obtained in Synthesis Example 3 (A2) -1) A radiation sensitive resin composition was obtained and evaluated in the same manner as in Example 1 except that 20 parts was further blended. The results are shown in Table 1.

Example 4
The blending amount of the copolymer (A1-1) of p-vinylphenol and methyl methacrylate is changed from 100 parts to 60 parts, and the homopolymer of p-vinylphenol obtained in Synthesis Example 3 (A2) -1) A radiation-sensitive resin composition was obtained and evaluated in the same manner as in Example 1 except that 40 parts was further blended. The results are shown in Table 1.

Example 5
Copolymer (A1-3) of p-vinylphenol and n-butyl methacrylate obtained in Synthesis Example 4 instead of 100 parts of copolymer (A1-1) of p-vinylphenol and methyl methacrylate ) A radiation-sensitive resin composition was obtained and evaluated in the same manner as in Example 1 except that 100 parts were used. The results are shown in Table 1.

Example 6
The amount of epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolacto as the crosslinking agent (C) is 50 parts, and 2,2-bis (hydroxymethyl) as the crosslinking agent (C) ) A radiation-sensitive resin composition was obtained in the same manner as in Example 1 except that the 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol was not blended, and was similarly evaluated. Went. The results are shown in Table 1.

Example 7
Except for further blending 5 parts of a block carboxylic acid group-containing compound ("Nofcure TN-1", manufactured by NOF Corporation) as the compound (D) having an acidic group or a thermal latent acidic group, the same as in Example 1 Thus, a radiation sensitive resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 1 >>
Instead of using 100 parts of the copolymer (A1-1) of p-vinylphenol and methyl methacrylate, 100 parts of the homopolymer of p-vinylphenol (A2-1) obtained in Synthesis Example 3 was used. In the same manner as in Example 1, a radiation-sensitive resin composition was obtained and evaluated in the same manner. The results are shown in Table 1.

<< Comparative Example 2 >>
Instead of 100 parts of copolymer (A1-1) of p-vinylphenol and methyl methacrylate, 100 parts of copolymer (A1-4) of p-vinylphenol and styrene obtained in Synthesis Example 5 were used. Except having used, it carried out similarly to Example 1, and obtained the radiation sensitive resin composition, and evaluated it similarly. The results are shown in Table 1.

  As shown in Table 1, from the results of Examples 1 to 7, the polymer (A1) having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2). An organic insulating film made of a radiation-sensitive resin composition containing a polymer (A) containing radiation, a radiation-sensitive compound (B), and a crosslinking agent (C) has high exposure sensitivity, and has pattern dimension heat resistance (heat-resistant shape retention). In addition, when used as a pixel separation film of an organic electroluminescence element, the obtained organic electroluminescence element has a long lifetime and high reliability. In this example, the pattern dimension heat resistance was evaluated by forming a line-and-space pattern, but it can be expected that good results can be obtained even when a through hole is formed. Furthermore, in this example, evaluation was performed when an organic insulating film made of a radiation-sensitive resin composition was used as a pixel separation film. However, even when used as a planarization film, good results can be obtained similarly. Can be expected.

On the other hand, in Comparative Example 1 using only the polymer having only the structural unit represented by the general formula (2), the obtained organic insulating film has low exposure sensitivity and has pattern dimension heat resistance (heat resistance shape retention). Furthermore, when used as a pixel separation film of an organic electroluminescence element, the obtained organic electroluminescence element has a short lifetime and is inferior in reliability.
Furthermore, also in Comparative Example 2 using a copolymer of the structural unit represented by the general formula (2) and styrene, the obtained organic insulating film has low exposure sensitivity, and has a pattern dimension heat resistance (heat resistant shape). In addition, when used as a pixel separation film of an organic electroluminescence element, the obtained organic electroluminescence element has a short lifetime and is inferior in reliability.

DESCRIPTION OF SYMBOLS 1 ... Organic electroluminescent element 2 ... Substrate 3 ... Thin film transistor 4 ... Flattening film 5 ... Through-electrode 6 ... Pixel separation film 7, 8, 9 ... Organic light emitting layer 10 ... Electrode

Claims (6)

A polymer (A) containing a polymer (A1) having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), a radiation sensitive compound (B) and An organic electroluminescence device comprising an organic insulating film made of a radiation-sensitive resin composition containing a crosslinking agent (C).

(In the general formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.)

(In the general formula (2), R ³ is a chemical single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and R ⁴ is a hydrogen atom. Or a monovalent hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.)   2. The organic electroluminescence element according to claim 1, wherein the organic insulating film is a pixel separation film for separating adjacent organic light emitting layers constituting the organic electroluminescence element.   The organic electroluminescence element according to claim 1, wherein the organic insulating film is a planarization film for planarizing the surface of the organic electroluminescence element.   The said electropolymer (A) further contains the polymer (A2) which consists only of a structural unit represented by the said General formula (2), The organic electro in any one of Claims 1-3 characterized by the above-mentioned. Luminescence element.   The organic electroluminescent device according to any one of claims 1 to 4, wherein the crosslinking agent (C) contains two or more different compounds.   6. The organic electroluminescence device according to claim 1, wherein the radiation-sensitive resin composition further contains a compound (D) having an acidic group or a thermal latent acidic group.

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