JP7385715B2 - Encapsulants for electronic devices - Google Patents

Description

The present invention relates to a sealant for electronic devices that has low outgassing properties and excellent wetting and spreading properties on a substrate or an inorganic material film. The present invention also relates to a sealant for organic EL display elements using the sealant for electronic devices.

In recent years, research has been progressing on electronic devices using organic thin film elements such as organic electroluminescent (hereinafter also referred to as organic EL) display elements and organic thin film solar cell elements. Organic thin film elements can be easily manufactured by vacuum evaporation, solution coating, etc., and therefore have 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 into this organic light emitting material layer from one electrode, and electrons are injected from the other electrode. By injecting holes, electrons and holes combine within the organic light emitting material layer to emit light. Since organic EL display elements emit light by themselves, they have better visibility than liquid crystal display elements that require a backlight, can be made thinner, and can be driven at low DC voltages. It has the advantage of

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

These organic thin film devices have a problem in that their performance deteriorates rapidly when the organic layers and electrodes are exposed to the outside air. Therefore, in order to improve stability and durability, it is essential to seal the organic thin film element to isolate it from moisture and oxygen in the atmosphere.
Conventionally, as a method for sealing an organic thin film element, a method of sealing with a sealing can provided with a water-absorbing agent inside has been a common method. However, with the method of sealing with a sealing can, it is difficult to make the electronic device thinner. Therefore, development of a sealing method for organic thin film elements that does not use a sealing can is underway.

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 the role of preventing pressure on the organic layer and electrodes 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 may be damaged when forming the silicon nitride film due to unevenness on the surface of the organic thin film element, adhesion of foreign matter, cracks due to internal stress, etc. may not be completely covered. If the coverage with the silicon nitride film is incomplete, moisture will penetrate into the organic layer through the silicon nitride film.
As a method for preventing moisture from penetrating into the organic layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film, and Patent Documents 3 and 4 disclose , discloses a method of forming a resin film on an inorganic material film.

As a method for forming a resin film, there is a method of applying a liquid curable resin composition onto a substrate and then curing the curable resin composition. If an inkjet method or the like is used as a coating method, a resin film can be formed uniformly at high speed. When applying a sealant for electronic devices made of a curable resin composition to a base material, the viscosity of the sealant needs to be low from the viewpoint of coatability. Possible methods for adjusting the viscosity of the encapsulant for electronic devices include adding an organic solvent to the encapsulant for electronic devices, and using a curable resin with a low molecular weight. This method has problems such as the tendency to generate outgas.

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

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

An object of the present invention is to provide a sealant for electronic devices that has low outgas properties and excellent wetting and spreading properties on a substrate or an inorganic material film. Another object of the present invention is to provide a sealant for organic EL display elements using the sealant for electronic devices.

The present invention is an encapsulant for electronic devices containing a curable resin and a polymerization initiator and/or a thermosetting agent, wherein the curable resin is a silicone compound represented by the following formula (1). This is an electronic device encapsulant containing a silicone compound represented by the following formula (3).

In formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and may be the same or different. 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 (2-4) represents a group represented by However, 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 a carbon number 1 It represents an alkyl group of 6 or less, R ⁴ represents a bond or a methylene group, and in formula (2-4), R ⁵ represents hydrogen or a methyl group.

In formula (3), R ⁶ represents an alkyl group having 1 or more and 10 or less carbon atoms, and may be the same or different. X ³ and X ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, or the following formula (4-1), (4-2), (4-3), or (4-4) X ⁵ represents a group represented by the following formula (4-1), (4-2), (4-3), or (4-4). m is an integer from 0 to 1000, and n is an integer from 1 to 100.

In the formulas (4-1) to (4-4), R ⁷ represents a bond or an alkylene group having 1 to 6 carbon atoms, and in the formula (4-3), R ⁸ is hydrogen or a carbon number 1 It represents an alkyl group of 6 or less, R ⁹ represents a bond or a methylene group, and in formula (4-4), R ¹⁰ represents hydrogen or a methyl group.
The present invention will be explained in detail below.

The present inventors have discovered that a specific silicone compound with a short molecular chain having a polymerizable group at the end has excellent low outgas properties. However, when such a specific silicone compound with a short molecular chain having a polymerizable group at the end is used, there is a problem in that the resulting sealant has poor wetting and spreading properties on the substrate or inorganic material film. . On the other hand, specific silicone compounds with long molecular chains having a polymerizable group at the end have excellent wetting and spreading properties on an inorganic material film, but have the problem of easily generating outgas due to scission of the silicone chain. As a result of further intensive study, the present inventors investigated the use of a combination of a specific silicone compound with a short molecular chain having a polymerizable group at the end and a specific silicone compound having a polymerizable group in the side chain. As a result, the present inventors discovered that it is possible to obtain a sealant for electronic devices that has low outgas properties and excellent wetting and spreading properties on substrates or inorganic material films, and has completed the present invention.
The encapsulant for electronic devices of the present invention can be easily formed into a thin film by an inkjet method.

The encapsulant for electronic devices of the present invention contains a 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 excellent low outgas properties, and the cured product has excellent impact resistance and heat resistance. becomes.

In the above formula (1), R ¹ represents an alkyl group having 1 or more and 10 or less carbon atoms, and each may be the same or different. The above R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.

