KR20170140149A - Sealant for electronic device, and method for manufacturing electronic device - Google Patents

Abstract

An object of the present invention is to provide an electronic device encapsulant that can be easily applied by an inkjet method and can reduce the damage of an inkjet apparatus. It is another object of the present invention to provide a method of manufacturing an electronic device using the sealing agent for electronic devices.
The present invention relates to a sealing agent for an electronic device, which contains a curable resin, a polymerization initiator and / or a thermosetting agent and is used for coating by an inkjet method, wherein the curable resin contains a silicone compound represented by the following formula (1) Which is a sealing agent for electronic devices. (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, X ¹ and X ² each independently represent an alkyl group having 1 to 10 carbon atoms, , (2-3) or (2-4), and X ³ represents a group represented by the following formulas (2-1), (2-2), (2-3) or (2-4) . m is an integer of 0 to 100, and n is an integer of 0 to 100. Provided that when n is 0, at least one of X ¹ and X ² represents a group represented by the following formula (2-1), (2-2), (2-3) or (2-4). In the formulas (2-1) to (2-4), R ² represents a bond or an alkylene group having 1 to 6 carbon atoms, and in the formula (2-3), R ³ represents hydrogen or an alkylene group having 1 to 6 carbon atoms R ⁴ represents a bond or methylene group, and in the formula (2-4), R ⁵ represents hydrogen or a methyl group.

Description

TECHNICAL FIELD [0001] The present invention relates to a sealant for electronic devices and a method for manufacturing the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a sealing agent for an electronic device which can be easily applied by an ink-jet method and can reduce the damage of an ink-jet apparatus. The present invention also relates to a method of manufacturing an electronic device using the sealing agent for electronic devices.

BACKGROUND ART In recent years, research on electronic devices using organic thin film devices such as organic electroluminescence (hereinafter also referred to as organic EL) display devices and organic thin film solar cell devices is underway. Since the organic thin film device can be easily manufactured by vacuum deposition or solution coating, the productivity is also excellent.

The organic EL display device has a laminate structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and electrons are injected from one electrode into the organic light emitting material layer, and holes are injected from the other electrode Whereby electrons and holes are combined in the organic light emitting material layer to emit light. As described above, the organic EL display device is advantageous in that visibility is good and thinner than a liquid crystal display device or the like that requires a backlight, and furthermore, a low-voltage direct current drive is possible.

Organic thin film solar cell devices are superior in cost, large size, and ease of manufacturing process compared with solar cells using inorganic semiconductors, and various structures have been proposed. Specifically, for example, Non-Patent Document 1 discloses an organic solar cell device using a laminated film of phthalocyanine copper and a perylene dye.

These organic thin film devices have a problem that the performance of the organic thin film element is rapidly deteriorated when the organic layer or the electrode is exposed to the outside air. Therefore, in order to improve the stability and durability, it is essential to seal the organic thin film element and shield it from moisture or oxygen in the atmosphere. As a method of sealing the organic thin film element, there has been generally employed a method of sealing the inside with a sealing can having an absorbent formed therein. However, in the method of sealing with the sealing can, it is difficult to make the electronic device thinner. Therefore, development of a sealing method of an organic thin film element without using a sealing can is progressing.

Patent Document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element by a laminated film of a silicon nitride film and a resin film formed by the CVD method. Here, the resin film has a role of preventing the organic layer or the electrode from being pressed against by the internal stress of the silicon nitride film.

In the method of sealing with the silicon nitride film disclosed in Patent Document 1, when the silicon nitride film is formed, irregularities on the surface of the organic thin film element, attachment of foreign matter, cracks due to internal stress, or the like, There is a case that can not be. If the coating with the silicon nitride film is incomplete, the moisture invades into the organic layer through the silicon nitride film.

Patent Document 2 discloses a method for alternately depositing an inorganic material film and a resin film as a method for preventing moisture intrusion into the organic layer. Patent Document 3 and Patent Document 4 disclose a method in which a resin film A method of forming the same is disclosed.

As a method of forming a resin film, there is a method of applying a liquid curable resin composition on a substrate using an inkjet method and curing the curable resin composition. By using such a coating method by the ink-jet method, a resin film can be uniformly formed at a high speed. When a sealing agent for an electronic device comprising a curable resin composition is applied to a base material by an inkjet method, the viscosity of the sealing agent needs to be set at a low point in order to discharge the base material stably from the nozzle. As a method of making the sealing agent for electronic devices suitable for the inkjet method, a method of blending an organic solvent with a sealing agent for an electronic device or a method of using a resin having a low molecular weight as a curable resin to be blended can be considered. There is a problem that the organic light emitting material layer is deteriorated by the residual organic solvent or the outgas is generated by the plasma. In the case of using the curable resin having a small molecular weight, There has been a problem that the apparatus is damaged by swelling the adhesive or the rubber material used in the head portion or the like.

Japanese Patent Application Laid-Open No. 2000-223264 Japanese Patent Publication No. 2005-522891 Japanese Laid-Open Patent Publication No. 2001-307873 Japanese Laid-Open Patent Publication No. 2008-149710

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

An object of the present invention is to provide an electronic device encapsulant that can be easily applied by an inkjet method and can reduce the damage of an inkjet apparatus. It is another object of the present invention to provide a method of manufacturing an electronic device using the sealing agent for electronic devices.

The present invention relates to a sealing agent for an electronic device, which contains a curable resin, a polymerization initiator and / or a thermosetting agent and is used for coating by an inkjet method, wherein the curable resin contains a silicone compound represented by the following formula (1) Which is a sealing agent for electronic devices.

[Chemical Formula 1]

(1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, X ¹ and X ² each independently represent an alkyl group having 1 to 10 carbon atoms, , (2-3) or (2-4), and X ³ represents a group represented by the following formulas (2-1), (2-2), (2-3) or (2-4) . m is an integer of 0 to 100, and n is an integer of 0 to 100. Provided that when n is 0, at least one of X ¹ and X ² represents a group represented by the following formula (2-1), (2-2), (2-3) or (2-4).

