JPH10144469A - Organic electroluminescent element and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method enabling light weight, superior mechanical strength and high productivity by providing an organic electroluminescent element and a substrate consisting of a light curing resin so as to be surface roughness (Rz) of one plate face of the substrate. SOLUTION: An organic electroluminescent element 10 comprises a substrate 1, an anode 2, an organic luminescent layer 3, and a cathode 4, and the substrate 1 is a support of an entire element. Superior optical characteristics, heat resistance, surface precision, mechanical strength, light weight, and gas barrier properties are required. Light double refraction of a photocuring resin substrate is preferably 20nm or less. Thickness of the substrate is ordinary 0.1 to 5mm or preferably 0.3 to 1mm. Surface roughness on a luminescent element fabrication face of a resin substrate is 1 to 50nm in 10-point average roughness Rz and is preferably 2 to 20nm. When Rz is greater than 50nm, short circuit is likely to occur between element electrodes, and when it is smaller than 1nm, adhesive force between an organic layer and the substrate is weakened and is not preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device and a method of manufacturing the same, and more particularly, to an improvement in a support substrate of a thin film type light emitting device which emits light by applying an electric field to a light emitting layer made of an organic compound. It is about.

[0002]

2. Description of the Related Art Conventionally, as a thin film type electroluminescent (EL) element, Zn, which is an inorganic II-IV compound semiconductor, is used.
Generally, S, CaS, SrS, and the like are doped with Mn or a rare earth element (Eu, Ce, Tb, Sm, or the like) which is a luminescence center. Is required (generally 50 to 1000
Hz). The driving voltage is high (generally about 200 V). It is difficult to make full color. In particular, there is a problem with blue. The cost of the peripheral drive circuit is high. There is a problem that.

However, in recent years, in order to improve the above problems,
Development of EL devices using organic thin films has been started. In particular, in order to increase the luminous efficiency, the type of the electrode is optimized for the purpose of improving the efficiency of carrier injection from the electrode, and the organic hole transport layer composed of an aromatic diamine and the organic layer composed of an aluminum complex of 8-hydroxyquinoline are used. Development of an organic electroluminescent device provided with a light emitting layer (Appl. Ph.
ys. Lett. , Vol. 51, p. 913, 1987), the luminous efficiency is greatly improved as compared with a conventional electroluminescent device using a single crystal such as anthracene, and the practical characteristics are approaching.

In addition to the above-described electroluminescent device using a low molecular material, poly (p) is used as a material for an organic light emitting layer.
-Phenylene vinylene) (Nature, 347, 5)
39, 1990 et al.), Poly [2-methoxy-5-
(2-ethylhexyloxy) -1,4-phenylenevinylene] (Appl. Phys. Lett., Vol. 58,
1982, etc.), poly (3-alkylthiophene) (J
pn. J. Appl. Phys., Vol. 30, L1938, etc.) and the development of an electroluminescent device using a polymer material, and a device in which a low molecular light emitting material and an electron transfer material are mixed with a polymer such as polyvinyl carbazole (Applied Physics, Vol. 61) , 10
44, 1992).

In the above-described organic electroluminescent devices, glass is usually used as a substrate. However, when glass is used as a substrate for display panels of personal computers and portable terminals, which are regarded as important applications of organic electroluminescent elements, the weight and thickness of the glass are reduced due to the problems of low density and mechanical strength of the glass. In addition to the limitations on the production, there is also a problem in terms of productivity from the viewpoint of moldability and workability. Therefore, development of an organic electroluminescent device using a plastic as a substrate is strongly desired.

[0006]

However, the conventional plastic substrate has the following problems.

(1) Transparency and optical characteristics suitable for an organic electroluminescent device cannot be satisfied. (2) Poor heat resistance. (3) Poor surface accuracy. In particular, regarding the optical isotropy, the birefringence Δ
At present, n · d is 1 nm or less, while that of a plastic substrate exceeds 10 nm. This problem of birefringence is difficult to solve when a molding method is employed in which some stretching operation or material flow operation is performed on the resin. In the case where a relatively thick substrate (for example, 0.4 mm or more) is used, molding is difficult by extruding a thermoplastic resin or forming a belt. On the other hand, when a thermosetting resin is used, several hours are required for molding, and there is a problem in productivity.

The present invention solves the above-mentioned conventional problems and uses a plastic substrate having transparency and optical properties suitable for an organic electroluminescent device, excellent heat resistance, excellent surface accuracy, and good moldability. An object of the present invention is to provide a light-weight organic electroluminescent device excellent in mechanical strength and productivity and a method for manufacturing the same.

[0009]

The organic electroluminescent device of the present invention is an organic electroluminescent device in which an anode, an organic luminescent layer and a cathode are laminated on one surface of a substrate. It is made of a curable resin, and has a surface roughness (Rz) of the one plate surface of the substrate of 1 to 50 nm.

In the case of a substrate made of a photocurable resin, the substrate can be easily formed by shaping a photocurable liquid monomer into a plate shape, irradiating the monomer with an active energy ray, and polymerizing and curing the monomer. In addition, such a photo-curable resin substrate has transparency and optical characteristics suitable for an organic electroluminescent element, and is excellent in heat resistance and surface accuracy.

The surface roughness (Rz) of the laminated surface of the substrate, that is, the surface on which the anode, the organic light emitting layer, and the cathode are laminated (hereinafter referred to as the “light emitting element fabrication surface”) is in the range of 1 to 50 nm. By doing so, it becomes possible to form an element constituent layer with good adhesiveness on the substrate without causing a short circuit of the element.

In the present invention, the photocurable resin is preferably obtained by photopolymerizing a monomer containing a polyfunctional (meth) acrylate having two or more functional groups in the molecule. The polyfunctional (meth) acrylate having two or more functional groups therein is at least one selected from the group consisting of a compound represented by the following general formula [I] and a compound represented by the following general formula [II] It is preferable to use a bis (meth) acrylate.

[0013]

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(In the above formula [I], R ¹ and R ² are each hydrogen or a methyl group, and R ³ and R ⁴ are each a C 1-6 carbon atom which may contain an ether group and / or a thioether group. X represents a halogen atom or an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and k represents 0 to 0.
Indicates an integer of 4. )

[0015]

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(In the formula [II], R ⁵ and R ⁶ each represent hydrogen or a methyl group, m represents 1 or 2, and n represents 0 or 1.) The photocurable resin according to the present invention is In particular, it is preferably obtained by copolymerizing a polyfunctional (meth) acrylate having two or more functional groups in a molecule and a polyfunctional mercapto compound having two or more functional groups in a molecule.