In the above formula (1), X ¹ and X ² are each independently an alkyl group having 1 to 10 carbon atoms, or the above formulas (2-1), (2-2), (2-3), Alternatively, it represents a group represented by (2-4). However, at least one of X ¹ and X ² represents a group represented by the above formula (2-1), (2-2), (2-3), or (2-4).
In the silicone compound represented by the above formula (1), both X ¹ and X ² in the above formula (1) are the above formulas (2-1), (2-2), (2-3), Alternatively, it is preferably a compound that is a group represented by (2-4), and is a group represented by the above formula (2-1), (2-2), or (2-3), respectively. More preferably, it is a compound.

In the above formulas (2-1) to (2-4), R ² represents a bond or an alkylene group having 1 or more and 6 or less carbon atoms. The above R ² is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a dimethylene group or a trimethylene group.

In the above formula (2-3), R ³ represents hydrogen or an alkyl group having 1 or more and 6 or less carbon atoms. The above R ³ is preferably hydrogen or an alkyl group having 1 or more and 3 or less carbon atoms, and more preferably hydrogen or an ethyl group.

In the above formula (2-3), R ⁴ represents a bond or a methylene group. The above R ⁴ is preferably a bond.

In the above formula (2-4), R ⁵ represents hydrogen or a methyl group. The above R ⁵ is preferably a methyl group.

The preferred lower limit of the content of the silicone compound represented by formula (1) in 100 parts by weight of the curable resin is 5 parts by weight, and the preferred upper limit is 90 parts by weight. When the content of the silicone compound represented by the above formula (1) is within this range, the obtained sealant for electronic devices has low outgas properties and excellent wetting and spreading properties on a substrate or an inorganic material film. A more preferable lower limit of the content of the silicone compound represented by the above formula (1) is 10 parts by weight, an even more preferable lower limit is 30 parts by weight, and an especially preferable lower limit is 50 parts by weight. Further, a more preferable upper limit of the content of the silicone compound represented by the above formula (1) is 70 parts by weight.

The curable resin contains a silicone compound represented by the above formula (3). By containing the silicone compound represented by the above formula (3), the encapsulant for electronic devices of the present invention has excellent wetting and spreading properties on a substrate or an inorganic material film.

In the above formula (3), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, and may be the same or different. The above R ⁶ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.

In the above formula (3), X ³ and X ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, or the above formula (4-1), (4-2), (4-3), Alternatively, it represents a group represented by (4-4).
In the silicone compound represented by the above formula (3), both X ³ and X ⁴ in the above formula (3) may each be an alkyl group having 1 to 10 carbon atoms, or one of them may be a carbon It may be an alkyl group of number 1 or more and 10 or less, or both are groups represented by the above formula (4-1), (4-2), (4-3), or (4-4). There may be.

In the above formula (3), X ⁵ represents a group represented by the above formula (4-1), (4-2), (4-3), or (4-4).
In the above formula (3), the above X 3 and the above ^{X 4 when} they become a group represented by the above formula (4-1), (4-2), (4-3), or (4-4) , and the group represented by the formula (4-1), (4-2), (4-3), or (4-4) in the above X ⁵ is a polymerizable group. The polymerizable group is preferably a group represented by the above formula (4-1), (4-2), or (4-3).

The preferable lower limit of the polymerizable group equivalent of the silicone compound represented by the above formula (3) is 300 g/mol, and the preferable upper limit is 5000 g/mol. When the polymerizable group equivalent of the silicone compound represented by the above formula (3) is within this range, the resulting sealant for electronic devices has low outgas properties and excellent wetting and spreading properties on the substrate or inorganic material film. Become. A more preferable lower limit of the polymerizable group equivalent of the silicone compound represented by the above formula (3) is 400 g/mol, and a more preferable upper limit is 2000 g/mol.
In addition, the polymerizable group equivalent of the silicone compound represented by the above formula (3) is the weight (g) of the silicone compound represented by the above formula (3) in the silicone compound represented by the above formula (3). It is a value obtained by dividing by the number of moles (mol) of polymerizable groups included.

In the above formula (3), m is an integer of 0 or more and 1000 or less. The preferable lower limit of m in the above formula (3) is 1, the preferable upper limit is 20, the more preferable lower limit is 3, and the more preferable upper limit is 10.

In the above formula (3), n is an integer of 1 or more and 100 or less. A preferable lower limit of n in the above formula (3) is 2, a preferable upper limit is 20, and a more preferable upper limit is 10.

In the above formulas (4-1) to (4-4), R ⁷ represents a bond or an alkylene group having 1 or more and 6 or less carbon atoms. The above R ⁷ is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a dimethylene group or a trimethylene group.

In the above formula (4-3), R ⁸ represents hydrogen or an alkyl group having 1 or more and 6 or less carbon atoms. The above R ⁸ is preferably hydrogen or an alkyl group having 1 or more and 3 or less carbon atoms, and more preferably hydrogen or an ethyl group.

In the above formula (4-3), R ⁹ represents a bond or a methylene group. The above R ⁹ is preferably a bond.

In the above formula (4-4), R ¹⁰ represents hydrogen or a methyl group. The above R ¹⁰ is preferably a methyl group.