(2)

In the formulas (2-1) to (2-4), R ² represents a bond or an alkylene group having 1 to 6 carbon atoms, and in the formula (2-3), R ³ represents hydrogen or an alkylene group having 1 to 6 carbon atoms R ⁴ represents a bond or methylene group, and in the formula (2-4), R ⁵ represents hydrogen or a methyl group.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have found that a silicone compound having a specific structure hardly swells a rubber material or an adhesive, and since the intermolecular force is weak, the viscosity is not excessively increased even if the molecular weight is increased to some extent. Therefore, the present inventors can obtain a sealing agent for an electronic device which can be easily applied by an ink-jet method and can reduce the damage of an ink-jet apparatus by blending a silicone compound having the specific structure as a curable resin And have accomplished the present invention.

Further, since the silicon compound having the specific structure has a low surface tension, the obtained sealing agent for electronic devices is excellent in wettability and can be easily thinned by the ink-jet method.

The sealing agent for an electronic device of the present invention contains a curable resin.

The curable resin contains the silicone compound represented by the formula (1).

By containing the silicone compound represented by the above formula (1), the sealing agent for electronic devices of the present invention has a favorable viscosity for application by the ink-jet method and can reduce the device damage.

In the formula (1), the lower limit of m is preferably 1, and the upper limit is preferably 10. [ When m is 1 or more, the effect of suppressing the swelling of the rubber material or the adhesive is more excellent. When m is 10 or less, the inkjet coating property and the low outgassing property are more excellent, and the cured product has a more preferable hardness. The more preferable upper limit of m is 5.

In the above formula (1), the preferable upper limit of n is 10. When n is 10 or less, the inkjet coating property and the low outgassing property are more excellent, and the cured product has more preferable hardness. The more preferable upper limit of n is 5.

As the silicone compound represented by the above formula (1), at least one of X ¹ , X ² and X ³ in the formula (1) is a group represented by the formula (2-1), (2-2) Is preferably a compound and is at least one selected from the group consisting of a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3) desirable.

(3)

In Formula (3-1), o is an integer of 1 to 10, and in Formula (3-2), p is an integer of 1 to 10, and in Formula (3-3), q is an integer of 1 to 10 .

(O) in formula (3-1), p in formula (3-2), and formula (3-2) in view of the anti-swelling properties of rubber materials and the like, the ink jet application properties, the low outgassing property, 3), q is preferably an integer of 1 to 6, respectively.

The curable resin may contain, in addition to the silicone compound represented by the above formula (1), other curable resins for the purpose of improving adhesion.

The other curable resin may be an epoxy compound having no structure represented by the formula (1) (hereinafter, also referred to as "other epoxy compound"), an oxetane compound having no structure represented by the formula (1) (Also referred to as "other oxetane compound"), a (meth) acrylic compound having no structure represented by the above formula (1) (hereinafter also referred to as "other (meth) acrylic compound"), and a vinyl ether compound Lt; / RTI > is preferred.

In the present specification, the term "(meth) acryl" means acryl or methacryl, "(meth) acrylic compound" means a compound having a (meth) acryloyl group, Lower alkyl "means acryloyl or methacryloyl.

Examples of other epoxy compounds include bisphenol A type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol O type epoxy resins, 2,2'-diallyl bisphenol A-type epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin , Dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalene phenol novolak Alkoxypolyol type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, There may be mentioned resins, glycidyl ester compounds. Among them, an alicyclic epoxy resin is preferable.

Examples of commercially available products of the alicyclic epoxy resin include Cellockide 2000, Celloxide 2021P, Celloxide 2081, Celloxide 3000, Cellockide 8000, Cyclomer M-100 (all manufactured by Daicel Chemical Industries, Ltd.) Low EPS (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Among the above-mentioned alicyclic epoxy resins, it is preferable not to have an ether bond or an ester bond other than those contained in the epoxy group from the viewpoint of suppressing the generation of outgas. Examples of commercially available alicyclic epoxy resins having no ether bond or ester bond other than those contained in the epoxy group include Celloxide 2000, Celloxide 3000, Celloxide 8000, and the like.

These other epoxy compounds may be used alone, or two or more of them may be used in combination.

Examples of other oxetane compounds include 3- (allyloxy) oxetane, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl- 3- (phenoxymethyl) Ethyl-3 - ((3- (triethoxysilyl) propoxy) methyl) oxetane, 3-ethyl- ((3-ethyloxetan-3-yl) methoxy) methyl) oxetane, oxetanylsil sesquioxane, phenol novolak oxetane, 1,4-bis ) Methoxy) methyl) benzene, and the like.

These other oxetane compounds may be used alone, or two or more of them may be used in combination.

Examples of the other (meth) acrylic compounds include glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl 12-dodecanediol (meth) acrylate, lauryl (meth) acrylate, and the like.

These other (meth) acrylic compounds may be used alone, or two or more of them may be used in combination.

In the present specification, the term "(meth) acrylate" means acrylate or methacrylate.

Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexanedimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol Divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, and the like.

These vinyl ether compounds may be used alone or in combination of two or more.

Among them, alicyclic epoxy resin, 3- (allyloxy) oxetane, 3-ethyl-3 - ((2-ethylhexyloxy) methyl) oxetane , And 3-ethyl-3 (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane.

When the other curable resin is contained, the content of the silicone compound represented by the formula (1) is preferably 5 parts by weight based on 100 parts by weight of the entire curable resin. Since the content of the silicone compound represented by the formula (1) is 5 parts by weight or more, both the excellent effect of coating by the ink-jet method and the effect of reducing the damage of the ink-jet apparatus are more excellent. A more preferable lower limit of the content of the silicone compound represented by the above formula (1) is 10 parts by weight.

When the other curable resin is contained, the content of the silicone compound represented by the formula (1) is preferably 90 parts by weight per 100 parts by weight of the entire curable resin, to be. When the content of the silicone compound represented by the above formula (1) is 90 parts by weight or less, the other curable resin can further exhibit the effects such as improving the adhesiveness.

