JP2012190612A - Manufacturing method of organic optical device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an organic optical device capable of being thinned and sufficiently preventing moisture intrusion.SOLUTION: A manufacturing method of an organic optical device formed by sealing an organic thin film element disposed on a substrate comprises: a step 1 of coating the organic thin film element disposed on the substrate with an inorganic protective layer A; a step 2 of forming an organic protective layer by coating a cationic polymerizable resin composition containing a cationic polymerizable compound and an optical cationic polymerization initiator or a thermal cationic polymerization initiator so as to cover a region including the organic thin film element coated with the inorganic protective layer A and curing the cationic polymerizable resin composition by light irradiation or heating; and a step 3 of coating the resin protective layer with an inorganic protective layer B so as to cover above and an outer peripheral part of the resin protective layer.

Description

The present invention relates to a method for manufacturing an organic optical device that can be reduced in thickness and can sufficiently prevent moisture from entering.

In recent years, research on organic optical devices using organic thin film elements such as organic electroluminescence elements and organic thin film solar cell elements has been advanced. The organic thin film element can be easily produced by vacuum deposition, solution coating, or the like, and thus has excellent productivity.

The organic electroluminescence element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. When electrons are injected from one electrode into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-light emission. Since it has the advantages of better visibility than liquid crystal display elements that require a backlight, making it thinner, and being capable of DC low-voltage drive, it has attracted attention as a next-generation display. Yes.

Organic thin-film solar cell elements are superior to solar cells using inorganic semiconductors in terms of cost, large area, ease of manufacturing process, and the like, and organic solar cells having various configurations have been proposed. Specifically, for example, Non-Patent Document 1 describes an organic solar cell element using a laminated film of phthalocyanine copper and a perylene dye.

These organic thin film elements have a problem that when the organic layer and the electrode are exposed to the outside air, the performance is rapidly deteriorated. Therefore, in order to improve stability and durability, it is an indispensable technique to seal the organic thin film element and shield it from moisture and oxygen in the atmosphere. As a method of sealing the organic thin film element, a method of sealing with a metal can provided with a water absorbing agent inside is generally used. However, in the method of sealing with a metal can, it is difficult to reduce the thickness of the organic optical device. Therefore, development of a method for sealing an organic thin film element that does not use a metal can has been promoted.

Patent Document 1 describes a method in which an organic layer and an electrode of an organic thin film element are sealed with a laminated film of a resin film formed by a CVD method and a silicon nitride (SiN _x ) film. Here, the resin film has a role of preventing pressure on the organic layer and the electrode due to internal stress of the silicon nitride film.

In the method of sealing with a silicon nitride film described in Patent Document 1, the silicon nitride film is formed due to surface irregularities of the organic thin film element, adhesion of foreign matters such as particles, cracks due to internal stress, and the like. In some cases, the organic thin film element cannot be completely covered with a film. If the coating with the silicon nitride film is incomplete, moisture will enter the organic layer through the silicon nitride film.
In order to prevent this, Patent Document 2 describes a method of alternately depositing an inorganic film and an organic film, and Patent Document 3 applies a liquid acrylic resin on the inorganic film. A method for forming a resin film is described.

However, in the method described in Patent Document 2, sufficient effects cannot be obtained unless the thickness of the silicon nitride film is increased in order to completely cover large unevenness and foreign matter. There was a problem that internal stress increased or productivity deteriorated. Further, the method described in the cited document 3 has problems such as insufficient adhesion between the inorganic film and the resin film, and internal stress due to curing shrinkage of the resin film.

JP 2000-223264 A Japanese translation of PCT publication No. 2004-522891 JP 2001-307873 A

Applied Physics Letters (1986, Vol. 48, P. 183)

An object of this invention is to provide the manufacturing method of the organic optical device which can be reduced in thickness and can fully prevent moisture permeation.

The present invention is a method for producing an organic optical device in which an organic thin film element disposed on a substrate is sealed, wherein the organic thin film element disposed on the substrate is coated with an inorganic protective layer A, A cation polymerizable resin composition containing a cation polymerizable compound and a photo cation polymerization initiator or a thermal cation polymerization initiator is coated so as to cover a region including the organic thin film element coated with the inorganic protective layer A. Step 2 of curing the cationic polymerizable resin composition by light irradiation or heating to form an organic protective layer, and covering with the inorganic protective layer B so as to cover the resin protective layer and the outer periphery of the resin protective layer The manufacturing method of the organic optical device which has the process 3 to do.
The present invention is described in detail below.

