JP2002169277A - Radiation sensitive resin composition for formation of insulating film of organic el display device, insulating film formed from the composition and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulating film for an organic EL element having sufficiently low water permeability and a preferable cross-sectional form, to provide a radiation-sensitive resin composition to form the above film, and to provide an organic EL display element having the above insulating film. SOLUTION: The radiation-sensitive resin composition contains (a) a novolac resin and (b) a 1,2-quinone diazide compound. The insulating film is formed from the radiation-sensitive resin composition. The organic EL display device has the above insulating film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition for an organic EL insulating film. More specifically, the present invention relates to a positive radiation-sensitive resin composition suitable for forming an insulating film using radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, and proton beams.

[0002]

2. Description of the Related Art An organic EL device emits light by itself and has no dependence on viewing angle, and since it is a solid device, it has excellent impact resistance.
There are various advantages over liquid crystal display elements, such as low voltage driving, low power consumption, and high operation stability in a low temperature range. Further, the passive type has a merit of low cost since it is a simple matrix. Since the organic EL element has these advantages, it is particularly expected to be applied to mobile applications such as mobile terminals and vehicles, and has been actively studied. The production of such an organic EL device is generally performed by the following method. Tin-doped indium oxide (IT
O) and a pattern of a transparent electrode (hole injection electrode) and a hole transport layer. Next, the passive organic E
In the case of the L element, after the pattern of the insulating film and the pattern of the cathode partition are formed, the organic EL layer, the electron transport layer, and the cathode are patterned by vapor deposition. Further, in the case of the active organic EL element, after forming an ITO pattern and a hole transport layer pattern, forming a pattern of an insulating film also serving as a partition of the organic EL layer, forming a pattern of the organic EL layer by a masking method, Next, an electron transport layer and a cathode are formed. Here, Alq ₃ ,
A material such as BeBq _{3 in which} a base material is doped with quinacridone or coumarin is used. As a cathode material, Mg or Ag is used.
In general, a material mainly composed of a metal having a low work function, such as As the insulating film material, an alkali-developable acrylic material, an organic-developable polyimide-based material, and the like are generally used, but in this case, there are the following problems. The hole transporting layer, the organic EL layer, and the electron transporting layer are often made of a basic material such as an amine-based material due to a demand for a material suitable for transporting holes and electrons. However, since these materials are liable to change in structure due to a small amount of moisture and deteriorate due to organic substances, if the insulating film material has a high water permeability or if there is residual development during formation of the insulating film pattern, the non-light-emitting portion (Dark area) spreads. Further, a cathode formed mainly of a metal having a low work function is easily oxidized, so that the same problem occurs. In particular, in the case of a passive type, a structure in which a portion made of these basic materials is in direct contact with the insulating film is adopted. Since this insulating film is required to have alkali developability or organic developability, it exhibits carboxylic acid or phenolic acidity, reacts on the contact surface with the basic material via moisture, or the moisture directly forms a structure. Will be changed. When the water permeability of the insulating film is large, it is a cause of further promoting erosion by acid. In addition, a cathode formed mainly of a metal having a low work function reacts with an acid and is corroded, so that a dark spot (non-light-emitting spot) may be generated. In addition, the sectional shape of the formed insulating film is
If the angle (taper angle) between the base and the tangent to the edge is a large value, cracks may be generated in the organic EL layer formed by vapor deposition, and light may enter due to the penetration of moisture from the cracks. It may cause a defect. Furthermore, in the case of an insulating film using a conventionally known material, resistance to a resist stripping solution used at the time of forming a cathode, particularly in the case of a passive type, is insufficient, and an organic EL display element cannot be manufactured stably. Conventionally, no insulating film material capable of solving such a problem has been proposed, and an organic EL element having a sufficiently long life cannot be stably manufactured.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a radiation sensitive film for forming an insulating film which contributes to the stable production of a long-life organic EL device. It is to provide a resin composition. Another object of the present invention is to provide an insulating film formed from the above radiation-sensitive resin composition. Still another object of the present invention is to provide an organic EL device having the above-mentioned insulating film.

[0004]

According to the present invention, the above object of the present invention is to provide (a) a novolak resin, and (b)
This is achieved by a radiation-sensitive resin composition for forming an insulating film of an organic EL display element, which comprises a 1,2-quinonediazide compound. Another object of the present invention is achieved by an insulating film of an organic EL display element formed from the above-mentioned radiation-sensitive resin composition. Still another object of the present invention is to provide an organic EL device having the above-described organic EL display device having an insulating film.
This is achieved by the L display element. Hereinafter, the organic E of the present invention
Each component of the radiation-sensitive resin composition for forming an insulating film of an L display element will be described.

(A) Novolak resin The (a) novolak resin used in the present invention is obtained by polycondensing a phenol and an aldehyde in the presence of an acid catalyst. Phenols used at this time include, for example, phenol, o-cresol, m-cresol, p-
-Cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol,
2,3-xylenol, 2,4-xylenol, 2,5-
Xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, β-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester, o-nitrophenol, m-
Examples thereof include nitrophenol, p-nitrophenol, o-chlorophenol, m-chlorophenol, and p-chlorophenol. Of these compounds, o
-Cresol, m-cresol, p-cresol, 2,
3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and the like are preferred. These phenols can be used alone or in combination of two or more.

