JPWO2016167347A1 - Sealant for electronic device for inkjet coating and method for producing electronic device - Google Patents

Abstract

An object of this invention is to provide the sealing agent for electronic devices which can be apply | coated easily by the inkjet method and can reduce the damage of an inkjet apparatus. Another object of the present invention is to provide an electronic device manufacturing method using the electronic device sealant. The present invention is an electronic device sealant that 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 has the following formula (1): The sealing agent for electronic devices containing the silicone compound represented by this. In formula (1), R1 represents a C1-C10 alkyl group, X1 and X2 are each independently a C1-C10 alkyl group, or following formula (2-1), (2 -2), (2-3), or a group represented by (2-4), and X3 represents the following formula (2-1), (2-2), (2-3), or The group represented by (2-4) is represented. m is an integer of 0 to 100, and n is an integer of 0 to 100. However, when n is 0, at least one of X1 and X2 is a group represented by the following formula (2-1), (2-2), (2-3), or (2-4). To express. In formulas (2-1) to (2-4), R2 represents a bond or an alkylene group having 1 to 6 carbon atoms, and in formula (2-3), R3 is hydrogen or 1 to 6 carbon atoms. Represents an alkyl group, R4 represents a bond or a methylene group, and in formula (2-4), R5 represents hydrogen or a methyl group; [Chemical 1] [Chemical 2]

Description

The present invention relates to a sealant for electronic devices that can be easily applied by an ink jet method and can reduce damage to an ink jet apparatus. Moreover, this invention relates to the manufacturing method of an electronic device using this sealing agent for electronic devices.

In recent years, research on electronic devices using organic thin film elements such as organic electroluminescence (hereinafter also referred to as organic EL) display 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.

An organic EL display element has a laminated 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 positive from the other electrode. When holes are injected, electrons and holes are combined in the organic light emitting material layer to emit light. Thus, since the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.

Organic thin-film solar cell elements are superior to solar cells using inorganic semiconductors in terms of cost, large area, ease of manufacturing processes, and the like, and various configurations have been proposed. Specifically, for example, Non-Patent Document 1 discloses 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 indispensable to seal the organic thin film element and shield it from moisture and oxygen in the atmosphere.
As a method for sealing an organic thin film element, conventionally, a method of sealing with a sealing can provided with a water-absorbing agent is generally used. However, in the method of sealing with a sealing can, it is difficult to reduce the thickness of the electronic device. Therefore, development of a method for sealing an organic thin film element that does not use a sealing can is being promoted.

Patent Document 1 discloses a method of sealing an organic light emitting material layer and an electrode of an organic EL display element with a laminated film of a silicon nitride film and a resin film formed by a CVD method. 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 disclosed in Patent Document 1, the organic thin film element is formed when the silicon nitride film is formed due to unevenness on the surface of the organic thin film element, adhesion of foreign matters, generation of cracks due to internal stress, or the like. May not be completely covered. If the coating with the silicon nitride film is incomplete, moisture will enter the organic layer through the silicon nitride film.
As a method for preventing moisture from entering the organic layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film, and Patent Document 3 and Patent Document 4 disclose. A method of forming a resin film on an inorganic material film is disclosed.

As a method for forming a resin film, there is a method in which a liquid curable resin composition is applied on a substrate using an inkjet method, and then the curable resin composition is cured. If such a coating method by the ink jet method is used, a resin film can be uniformly formed at high speed. When applying the sealing agent for electronic devices which consists of curable resin composition to a base material by the inkjet method, in order to discharge stably from a nozzle, it is necessary to make the viscosity of a sealing agent low viscosity. As a method of making the sealing agent for electronic devices suitable for the ink jet method, it is conceivable to use an organic solvent in the sealing agent for electronic devices or to use a low molecular weight curable resin. However, the resin film manufactured using an organic solvent has problems such as deterioration of the organic light emitting material layer due to the remaining organic solvent and generation of outgas due to plasma. A curable resin having a low molecular weight is used. In such a case, there has been a problem of damaging the apparatus such as swelling of an adhesive or a rubber material used for a head portion of the ink jet apparatus.

JP 2000-223264 A JP 2005-522891 A JP 2001-307873 A JP 2008-149710 A

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

An object of this invention is to provide the sealing agent for electronic devices which can be apply | coated easily by the inkjet method and can reduce the damage of an inkjet apparatus. Another object of the present invention is to provide an electronic device manufacturing method using the electronic device sealant.

The present invention is an electronic device sealant that 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 is represented by the following formula (1). The sealing agent for electronic devices containing the silicone compound represented by this.

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

In formulas (2-1) to (2-4), R ² represents a bond or an alkylene group having 1 to 6 carbon atoms, and in formula (2-3), R ³ represents hydrogen or 1 to carbon atoms. 6 represents an alkyl group, R ⁴ represents a bond or a methylene group, and in formula (2-4), R ⁵ represents hydrogen or a methyl group.
The present invention is described in detail below.

The present inventors have found that a silicone compound having a specific structure is difficult to swell rubber materials and adhesives, and because the intermolecular force is weak, the viscosity does not become too high even if the molecular weight is large to some extent. It was. Therefore, the present inventors can encapsulate the silicone compound having the specific structure as a curable resin so that it can be easily applied by an ink jet method and can reduce damage to an ink jet apparatus. The present inventors have found that an agent can be obtained and have completed the present invention.
Moreover, since the silicone compound which has this specific structure has low surface tension, the sealing agent for electronic devices obtained is excellent in wet-spreading property, and can be easily thinned by an inkjet method.

