JP2002189290A - Radiation-sensitive resin composition for forming insulating film and insulating film for organic electroluminescence device - Google Patents

Abstract

(57) Abstract: A radiation-sensitive resin composition and an organic E that provide an insulating film having a flared shape suitable as an insulating film for an organic EL device.
Provided is an insulating film for an L element. (A) an alkali-soluble resin, (B) a quinonediazidesulfonic acid ester, (C) an organic solvent,
(D) A radiation-sensitive resin composition containing a thermosetting component, and a resin film having a desired pattern formed using the resin composition, which is heated and cured, and has a thickness of 0.3. This is an insulating film for an organic EL element having a flared shape of up to 3 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition for forming an insulating film, an insulating film for an organic electroluminescent device (hereinafter, electroluminescence is abbreviated as "EL"), and the insulating film. The present invention relates to an organic EL device. More specifically, the present invention relates to a positive radiation-sensitive resin composition used for forming an insulating film for an organic EL element having a flared shape, and a flared-type resin composition formed using the radiation-sensitive resin composition. The present invention relates to an organic EL element insulating film having a shape, and an organic EL element having the flared insulating film.

[0002]

2. Description of the Related Art An EL element utilizing electroluminescence is highly visible due to self-emission and is a completely solid state element.
Due to its characteristics such as excellent impact resistance, attention has been paid to its use as a light emitting element in various display devices. This EL element includes an inorganic EL element using an inorganic compound as a light-emitting material and an organic EL element using an organic compound. Among them, an organic EL element can significantly reduce the applied voltage. Since it is easy to reduce the size, consumes low power, can emit light in a plane, and easily emits light in three primary colors, research on its practical use as a next-generation light-emitting element has been actively made. The configuration of the light emitting portion of the organic EL element generally includes a transparent electrode layer (anode) / organic light emitting thin film layer (organic light emitting layer) / metal electrode layer (cathode) sequentially provided on a transparent substrate. Basically, this is provided with a hole injection / transport layer or an electron injection layer as appropriate, such as anode / hole injection / transport layer / organic light emitting layer / cathode, or anode / hole injection / transport layer / organic light emitting layer / electron injection. Structures such as layers / cathodes are known. The hole injection transport layer has a function of transmitting holes injected from the anode to the light emitting layer,
The electron injection layer has a function of transmitting electrons injected from the cathode to the light emitting layer. By interposing the hole injection transport layer between the light emitting layer and the anode, many holes are injected into the light emitting layer at a lower electric field, and further injected into the light emitting layer from the cathode or the electron injection layer. It is known that the collected electrons accumulate at the interface between the hole injection / transport layer and the light emitting layer because the hole injection / transport layer does not transport the electrons, thereby increasing the luminous efficiency. FIG. 1 is a principle diagram of one example of an organic EL element. As shown in FIG.
On the transparent electrode layer (anode) 2 provided thereon, an organic EL material layer 5 including a hole injection / transport layer 7, an organic light emitting layer 8, and an electron injection layer 9 is laminated, and a metal electrode layer is further formed thereon. (Cathode) 6 is laminated. Then, by passing a current between the anode and the cathode, the organic light emitting layer 8 is formed.
In this case, light emission is taken out from the transparent substrate 1 side. To manufacture this organic EL device,
First, a transparent electrode layer (anode) patterned on a transparent substrate such as a glass plate by vapor deposition or sputtering
Is formed, an insulating film having a desired pattern is provided thereon. This insulating film can be provided by, for example, an etching method of a polyimide resin film or a photolithography method using a photoresist. Note that the insulating film can also serve as a light-shielding film. Next, a resist pattern layer having a rectangular or reverse tapered cross section is provided by a photolithography method via the insulating film provided on the transparent substrate in this manner, and this resist pattern layer is used as a resin partition layer. , By a vacuum deposition method between each partition layer,
For example, an organic EL material layer is formed by sequentially providing a hole injecting / transporting layer, an organic light emitting layer, and an electron injecting layer, and a metal electrode layer (cathode) is laminated thereon to form a light emitting portion. Finally, a sealed organic EL element is obtained by forming a sealing layer on the light emitting portion. FIG. 2 is a partial cross-sectional view showing a configuration of an example of a light emitting section in a general organic EL element. That is, on the transparent substrate 1 on which the patterned transparent electrode layer 2 is provided, a resist pattern layer (resin partition layer) 4 having a reverse tapered cross section is provided via an insulating film 3. An organic EL material layer having a metal electrode layer 6 on its surface (a hole injection transport layer, an organic light emitting layer, and an electron injection layer are provided in this order from the transparent electrode layer side) between the resist pattern layers. 5) is provided, and the luminous body portion is formed in a non-contact and independent state with the resist pattern layer 4. The organic EL material layer 5a having the metal electrode layer 6a on the surface is also formed on the resist pattern layer 4, although it is not necessary for the function, but for convenience in manufacturing. As shown in FIG. 2, the insulating film 3 in the organic EL element having such a configuration usually has a rectangular cross section. However, when the cross-sectional shape of the insulating film is rectangular, an organic EL material layer is formed by vacuum evaporation on the transparent electrode layer 2 between the resin partition layers 4, and a metal electrode layer (cathode) is further formed thereon. When the luminous body part is formed by laminating the luminous body part, the side surface of the luminous body part is unlikely to be a vertical flat surface due to the nature of vacuum deposition, and in some cases, when the metal electrode layer is deposited, the side surface of the metal electrode material There is a problem that the frequency of occurrence of defective products is high, such as nonuniform light emission due to sneaking into the part or short-circuiting due to the metal electrode material adhering to the transparent electrode. In order to solve such a problem, it is conceivable that the shape of the insulating film has a shape in which the edge of the upper surface is rounded and the shape of the skirt is widened. When the insulating film has such a shape, it is difficult for the metal electrode material to wrap around when the metal electrode layer is deposited. In recent years,
A plurality of holes having a transparent electrode layer exposed on the bottom surface are provided in a desired pattern on the substrate, and a polymer organic EL material is jetted into the holes by a nozzle by an ink jet method to form an organic EL material layer. A technique for manufacturing an organic EL element by laminating a metal electrode layer thereon has been developed. In this case, a bank made of an insulating film (which can also serve as a light-shielding film) is provided between the holes. It is believed that a rounded edge and a flared shape are advantageous.