Examples of the aldehydes polycondensed with the phenols include formaldehyde, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, and o-hydroxybenzaldehyde. M-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde,
m-methylbenzaldehyde, p-methylbenzaldehyde, o-ethylbenzaldehyde, m-ethylbenzaldehyde, p-ethylbenzaldehyde, pn-butyraldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2-hydroxy-1- Naphthaldehyde and the like can be mentioned. In addition, trioxane or the like can be used as a compound that generates an aldehyde during the reaction, similarly to the aldehydes. Of these,
Particularly, formaldehyde can be suitably used. These aldehydes and compounds that produce aldehydes can be used alone or in combination of two or more. Aldehydes are used per mole of phenols.
Usually, it is used in a ratio of 0.7 to 3 mol, preferably 0.7 to 2 mol.

[0007] Acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, p-
Toluenesulfonic acid, formic acid, acetic acid, oxalic acid and the like can be used. The use amount thereof is preferably 1 × 10 ^{-4 to} 5 × 10 ^-1 mol per mol of phenols. Water is usually used as a reaction medium in the polycondensation reaction, but if the phenol used in the polycondensation reaction does not dissolve in the aqueous solution of the aldehyde and becomes a heterogeneous system from the beginning of the reaction, A hydrophilic organic solvent can also be used as a medium. Examples of the solvent used at this time include alcohols such as methanol, ethanol and butanol; and cyclic ethers such as tetrahydrofuran and dioxane. The use amount of these reaction media is preferably 20 to 100 parts by weight per 100 parts by weight of the reaction raw materials.

[0008] The reaction temperature of the condensation can be appropriately adjusted depending on the reactivity of the reaction raw materials.
° C. After the completion of the polycondensation reaction, the temperature is generally raised to 130 to 230 ° C., and the volatile components are distilled off under reduced pressure to remove unreacted raw materials, catalyst and reaction medium present in the system. Resin can be recovered. At this time, if necessary, the reaction mixture after the polycondensation reaction may be washed with a suitable solvent, and then a novolak resin recovery step may be performed. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the novolak resin is usually 2,2.
Range from 000 to 20,000, and from 3,000 to 15,
000 is preferred. Mw is 20,000
If it exceeds 0, it may be difficult to uniformly apply the composition to the wafer, and further, the developability and sensitivity may be reduced. On the other hand, when Mw is less than 2,000, not only the radiation-irradiated portions but also the non-radiation-irradiated portions have solubility in the developing solution in the later-described developing step, so that pattern formation may not be performed. .

(B) 1,2-quinonediazide compound As the (b) 1,2-quinonediazide compound used in the present invention, a 1,2-quinonediazide compound having a structure capable of absorbing radiation to generate a carboxylic acid is preferable. For example, 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidosulfonic acid ester, 1,2-benzoquinonediazidosulfonic acid amide, 1,2-naphthoquinonediazidosulfonic acid amide and the like can be mentioned. .

Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4
1,2-naphthoquinonediazidesulfonic acid esters of trihydroxybenzophenone, such as -sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;
2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonate, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide 5-
Sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-
4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone- 1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 2,
3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-
3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4 '
-Tetrahydroxy-3'-methoxybenzophenone-
1,2-naphthoquinonediazidosulfonic acid ester of tetrahydroxybenzophenone, such as 1,2-naphthoquinonediazide-5-sulfonic acid ester;

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4
1,2-naphthoquinonediazidesulfonic acid ester of pentahydroxybenzophenone, such as -sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester; , 4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′,
4 ', 5'-hexahydroxybenzophenone-1,2
-Naphthoquinonediazide-5-sulfonic acid ester,
3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone 1,2-naphthoquinonediazidosulfonic acid ester of hexahydroxybenzophenone, such as -1,2-naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester , Bis (p-hydroxyphenyl) methane-1,
2-naphthoquinonediazide-4-sulfonic acid ester,
Bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tri (p
-Hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p -Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p
-Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4
-Trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2
3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2
-Bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2- Naphthoquinonediazide-5
-Sulfonic acid esters, 1,1,3-tris (2,5-
Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-
4-hydroxyphenyl) -3-phenylpropane-
1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene]
Bisphenol-1,2-naphthoquinonediazide-4-
Sulfonate, 4,4 '-[1- [4- [1-
[4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5
-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4
-Sulfonic acid ester, bis (2,5-dimethyl-4-
(Hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-
Spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-
1,1′-spirobiindene-5,6,7,5 ′,
6 ', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1,2
-Naphthoquinonediazide-4-sulfonic acid ester,
1,2-naphthoquinonediazide sulfonic acid ester of (polyhydroxyphenyl) alkane such as 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester Is mentioned.

In addition to these compounds, J. Kosar, "L.
ight-Sensitive Systems ”339-352 (1965), John Wil
"Photo by ey & Sons (New York) and WS De Fores
resist "50 (1975) 1,2-quinonediazide compounds described in McGraw-Hill, Inc. (New York) can be used. These can be partially or wholly reacted with the above (a) novolak resin. You may use it in the form which made the condensate formed.

Of these 1,2-quinonediazide compounds, preferably 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone- 1,2-Naphthoquinonediazide-5-sulfonic acid ester
Naphthoquinonediazidosulfonic acid esters; 2,3
4,3′-tetrahydroxybenzophenone-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, 2,
3,4,4'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-4-sulfonic acid ester,
2,3,4,4'-tetrahydroxybenzophenone-
1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-
1,2-naphthoquinonediazidosulfonic acid ester of tetrahydroxybenzophenone such as 5-sulfonic acid ester; bis (2,4-dihydroxyphenyl) methane-
1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-
Naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-
Tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,2-bis (2,3,4-trihydroxyphenyl)
Propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-
1,2-naphthoquinonediazide-5-sulfonic acid ester is exemplified.