The sealing agent for an electronic device of the present invention contains a polymerization initiator and / or a thermosetting agent.

As the polymerization initiator, a photo cationic polymerization initiator, a thermal cation polymerization initiator, a photo radical polymerization initiator, and a thermal radical polymerization initiator are preferably used.

The photo cationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid generator or a nonionic photoacid generator.

Examples of the photo cationic polymerization initiator of the above-mentioned ionic photoacid generator include those wherein the anion moiety is BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (where X is at least 2 An aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, an aromatic ammonium salt, (2,4-cyclopentadien-1-yl) (( 1-methylethyl) benzene) -Fe salt.

Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonyl) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonyl) phenyl) sulfide bishexafluoro (Pentafluorophenyl) borate, bis (4- (diphenylsulfonyl) phenyl) sulfide tetrakis (pentafluorophenyl) borate, bis (Phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetra (Phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium Tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) Bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonyl) phenyl) sulfide bishexafluorophosphate, bis Phenyl) sulfide bis hexafluoroantimonate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonyl) phenyl) sulfide bis tetrafluoro (4- (4-acetoxyphenyl) phenyl) sulfide tetrakis (pentafluorophenyl) borate, tris (4- (4-acetoxyphenyl) Thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.

The aromatic iodonium salt includes, for example, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluoro Bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis ), Iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4- 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate and the like can be used. .

The aromatic diazonium salt includes, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate And the like.

Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl- (Pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylphenyl) 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium Tetrakis (pentafluorophenyl) borate, and the like.

The (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt includes, for example, (2-methylethyl) benzene) -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, ) Benzene) -Fe (II) tetrakis (pentafluorophenyl) borate.

Examples of the nonionic photoacid generator-type photo cationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimidosulfonate, etc. have.

UVI6990, UVI6974 (all manufactured by Union Carbide Corp.), SP-150, and SP-170 (all manufactured by ADEKA) are commercially available as commercially available photocationic polymerization initiators. Examples of commercially available photocationic polymerization initiators include DTS- IRGACURE 261, IRGACURE 290 (manufactured by BASF), PI2074 (manufactured by Rodia), and the like.

As the thermal cationic polymerization initiator, the anion moiety may be BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (wherein X is at least two fluorine or trifluoromethyl groups A phenyl group, and the like), and the like. Of these, sulfonium salts and ammonium salts are preferable.

Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, and the like.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) Ammonium salts such as ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (Pentafluorophenyl) borate, methylphenyldibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium hexafluorophosphate (Pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethyl- N, N-diethyl-N-benzyl anilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, -Benzylpyridinium trifluoromethanesulfonic acid, and the like.

Examples of commercially available thermal cationic polymerization initiators include, but are not limited to, acid aids SI-60, acid aide SI-80, acid aide SI-B3, acid aide SI-B3A, Ltd.), CXC1612 and CXC1821 (all manufactured by King Industries), and the like.

Examples of the photo radical polymerization initiator include a benzophenone based compound, an acetophenone based compound, an acylphosphine oxide based compound, a titanocene based compound, an oxime ester based compound, a benzoin ether based compound, benzyl, Compounds and the like.

IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, lucylline TPO (all manufactured by BASF), and the like, Benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (both manufactured by Tokyosho Kagaku Kogyo Co., Ltd.).

Examples of the thermal radical polymerization initiator include azo compounds, organic peroxides, and the like.

Examples of the azo compound include 2,2'-azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, and the like.

Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, peroxydicarbonate, and the like.

Examples of commercially available thermal radical polymerization initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 and V-501 have.

The content of the polymerization initiator is preferably 0.01 part by weight, and more preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the polymerization initiator is 0.01 part by weight or more, the obtained sealing agent for electronic devices is more excellent in curability. When the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the obtained electronic device encapsulant is not excessively quick, the workability is better, and the cured product can be made more uniform. A more preferable lower limit of the content of the polymerization initiator is 0.05 part by weight, and a more preferable upper limit is 5 parts by weight.

Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, adducts of various amines and epoxy resins, and the like.

Examples of the hydrazide compound include 1,3-bis (hydrazinocarbonoethyl-5-isopropylhydantoin), sebacic acid dihydrazide, isophthalic acid dihydrazide, Drageid, and Malonoic acid dihydrazide.

Examples of the imidazole derivatives include 1-cyanoethyl-2-phenylimidazole, N- (2- (2-methyl-1-imidazolyl) ethyl) urea, 2,4- N ', N'-bis (2-methylimidazolylethyl) urea, N, N'- Methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, .

Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydrotrimellitate), and the like.

These heat curing agents may be used alone or in combination of two or more.

Examples of commercially available thermosetting resins include SDH, ADH (all manufactured by Otsuka Chemical), Amicure VDH, Amicure VDH-J, and Amicure UDH (both manufactured by Ajinomoto Fine Techno Co., Ltd.) .

The content of the thermosetting agent is preferably 0.5 parts by weight, and more preferably 30 parts by weight, based on 100 parts by weight of the curable resin. When the content of the thermosetting agent is 0.5 parts by weight or more, the obtained sealing material for electronic devices is more excellent in the thermosetting property. When the content of the thermosetting agent is 30 parts by weight or less, the obtained sealing material for electronic devices is further excellent in storage stability, and the cured product is further excellent in moisture resistance. A more preferable lower limit of the content of the thermosetting agent is 1 part by weight, and a more preferable upper limit is 15 parts by weight.

The sealing agent for an electronic device of the present invention may contain a sensitizer. The sensitizer further improves the polymerization initiation efficiency of the polymerization initiator and has the role of further promoting the curing reaction of the sealing agent for electronic devices of the present invention.

Examples of the sensitizer include thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2 , 4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone and 4-benzoyl-4'-methyldiphenylsulfide.

