JP2008218421A - Organic electroluminescent element and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent element which is light in weight and has excellent mechanical strength and productivity by using a plastic substrate which has transparency and optical characteristics suitable for an organic electroluminescent element, and is excellent in heat resistance and surface precision and moldability. <P>SOLUTION: The organic electroluminescent element is provided with a cathode, an organic light emitting layer and an anode laminated on the one surface side of a substrate, and the substrate is composed of an optical hardening resin and the surface roughness (Rz) of one plate face of the substrate is 1 to 50 nm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an organic electroluminescent device and a method for manufacturing the same, and more particularly to an improvement in a support substrate of a thin film light emitting device that emits light by applying an electric field to a light emitting layer made of an organic compound.

Conventionally, as thin film type electroluminescent (EL) elements, ZnS, CaS, SrS, etc., which are inorganic material II-IV group compound semiconductors, Mn or rare earth elements (Eu, Ce, Tb, Sm, etc.) that are emission centers ) Is generally used, but an EL element made from the above inorganic material is
(1) AC drive is required (generally 50 to 1000 Hz),
(2) Drive voltage is high (generally around 200V),
(3) Full color is difficult, especially blue
(4) The cost of the peripheral drive circuit is high.
Have the following problems.

  However, in recent years, an EL element using an organic thin film has been developed to improve the above problems. In particular, in order to improve luminous efficiency, the type of electrode is optimized for the purpose of improving the efficiency of carrier injection from the electrode, and an organic hole transport layer composed of aromatic diamine and an organic complex composed of 8-hydroxyquinoline aluminum complex. The development of an organic electroluminescent device provided with a light emitting layer (Non-patent Document 1) significantly improves the luminous efficiency compared with conventional electroluminescent devices using a single crystal such as anthracene and approaches practical characteristics. It is coming.

  In addition to the electroluminescent element using the low molecular material as described above, as a material for the organic light emitting layer, poly (p-phenylene vinylene) (Non-Patent Document 2, etc.), poly [2-methoxy-5 -(2-Ethylhexyloxy) -1,4-phenylenevinylene] (Non-patent Document 3, et al.), Poly (3-alkylthiophene) (Non-patent Document 4, et al.), Etc. Development of a device in which a low molecular light emitting material and an electron transfer material are mixed in a polymer such as polyvinyl carbazole (Non-Patent Document 5) is also underway.

In the organic electroluminescence device as described above, glass is usually used as the substrate. However, in the display panels of personal computers and portable terminals, which are considered to be important applications of organic electroluminescence devices, when glass is used as the substrate, the weight is reduced and the thickness is reduced due to the low density and mechanical strength of the glass. In addition, there is a problem in terms of formability and workability in terms of improving productivity. For this reason, development of an organic electroluminescent element using plastic as a substrate is strongly desired.
Appl. Phys. Lett. 51, 913, 1987) Nature, 347, 539, 1990, etc.) Appl. Phys. Lett. 58, 1982, etc.) Jpn. J. et al. Appl. Phys, 30, vol. 1938 Applied Physics, 61, 1044, 1992)

  However, the conventional plastic substrate has the following problems.

(1) Transparency and optical properties suitable for organic electroluminescence devices cannot be satisfied.
(2) Inferior heat resistance.
(3) Inferior surface accuracy.
In particular, regarding the optical isotropy, the birefringence Δn · d of the glass substrate is 1 nm or less, whereas the plastic substrate exceeds 10 nm. This birefringence problem is difficult to solve in the case of employing a molding method in which some stretching operation or material flow operation is applied to the resin. In addition, when a relatively thick substrate (for example, 0.4 mm or more) is used, molding is difficult by extrusion of a thermoplastic resin or belt formation. On the other hand, when a thermosetting resin is used, molding takes several hours, and there is a problem in terms of productivity.

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

  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 plate surface of the substrate, the substrate is made of a photocurable resin, and the substrate The surface roughness (Rz) of the one plate surface is 1 to 50 nm.

  If the substrate is a photocurable resin substrate, the substrate can be easily formed by shaping the photocurable liquid monomer into a plate shape, irradiating the monomer with active energy rays and polymerizing and curing the monomer. Such a photocurable 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 “light emitting element fabrication surface”) is in the range of 1 to 50 nm. Thus, the element constituent layer can be formed on the substrate with good adhesion 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 one or more functional groups is at least one bis (%) 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]. A meth) acrylate is preferred.

(In the formula [I], R ¹ and R ² are each a hydrogen atom 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, respectively. Group, X represents a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and k represents an integer of 0 to 4).