[0003]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides an insulating film having a rounded upper edge and a flared shape, which is suitable as an insulating film for an organic EL device. Radiation-sensitive resin composition, an insulating film for an organic EL device having the flared shape obtained by using the resin composition, and an organic EL having the insulating film having the flared shape
The purpose is to provide an element.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a positive-type radiation-sensitive resin composition containing a thermosetting component which cures at a specific temperature has been obtained. The edge of the upper surface is rounded, and it can be adapted for the purpose for forming an insulating film of a flared type, and by using this composition, a desired pattern is formed by photolithography or electron beam irradiation. It has been found that an insulating film for an organic EL element having a desired flared shape can be obtained by forming a resin film having the following formula, heating and curing the resin film. The present invention has been completed based on such findings. That is, the present invention provides a radiation-sensitive resin composition containing (1) (A) an alkali-soluble resin, (B) a quinonediazidesulfonic acid ester, (C) an organic solvent, and (D) a thermosetting component. Wherein the (D) thermosetting component is a resin film formed using the radiation-sensitive resin composition comprising the (A) alkali-soluble resin, (B) quinonediazidesulfonic acid ester, and (C) an organic solvent. A radiation-curable resin composition for forming an insulating film of an organic electroluminescence element, wherein the alkali-soluble resin as the component (A) is a phenol and an aldehyde. The radiation-sensitive resin composition for forming an insulating film according to claim 1, which is a novolak resin obtained by polycondensation with a compound or a ketone,
(3) The alkali-soluble resin of the component (A) is represented by the general formula [1]:

Embedded image (R ¹ in the formula is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
m represents an integer of 0 or 1 to 3, and when m is 2 or 3,
Each R ¹ may be the same or different. ) Which contains at least an alkali-soluble resin containing an amino group-containing aromatic compound represented by the formula (1) as a component of a monomer.
Item 4. The radiation-sensitive resin composition for forming an insulating film according to the above item, (4)
The thermosetting component (D) is represented by the general formula [2]:

Embedded image [R ² in the formula is

Embedded image (N is an integer of 3 to 8). Item 4. The radiation-sensitive resin composition for forming an insulating film according to item 1, 2 or 3, which is a thermosetting imide resin represented by the formula (5):
5. The radiation-sensitive resin composition for forming an insulating film according to any one of Items 1 to 4, which contains 1 to 20 parts by weight of the component (D) per 100 parts by weight of the component (A). 6. An organic electroluminescent device having a flared shape having a thickness of 0.3 to 3 μm, obtained by heating and curing a resin film having a desired pattern formed using the resin composition according to any one of items 5 to 5. An organic EL device comprising: an insulating film for a luminescence device; and (7) the insulating film according to item 6.
Is provided.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a radiation-sensitive resin composition for forming an insulating film of an organic EL device of the present invention (hereinafter, may be simply referred to as "radiation-sensitive resin composition of the present invention"). explain. The radiation-sensitive resin composition of the present invention,
A positive radiation-sensitive resin composition containing (A) an alkali-soluble resin, (B) a quinonediazide sulfonic acid ester, (C) an organic solvent, and (D) a thermosetting component. The alkali-soluble resin as the component (A) is not particularly limited, and an arbitrary one is appropriately selected from alkali-soluble resins conventionally used in positive photoresists using quinonediazidesulfonic acid ester as a photosensitive agent. Can be used. Specific examples of the alkali-soluble resin include a condensation reaction product of a phenol and an aldehyde or a ketone (a novolak resin), a vinylphenol-based polymer, an isopropenylphenol-based polymer,
Hydrogenation reaction products of these phenol resins can be exemplified. These condensation reaction products are prepared in a conventional manner,
For example, it can be obtained by reacting a phenol with an aldehyde or a ketone in the presence of an acidic catalyst. Examples of the phenols used as a raw material in the condensation reaction product of phenols with aldehydes or ketones in the above resins include phenol, o-cresol, m-cresol, p-cresol, 2,3 −
Xylenol, 2,4-xylenol, 3,5-xylenol, 2,6-xylenol, 1,2,3-trimethylphenol, 2,3,4-trimethylphenol, 2,3,5
-Trimethylphenol, o-ethylphenol, m-
Ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-butylphenol, m-butylphenol, p-butylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, Monohydric phenols such as o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, and 3-methylmethoxyphenol; polyhydric phenols such as resorcinol, pyrocatechol, hydroquinone, bisphenol A, phloroglucinol, and pyrogallol Is mentioned. One of these may be used alone, or two or more may be used in combination.

Examples of aldehydes include formaldehyde, paraformaldehyde, benzaldehyde, hydroxybenzaldehyde, terephthalaldehyde, acetaldehyde, and hydroxyacetaldehyde. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. Can be

On the other hand, vinylphenol-based polymers and isopropenylphenol-based polymers are selected from homopolymers of vinylphenol and isopropenylphenol and copolymers with components copolymerizable with vinylphenol and isopropenylphenol. Selected. Specific examples of the copolymerizable component include acrylic acid, methacrylic acid, styrene,
Examples thereof include maleic anhydride, maleic imide, vinyl acetate, acrylonitrile, and derivatives thereof. The copolymer can be obtained by a known method. further,
The hydrogenation reaction product of a phenolic resin can be obtained by any known method, for example, by dissolving the phenolic resin in an organic solvent and performing hydrogenation in the presence of a homogeneous or heterogeneous catalyst. It is. These alkali-soluble resins can be used as those whose molecular weight and molecular weight distribution are controlled by known means. As a method for controlling the molecular weight or molecular weight distribution, a method of crushing the resin and performing solid-liquid extraction with an organic solvent having appropriate solubility,
A method of dissolving the resin in a good solvent and dropping it into a poor solvent, or a method of dropping a poor solvent and performing solid-liquid or liquid-liquid extraction is mentioned. As the alkali-soluble resin of the component (A), one type may be used alone, or two or more types may be used in combination. Further, in the present invention, among the above alkali-soluble resins, particularly, phenols and aldehydes, alkali-soluble phenolic novolak type resin obtained by polycondensation in the presence of an acid catalyst, and the phenolic novolak type resin A mixture of the resin and a novolak resin containing an aniline structure represented by the following general formula [1] is preferable. As the phenols used for these novolak resins, a mixed cresol of m-cresol and p-cresol is preferable.

In the present invention, as the alkali-soluble resin, in addition to those described above, the general formula [1]

Embedded image (R ¹ in the formula is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
m represents an integer of 0 or 1 to 3, and when m is 2 or 3,
Each R ¹ may be the same or different. An alkali-soluble resin (hereinafter, referred to as an aniline structure-containing resin) containing the amino group-containing aromatic compound represented by the formula (1) as a component of the monomer can be used. By using such an aniline structure-containing resin as at least a part of an alkali-soluble resin, an insulating film having particularly excellent adhesion to a substrate can be obtained.