The preferred lower limit of the content of the silicone compound represented by formula (3) in 100 parts by weight of the curable resin is 0.01 parts by weight, and the preferred upper limit is 30 parts by weight. When the content of the silicone compound represented by the above formula (3) is within this range, the obtained sealant for electronic devices has low outgas properties and excellent wetting and spreading properties on a substrate or an inorganic material film.
In particular, when the polymerizable group equivalent of the silicone compound represented by the above formula (3) is 300 g/mol or more, the content of the silicone compound represented by the above formula (3) in 100 parts by weight of the above curable resin A preferable lower limit is 0.01 parts by weight, a more preferable lower limit is 0.1 parts by weight, a preferable upper limit is 30 parts by weight, a more preferable upper limit is 20 parts by weight, and an even more preferable upper limit is 10 parts by weight. Further, when the polymerizable group equivalent of the silicone compound represented by the above formula (3) is less than 300 g/mol, the content of the silicone compound represented by the above formula (3) in 100 parts by weight of the above curable resin The preferable lower limit is 0.1 parts by weight, the preferable upper limit is 30 parts by weight, and the more preferable upper limit is 20 parts by weight. In addition, when the above-mentioned curable resin contains multiple types of compounds as the silicone compound represented by the above formula (3), the polymerizable group equivalent of the silicone compound represented by the above formula (3) is the number average value. means.

In addition to the silicone compound represented by the above formula (1) and the silicone compound represented by the above formula (3), the above curable resin contains other curable resins for the purpose of improving adhesiveness, etc. You may.
The other curable resins mentioned above include epoxy compounds that do not have the structure represented by the above formula (1) and the above formula (3) (hereinafter also referred to as "other epoxy compounds"), the above formula (1) and Oxetane compounds that do not have the structure represented by the above formula (3) (hereinafter also referred to as "other oxetane compounds"), oxetane compounds that do not have the structure represented by the above formula (1) and the above formula (3) At least one selected from the group consisting of meth)acrylic compounds (hereinafter also referred to as "other (meth)acrylic compounds") and vinyl ether compounds is preferred.
In addition, in this specification, the above-mentioned "(meth)acrylic" means acrylic or methacryl, "(meth)acrylic compound" means a compound having a (meth)acryloyl group, "(meth)acryloyl ” means acryloyl or methacryloyl.

Examples of the other epoxy compounds mentioned above include bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol O epoxy resin, and 2,2'-diallylbisphenol A 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, biphenyl novolac type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin Examples include resins, rubber-modified epoxy resins, glycidyl ester compounds, and the like. Among these, alicyclic epoxy resins are preferred.
Among the above-mentioned alicyclic epoxy resins, commercially available ones include, for example, alicyclic epoxy resins manufactured by Daicel Corporation and alicyclic epoxy resins manufactured by Shinnihon Rika Kogyo Co., Ltd.
Examples of the alicyclic epoxy resin manufactured by Daicel include Celoxide 2000, Celoxide 2021P, Celoxide 2081, Celoxide 3000, Celoxide 8000, and Cyclomer M-100.
Examples of the alicyclic epoxy resin manufactured by Shinnihon Rika Kogyo Co., Ltd. include Sansocizer EPS.
Among the above-mentioned alicyclic epoxy resins, those having no ether bond or ester bond other than those contained in the epoxy group are suitable from the viewpoint of suppressing the generation of outgas. Commercially available alicyclic epoxy resins having no ether bond or ester bond other than those contained in the epoxy group include Celoxide 2000, Celoxide 3000, Celoxide 8000, and the like.
These other epoxy compounds may be used alone or in combination of two or more.

Examples of the other oxetane compounds mentioned above 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-ethyloxetan-3-yl)methoxy ) methyl)oxetane, oxetanylsilsesquioxane, phenol novolak oxetane, 1,4-bis(((3-ethyl-3-oxetanyl)methoxy)methyl)benzene, and the like. These other oxetane compounds may be used alone or in combination of two or more.

Examples of the other (meth)acrylic compounds mentioned above include glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 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, ) acrylate, etc.
These other (meth)acrylic compounds may be used alone or in combination of two or more.
In addition, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate.

Examples of the vinyl ether compounds 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, and dipropylene glycol. Examples include 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, the other curable resins mentioned above include alicyclic epoxy resin, 3-(allyloxy)oxetane, and 3-ethyl-3-((2-ethylhexyloxy)methyl)oxetane because of their low viscosity and high reactivity. , and 3-ethyl-3-(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane.

The preferred lower limit of the content of the other curable resin in 100 parts by weight of the curable resin is 5 parts by weight, and the preferred upper limit is 90 parts by weight. When the content of the other curable resins is within this range, it is possible to achieve excellent effects such as improving adhesiveness without deteriorating coating properties and the like. A more preferable lower limit of the content of the other curable resins is 20 parts by weight. Further, a more preferable upper limit of the content of the other curable resin is 70 parts by weight, an even more preferable upper limit is 60 parts by weight, and an especially preferable upper limit is 40 parts by weight.

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

The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or Lewis acid upon irradiation with light, and may be an ionic photoacid generating type or a nonionic photoacid generating type. You can.

Examples of the anion moiety of the ionic photoacid-generating photocationic polymerization initiator include BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , (BX ₄ ) ^- (where X is at least two fluorine atoms). or a phenyl group substituted with a trifluoromethyl group). Further, as the above anion moiety, PF _m (C _n F _2n+1 ) _6-m ⁻ (wherein m is an integer of 0 to 5, and n is an integer of 1 to 6), etc. Can be mentioned.
Examples of the ionic photoacid-generating photocationic polymerization initiators include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4-cyclo Examples include pentadien-1-yl)((1-methylethyl)benzene)-Fe salt.