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

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

  Such an organic electroluminescent element of the present invention is a method of producing an organic electroluminescent element by laminating an anode, an organic light emitting layer and a cathode on a substrate, and the substrate is made of a photocurable resin, and The substrate is manufactured by using a substrate having a surface roughness (Rz) of at least one plate surface 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.

  In the present invention, the substrate is preferably a photocurable liquid monomer containing a polyfunctional (meth) acrylate having two or more functional groups in the molecule and a polyfunctional mercapto compound having two or more functional groups in the molecule. Is formed into a plate shape, and it is produced by irradiating it with an active energy ray and curing it by photopolymerization.

  According to the organic electroluminescent device and the method of manufacturing the same of the present invention, using a plastic substrate that is lightweight and has high mechanical strength, the light emitting characteristics are equivalent or superior to those of a device using a conventional glass substrate. An organic electroluminescent element can be obtained with high productivity.

  Therefore, the organic electroluminescent device according to the present invention is a light source (for example, a light source of a copying machine, a performance display, or a back of an instrument) utilizing characteristics of a flat panel display (for example, for OA computers or wall-mounted televisions) or a surface light emitter. It is expected to be applied to light sources), display boards, and sign lamps, and its technical value is extremely large.

  Below, the organic electroluminescent element of this invention and its manufacturing method are demonstrated, referring drawings.

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

  The substrate 1 serves as a support for the organic electroluminescence 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 photocurable resin substrate is employed as the plastic substrate having excellent characteristics. The substrate material used in the present invention will be described below.

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

Each symbol in the 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 : an ether group (ether bond: C—O—C), a hydrocarbon group having 1 to 6 carbon atoms which may contain a thioether group (thioether bond: C—S—C), preferably 2 to 2 carbon atoms 4 alkylene group R ⁴ : a hydrocarbon group having 1 to 6 carbon atoms which may contain an ether group or a thioether group, preferably an alkylene group having 1 to 3 carbon atoms X: a halogen atom or an alkyl having 1 to 6 carbon atoms Group or alkoxy group 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, “comprising” of the “photocurable monomer composition comprising (meth) acrylate” means that the composition does not impair the gist of the present invention, and other than polyfunctional (meth) acrylate. It means that a small amount of auxiliary components may be included. That is, an 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, for example, a photocurable monomer as described later. It means that it may be contained in a range of up to about 30 parts by weight with respect to 100 parts by weight of the composition. Moreover, you may use multiple types of each component in this composition together between components and / or in a component.

  Moreover, in this specification, "(meth) acrylate" is a general term for acrylate and / or methacrylate.

Specific examples of the sulfur-containing bis (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

  These compounds can be synthesized, for example, by the method disclosed in JP-A No. 62-195357.

Further, 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 (oxy Methyl) 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 [6.5.1.1 ^3,6 . 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 combination or within groups.

  These compounds can be synthesized, for example, by the method disclosed in JP-A-62-225508.

  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 resulting substrate has a relatively high refractive index of 1.55 to 1.65 at room temperature in the sodium D line (589.3 mm). On the other hand, when the compound of general formula [II] is used alone, it has a relatively low refractive index of 1.47 to 1.55. Therefore, a low birefringence resin substrate having a desired refractive index between 1.47 and 1.65 is obtained by using one or more compounds represented by general formulas [I] and [II]. Can do.

<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. As described above, a small amount of auxiliary components may be included.

  Therefore, the resin substrate according to the present invention is prepared by mixing other monomers capable of radical polymerization and addition polymerization in an amount of up to about 30 parts by weight with respect to 100 parts by weight of the photocurable monomer composition before curing. It can also be produced by copolymerizing with a polyfunctional (meth) acrylate. Examples of other monomers used in this case include methyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, methacryloyloxymethyltetracyclododecane, methacryloyloxymethyltetracyclododecene, and 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, trimethylolpropane tri (meth) acrylate, and styrene , Styrene, chlorostyrene, divinylbenzene, α-methylstyrene and the like, and / or side chain-substituted, unsubstituted styrene, etc., are preferred, preferably represented by the following general formulas [III], [IV] and [V]: And one or more mercapto compounds selected from the group consisting of polyfunctional mercapto compounds having two or more functional groups (thiol groups) in the molecule.