The substrate is preferably made of a photocurable resin having a birefringence of 20 nm or less.

The organic electroluminescent device of the present invention has the following features.
In a method of manufacturing an organic electroluminescent device by laminating an anode, an organic light-emitting layer, and a cathode on a substrate, the substrate is made of a photocurable resin, and the surface roughness (Rz) of at least one plate surface thereof Is manufactured by laminating an anode, an organic luminescent layer, and a cathode on the one plate surface of the substrate.

In the present invention, the substrate is preferably a photocurable composition containing a polyfunctional (meth) acrylate having two or more functional groups in a molecule and a polyfunctional mercapto compound having two or more functional groups in a molecule. It is manufactured by shaping an aqueous liquid monomer into a plate shape and irradiating the plate with an active energy ray to photopolymerize and cure.

[0020]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an organic electroluminescent device of the present invention and a method for manufacturing the same will be described with reference to the drawings.

1 to 3 are schematic cross-sectional views showing examples of the structure of the organic electroluminescent device of the present invention. In the figures, 1 is a substrate, 2 is an anode, 3 is an organic light emitting layer, and 3a is a hole transport layer. , 3b is an electron transport layer, 3c is a hole injection layer, 4 is a cathode, 10, 10A,
10B is an organic electroluminescent element.

The substrate 1 serves as a support for the organic electroluminescent device, and is required to have excellent characteristics such as optical characteristics, heat resistance, surface accuracy, mechanical strength, light weight, and gas barrier properties. In the present invention, a photo-curable resin substrate is employed as a plastic substrate having excellent characteristics. Hereinafter, the substrate material used in the present invention will be described.

<Polyfunctional (meth) acrylate> The substrate according to the present invention is, for example, a polyfunctional (meth) acrylate represented by the following sulfur-containing (meth) acrylate represented by the following general formula [I] and the following general formula [II]: A photocurable monomer composition comprising one or more bis (meth) acrylates selected from the group consisting of alicyclic skeleton bis (meth) acrylates, and irradiating this with an active energy ray. It is composed of a photocurable resin obtained by photopolymerization and curing.

[0024]

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[0025]

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Each symbol in the above general formulas [I] and [II] has the following meaning. R ¹ and R ² : a hydrogen atom or a methyl group. R ¹ and R ² may be the same or different.

R ³ : ether group (ether bond: CO)
-C), a thioether group (thioether bond: C—S—
Hydrocarbon group of carbon atoms which may contain 1-6 to C), preferably an alkylene group having 2 to 4 carbon atoms R ^4: ether group, a hydrocarbon having 1 to 6 carbon atoms which may contain a thioether group A group, preferably an alkylene group having 1 to 3 carbon atoms X: a halogen atom or an alkyl group or an alkoxy group having 1 to 6 carbon atoms k: an integer of 0 to 4 R ⁵ and R ⁶ : a hydrogen atom or a methyl group. R ⁵ and R ⁶ may be the same or different. M: 1 or 2 n: 0 or 1 In addition, “contains” in the “photocurable monomer composition comprising (meth) acrylate” "Means that the composition may contain a small amount of an auxiliary component other than the polyfunctional (meth) acrylate within a range not to impair the purpose of the present invention. That is, the auxiliary component such as another monomer copolymerizable with the polyfunctional (meth) acrylate specified as the main component of the photocurable monomer composition in the present invention is, for example, a photocurable monomer as described later. It means that it may be contained in a range up to about 30 parts by weight with respect to 100 parts by weight of the composition. In addition, each of the components in the composition may be used in combination of plural types between and / or within the components.

In the present specification, “(meth) acrylate” is a general term for acrylate and / or methacrylate.

Specific examples of the sulfur-containing (meth) acrylate compound represented by the general formula [I] include, for example, p-bis (β-methacryloyloxyethylthio)
Xylylene (R ¹ : methyl, R ² : methyl, R ³ : ethylene, R ⁴ : methylene, k: 0), p-bis (β-acryloyloxyethylthio) xylylene, m-bis (β
-Methacryloyloxyethylthio) xylylene, m-
Bis (β-acryloyloxyethylthio) xylylene, p-bis (β-methacryloyloxyethyloxyethylthio) xylylene, p-bis (β-methacryloyloxyethylthio) xylylene, p-bis (β-methacryloyloxyethylthio) Tetrabromoxylylene, m-bis (β-methacryloyloxyethylthio)
Tetrachloroxylylene and the like.

These compounds are described, for example, in JP-A-62-1
The compound can be synthesized by the method disclosed in Japanese Patent No. 95357.

Specific examples of the alicyclic skeleton bis (meth) acrylate compound represented by the general formula [II] include bis (oxymethyl) tricyclo [5.2.0 ^2,6 ] decane diacrylate; Bis (oxymethyl) tricyclo [5.2.0 ^2,6 ] decane dimethacrylate, bis (oxymethyl) tricyclo [5.2.0 ^2,6 ] decane = acrylate methacrylate, and mixtures thereof;
Bis (oxymethyl) pentacyclo [6.5.1.1
^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane diacrylate, bis (oxymethyl) pentacyclo [6.5.1.
^13-6 . 0 ^2,7 . 0 ^{9, 13]} pentadecane = dimethacrylate, bis (oxymethyl) pentacyclo [6.5.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane acrylate methacrylate and mixtures thereof.
Two or more of these tricyclodecane compounds and pentacyclopentadecane compounds may be used in groups or between groups.

These compounds are described, for example, in JP-A-62-2
It can be synthesized by the method disclosed in Japanese Patent No. 25508.

The polyfunctional (meth) acrylates represented by the general formulas [I] and [II] can be used alone or in combination of two or more. When the compound of the general formula [I] is used alone, the refractive index of the obtained substrate is D
1.55 to 1.6 at room temperature on line (589.3 mm)
A relatively high refractive index of 5. On the other hand, when the compound of the general formula [II] is used alone, it has a relatively low refractive index of 1.47 to 1.55. Accordingly, by using one or more compounds represented by the general formulas [I] and [II] in combination,
A low birefringent resin substrate having a desired refractive index between 1.47 and 1.65 can be obtained.