The sealing agent for electronic devices of this invention contains curable resin.
The curable resin contains a silicone compound represented by the above formula (1). By containing the silicone compound represented by the above formula (1), the encapsulant for electronic devices of the present invention has a viscosity suitable for application by an ink jet method and can reduce apparatus damage. .

In the above formula (1), the preferable lower limit of m is 1, and the preferable upper limit is 10. When m is 1 or more, the effect of suppressing the swelling of the rubber material and the adhesive is excellent. When m is 10 or less, the ink jet coating property and the low outgassing property are excellent, and the cured product has a more suitable hardness. A 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 ink jet coating property and the low outgassing property are excellent, and the cured product has a more suitable 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 represented by the formula (2-1), (2-2), or It is preferable that it is a compound which is group represented by (2-3), the compound represented by the following formula (3-1), the compound represented by the following formula (3-2), and the following formula More preferably, it is at least one selected from the group consisting of compounds represented by (3-3).

In formula (3-1), o is an integer of 1 to 10, in formula (3-2), p is an integer of 1 to 10, and in formula (3-3), q is 1 It is an integer of -10.
From the viewpoints of anti-swelling properties such as rubber materials, inkjet coating properties, low outgassing properties, and flexibility (hardness) of the cured product, o in formula (3-1) and p in formula (3-2) And q in Formula (3-3) are each preferably an integer of 1 to 6, respectively.

In addition to the silicone compound represented by the above formula (1), the curable resin may contain other curable resins for the purpose of improving adhesiveness.
Examples of the other curable resin include an epoxy compound having no structure represented by the above formula (1) (hereinafter, also referred to as “other epoxy compound”) and a structure represented by the above formula (1). Oxetane compounds (hereinafter also referred to as “other oxetane compounds”), (meth) acrylic compounds not having the structure represented by the above formula (1) (hereinafter also referred to as “other (meth) acrylic compounds”) And at least one selected from the group consisting of vinyl ether compounds.
In the present specification, “(meth) acryl” means acryl or methacryl, “(meth) acryl compound” means a compound having a (meth) acryloyl group, and “(meth) acryloyl”. "Means acryloyl or methacryloyl.

Examples of the other epoxy compounds include bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol O type epoxy resin, and 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 novolac type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, bif Examples thereof include an enyl novolac type epoxy resin, a naphthalene phenol novolak type epoxy resin, a glycidyl amine type epoxy resin, an alkyl polyol type epoxy resin, a rubber-modified epoxy resin, and a glycidyl ester compound. Of these, alicyclic epoxy resins are preferred.
Examples of commercially available alicyclic epoxy resins include Celoxide 2000, Celoxide 2021P, Celoxide 2081, Celoxide 3000, Celoxide 8000, Cyclomer M-100 (all manufactured by Daicel Corporation), and Sun Socizer EPS ( New Nippon Rika Kogyo Co., Ltd.).
Among the alicyclic epoxy resins, those having no ether bond and ester bond other than those contained in the epoxy group are preferable from the viewpoint of suppressing the generation of outgas. Examples of commercially available alicyclic epoxy resins having no ether bond and no ester bond other than those contained in the epoxy group include Celoxide 2000, Celoxide 3000, and Celoxide 8000.
These other epoxy compounds may be used alone or in combination of two or more.

Examples of the other oxetane compounds include 3- (allyloxy) oxetane, phenoxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-((2 -Ethylhexyloxy) methyl) oxetane, 3-ethyl-3-((3- (triethoxysilyl) propoxy) methyl) oxetane, 3-ethyl-3 (((3-ethyloxetane-3-yl) methoxy) methyl) Examples include oxetane, oxetanylsilsesquioxane, phenol novolac oxetane, 1,4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene.
These other oxetane compounds may be used alone or in combination of two or more.

Examples of the other (meth) acrylic compounds include glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and dicyclopentenyl (meth) acrylate. , Dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, trimethylolpropane tri (meth) arylate, 1,12-dodecanediol di (meth) acrylate, lauryl (meth) ) Acrylate and the like.
These other (meth) acrylic compounds may be used alone or in combination of two or more.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate.

Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexane dimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol. Examples thereof include divinyl ether and tripropylene glycol divinyl ether.
These vinyl ether compounds may be used alone or in combination of two or more.

Among these, since the viscosity is low and the reactivity is high, the above other curable resins include alicyclic epoxy resins, 3- (allyloxy) oxetane, 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane. And at least one selected from the group consisting of 3-ethyl-3 (((3-ethyloxetane-3-yl) methoxy) methyl) oxetane.

When the other curable resin is contained, the preferable lower limit of the content of the silicone compound represented by the formula (1) is 5 parts by weight with respect to 100 parts by weight of the entire curable resin. When the content of the silicone compound represented by the above formula (1) is 5 parts by weight or more, both the effect of excellent applicability by the ink jet method and the effect of reducing damage of the ink jet device are obtained. . The minimum with more preferable content of the silicone compound represented by the said Formula (1) is 10 weight part.
The other curable resin may not be contained, but when the other curable resin is contained, the content of the silicone compound represented by the formula (1) is 100% of the entire curable resin. A preferable upper limit is 90 parts by weight with respect to parts by weight. 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 exhibit more effects such as improving the adhesiveness.