Examples of the aromatic sulfonium salts include bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate, and bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate. diphenylsulfonio)phenyl) sulfide bistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(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 hexa Fluoroantimonate, 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(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate, tris(4-(4-acetylphenyl)thiophenyl) Examples include sulfonium tetrakis(pentafluorophenyl)borate.

Examples of the aromatic iodonium salts 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)iodoniumtetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyl iodonium hexa Fluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylphenyl-4-( Examples include 1-methylethyl) phenyl iodonium tetrakis (pentafluorophenyl) borate.

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 hexafluoroantimonate. -2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, and the like.

As the above (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, for example, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene )-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) hexafluoroantimonate, (2,4-cyclopentadien-1 -yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrakis(penta Examples include fluorophenyl) borate and the like.

Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic esters, diazonaphthoquinone, N-hydroxyimidosulfonate, and the like.

Among the above photocationic polymerization initiators, commercially available ones include, for example, a cationic photopolymerization initiator manufactured by Midori Kagaku Co., Ltd., a cationic photopolymerization initiator manufactured by Union Carbide, a cationic photopolymerization initiator manufactured by ADEKA, Examples include a cationic photopolymerization initiator manufactured by 3M, a cationic photopolymerization initiator manufactured by BASF, and a cationic photopolymerization initiator manufactured by Rhodia.
Examples of the photocationic polymerization initiator manufactured by Midori Kagaku Co., Ltd. include DTS-200.
Examples of the photocationic polymerization initiator manufactured by Union Carbide include UVI6990 and UVI6974.
Examples of the photocationic polymerization initiator manufactured by ADEKA include SP-150 and SP-170.
Examples of the cationic photopolymerization initiator manufactured by 3M include FC-508 and FC-512.
Examples of the photocationic polymerization initiator manufactured by BASF include IRGACURE 261 and IRGACURE 290.
Examples of the photocationic polymerization initiator manufactured by Rhodia include PI2074.

The above-mentioned thermal cationic polymerization initiator has an anion moiety of BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (wherein, X is substituted with at least two or more fluorine or trifluoromethyl groups). sulfonium salts, phosphonium salts, ammonium salts, etc., which are composed of phenyl groups). Among these, sulfonium salts and ammonium salts are preferred.

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

Examples of the phosphonium salts include ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, and the like.

Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, 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 hexafluoroantimonate, Methylphenyldibenzylammonium tetrakis(pentafluorophenyl)borate, Phenyltribenzylammonium tetrakis(pentafluorophenyl)borate, Dimethylphenyl(3,4-dimethyl) benzyl) ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-diethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N- Examples include benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, and the like.

Among the above-mentioned thermal cationic polymerization initiators, commercially available ones include, for example, thermal cationic polymerization initiators manufactured by Sanshin Kagaku Kogyo Co., Ltd. and thermal cationic polymerization initiators manufactured by King Industries.
Examples of the thermal cationic polymerization initiator manufactured by Sanshin Kagaku Kogyo Co., Ltd. include Sanaid SI-60, Sanaid SI-80, Sanaid SI-B3, Sanaid SI-B3A, and Sanaid SI-B4.
Examples of the thermal cationic polymerization initiator manufactured by King Industries include CXC1612 and CXC1821.

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

Among the above-mentioned radical photopolymerization initiators, commercially available ones include, for example, radical photopolymerization initiators manufactured by BASF, and radical photopolymerization initiators manufactured by Tokyo Kasei Kogyo.
Examples of the photoradical polymerization initiators manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Examples include phosphorus TPO.
Examples of the photoradical polymerization initiator manufactured by Tokyo Kasei Kogyo Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.

Examples of the thermal radical polymerization initiator include those consisting of azo compounds, organic peroxides, and the like.
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, peroxy ester, diacyl peroxide, peroxydicarbonate, and the like.

Among the above thermal radical polymerization initiators, commercially available ones include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (manufactured by), etc.

The content of the polymerization initiator has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight based on 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 sealant for electronic devices has better curability. When the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the resulting electronic device encapsulant does not become too rapid, resulting in better workability and a more uniform cured product. be able to. A more preferable lower limit of the content of the polymerization initiator is 0.05 parts 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, and addition products of various amines and epoxy resins.
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)-adipoamide, 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 alone or in combination of two or more.

Among the above thermosetting agents, commercially available ones include, for example, a thermosetting agent manufactured by Otsuka Chemical Co., Ltd., a thermosetting agent manufactured by Ajinomoto Fine Techno Co., Ltd., and the like.
Examples of the thermosetting agent manufactured by Otsuka Chemical Co., Ltd. include SDH, ADH, and the like.
Examples of the thermosetting agent manufactured by Ajinomoto Fine Techno include Amicure VDH, Amicure VDH-J, and Amicure UDH.

The preferable lower limit of the content of the thermosetting agent is 0.5 parts by weight and the preferable upper limit is 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 resulting electronic device encapsulant has better thermosetting properties. When the content of the thermosetting agent is 30 parts by weight or less, the obtained sealant for electronic devices has better storage stability, and the cured product has better 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 encapsulant for electronic devices of the present invention may contain a sensitizer. The sensitizer has the role of further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the encapsulant for electronic devices of the present invention.