As a result of intensive studies, the inventor of the present application sealed the organic thin film element with a protective film having a three-layer structure of an inorganic protective layer A, an organic protective layer, and an inorganic protective layer B. It has been found that a thin optical device can be manufactured because the organic thin film element can be reliably sealed without using glass or sealing glass to sufficiently prevent moisture from entering. Further, the organic protective layer is formed by using a cationic polymerizable resin composition containing a cationic polymerizable compound and a photo cationic polymerization initiator or a thermal cationic polymerization initiator, and curing it by light irradiation or heating. By adopting this method, it is possible to prevent the organic thin film element from peeling or cracking due to curing shrinkage of the organic protective layer. In addition, the adhesion between the inorganic protective layer and the organic protective layer is excellent. As a result, the present invention was completed.
A schematic diagram illustrating the method for producing an organic optical device of the present invention is shown in FIG. The present invention will be described below with reference to FIG.

The manufacturing method of the organic optical device of this invention has the process 1 which coat | covers the organic thin film element arrange | positioned on a board | substrate with the inorganic protective layer A (FIG. 1 (a), (b)).
The organic thin film element is not particularly limited, and examples thereof include an organic electroluminescence element (hereinafter also referred to as “organic EL element”) or an organic thin film solar cell element (hereinafter also referred to as “solar cell element”).

The organic EL element is formed, for example, by vacuum-depositing a hole injection electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and an electron injection electrode in order on a substrate. Can do.
When the organic thin film element is an organic EL element, it is possible to reduce the thickness of the organic optical device, sufficiently prevent moisture from entering the organic EL element, and improve the durability of light emission. Can do.
When the organic thin film element is an organic EL element, the organic optical device may have a bottom emission structure in which light is extracted from the lower surface side (side where the element is not formed on the substrate), or the upper surface side (element is formed on the substrate). A top emission structure in which light is extracted from the other side.

When the organic thin film element is a solar cell element, it is possible to reduce the thickness of the organic optical device, sufficiently prevent moisture from entering the solar cell element, and maintain high conversion efficiency. it can.

The substrate is not particularly limited. For example, in a simple matrix type (passive type) optical device, a transparent glass substrate can be used. In an active matrix type optical device, a plurality of TFTs (thin film transistors) are formed on the transparent glass substrate. In addition, a TFT substrate provided with a planarization layer can be used.

In step 1, the organic thin film element disposed on the substrate is covered with an inorganic protective layer A3. At this time, the inorganic protective layer A is formed so as to cover a region including the organic thin film element.

The inorganic protective layer A is not particularly limited, and examples thereof include those made of an inorganic film made of silicon nitride (SiN _x ) or silicon oxide (SiO _x ).
The inorganic protective layer A may be a single layer or may be a laminate of a plurality of types of layers.

The coating method is not particularly limited, and when the inorganic protective layer A is an inorganic film made of silicon nitride or silicon oxide, a vacuum deposition (sputtering) method, an electron cyclotron resonance (ECR) plasma CVD method, or the like can be given. It is done.
The vacuum deposition method is preferably performed, for example, using a single or mixed gas such as argon gas or nitrogen gas as a carrier gas, under conditions of room temperature, power of 50 to 1000 W, and pressure of 0.001 to 0.1 Torr.
The ECR plasma CVD is performed using, for example, a mixed gas of SiH ₄ and O ₂ (in the case of silicon oxide) or a mixed gas of SiH ₄ and N ₂ (in the case of silicon nitride) at a temperature of 30 ° C. to 100 ° C. and a pressure. It is preferable to carry out under the conditions of 10 mTorr to 1 Torr, frequency 2.45 GHZ, power 10 to 1000 W.

In the case where the inorganic protective layer A is a laminate of a plurality of types of layers, an organic layer may be inserted between the layers by a method such as a vacuum evaporation method for stress relaxation.
Examples of the material for forming the organic layer include polymers such as polyurea, polyurethane, polyamide, polyimide, polyacrylate, and polymethacrylate, oligomers and monomers of these polymers, and the like.

Although the thickness of the said inorganic protective layer A is not specifically limited, A preferable minimum is 0.05 micrometer and a preferable upper limit is 100 micrometers. If the thickness of the inorganic protective layer A is less than 0.05 μm, defects may occur and water intrusion may not be sufficiently prevented. If the thickness exceeds 100 μm, internal stress becomes strong and cracks tend to occur. The time required for film formation also becomes longer. The minimum with more preferable thickness of the said inorganic protective layer A is 0.1 micrometer, and a more preferable upper limit is 10 micrometers.