The encapsulant for electronic devices of the present invention contains a polymerization initiator and / or a thermosetting agent.
As the polymerization initiator, a cationic photopolymerization initiator, a thermal cationic polymerization initiator, a radical photopolymerization initiator, and a thermal radical polymerization initiator are preferably used.

The photocationic 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 generating type or a nonionic photoacid generating type. May be.

Examples of the ionic photoacid-generating photocationic polymerization initiator include an anionic moiety of BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or (BX ₄ ) ⁻ (wherein X is at least two or more. An aromatic sulfonium salt, an aromatic iodonium salt, an aromatic diazonium salt, an aromatic ammonium salt, (2,4-cyclopentadiene-1) -Yl) ((1-methylethyl) benzene) -Fe salt and the like.

Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (diphenylsulfonio) phenyl) sulfide bishexafluoroantimonate, and bis (4- ( Diphenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- ( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) Phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (di ( 4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluorophosphate, bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bishexafluoroantimonate, Bis (4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide bistetrafluoroborate, bis (4- (di ( - (2-hydroxyethoxy)) phenylsulfonio) phenyl) sulfide tetrakis (pentafluorophenyl) borate, tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like.

Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (Dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexa Fluorophosphate, 4-methylphenyl-4- (1-methylethyl) Such as phenyl iodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Can be mentioned.

Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.

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

Examples of the (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene. ) -Fe (II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -Yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrakis (penta Fluorophenyl) borate and the like.

Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, and the like.

Examples of commercially available photocationic polymerization initiators include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide), SP-150, SP-170 (all ADEKA), FC-508, FC-512 (all from 3M), IRGACURE261, IRGACURE290 (BASF), PI2074 (Rhodia) and the like.

As the thermal cationic polymerization initiator, the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or (BX ₄ ) ⁻ (where X is substituted with at least two fluorine or trifluoromethyl groups. A sulfonium salt, a phosphonium salt, an ammonium salt, and the like. Of these, sulfonium salts and ammonium salts are preferable.

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

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, and dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl). Borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyl Dibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium Safluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3,4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N , N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl -N-benzylpyridinium trifluoromethanesulfonic acid etc. are mentioned.

Examples of commercially available thermal cationic polymerization initiators include, for example, Sun-Aid SI-60, Sun-Aid SI-80, Sun-Aid SI-B3, Sun-Aid SI-B3A, and Sun-Aid SI-B4 (all Sanshin Chemical Industries, Ltd. Product), CXC1612, CXC1821 (all manufactured by King Industries) and the like.

Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone compounds, and the like.

Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucin TPO (all manufactured by BASF Methyl, Examples include benzoin ethyl ether and benzoin isopropyl ether (both manufactured by Tokyo Chemical Industry Co., Ltd.).

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile) and azobisisobutyronitrile.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

Examples of commercially available thermal radical polymerization initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all manufactured by Wako Pure Chemical Industries, Ltd.). ) And the like.

The content of the polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the polymerization initiator is 0.01 parts by weight or more, the obtained encapsulant 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 sealant for electronic devices does not become too fast, and the workability becomes excellent, and the cured product becomes more uniform. be able to. The minimum with more preferable content of the said polymerization initiator is 0.05 weight part, and a more preferable upper limit is 5 weight part.

Examples of the thermosetting agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamides, guanidine derivatives, modified aliphatic polyamines, addition products 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, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of the imidazole derivatives include 1-cyanoethyl-2-phenylimidazole, N- (2- (2-methyl-1-imidazolyl) ethyl) urea, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2- Examples include phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride, ethylene glycol bis (anhydrotrimellitate), and the like.
These thermosetting agents may be used independently and 2 or more types may be used in combination.

Examples of commercially available thermosetting agents include SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like. It is done.

The content of the thermosetting agent is preferably 0.5 parts by weight and preferably 30 parts by weight with respect to 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 electronic device sealing agent is more excellent in thermosetting. When the content of the thermosetting agent is 30 parts by weight or less, the obtained sealing agent for electronic devices is excellent in storage stability, and the cured product is excellent in moisture resistance. The minimum with more preferable content of the said thermosetting agent is 1 weight part, and a more preferable upper limit is 15 weight part.

The encapsulant for electronic devices of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the electronic device sealing agent 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, o- Examples include methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like.

The content of the sensitizer is preferably 0.01 parts by weight and preferably 3 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption. The minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.

It is preferable that the sealing agent for electronic devices of this invention contains a silane coupling agent further. The said silane coupling agent has a role which improves the adhesiveness of the sealing agent for electronic devices of this invention, a board | substrate, etc.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane. These silane compounds may be used independently and 2 or more types may be used together.

The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness of the obtained sealant for electronic devices is suppressed while suppressing bleeding out due to the excess silane coupling agent. . The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 5 weight part.

The encapsulant for electronic devices of the present invention may contain a curing retarder. By containing the said hardening retarder, the pot life of the sealing agent for electronic devices obtained can be lengthened.

As said hardening retarder, a polyether compound etc. are mentioned, for example.
Examples of the polyether compound include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and a crown ether compound. Of these, crown ether compounds are preferred.