Examples of the sensitizer include thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4 '-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and the like.
Examples of the thioxanthone compounds include 2,4-diethylthioxanthone.

The preferable lower limit of the content of the sensitizer is 0.01 parts by weight and the preferable upper limit is 3 parts by weight based on 100 parts by weight of the curable resin. When the content of the sensitizer is 0.01 part by weight or more, the sensitizing effect is more effectively exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted deep into the body 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 encapsulant for electronic devices of the present invention may further contain a silane coupling agent. The silane coupling agent has the role of improving the adhesiveness between the electronic device encapsulant of the present invention and a substrate or the like.

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

The content of the silane coupling agent has a preferable lower limit of 0.1 parts by weight and a preferable upper limit of 10 parts by weight based on 100 parts by weight of the curable resin. When the content of the silane coupling agent is within this range, the resulting electronic device encapsulant has an excellent effect of improving the adhesiveness while suppressing bleed-out due to 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 encapsulant for electronic devices of the present invention may contain a curing retarder. By containing the above-mentioned curing retarder, the pot life of the resulting electronic device encapsulant can be extended.

Examples of the curing retarder include polyether compounds.
Examples of the polyether compounds include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and crown ether compounds. Among these, crown ether compounds are preferred.

The content of the curing retarder has a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 5.0 parts by weight based on 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 curing the obtained sealant for electronic devices. A more preferable lower limit of the content of the curing retarder is 0.1 parts by weight, and a more preferable upper limit is 3.0 parts by weight.

The encapsulant for electronic devices of the present invention may further contain a surface modifier within a range that does not impede the object of the present invention. By containing the above-mentioned surface modifier, the flatness of the coating film can be imparted to the encapsulant for electronic devices of the present invention.
Examples of the surface modifier include surfactants, leveling agents, and the like.

Examples of the surface modifier include silicone-based, acrylic-based, fluorine-based, and the like.
Among the above-mentioned surface modifiers, commercially available ones include, for example, a surface modifier manufactured by BIC Chemie Japan Co., Ltd., a surface modifier manufactured by AGC Seimi Chemical Co., Ltd., and the like.
Examples of the surface modifier manufactured by BYK Chemie Japan include BYK-340 and BYK-345.
Examples of the surface modifier manufactured by AGC Seimi Chemical include Surflon S-611.

The encapsulant for electronic devices of the present invention contains a compound or ion exchange resin that reacts with the acid generated in the encapsulant in order to improve the durability of the element electrodes, within a range that does not impair the transparency of the cured product. May be contained.

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

As the above-mentioned ion exchange resin, any of cation exchange type, anion exchange type, and amphoteric ion exchange type can be used, but in particular, cation exchange type or amphoteric ion exchange type can adsorb chloride ions. is suitable.

Furthermore, the encapsulant for electronic devices of the present invention may contain various known additives such as reinforcing agents, softeners, plasticizers, viscosity modifiers, ultraviolet absorbers, and antioxidants, if necessary. good.

As a method for manufacturing the encapsulant for electronic devices of the present invention, for example, a curable resin and a polymerization Examples include a method of mixing an initiator and/or a thermosetting agent with an additive such as a silane coupling agent added as necessary.

The preferable lower limit of the viscosity of the encapsulant for electronic devices of the present invention is 5 mPa·s, and the preferable upper limit is 200 mPa·s, as measured using an E-type viscometer at 25° C. and 100 rpm. When the viscosity is within this range, the encapsulant for electronic devices of the present invention has better inkjet applicability and shape retention after application. A more preferable lower limit of the viscosity of the electronic device encapsulant is 10 mPa·s, and a more preferable upper limit is 80 mPa·s.
In addition, the sealant for electronic devices of the present invention may be heated during application by inkjet to reduce the viscosity before application.

A preferable lower limit of the total light transmittance of the cured product of the encapsulant for electronic devices of the present invention at wavelengths of 380 nm to 800 nm is 80%. When the total light transmittance is 80% or more, it can be suitably used for organic EL display elements and the like. 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 METER MODEL TC-III DPK (manufactured by Tokyo Denshoku Co., Ltd.).
In addition, if the cured product used in the measurement of the total light transmittance is a photocurable sealant, it can be obtained, for example, by irradiating the sealant with 3000 mJ/cm ² of ultraviolet light with a wavelength of 365 nm using an LED lamp. If it is a thermosetting sealant, it can be obtained, for example, by heating at 80° C. for 1 hour.

The sealant 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 irradiating the cured product with ultraviolet rays for 100 hours. When the transmittance after irradiation with the ultraviolet rays for 100 hours is 85% or more, the film has better transparency, less loss of light emission, and better color reproducibility. A more preferable lower limit of the transmittance after irradiation with the ultraviolet rays for 100 hours is 90%, and an even more preferable lower limit is 95%.
As a 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, for example.
In addition, if the cured product used to measure the transmittance after 100 hours of irradiation with the ultraviolet rays is a photocurable sealant, for example, the sealant may be exposed to ultraviolet rays with a wavelength of 365 nm at 3000 mJ/cm using an LED lamp. If it is ^a thermosetting sealant, it can be obtained by heating at 80° C. for 1 hour, for example.