More preferably, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide- 4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4 ′
-Tetrahydroxy-3'-methoxybenzophenone-
1,2-naphthoquinonediazidosulfonic acid ester of tetrahydroxybenzophenone such as 1,2-naphthoquinonediazide-5-sulfonic acid ester; 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, bis (2
3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2
-Bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-
(Hydroxyphenyl) -3-phenylpropane-1,2
-Naphthoquinonediazide-5-sulfonic acid ester.

The above 1,2-quinonediazide compounds can be used alone or as a mixture of two or more. (B) The amount of the 1,2-quinonediazide compound added is (a)
Preferably 5 to 100 parts by weight of novolak resin
100 parts by weight, more preferably 10 to 50 parts by weight. When the amount is less than 5 parts by weight, patterning may be difficult. On the other hand, when the amount exceeds 100 parts by weight, development with a developing solution composed of an alkaline aqueous solution may be difficult.

The above (a) novolak resin, and (b)
The insulating film formed from the radiation-sensitive resin composition containing the 1,2-quinonediazide compound has no development residue, and has a sufficiently low water permeability for use in an organic EL device, and has a dark area due to a trace amount of moisture. The occurrence can be suppressed.

(C) Basic Nitrogen-Containing Compound In the radiation-sensitive resin composition of the present invention, (c) the insulating film formed from the composition by using the basic nitrogen-containing compound is made of a basic material. The reactivity with the hole transport layer, the organic EL layer, the electron transport layer, and the cathode mainly composed of a metal having a low work function is sufficiently suppressed. The occurrence can be suppressed. The (c) basic nitrogen-containing compound used in the present invention is preferably a nitrogen-containing organic compound whose basicity does not change upon exposure or baking. For example, the following general formula (1): R ¹ R ² R ³ N. . . (1) (wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, provided that R ¹ , R ² and R ³ simultaneously represent a hydrogen atom (Hereinafter, referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter, “nitrogen-containing compound (II)”) ), A polymer having three or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (III)"), an amide group-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound. Can be used.

Specific examples of the nitrogen-containing compound (I) include:
monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; di-n-butylamine, di-n-
Dialkylamines such as pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine and di-n-decylamine; triethylamine, tri-n-propylamine, Tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine,
Tri-n-octylamine, tri-n-nonylamine,
Trialkylamines such as tri-n-decylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenyl Examples thereof include aromatic amines such as amine and naphthylamine. Of these, trialkylamines are preferred.

Specific examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenyl ether, 4,
4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl)
Propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl)
-2- (3-hydroxyphenyl) propane, 2- (4
-Aminophenyl) -2- (4-hydroxyphenyl)
Propane, 1,4-bis [1- (4-aminophenyl)
-1-methylethyl] benzene, 1,3-bis [1-
(4-aminophenyl) -1-methylethyl] benzene and the like.

Specific examples of the nitrogen-containing compound (III) include poly (4-pyridine), poly (2-pyridine), poly (N-2-pyrrolidone), polyethyleneimine, polyallylamine, and poly (dimethylaminoethylacrylamide). ) And the like.

Specific examples of the amide group-containing compound include formamide, N-methylformamide, N, N-
Examples thereof include dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, and N-methylpyrrolidone. Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tributylthiourea. Can be mentioned.

Specific examples of the above nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole; pyridine, 2-methylpyridine,
4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, In addition to pyridines such as acridine, pyrazine,
Pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4
-Diazabicyclo [2.2.2] octane and the like. Of these, pyridines are particularly preferably used.

Of these basic nitrogen-containing compounds, nitrogen-containing compounds (I) and nitrogen-containing heterocyclic compounds are preferably used. In the present invention, the basic nitrogen-containing compound (c) can be used alone or in combination of two or more. The amount of the basic nitrogen-containing compound used in the present invention is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, per 100 parts by weight of the novolak resin (a).
Parts by weight. In this case, if the amount of the basic nitrogen-containing compound is less than 0.01 part by weight, the effect of improving the life of the organic EL device may not be sufficiently obtained, and if it exceeds 20 parts by weight, the radiation-sensitive resin In some cases, the sensitivity as a composition and the developability of an exposed portion may be reduced.

(D) Melamine compound and epoxy compound
At least one compound selected from the group consisting of (d) at least one compound selected from a melamine compound and an epoxy compound in the radiation-sensitive resin composition of the present invention; The insulating film thus obtained has a sufficiently high resistance to a resist stripping solution used particularly when forming a cathode of a passive liquid crystal display element, and the insulating film does not strip even when exposed to the resist stripping solution.

The melamine used in the present invention is represented by the following general formula (2).