The content of the sensitizer is preferably 0.01 part by weight, and more preferably 3 parts by weight, based on 100 parts by weight of the curable resin. When the content of the sensitizer is 0.01 parts by weight or more, the effect of increasing or decreasing is further exerted. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to the core portion without excessively increasing absorption. A more preferable lower limit of the content of the sensitizer is 0.1 part by weight, and a more preferable upper limit is 1 part by weight.

The sealing agent for an electronic device of the present invention preferably further contains a silane coupling agent. The silane coupling agent has a role of improving the adhesiveness between the sealing agent for electronic devices of the present invention and the substrate or the like.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, etc. . These silane compounds may be used alone, or two or more of them may be used in combination.

The content of the silane coupling agent is preferably 0.1 part by weight, and more preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the silane coupling agent is in this range, the effect of improving the adhesiveness of the obtained sealing agent for electronic devices is further improved while suppressing bleeding out by the excess silane coupling agent. A more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.

The sealing agent for an electronic device of the present invention may contain a curing retarder. By containing the above-mentioned curing retardant, the resulting pot life of the sealing agent for electronic devices can be lengthened.

Examples of the curing retarder include polyether compounds and the like.

Examples of the polyether compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, crown ether compounds and the like. Among them, a crown ether compound is preferable.

The content of the curing retarder is preferably 0.05 parts by weight, and more preferably 5.0 parts by weight, based on 100 parts by weight of the curable resin. When the content of the hardening retarder is within this range, the retarding effect can be further exerted while suppressing the generation of outgas when the resulting sealing agent for electronic devices is cured. A more preferable lower limit of the content of the curing retardant is 0.1 part by weight, and a more preferable upper limit is 3.0 part by weight.

The sealing agent for an electronic device of the present invention may contain a surface modifier within a range not hindering the object of the present invention. By containing the above surface modifier, the flatness of the coating film can be imparted to the sealing agent for electronic devices of the present invention.

Examples of the surface modifier include surfactants and leveling agents.

Examples of the surfactant and the leveling agent include silicon-based, acrylic-based, and fluorine-based surfactants.

Examples of commercially available surfactants and leveling agents include BYK-340, BYK-345 (all manufactured by Big Chemical Japan), Surflon S-611 (manufactured by AGC Seiyaku Chemical Co., Ltd.) .

The sealing agent for an electronic device of the present invention may contain a compound or an ion-exchange resin that reacts with an acid generated in the sealing agent to improve the durability of the element electrode within a range that does not impair the transparency of the cured product.

Examples of the compound reacting with the generated acid include a substance which is neutralized with an acid, for example, a carbonate or hydrogencarbonate of an alkali metal or an alkaline earth metal. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium bicarbonate and the like are used.

As the ion exchange resin, any of a cation exchange type, anion exchange type, and both ion exchange type may be used, and in particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ion is preferable.

The sealing agent for an electronic device of the present invention may contain various known additives such as a reinforcing agent, a softening agent, a plasticizer, a viscosity adjusting agent, an ultraviolet absorber and an antioxidant, if necessary.

As a method for producing an encapsulant for electronic devices of the present invention, for example, a mixer such as homodisperse, homomixer, universal mixer, planetary mixer, kneader, A method of mixing an additive such as an initiator and / or a thermosetting agent and a silane coupling agent to be added as needed, and the like.

The sealing agent for an electronic device of the present invention preferably has a viscosity lower limit of 5 mPa · s and a preferable upper limit of 200 mPa · s as measured at 25 ° C. and 100 rpm using an E-type viscometer. When the viscosity is within this range, the sealing agent for an electronic device of the present invention is more excellent in inkjet coating property and shape retaining property after application. A more preferable lower limit of the viscosity of the sealing agent for electronic devices is 10 mPa · s, and a more preferable upper limit is 80 mPa · s.

Further, the sealing agent for electronic devices of the present invention may be heated at the time of application by inkjet to reduce the viscosity.

The preferable lower limit of the total light transmittance of the cured product of the sealing agent for electronic devices of the present invention at a wavelength of 380 to 800 nm is 80%. Since the total light transmittance is 80% or more, the organic EL display device can more preferably be used. A more preferable lower limit of the total light transmittance is 85%.

The total light transmittance can be measured using, for example, a spectrometer such as AUTOMATIC HAZE MATER MODEL TC = III DPK (manufactured by Tokyo Denshoku Co., Ltd.).

It is preferable that the sealing agent for an electronic device of the present invention has a transmittance of at least 85% at an optical path length of 20 m at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours. When the ultraviolet rays are irradiated for 100 hours and the transmittance is 85% or more, transparency becomes more excellent, loss of light emission is small, and color reproducibility is further improved. A more preferable lower limit of the transmittance after irradiating the ultraviolet ray for 100 hours is 90%, and a more preferable lower limit is 95%.

As the light source for irradiating the ultraviolet ray, for example, a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.

According to JIS Z 0208, the sealing agent for electronic devices of the present invention preferably has a moisture permeability of 100 g / m 2 or less at a thickness of 100 μm measured by exposing the cured product to 85 ° C and 85% RH for 24 hours . When the moisture permeability is 100 g / m < 2 > or less, for example, when the organic EL display device is manufactured as an electronic device, the effect of suppressing the occurrence of dark spots due to moisture reaching the organic light- .

It is preferable that the moisture content of the cured product is less than 0.5% when the cured product of the electronic device of the present invention is exposed for 24 hours under the environment of 85 캜 and 85% RH. When the water content of the cured product is less than 0.5%, for example, when used as an electronic device in the production of an organic EL display device, the effect of suppressing deterioration of the organic light emitting material layer due to moisture in the cured product is more excellent. A more preferable upper limit of the water content of the cured product is 0.3%.

As the method of measuring the water content, for example, there can be mentioned a method of obtaining by Karl Fischer method in accordance with JIS K 7251, and a method of obtaining weight increment after absorption in accordance with JIS K 7209-2.

The sealing agent for an electronic device of the present invention is used for application by an ink-jet method.