Examples of the amino group-containing aromatic compound represented by the general formula [1] include aniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6 -Dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2,6-diethylaniline, 2,6-diisopropylaniline, 3,5-
Di-tert-butylaniline, 2,4,6-trimethylaniline, 2,4,6-tri-tert-butylaniline, o-aminophenol, p-aminophenol, m
-Aminophenol and the like. One of these may be used alone, or two or more may be used in combination. As the aniline structure-containing resin, a novolak-type resin (hereinafter referred to as an aniline structure-containing resin) obtained by polycondensing the phenol, the amino group-containing aromatic compound, and the aldehyde or ketone in the presence of an acidic catalyst. Novolak-type resin). This novolak resin containing an aniline structure usually contains 0.1 to 60 parts by weight of an amino group-containing aromatic compound represented by the above general formula [1] and 10 to 10 parts by weight of aldehydes, based on 100 parts by weight of phenols.
It can be produced by mixing 20 parts by weight and 1 to 3 parts by weight of oxalic acid and reacting at a temperature of 70 to 95 ° C. for about 1 to 5 hours. The thus obtained novolak resin containing an aniline structure preferably has a weight average molecular weight in the range of 500 to 10,000, preferably 1,000 to 5,000 in terms of polystyrene. In the present invention, as the alkali-soluble resin of the component (A), the aniline structure-containing resin may be used alone, or may be used in combination with another alkali-soluble resin. Generally, the content of the amino group-containing aromatic compound component represented by the general formula [1] in the total alkali-soluble resin is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight.

In the radiation-sensitive resin composition of the present invention,
There is no particular limitation on the quinonediazidesulfonic acid ester used as the component (B), and any one can be appropriately selected from those conventionally known as a photosensitive agent. As the quinonediazidesulfonic acid ester, for example, a phenolic hydroxyl group of a polyphenol compound is converted into 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester at a fixed ratio, 1,2-naphthoquinonediazide-6-sulfonic acid esterification, 1,2-
Benzoquinonediazide-5-sulfonic acid esterification,
Examples thereof include 1,2-benzoquinonediazide-4-sulfonic acid esterified products. Among these, 1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazide-4-sulfonic acid ester are preferable, and 1,2-naphthoquinonediazide-5-sulfonic acid ester is more preferable. By using 1,2-naphthoquinonediazide-5-sulfonic acid ester, a radiation-sensitive resin composition having a good balance between sensitivity and resolution can be provided.

The polyphenols used herein have two or more, preferably three or more, and more preferably four phenolic hydroxyl groups in the molecule. Examples of the polyphenols include 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,4,2 ′, 4 Polyhydroxybenzophenones such as '-tetrahydroxybenzophenone, 2,3,4,2', 4'-pentahydroxybenzophenone; tris (4-
(Hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane,
1,1,1-tris (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxy-3-methylphenyl)-
1- (4-hydroxyphenyl) ethane, bis (4-hydroxy-3-methylphenyl) -2-hydroxy-4-
Polyhydroxytrisphenylalkanes such as methoxyphenylmethane; trimers of phenols and formalin; tetramers of phenols and formalin; and novolak resins, but are not limited thereto. As polyphenols,
In particular, quinonediazidesulfonic acid esters obtained using tri- or tetrahydroxybenzophenones are preferred because they provide good sensitivity and resolution. The method for producing these esters is not particularly limited, but quinonediazidesulfonic acid halide (preferably quinonediazidesulfonic acid chloride) is converted to sodium carbonate or sodium carbonate in a solvent such as acetone, dioxane, or tetrahydrofuran according to a conventional method.
Sodium hydrogen carbonate, inorganic bases such as sodium hydroxide and potassium hydroxide, or, trimethylamine, triethylamine, tripropylamine, diisopropylamine,
It can be obtained by reacting with a polyphenol compound in the presence of an organic base such as tributylamine, pyrrolidine, piperidine, piperazine, morpholine, pyridine and dicyclohexylamine.

In the ester used in the present invention, the ratio (average esterification ratio) of the quinonediazidesulfonic acid esterified hydroxyl groups of the hydroxyl groups of these polyphenols is determined by the number of equivalents of the hydroxyl groups of the polyphenols used in the reaction and the quinonediazidesulfonic acid. This is a value calculated from the number of moles of halide, and is usually 60% or more, preferably 65% or more.
%, And the upper limit is usually 100%, preferably 90%.
%. When the average esterification rate is 60% or more, the pattern shape and the resolution can be improved.
In the present invention, the quinonediazide sulfonic acid ester of the component (B) may be used alone or may be used alone.
Although 1,2-naphthoquinonediazide-4-sulfonic acid ester may be used in combination of at least 20% by weight, preferably at most 10% by weight, This is advantageous from the viewpoint of storage stability of the composition. In the radiation-sensitive resin composition of the present invention, the content of the quinonediazide sulfonic acid ester of the component (B) is generally 1 to 50 parts by weight, preferably 100 parts by weight, per 100 parts by weight of the alkali-soluble resin of the component (A). 10-3
It is selected in the range of 0 parts by weight. When the content of the component (B) is within the above range, a radiation-sensitive resin composition having an excellent balance between the resist characteristics such as effective sensitivity, residual film ratio, and resolution can be obtained.