The encapsulant for electronic devices of the present invention has a moisture permeability of 100 g/m ² at a thickness of 100 μm, which is measured by exposing the cured product to an environment of 85° C. and 85% RH for 24 hours, in accordance with JIS Z 0208. It is preferable that it is below. By having the moisture permeability of 100 g/ ^m2 or less, for example, when used in the production of an organic EL display element as an electronic device, it has the effect of suppressing the occurrence of dark spots due to moisture reaching the organic light emitting material layer. Become excellent.
In addition, if the cured product used in the moisture permeability measurement is a photocurable sealant, it can be obtained by, for example, irradiating the sealant with 3000 mJ/cm ² of ultraviolet light with a wavelength of 365 nm using an LED lamp. If it is a thermosetting sealant, it can be obtained, for example, by heating at 80° C. for 1 hour.

Further, in the electronic device encapsulant of the present invention, it is preferable that the cured product 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. Since the moisture content of the cured product is less than 0.5%, for example, when used in the production of organic EL display elements as electronic devices, it has the effect of suppressing deterioration of the organic light emitting material layer due to moisture in the cured product. Become excellent. A more preferable upper limit of the moisture content of the cured product is 0.3%.
Examples of methods for measuring the moisture content include a method of determining it by the Karl Fischer method in accordance with JIS K 7251, and a method of determining the weight increase after water absorption in accordance with JIS K 7209-2.
In addition, if the cured product used for measuring the moisture content is a photocurable sealant, it can be obtained by, for example, irradiating the sealant with 3000 mJ/cm ² of ultraviolet light with a wavelength of 365 nm using an LED lamp. If it is a thermosetting sealant, it can be obtained, for example, by heating at 80° C. for 1 hour.

A method for manufacturing an electronic device using the encapsulant for electronic devices of the present invention includes, for example, a step of applying the encapsulant for electronic devices of the present invention to at least one of two base materials; Examples include a method including a step of curing the sealant for electronic devices by light irradiation and/or heating, and a step of bonding the two base materials together.

In the step of applying the encapsulant for electronic devices of the present invention to at least one of the two base materials, the encapsulant for electronic devices of the present invention may be applied to the entire surface of the base material; It may be applied to some areas. For example, when manufacturing an organic EL display element as an electronic device, the shape of the sealing part of the sealant for electronic devices of the present invention formed by coating is such that the laminate having the organic light emitting material layer is protected from the outside air. It is not particularly limited as long as it has a transparent shape. That is, the pattern may be such that it completely covers the laminate, a closed pattern may be formed around the periphery of the laminate, or a pattern may be partially formed around the periphery of the laminate. A pattern of shapes may also be formed.
Moreover, as a method for applying the sealant for electronic devices of the present invention, an inkjet method is preferable.

When manufacturing an organic EL display element as the above-mentioned electronic device, the base material (hereinafter also referred to as one base material) to which the electronic device encapsulant of the present invention is applied is formed of a laminate having an organic light emitting material layer. The base material may be a base material with a laminate formed thereon, or a base material on which the laminate is not formed.
If one of the base materials is a base material on which the laminate is not formed, the present invention is applied to the one base material so that the laminate can be protected from the outside air when the other base material is bonded to the other base material. A sealant for electronic devices may be applied. That is, the area that will be the position of the laminate when the other base material is bonded is completely coated, or the area that will be the position of the laminate when the other base material is bonded is completely coated. A closed pattern of the sealant portion may be formed in a shape that fits within.

Further, the laminate may be coated with an inorganic material film.
Conventionally known inorganic materials can be used as the inorganic material constituting the inorganic material film, 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 composed of a plurality of laminated layers. Further, the laminate may be coated by alternately repeating the inorganic material film and the resin film made of the electronic device encapsulant of the present invention.

The step of curing the electronic device encapsulant by light irradiation and/or heating may be performed before the step of bonding the two base materials together, or before the step of bonding the two base materials together. You can do it later.
When the step of curing the electronic device encapsulant by light irradiation and/or heating is performed before the step of bonding the two base materials together, the electronic device encapsulant of the present invention can be cured by light irradiation and/or heating. It is preferable that the pot life is 1 minute or more after heating until curing reaction progresses and adhesion becomes impossible. By setting the above-mentioned pot life to 1 minute or more, it is possible to suppress the progress of curing before bonding the two base materials together, and to further increase the adhesive strength after bonding the two base materials together.

When the above encapsulant for electronic devices is cured by light irradiation, the encapsulant for electronic devices of the present invention is irradiated with light having a wavelength of 300 nm or more and 400 nm or less and an integrated light amount of 300 mJ/cm ² or more and 3000 mJ/cm ² or less. By doing so, it can be suitably cured.

Examples of light sources used for the above-mentioned light irradiation include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, halogen lamps, and xenon lamps. Examples include lamps, LED lamps, fluorescent lamps, sunlight, and electron beam irradiation devices. These light sources may be used alone, or two or more types may be used in combination.
These light sources are appropriately selected according to the absorption wavelength of the photocationic polymerization initiator and the photoradical polymerization initiator.

Examples of the means for irradiating the encapsulant for electronic devices of the present invention with light include simultaneous irradiation with various light sources, sequential irradiation with time differences, and combination irradiation of simultaneous irradiation and sequential irradiation. Irradiation means may also be used.

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

In the step of bonding the two base materials together, the method of bonding the two base materials together is not particularly limited, but it is preferable to bond the two base materials together under a reduced pressure atmosphere.
The preferable lower limit of the degree of vacuum under the reduced pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa. Since the degree of vacuum under the reduced pressure atmosphere is within this range, it is possible to achieve a vacuum state without spending a long time due to the airtightness of the vacuum equipment and the capacity of the vacuum pump, and when bonding two base materials together. Air bubbles can be removed more efficiently from the encapsulant for electronic devices of the present invention.