The content of the curing retarder is preferably 0.05 parts by weight and preferably 5.0 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the curing retarder is within this range, the retardation effect can be further exhibited while suppressing the generation of outgas when the obtained sealing agent for electronic devices is cured. The minimum with more preferable content of the said retarder is 0.1 weight part, and a more preferable upper limit is 3.0 weight part.

The encapsulant for electronic devices of the present invention may further contain a surface modifier as long as the object of the present invention is not impaired. By containing the surface modifier, the flatness of the coating film can be imparted to the electronic device sealant of the present invention.
Examples of the surface modifier include surfactants and leveling agents.

Examples of the surfactant and the leveling agent include silicones, acrylics, and fluorines.
Examples of commercially available surfactants and leveling agents include BYK-340, BYK-345 (all manufactured by Big Chemie Japan), Surflon S-611 (manufactured by AGC Seimi Chemical), and the like. Can be mentioned.

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

Examples of the compound that reacts with the generated acid include substances that neutralize the acid, such as carbonates or bicarbonates of alkali metals or alkaline earth metals. Specifically, for example, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like are used.

As the ion exchange resin, any of a cation exchange type, an anion exchange type, and a both ion exchange type can be used, and in particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ions. Is preferred.

Moreover, the sealing agent for electronic devices of this invention may contain well-known various additives, such as a reinforcing agent, a softening agent, a plasticizer, a viscosity modifier, a ultraviolet absorber, antioxidant, as needed. Good.

As a method for producing the sealing agent for electronic devices of the present invention, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin and a polymerization Examples thereof include a method of mixing an initiator and / or a thermosetting agent and an additive such as a silane coupling agent added as necessary.

The electronic device sealant of the present invention has a preferred lower limit of 5 mPa · s and a preferred upper limit of 200 mPa · s, measured using an E-type viscometer at 25 ° C. and 100 rpm. When the viscosity is within this range, the sealing agent for electronic devices of the present invention is more excellent in ink jet coating property and shape retention after coating. The minimum with a more preferable viscosity of the said sealing agent for electronic devices is 10 mPa * s, and a more preferable upper limit is 80 mPa * s.
In addition, the sealing agent for electronic devices of this invention may be heated at the time of application | coating by inkjet, and it may apply | coat by reducing a viscosity.

A preferable lower limit of the total light transmittance of light at a wavelength of 380 to 800 nm of the cured product of the encapsulant for electronic devices of the present invention is 80%. When the total light transmittance is 80% or more, it can be suitably used for an organic EL display element or the like. A more preferable lower limit of the total light transmittance is 85%.
The total light transmittance can be measured using a spectrometer such as AUTOMATIC HAZE MATER MODEL TC = III DPK (manufactured by Tokyo Denshoku Co., Ltd.).

The encapsulant for electronic devices of the present invention preferably has a transmittance at 400 nm of 85% or more at an optical path length of 20 μm after the cured product is irradiated with ultraviolet rays for 100 hours. When the transmittance after irradiating the ultraviolet rays for 100 hours is 85% or more, the transparency is excellent, the loss of light emission is small, and the color reproducibility is excellent. A more preferable lower limit of the transmittance after irradiation with the ultraviolet rays for 100 hours is 90%, and a more preferable lower limit is 95%.
As the light source for irradiating the ultraviolet rays, a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.

The electronic device sealant of the present invention has a moisture permeability of 100 g / m ² at a thickness of 100 μm as measured by exposing a cured product to an environment of 85 ° C. and 85% RH for 24 hours in accordance with JIS Z 0208. The following is preferable. When the moisture permeability is 100 g / m ² or less, for example, when used in the manufacture of an organic EL display element as an electronic device, the effect of suppressing the generation of dark spots due to moisture reaching the organic light emitting material layer It will be excellent.

Furthermore, the sealing agent for electronic devices of the present invention preferably has a moisture content of less than 0.5% when the cured product is exposed to an environment of 85 ° C. and 85% RH for 24 hours. When the moisture content of the cured product is less than 0.5%, for example, when used for manufacturing an organic EL display element as an electronic device, the effect of suppressing deterioration of the organic light-emitting material layer due to moisture in the cured product It will be excellent. A more preferable upper limit of the moisture content of the cured product is 0.3%.
Examples of the method for measuring the moisture content include a method of obtaining by a Karl Fischer method in accordance with JIS K 7251, and a method of obtaining a weight increment after water absorption in accordance with JIS K 7209-2.

The sealing agent for electronic devices of this invention is used for application | coating by the inkjet method.
A step of applying the electronic device sealant of the present invention to at least one of the two substrates by an inkjet method, a step of curing the applied electronic device sealant by light irradiation and / or heating, The manufacturing method of an electronic device which has the process of bonding together the said 2 base material is also one of this invention.

In the step of applying the electronic device sealant of the present invention to at least one of the two substrates, the electronic device sealant of the present invention may be applied to the entire surface of the substrate. You may apply to a part. For example, when manufacturing an organic EL display element as an electronic device, the shape of the sealing part of the sealing agent for electronic devices of the present invention formed by coating is to protect the laminate having an organic light emitting material layer from the outside air. The shape is not particularly limited as long as it can be formed, and may be a shape that completely covers the laminate, or may form a closed pattern on the periphery of the laminate, or the periphery of the laminate A pattern having a shape in which a part of the openings is provided may be formed.