The method for producing an organic optical device of the present invention comprises a cationically polymerizable compound and a photocationic polymerization initiator or a thermal cationic polymerization initiator so as to cover a region including the organic thin film element covered with the inorganic protective layer A. Coating the cationic polymerizable resin composition to be applied, and irradiating or heating to cure the cationic polymerizable resin composition to form an organic protective layer (FIGS. 1 (c) and (d)). .
The cationic polymerizable resin composition has little curing shrinkage at the time of curing, and the cured product is excellent in adhesion to the inorganic protective layer.

The cationic polymerizable resin composition contains a cationic polymerizable compound and a photo cationic polymerization initiator or a thermal cationic polymerization initiator.
The cationic polymerizable compound is not particularly limited as long as it has at least one cationic polymerizable functional group in the molecule. For example, the cationic polymerizable compound has at least one epoxy group, oxetanyl group or the like in the molecule. Compounds and the like. Among them, since cationic polymerization is high and curing proceeds efficiently, a compound having at least one epoxy group in the molecule (hereinafter also referred to as epoxy compound), or at least one in the molecule. A compound having an oxetanyl group (hereinafter also referred to as an oxetanyl compound) is preferably used.
The properties (molecular weight) of these cationically polymerizable compounds are not particularly limited, and any of monomers, oligomers, and polymers may be used. Moreover, these cationically polymerizable compounds may be used independently and 2 or more types may be used together.

The epoxy compound is not particularly limited. For example, a bisphenol type epoxy compound such as a bisphenol A type epoxy compound or a bisphenol F type epoxy compound, a novolac type epoxy compound such as a phenol novolac type epoxy compound or a cresol novolac type epoxy compound, Naphthalene type epoxy compound, aliphatic epoxy compound, alicyclic epoxy compound, heterocyclic epoxy compound, polyfunctional epoxy compound, biphenyl type epoxy compound, glycidyl ether type epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy Compounds, alcohol-type epoxy compounds such as hydrogenated bisphenol A type epoxy compounds, halogenated epoxy compounds such as brominated epoxy compounds, rubber-modified epoxy compounds, urethane modifications Epoxy compounds, epoxidized polybutadiene, epoxidized styrene - butadiene - styrene block copolymer, epoxy group-containing polyester compounds, epoxy group-containing polyurethane compound, an epoxy group-containing acrylic compounds. Of these, bisphenol A-type epoxy compounds, naphthalene-type epoxy compounds, alicyclic epoxy compounds, and the like are preferably used because of their higher cationic polymerizability and efficient photocuring. These epoxy compounds may be used independently and 2 or more types may be used together.

Examples of commercially available epoxy compounds include “Epicoat” series such as “Epicoat 806”, “Epicoat 828”, “Epicoat 1001”, and “Epicoat 1002” manufactured by Japan Epoxy Resin Co., Ltd. And “Celoxide” series such as “Celoxide 2021” manufactured by Daicel Chemical Industries, Ltd.

The epoxy compound preferably has a cycloalkane skeleton.
The epoxy compound having a cycloalkane skeleton is not particularly limited, and may be one having at least one cycloalkane skeleton in the structure or in the repeating unit, but is a compound having a cycloalkane skeleton in the repeating unit. It is preferable. When the compound has a cycloalkane skeleton in the repeating unit, it may be a compound having only one cycloalkane skeleton within a single repeating unit, or a compound having two or more.

The epoxy compound containing the cycloalkane skeleton is not particularly limited as long as it has the above structure. However, since the film has excellent smoothness, the group consisting of the following general formulas (1), (2) and (3) Epoxy compounds having at least one structure selected more are preferred.

Examples of commercially available epoxy compounds having the cycloalkane skeleton include YX-8040, YX-8034, YX-8000 (manufactured by Mitsubishi Chemical Corporation), EP-4088 (manufactured by ADEKA), and the like. It is done.

The oxetanyl-based compound is not particularly limited. For example, phenoxymethyl oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, di [1-ethyl (3-oxetanyl)] methyl ether Oxetanylsilsesquioxane, phenol novolac oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. These oxetanyl compounds may be used alone or in combination of two or more.

Among the above oxetanyl compounds, examples of commercially available compounds include OXT-101, OXT-211, OXT-221 (all manufactured by Toagosei Co., Ltd.) and the like.