The encapsulant for electronic devices of the present invention has excellent low outgassing properties and excellent wetting and spreading properties on substrates or inorganic material films, and therefore can be particularly suitably used as a encapsulant for organic EL display elements. An encapsulant for organic EL display elements using the encapsulant for electronic devices of the present invention is also one of the aspects of the present invention.

According to the present invention, it is possible to provide a sealant for electronic devices that has low outgas properties and excellent wetting and spreading properties on a substrate or an inorganic material film. Further, according to the present invention, it is possible to provide a sealant for an organic EL display element using the sealant for electronic devices.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

(Examples 1 to 13, Reference Example 14, Comparative Examples 1 and 2)
Examples 1 to 13, Reference Example 14, and Comparative Examples 1 to 13, Reference Example 14 , and Comparison were prepared by stirring and mixing each material uniformly at a stirring speed of 3000 rpm using a homodisper type stirring mixer according to the compounding ratios listed in Tables 1 to 3 . Encapsulants for electronic devices in Examples 1 and 2 were produced. As the homodisper type stirring mixer, a homodisper type L (manufactured by Primix Co., Ltd.) was used.
In addition, the silicone compound represented by Formula (1) and the silicone compound represented by Formula (3) in the table are explained in detail below.
"X-22-163" is represented by formula (1), where R ¹ is a methyl group, and X ¹ and X ² are groups represented by the above formula (2-1) (R ² is a trimethylene group). It is a silicone compound (polymerizable group equivalent: 200 g/mol).
"SIB1092.0" is represented by formula (1), where R ¹ is a methyl group, and X ¹ and X ² are groups represented by the above formula (2-2) (R ² is a dimethylene group). It is a silicone compound (polymerizable group equivalent: 191 g/mol).
"X-22-164" is a group in which R ¹ is a methyl group, and X ¹ and X ² are a group represented by the above formula (2-4) (R ² is a trimethylene group, R ⁵ is a methyl group) It is a silicone compound represented by formula (1) (polymerizable group equivalent: 190 g/mol).
"A silicone compound having an oxetanyl group" is a group in which R ¹ is all a methyl group, and X ¹ and X ² are a group represented by the above formula (2-3) (R ² is a trimethylene group, R ³ is an ethyl group, R ⁴ is a methylene group), which is a silicone compound represented by formula (1) (polymerizable group equivalent: 223 g/mol).
"X-22-343" is a group in which R ⁶ is a methyl group, X ³ and X ⁴ are methyl groups, and X ⁵ is a group represented by the above formula (4-1) (R ⁷ is a trimethylene group) It is a silicone compound (polymerizable group equivalent: 525 g/mol) represented by formula (3) where m is 7 and n is 2.
In "KF-102", R ⁶ is a methyl group, X ³ and X ⁴ are methyl groups, and X ⁵ is a group represented by the above formula (4-2) (R ⁷ is a methylene group). , m is 90, and n is 2, which is a silicone compound represented by formula (3) (polymerizable group equivalent: 3600 g/mol).
"X-22-9002" is a group in which R ⁶ is a methyl group, X ³ , X ⁴ and X ⁵ are a group represented by the above formula (4-1) (R ⁷ is a trimethylene group), This is a silicone compound represented by formula (3) where m is 260 and n is 2 (polymerizable group equivalent: 5000 g/mol).

<Evaluation>
The following evaluations were performed on each of the electronic device encapsulants obtained in Examples , Reference Examples, and Comparative Examples. The results are shown in Tables 1-3.

(viscosity)
The viscosity of each of the electronic device encapsulants obtained in Examples , Reference Examples, and Comparative Examples was measured using an E-type viscometer at 25° C. and 100 rpm. As the E-type viscometer, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) was used.

(Low outgassing)
Outgas generated during heating of the cured products of each of the electronic device encapsulants obtained in Examples , Reference Examples, and Comparative Examples was measured using a gas chromatograph using a headspace method as shown below.
First, 100 mg of each electronic device encapsulant was applied to a thickness of 300 μm using an applicator. Next, the sealant was cured by irradiating 3000 mJ/ ^cm2 of ultraviolet light with a wavelength of 365 nm using an LED lamp, and then the cured sealant was put into a headspace vial and the vial was sealed. It was heated at ℃ for 30 minutes and the generated gas was measured by the head space method. Note that the sealant obtained in Example 13 was cured by heating at 80° C. for 1 hour instead of irradiating with ultraviolet rays.
The low outgassing property was evaluated as "○" when the gas generated was less than 300 ppm, "Δ" when it was 300 ppm or more but less than 500 ppm, and "x" when it was 500 ppm or more.

(wetting and spreading properties)
Each of the electronic device encapsulants obtained in Examples , Reference Examples, and Comparative Examples was dropped onto non-alkali glass that had been washed with alkali using an inkjet ejection device in a droplet volume of 10 picoliters, The diameter of the droplet on the alkali-free glass was measured 5 minutes after dropping. A material printer DMP-2831 (manufactured by Fuji Film Corporation) was used as the inkjet ejection device, and AN100 (manufactured by AGC Corporation) was used as the alkali-free glass.