A step of applying the sealing agent for an electronic device of the present invention to at least one of two substrates by an inkjet method, a step of curing the applied sealing agent for electronic devices by light irradiation and / or heating, A method of manufacturing an electronic device having a step of bonding a substrate is also one of the present invention.

In the step of applying the sealing agent for electronic devices of the present invention to at least one of the two sheets of substrates, the sealing agent for electronic devices of the present invention may be applied to the entire surface of the substrate or may be applied to a part of the substrate. For example, in the case of manufacturing an organic EL display device as an electronic device, in the sealing portion shape of the sealing agent for an electronic device of the present invention formed by coating, a laminate having an organic light- And a closed pattern may be formed in the periphery of the laminate, and a pattern having a shape in which a part of the opening is formed in the periphery of the laminate may be formed .

When the organic EL display device is manufactured as the electronic device, the substrate (hereinafter, also referred to as one substrate) to which the sealing agent for an electronic device of the present invention is applied may be a substrate on which a laminate having an organic light- , Or a substrate on which the laminate is not formed.

When the one substrate is a substrate on which the laminate is not formed, when the other substrate is laminated, the sealing agent for an electronic device of the present invention is applied to the one substrate so as to protect the laminate from external air do. That is, when the other substrate is laminated, it is applied to the place where the laminate is to be placed on the whole, or when the other substrate is laminated, The sealing portion may be formed.

The laminate may be covered with an inorganic material film.

As the inorganic material constituting the inorganic material film, conventionally known ones can be used, and examples thereof include silicon nitride (SiN _x ) and silicon oxide (SiO _x ). The inorganic material film may be composed of one layer or may be a laminate of plural kinds of layers. The above-mentioned laminate may be coated by alternately repeating the above-mentioned inorganic material film and the resin film comprising the sealing agent for electronic devices of the present invention.

The step of curing the sealing agent for electronic devices by light irradiation and / or heating may be carried out before the step of joining the two substrates together, or after the step of joining the two substrates together.

In the case where the step of curing the electronic device encapsulant by light irradiation and / or heating is performed before the step of joining the two substrates, the encapsulant for electronic devices of the present invention is subjected to light irradiation and / or heating It is preferable that the curing reaction is allowed to proceed so that the curing reaction time until the curing reaction becomes impossible becomes 1 minute or more. Since the above-mentioned pot life is 1 minute or longer, the progress of the curing before the two substrates are bonded can be suppressed, and the bonding strength after the bonding can be further increased.

When the sealing agent for an electronic device is cured by light irradiation, the sealing agent for an electronic device of the present invention is preferably cured by irradiating light having a wavelength of 300 nm to 400 nm and an integrated amount of light of 300 to 3000 mJ / .

Examples of the light source for irradiating light to the electronic device encapsulant of the present invention include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, A halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED lamp, a fluorescent lamp, a solar light, and an electron beam irradiating device. These light sources may be used alone, or two or more of them may be used in combination.

These light sources are suitably selected in accordance with the absorption wavelengths of the photo cationic polymerization initiator and the photo radical polymerization initiator.

Examples of the light irradiation means for the electronic device encapsulant of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, and combination irradiation of simultaneous irradiation and sequential irradiation. May be used.

In the case of curing the sealing agent for electronic devices by heating, for example, from the viewpoint of sufficiently curing while reducing the damage to the laminate having the organic light emitting material layer when the organic EL display device is manufactured as an electronic device, The heating temperature is preferably 50 to 120 ° C.

In the step of joining the two sheets of substrates, the method of joining the two sheets of substrates is not particularly limited, but it is preferable that the joining is performed in a reduced-pressure atmosphere.

The lower limit of the degree of vacuum under the reduced-pressure atmosphere is preferably 0.01 mm, and the upper limit is preferably 10 mm. The degree of vacuum in the reduced-pressure atmosphere is in this range, so that the sealing of the electronic device of the present invention when the two substrates are bonded together without consuming a long time for achieving the vacuum state from the airtightness of the vacuum apparatus or the ability of the vacuum pump The bubbles can be removed more efficiently from the vessel.

According to the present invention, it is possible to provide an electronic device encapsulant that can be easily applied by an inkjet method and can reduce device damage. Further, according to the present invention, it is possible to provide a method of manufacturing an electronic device using the sealing agent for electronic devices.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

(Production Example 1)

To a four-necked flask equipped with a dropping funnel, a stirrer, a thermometer, and a septum, 20 ml of toluene was added. A mixed solution of 45.7 g (0.4 mol) of 3- (allyloxy) oxetane and 76 g (0.15 mol) of hydrogen-terminated tridymethylsiloxane ("DMS-03H" manufactured by Gelest Co.) was added to a dropping funnel, 3 ml of the mixed solution was dropped from the funnel into toluene in the flask, and the temperature in the flask was raised to 80 캜.

Next, 800 벤 of a benzonitrile solution (chloroplatinic acid concentration: 0.1 wt%) of chloroplatinic acid hexaphosphate (H ₂ PtCl ₆揃 6H ₂ O) as a catalyst from the septum was added to the flask using a syringe. Thereafter, a mixed solution of 3- (allyloxy) oxetane and hydrogen-terminated tridymethylsiloxane was further added dropwise from the dropping funnel over 40 minutes. After completion of the dropwise addition, 3- (allyloxy) oxetane and hydrogen end-tridimethylsiloxane were reacted by heating the flask at 80 ° C to 85 ° C for 2 hours. After completion of the reaction, volatile compounds such as toluene were removed by distillation under reduced pressure. Thus, a compound in which q in the formula (3-3) having a purity of 95% was 2 was obtained.

(Example 1)

100 parts by weight of a compound having o in the formula (3-1) (X-22-163, Shin-Etsu Chemical Co., Ltd.) as a silicone compound represented by the formula (1) 1 part by weight of 4,4'-bis (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate (IRGACURE 290, manufactured by BASF) was added to a homodisperse type stirring mixer Disper L type ") at a stirring speed of 3000 rpm to prepare a sealing agent for electronic devices.