[0027]

Embedded image

(Wherein, R ^{4 to} R ⁹ may be the same or different and each represents a hydrogen atom or a —CH ₂ OR group, and R represents a hydrogen atom or a C _{1 to} C ₆ alkyl group. R
Of ⁴ to R ^9, at least one is always -CH ₂ OR group. Examples of the melamine represented by the general formula (2) include hexamethylol melamine, hexabutyrol melamine, partially methylolated melamine and its alkylated product, tetramethylol benzoguanamine, partially methylolated benzoguanamine and its alkylated product, and the like. Can be mentioned. Of these melamines, commercially available Cymel 300, 301, 303, 370, 32
5,327,701,266,267,238,114
1, 272, 202, 1156, 1158, 1123,
1170, 1174, UFR65, 300 (all manufactured by Mitsui Cyanamid Co., Ltd.), Nicaraq Mx-750,
-032, -706, -708, -40, -31, Nikarac Ms-11, Nikarac Mw-30 (all manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

The amount of the melamine added is preferably from 1 to 10 parts by weight based on 100 parts by weight of the novolak resin (a).
0 parts by weight, more preferably 5 to 50 parts by weight. If the amount is less than 1 part by weight, the crosslinking density is reduced, and the alkali resistance after the formation of the insulating film may be poor. If the amount is more than 100 parts by weight, the alkali solubility of the entire composition becomes too high. The problem that the residual film ratio decreases tends to occur.

The epoxy resin used in the present invention includes phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cycloaliphatic epoxy resin, aliphatic polyglycidyl ether and the like. However, specifically, for example, the following commercially available products can be used.

Examples of the phenol novolak type epoxy resin include Epicoat 152, 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN 201, 202 (manufactured by
Nippon Kayaku Co., Ltd.) and the like; cresol novolak type epoxy resins include EOCN-102, 103S, 104
S, 1020, 1025, and 1027 (all manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like; bisphenol A type epoxy resins include Epicoat 1001, 1002, 1003, and 1
004, 1007, 1009, 1010, 828 (all manufactured by Yuka Shell Epoxy Co., Ltd.) and the like; As the bisphenol F type epoxy resin, Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like; cycloaliphatic epoxy As the resin, CY-175, 177, 179 (all manufactured by Ciba-Geigy), ERL-4234, 4299, 42
21, 4206 (manufactured by UUC Corporation), Shodyne 509 (manufactured by Showa Denko KK), Aldarite CY
-182, 192, 184 (Ciba Geigy)
Manufactured by Daikoku Ink Co., Ltd.), Epicoat 871, 872 (manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661, 5662.
(Above, manufactured by Celanese Coatings Co., Ltd.); aliphatic polyglycidyl ether is Epolite 100M
F, 200E, 400E (all manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and Epiol TMP (manufactured by NOF Corporation).

These can be used in combination of two or more. The amount of the epoxy resin to be added is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the novolak resin (a).

Other Additives Other additives can be used in the radiation-sensitive resin composition of the present invention as long as the object of the present invention is not impaired. Examples of such other additives include a sensitizer, a surfactant, an adhesion aid, a storage stabilizer, and an antifoaming agent.

The above sensitizer can be added for the purpose of improving the radiation sensitivity of the radiation-sensitive composition of the present invention. Examples of the sensitizer include 2H-pyrido- (3,
2-b) -1,4-oxazin-3 (4H) -ones,
10H-pyrido- (3,2-b)-(1,4) -benzothiazines, urazoles, hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxane , Maleimides and the like. The amount of these sensitizers is preferably 1 to 100 parts by weight of (b) 1,2-quinonediazide compound.
It is not more than 00 parts by weight, more preferably 1 to 50 parts by weight.

The above-mentioned surfactant can be blended in order to improve the coating properties, for example, the developability of the radiation-irradiated portion after the formation of a striation or a dried coating film. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether; polyoxyethylene such as polyoxyethylene nonyl phenyl ether; Nonionic surfactants such as polyethylene glycol dialkyl esters such as ethylene aryl ethers, polyethylene glycol dilaurate, and polyethylene glycol distearate; EFTOP EF3
01, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, 172, 173 (Dainippon Ink Co., Ltd.)
Co., Ltd.), Florado FC430, 431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-
382, SC-101, 102, 103, 104, 10
5, 106 (manufactured by Asahi Glass Co., Ltd.), fluorine surfactants, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid (co) polymer polyflow No. 57, 95 (Manufactured by Kyoeisha Chemical Co., Ltd.). The amount of such a surfactant is usually 2 parts by weight or less, preferably 1 part by weight or less, based on the solid content of the composition.

The above-mentioned adhesion aid can be used for improving the adhesion between the insulating film formed from the radiation-sensitive composition of the present invention and the substrate. As such an adhesion aid, a functional silane coupling agent is preferably used,
For example, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group may be used. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. The amount of such a surfactant is usually 15 parts by weight or less, preferably 10 parts by weight or less, per 100 parts by weight of the solid content of the composition.

The radiation-sensitive resin composition of the present invention is usually used after being dissolved in a solvent. The solvent used for preparing the radiation-sensitive resin composition of the present invention includes (a) the novolak resin, (b) a 1,2-quinonediazide compound, (c) a basic nitrogen-containing compound, and (d)
Melamines, epoxy resins, and other additives that are optionally added are uniformly dissolved and do not react with each component.

Specific examples of the solvent used for preparing the radiation-sensitive resin composition of the present invention include glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; and ethylene such as methyl cellosolve acetate and ethyl cellosolve acetate. Glycol alkyl ether acetates; diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate;
Propylene glycol alkyl ether acetates such as propylene glycol propyl ether acetate;
Aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; methyl 2-hydroxypropionate; ethyl 2-hydroxypropionate;
Ethyl-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3 -Methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate,
Esters such as ethyl acetate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and butyl 3-methoxypropionate can be exemplified.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, esters and the like are preferred in view of solubility, reactivity with each component, and ease of forming a coating film. And diethylene glycols are preferably used. These solvents can be used alone or as a mixture.

If necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl High boiling solvents such as alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate and the like can also be added.

The radiation-sensitive composition of the present invention is prepared using the above-mentioned solvent. Depending on the purpose of use, an appropriate solid content concentration can be adopted.
% By weight. Further, the composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore diameter of about 0.2 μm.

Method for Forming Insulating Film for Organic EL Display Element Using the radiation-sensitive resin composition of the present invention, an insulating film for an organic EL display element can be formed, for example, as follows. The radiation-sensitive resin composition of the present invention can be applied to the surface of an underlying substrate, and the solvent can be removed by pre-baking to form a coating film. As the coating method, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method, and a bar coating method can be adopted. The conditions of the pre-bake vary depending on the type of each component, the blending ratio, and the like, but the optimal conditions are usually 60 to 110 ° C. for about 0.5 to 15 minutes. The film thickness after prebaking can be a desired value depending on the solid content concentration of the radiation-sensitive composition and the application conditions, but can be about 0.25 to 4 μm.

Next, radiation is applied to the formed coating film through a mask having a predetermined pattern. Examples of the radiation used here include ultraviolet rays such as g-ray (wavelength 436 nm) and i-ray (wavelength 365 nm), far ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, and charged particle rays such as electron beams. No. Of these, g-line and i-line are preferred. After the irradiation with the radiation, a desired pattern can be obtained by removing the irradiated part by performing a development treatment using a developing solution. Examples of the developer used herein include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine. Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; dimethylethanolamine and triethanol-
Alcoholamines such as ruamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline;
, Piperidine, 1,8-diazabicyclo- (5.4.
0) -7-undecene, 1,5-diazabicyclo-
An aqueous alkali solution in which a cyclic amine such as (4.3.0) -5-nonane is dissolved in water is preferably used. In addition, the developer includes a water-soluble organic solvent such as methanol and ethanol.
Alcohols and surfactants can be added in appropriate amounts. Further, various organic solvents that dissolve the composition of the present invention can also be used as the developer. As a developing method, a puddle method, a dipping method, a rocking dipping method, or the like can be used.

After the development process, the patterned film may be subjected to a rinsing process, for example, by washing with running water.
Furthermore, by irradiating the entire surface with radiation from a high-pressure mercury lamp or the like, a 1,2-quinonediazide compound remaining in the film can be decomposed.

Thereafter, the film is cured by heating using a heating device such as a hot plate oven. The heating temperature in this curing process is, for example, 150
The heating time can be 5 to 30 minutes when firing on a hot plate, and 30 to 90 minutes when firing in an oven.

Production of Organic EL Device The organic EL device of the present invention has the insulating film formed as described above. The organic EL device of the present invention is manufactured, for example, as follows. A transparent electrode such as ITO is formed on a glass substrate by sputtering, and a pattern of a positive photoresist is formed thereon. Next, the ITO film is etched with, for example, a hydrochloric acid-based etchant, the resist film is stripped, and the transparent electrode is patterned, for example, into a stripe pattern. On the substrate having the patterned transparent electrode, the pattern of the insulating film of the present invention is formed as described above. Next, an electron transporting layer and a cathode tapered cathode partition are formed, and a hole transporting layer, an organic EL light emitting layer, and a cathode layer are sequentially formed. As the hole transport layer, for example, CuP
A phthalocyanine-based material such as c or H ₂ Pc, or an aromatic amine is used. Examples of the organic EL light emitting material include a so-called low molecular organic EL material such as a material obtained by doping quinacridone or coumarin into a base material such as Alq ₃ or BeBq ₃ , or a high molecular organic EL material such as a polyphenylene vinylene or fluorene. Materials are used. Further, as a cathode material, for example, Mg-Al, Al-
Li, Al-Li ₂ O, etc. Al-LiF is used. Next, the hollow SUS can and the substrate are sealed with a sealing material such as an epoxy resin, and then assembled into a module to obtain an organic EL element.

The radiation-sensitive resin composition for forming an insulating film of the present invention comprises: (a) a novolak resin; and (b) a composition containing a 1,2-quinonediazide compound; (a) a novolak resin; A) a 1,2-quinonediazide compound and a composition containing (c) a nitrogen-containing basic compound, (a) a novolak resin, (b) a 1,2-quinonediazide compound, and (d) a melamine compound and an epoxy compound. A composition containing at least one compound selected from the group consisting of (a) a novolak resin, (b) a 1,2-quinonediazide compound, (c) a nitrogen-containing basic compound, and (d) a melamine compound and an epoxy compound. Various embodiments of the composition containing at least one selected compound can be adopted. When a low molecular weight organic EL material is used as the organic EL light emitting material, a vapor deposition method is generally employed for forming the organic EL light emitting layer.
As the composition for forming an insulating film used for the L display element, all of the above-mentioned aspects can be preferably used. When a polymer organic EL material is used as the organic EL light emitting material, a method of dissolving the organic EL light emitting material in a solvent and coating the organic EL light emitting material is generally used for forming the organic EL light emitting layer. As the composition for forming an insulating film used for a display element, the above and the above embodiments can be preferably used.

[0048]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The molecular weight measured below is a weight average molecular weight in terms of polystyrene measured by GPC Chromatograph HLC-8020 manufactured by Toyo Soda.