(Display performance of organic EL display element)
(Preparation of a substrate on which a laminate having an organic light emitting material layer is arranged)
A glass substrate having a length of 25 mm, a width of 25 mm, and a thickness of 0.7 mm on which an ITO electrode was formed to a thickness of 1000 Å was used as a substrate. The above substrate was ultrasonically cleaned with acetone, aqueous alkaline solution, ion-exchanged water, and isopropyl alcohol for 15 minutes each, then cleaned with boiled isopropyl alcohol for 10 minutes, and then immediately treated with a UV-ozone cleaner. went. As the UV-ozone cleaner, NL-UV253 (manufactured by Nippon Laser Electronics Co., Ltd.) was used.
Next, the substrate immediately after the treatment was fixed to the substrate holder of the vacuum evaporation equipment, and 200 mg of N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (α-NPD) was placed in an unglazed crucible. 200 mg of tris(8-quinolinolato)aluminum (Alq ₃ ) was placed in another unglazed crucible, and the pressure inside 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 hole transport layer with a thickness of 600 Å. Next, the crucible containing Alq ₃ was heated to form an organic light emitting material layer with a thickness of 600 Å at a deposition rate of 15 Å/s. Thereafter, the substrate on which the hole transport layer and the organic light-emitting material layer were formed was transferred to another vacuum evaporation apparatus having a tungsten resistance heating boat, and lithium fluoride was placed in one of the tungsten resistance heating boats in the vacuum evaporation apparatus. Then, 1.0 g of aluminum wire was placed in another tungsten resistance heating boat. Thereafter, the pressure inside the vacuum evaporator was reduced to 2×10 ^-4 Pa, and lithium fluoride was deposited at a deposition rate of 5 Å at a deposition rate of 0.2 Å/s, and then aluminum was deposited at a deposition rate of 100 Å at a rate of 20 Å/s. did. The pressure inside the evaporator was returned to normal pressure using nitrogen, and the substrate on which the laminate having a 10 mm x 10 mm organic light emitting material layer was disposed was taken out.

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

(Formation of resin protective film)
Each of the electronic device encapsulants obtained in Examples , Reference Examples, and Comparative Examples was pattern coated on the substrate coated with the inorganic material film A at 40° C. using an inkjet discharge device. Material printer DMP-2831 (manufactured by Fujifilm) was used as an inkjet ejection device.
Thereafter, the electronic device sealant was cured by irradiating 3000 mJ/cm ² of ultraviolet light with a wavelength of 365 nm using an LED lamp to form a resin protective film. Note that the sealant obtained in Example 13 was cured by heating at 80° C. for 1 hour instead of irradiating with ultraviolet rays to form a resin protective film.

(Coating with inorganic material film B)
After forming the resin protective film, a mask having an opening of 12 mm x 12 mm is placed on the substrate, and an inorganic material film B is formed to cover the entire resin protective film by plasma CVD to form an organic EL display element. I got it.
The plasma CVD method was performed under the same conditions as in "(Coating with inorganic material film A)" above.
The thickness of the formed inorganic material film B was about 1 μm.

(Light emission state of organic EL display element)
The obtained organic EL display element was exposed for 100 hours in an environment with a temperature of 85°C and a humidity of 85%, and then a voltage of 3V was applied to determine the luminescence state of the organic EL display element (presence or absence of dark spots and quenching around pixels). was visually observed. The organic EL display element is evaluated as ``○'' if the light is emitted uniformly without dark spots or peripheral quenching, ``△'' if dark spots or peripheral quenching are observed, and ``x'' if the non-emissive area is significantly enlarged. Display performance was evaluated.

According to the present invention, it is possible to provide a sealant for electronic devices that has low outgas properties and excellent wetting and spreading properties on a substrate or an inorganic material film. Further, according to the present invention, it is possible to provide a sealant for an organic EL display element using the sealant for electronic devices.

Claims (1)

An encapsulant for electronic devices containing a curable resin, a polymerization initiator and/or a thermosetting agent,
The curable resin contains a silicone compound represented by the following formula (1) and a silicone compound represented by the following formula (3),
The silicone compound represented by the formula (3) has a polymerizable group equivalent of 300 g/mol or more,
The content of the silicone compound represented by the formula (3) in 100 parts by weight of the curable resin is 10 parts by weight or less.
An encapsulant for electronic devices characterized by:

In formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and may be the same or different. 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 (2-4) represents a group represented by However, 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 a carbon number 1 It represents an alkyl group of 6 or less, R ⁴ represents a bond or a methylene group, and in formula (2-4), R ⁵ represents hydrogen or a methyl group.

In formula (3), R ⁶ represents an alkyl group having 1 or more and 10 or less carbon atoms, and may be the same or different. X ³ and X ⁴ are each independently an alkyl group having 1 to 10 carbon atoms, or the following formula (4-1), (4-2), (4-3), or (4-4) X ⁵ represents a group represented by the following formula (4-1), (4-2), (4-3), or (4-4). m is an integer from 0 to 1000, and n is an integer from 1 to 100.

In the formulas (4-1) to (4-4), R ⁷ represents a bond or an alkylene group having 1 to 6 carbon atoms, and in the formula (4-3), R ⁸ is hydrogen or a carbon number 1 It represents an alkyl group of 6 or less, R ⁹ represents a bond or a methylene group, and in formula (4-4), R ¹⁰ represents hydrogen or a methyl group.