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

R ⁷ : Methylene group or ethylene group R ⁸ : A hydrocarbon group having 2 to 15 carbon atoms which may contain an ether group or a thioether group. Preferably a hydrocarbon group having 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 from 0 to 2, d is an integer from 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 e, f: 0 or 1
g: 1 or 2

  The mercapto compound represented by the general formula [III] is a divalent to hexavalent thioglycolic acid ester or thiopropionic acid ester. Specific examples of the compound of the formula [III] include, for example, pentaerythritol tetrakis (β-thiopropionate), pentaerythritol tetrakis (thioglycolate), trimethylolpropane tris (β-thiopropionate), trimethylolpropane. Tris (thioglycolate), diethylene glycol bis (β-thiopropionate), diethylene glycol bis (thioglycolate), triethylene glycol bis (β-thiopropionate), triethylene glycol bis (thioglycolate), di Examples include pentaerythritol hexacis (β-thiopropionate) and dipentaerythritol hexacis (thioglycolate).

  The compound represented by the general formula [IV] is an X-SH group-containing triisocyanurate. Specific examples of the compound of the formula [IV] include, for example, tris [2- (β-thiopropionyloxy) ethyl] isocyanurate, tris (2-thioglyconyloxyethyl) isocyanurate, tris [2- (β-thio Propionyloxyethoxy) ethyl] isocyanurate, tris (2-thioglyconyloxyethoxyethyl) isocyanurate, tris [3- (β-thiopropionyloxy) propyl] isocyanurate, tris (3-thioglyconyloxypropyl) isocyanate Examples include nurate.

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

  By blending these mercapto compounds, in the production of resin substrates, the action as a chain transfer agent with a thiol group is effectively exerted, the polymerization and curing progresses gently and uniformly, and the birefringence of the resulting cured resin Can be reduced. Further, these mercapto compounds enter a three-dimensional network structure formed of bis (meth) acrylate, and appropriate toughness is imparted to the resulting resin substrate. Furthermore, by using a polyfunctional mercapto compound having two or more thiol groups in the molecule, it is possible to improve birefringence, mechanical strength, etc. without significantly impairing the heat resistance of the resulting cured resin. it can.

  When the polyfunctional (meth) acrylate and the mercapto compound are used in combination as the substrate material according to the present invention, the composition ratio is 0.7 to 99.9 parts by weight of the polyfunctional (meth) acrylate. The amount is preferably 1 to 30 parts by weight, and more preferably 1 to 20 parts by weight of the mercapto compound with respect to 80 to 99 parts by weight of the polyfunctional (meth) acrylate. If the proportion of the mercapto compound is too small, the effect of improving the birefringence of the cured resin cannot be obtained.

  In addition to the mercapto compound, antioxidants, ultraviolet absorbers, dyes and pigments, and the like can be used as auxiliary components.

<Shaping and polymerization curing>
The photocurable monomer composition according to the present invention is shaped and cured. The curing is performed by a known radical polymerization in which a photopolymerization initiator that generates radicals by active energy rays such as ultraviolet rays is added. Examples of the photopolymerization initiator used here include benzophenone, benzoylmethyl ether, benzoylisopropyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl. Examples include benzoyldiphenylphosphine oxide. 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 addition amount of these photoinitiators is 0.01-1 weight part with respect to 100 weight part of monomers, Preferably it is 0.02-0.3 weight part. When the addition amount of the photopolymerization initiator is too large, the polymerization proceeds rapidly and not only causes an increase in birefringence but also deteriorates the hue. If the amount is too small, the photocurable monomer composition cannot be sufficiently cured.

  The amount of active energy rays to be irradiated is arbitrary as long as the photopolymerization initiator generates radicals, but if it is extremely small, the polymerization is incomplete and the cured product has sufficient heat resistance and mechanical properties. If it is not expressed and, on the contrary, extremely excessive, it causes deterioration due to light such as yellowing of the cured product. Therefore, it is preferable to use 200 to 400 nm ultraviolet rays according to the monomer composition and the type and amount of the photopolymerization initiator. Irradiation is in the range of 0.1 to 200J. Specific examples of the lamp used include a metal halide lamp, a high-pressure mercury lamp, and the like.

  For the purpose of promptly completing the curing, 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 for better completion of the polymerization, but excessive use thereof results in an increase in birefringence and a deterioration in hue. Specific examples of the thermal polymerization initiator include benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate), and the amount used is 1 part by weight or less based on 100 parts by weight of the monomer. Is preferred.

  In the present invention, after performing radical polymerization by light irradiation, the cured product can be heated to complete the polymerization reaction and reduce internal strain generated during the polymerization. In this case, the heating temperature is appropriately selected according to the composition of the cured product and the glass transition temperature. However, excessive heating causes the hue of the cured product to deteriorate, and therefore, a temperature around or below the glass transition temperature is preferable.