The organic solvent of component (C) used in the radiation-sensitive resin composition is not particularly limited, and may be any of those conventionally known as solvents for photoresists, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, and the like. Linear ketones such as 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol Alcohols such as;
Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dioxane;
Alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; esters such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, and 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 glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether Propylene glycols such as diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol such as diethylene glycol methyl ethyl ether; .gamma.-butyrolactone,
saturated γ-lactones such as γ-valerolactone, γ-caprolactone, γ-caprylolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; dimethylacetamide, dimethylformamide, N- And polar solvents such as methylacetamide. These solvents may be used alone or in combination of two or more. Further, the amount of the solvent used may be an amount sufficient to uniformly dissolve or disperse each of the above components. In the present invention, the heat-resistant temperature of the resin film formed using the radiation-sensitive resin composition comprising the component (A), the component (B) and the organic solvent (C) is usually 9
It is advantageous to use one having a thermal characteristic in the range of 0 to 130 ° C, preferably 95 to 125 ° C. The heat-resistant temperature of this resin film is a value measured by the following method. On a 0.7 μm thick glass substrate, 30
A radiation-sensitive resin comprising the above-mentioned component (A), component (B) and (C) organic solvent on an ITO substrate having a 0 nm ITO (indium tin oxide) film formed thereon and containing no component (D) described below. Apply the composition and dry to a thickness of 1.2
After providing a μm resist film, 10 μm
A line and space pattern of m is formed, and then heated on a hot plate for 5 minutes. The temperature when the line width exceeds 120% of the line width before heating is defined as the heat resistant temperature of the resin film. As the thermosetting component (D) in the radiation-sensitive resin composition of the present invention, a thermosetting component that is cured at a temperature higher than the heat resistant temperature of the resin film measured by the above method is used. If the curing temperature of the thermosetting component is lower than the heat resistance temperature of the resin film, a desired flared type insulating film cannot be obtained. A preferred curing start temperature is a temperature higher than the heat resistant temperature of the resin film by 5 ° C. or more, and more preferably a temperature higher by 10 ° C. or more. On the other hand, if the curing start temperature is too high than the heat resistant temperature of the resin film, the skirt spread rate becomes too large, and it becomes impossible to obtain an insulating film having a desired shape. Therefore, the curing start temperature is preferably not higher than 50 ° C. higher than the heat resistance temperature of the resin film, and more preferably 3 ° C.
The temperature is 0 ° C. or higher.

The thermosetting component (D) is not particularly limited as long as it has a curing initiation temperature in the above-mentioned range and does not impair the resist properties and the insulating properties of the obtained film. , Various thermosetting compounds, specifically epoxy resin, guanamine resin, phenol resin,
Unsaturated polyester resin, imide resin, polyurethane,
Although a maleic acid resin, a melamine resin, a urea resin, and the like can be used, an imide resin, particularly, a thermosetting imide resin is preferable among these. As such a thermosetting imide resin, for example, the general formula [2]

Embedded image [R ² in the formula is

Embedded image (N is 3 to 8). And allylnadiimide represented by the formula: This bisallylnadiimide is cured by heat and shows high heat resistance. As the thermosetting component (D), one type may be used alone, or two or more types may be used in combination. The content of the radiation-sensitive resin composition in the alkali-soluble resin (A) is preferably 10% in view of the effect.
0 to 1 part by weight, usually 1 to 20 parts by weight, preferably 3 to
It is selected in the range of 15 parts by weight.

In the radiation-sensitive resin composition of the present invention, carbon black, chromium oxide, iron oxide, titanium black, aniline black, black, and the like may be used for the purpose of imparting a function as a light-shielding film to the formed insulating film. At least one selected from organic pigments including mixed color organic pigments obtained by mixing at least two types of organic pigments selected from organic pigments, red, blue, green, purple, yellow, cyan, and magenta to obtain a pseudo black color; Can be contained. This light-shielding material is preferably contained in the radiation-sensitive resin composition at a ratio of 20 to 80% by weight, and titanium black is particularly preferable from the viewpoint of light-shielding properties. Further, the radiation-sensitive resin composition of the present invention may optionally contain the polyhydroxybenzophenones, 1- [1- (4-
(Hydroxyphenyl) isopropyl] -4- [1,1-bis
Phenolic compounds such as (4-hydroxyphenyl) ethyl] benzene, tris (hydroxyphenyl) methanes and methyl-substituted products thereof, or mercaptooxazole, mercaptobenzoxazole, mercaptooxazoline, mercaptobenzothiazole, benzooxazoline, benzothiazolone, mercaptobenzo It can contain imidazole, urazole, thiouracil, mercaptopyrimidine, imidazolone and derivatives thereof. Further, in the radiation-sensitive resin composition of the present invention, an isocyanurate-based compound may be blended as an auxiliary agent for improving the resolution and the residual film ratio. Examples of the isocyanurate compound include 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-diethylbenzyl) isocyanurate,
1,3,5-tris (3,5-di-tert-butyl-4-
(Hydroxybenzyl) isocyanurate and the like. The radiation-sensitive resin composition of the present invention further comprises a compatible additive as necessary, such as an additional resin for improving the performance of the resin film, a plasticizer, a stabilizer,
Conventional components such as surfactants can be added.

Next, the insulating film for an organic EL device of the present invention comprises:
Using the above-described radiation-sensitive resin composition, a heat-treated resin film having a desired pattern formed on a substrate by a photolithography method has a rounded bottom surface and an insulating film in a skirt-spreading shape. It is. The area of the part in contact with the substrate of the pattern after the heat treatment, with respect to the area before the heat treatment,
It is desirable that the size be 140% or less. If the skirt spread ratio (the ratio (%) of the area of the portion in contact with the substrate to the area before the heat treatment) exceeds 140%, an insulating film having a desired pattern shape and a desired thickness may not be obtained. . Conversely, if the skirt spread ratio is small, a desired skirt spread type shape may not be obtained when the shape before heating is a rectangle or a shape close thereto. From such a viewpoint, the skirt spread rate is
Preferably it is more than 100% and 140% or less, more preferably in the range of 102 to 130%. The thickness of the insulating film is in the range of 0.3 to 3 μm, preferably 0.5 to 2 μm, and more preferably 1 to 1.5 μm. FIG. 3 is an explanatory view showing an example of a shape change when a resin film formed by a photolithography method is subjected to a heat treatment in the insulating film of the present invention. A portion surrounded by a solid line is a rectangular resin. A cross-sectional view of the film is shown, and a portion surrounded by a broken line shows a cross-sectional view of the insulating film of the present invention obtained by heat-treating the resin film.
The value of 100 × (b / a) ² is the skirt spread rate. As the substrate on which the insulating film for an organic EL element of the present invention is provided, a substrate having a transparent electrode layer (anode) patterned on a transparent substrate can be used. The transparent substrate has a light transmittance of 50 to 400 nm in a visible region of 50 nm.
% And a smooth substrate is desirable. Examples of such a transparent substrate include a glass plate and a polymer plate. Preferable examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic resin, polyethylene terephthalate, polyether sulfide, and polysulfone. Of these, a glass plate is usually preferably used.