<Auxiliary Component> The substrate material according to the present invention is obtained by polymerizing and curing a polyfunctional (meth) acrylate-containing photocurable monomer composition containing a polyfunctional (meth) acrylate as an essential component. It has been mentioned above that the photocurable monomer composition may contain small amounts of auxiliary components.

Therefore, the resin substrate according to the present invention can be used in an amount of 30 parts by weight per 100 parts by weight of the photocurable monomer composition before curing.
It is also possible to produce the mixture by mixing other monomers capable of radical polymerization and addition polymerization in an amount of up to about parts by weight and copolymerizing with the above polyfunctional (meth) acrylate. Other monomers used at this time include, for example, methyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methacryloyloxymethyltetracyclododecane, methacryloyloxymethyltetracyclododecene, ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,2-bis [4- (β-methacryloyloxyethoxy) phenyl] propane, 2,2′- (Meth) acrylate compounds such as bis [4- (β-methacryloyloxyethoxy) cyclohexyl] propane, 1,4-bis (methacryloyloxymethyl) cyclohexane, and trimethylolpropane tri (meth) acrylate; , Chlorostyrene, divinylbenzene, alpha
Nucleus such as -methylstyrene and / or side chain-substituted, unsubstituted styrene, etc .;
One or two or more mercapto compounds selected from the group consisting of mercapto compounds having two or more thiol groups in the molecule represented by [II], [IV] and [V].

[0036]

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[0037]

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[0038]

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The symbols in the above general formulas [III], [IV] and [V] have the following meanings.

R ⁷ : a methylene group or an ethylene group R ⁸ : a hydrocarbon group having 2 to 15 carbon atoms which may contain an ether group or a thioether group. Preferably 2 to 6 carbon atoms
A: an integer of 2 to 6 R: HS— (CH ₂ —) _b (CO) — (OCH ₂ ) _d —
(CH _2- ) _c- (where b and c are integers of 0 to 2, d is an integer of 1 to 4) R ⁹ : a hydrocarbon group having 1 to 3 carbon atoms R ¹⁰ : a hydrocarbon group having 1 to 3 carbon atoms Groups e, f: 0 or 1 g: 1 or 2 The mercapto compound represented by the above general formula [III] is a compound of the formula
Hexavalent thioglycolate or thiopropionate. Specific examples of the compound of the formula [III] include
For example, pentaerythritol tetrakis (β-thiopropionate), pentaerythritol tetrakis (thioglycolate), trimethylolpropane tris (β-thiopropionate)
Thiopropionate), trimethylolpropane tris (thioglycolate), diethylene glycol bis (β
-Thiopropionate), diethylene glycol bis (thioglycolate), triethylene glycol bis (β-thiopropionate), triethylene glycol bis (thioglycolate), dipentaerythritol hexacis (β-thiopropionate) ), Dipentaerythritol hexacis (thioglycolate) and the like.

The compound represented by the general formula [IV] is X-SH
It is a group-containing triisocyanurate. Specific examples of the compound of the formula [IV] include tris [2- (β-thiopropionyloxy) ethyl] isocyanurate and tris (2
-Thioglyconyloxyethyl) isocyanurate, tris [2- (β-thiopropionyloxyethoxy) ethyl] isocyanurate, tris (2-thioglyconyloxyethoxyethyl) isocyanurate, tris [3
-(Β-thiopropionyloxy) propyl] isocyanurate, tris (3-thioglyconyloxypropyl) isocyanurate and the like.

The compound represented by the general formula [V] is α, X-
It is an SH group-containing compound. Specific examples of the compound of the formula [V] include, for example, benzene dimercaptan, xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide and the like.

By incorporating these mercapto compounds, the action as a chain transfer agent having a thiol group can be effectively exerted in the production of a resin substrate, and the polymerization and curing proceed gently and uniformly, and the resulting cured resin is obtained. Can be reduced. In addition, these mercapto compounds enter the three-dimensional network structure formed by bis (meth) acrylate, and impart an appropriate toughness to the obtained resin substrate. Furthermore, by using a polyfunctional mercapto compound having two or more thiol groups in the molecule, that is,
Birefringence, mechanical strength, etc. can be improved without significantly impairing the heat resistance of the obtained cured resin.

When the above polyfunctional (meth) acrylate and the above mercapto compound are used in combination as the substrate material according to the present invention, the composition ratio is from 70 to 99.9 parts by weight of the polyfunctional (meth) acrylate to the mercapto compound. Compound 0.
The content is preferably 1 to 30 parts by weight, more preferably 80 to 99 parts by weight of the polyfunctional (meth) acrylate.
The range is from 1 to 20 parts by weight of the mercapto compound. If the proportion of the mercapto compound is too small, the effect of improving the birefringence of the cured resin will not be obtained, and if it is too large, the heat resistance of the cured resin will decrease.

As auxiliary components, in addition to the above-mentioned mercapto compounds, antioxidants, ultraviolet absorbers, dyes and pigments, fillers and the like can be used.

<Shaping / Polymerization Curing> The photocurable monomer composition according to the present invention is shaped and cured. The curing is
It is carried out by a known radical polymerization in which a photopolymerization initiator which generates a radical by active energy rays such as ultraviolet rays is added. As the photopolymerization initiator used at that time, for example, benzophenone, benzoyl methyl ether, benzoyl isopropyl ether, diethoxyacetophenone,
1-hydroxycyclohexyl phenyl ketone, 2,6
-Dimethylbenzoyldiphenylphosphine oxide,
2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Of these, preferred photopolymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzophenone. Two or more of these photopolymerization initiators may be used in combination.

The amount of the photopolymerization initiator is 0.01 to 1 part by weight, preferably 0.02 to 0.3 part by weight, per 100 parts by weight of the monomer. If the amount of the photopolymerization initiator is too large, the polymerization proceeds rapidly, causing not only an increase in birefringence but also a deterioration in hue. If the amount is too small, the photocurable monomer composition cannot be sufficiently cured.

The amount of the active energy rays to be irradiated is arbitrary as long as the photopolymerization initiator generates radicals. However, if the amount is extremely small, the polymerization becomes incomplete and the heat resistance and mechanical properties of the cured product become poor. Is not sufficiently expressed, and conversely, if it is excessively excessive, deterioration of the cured product due to light, such as yellowing, occurs. Therefore, ultraviolet rays having a wavelength of 200 to 400 nm according to the monomer composition and the type and amount of the photopolymerization initiator are used. Is preferably 0.1 to
Irradiate in the range of 200J. Specific examples of the lamp to be used include a metal halide lamp and a high-pressure mercury lamp.