When an organic EL display element is manufactured as the electronic device, the base material (hereinafter also referred to as one base material) to which the electronic device sealing agent of the present invention is applied is formed of a laminate having an organic light emitting material layer. The base material which this may be may be sufficient, and the base material in which this laminated body is not formed may be sufficient.
When the one base material is a base material on which the laminate is not formed, the one base material of the present invention can be protected from the outside air when the other base material is bonded. What is necessary is just to apply | coat the sealing agent for electronic devices. That is, apply the entire surface to the location of the laminate when the other substrate is bonded, or the location of the laminate is complete when the other substrate is bonded. The sealing agent portion having a closed pattern may be formed in a shape that fits in the shape.

Moreover, the said laminated body may be coat | covered with the inorganic material film | membrane.
As the inorganic material forming the inorganic material layer can be a conventionally known, for example, silicon nitride (SiN _x), silicon oxide (SiO _x), and the like. The inorganic material film may be a single layer or may be a laminate of a plurality of types of layers. Moreover, you may coat | cover the said laminated body by repeating alternately the said inorganic material film | membrane and the resin film which consists of the sealing agent for electronic devices of this invention.

The step of curing the electronic device sealant by light irradiation and / or heating may be performed before the step of bonding the two substrates, or the step of bonding the two substrates. It may be done later.
When the step of curing the electronic device sealant by light irradiation and / or heating is performed before the step of laminating the two substrates, the electronic device sealant of the present invention comprises light irradiation and It is preferable that the pot life is 1 minute or more from the heating until the curing reaction proceeds and adhesion cannot be performed. When the pot life is 1 minute or longer, the progress of curing before bonding the two substrates can be suppressed, and the adhesive strength after bonding can be further increased.

When hardening the said sealing agent for electronic devices by light irradiation, the sealing agent for electronic devices of this invention is suitably by irradiating the light of the wavelength of 300 nm-400 nm and the integrated light quantity of 300-3000 mJ / cm < ² >. It can be cured.

Examples of the light source for irradiating the electronic device sealant of the present invention with light include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, and a microwave excitation mercury lamp. , Metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, electron beam irradiation devices, and the like. These light sources may be used independently and 2 or more types may be used together.
These light sources are appropriately selected according to the absorption wavelength of the photocationic polymerization initiator or the photoradical polymerization initiator.

Examples of the light irradiation means for the electronic device sealant of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc. Irradiation means may be used.

When curing the electronic device sealant by heating, for example, from the viewpoint of sufficiently curing while reducing damage to the laminate having an organic light emitting material layer when producing an organic EL display element as an electronic device, The heating temperature is preferably 50 to 120 ° C.

In the step of bonding the two substrates, the method of bonding the two substrates is not particularly limited, but it is preferable to bond the substrates in a reduced pressure atmosphere.
The preferable lower limit of the degree of vacuum in the reduced-pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa. When the degree of vacuum in the reduced-pressure atmosphere is within this range, it is not necessary to spend a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump. Bubbles can be more efficiently removed from the encapsulant for electronic devices of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for electronic devices which can be apply | coated easily by the inkjet method and can reduce an apparatus damage can be provided. Moreover, according to this invention, the manufacturing method of an electronic device using this sealing agent for electronic devices can be provided.

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

(Production Example 1)
20 mL of toluene was added to a four-necked flask equipped with a dropping funnel, a stirrer, a thermometer, and a septum. Further, a mixed solution of 45.7 g (0.4 mol) of 3- (allyloxy) oxetane and 76 g (0.15 mol) of hydrogen-terminated tridimethylsiloxane (Gelest, “DMS-03H”) was placed in the dropping funnel, From the dropping funnel, 3 mL of the mixed solution was dropped into toluene in the flask, and the temperature in the flask was raised to 80 ° C.
Then, benzonitrile solution of chloroplatinic acid hexahydrate as catalyst through the septum using a syringe _{(H 2 PtCl 6 · 6H 2} O) ( chloroplatinic acid concentration: 0.1 wt%) added to 800μL to the flask did. Thereafter, a mixed solution of 3- (allyloxy) oxetane and hydrogen-terminated tridimethylsiloxane was further dropped from the dropping funnel over 40 minutes. After completion of the dropwise addition, the inside of the flask was heated at 80 ° C. to 85 ° C. for 2 hours to react 3- (allyloxy) oxetane with hydrogen-terminated tridimethylsiloxane. After completion of the reaction, volatile compounds such as toluene were removed by distillation under reduced pressure. In this way, a compound in which q in the above formula (3-3) having a purity of 95% was 2 was obtained.

Example 1
As a silicone compound represented by the above formula (1), 100 parts by weight of a compound (“X-22-163” manufactured by Shin-Etsu Chemical Co., Ltd.) in which o in the above formula (3-1) is 1, a photocation As a polymerization initiator, 1 part by weight of tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate (manufactured by BASF, “IRGACURE290”) is mixed with a homodisper type stirring mixer (manufactured by PRIMIX Corporation). , “Homodisper L-type”), and uniformly stirred and mixed at a stirring speed of 3000 rpm to prepare an electronic device sealant.

(Example 2)
In the above formula (3-1), the compounding amount of the compound in which o is 1 (“X-22-163” manufactured by Shin-Etsu Chemical Co., Ltd.) is changed to 50 parts by weight. A sealing agent for electronic devices was produced in the same manner as in Example 1 except that 50 parts by weight of 4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”) was blended.