The cationic polymerizable compound may contain other cationic polymerizable monomers other than the epoxy compound and the oxetanyl compound as long as the moisture permeability, adhesiveness, and curing shrinkage are not affected. .
The other cationic polymerizable monomer is not particularly limited as long as it is a polymerizable monomer having at least one cationic polymerizable functional group in the molecule. For example, at least one hydroxyl group in the molecule, Examples thereof include compounds having a cationic polymerizable functional group such as a vinyl ether group, an episulfide group, and an ethyleneimine group.

Commercially available products of the other cationic polymerizable compounds include, for example, 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 4-hydroxybutyl vinyl ether (HBVE) having a vinyl ether group (manufactured by Maruzen Petrochemical Co., Ltd.) Etc.

In the case where the epoxy compound represented by the above formulas (1) to (3) or the oxetanyl compound and the other cationic polymerizable compound are used in combination as the photo cationic polymerizable compound, the total of all the photo cationic polymerizable compounds The minimum with preferable content of the epoxy compound represented by said Formula (1)-(3) with respect to 100 weight part or the said oxetanyl type compound is 20 weight part, and a preferable upper limit is 80 weight part. When the content of the epoxy compound represented by the above formulas (1) to (3) or the oxetanyl compound is less than 20 parts by weight, the storage elastic modulus at high temperature of the cured product may not be sufficiently high. When it exceeds the weight part, the adhesion reliability of the obtained adhesive for electronic parts may be lowered. The more preferable lower limit of the content of the epoxy compound represented by the above formulas (1) to (3) and the oxetanyl compound is 30 parts by weight, the more preferable upper limit is 60 parts by weight, and the more preferable upper limit is 40 parts by weight. is there.

The photocationic polymerization initiator is not particularly limited, and may be, for example, an ionic photoacid generation type or a nonionic photoacid generation type.

The ionic photoacid-generating photocationic polymerization initiator is not particularly limited, and examples thereof include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, iron-allene complexes, titanocene complexes, and arylsilanols. -Organometallic complexes such as aluminum complexes. These ionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.

Commercially available products of the ionic photoacid-generating photocationic polymerization initiator are not particularly limited. For example, “Adekaopter” such as “Adekaoptomer SP150” and “Adekaoptomer SP170” manufactured by Asahi Denka Kogyo Co., Ltd. Mar "series.

The nonionic photoacid generation type photocationic polymerization initiator is not particularly limited, and examples thereof include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimidosulfonate and the like. Can be mentioned.

The nonionic photoacid-generating photocationic polymerization initiator is not particularly limited, and examples thereof include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, and N-hydroxyimidophosphonate. Can be mentioned. These nonionic photoacid-generating photocationic polymerization initiators may be used alone or in combination of two or more.

As the thermal cationic polymerization initiator, any thermal cationic polymerization initiator that is activated by heating to induce ring opening of a ring-opening polymerizable group is used, and various oniums such as quaternary ammonium salts, phosphonium salts, and sulfonium salts are used. Salts are exemplified.

Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N-dimethyl- N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyltrifluor Lomethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl-N (4-methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, and diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.

Commercial products of the thermal cationic polymerization initiator include, for example, Adeka Opton CP-66, Adeka Opton CP-77 (both trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L. (All are trade names, manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.) and the like.

The content of the photo cationic polymerization initiator or the thermal cationic polymerization initiator in the cationic polymerizable resin composition is not particularly limited, but the preferable lower limit with respect to 100 parts by weight of the cationic polymerizable compound is 0.1 parts by weight, and the preferable upper limit is 10 parts. Parts by weight. When the content of the cationic polymerization initiator is less than 0.1 parts by weight, the cationic polymerization of the cationic polymerizable compound may not sufficiently proceed or the curing may be delayed. When the content of the cationic polymerization initiator exceeds 10 parts by weight, the initiator may attack the inorganic film or be colored.

The cationic polymerizable resin composition is, as necessary, a filler for further improving the strength of the cured product, an adhesiveness imparting agent for further improving the adhesiveness, a viscosity modifier for adjusting the viscosity, Thixotropic agents (thixotropic agents) for imparting thixotropic properties (thixotropic properties), physical property modifiers for improving tensile properties, bulking agents, reinforcing agents, softeners (plasticizers), antioxidants (aging) Inhibitors), heat stabilizers, flame retardants, antistatic agents, antifoaming agents, leveling agents, ultraviolet absorbers, organic solvents, and other various additives.