In order to complete the curing promptly, thermal polymerization may be used in combination. That is, the composition and the entire mold are heated in the range of 30 to 300 ° C. simultaneously with the light irradiation. In this case, a thermal polymerization initiator may be added to complete the polymerization better, but its excessive use leads to an increase in birefringence and a deterioration in hue. Specific examples of the thermal polymerization initiator include benzoyl peroxide, diisopropylperoxycarbonate, t-butylperoxy (2-ethylhexanoate), and the amount used is 100
It is preferably 1 part by weight or less based on parts by weight.

In the present invention, the completion of the polymerization reaction and the internal strain generated during the polymerization can be reduced by heating the cured product after performing the radical polymerization by light irradiation. In this case, the heating temperature is appropriately selected according to the composition of the cured product and the glass transition temperature. However, since excessive heating results in deterioration of the hue of the cured product, a temperature around the glass transition temperature or lower is preferable.

As a mold for shaping, an optically polished glass plate and a silicon plate having a predetermined thickness as a spacer are usually used. Since the surface roughness of the glass plate used affects the surface roughness of the obtained resin substrate, it is necessary to control the surface roughness of the glass plate according to the required surface roughness of the resin substrate. Generally, the surface roughness R
In order to obtain a resin substrate having z of 2 to 50 nm, the surface roughness Rz of the glass plate used as the mold is desirably 0.2 to 20 nm. Factors affecting the surface roughness of the resin substrate include, in addition to the surface roughness of the glass plate described above, the amount of ultraviolet irradiation, the amount of photoinitiator, and the like. Therefore, each parameter is determined as necessary. For example, the surface roughness R of the resin substrate
In order to obtain those having a z of 5 to 10 nm, a glass plate having a surface roughness Rz of 1 to 5 nm is used, a silicon plate is arranged as a spacer on this glass plate, and a polyfunctional (meth) acrylate is used. Then, the photocurable monomer composition defoamed by mixing the auxiliary components at a predetermined ratio is injected, and ultraviolet light is irradiated for 10 minutes between metal halide lamps having an output of 80 W / cm and separated from the glass surface by 40 cm vertically.

<Physical Properties of Resin Substrate> The optical birefringence of the photocurable resin substrate according to the present invention is preferably 20 nm or less from the viewpoint of optical characteristics as a substrate for an organic electroluminescent device.

The thickness of the resin substrate according to the present invention is usually 0.1 to 5 mm, preferably 0.3 to 1 mm.
It is.

Further, the surface roughness of the resin substrate according to the present invention on the light emitting element forming surface side is 1 to 50 n at 10-point average roughness Rz.
m, preferably 2 to 20 nm. When Rz of the resin substrate is larger than 50 nm, short-circuiting easily occurs between the electrodes of the organic electroluminescent element formed on the substrate surface, which is not suitable as a substrate. On the other hand, if Rz is smaller than 1 nm, the adhesive force between the organic layer formed on the substrate surface and the substrate is reduced, and the organic layer is easily peeled off by the stress at the time of deposition of the subsequent cathode metal layer and the like, which is also suitable as a substrate. Disappears.

For the purpose of further improving the gas barrier properties of the resin substrate, a dense silicon oxide film or the like may be provided on at least one surface of the substrate.

Next, the constituent layers of the organic electroluminescent device of the present invention using such a photo-curable resin substrate will be described.

The anode 2 formed on the substrate 1 plays a role of injecting holes into the organic light emitting layer 3. This anode 2 is usually made of aluminum, gold, silver, platinum, nickel,
Metals such as palladium and platinum, metal oxides such as oxides of indium and / or tin, metal halides such as copper iodide, carbon black, or conductive materials such as poly (3-methylthiophene), polypyrrole, and polyaniline It is preferably formed of indium tin oxide, such as a polymer. The anode 2 is usually formed by a sputtering method,
It is often performed by a vacuum deposition method or the like. Fine metal particles such as silver, fine particles such as copper iodide, carbon black,
When conductive metal oxide fine particles, conductive polymer fine powder, or the like is used, the anode 2 can be formed by dispersing the fine particles in a suitable binder resin solution and applying the dispersion on the substrate 1. When using a conductive polymer,
The anode 2 can also be formed by forming a thin film directly on the substrate 1 by electrolytic polymerization or by coating a conductive polymer on the substrate 1 (Appl. Phys. Let.
t. 60, 2711, 1992). The anode 2 can be formed by laminating different materials.

The thickness of the anode 2 varies depending on whether transparency is required. When transparency is required, it is desirable that the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness is usually 5 to 100.
0 nm, preferably about 10 to 500 nm. When the anode 2 may be opaque, it may be made of the same material as the substrate 1. Further, different conductive materials can be laminated on the anode 2.

The organic light emitting layer 3 formed on the anode 2
It is made of a material that efficiently transports and recombines holes injected from the anode 2 and electrons injected from the cathode 4 between the electrodes to which an electric field is applied, and emits light efficiently by the recombination. Normally, as shown in FIG. 2, the organic light emitting layer 3 is of a function-separated type in which the organic light emitting layer 3 is divided into a hole transport layer 3a and an electron transport layer 3b (Appl. Phys. Lett., 51, 913
1987).

Function-separated type organic electroluminescent device 1 shown in FIG.
At 0A, the material of the hole transport layer 3a is the anode 2
It is necessary that the material has a high hole injection efficiency and a material capable of efficiently transporting the injected holes. For that purpose, it is required that the ionization potential is small, the hole mobility is large, the stability is further improved, and impurities serving as traps during production or use are hardly generated.