(Example 3)
As another curable resin, 1,2-epoxy-4-vinylcyclohexane (Daicel) was used instead of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”). A sealing agent for electronic devices was produced in the same manner as in Example 2 except that 50 parts by weight of “Celoxide 2000” manufactured by the company was blended.

Example 4
As another curable resin, in place of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”), 3-ethyl-3 (((3-ethyloxetane A sealing agent for electronic devices was produced in the same manner as in Example 2 except that 50 parts by weight of -3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd., “Aron oxetane OXT-221”) was blended. .

(Example 5)
As another curable resin, instead of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”), 3-allyloxyoxetane (manufactured by Yokkaichi Chemical Co., Ltd., “ AL-OX ") was prepared in the same manner as in Example 2 except that 50 parts by weight was blended.

(Example 6)
As another curable resin, instead of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel Corporation, “Celoxide 8000”), cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide Corporation, “ CHDVE ") A sealing agent for electronic devices was produced in the same manner as in Example 2 except that 50 parts by weight was blended.

(Example 7)
As a silicone compound represented by the above formula (1), instead of 50 parts by weight of a compound (“X-22-163” manufactured by Shin-Etsu Chemical Co., Ltd.) in which o in the above formula (3-1) is 1, In the above formula (1), R ¹ is a methyl group, X ¹ and X ² are methyl groups, X ³ is a group represented by the above formula (2-1) (R ² is an ethylene group), m is 5, n Was prepared in the same manner as in Example 2 except that 50 parts by weight of a compound having a compound No. 3 (manufactured by Shin-Etsu Chemical Co., Ltd., “X-22-343”) was blended.

(Example 8)
As another curable resin, in place of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”), 3-ethyl-3 (((3-ethyloxetane A sealing agent for electronic devices was produced in the same manner as in Example 7 except that 50 parts by weight of -3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd., “Aron oxetane OXT-221”) was blended. .

Example 9
As a silicone compound represented by the above formula (1), instead of 100 parts by weight of a compound (“X-22-163” manufactured by Shin-Etsu Chemical Co., Ltd.) in which o in the above formula (3-1) is 1, A sealing agent for electronic devices was prepared in the same manner as in Example 1 except that 100 parts by weight of the compound (“DMS-EC13”, manufactured by Gelest Co.) in which p in the formula (3-2) was 9 was blended. Produced.

(Example 10)
In the above formula (3-2), the compounding amount of the compound in which p is 9 (manufactured by Gelest, “DMS-EC13”) was changed to 50 parts by weight, and as other curable resins, 3, 4, 3 ′ , 4′-diepoxy bicyclohexane (manufactured by Daicel Corporation, “Celoxide 8000”) was mixed in the same manner as in Example 9 to prepare an electronic device sealant.

(Example 11)
As another curable resin, in place of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”), 3-ethyl-3 (((3-ethyloxetane A sealing agent for electronic devices was produced in the same manner as in Example 10 except that 50 parts by weight of -3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd., “Aron oxetane OXT-221”) was blended. .

(Example 12)
Instead of the photocationic polymerization initiator, 1 part by weight of dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate (manufactured by King Industries, "CXC-1612") was added as a thermal cationic polymerization initiator. Produced an encapsulant for electronic devices in the same manner as in Example 11.

(Example 13)
As a silicone compound represented by the above formula (1), instead of 50 parts by weight of a compound (“X-22-163” manufactured by Shin-Etsu Chemical Co., Ltd.) in which o in the above formula (3-1) is 1, An encapsulant for electronic devices was produced in the same manner as in Example 4 except that 50 parts by weight of the compound having q of 2 in the above formula (3-3) obtained in Production Example 1 was blended.

(Example 14)
As a silicone compound represented by the above formula (1), R ¹ in the above formula (1) is a methyl group, X ¹ and X ² are groups represented by the above formula (2-4) (R ² is n- 50 parts by weight of a propylene group, R ⁵ is a methyl group, m is 1, and n is 0 (Shin-Etsu Chemical Co., Ltd., “X-22-164”) and other curable resins are 1,6 -50 parts by weight of hexanediol diacrylate and 2 parts by weight of diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide (manufactured by BASF, "Lucirin TPO") as a photo radical polymerization initiator Using a stirrer / mixer ("Homodisper L type", manufactured by Primix Co., Ltd.), the mixture was uniformly stirred and mixed at a stirring speed of 3000 rpm to produce an electronic device sealant.

(Example 15)
As a silicone compound represented by the above formula (1), 100 parts by weight of a compound in which p in the above formula (3-2) is 1 (manufactured by Gelest, “SIB1092.0”), and a photocationic polymerization initiator , 1 part by weight of tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate (manufactured by BASF, “IRGACURE290”) is mixed with a homodisper type stirring mixer (manufactured by Primics, “Homodisper L type "), and uniformly stirred and mixed at a stirring speed of 3000 rpm to produce an electronic device sealant.

(Example 16)
In the above formula (3-2), the compounding amount of the compound wherein p is 1 (manufactured by Gelest, “SIB1092.0”) is changed to 50 parts by weight, and other curable resins are 3, 4, 3 ′ , 4′-diepoxy bicyclohexane (manufactured by Daicel, “Celoxide 8000”) was mixed in the same manner as in Example 15 except that 50 parts by weight of a sealing agent for electronic devices was prepared.