The filler is not particularly limited. For example, colloidal silica, talc, clay, mica (mica), powders such as titanium oxide, inorganic hollow bodies such as glass balloons, alumina balloons, ceramic balloons, nylon beads, acrylic beads, Examples thereof include organic spherical bodies such as silicone beads and Teflon (registered trademark) beads, organic hollow bodies such as vinylidene chloride balloons and acrylic balloons, and single fibers such as glass, polyester, rayon, nylon and cellulose. Of these, talc, clay, and mica are preferred because they have an excellent baffle effect that prevents moisture from entering. These fillers may be used independently and 2 or more types may be used together.

The adhesiveness-imparting agent is not particularly limited. For example, silane coupling such as glycidoxytrimethoxysilane, glycidoxypropylmethyldiethoxysilane, N- (aminoethyl) aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, etc. Agents, titanium coupling agents, aluminum coupling agents and the like. These adhesiveness imparting agents may be used alone or in combination of two or more.

The viscosity of the cationic polymerizable resin composition is not particularly limited. For example, the preferable lower limit of viscosity at 25 ° C. and 5 rpm is 5 mPa · s, and the preferable upper limit is 500,000 mPa · s. When the viscosity is less than 5 mPa · s, the liquid may spread out from the coated part, and when it exceeds 500,000 mPa, it may not be possible to print uniformly and accurately by screen printing.
In addition, the said viscosity is a value obtained when it measures on the said conditions using an E-type viscosity meter (For example, the Toki Sangyo company make, TV-22 type | mold).

The method for preparing the cationic polymerizable resin composition is not particularly limited. For example, the cationic polymerizable compound, the photo cationic polymerization initiator or the thermal cationic polymerization initiator, and various additives to be added as necessary. For quantification, a known various kneaders such as a planetary stirrer, a homodisper, a universal mixer, a Banbury mixer, a kneader, a two-roll, a three-roll, and an extruder may be used alone or in combination at room temperature or heated. Below, there is a method of uniformly kneading under conditions such as normal pressure, reduced pressure, pressurized pressure or inert gas flow.

Examples of the method for applying the cationic polymerizable resin composition include screen printing, flexographic printing, dispensing, slit coating, spin coating, and inkjet. Among these, since a uniform film can be easily formed into a predetermined shape, screen printing and slit coating are preferable. In addition, since the inorganic protective layer can be delivered while maintaining the vacuum when forming the inorganic protective layer in Step 1 and Step 3, the coating is preferably performed in a vacuum environment.

In step 2, the cationic polymerizable resin composition is applied so as to cover a region including the organic thin film element covered with the inorganic protective layer A. At this time, the cationic polymerizable resin composition may cover the organic EL element, may cover the entire inorganic protective layer A, or may not cover a part of the inorganic protective layer A.

In step 2, the organic protective layer is then formed by curing the cationic polymerizable resin composition by light irradiation or heating.
The organic protective layer thus obtained preferably has a refractive index of 1.52 to 1.65. When the refractive index of the organic protective layer is out of the range of 1.52 to 1.65, the difference in refractive index between the inorganic protective layer A and the inorganic protective layer B becomes large, and the reflected light increases.
In the present specification, the refractive index means a value measured by using an Abbe refractometer and a sodium D line as a light source at 25 ° C. with respect to a sample having a thickness of 100 μm.

The manufacturing method of the organic optical device of this invention has the process 3 coat | covered with the inorganic protective layer B so that the outer peripheral part of the said resin protective layer and the resin protective layer may be covered (FIG.1 (e)).
The material and the formation method of the inorganic protective layer B are the same as the material and the formation method of the inorganic protective layer A in Step 1 above. In addition, the material of the said inorganic protective layer B may be the same as the material of the said inorganic protective layer A, and may differ.

Although the thickness of the said inorganic protective layer B is not specifically limited, A preferable minimum is 0.05 micrometer and a preferable upper limit is 100 micrometers. If the thickness of the inorganic protective layer B is less than 0.05 μm, defects may occur and water intrusion may not be sufficiently prevented. If the thickness exceeds 100 μm, internal stress becomes strong and cracks are likely to occur. The time required for film formation also becomes longer. The minimum with more preferable thickness of the said inorganic protective layer A is 0.1 micrometer, and a more preferable upper limit is 10 micrometers.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the organic optical device which can be reduced in thickness and can fully prevent moisture permeation can be provided.

It is a schematic diagram explaining the manufacturing method of the organic optical device of this invention.

Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(1) Production of a substrate on which an organic EL element is disposed A glass substrate (25 mm × 25 mm × 0.7 mm) having an ITO electrode formed in a thickness of 1000 mm was used as a substrate. The substrate was ultrasonically cleaned with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes each, then washed with boiled isopropyl alcohol for 10 minutes, and further UV-ozone cleaner (NL-UV253, Nippon Laser Electronics). The product was subjected to the last treatment.
Next, this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put into an unglazed crucible in other different ways. 200 mg of tris (8-hydroxyquinola) aluminum (Alq3) was put in an unglazed crucible, and the inside of the vacuum chamber was decompressed to 1 × 10 ⁻⁴ Pa. Thereafter, the crucible containing α-NPD was heated and α-NPD was deposited on the substrate at a deposition rate of 15 Å / s to form a 600 正 孔 hole transport layer. Next, the Alq3 crucible was heated to form a light-emitting layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the transparent support substrate was transferred to another vacuum deposition apparatus, and 200 mg of lithium fluoride was placed in a tungsten resistance heating boat in the vacuum deposition apparatus, and 1.0 g of aluminum wire was placed in another tungsten boat. Thereafter, the vacuum chamber was depressurized to 2 × 10 ⁻⁴ Pa and 5 μm of lithium fluoride was deposited at a deposition rate of 0.2 Å / s, and then 1000 μm of aluminum was deposited at a rate of 20 Å / s. The inside of the vapor deposition apparatus was returned to normal pressure with nitrogen, and the substrate was taken out to obtain a substrate on which 10 mm × 10 mm organic EL elements were arranged.

(2) Coating with inorganic protective layer A A mask having a 13 mm × 13 mm opening is placed on the substrate on which the obtained organic EL element is arranged so as to cover the entire organic EL element, and is applied to the plasma CVD method. Thus, an inorganic protective layer A was formed.
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, the RF power is 10 W (frequency: 2.45 GHz), the chamber temperature is 100 ° C., and the chamber pressure is The test was performed under the condition of 0.9 Torr.
The formed inorganic protective layer A had a thickness of about 1 μm.

(3) Formation of organic protective layer According to the composition shown in Table 1, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Homodisper L type, manufactured by Tokushu Kika Co., Ltd.). A cationically polymerizable resin composition was prepared.
A 200 mesh / inch stainless steel printing mesh is used in a 11 mm × 11 mm square portion including the organic EL element so as to cover the entire organic EL element covered with the inorganic protective layer A, and the screen printing machine is adjusted to a vacuum degree. Was placed in a vacuum apparatus of 70 Pa, and the obtained cationic polymerizable resin composition was screen-printed. Screen printing was performed at a printing speed of 100 mm / sec with a printing thickness of 20 μm.
The film obtained after screen printing is irradiated with ultraviolet light having a wavelength of 365 nm using a high-pressure mercury lamp in a vacuum environment so that the irradiation amount is 3000 mJ / cm ² , or by heating at 80 ° C. for 10 minutes. The cationic polymerizable resin composition was cured to form an organic protective layer.

(4) Covering with inorganic protective layer B A mask having an opening of 12 mm × 12 mm is installed so as to cover the entire 11 mm × 11 mm resin layer of the organic EL element substrate on which the organic protective layer is formed, and plasma CVD method Inorganic protective layer B was formed to obtain an organic optical device (organic EL device).
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, the RF power is 10 W (frequency: 2.45 GHz), the chamber temperature is 100 ° C., and the chamber pressure is The test was performed under the condition of 0.9 Torr.
The formed inorganic protective layer B had a thickness of about 1 μm.

(Examples 2 to 7)
An organic optical device was produced by the same method as in Example 1 except that the cationic polymerizable resin composition prepared according to the composition shown in Table 1 was used.
In Table 1, bisphenol A type epoxy resin is “Epicoat 828” manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A type epoxy resin is “Epicoat YX-8000” manufactured by Mitsubishi Chemical Corporation, and dicyclopentadiene type epoxy is “EP-4088” manufactured by Asahi Denka Co., Ltd., “Ogsol EG” manufactured by Osaka Gas Chemical Co., Ltd. as fluorene type epoxy resin, and “Epicron HP-4032D” manufactured by DIC Inc. as biphenyl monoglycidyl. Ether is “Denacol EX-142” manufactured by Nagase ChemteX, di {1-ethyl (3-oxetanyl)} methyl ether is “Aron Oxetane OXT-221” manufactured by Toagosei Co., Ltd., and silica particles are Nippon Aerosil "RX300" manufactured by KK is γ-glycidoxypropyltrimethoxy Silane, was used Etsu Silicone Co., Ltd., "KBM-403".