As such a hole transport material, for example, an aromatic diamine compound in which tertiary aromatic amine units such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane are linked (Japanese Patent Application Laid-open No. 1959-19439
No. 3), 4,4′-bis [N- (1-naphthyl)-
N-phenylamino] aromatic amines containing two or more tertiary amines represented by biphenyl and having two or more condensed aromatic rings substituted by nitrogen atoms (JP-A-5-234681); Aromatic triamines having a starburst structure in derivatives (US Pat. No. 4,92
Aromatic diamines such as N, N'-diphenyl-N, N'-bis (3-methylphenyl) biphenyl-4,4'-diamine (U.S. Pat. No. 4,764,62)
No. 5), α, α, α ′, α′-tetramethyl-α, α ′
-Bis (4-di-p-tolylaminophenyl) -p-xylene (JP-A-3-269084), a triphenylamine derivative which is sterically asymmetric as a whole molecule (JP-A-4-129271), bienyl In which a plurality of aromatic diamino groups are substituted on a group (JP-A-4-17539)
No. 5), an aromatic diamine in which a tertiary aromatic amine unit is linked by an ethylene group (JP-A-4-264189), an aromatic diamine having a styryl structure (JP-A-Hei-4).
(Japanese Patent Application Laid-Open No. 4-290466), a compound in which an aromatic tertiary amine unit is linked by a thiophene group (JP-A-4-304466).
JP-A-4-308688), a benzylphenyl compound (JP-A-4-364153), and a fluorene group of 3
Tertiary amine compound (JP-A-5-239455), bisdipyridylaminobiphenyl (JP-A-5-3473)
20634), N, N, N-triphenylamine derivatives (JP-A-6-1972), and aromatic diamines having a phenoxazine structure (JP-A-7-138562).
JP, JP-A-7-252474, a hydrazone compound (JP-A-2-311591), a silazane compound (U.S. Pat. No. 4,950,950), and a silanamin derivative ( JP-A-6-49079), phosphamine derivatives (JP-A-6-25659), and quinacridone compounds. These compounds may be used alone or, if necessary, in combination of two or more.

In addition to the above compounds, the hole transport layer 3
As a material of a, polyvinyl carbazole or polysilane (Appl. Phys. Lett., Vol. 59, 2760)
P. 1991), polyphosphazene (JP-A-5-3)
No. 10949), polyamide (JP-A-5-3109)
No. 49), polyvinyl triphenylamine (Japanese Patent Application Laid-Open No. 7-53953), a polymer having a triphenylamine skeleton (Japanese Patent Application Laid-Open No. 4-133065), and a polymer in which triphenylamine units are linked by a methylene group or the like. (S
Synthetic Metals, 55-57, 41
63, 1993), polyamines containing aromatic amines (J. Polym. Sci., Poly).
m. Chem. Ed. , 21, 969, 1983.
) Can be used.

The hole transport layer 3a is formed on the anode 2 by depositing these hole transport materials by a coating method or a vacuum evaporation method.

In the case of the coating method, one or more hole transport materials and, if necessary, additives such as a binder resin or a coating improver which do not trap holes are added and dissolved in a solvent. Then, a coating solution is prepared, applied to the anode 2 by a method such as spin coating, and dried to form an organic hole transport layer 3a. In this case, examples of the binder resin include polycarbonate, polyarylate, and polyester. Since a large amount of the binder resin decreases the hole mobility, a small amount is desirable.
It is preferably at most 50% by weight.

On the other hand, in the case of the vacuum evaporation method, the hole transporting material is put into a crucible provided in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ^-4 Pa by a suitable vacuum pump. Is heated to evaporate the hole transporting material, and the hole transporting layer 3a is formed on the anode 2 on the substrate 1 arranged opposite to the crucible.
To form

When the hole transport layer 3a is formed in this manner, a metal complex and / or metal salt of an aromatic carboxylic acid (JP-A-4-320484), a benzophenone derivative and a thiobenzophenone derivative are further used as acceptors. (JP-A-5-295361), fullerenes (JP-A-5-331458) and the like are doped at a concentration of 10 ⁻³ to 10% by weight to generate holes as free carriers, thereby reducing the amount of holes. Voltage driving can be enabled.

The thickness of the hole transport layer 3a is usually 10 to 3
00 nm, preferably 30 to 100 nm. In order to uniformly form such a thin hole transport layer,
Generally, it is preferable to employ a vacuum deposition method.

For the purpose of further improving the hole injection efficiency and improving the adhesion of the entire organic layer to the anode 2,
As shown in FIG. 3, a hole injection layer 3c is formed between the hole transport layer 3a and the anode 2. As a material used for the hole injection layer 3c, a material having a low ionization potential, high conductivity, and capable of forming a thermally stable thin film on the anode 2 is desirable. A phthalocyanine compound or a porphyrin compound (Japanese Patent Application Laid-Open No. 57-51781, JP-A-63-29569).
By interposing such a hole injection layer 3c, it is possible to obtain the effect of reducing the initial drive voltage of the device and suppressing the voltage rise when the device is continuously driven with a constant current. The conductivity of the hole injection layer 3c can also be improved by doping the acceptor similarly to the hole transport layer 3a.

The thickness of the hole injection layer 3c is usually 2 to 10
0 nm, preferably 5 to 50 nm. In order to uniformly form such a thin hole injection layer, it is generally preferable to employ a vacuum evaporation method.

The electron transport layer 3b formed on the hole transport layer 3a is a compound capable of efficiently transporting electrons from the cathode in the direction of the hole transport layer 3a between electrodes to which an electric field is applied. It consists of.

The electron transporting compound used in the electron transporting layer 3b needs to be a compound having a high electron injection efficiency from the cathode 4 and capable of transporting the injected electrons efficiently. For that purpose, it is required that the compound has a high electron affinity, high electron mobility, excellent stability, and hardly generates impurities serving as traps during production or use.

Materials satisfying such conditions include aromatic compounds such as tetraphenylbutadiene (Japanese Unexamined Patent Publication No.
And metal complexes such as aluminum complexes of 8-hydroxyquinoline (JP-A-59-1943).
No. 93), cyclopentadiene derivatives (Japanese Unexamined Patent Publication No.
289675), perinone derivatives (JP-A 2-2)
No. 89676), oxadiazole derivatives (Japanese Patent Application Laid-Open No. 2-216991), and bisstyrylbenzene derivatives (Japanese Patent Application Laid-Open Nos. 1-245087 and 2-222448).
No. 4), perylene derivatives (JP-A-2-189890)
JP-A-3-7991), coumarin compounds (JP-A-2-191694 and JP-A-3-792), rare-earth complexes (JP-A-1-256584), and distyrylpyrazine derivatives (JP-A-Heisei 2). 252793)),
p-phenylene compound (JP-A-3-33183), thiadiazolopyridine derivative (JP-A-3-372)
No. 92), pyrrolopyridine derivatives (JP-A-3-37)
293), naphthyridine derivatives (JP-A-3-20
3982) and the like.