  In addition, 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 to be used affects the surface roughness of the resulting resin substrate, it is necessary to control the surface roughness of the glass plate in accordance with the surface roughness required for the resin substrate. Generally, in order to obtain a resin substrate having a surface roughness Rz of 1 to 50 nm, it is desirable that the surface roughness Rz of a glass plate used as a mold is 0.2 to 20 nm. As factors that affect the surface roughness of the resin substrate, in addition to the surface roughness of the glass plate, there are an ultraviolet irradiation amount, a photoinitiator amount, and the like, so that each parameter is determined as necessary. For example, in order to obtain a resin substrate having a surface roughness Rz of 5 to 10 nm, a glass plate having a surface roughness Rz of 1 to 5 nm is used, and a silicon plate is disposed on the glass plate as a spacer. Then, a photocurable monomer composition obtained by mixing polyfunctional (meth) acrylate and auxiliary components at a predetermined ratio and defoaming was injected, and between the metal halide lamps with an output of 80 W / cm separated by 40 cm above and below the glass surface. Irradiate with UV for 10 minutes.

<Physical properties of resin substrate>
From the viewpoint of optical characteristics as a substrate for an organic electroluminescent element, the optical birefringence of the photocurable resin substrate according to the present invention is preferably 20 nm or less.

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

  Further, the surface roughness of the resin substrate according to the present invention on the light emitting element production surface side is 1 to 50 nm, preferably 2 to 20 nm in terms of 10-point average roughness Rz. If the Rz of the resin substrate is larger than 50 nm, a short circuit is likely to occur between the electrodes of the organic electroluminescent element produced on the substrate surface, which is not suitable as a substrate. If Rz is less than 1 nm, the adhesion 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 during the subsequent deposition of the cathode metal layer, etc., which is also suitable as a substrate. Disappear.

  For the purpose of further improving the gas barrier property 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 element of the present invention using such a photocurable resin substrate will be described.

  The anode 2 formed on the substrate 1 plays a role of hole injection into the organic light emitting layer 3. This anode 2 is usually made of metal such as aluminum, gold, silver, platinum, nickel, palladium, platinum, metal oxide such as oxide of indium and / or tin, metal halide such as copper iodide, carbon black, Alternatively, a conductive polymer such as poly (3-methylthiophene), polypyrrole, polyaniline, or the like, preferably made of indium tin oxide. In general, the anode 2 is often formed by sputtering, vacuum deposition, or the like. In the case of using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., these are dispersed in an appropriate binder resin solution and the substrate 1 is used. It is also possible to form the anode 2 by applying it on top. When a conductive polymer is used, the anode 2 can be formed by forming a thin film directly on the substrate 1 by electrolytic polymerization or by applying a conductive polymer on the substrate 1 (Appl). Phys. Lett., 60, 2711, 1992). The anode 2 can be formed by stacking different materials.

  The thickness of the anode 2 varies depending on whether or not transparency is required. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness is usually 5 to 1000 nm, preferably 10 to 10%. It is about 500 nm. When the anode 2 may be opaque, the same material as the substrate 1 may be used. It is also possible to laminate different conductive materials on the anode 2.

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

  In the function-separated organic electroluminescent device 10A shown in FIG. 2, as a material of the hole transport layer 3a, the hole injection efficiency from the anode 2 is high, and the injected holes can be efficiently transported. It must be a material. For this purpose, it is required that the ionization potential is low, the hole mobility is high, the stability is high, and impurities that become traps during production and use are hardly generated.

  As such a hole transport material, for example, an aromatic diamine compound in which a tertiary aromatic amine unit such as 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane is linked (Japanese Patent Laid-Open No. 59-86). No. 194393), 4,4′-bis [N- (1-naphthyl) -N-phenylamino] containing two or more tertiary amines represented by biphenyl, and two or more condensed aromatic rings are nitrogen atoms Aromatic amines substituted with the above (Japanese Patent Laid-Open No. 5-234681), triphenylbenzene derivatives and aromatic triamines having a starburst structure (US Pat. No. 4,923,774), N, N′-diphenyl-N , N′-bis (3-methylphenyl) biphenyl-4,4′-diamine and other aromatic diamines (US Pat. No. 4,764,625), α, α, α ′, α′-tetramethyl -Α, α'-bis (4-di-p-tolylaminophenyl) -p-xylene (Japanese Patent Laid-Open No. 3-269084), a sterically asymmetric triphenylamine derivative as a whole molecule (Japanese Patent Laid-Open No. 4-129271) No. 1), a compound in which a biphenyl group is substituted with a plurality of aromatic diamino groups (Japanese Patent Laid-Open No. 4-175395), and an aromatic diamine in which a tertiary aromatic amine unit is linked with an ethylene group (Japanese Patent Laid-Open No. 4-264189) ), Aromatic diamines having a styryl structure (Japanese Patent Laid-Open No. 4-290851), those obtained by linking aromatic tertiary amine units with a thiophene group (Japanese Patent Laid-Open No. 4-304466), starburst aromatic triamines (specialty) Kaihei 4-308688), benzylphenyl compounds (JP-A-4-364153), tertiary amines with fluorene groups Conjugated compounds (JP-A-5-25473), triamine compounds (JP-A-5-239455), bisdipyridylaminobiphenyl (JP-A-5-320634), N, N, N-triphenylamine derivatives ( JP-A-6-1972), aromatic diamine having a phenoxazine structure (JP-A-7-138562), diaminophenylphenanthridine derivative (JP-A-7-252474), hydrazone compound (JP-A-2-2-1) 315991), silazane compounds (US Pat. No. 4,950,950), silanamine derivatives (JP-A-6-49079), phosphamine derivatives (JP-A-6-25659), quinacridone compounds and the like. . These compounds may be used alone or in combination of two or more as required.