(Comparative Example 1)
In accordance with the composition shown in Table 2, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Homodisper L type, manufactured by Tokushu Kika Co., Ltd.) to obtain a radical polymerizable acrylic resin composition. Prepared.
An organic optical device was produced in the same manner as in Example 1 except that the obtained radical polymerizable acrylic resin composition was used.

(Evaluation)
The cationic polymerizable resin compositions and organic optical devices obtained in Examples and Comparative Examples were evaluated by the following methods.
The results are shown in Tables 1 and 2.

(1) Measurement of refractive index and total light transmittance of organic protective layer The obtained cationic polymerizable resin composition was formed to a thickness of 20 μm between two 75 mm × 25 mm × 1 mm glass plates, and in a vacuum environment An organic protective layer was obtained by irradiating with ultraviolet light having a wavelength of 365 nm using a high pressure mercury lamp so that the irradiation amount was 3000 mJ / cm ² or by heating at 80 ° C. for 10 minutes. About the obtained organic protective layer, the refractive index and the total light transmittance were measured.

(2) Measurement of moisture permeability of organic protective layer The obtained cationic polymerizable resin composition was applied on a thermostatic plate with a Baker type applicator (manufactured by Tester Sangyo Co., Ltd.) so as to have a thickness of 100 μm. An organic protective layer was obtained by irradiating ultraviolet rays having a wavelength of 365 nm using a high pressure mercury lamp in a vacuum environment so that the irradiation amount was 3000 mJ / cm ² or by heating at 80 ° C. for 10 minutes. The moisture permeability of the obtained organic protective layer was measured according to JIS Z 0208 by exposing it to conditions of 85 ° C. and 85% RH for 24 hours.

(3) Evaluation of the state of the organic optical device When the obtained organic optical device is visually observed and no peeling or cracking is observed, “○” is indicated, and when any peeling or cracking is recognized. Was evaluated as “×”.

(4) Evaluation of light emission state of organic optical device After the obtained organic optical device was exposed for 100 hours under conditions of 60 ° C. and 90% RH, a voltage of 6 V was applied, and the light emission state of the organic optical device (light emission and Observe the presence or absence of dark spots and pixel peripheral extinctions), and evaluate that “○” indicates that there are no dark spots or peripheral extinction, and “×” indicates that even a slight dark spot or peripheral extinction is observed. did.

(Example 8)
(1) Production of a substrate on which an organic thin film solar cell element is disposed A mask having an opening of 10 mm × 10 mm is placed on a glass substrate (25 mm × 25 mm × 0.7 mm) on which ITO is vapor-deposited, and a vacuum of a vacuum vapor deposition apparatus After being placed in a container and depressurized to 1 × 10 ⁻⁵ Torr, N, N′-dimethylperylenetetracarboxylic acid diimide was resistance-heated in an alumina crucible, and 1000 kg of N, N′-dimethyl was deposited on the ITO film. A perylenetetracarboxylic acid diimide film was deposited.
Next, a 30-thick metal-free phthalocyanine film and a 1000-thick 2,9-dimethylquinacridone film were sequentially laminated on this film in the same manner as N, N'-dimethylperylenetetracarboxylic acid diimide. Finally, gold was vacuum-deposited to a thickness of 300 mm under a reduced pressure of 1 × 10 ⁻⁵ Torr. The inside of the vapor deposition unit was returned to normal pressure, and the substrate was taken out to obtain a substrate on which 10 mm × 10 mm organic thin film solar cell elements were arranged.

(2) Coating with the inorganic protective layer A A mask having an opening of 13 mm × 13 mm is installed so as to cover the whole organic thin film solar cell element of the substrate on which the obtained organic thin film solar cell element is arranged, An inorganic protective layer A was formed by plasma CVD.
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, the RF power is 10 W (frequency: 2.45 GHz), the chamber temperature is 100 ° C., and the chamber pressure is The test was performed under the condition of 0.9 Torr.
The formed inorganic protective layer A had a thickness of about 1 μm.

(3) Formation of organic protective layer According to the composition shown in Table 3, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Homodisper L type, manufactured by Tokushu Kika Co., Ltd.). A cationically polymerizable resin composition was prepared.
Screen printing is performed using a 200 mesh / inch stainless steel printing mesh on a 11 mm × 11 mm square portion including the organic thin film solar cell element so as to cover the entire organic thin film solar cell element coated with the inorganic protective layer A. The machine was placed in a vacuum apparatus with a degree of vacuum of 70 Pa, and the resulting cationic polymerizable resin composition was screen printed. Screen printing was performed at a printing speed of 100 mm / sec with a printing thickness of 20 μm.
The film obtained after screen printing is irradiated with ultraviolet light having a wavelength of 365 nm using a high-pressure mercury lamp in a vacuum environment so that the irradiation amount is 3000 mJ / cm ² , thereby curing the cationic polymerizable resin composition. An organic protective layer was formed.