Novolak Resin Synthesis Example 1 Metacresol 57 was placed in a 1 L stainless steel (SUS316L) kettle equipped with a cooling pipe, stirrer and thermometer.
g (0.6 mol), paracresol 38 g (0.4
mol), 375.5% by weight aqueous solution of formaldehyde 75.5
g (equivalent to 0.93 mol of formaldehyde), 0.95 g of p-toluenesulfonic acid monohydrate (0.005 m
ol) and 264 g of methyl isobutyl ketone, the flask was immersed in an oil bath, and polycondensation was carried out at 130 ° C. for 4 hours with stirring while refluxing the reaction solution. Next, the temperature of the oil bath was raised to 180 ° C. over 3 hours, and then the pressure in the kettle was reduced to 30 mmHg to remove volatile components, and the molten resin was cooled to room temperature and collected. After dissolving this resin in ethyl acetate so that the resin component became 30%, 1.3 times the amount of methanol and 0.9 times the amount of water of this solution were added, and the mixture was stirred and left. The lower layer separated into two layers was taken out, concentrated and dried to collect Resin 1. The weight average molecular weight (Mw) of this resin 1 is 8.0
00.

Synthesis Example 2 of Novolac Resin Metacresol 76 was placed in a 1 L stainless steel (SUS316L) kettle equipped with a cooling tube, stirrer and thermometer.
g (0.8 mol), 13.9 g of 2,3-xylenol
(0.12 mol), 9.3 g of 3,4-xylenol
(0.08 mol), 78 g of a 37% by weight aqueous solution of formaldehyde (equivalent to 0.96 mol of formaldehyde), 0.95 g of p-toluenesulfonic acid monohydrate
(0.005 mol) and 264 g of methyl isobutyl ketone, the kettle was immersed in an oil bath, and polycondensation was carried out for 4 hours with stirring while refluxing the reaction solution. Next, the temperature of the oil bath was raised to 180 ° C. over 3 hours, and then the pressure in the kettle was reduced to 30 mmHg to remove volatile components, and the molten resin was cooled to room temperature and collected.
After dissolving this resin in ethyl acetate so that the resin component became 30%, 1.3 times the amount of methanol and 0.9 times the amount of water of this solution were added, and the mixture was stirred and left. The lower layer separated into two layers was taken out, concentrated and dried to collect the resin 2. The weight average molecular weight (Mw) of this resin 2 is 7,50
It was 0.

Synthesis Example 3 of Novolak Resin In a 1 L flask equipped with a stirrer and a thermometer, 54.07 g (0.50 mol) of meta-cresol, 54.07 g (0.50 mol) of para-cresol, and 71 g of a 37% by weight aqueous solution of formaldehyde ( Formaldehyde 0.88 mol), oxalic acid dihydrate 6.3 g
(0.05 mol), the flask was immersed in an oil bath, and a polycondensation reaction was performed for 120 minutes while stirring at an internal temperature of 100 ° C. Next, the temperature of the oil bath was raised to 180 ° C., the pressure in the flask was reduced to 30 mHg, and volatile components were removed. Then, the molten resin 3 was returned to room temperature and collected. The weight average molecular weight (Mw) of the resin 3 is 8,800.
Met.

Example 1 Radiation-sensitive resin containing components (a) and (b)
Preparation of Composition 100 parts by weight of resin 1 obtained in Synthesis Example 1 as component (a) and 1,1,3-tris (2,2,3) as component (b)
Condensate (1,1,3-mol) of 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol) 30 parts by weight of tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonate are mixed to obtain a solid content of 30% by weight. −
After diluting and dissolving with methyl methoxypropionate, the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution.

(1) Evaluation of Radiation Sensitivity The composition solution prepared above was placed on a glass substrate in an amount of 1.0 μm.
m at a film thickness of 80 m.
Pre-baked on a hot plate for minutes. Then 30
Nikon NSR1755i7A reduction projection exposure machine (N) through a μm line and space pattern mask.
(A = 0.50, λ = 365 nm) and then exposed to an aqueous solution of tetramethylammonium hydroxide for 25 minutes.
Developed at 1 ° C. for 1 minute. Then, the film was washed with running water and dried to form a pattern on the wafer, and the minimum exposure amount at which a 30 μm pattern could be formed was examined. This value is shown in Table 1. When this value is 200 mJ / cm ² or less, it can be said that the radiation sensitivity is good.

(2) Formation of Patterned Thin Film The composition solution prepared above was placed on a glass substrate by 1.0 μm.
m at a film thickness of 80 m.
Pre-baked on a hot plate for minutes. Then, through a predetermined pattern mask, Nikon NSR1755i
7A reduction projection exposure machine (NA = 0.50, λ = 365n)
Exposure was performed in m). The exposure amount at this time is as described in (1) above.
And the minimum exposure amount at which a 30 μm pattern was formed. Thereafter, development was performed at 25 ° C. for 1 minute with an aqueous solution of tetramethylammonium hydroxide. Thereafter, the film was washed with running water and dried to form a pattern on the wafer. Then, using an aligner PLA501F manufactured by Canon Inc., ultraviolet rays of 300 mJ / cm ² were irradiated with a ghi mixed line, and further heated at 220 ° C. for 60 minutes in an oven.
A patterned thin film was formed.