(Example 17)
In the above formula (3-2), the compounding amount of the compound wherein p is 1 (manufactured by Gelest, “SIB1092.0”) was changed to 40 parts by weight, and 3,4,3 ′, 4′-diepoxybi The amount of cyclohexane (manufactured by Daicel, “Celoxide 8000”) was changed to 30 parts by weight, and as another curable resin, 3-allyloxyoxetane (manufactured by Yokkaichi Gosei Co., Ltd., “AL-OX”) 20 wt. An electronic device sealant was produced in the same manner as in Example 16 except that the parts were blended.

(Example 18)
As another curable resin, 1,2-epoxy-4-vinylcyclohexane (Daicel) was used instead of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”). A sealing agent for electronic devices was produced in the same manner as in Example 16 except that 50 parts by weight of “Celoxide 2000” manufactured by the company was blended.

(Example 19)
As another curable resin, in place of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”), 3-ethyl-3 (((3-ethyloxetane A sealing agent for electronic devices was produced in the same manner as in Example 16 except that 50 parts by weight of -3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd., “Aron oxetane OXT-221”) was blended. .

(Example 20)
As another curable resin, instead of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel, “Celoxide 8000”), 3-allyloxyoxetane (manufactured by Yokkaichi Chemical Co., Ltd., “ AL-OX ") was prepared in the same manner as in Example 16 except that 50 parts by weight was blended to prepare an electronic device sealant.

(Example 21)
As another curable resin, instead of 50 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel Corporation, “Celoxide 8000”), cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide Corporation, “ CHDVE ”) was prepared in the same manner as in Example 16 except that 50 parts by weight was blended to prepare an electronic device sealant.

(Comparative Example 1)
100 parts by weight of 3,4,3 ′, 4′-diepoxybicyclohexane (manufactured by Daicel Corporation, “Celoxide 8000”) is used as the other curable resin without blending the silicone compound represented by the above formula (1). An electronic device sealant was produced in the same manner as in Example 1 except that the above was blended.

(Comparative Example 2)
The silicone compound represented by the above formula (1) is not blended, and as other curable resin, 3-ethyl-3 (((3-ethyloxetane-3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd.) The sealing agent for electronic devices was produced like Example 1 except having mix | blended 100 weight part of "Aron oxetane OXT-221").

(Comparative Example 3)
3-ethyl-3 (((3-ethyloxetane-3-yl) methoxy) methyl) oxetane (manufactured by Toagosei Co., Ltd.), which does not contain the silicone compound represented by the above formula (1), is another curable resin. The sealing agent for electronic devices was produced like Example 12 except having changed the compounding quantity of "Aron oxetane OXT-221") into 100 weight part.

(Comparative Example 4)
The same as in Example 14 except that the silicone compound represented by the above formula (1) was not blended and the blending amount of 1,6-hexanediol diacrylate, which is another curable resin, was changed to 100 parts by weight. Thus, a sealing agent for electronic devices was produced.

<Evaluation>
The following evaluation was performed about each sealing agent for electronic devices obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(viscosity)
About the sealing agent for electronic devices obtained by the Example and the comparative example, the viscosity in the conditions of 25 degreeC and 100 rpm was measured using the E-type viscosity meter (the Toki Sangyo company make, "VISCOMETER TV-22"). did.

(Wet spreadability)
The alkali-free glass obtained by alkali-washing each electronic device sealant obtained in Examples and Comparative Examples with an ink jet discharge device (“NanoPrinter300” manufactured by Microjet Co., Ltd.) with a droplet volume of 80 picoliters. (Asahi Glass Co., Ltd., “AN100”), and after 10 minutes, the diameter of the droplets on the alkali-free glass was measured.

(Adhesiveness)
Each electronic device sealant obtained in the Examples and Comparative Examples was applied to a thickness of 10 μm on alkali-free glass (manufactured by Asahi Glass Co., Ltd., “AN100”) using a spin coater, and then Example 1 ˜11, 13-21, and each sealing agent for electronic devices obtained in Comparative Examples 1, 2, and 4 were irradiated with 3000 mJ / cm ² of ultraviolet light having a wavelength of 365 nm using an LED lamp. 12, About the sealing agent for electronic devices obtained by the comparative example 3, it heated for 30 minutes at 100 degreeC, the sealing agent for electronic devices was hardened, and the resin film was obtained.
The formed resin film was subjected to a cross-cut test with a cut interval of 1 mm in accordance with JIS K 5600-5-6.
When the cross-cut test was performed, the peeling was 5% or less, “◎”, when the peeling was more than 5% and 35% or less, “◯”, and the peeling was more than 35% and 65% or less. The adhesiveness was evaluated as “Δ” for the case of “x” and “x” for the case where the peeling exceeded 65%.

(Swellability of adhesive piece (device damage))
About 0.15 g of an epoxy adhesive (manufactured by Nichiban Co., Ltd., “Araldite AR-S30”) was cured to produce an adhesive piece, and the weight (W ₁ ) was measured. After that, each electronic device sealant obtained in Examples and Comparative Examples was put into a brown screw tube, the prepared adhesive piece was immersed and covered, and allowed to stand at 60 ° C. for 7 days. After removing the piece and wiping the surface with a waste cloth, 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
When the rate of weight change is less than 1%, “◎”, when it is 1% or more and less than 10%, “◯”, when it is 10% or more and less than 20%, “△”, when it is 20% or more The case where there existed was evaluated as "x", and the swelling property (device damage) of the adhesive piece was evaluated.