(4) Covering with inorganic protective layer B A mask having an opening of 12 mm × 12 mm is installed so as to cover the entire 11 mm × 11 mm resin layer of the organic thin-film solar cell element substrate on which the organic protective layer is formed, and plasma An inorganic protective layer B was formed by a CVD method to obtain an organic optical device.
In the plasma CVD method, SiH ₄ gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, the RF power is 10 W (frequency: 2.45 GHz), the chamber temperature is 100 ° C., and the chamber pressure is The test was performed under the condition of 0.9 Torr.
The formed inorganic protective layer B had a thickness of about 1 μm.

Example 9
An organic optical device was produced in the same manner as in Example 8 except that the cationic polymerizable resin composition prepared according to the composition shown in Table 3 was used.

(Comparative Example 2)
According to the composition shown in Table 4, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Homodisper L type, manufactured by Tokushu Kika Co., Ltd.) to obtain a radical polymerizable acrylic resin composition. Prepared.
An organic optical device (organic thin film solar cell) was produced in the same manner as in Example 1 except that the obtained radical polymerizable acrylic resin composition was used.

(Evaluation)
The cationic polymerizable resin compositions and organic optical devices obtained in Examples and Comparative Examples were evaluated by the following methods.
The results are shown in Tables 3 and 4.

(1) Measurement of refractive index and total light transmittance of organic protective layer The obtained cationic polymerizable resin composition was formed to a thickness of 20 μm between two 75 mm × 25 mm × 1 mm glass plates, and in a vacuum environment An organic protective layer was obtained by irradiating with ultraviolet light having a wavelength of 365 nm using a high pressure mercury lamp so that the irradiation amount was 3000 mJ / cm ² or by heating at 80 ° C. for 10 minutes. About the obtained organic protective layer, the refractive index and the total light transmittance were measured.

(2) Measurement of moisture permeability of organic protective layer The obtained cationic polymerizable resin composition was applied on a thermostatic plate with a Baker type applicator (manufactured by Tester Sangyo Co., Ltd.) so as to have a thickness of 100 μm. An organic protective layer was obtained by irradiating ultraviolet rays having a wavelength of 365 nm using a high pressure mercury lamp in a vacuum environment so that the irradiation amount was 3000 mJ / cm ² or by heating at 80 ° C. for 10 minutes. The moisture permeability of the obtained organic protective layer was measured according to JIS Z 0208 by exposing it to conditions of 85 ° C. and 85% RH for 24 hours.

(3) Evaluation of the state of the organic optical device When the obtained organic optical device is visually observed and no peeling or cracking is observed, “○” is indicated, and when any peeling or cracking is recognized. Was evaluated as “×”.

(4) Evaluation of photoelectric conversion characteristics of organic optical device The obtained organic optical device was allowed to stand at room temperature and high temperature and high humidity (60 ° C, 95%) for 500 hours, and then air mass 2 (AM2) light from the ITO electrode side. (75 mW / cm ² ), current-voltage characteristics are measured, and photoelectric conversion characteristics [open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (ff), and energy conversion efficiency (η)] are determined. evaluated.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the organic optical device which can be reduced in thickness and can fully prevent moisture permeation can be provided.

1 Organic thin film element 2 Substrate 3 Inorganic protective layer A
4 Cationic polymerizable resin composition 5 Organic protective layer 6 Inorganic protective layer B

Claims (3)

A method for producing an organic optical device in which an organic thin film element disposed on a substrate is sealed,
Step 1 of covering the organic thin film element disposed on the substrate with the inorganic protective layer A,
A cation polymerizable resin composition containing a cation polymerizable compound and a photo cation polymerization initiator or a thermal cation polymerization initiator is coated so as to cover a region including the organic thin film element coated with the inorganic protective layer A. Step 2 of curing the cationic polymerizable resin composition by light irradiation or heating to form an organic protective layer;
And a step 3 of coating with an inorganic protective layer B so as to cover the resin protective layer and the outer periphery of the resin protective layer. 2. The method of manufacturing an organic optical device according to claim 1, wherein the organic thin film element is an organic electroluminescence element. 2. The method of manufacturing an organic optical device according to claim 1, wherein the organic thin film element is an organic thin film solar cell element.

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