(Example 2)

The blending amount of the compound o in the formula (3-1) of 1 ("X-22-163" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 50 parts by weight, and the other curing resins were 3,4,3 ' (Manufactured by Daicel Co., Ltd., " Celloxide 8000 ") were mixed in a mortar to prepare an encapsulant for electronic devices.

(Example 3)

Epoxy-4-vinylcyclohexane (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) instead of 50 parts by weight of 3,4, 3,3'4'-diepoxybicyclohexane Manufactured by Cell Co., Ltd., " Celloxide 2000 ") were mixed in a ratio of 50 parts by weight.

(Example 4)

Except that 50 parts by weight of 3,4, 3 ', 4'-diepoxybicyclohexane ("Celloxide 8000" manufactured by Daicel Chemical Industries, Ltd.) was used as the other curable resin, 3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd., "Aronoxetan OXT-221") were added.

(Example 5)

Except that 50 parts by weight of 3,4, 3 ', 4'-diepoxybicyclohexane ("Celloxide 8000" manufactured by Daicel Chemical Industries, Ltd.) was used as the other curable resin, 3-allyloxyoxetane AL-OX ") were added in an amount of 50 parts by weight based on the total weight of the composition.

(Example 6)

Except that 50 parts by weight of cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide Co., Ltd.) was used instead of 50 parts by weight of 3,4, 3,3 ', 4'-diepoxybicyclohexane ("Celloxide 8000" , &Quot; CHDVE ") were added in the amount of 50 parts by weight.

(Example 7)

Instead of 50 parts by weight of the silicone compound represented by the formula (1) in which o is 1 in the formula (3-1) ("X-22-163" manufactured by Shin-Etsu Chemical Co., ¹ (wherein X ¹ and X ² are methyl, X ³ is a group represented by the above formula (2-1) (R ² is an ethylene group), m is 5 and n is 3 -22-343 ") were added in an amount of 50 parts by weight based on the total weight of the composition.

(Example 8)

Except that 50 parts by weight of 3,4, 3 ', 4'-diepoxybicyclohexane ("Celloxide 8000" manufactured by Daicel Chemical Industries, Ltd.) was used as the other curable resin, -3-yl) methoxy) methyl) oxetane (AARON OXETAN OXT-221, manufactured by Toagosei Co., Ltd.).

(Example 9)

(3-2) instead of 100 parts by weight of the silicone compound represented by the above formula (1) wherein o is 1 in the formula (3-1) ("X-22-163" Was prepared in the same manner as in Example 1, except that 100 parts by weight of a compound in which p was 9 ("DMS-EC13" manufactured by Gelest Co., Ltd.) was added.

(Example 10)

The compounding amount of the compound having p = 9 in the formula (3-2) ("DMS-EC13" manufactured by Gelest) was changed to 50 parts by weight, and as the other curable resin, 3,4,3 ', 4'- And 50 parts by weight of bicyclohexane ("Celloxide 8000", manufactured by Daicel Chemical Industries, Ltd.) were blended together to prepare an encapsulant for electronic devices.

(Example 11)

Except that 50 parts by weight of 3,4, 3 ', 4'-diepoxybicyclohexane ("Celloxide 8000" manufactured by Daicel Chemical Industries, Ltd.) was used as the other curable resin, -3-yl) methoxy) methyl) oxetane (AARON OXETHANE OXT-221, manufactured by Toagosei Co., Ltd.) were added.

(Example 12)

Except that 1 part by weight of dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate (manufactured by King Industries, Inc., "CXC-1612") as a thermal cation polymerization initiator was used instead of the photocathione polymerization initiator. A sealing agent for an electronic device was produced in the same manner as in Example 11.

(Example 13)

(X-22-163, manufactured by Shin-Etsu Chemical Co., Ltd.) in which o is 1 in the formula (3-1) as the silicone compound represented by the formula (1) , And 50 parts by weight of a compound in which q in the general formula (3-3) was 2 were compounded, to prepare a sealing agent for electronic devices.

(Example 14)

Wherein R ¹ in the formula (1) is a methyl group, X ¹ and X ² are groups represented by the formula (2-4) (R ² is an n-propylene group, R ⁵ is a methyl group , 50 parts by weight of a compound (X-22-164, manufactured by Shin-Etsu Chemical Co., Ltd.) having m = 1 and n = 0, 50 parts by weight of 1,6-hexanediol diacrylate as other curable resin, And 2 parts by weight of diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide ("Lucirin TPO", manufactured by BASF Corporation) as a radical polymerization initiator were mixed in a homodisperse type stirring mixer (manufactured by Freimix Co., Quot; L-type ") at a stirring speed of 3000 rpm to prepare a sealing agent for electronic devices.

(Example 15)

100 parts by weight of a compound represented by the formula (1) in which p in the formula (3-2) is 1 ("SIB1092.0" manufactured by Gelest Co., Ltd.) and 10 parts by weight of tris 1 part by weight of a homodisperse type stirring mixer (manufactured by Freimix Co., Ltd., homodisperse type L-type (trade name: ) At a stirring speed of 3000 rpm to prepare a sealing agent for electronic devices.

(Example 16)

The compounding amount of the compound having p = 1 in the formula (3-2) ("SIB1092.0" manufactured by Gelest) was changed to 50 parts by weight, and as the other curable resin, 3,4,3 ', 4'- A sealing agent for electronic devices was produced in the same manner as in Example 15 except that 50 parts by weight of bicyclohexane ("Celloxide 8000", manufactured by Daicel Chemical Industries, Ltd.) was added.