The anode has a large work function (4
eV or more) A transparent electrode using a metal, an alloy, an electrically conductive compound or a mixture thereof as an electrode material is preferably used. The sheet resistance of the anode is preferably several hundreds Ω / cm ² or less. Such materials include ITO, Sn
Examples of the electrode material include a conductive material such as O ₂ , ZnO, or In—Zn—O. In order to form this anode, a thin film may be formed from these electrode substances by a method such as a vapor deposition method or a sputtering method. The thickness of the anode depends on the material, but is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

Such an insulating film for an organic EL device of the present invention can be efficiently manufactured by the following method. First, using the above-described radiation-sensitive resin composition, a desired pattern is formed on a substrate, specifically, a transparent substrate having a patterned transparent electrode layer (anode) by a photolithography method, an electron beam drawing method, or the like. A resin film having a substantially rectangular cross section is formed. Next, the resin film is subjected to a heat treatment at a temperature higher than the heat resistant temperature obtained by the above-described method to cure the thermosetting component, which is the component (D) in the resin film. Along with being round,
An insulating film for an organic EL device of the present invention having a flared shape is obtained.

Next, a specific method of manufacturing the insulating film will be described. On a transparent substrate having a transparent electrode layer (anode) to be patterned, the aforementioned radiation-sensitive resin composition is
It is applied with a spinner or the like and dried to form a resin layer. At this time, the thickness of the resin layer is controlled so that the finally obtained insulating film has a predetermined thickness. Next, this is irradiated with ultraviolet rays, deep-UV, excimer laser light, or the like through a desired mask pattern by a reduction projection exposure apparatus or the like, or drawn by an electron beam and heated. Thereafter, this is developed using a developing solution, for example, an alkaline aqueous solution such as an aqueous solution of 1 to 10% by weight of tetramethylammonium hydroxide to form a resin film having a substantially rectangular cross section having a pattern of a desired shape. I do.

Next, the resin film thus formed is subjected to a heat treatment at a temperature higher than the heat resistant temperature obtained by the above-described method, preferably at a temperature higher than 5 ° C., more preferably at a temperature higher than 10 ° C. Then, the thermosetting component in the resin film is cured. At this time, the heat treatment temperature is controlled in accordance with the heat-resistant temperature and the curing start temperature of the thermosetting component to be used so that an insulating film having a skirt-spreading shape with a rounded upper edge is formed. It is important to do it. The heat resistant temperature is preferably in the range of 90 to 200C, more preferably in the range of 95 to 180C. Further, the heat treatment temperature of the resin film is preferably in the range of 130 to 300 ° C.,
Particularly, a range of 150 to 250 ° C. is preferable. In addition, the heat treatment time depends on the heat treatment temperature and the heat treatment device and cannot be unconditionally determined. However, when a hot plate is used as the heat treatment device, it is usually about 30 to 900 seconds, and when the oven is used. Is about 10 to 120 minutes. Thus, the insulating film for an organic EL device of the present invention can be efficiently obtained. Since the insulating film has been subjected to the heat treatment at a high temperature as described above, the volatile components in the film are almost completely removed, and do not adversely affect the organic EL element.

The present invention also provides an organic EL device having an insulating film manufactured as described above. Next, a method for manufacturing an example of the organic EL device of the present invention will be described.
As described above, a resist pattern layer is formed by a conventionally known method via the flared type insulating film of the present invention provided on the transparent substrate having the patterned transparent electrode layer (anode). The cross-sectional shape of the resist pattern layer may be any of a rectangular type and a reverse taper type. When forming a resist pattern layer having a rectangular cross-sectional shape, the radiation-sensitive resin composition used may be any of a non-chemically amplified type and a chemically amplified type, and may be any of a positive type and a negative type. There may be. Examples of such a radiation-sensitive resin composition include (1) an alkali-soluble novolak resin, a non-chemically amplified positive photoresist containing a quinonediazide group-containing compound as an essential component, and (2) an alkali by the action of an acid. A resin capable of changing its solubility in water, a chemically amplified positive photoresist containing a compound capable of generating an acid upon irradiation with radiation as an essential component, and (3) an alkali-soluble resin, an acid crosslinkable substance, and irradiation with radiation. A photoresist such as a chemically amplified negative photoresist containing a compound capable of generating an acid as an essential component can be used. On the other hand, when forming a resist pattern layer having a reverse tapered cross section,
As the radiation-sensitive resin composition to be used, for example, those described in Japanese Patent No. 2989064, specifically (A) a component which is crosslinked by exposure to light or by heat treatment following exposure, (B) an alkali-soluble resin, and (C)
Negative photoresists containing at least one compound that absorbs light to be exposed and using an alkaline aqueous solution as a developer can be used.

There is no particular limitation on the method of providing a resist pattern layer using these photoresists, and a resist pattern layer having a rectangular or reverse-tapered cross-sectional shape may be formed by a conventional photolithography method. Can be. The thickness of this resist pattern layer is usually about 0.5 to several μm. Then, like this:
On a transparent substrate having a patterned transparent electrode layer,
After forming a resist pattern layer via the insulating film of the present invention, first, a hole injection / transport layer is provided by a vacuum evaporation method. In this case, the deposition conditions vary depending on the compound used (the material of the hole injection transport layer), the crystal structure and the recombination structure of the target hole injection transport layer, etc.
450 ° C., degree of vacuum 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature −50 to 300
It is preferable to appropriately select the temperature in the range of 5 nm to 1 μm. Next, an organic light emitting layer is formed on the hole injection transport layer by a vacuum evaporation method. In this case, the deposition conditions vary depending on the compound used, but can be generally selected from the same condition ranges as in the formation of the hole injection / transport layer. The thickness is preferably in the range of 10 to 40 nm. Next, an electron injection layer is provided on the organic light emitting layer by a vacuum evaporation method. In this case, the deposition conditions can be selected from the same condition ranges as those of the hole injection / transport layer and the organic light emitting layer. The film thickness is 5
It is preferable to appropriately select from the range of nm to 1 μm. Finally, a cathode is laminated by a vacuum deposition method. The cathode is made of metal and has a thickness of 50
The range of -200 nm is preferred. Thus, on the transparent substrate, a laminate (luminous body) composed of the transparent electrode layer (anode), the organic EL material layer (hole injection / transport layer, organic light emitting layer, electron injection layer) and the metal electrode layer (cathode) Part) is formed. FIG. 4 is a partial cross-sectional view showing a configuration of an example of a light emitting section in the organic EL element of the present invention. That is, a resist pattern layer (resin partition layer) 4 having a reverse tapered cross section is formed on a transparent substrate 1 on which a patterned transparent electrode layer 2 is provided, via a flared insulating film 3 ′ of the present invention. Is provided. An organic EL material layer having a metal electrode layer 6 on its surface (a hole injection transport layer, an organic light emitting layer, and an electron injection layer are provided in this order from the transparent electrode layer side) between the resist pattern layers. 5) is provided, and a light emitting portion is formed. Also,
The resist pattern layer 4 is not necessary for the function, but for convenience of manufacture, the organic E layer having the metal electrode layer 6a on the surface is used.
An L material layer 5a is formed. In such an organic EL device, since the insulating film 3 'has a flared shape as shown in FIG. 4, when the metal electrode layer 6 is laminated by vapor deposition, the transparentness due to the wraparound of the metal electrode material occurs. Since no adhesion occurs on the electrode layer 2, an undesirable situation such as a short circuit does not occur.