Electron transport layer 3b using these compounds
Can generally simultaneously fulfill the role of transporting electrons and the role of providing light emission when holes and electrons recombine.

When the hole transporting layer 3a has a light emitting function, the electron transporting layer 3b may only play the role of transporting electrons.

For the purpose of improving the luminous efficiency of the device and changing the luminescent color, for example, doping a fluorescent dye for laser such as coumarin using an 8-hydroxyquinoline aluminum complex as a host material (J. Appl. Ph.
ys. 65, 3610, 1989). In the present invention, the above-mentioned organic electron transporting material is used as a host material to dope various fluorescent dyes by 10 ^-3 to 10 mol%. In addition, the light emitting characteristics of the device can be further improved.

The thickness of the electron transport layer 3b is usually 10 to 2
00 nm, preferably 30 to 100 nm.

The electron transporting layer can be formed in the same manner as the hole transporting layer, but usually, a vacuum evaporation method is used.

The organic light emitting layer 3 of the single-layer type which does not perform the function separation as shown in FIG.
-Phenylene vinylene) (Nature, 347, 5)
39, 1990 et al.), Poly [2-methoxy-5-
(2-ethylhexyloxy) -1,4-phenylenevinylene] (Appl. Phys. Lett., Vol. 58,
1982, 1991, etc.), poly (3-alkylthiophene) (Jpn. J. Appl. Phys. 30, vol.
L1938, 1991, etc.) or a system in which a light emitting material and an electron transfer material are mixed with a polymer such as polyvinyl carbazole (Applied Physics, vol. 61, p. 1044, 19).
1992).

The cathode 4 plays a role of injecting electrons into the organic light emitting layer 3. As the material used for the cathode 4, the material used for the anode 2 can be used. However, for efficient electron injection, a metal having a low work function is preferable, and tin, magnesium, indium, calcium,
Suitable metals such as aluminum and silver or alloys thereof are preferred. The thickness of the cathode 4 is usually about the same as that of the anode 2.

For the purpose of protecting the cathode made of a metal having a low work function, the stability of the device can be increased by further laminating a metal layer having a high work function and being stable to the atmosphere on this cathode. Metals such as aluminum, silver, nickel, chromium, gold, and platinum are used for the metal layer for this purpose.

FIGS. 1 to 3 show an example of an element main body employed in the present invention. The present invention is applied to an element main body having the following layer structure other than the illustrated one. can do.

Anode / hole transport layer / electron transport layer / interface layer /
Cathode, anode / hole transport layer / electron transport layer / other electron transport layer / cathode, anode / hole transport layer / electron transport layer / other electron transport layer / interface layer / cathode, anode / hole injection layer / Hole transport layer / electron transport layer / interface layer /
Cathode, anode / hole injection layer / hole transport layer / electron transport layer / other electron transport layer / cathode In the above layer structure, the interface layer is for improving the contact between the cathode and the organic layer, and is aromatic. Diamine compounds (JP-A-6-267658), quinacridone compounds (JP-A-6-330031), naphthacene derivatives (JP-A-6-330032), organic silicon compounds (JP-A-6-325871), organic compounds Phosphorus compounds (Japanese Patent Application Laid-Open No. Hei 6-325872) and compounds having an N-phenylcarbazole skeleton (Japanese Patent Application No. Hei 6-199562)
No.), N-vinylcarbazole polymer (Japanese Patent Application No. 6-20)
0942) and the like. The thickness of the interface layer is usually 2 to 100 nm, preferably 5 to 30 n.
m. Instead of providing the interface layer, a region containing 50% by weight or more of the material for the interface layer may be provided near the cathode interface between the organic light emitting layer and the electron transport layer.

Further, another electron transport layer is further formed on the electron transport layer in order to further improve the luminous efficiency of the organic electroluminescent device. Is easy to inject electrons from the cathode,
It is required that the ability to transport electrons is further increased. As such an electron transporting material, an oxadiazole derivative (Appl. Phys. Lett., Vol. 55, 1489)
1989, etc.) and a system in which they are dispersed in a resin such as polymethyl methacrylate (PMMA) (Appl. Phys.
s. Lett. 61, 2793, 1992),
Phenanthroline derivatives (JP-A-5-331559), n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide and the like. The thickness of the other electron transporting layer is usually 5 to 200 nm, preferably 1 to 200 nm.
0-100 nm.

The organic electroluminescent device of the present invention is applicable to any of a single device, a device having a structure arranged in an array, and a device having a structure in which an anode and a cathode are arranged in an XY matrix. be able to.

[0085]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the description of the following examples unless it exceeds the gist.

Example 1 99 parts by weight of p-bis (β-methacryloyloxyethylthio) xylylene, 1 part by weight of pentaerythritol tetrakis (β-thiopropionate), 2,4,6-trimethylbenzoyl as a photopolymerization initiator Diphenylphosphine oxide ("Lucillin TPO" manufactured by BASF)
After uniformly stirring and mixing 0.05 parts by weight and benzophenone 0.02 parts by weight, the mixture was defoamed to obtain a photocurable monomer composition.

On the other hand, as a mold for shaping the resin, an optically polished glass plate and a spacer having a thickness of 1 mm were used.
Using a silicon plate of the above, the photocurable monomer composition,
The liquid is poured into the mold of the optically polished glass and the distance from the glass surface is 4
Ultraviolet rays were irradiated for 10 minutes between a metal halide lamp with an output of 80 W / cm at a vertical position of 0 cm. After the ultraviolet irradiation, the mold was released and heated at 120 ° C. for 1 hour to obtain a cured product. This cured product is shaped like a slide glass (25 x 75 mm)
To obtain a substrate A. Various characteristics of the substrate A were as shown in Table 1. The evaluation of each characteristic was performed by the following method.