(Example 17)

The compounding amount of the compound in which p is 1 in the formula (3-2) ("SIB1092.0" manufactured by Gelest) was changed to 40 parts by weight and 3,4,3 ', 4'-diepoxybicyclohexane Except that 20 parts by weight of 3-allyloxyoxetane ("AL-OX" manufactured by Yokkaichi Chemical Co., Ltd.) was further blended as the other curable resin in the blending amount of 30 parts by weight of "Celllock 8000" , And a sealing agent for an electronic device was produced in the same manner as in Example 16. [

(Example 18)

Epoxy-4-vinylcyclohexane (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) instead of 50 parts by weight of 3,4, 3,3'4'-diepoxybicyclohexane Manufactured by Cell Co., Ltd., " Celloxide 2000 ") were mixed in a ratio of 50 parts by weight.

(Example 19)

Except that 50 parts by weight of 3,4, 3 ', 4'-diepoxybicyclohexane ("Celloxide 8000" manufactured by Daicel Chemical Industries, Ltd.) was used as the other curable resin, -3-yl) methoxy) methyl) oxetane ("AARON OXETAN OXT-221", manufactured by Toagosei Co., Ltd.) was added to the mixture.

(Example 20)

Except that 50 parts by weight of 3,4, 3 ', 4'-diepoxybicyclohexane ("Celloxide 8000" manufactured by Daicel Chemical Industries, Ltd.) was used as the other curable resin, 3-allyloxyoxetane AL-OX " manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

(Example 21)

Except that 50 parts by weight of cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide Co., Ltd.) was used instead of 50 parts by weight of 3,4, 3,3 ', 4'-diepoxybicyclohexane ("Celloxide 8000" , And 50 parts by weight of " CHDVE ") were mixed in the same manner as in Example 16.

(Comparative Example 1)

100 parts by weight of 3,4,3 ', 4'-diepoxybicyclohexane ("Celloxide 8000", manufactured by Daicel Chemical Industries, Ltd.) was blended as the other curable resin without adding the silicone compound represented by the formula (1) , A sealing agent for an electronic device was produced in the same manner as in Example 1.

(Comparative Example 2)

(3-ethyloxetan-3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd.) as the other curable resin without adding the silicone compound represented by the above formula (1) AARON OXETHANE OXT-221 ") was prepared in the same manner as in Example 1, except that 100 parts by weight of a polyolefin resin

(Comparative Example 3)

3-ethyl-3 (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd., AARON oxetane OXT-221 ") was changed to 100 parts by weight, a sealing agent for electronic devices was produced.

(Comparative Example 4)

Except that the silicone compound represented by the formula (1) was not blended and the amount of 1,6-hexanediol diacrylate as the other curable resin was changed to 100 parts by weight, .

<Evaluation>

The following evaluations were performed on the sealing agents for electronic devices obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(Viscosity)

The viscosities of the sealing agents for electronic devices obtained in Examples and Comparative Examples were measured under the conditions of 25 ° C and 100 rpm using an E-type viscometer ("VISCOMETER TV-22" manufactured by Toki Industries Co., Ltd.).

(Wetting Diffusion)

Alkali glass (manufactured by Asahi Glass Co., Ltd.) in which the sealing agents for electronic devices obtained in Examples and Comparative Examples were alkali-washed with a liquid amount of 80 picoliters using an inkjet ejecting apparatus ("NanoPrinter300" &Quot; AN100 &quot;), and after 10 minutes, the diameter of the droplet on the alkali-free glass was measured.

(Adhesive property)

Each of the sealing agents for electronic devices obtained in Examples and Comparative Examples was applied on a non-alkali glass ("AN100" manufactured by Asahi Glass Co., Ltd.) using a spin coater to a thickness of 10 μm, , 13 to 21, and Comparative Examples 1, 2, and 4 were subjected to 3000 mJ / cm 2 of ultraviolet light having a wavelength of 365 nm using an LED lamp to obtain an electronic device obtained in Examples 12 and 3, The sealing agent for devices was heated at 100 占 폚 for 30 minutes to cure the sealing agent for electronic devices to obtain a resin film.

The formed resin film was subjected to a cross-cut test with an infeed interval of 1 mm in accordance with JIS K 5600-5-6.

A "when the peeling was 5% or more and 35% or less when the peeling was less than 5% and a case where the peeling was less than 35% and 65% or less when the cross-cut test was performed was" , And the case where the peeling exceeded 65% was evaluated as &quot; x &quot;, and the adhesiveness was evaluated.

(Swelling property of adhesive piece (device damage))

About 0.15 g of an epoxy adhesive ("ARALIDITE AR-S30" manufactured by Nichibei Reflective Co., Ltd.) was cured to prepare an adhesive piece, and the weight (W ₁ ) was measured. Then, the sealant for each electronic device obtained in Examples and Comparative Examples was placed in a brown screw tube, the prepared adhesive piece was immersed, the lid was closed, and the adhesive was immediately stopped at 60 DEG C for 7 days, After the surface was wiped with a wastepaper, the weight (W ₂ ) was measured, and the weight change rate of the adhesive piece was calculated by the following formula.

Weight change rate (%) = ((W ₂ -W ₁ ) / W ₁ ) × 100

, The case where the weight change rate was less than 1% was evaluated as &quot; &quot;, the case where the weight change rate was less than 10% was evaluated as &quot; The swelling of the adhesive piece (device damage) was evaluated.

(Display performance of organic EL display device)

(Fabrication of a substrate on which a laminate having an organic light emitting material layer is disposed)

An ITO electrode having a thickness of 1000 angstroms was formed on a glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) as a substrate. The substrate was ultrasonically cleaned with acetone, an aqueous alkaline solution, ion exchanged water and isopropyl alcohol for 15 minutes, and then washed with mercury isopropyl alcohol for 10 minutes. Then, a UV-ozone cleaner (NL -UV253 &quot;).