The insulating film of the present invention is used for the above-mentioned applications in an organic EL device. In addition, a polymer organic EL material is jetted from a nozzle into a hole of a desired pattern provided on a substrate by an ink jet method. And organic E
In an organic EL device obtained by forming an L material layer, the organic EL device can also be used for a bank including an insulating film provided between holes. In the organic EL device, the organic light-emitting layer is (1) when an electric field is applied,
An injection function capable of injecting holes from the anode or the hole injection transport layer and injecting electrons from the cathode or the electron injection layer, and (2) applying the injected charges (electrons and holes) to an electric field. And (3) a light emitting function of providing a field of recombination of electrons and holes inside the light emitting layer and connecting the light to light emission. There is no particular limitation on the type of light-emitting material used for this light-emitting layer.
A known material can be used as a light emitting material in the element. Specific examples of such a luminescent material include benzothiazole-based, benzimidazole-based, benzoxazole-based fluorescent brighteners, metal chelated oxinoid compounds, styrylbenzene-based compounds, distyrylpyrazine derivatives, and aromatic dimethylidene compounds. And the like. The hole injecting and transporting layer is a layer made of a hole transporting compound and has a function of transmitting holes injected from the anode to the light emitting layer. , Many holes are injected into the light emitting layer at a lower electric field. In addition, electrons injected into the light emitting layer by the cathode or the electron injection layer are accumulated near the interface in the light emitting layer due to the electron barrier existing at the interface between the light emitting layer and the hole injection transport layer, and the light emission of the EL element is reduced. Efficiency can be improved and an EL element having excellent light-emitting performance can be obtained. There is no particular limitation on the hole transporting compound used in the hole injecting / transporting layer, and any known hole transporting compound in an organic EL device can be used. Specific examples of the hole transport compound include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, and styryl Specific conductive high molecular oligomers such as anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane compounds, aniline copolymers, and thiophene oligomers are exemplified.

The electron injection layer has a function of transmitting electrons injected by the cathode to the organic light emitting layer. There is no particular limitation on the electron transfer compound used in the electron injection layer, and a known electron transfer compound in an organic EL device can be used. Specific examples of such electron transfer compounds include nitro-substituted fluorenone derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, fluorenylidene Methane derivatives, anthrone derivatives, oxadiazole derivatives, and also metal complexes of 8-quinolinol or its derivatives, for example, tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, bis (benzo-8-quinolinol) zinc,
Bis (2-methyl-8-quinolinol) aluminum oxide, tris (8-quinolinol) indium, tris (5-methyl-8-quinolinol) aluminum, 8
-Quinolinol lithium, tris (5-chloro-8-quinolinol) potassium, bis (5-chloro-8-quinolinol) calcium, tris (5,7-dichloro-8-)
Quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, bis (8-quinolinol) beryllium, bis (2-methyl-8-quinolinol) beryllium, bis (8-quinolinol) zinc,
Bis (2-methyl-8-quinolinol) zinc, bis (8
-Quinolinol) tin, tris (7-propyl-8-quinolinol) aluminum and the like. Note that the organic light-emitting layer, the hole injection transport layer, and the electron injection layer may be formed of one or two or more layers of each material, or two or more layers of different materials are stacked. It may be something. As the cathode, a metal electrode using a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a low work function (4 eV or less) as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium,
Examples include lithium, magnesium / silver alloy, Al / aluminum oxide, indium, and rare earth metals. Further, the sheet resistance as an electrode is preferably several hundred Ω / cm ² or less.

[0025]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 Synthesis of Novolak Type Resin A Containing Aniline Structure 50.0 g (0.520 mol) of m-cresol, 50.0 g (0.520 mol) of p-cresol, 25.0 aniline
g (0.268 mol), 37% by weight formaldehyde 1
08.4 g (1.308 × 1.0 mol), oxalic acid 0.60
g was charged into a 2 liter flask equipped with a condenser and a stirrer, and reacted for 4 hours while maintaining the reaction temperature at 95 to 100 ° C. Thereafter, the pressure was further reduced to 1.33 kPa while the temperature was raised to 180 ° C., and after removing unreacted monomers and water, the mixture was returned to room temperature and collected, to obtain 138.2 g of a novolak type resin A containing an aniline structure. . The polystyrene equivalent weight average molecular weight of this resin was 3,200. Synthesis Example 2 Synthesis of aniline structure-containing novolak resin B The same reaction as in Synthesis Example 1 was performed except that aniline 25.0 g was changed to p-aminophenol 25.0 g, and aniline structure-containing novolak was obtained. 143.6 g of mold resin B was obtained. The polystyrene equivalent weight average molecular weight of this resin was 2,800.

Example 1 Preparation of Positive Resist (A-1) A mixture of m-cresol / p-cresol (50/50 by weight) and formalin were obtained by condensation in the presence of an oxalic acid catalyst. 100 parts by weight of a novolak resin having a weight average molecular weight of 5,500, 1,2-naphthoquinonediazide-5 of 2,3,4-trihydroxybenzophenone
-Sulfonic acid ester (esterification rate 67 mol%) 22
5 parts by weight, thermosetting imide resin "BANI-M" (trade name, manufactured by Maruzen Petrochemical Co., Ltd.) and 5 parts by weight of polyethylene glycol monomethyl ether acetate (PGMEA) 4
After 50 parts by weight were mixed and completely dissolved, the mixture was filtered through a polytetrafluoroethylene membrane filter having a pore size of 0.5 μm (manufactured by Millipore) to prepare a positive resist (A-1). Example 2 Preparation of Positive Resist (A-2) To the positive resist (A-1) obtained in Example 1,
Titanium black 30 dispersed with a polyester dispersant per 100 parts by weight of novolak resin therein
Parts by weight (as pure titanium black) and PGMEA1
06 parts by weight were mixed and completely uniformly dispersed to prepare a positive resist (A-2). Example 3 Preparation of Positive Resist (A-3) 70 parts by weight of novolak resin used in Example 1, aniline structure-containing novolak resin A3 obtained in Synthesis Example 1
0 parts by weight, 25 parts by weight of 1,2-naphthoquinonediazide-5-sulfonic acid ester of 2,3,4-trihydroxybenzophenone (esterification ratio: 67 mol%), thermosetting imide resin "BANI-M" [Maruzen 5 parts by weight of Petrochemical Co., Ltd. and 450 parts by weight of PGMEA are mixed and completely dissolved, and then filtered through a polytetrafluoroethylene membrane filter having a pore size of 0.5 μm [manufactured by Millipore]. A positive resist (A-3) was prepared. Example 4 Preparation of Positive Resist (A-4) In Example 3, the aniline structure-containing novolak resin A30 obtained in Synthesis Example 1 was replaced by 30 parts by weight of the aniline structure-containing resin obtained in Synthesis Example 2. Novolak resin B3
A positive resist (A-4) was prepared in the same manner as in Example 3 except that 0 parts by weight was used.