(1) Appearance: Evaluated visually. (2) Specific gravity: Evaluated by measuring the weight and volume of a test piece having a width and length of 5 cm each and a thickness of 1 mm. (3) Falling ball impact test: width and length each 5 cm, thickness 1 mm
The test piece was evaluated at the lowest height at which the test piece was broken by allowing a steel ball of 16 g to fall naturally on the test piece. (4) Flexural modulus: A plate having a width of 1 cm and a thickness of 1 mm was evaluated at 25 ° C. by using an autograph at a distance between supporting points of 3 cm. (5) Surface roughness Rz: stylus type surface roughness meter (Taristep manufactured by Rank Taylor Hobson Co .;
× 0.2 μm square) using 10 point average roughness (JISB060)
1) was evaluated. (6) Refractive index: 2 using Abbe refractometer (manufactured by Atago)
The evaluation was performed at 5 ° C. (7) Birefringence: Evaluated at 25 ° C. using a birefringence measuring device (manufactured by Oak). (8) Water absorption: Evaluated by saturated water absorption when immersed in water at 60 ° C. for one week. (9) Glass transition temperature: 5 for a 1 mm thick test piece
Evaluation was performed using a TMA (thermomechanical analyzer) with a weight of 0 g.

Next, a transparent conductive film of indium tin oxide (ITO) was deposited on the substrate A to a thickness of 120 nm (manufactured by Howa Sangyo Co., Ltd .: low-temperature sputtered film: sheet resistance: 20 Ω).
A TO substrate A was used.

Using this ITO substrate A, an organic electroluminescent device having the structure shown in FIG. 3 was manufactured by the following method.
First, the anode was formed by patterning the ITO transparent conductive film deposited on the ITO substrate A into stripes having a width of 2 mm by using ordinary photolithography and hydrochloric acid etching.

The patterned ITO substrate is cleaned in the order of ultrasonic cleaning with acetone, water cleaning with pure water, ultrasonic cleaning with isopropyl alcohol, dried with nitrogen blow, and finally with ultraviolet and ozone cleaning to perform vacuum deposition. Installed inside the device. After rough exhaust of the apparatus is performed by an oil rotary pump, the degree of vacuum in the apparatus is 2 × 10 ⁻⁶ Torr (about ^2.10 Torr).
Evacuation was performed using an oil diffusion pump equipped with a liquid nitrogen trap until the pressure became 7 × 10 ⁻⁴ Pa) or less.

The following copper phthalocyanine (H1) (having a β-type crystal form) placed in a molybdenum boat placed in the above apparatus was deposited by heating. The steam has a degree of vacuum of 1.
The deposition was performed at 1 × 10 ⁻⁶ torr (about 1.5 × 10 ⁻⁴ Pa) for 1 minute to form a hole injection layer 3c having a thickness of 20 nm.

[0093]

Embedded image

Next, the following 4,4′-bis [N- (1) was placed in a ceramic crucible placed in the above apparatus.
-Naphthyl) -N-phenylamino] bisphenol (H2) was laminated on the hole injection layer 3c by heating with a tantalum wire heater around the crucible. At this time, the temperature of the crucible was controlled in the range of 230 to 240 ° C. The hole transport layer 3a having a thickness of 60 nm was formed with a degree of vacuum of 8 × 10 ⁻⁷ Torr (about 1.1 × 10 ⁻⁴ Pa) during the deposition and a deposition time of 1 minute and 50 seconds.

[0095]

Embedded image

Subsequently, the electron transport layer 3 having a light emitting function
As a material b, an 8-hydroxyquinoline complex of aluminum shown below: Al (C ₉ H ₆ NO) ₃ (E1) was vapor-deposited on the hole transport layer 3a in the same manner. At this time, the temperature of the crucible was controlled in the range of 310 to 320 ° C.
The degree of vacuum during vapor deposition is 9 × 10 ⁻⁷ Torr (about 1.2 × 10 Torr).
^-4 Pa), a vapor deposition time of 2 minutes and 40 seconds, and a 75 nm-thick electron transport layer 3b was formed.

[0097]

Embedded image

The substrate temperature during vacuum deposition of the hole injection layer 3c, the hole transport layer 3a and the electron transport layer 3b was kept at room temperature.

The substrate on which the hole injection layer 3c, the hole transport layer 3a and the electron transport layer 3b have been formed is once taken out of the vacuum evaporation apparatus into the atmosphere, and 2 m is used as a mask for cathode evaporation.
An m-width striped shadow mask is applied to the anode 2 ITO
It is provided in close contact with the stripe so as to be perpendicular to the stripe, and is installed in another vacuum evaporation apparatus, and the degree of vacuum in the apparatus is set to 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ^-Four
Pa). Subsequently, as a cathode 4, an alloy electrode of magnesium and silver was deposited to a thickness of 100 nm by a binary simultaneous deposition method. The vapor deposition was performed using a molybdenum boat at a degree of vacuum of 1 × 10 ⁻⁵ Torr (about 1.3 × 10 ⁻³ Pa) and a vapor deposition time of 3 minutes and 10 seconds.
The atomic ratio of magnesium to silver was 10: 1.2. Subsequently, without breaking the vacuum of the apparatus, a cathode 4 was completed by laminating aluminum with a thickness of 100 nm on the magnesium-silver alloy film using a molybdenum boat. The degree of vacuum during aluminum deposition is 2.3 × 10 ^-5 To
rr (about 3.1 × 10 ⁻³ Pa), and the deposition time was 1 minute and 40 seconds. The substrate temperature at the time of vapor deposition of the two-layered cathode of magnesium / silver alloy and aluminum was kept at room temperature.

As described above, an organic electroluminescent device having a size of 2 mm × 2 mm was obtained. After the device was taken out of the cathode vapor deposition apparatus, a positive DC voltage was applied to the anode 2 and a negative DC voltage was applied to the cathode 4 to emit light, and the emission characteristics were measured.

FIG. 4 shows a change in light emission luminance when the applied voltage is changed in a range of 1 to 15 V in 1 V steps. Table 2 shows the light emission luminance when 15 V is applied to the device, the light emission efficiency at 15 V, and L / J (a slope corresponding to the quantum efficiency when the luminance-current density characteristic is approximated by a straight line).
It was shown to.

Example 2 Bis (oxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane = dimethacrylate 96 as a monomer component
Example 1 except that parts by weight and 4 parts by weight of pentaerythritol tetrakis (β-thiopropionate) were used.
A cured product was obtained in the same manner as described above. The cured product was cut into a slide glass to obtain a substrate B. Various characteristics of the substrate B were as shown in Table 1.

Next, an ITO transparent conductive film was deposited on the substrate B by the same low-temperature sputtering method as in Example 1 to obtain an ITO substrate B. The sheet resistance of the ITO substrate B was 20Ω.