  In addition to the above-mentioned compounds, polyvinyl carbazole, polysilane (Appl. Phys. Lett., 59, 2760, 1991), polyphosphazene (Japanese Patent Laid-Open No. Hei 5-310949) can be used as the material for the hole transport layer 3a. ), Polyamide (JP-A-5-310949), polyvinyltriphenylamine (JP-A-7-53953), a polymer having a triphenylamine skeleton (JP-A-4-133565), and a triphenylamine unit. Polymers linked by a methylene group (Synthetic Metals, 55-57, 4163, 1993), polymethacrylates containing aromatic amines (J. Polym. Sci., Polym. Chem. Ed., 21), 969 (1983), etc. Kill.

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

  In the case of the coating method, one or more hole transport materials and, if necessary, additives such as a binder resin and a coating property improving agent that do not trap holes are added and dissolved in a solvent to form a coating solution. Is coated on the anode 2 by a method such as spin coating and dried to form the organic hole transport layer 3a. In this case, examples of the binder resin include polycarbonate, polyarylate, and polyester. When the amount of the binder resin added is large, the hole mobility is lowered. Therefore, a smaller amount is desirable, and usually 50% by weight or less is preferable.

On the other hand, in the case of the vacuum evaporation method, the hole transport material is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁻⁴ Pa with an appropriate vacuum pump, and then the crucible is heated. Then, the hole transport material is evaporated, and the hole transport layer 3a is formed on the anode 2 on the substrate 1 disposed opposite to the crucible.

In the case of forming the hole transport layer 3a in this way, further, as an acceptor, a metal complex and / or metal salt of an aromatic carboxylic acid (Japanese Patent Laid-Open No. 4-320484), a benzophenone derivative and a thiobenzophenone derivative (Japanese Patent Laid-Open No. 5-295361), fullerenes (Japanese Patent Laid-Open No. 5-331458) and the like are doped at a concentration of 10 ⁻³ to 10% by weight to generate holes as free carriers, thereby driving at a low voltage. Can be possible.

  The thickness of the hole transport layer 3a is usually 10 to 300 nm, preferably 30 to 100 nm. In order to form such a thin hole transport layer uniformly, it is generally preferable to employ a vacuum deposition method.

  Further, for the purpose of further improving the hole injection efficiency and improving the adhesion of the whole organic layer to the anode 2, the hole injection is performed between the hole transport layer 3 a and the anode 2 as shown in FIG. Formation of the layer 3c is also performed. The material used for the hole injection layer 3c is preferably a material having a low ionization potential, high conductivity, and capable of forming a thermally stable thin film on the anode 2, such as a phthalocyanine compound or a porphyrin compound (Japanese Patent Laid-Open No. 57-51781 and JP-A-63-295695) are used. By interposing such a hole injection layer 3c, the driving voltage of the initial element is lowered, and at the same time, an effect of suppressing the voltage increase when the element is continuously driven with a constant current can be obtained. The hole injection layer 3c can also be improved in conductivity by doping with an acceptor in the same manner as the hole transport layer 3a.

  The film thickness of the hole injection layer 3c is usually 2 to 100 nm, preferably 5 to 50 nm. In order to form such a thin hole injection layer uniformly, it is generally preferable to employ a vacuum deposition method.

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

  The electron transporting compound used for the electron transport layer 3b needs to be a compound that has high electron injection efficiency from the cathode 4 and can efficiently transport the injected electrons. For this purpose, it is required to be a compound that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate impurities that become traps during production and use.