Comparative Example 1 Preparation of Positive Resist (A-5) A mixture of m-cresol / p-cresol (50/50 by weight) and formalin were condensed in the presence of an oxalic acid catalyst. 100 parts by weight of a novolak resin having a weight average molecular weight of 5,500, 1,2-naphthoquinonediazide-5 of 2,3,4-trihydroxybenzophenone
-Sulfonate (average esterification rate 67 mol%)
After 22 parts by weight and 430 parts by weight of PGMEA are mixed and completely dissolved, a membrane filter made of polytetrafluoroethylene having a pore size of 0.5 μm [manufactured by Millipore]
Then, a positive resist (A-5) was prepared.

Heat Resistance Test Example The positive resist (A-1) obtained in Example 1 and the positive resist (A) obtained in Example 2 were formed on a transparent glass substrate.
-2), the positive resist (A-
3) The positive resist (A-4) obtained in Example 4 and the positive resist (A-5) obtained in Comparative Example 1 were each dried by a spin coater to a dry film thickness of 1.0 μm. 9 on a hot plate at 100 ° C
Heating was performed for 0 second to form a photoresist layer. Next, the photoresist layer was used as an exposure machine by “PLA501F”
Using a [manufactured by Canon Inc.], 120 mJ /
Exposure was performed with an energy of ² cm ² to obtain a latent image.
After a paddle development process for 0 second, a substantially rectangular resist pattern [30 μm line and space (L
/ S)]. Next, each resin film was heated on a hot plate at a temperature shown in Table 1 for 180 seconds to produce a flared type insulating film. Hem spread rate [100
× (b / a) ² %] was determined by a scanning electron microscope (SEM) photograph. Table 1 shows the results.

[0029]

[Table 1]

As can be seen from Table 1, the insulating films of Examples 1 to 4 have a much smaller foot spreading ratio than the insulating film of Comparative Example 1. In each of the insulating films, the upper edge was rounded, and the relative dielectric constant measured by JIS C6481 was in the range of 3.3 to 3.5.

Adhesion Test Example The positive resist (A-3) obtained in Example 3, the positive resist (A-4) obtained in Example 4, and the positive resist (A-4) obtained in Comparative Example 1 A-5) was prepared by placing I on a glass plate.
A dry film thickness of 1.0 μm was formed on a transparent glass substrate on which TO was formed to a thickness of 300 nm by a spin coater.
And heated on a hot plate at 100 ° C. for 90 seconds to form a photoresist layer. next,
The photoresist layer was used as an exposing machine in “PLA501
F "(manufactured by Canon Inc.), 100m through a mask
Exposure with an energy of J / cm ² to obtain a latent image
Paddle development treatment was performed with an 8% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds to form a resist pattern (L / S of 30 μm) having a substantially rectangular cross section.
Using the pattern obtained here as a mask, a mixed aqueous solution of hydrochloric acid and ferric chloride (37% hydrochloric acid / pure water / ferric chloride = 50)
(wt% / 25 wt% / 25 wt%) and an etching treatment was performed at 45 ° C. ITO without resist applied
The time during which the substrate was immersed in the etchant and the 300 nm ITO film was completely removed was defined as the just etching time, and the actual etching time was determined as just etching time × 1.5. After etching, ITO under the resist
Was measured using SEM. Also, it is generally known that performing post-baking before etching reduces the amount of side etching.
The same examination was carried out for those which were post-baked at 130 ° C. for 3 minutes on a hot plate. Table 2 shows the side etching amount.

[0032]

[Table 2]

From Table 2, it was found that the use of a novolak resin containing an aniline structure improved the adhesion.

Example 5 (1) Preparation of Insulating Film A positive electrode obtained in Example 2 was placed on a 25 × 75 × 1.1 mm glass substrate having a 120 nm-thick ITO transparent electrode film patterned on the surface. Mold resist (A-2)
Was applied by a spin coater to a dry film thickness of 1.0 μm, and heated on a hot plate at 100 ° C. for 90 seconds to form a resist layer. Then, using “PLA501F” (described above) as an exposure machine, the resist layer was exposed to 120 mJ / m through a mask having a desired pattern.
Exposure was performed with an energy of ² cm ² to obtain a latent image.
Paddle development was performed for 0 seconds. Then, on a hot plate, by performing a heat treatment at 200 ° C. for 180 seconds,
An insulating film in a flared shape having a flared rate of 117% and a thickness of 1.0 μm was produced.

(2) Formation of a reverse tapered resist pattern 100 parts by weight of a novolak resin having a weight average molecular weight of 5200 which was addition-condensed with formaldehyde in a m-cresol / p-cresol weight ratio of 60/40, and hexamethoxymethylated melamine 10 parts by weight, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-
A photosensitive composition was prepared by dissolving 3 parts by weight of triazine and 3 parts by weight of 4- (4-dimethylaminophenylazo) -phenol in 300 parts by weight of ethyl cellosolve acetate and filtering through a membrane filter. Next, the above composition is spin-coated on a glass substrate provided with the insulating film obtained in the above (1), and heated on a hot plate at 90 ° C. for 60 seconds to form a resin film having a thickness of 1.5 μm. Was formed. Next, using a “PLA501F type” (described above) as an exposure machine, through a mask having a desired pattern,
After exposing the resist film, the resist film was subjected to a paddle development treatment with a 0.5% by weight aqueous solution of NaOH for 60 seconds. By this operation,
A reverse tapered resist pattern was formed on the insulating film. Next, a high-pressure mercury lamp having an illuminance of 254 nm and a light intensity of 1.2 mW / cm ² was irradiated for 200 seconds to harden the resist pattern, thereby producing a member for an organic EL device.