Further, Example 1 was performed using this ITO substrate B.
An organic electroluminescent device having the structure shown in FIG. 3 was produced in the same manner as in the above, and the luminescence characteristics were measured in the same manner. The results are shown in FIG.

Comparative Example 1 7059 glass manufactured by Corning Incorporated was cut into a slide glass to obtain a substrate C. Various characteristics of the substrate C were as shown in Table 1.

Next, an ITO transparent conductive film was deposited on the substrate C by the same low-temperature sputtering method as in Example 1 to obtain an ITO substrate C. The sheet resistance of the ITO substrate C was 20Ω.

Further, Embodiment 1 was carried out using this ITO substrate C.
An organic electroluminescent device having the structure shown in FIG. 3 was produced in the same manner as in the above, and the luminescence characteristics were measured in the same manner. The results are shown in FIG.

Comparative Example 2 In the same manner as in Comparative Example 1, 7059 glass manufactured by Corning Incorporated was used as a substrate, and an ITO transparent conductive film was deposited on this substrate by an electron beam evaporation method (manufactured by Geomatic) to obtain an ITO substrate D. The sheet resistance of the ITO substrate D was 15Ω. Further, when the X-ray diffraction analysis of the ITO substrate D was performed, the diffraction peak intensity of the In ₂ O ₃ crystal around 2θ = 30.6 ° was larger than that of the ITO substrate C of Comparative Example 1 by the low-temperature sputtering method. It was found that the crystallinity was high.

Using this ITO substrate D, an organic electroluminescent device having the structure shown in FIG. 3 was produced in the same manner as in Example 1, and the luminescence characteristics were measured in the same manner. The results are shown in FIG.

Comparative Example 3 A cured product was obtained in the same manner as in Example 1, except that the surface of the glass mold into which the photocurable monomer composition was injected was not optically polished. The cured product was cut into a slide glass to obtain a substrate E. Various characteristics of the substrate E were as shown in Table 1.

Next, an ITO transparent conductive film was deposited on the substrate E by the same low-temperature sputtering method as in Example 1 to obtain an ITO substrate E. The sheet resistance of the ITO substrate E was 20Ω.

Using this ITO substrate E, an organic electroluminescent device having the structure shown in FIG. 3 was fabricated in the same manner as in Example 1, and evaluated by the same method. As a result, the device was short-circuited when 5 V was applied. Destroyed.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

As described above in detail, according to the organic electroluminescent device and the method of manufacturing the same of the present invention, a plastic substrate which is lightweight and has high mechanical strength is used, and a conventional glass substrate is used in light emission characteristics. An organic electroluminescent device having characteristics equal to or higher than that of the conventional device can be obtained with high productivity.

Accordingly, the organic electroluminescent device according to the present invention can be used as a light source (for example, a light source of a copying machine, a performance display or an instrument) utilizing the characteristics of a flat panel display (for example, for an OA computer or a wall-mounted television) or a surface light emitting body. It is expected to be applied to various types of backlight sources, display boards, and sign lights, and its technical value is extremely large.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one embodiment of the organic electroluminescent device of the present invention.

FIG. 2 is a schematic sectional view showing another embodiment of the organic electroluminescent device of the present invention.

FIG. 3 is a schematic sectional view showing another embodiment of the organic electroluminescent device of the present invention.

FIG. 4 is a graph showing the applied voltage dependence of the light emission luminance of the organic electroluminescent devices in Examples 1 and 2 and Comparative Examples 1 and 2.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Organic light emitting layer 4 Cathode 3a Hole transport layer 3b Electron transport layer 3c Hole injection layer 10, 10A, 10B Organic electroluminescent element

Claims (8)

[Claims] 1. An organic electroluminescent device in which an anode, an organic light emitting layer and a cathode are laminated on one plate surface of a substrate, wherein the substrate is made of a photo-curable resin, and An organic electroluminescent device, wherein a surface roughness (Rz) of a plate surface is 1 to 50 nm. 2. The photocurable resin according to claim 1, wherein the photocurable resin is obtained by photopolymerizing a monomer containing a polyfunctional (meth) acrylate having two or more functional groups in a molecule. Organic electroluminescent device. 3. A polyfunctional (meth) acrylate having two or more functional groups in a molecule, the group comprising a compound represented by the following general formula [I] and a compound represented by the following general formula [II]: The organic electroluminescent device according to claim 2, wherein the organic electroluminescent device is at least one kind of bis (meth) acrylate selected from the group consisting of: Embedded image (In the above formula [I], R ¹ and R ² are each hydrogen or a methyl group, and R ³ and R ⁴ are each a hydrocarbon having 1 to 6 carbon atoms which may contain an ether group and / or a thioether group. And the group X represents a halogen atom or an alkyl group or an alkoxy group having 1 to 6 carbon atoms, and k represents an integer of 0 to 4.) (In the formula [II], R ⁵ and R ⁶ each represent hydrogen or a methyl group, m represents 1 or 2, and n represents 0 or 1.) 4. A photocurable resin obtained by copolymerizing a polyfunctional (meth) acrylate having two or more functional groups in a molecule and a polyfunctional mercapto compound having two or more functional groups in a molecule. The organic electroluminescent device according to claim 2, wherein the organic electroluminescent device is used. 5. The organic electroluminescent device according to claim 1, wherein the substrate is made of a photocurable resin having a birefringence of 20 nm or less. 6. A method of manufacturing an organic electroluminescent device by laminating an anode, an organic light emitting layer and a cathode on a substrate, wherein the substrate is made of a photocurable resin, and at least one of the plate surfaces A method for producing an organic electroluminescent device, comprising using a substrate having a surface roughness (Rz) of 1 to 50 nm, and laminating an anode, an organic light emitting layer, and a cathode on the one plate surface of the substrate. 7. A photocurable resin obtained by copolymerizing a polyfunctional (meth) acrylate having two or more functional groups in a molecule and a polyfunctional mercapto compound having two or more functional groups in a molecule. The method for manufacturing an organic electroluminescent device according to claim 6, wherein: 8. The substrate is produced by shaping a photocurable monomer containing a polyfunctional (meth) acrylate and a polyfunctional mercapto compound into a plate, irradiating the plate with an active energy ray, and photopolymerizing and curing the same. The method for manufacturing an organic electroluminescent device according to claim 7, wherein