(3) Evaluation of Cross-Sectional Shape The cross-sectional shape of the patterned thin film formed above was measured with a scanning electron microscope (manufactured by Hitachi, Ltd., model “S-420”).
0 "), and the taper angle of the cross-sectional shape (the angle between the bottom of the cross-sectional shape of the pattern and the tangent to the edge; the same applies hereinafter) was measured. Table 1 shows the results. When this value is 50 ° or less, it can be said that the cross-sectional shape of the pattern is good.

(4) Presence or Absence of Residual Development A patterned thin film was formed on a glass substrate on which ITO was deposited in the same manner as in (2), and the presence or absence of residual development was examined by the following two methods. Observed visually using a green lamp (Funatec Co., Ltd.). Scanning electron microscope (manufactured by Hitachi, Ltd., type "S-
4200 ") and observed at a magnification of 40,000.
Table 1 shows the observation results.

(5) On a polyimide sheet having a water permeability of 25 μm, the composition solution was applied by a spin method so as to have a film thickness of 10 μm,
For 1.5 minutes, and then heated at 220 ° C. for 60 minutes to form a cured film on the polyimide sheet. The membrane was sealed with an aluminum cup containing 15 g of distilled water. This was put in a thermostat at 50 ° C., the weight loss of the cup after 150 hours was measured, and the water permeability per unit area was calculated. The results are shown in Table 1. This value is 5
When it is not more than 00 g / cm ² , it can be said that the water permeability is sufficiently low.

[0058](6) Unlit area An organic EL panel for evaluation was prepared and 100 cd / m^Two {
(Red: 100 + Green: 200 + Blue: 10
0) cd / m^Two÷ 3 × 0.7 ≒ 100 cd / m ^Two } Screen
Perform a lighting test with brightness and visually check for unlit areas
Was. Table 1 shows the results.

[0059](7) Luminance half life An organic EL panel for evaluation was prepared and 100 cd / m^Two {
(Red: 100 + Green: 200 + Blue: 10
0) cd / m^Two÷ 3 × 0.7 ≒ 100 cd / m ^Two } Screen
A lighting acceleration test was conducted at a luminance of 105 ° C. Screen brightness
Table 1 shows the time required for the value to decrease by half. This value is 400
When the time is longer than the time, it can be said that the luminance half life is good.

Examples 2 and 3 Evaluations were made in the same manner as in Example 1 except that the types and amounts of the components (a) and (b) were changed as shown in Table 1. The results are shown in Table 1.

[0061]

[Table 1]

However, in Table 1, the unit of the amount added is parts by weight, and the compounds a, a and c represent the following compounds. Compound A: 1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol) (1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-
Phenylpropane-1,2-naphthoquinonediazide-5
-Sulfonate) Compound I: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2- Naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)
(4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester) Compound c: 2,3,4-hydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5
Condensate (2,2) with sulfonic acid chloride (2.0 mol)
3,4-hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester)

Example 4 Sensitive Containing Components (a), (b) and (c)
Preparation of Radiation Resin Composition 100 parts by weight of resin 3 obtained in Synthesis Example 3 as component (a) and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) as component (b) -3-phenylpropane (1.0 mol) and 1,2-naphthoquinonediazide-
Condensation product with 5-sulfonic acid chloride (1.9 mol) (1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5) 40 parts by weight of sulfonic acid ester) and 1 part by weight of N, N-dimethylpyridine as the component (c) were mixed to give a solid concentration of 30% by weight.
After diluting and dissolving with methyl methoxypropionate, the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution.

Using the above composition solution, the same procedure as in Example 1 was carried out.
The water permeability, the presence or absence of a non-light emitting portion, and the half life of luminance were evaluated. Table 2 shows the results.

Examples 5 and 6 The same procedures as in Example 4 were carried out except that the types and amounts of the components (a), (b) and (c) were changed as shown in Table 2. ,evaluated. The results are shown in Table 2.

[0066]

[Table 2]

However, in Table 2, the unit of the amount added is parts by weight, Compounds A, A and C are the same as Table 1, and Compounds A, B, C and D represent the following compounds. Compound A: N, N-dimethylpyridine Compound B: Triphenylamine Compound C: Triactylamine Compound D: Nicotinamide

Example 7 Sensitive Properties Containing Components (a), (b) and (d)
Preparation of Radiation Resin Composition 100 parts by weight of resin 2 obtained in Synthesis Example 2 as component (a) and 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) as component (b) -3-phenylpropane (1.0 mol) and 1,2-naphthoquinonediazide-
Condensation product with 5-sulfonic acid chloride (1.9 mol) (1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5) 30 parts by weight of sulfonic acid ester) and 25 parts by weight of Cymel 300 (a melamine compound manufactured by Mitsui Cyanamid Co., Ltd.) as the component (d) are mixed, and methyl 3-methoxypropionate is adjusted to have a solid content concentration of 30% by weight. After diluting and dissolving with
The solution was filtered through a μm membrane filter to prepare a composition solution.

Using the above composition solution, the same procedure as in Example 1 was carried out.
The water permeability, the presence or absence of a non-light emitting portion, and the half life of luminance were evaluated. Table 3 shows the results.

(8) Evaluation of Alkali Resistance The glass substrate on which the patterned thin film was formed was immersed in a 1% NaOH aqueous solution whose temperature was controlled at 25 ° C. for 20 minutes.
The film thickness before immersion at this time is T1, the film thickness after immersion is t1, and the ratio of the film thickness before and after immersion (t1 / T1) × 100 [%]
Was calculated. The results are shown in Table 3. This value is 95-
When it is 105%, it can be said that the alkali resistance is good.