(3) Preparation of Organic EL Device The organic EL device member prepared in (2) above was used as a substrate, and was fixed to a substrate holder of a commercially available vapor deposition device [manufactured by Nippon Vacuum Engineering Co., Ltd.]. 200 mg of N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine (hereinafter abbreviated as TPD) to a resistance heating boat made of And put the molybdenum resistance heating boat in 4,4'-bis (2,2'-
After charging 200 mg of diphenylvinyl) biphenyl (hereinafter abbreviated as DPVBi), the vacuum chamber was set to 1 × 10 ^-4 P
The pressure was reduced to a. Next, 215 boats containing TPD
Up to 220 ° C. to evaporate the TPD at a rate of 0.1 to 0.3.
The hole injection / transport layer having a thickness of 60 nm was formed by evaporation at a rate of nm / sec. The substrate temperature at this time was room temperature. The DPVBi-containing boat was heated to 240 ° C. without removing the DPVBi from the vacuum chamber, and the DPVBi was deposited at a deposition rate of 0.1 to 0.1 ° C.
Evaporation was performed on the hole injecting and transporting layer at a rate of 0.3 nm / sec to form a light emitting layer having a thickness of 40 nm. The substrate temperature at this time was also room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light-emitting layer, and fixed again to the substrate holder. Then, tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was placed in a molybdenum boat. 200 mg, another 1 g of magnesium ribbon in another molybdenum boat, 500 mg of silver wire in a tungsten basket, and these boats were mounted in a vacuum tank. Next, the vacuum chamber was set to 1 × 10
^After reducing the pressure to ^-4 Pa, the boat containing Alq ₃
Heat to 0 ° C. and deposit Alq ₃ at a deposition rate of 0.01 to 0.03.
An electron injection layer having a thickness of 20 nm was formed by vapor deposition on the light emitting layer at a rate of nm / sec. Furthermore, silver was deposited at a deposition rate of 0.1 n.
At the same time as vapor deposition on the electron injection layer at m / sec, magnesium is vapor deposited on the electron injection layer at a deposition rate of 1.4 nm / sec to form a 150 nm thick cathode made of a mixed metal of magnesium and silver. As a result, a light emitting portion of the organic EL device shown in FIG. 4 was formed. Next, an organic EL element was manufactured by forming a sealing layer and the like according to a conventional method. When a DC voltage was applied to this device using the ITO film as the anode and the mixed metal film as the cathode, blue light emission was observed from 5 V in a light place, and the visibility was extremely good.

[0037]

The radiation-sensitive resin composition of the present invention contains a thermosetting component which cures at a specific temperature, and has a rounded top edge suitable for use as an insulating film for organic EL devices. And an insulating film having a flared shape can be provided. By using such an insulating film, an organic EL element can be manufactured stably with a low occurrence frequency of defective products.

[Brief description of the drawings]

FIG. 1 is a principle diagram of an example of an organic EL element.

FIG. 2 is a partial cross-sectional view showing a configuration of an example of a light emitting section in a general organic EL element.

FIG. 3 is an explanatory diagram showing an example of a shape change when a resin film formed by a photolithography method is subjected to a heat treatment in the insulating film of the present invention.

FIG. 4 is a partial cross-sectional view showing a configuration of an example of a light emitting section in the organic EL device of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 transparent substrate 2 transparent electrode layer 3, 3 ′ insulating film 4 reverse tapered resist pattern layer 5, 5a organic EL material layer 6, 6a metal electrode layer 7 hole injection transport layer 8 organic light emitting layer 9 electron injection layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/40 501 G03F 7/40 501 H05B 33/14 H05B 33/14 A 33/22 33/22 Z ( 72) Inventor Nobeki Abe 1-2-1 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa F-term in the Zeon Corporation Integrated Development Center (reference) 2H025 AB17 AC01 AD03 BE01 CB29 CB52 CC03 CC20 FA03 FA17 FA29 FA30 2H096 AA27 BA10 BA20 EA02 GA08 HA01 HA03 JA04 3K007 AB11 AB18 BA06 CA01 CB01 DA01 DB03 EB00 FA01 4J011 AA05 AA07 BA04 CA08 CB03 DA05 FA07 FB18 PA02 PA45 PA85 PC08 PC09 4J026 AB01 AC18 AC36 BA40 DB05 DB06 FA09 GA02 GA07 GA08

Claims (7)

[Claims] (1) an alkali-soluble resin, (B) a quinonediazidesulfonic acid ester, (C) an organic solvent,
In the radiation-sensitive resin composition containing (D) a thermosetting component, (D) the thermosetting component is the (A) alkali-soluble resin, (B) quinonediazide sulfonate, and (C) an organic solvent. A radiation-sensitive resin composition for forming an insulating film of an organic electroluminescence device, which is a compound that cures at a temperature higher than the heat resistance temperature of a resin film formed using the radiation-sensitive resin composition comprising: 2. The radiation-sensitive resin composition for forming an insulating film according to claim 1, wherein the alkali-soluble resin as the component (A) is a novolak resin obtained by polycondensation of a phenol and an aldehyde or a ketone. object. (3) The alkali-soluble resin as the component (A) has a general formula [1] (R ¹ in the formula is a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
m represents an integer of 0 or 1 to 3, and when m is 2 or 3,
Each R ¹ may be the same or different. 2. The radiation-sensitive resin composition for forming an insulating film according to claim 1, wherein the composition contains at least an alkali-soluble resin containing an amino group-containing aromatic compound represented by the formula (1) as a component of a monomer. 4. The thermosetting component (D) is a compound represented by the general formula [2]: [R ² in the formula is a compound of the formula: (N is an integer of 3 to 8). The radiation-sensitive resin composition for forming an insulating film according to claim 1, 2 or 3, which is a thermosetting imide resin represented by the following formula: 5. The radiation-sensitive resin composition for forming an insulating film according to claim 1, comprising 1 to 20 parts by weight of the component (D) per 100 parts by weight of the component (A). 6. A foot having a thickness of 0.3 to 3 μm, obtained by heating and curing a resin film having a desired pattern formed by using the resin composition according to claim 1. Spread-shaped insulating film for organic electroluminescent devices. 7. An organic electroluminescence device comprising the insulating film according to claim 6.