(Display performance of organic EL display elements)
(Production of a substrate on which a laminate having an organic light emitting material layer is arranged)
A glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) on which an ITO electrode was formed to a thickness of 1000 mm was used as the substrate. The substrate was ultrasonically washed 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 (manufactured by Nippon Laser Electronics Co., Ltd., The last treatment was performed with “NL-UV253”).
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-hydroxyquinoline) aluminum (Alq ₃ ) was put in an unglazed crucible, and the pressure in the vacuum chamber was reduced 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 crucible containing Alq ₃ was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire was added. Then, after reducing the pressure in the vapor deposition unit of the vacuum vapor deposition apparatus to 2 × 10 ⁻⁴ Pa and depositing 5 μm of lithium fluoride at a deposition rate of 0.2 kg / s, deposit 1000 μm of aluminum at a rate of 20 kg / s. did. The inside of the vapor deposition unit was returned to normal pressure with nitrogen, and the substrate on which the laminate having the organic light emitting material layer of 10 mm × 10 mm was arranged was taken out.

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

(Formation of resin protective film)
With respect to the obtained board | substrate, the sealing agent for electronic devices obtained by the Example and the comparative example was pattern-coated on the board | substrate using the inkjet discharge apparatus (The product made by Microjet, "NanoPrinter300").
Then, about each electronic device sealing agent obtained in Examples 1-11, 13-21, and Comparative Examples 1, 2, and 4, irradiation with 3000 mJ / cm < ² > of ultraviolet rays with a wavelength of 365 nm was carried out using the LED lamp. And about the sealing agent for electronic devices obtained in Example 12 and Comparative Example 3, it heated at 100 degreeC for 30 minute (s), the sealing agent for electronic devices was hardened, and the resin protective film was formed.

(Coating with inorganic material film B)
After forming the resin protective film, a mask having an opening of 12 mm × 12 mm is installed so as to cover the entire resin protective film, and the inorganic material film B is formed by plasma CVD to form an organic EL display element. Obtained.
The plasma CVD method was performed under the same conditions as the above “(Coating with inorganic material film A)”.
The formed inorganic material film B had a thickness of about 1 μm.

(Light emission state of organic EL display element)
The obtained organic EL display element is exposed for 100 hours in an environment of a temperature of 85 ° C. and a humidity of 85%, and then a voltage of 3 V is applied, and the light emission state of the organic EL display element (whether dark spots and pixel periphery quenching) Was visually observed. The organic EL display element is indicated as “◯” when there is no dark spot or peripheral extinction, “◯” when the dark spot or peripheral extinction is recognized, and “×” when the non-light emitting part is significantly enlarged. Display performance was evaluated.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for electronic devices which can be apply | coated easily by the inkjet method and can reduce an apparatus damage can be provided. Moreover, according to this invention, the manufacturing method of an electronic device using this sealing agent for electronic devices can be provided.

Claims (7)

A sealing agent for electronic devices, which contains a curable resin, a polymerization initiator and / or a thermosetting agent, and is used for coating by an inkjet method,
The said curable resin contains the silicone compound represented by following formula (1), The sealing agent for electronic devices characterized by the above-mentioned.

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

In formulas (2-1) to (2-4), R ² represents a bond or an alkylene group having 1 to 6 carbon atoms, and in formula (2-3), R ³ represents hydrogen or 1 to carbon atoms. 6 represents an alkyl group, R ⁴ represents a bond or a methylene group, and in formula (2-4), R ⁵ represents hydrogen or a methyl group. In the silicone compound represented by the formula (1), at least one of X ¹ , X ² , and X ^{3 in} the formula (1) is represented by the formula (2-1), (2-2), or ( The encapsulant for electronic devices according to claim 1, which is a compound which is a group represented by 2-3). The silicone compound represented by the formula (1) is represented by the compound represented by the following formula (3-1), the compound represented by the following formula (3-2), and the following formula (3-3). The sealing agent for electronic devices according to claim 1, wherein the sealing agent is at least one selected from the group consisting of:

In formula (3-1), o is an integer of 1 to 10, in formula (3-2), p is an integer of 1 to 10, and in formula (3-3), q is 1 It is an integer of -10. In addition to the silicone compound represented by the formula (1), the curable resin is represented by the formula (1), an epoxy compound having no structure represented by the formula (1) as another curable resin. It contains at least one selected from the group consisting of an oxetane compound having no structure, a (meth) acrylic compound having no structure represented by formula (1), and a vinyl ether compound. Item 4. A sealing agent for electronic devices according to item 1, 2 or 3. The curable resin includes other curable resins such as alicyclic epoxy resin, 3- (allyloxy) oxetane, 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane, and 3-ethyl-3 ( The encapsulant for electronic devices according to claim 4, comprising at least one selected from the group consisting of ((3-ethyloxetane-3-yl) methoxy) methyl) oxetane. 6. The sealing agent for electronic devices according to claim 1, wherein the viscosity measured at 25 ° C. and 100 rpm using an E-type viscometer is 5 to 200 mPa · s. . Applying an electronic device sealant according to claim 1, 2, 3, 4, 5 or 6 to at least one of the two substrates by an inkjet method;
Curing the applied encapsulant for electronic devices by light irradiation and / or heating;
And a step of bonding the two base materials together.