(9) Evaluation of Solvent Resistance The glass substrate on which the patterned thin film was formed was immersed in a dimethylsulfoxide / N-methylpyrrolidone mixed solution (weight ratio 70/30) at a temperature of 25 ° C. for 20 minutes.
At this time, the film thickness before immersion is T2, the film thickness after immersion is t2, and the ratio of the film thickness before and after immersion (t2 / T2) × 100 [%]
Was calculated. The results are shown in Table 3. This value is 95-
When it is 105%, it can be said that the solvent resistance is good.

(10) Evaluation of Heat Resistance The glass substrate on which the patterned thin film was formed was 220 ° C.
For an additional 60 minutes. At this time, the film thickness before the additional bake is T3, the film thickness after the additional bake is t3, and the ratio of the film thickness before and after the additional bake (t3 / T3) × 100.
[%] Was calculated. The results are shown in Table 3. When this value is 95 to 105%, it can be said that the heat resistance is good.

Examples 8 and 9 The same procedures as in Example 7 were carried out except that the types and amounts of the components (a), (b) and (d) were changed as shown in Table 3. ,evaluated. The results are shown in Table 3.

[0074]

[Table 3]

However, in Table 3, the unit of the amount added is parts by weight, the compounds a, i and c are the same as in Table 1, and melamine α, melamine β and epoxy α are as follows. Melamine α: “Cimel 300” manufactured by Mitsui Cyanamid Co., Ltd. Melamine β: “Cymel 370” manufactured by Mitsui Cyanamid Co., Ltd. Epoxy α: “Epicoat 152” manufactured by Yuka Shell Epoxy Co., Ltd.

Example 10 The components (a), (b), (c) and (d)
Preparation of radiation-sensitive resin composition containing 100 parts by weight of resin 1 obtained in Synthesis Example 1 as component (a) and 1,1,3-tris (2,5-dimethyl-) as component (b) 4-hydroxyphenyl) -3-phenylpropane (1.0 mol) and 1,2-naphthoquinonediazide-
Condensation product with 5-sulfonic acid chloride (1.9 mol) (1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5) 45 parts by weight of sulfonic acid ester), 5 parts by weight of nicotinamide as the component (c), and 30 parts by weight of Cymel 300 (a melamine compound manufactured by Mitsui Cyanamid Co., Ltd.) as the component (d) were mixed. After diluting and dissolving with methyl 3-methoxypropionate so as to have a concentration of 30% by weight, the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution.

Using the above composition solution, the same procedure as in Example 7 was carried out.
Water permeability, alkali resistance, solvent resistance, heat resistance, the presence or absence of a non-light emitting portion, and the luminance half life were evaluated. Table 4 shows the results.

Examples 11 and 12 In Example 10, the components (a), (b) and (c)
The evaluation was carried out and evaluated in the same manner as in Example 10 except that the types of the components and the component (d) and the amounts added were as shown in Table 4. The results are shown in Table 4.

[0079]

[Table 4]

However, in Table 3, the unit of the amount added is parts by weight, Compounds A, A and C are the same as Table 1, Compound A, Compound B and Compound D are the same as Table 2, Melamine α, melamine β and epoxy α are the same as in Table 3, and melamine γ and epoxy β are as follows. Melamine γ: “Symel 3” manufactured by Mitsui Cyanamid Co., Ltd.
03 ”Epoxy β: Yuko Shell Epoxy“ Epicoat 154 ”

[0081]

According to the present invention, there is provided an insulating film for an organic EL device having a sufficiently low water permeability and a good sectional shape, and a radiation-sensitive resin composition for forming the same. The radiation-sensitive resin composition for forming an insulating film of an organic EL display element of the present invention and the insulating film formed therefrom contribute to stable production of a long-life organic EL element. Further, the organic EL display element of the present invention has no emission failure and has a sufficiently long luminance half life.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 61/06 C08L 61/06 63/00 63/00 A G03F 7/022 G03F 7/022 H01L 21/027 H01L 21/30 502R (72) Inventor Kazuaki Niwa 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 2H025 AA11 AA14 AA20 AB20 AC01 AC04 AD03 BE01 CB29 CC17 CC20 4J002 CC03W CC04W CC05W CC06W CD01X CD02X CD05X CD06X EN028 EN038 EN068 EN078 EP018 EQ036 EU048 EU118 EU138 EU187 EU208 EU238 FD20X FD206 FD207 FD208 GP03

Claims (6)

[Claims] 1. A (a) novolak resin, and (b)
A radiation-sensitive resin composition for forming an insulating film of an organic EL display device, comprising a 1,2-quinonediazide compound. 2. The radiation-sensitive resin composition according to claim 1, further comprising (c) a nitrogen-containing basic compound. 3. The radiation-sensitive resin composition according to claim 1, further comprising (d) at least one compound selected from a melamine compound and an epoxy compound. 4. The radiation-sensitive resin composition according to claim 1, further comprising (c) a nitrogen-containing basic compound, and (d) at least one compound selected from a melamine compound and an epoxy compound. The radiation-sensitive resin composition according to claim 1, which contains the radiation-sensitive resin composition. 5. An insulating film for an organic EL display element formed from the radiation-sensitive resin composition according to claim 1. 6. Organic E having the insulating film according to claim 5.
L display element.