  Materials satisfying such conditions include aromatic compounds such as tetraphenylbutadiene (Japanese Patent Laid-Open No. 57-51781) and metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393). Cyclopentadiene derivatives (JP-A-2-289675), perinone derivatives (JP-A-2-289676), oxadiazole derivatives (JP-A-2-216791), bisstyrylbenzene derivatives (JP-A-1-245087). No. 2-22484), perylene derivatives (JP-A-2-189890, JP-A-3-791), coumarin compounds (JP-A-2-191694, JP-A-3-792), rare earths Complexes (Japanese Patent Laid-Open No. 1-256584), distyrylpyrazine derivatives (Japanese Patent Laid-Open No. 2-256854) 52793), p-phenylene compounds (JP-A-3-33183), thiadiazolopyridine derivatives (JP-A-3-37292), pyrrolopyridine derivatives (JP-A-3-37293), naphthyridine derivatives ( JP-A-3-203982).

  In general, the electron transport layer 3b using these compounds can simultaneously play a role of transporting electrons and a role of causing light emission upon recombination of holes and electrons.

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

For the purpose of improving the luminous efficiency of the device and changing the emission color, for example, doping a fluorescent dye for lasers such as coumarin with an aluminum complex of 8-hydroxyquinoline as a host material (J. Appl. Phys., Volume 65). , 3610, 1989), etc., but also in the present invention, by doping the above organic electron transporting material as a host material with various fluorescent dyes at 10 ⁻³ to 10 mol%, The light emission characteristics can be further improved.

  The film thickness of the electron transport layer 3b is usually 10 to 200 nm, preferably 30 to 100 nm.

  The electron transport layer can also be formed by the same method as the hole transport layer, but a vacuum deposition method is usually used.

  As the single-layer type organic light emitting layer 3 that does not perform functional separation as shown in FIG. 1, poly (p-phenylene vinylene) (Nature, 347, 539, 1990, etc.), poly, [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene] (Appl. Phys. Lett., 58, 1982, 1991 et al.), Poly (3-alkylthiophene) (Jpn. Phys., J. Appl. Phys, 30, L 1938, 1991, etc.), or a system in which a light emitting material and an electron transfer material are mixed in a polymer such as polyvinyl carbazole (Applied Physics, 61, 1044, 1992).

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

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

  1 to 3 show an example of an element body employed in the present invention, and the present invention can be applied to an element body having a layer structure as shown below, in addition to the illustrated one. it can.

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 includes an aromatic diamine compound (JP-A-6-267658), a quinacridone compound (JP-A-6-330031), naphthacene. Derivatives (JP-A-6-330032), organosilicon compounds (JP-A-6-325871), organophosphorus compounds (JP-A-6-325872), compounds having an N-phenylcarbazole skeleton (Japanese Patent Application No. 6) -199562), an N-vinylcarbazole polymer (Japanese Patent Application No. 6-200942) and the like. The thickness of the interface layer is usually 2 to 100 nm, preferably 5 to 30 nm. Instead of providing the interface layer, a region containing 50% by weight or more of the material of the interface layer may be provided in the vicinity of the cathode interface between the organic light emitting layer and the electron transport layer.

  The other electron transport layer is further laminated on the electron transport layer in order to further improve the light emission efficiency of the organic electroluminescent device. The compound used for this electron transport layer includes a cathode. Therefore, it is required that the electron injection is easy and the electron transport capacity is further increased. Examples of such electron transporting materials include oxadiazole derivatives (Appl. Phys. Lett., 55, 1489, 1989, etc.) and systems in which they are dispersed in a resin such as polymethyl methacrylate (PMMA) ( Appl. Phys. Lett., 61, 2793, 1992), phenanthroline derivative (Japanese Patent Laid-Open No. 5-33159), or n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type selenization. Zinc etc. are mentioned. The film thickness of the other electron transport layer is usually 5 to 200 nm, preferably 10 to 100 nm.

  The organic electroluminescent element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and an element having a structure in which an anode and a cathode are arranged in an XY matrix. .

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

Example 1
99 parts by weight of p-bis (β-methacryloyloxyethylthio) xylylene, 1 part by weight of pentaerythritol tetrakis (β-thiopropionate), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF) as a photopolymerization initiator “Lucirin TPO” manufactured by 0.05) and 0.02 part by weight of benzophenone were uniformly stirred and mixed, and then defoamed to obtain a photocurable monomer composition.