Next, this substrate was fixed to a substrate folder of a vacuum evaporator, and N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (? -NPD) was added to the crucible baked without glazing 200 mg of tris (8-hydroxyquinoline) aluminum (Alq ₃ ) was added to the crucible baked without applying the other glaze on the other side, and the pressure in the vacuum chamber was reduced to 1 x 10 ^-4 Pa. Thereafter, the crucible containing α-NPD was heated to deposit α-NPD on the substrate at a deposition rate of 15 Å / s to form a hole transporting layer having a film thickness of 600 Å. Subsequently, the crucible containing Alq ₃ was heated to form an organic light emitting material layer having a film thickness of 600 ANGSTROM at a deposition rate of 15 ANGSTROM / s. Thereafter, the substrate on which the hole transporting layer and the organic light emitting material layer were formed was transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride was charged in a resistive heating boat made of tungsten in the vacuum vapor deposition apparatus, and 1.0 g of an aluminum wire was placed in another boat made of tungsten. Thereafter, the inside of the evaporator of the vacuum evaporation apparatus was reduced to 2 x 10 &lt; ^-4 &gt; Pa and lithium fluoride was deposited at a deposition rate of 0.2 A / s at a deposition rate of 5 A and then aluminum at a deposition rate of 20 A / s. The inside of the evaporator was returned to atmospheric pressure by nitrogen, and a substrate on which a laminate having an organic light emitting material layer of 10 mm x 10 mm was placed was taken out.

(Coating with the inorganic material film A)

A mask having an opening of 13 mm x 3 mm was provided on the substrate on which the obtained laminate was placed so as to cover the entire laminate, and the inorganic material film A was formed by the plasma CVD method.

In the plasma CVD method, SiH ₄ gas and nitrogen gas were used as source gases, and the flow rates were set to 10 sccm for SiH ₄ gas and 200 sccm for nitrogen gas, RF power was set to 10 W (frequency: 2.45 GHz) 100 deg. C, and the chamber pressure was set to 0.9 Torr.

The thickness of the formed inorganic material film A was about 1 mu m.

(Formation of resin protective film)

With respect to the substrate thus obtained, the sealing agents for electronic devices obtained in Examples and Comparative Examples were pattern-coated on a substrate using an inkjet ejection apparatus ("NanoPrinter 300" manufactured by Microdeta).

Thereafter, the sealant for each electronic device obtained in Examples 1 to 11, 13 to 21 and Comparative Examples 1, 2, and 4 was irradiated with ultraviolet light having a wavelength of 365 nm at 3000 mJ / The sealing agent for electronic devices obtained in Example 12 and Comparative Example 3 was heated at 100 占 폚 for 30 minutes to cure the sealing agent for electronic devices to form a resin protective film.

(Coating with the inorganic material film B)

After forming the resin protective film, a mask having an opening of 12 mm x 12 mm was provided so as to cover the entire resin protective film, and an inorganic material film B was formed by the plasma CVD method to obtain an organic EL display element.

The plasma CVD method was carried out under the same conditions as the above (coating with the inorganic material film A).

The thickness of the formed inorganic material film B was about 1 mu m.

(Light emission state of the organic EL display element)

The obtained organic EL display device was exposed for 100 hours under an environment of a temperature of 85 캜 and a humidity of 85%, and then a voltage of 3 V was applied to visually observe the light emitting state (presence or absence of dark spots and pixel periphery extinction) Respectively. Quot ;, &quot; DELTA &quot; when a dark spot or peripheral extinction was recognized, and &quot; X &quot; when a non-light-emitting portion was remarkably enlarged was taken as &quot; And the display performance was evaluated.

According to the present invention, it is possible to provide an electronic device encapsulant which can be easily applied by an ink-jet method and which can reduce device damage. Further, according to the present invention, it is possible to provide a method of manufacturing an electronic device using the sealing agent for electronic devices.

Claims (7)

A sealing agent for an electronic device, which contains a curable resin, a polymerization initiator and / or a thermosetting agent and is used for coating by an inkjet method,
Wherein the curable resin contains a silicone compound represented by the following formula (1).
[Chemical Formula 1]

(1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, X ¹ and X ² each independently represent an alkyl group having 1 to 10 carbon atoms, , (2-3) or (2-4), and X ³ represents a group represented by the following formulas (2-1), (2-2), (2-3) or (2-4) . m is an integer of 0 to 100, and n is an integer of 0 to 100. Provided that when n is 0, at least one of X ¹ and X ² represents a group represented by the following formula (2-1), (2-2), (2-3) or (2-4).
(2)

In the formulas (2-1) to (2-4), R ² represents a bond or an alkylene group having 1 to 6 carbon atoms, and in the formula (2-3), R ³ represents hydrogen or an alkylene group having 1 to 6 carbon atoms R ⁴ represents a bond or methylene group, and in the formula (2-4), R ⁵ represents hydrogen or a methyl group. The method according to claim 1,
The silicone compound represented by the formula (1) is a compound in which at least one of X ¹ , X ² and X ³ in the formula (1) is a group represented by the formula (2-1), (2-2) or (2-3) &Lt; / RTI &gt; 3. The method according to claim 1 or 2,
The silicone compound represented by the formula (1) is at least one selected from the group consisting of a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3) Wherein the sealant is one kind of an inorganic filler.
(3)

In the formula (3-1), o is an integer of 1 to 10, p in the formula (3-2) is an integer of 1 to 10, and q in the formula (3-3) Lt; / RTI &gt; The method according to claim 1, 2, or 3,
The curable resin may contain, in addition to the silicone compound represented by formula (1), an epoxy compound having no structure represented by formula (1), an oxetane compound having no structure represented by formula (1) , A (meth) acrylic compound having no structure represented by the following formula (1), and a vinyl ether compound. 5. The method of claim 4,
As the other curable resin, an alicyclic epoxy resin, 3- (allyloxy) oxetane, 3-ethyl-3 - ((2-ethylhexyloxy) methyl) oxetane, (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane. The method of claim 1, 2, 3, 4, or 5,
Wherein the viscosity measured at 25 占 폚 and 100 rpm is from 5 to 200 mPa 占 퐏 using an E-type viscometer. A step of applying the sealing agent for an electronic device according to any one of claims 1, 2, 3, 4, 5, and 6 to at least one of the two substrates by an inkjet method;
A step of curing the applied sealing agent for electronic devices by light irradiation and / or heating,
And joining the two sheets of the base material together.