  On the other hand, as a mold for shaping the resin, using an optically polished glass plate and a 1 mm thick silicon plate as a spacer, the photocurable monomer composition was poured into this optically polished glass mold, Ultraviolet rays were irradiated for 10 minutes between metal halide lamps with an output of 80 W / cm at a vertical position of 40 cm from the glass surface. After the ultraviolet irradiation, the mold was released and heated at 120 ° C. for 1 hour to obtain a cured product. This cured product was cut into a glass slide (25 × 75 mm) to obtain a substrate A. Various characteristics of the substrate A were as shown in Table 1. Each characteristic was evaluated 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 a length of 5 cm each and a thickness of 1 mm.
(3) Falling ball impact test: Evaluation was performed at the lowest height at which a test piece was damaged by naturally dropping a 16 g steel ball onto a test piece having a width and length of 5 cm each and a thickness of 1 mm.
(4) Flexural modulus: Evaluation was performed at 25 ° C. using an autograph at a fulcrum distance of 3 cm for a plate having a width of 1 cm and a thickness of 1 mm.
(5) Surface roughness Rz: Ten-point average roughness (JISB0601) using a stylus type surface roughness meter (Taristep manufactured by Rank Taylor Hobson: tip shape of stylus is 0.2 × 0.2 μm square) evaluated.
(6) Refractive index: It evaluated at 25 degreeC using the Abbe refractometer (made by Atago Co., Ltd.).
(7) Birefringence: evaluated at 25 ° C. using a birefringence measuring apparatus (manufactured by Oak Co.).
(8) Water absorption rate: Evaluated by saturated water absorption rate when immersed in water at 60 ° C for 1 week.
(9) Glass transition temperature: A test piece having a thickness of 1 mm was evaluated using a TMA (thermomechanical analyzer) with a weight of 50 g.

  Next, an indium tin oxide (ITO) transparent conductive film was deposited to 120 nm on this substrate A (Toyo Sangyo Co., Ltd .: low-temperature sputtered film product: sheet resistance 20Ω) to obtain an ITO substrate A.

  Using this ITO substrate A, an organic electroluminescence device having the structure shown in FIG. 3 was produced by the following method. First, an ITO transparent conductive film deposited on the ITO substrate A was patterned into a stripe having a width of 2 mm using a normal photolithography technique and hydrochloric acid etching to form an anode.

The patterned ITO substrate is cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, then dried with nitrogen blow, and finally with ultraviolet ozone cleaning. installed. After performing rough exhaust of the device with an oil rotary pump, an oil diffusion pump equipped with a liquid nitrogen trap is used until the vacuum in the device is 2 × 10 ⁻⁶ Torr (about 2.7 × 10 ⁻⁴ Pa) or less. Exhausted.

The following copper phthalocyanine (H1) (crystal form is β type) placed in a molybdenum boat placed in the above apparatus was heated for vapor deposition. Vapor was performed at a degree of vacuum of 1.1 × 10 ⁻⁶ torr (about 1.5 × 10 ⁻⁴ Pa) and a deposition time of 1 minute to form a hole injection layer 3c having a thickness of 20 nm.

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

Subsequently, as a material of the electron transport layer 3b having a light emitting function, the following aluminum 8-hydroxyquinoline complex: Al (C ₉ H ₆ NO) ₃ (E1) is similarly formed on the hole transport layer 3a. Vapor deposited. 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 was 9 × 10 ⁻⁷ Torr (about 1.2 × 10 ⁻⁴ Pa), the vapor deposition time was 2 minutes and 40 seconds, and an electron transport layer 3b having a thickness of 75 nm was formed.

  In addition, the substrate temperature at the time of vacuum-depositing 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 are formed is once taken out into the atmosphere from the vacuum deposition apparatus, and a 2 mm wide stripe shadow mask is used as a cathode deposition mask. 2 in close contact with the ITO stripe, and placed in a separate vacuum deposition apparatus so that the degree of vacuum in the apparatus is 2 × 10 ⁻⁶ Torr (approximately 2. It exhausted until it became below 7 * 10 <^-4> Pa). Subsequently, an alloy electrode of magnesium and silver was deposited as the cathode 4 so as to have a film thickness of 100 nm by a binary simultaneous deposition method. Deposition was performed using a molybdenum boat with a degree of vacuum of 1 × 10 ⁻⁵ Torr (about 1.3 × 10 ⁻³ Pa) and a deposition time of 3 minutes and 10 seconds. The atomic ratio of magnesium and silver was 10: 1.2. Subsequently, the cathode 4 was completed by laminating aluminum on the magnesium / silver alloy film with a film thickness of 100 nm using a molybdenum boat without breaking the vacuum of the apparatus. The degree of vacuum during aluminum deposition was 2.3 × 10 ⁻⁵ Torr (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 above two-layer cathode of magnesium / silver alloy and aluminum was kept at room temperature.

  As described above, an organic electroluminescence device having a size of 2 mm × 2 mm was obtained. After the device was taken out from 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 light emission characteristics were measured.

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

Example 2
Implemented except that 96 parts by weight of bis (oxymethyl) tricyclo [5.2.1.0 ^2.6 ] decane = dimethacrylate and 4 parts by weight of pentaerythritol tetrakis (β-thiopropionate) were used as monomer components. A cured product was obtained in the same manner as in Example 1. This cured product was cut into a glass slide 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 value of this ITO substrate B was 20Ω.

  Further, using this ITO substrate B, an organic electroluminescent device having the structure shown in FIG. 3 was prepared in the same manner as in Example 1, and the emission characteristics were measured in the same manner. The results are shown in FIG.

Comparative Example 1
Corning 7059 glass was cut into a glass slide to form 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 value of the ITO substrate C was 20Ω.

  Further, using this ITO substrate C, an organic electroluminescent device having the structure shown in FIG. 3 was prepared in the same manner as in Example 1, and the emission 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 was used as a substrate, and an ITO transparent conductive film was deposited on this substrate by an electron beam evaporation method (manufactured by Geomatech) to obtain an ITO substrate D. The sheet resistance value of the ITO substrate D was 15Ω. Further, when X-ray diffraction analysis of the ITO substrate D was performed, the diffraction peak intensity of the In ₂ O ₃ crystal near 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 electroluminescence device having the structure shown in FIG. 3 was prepared in the same manner as in Example 1, and the emission 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. This cured product was cut into a glass slide 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 value of the ITO substrate E was 20Ω.

  Using this ITO substrate E, an organic electroluminescent device having the structure shown in FIG. 3 was prepared in the same manner as in Example 1, and evaluated in the same manner. When 5 V was applied, the device was short-circuited.

It is typical sectional drawing which shows one Example of the organic electroluminescent element of this invention. It is typical sectional drawing which shows the other Example of the organic electroluminescent element of this invention. It is typical sectional drawing which shows another Example of the organic electroluminescent element of this invention. It is a graph which shows the applied voltage dependence of the luminescent brightness | luminance of the organic electroluminescent element in Example 1, 2 and Comparative Example 1,2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Board | 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 (14)

  An organic electroluminescent element in which an anode, an organic light emitting layer and a cathode are laminated on one plate surface of a substrate, the substrate being made of a photocurable resin, and the surface of the one plate surface of the substrate An organic electroluminescent element having a roughness (Rz) of 1 to 50 nm and a silicon oxide film provided on at least one surface of the substrate.   The organic electroluminescent element 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. The polyfunctional (meth) acrylate having two or more functional groups in the molecule 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]. The organic electroluminescent element according to claim 2, which is a seed bis (meth) acrylate.

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

(In the formula [II], R ⁵ and R ⁶ each represent a hydrogen atom or a methyl group, m represents 1 or 2, and n represents 0 or 1.)   The photocurable resin is 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 the molecule. The organic electroluminescent element according to claim 2 or 3.   The organic electroluminescent element according to any one of claims 1 to 4, wherein the substrate is made of a photocurable resin having a birefringence of 20 nm or less.   A method for producing a resin substrate for use in 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 a photocurable monomer is formed into a plate shape on an optically polished glass plate The surface roughness (Rz) of the resin substrate is controlled to 1 to 50 nm by irradiating it with active energy rays and curing it by photopolymerization. Production method.   The surface roughness (Rz) of the surface which shapes the photocurable monomer of a glass plate is 0.2-20 nm, The manufacturing method of Claim 6 characterized by the above-mentioned.   The production method according to claim 6 or 7, wherein the photocurable monomer is 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 in the molecule 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]. The production method according to claim 8, which is a seed bis (meth) acrylate.

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

(In the formula [II], R ⁵ and R ⁶ each represents a hydrogen atom or a methyl group, m represents 1 or 2, and n represents 0 or 1.)   The photocurable monomer is a composition containing a polyfunctional (meth) acrylate having two or more functional groups in the molecule and a polyfunctional mercapto compound having two or more functional groups in the molecule. The manufacturing method of any one of Claims 6 thru | or 9.   The surface roughness (Rz) of the resin substrate is controlled to 5 to 10 nm by using a glass plate having a surface roughness (Rz) of 1 to 5 nm. The manufacturing method as described.   The method according to claim 6, further comprising providing a silicon oxide film on at least one surface of the resin substrate.   The resin substrate for organic electroluminescent elements manufactured by the method of any one of Claims 6 thru | or 12.   A method for producing an organic electroluminescent element, comprising laminating at least an anode, an organic light emitting layer and a cathode on a plate surface having a surface roughness (Rz) of 1 to 50 nm of the resin substrate according to claim 13.

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