JP7117295B2 - Sealant for electronic devices and sealant for organic EL display elements - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sealant for electronic devices that has low outgassing properties, wettability to a substrate or an inorganic material film, and excellent transparency. The present invention also relates to a sealant for organic EL display elements using the sealant for electronic devices.

In recent years, researches 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 have been advanced. Since the organic thin film element can be easily produced by vacuum deposition, solution coating, etc., it is excellent in productivity.

An organic EL display element has a laminate structure in which an organic light-emitting material layer is sandwiched between a pair of electrodes facing each other. By injecting holes, electrons and holes combine in the organic light-emitting material layer to emit light. Since the organic EL display element emits light by itself in this way, it has better visibility than a liquid crystal display element or the like that requires a backlight, can be made thinner, and can be driven at a low DC voltage. 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 structures have been proposed. Specifically, for example, Non-Patent Document 1 discloses an organic solar cell element using a laminated film of copper phthalocyanine and a perylene dye.

These organic thin film elements have a problem that their performance deteriorates rapidly when the organic layers and electrodes are exposed to the outside air. Therefore, in order to improve the stability and durability, it is essential to seal the organic thin film element to shield 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 has been 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 sealing method for an organic thin film element without using 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 a role of preventing the internal stress of the silicon nitride film from pressing the organic layer and the electrode.

In the method of sealing with a silicon nitride film disclosed in Patent Document 1, when forming the silicon nitride film, the organic thin film element may be damaged 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 silicon nitride film is incompletely covered, moisture will penetrate into the organic layer through the silicon nitride film.
As a method for preventing moisture from penetrating into an organic layer, Patent Document 2 discloses a method of alternately vapor-depositing an inorganic material film and a resin film, and Patent Documents 3 and 4 disclose the method. , a method for forming a resin film on an inorganic material film is disclosed.

As a method of 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 an electronic device sealing agent comprising a curable resin composition to a substrate, the viscosity of the sealing agent needs to be low from the viewpoint of coating properties. As a method for adjusting the viscosity of the sealant for electronic devices, a method of blending an organic solvent with the sealant for electronic devices, or using a curable resin having a low molecular weight as a blended resin is conceivable. However, the method has problems such as outgassing.

JP-A-2000-223264 Japanese Patent Publication No. 2005-522891 Japanese Patent Application Laid-Open No. 2001-307873 JP-A-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 outgassing properties, wettability to a substrate or an inorganic material film, and excellent transparency. 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 provides an electronic device sealant containing a curable resin, a polymerization initiator and/or a thermosetting agent, wherein the curable resin is a silicone compound represented by the following formula (1): and a silicone compound represented by the following formula (3), and the haze of the entire electronic device sealant is 10% or less.

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 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 is hydrogen or 1 carbon atom Represents an alkyl group of 6 or less, R ⁴ represents a bond or a methylene group, and R ⁵ in formula (2-4) represents hydrogen or a methyl group.

In formula (3), R ⁶ represents an alkyl group having 1 to 10 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) Represents a group represented by n is an integer of 1 or more and 1000 or less. However, at least one of X ³ and X ⁴ represents a group represented by formula (4-1), (4-2), (4-3) or (4-4) below.

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

The present inventors have found that a specific silicone compound having a polymerizable group at its end and a short molecular chain is excellent in low outgassing properties. However, when such a specific silicone compound with a short molecular chain having a polymerizable group at the terminal is used, there is a problem that the resulting sealant is inferior in wettability and spreadability to a substrate or an inorganic material film. . On the other hand, a specific silicone compound with a long molecular chain having a polymerizable group at its end has excellent wetting and spreading properties with respect to an inorganic material film, but has the problem of easily generating outgas due to breakage of the silicone chain. Therefore, 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 with a long molecular chain having a polymerizable group at the end was investigated. Some turbidity occurred. Therefore, as a result of intensive studies by the present inventors, by adjusting the type and content ratio of each component to a specific value or less, the haze can be reduced to a specific value or less, thereby achieving low outgassing, wettability to the substrate or inorganic material film, and transparency. The present inventors have found that an electronic device sealant having excellent properties can be obtained, and have completed the present invention.
The electronic device sealant of the present invention can be easily formed into a thin film by an inkjet method.

The electronic device sealant of the present invention contains a curable resin.
The curable resin contains a silicone compound represented by the formula (1). By containing the silicone compound represented by the above formula (1), the electronic device sealant of the present invention has excellent low outgassing properties, and the cured product has excellent impact resistance and heat resistance. becomes.

In formula (1) above, R ¹ represents an alkyl group having 1 to 10 carbon atoms and may be the same or different. R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, 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). At least one of X ¹ and X ² represents a group represented by formula (2-1), (2-2), (2-3) or (2-4) above.
In the silicone compound represented by the above formula (1), both X ¹ and X ² in the above formula (1) are represented by the above formulas (2-1), (2-2), (2-3), Alternatively, it is preferably a compound that is a group represented by (2-4), which is a group represented by the above formula (2-1), (2-2), or (2-3), respectively. Compounds are more preferred.

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

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

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

In formula (2-4) above, R ⁵ represents hydrogen or a methyl group. ^R5 above is preferably a methyl group.

The preferable lower limit of the content of the silicone compound represented by the formula (1) in 100 parts by weight of the curable resin is 5 parts by weight, and the preferable 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 resulting sealant for electronic devices will be excellent in low outgassing properties and in wetting and spreading properties with respect to a substrate or an inorganic material film. A more preferred lower limit for the content of the silicone compound represented by formula (1) is 10 parts by weight, a more preferred lower limit is 30 parts by weight, and a particularly preferred lower limit is 50 parts by weight. 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 formula (3). By containing the silicone compound represented by the above formula (3), the electronic device sealant of the present invention is excellent in wetting and spreading properties with respect to 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. R ⁶ is preferably an alkyl group having 1 to 6 carbon atoms, 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 formulas (4-1), (4-2), (4-3), Alternatively, it represents a group represented by (4-4). At least one of X ³ and X ⁴ represents a group represented by formula (4-1), (4-2), (4-3) or (4-4) above.
In the silicone compound represented by the above formula (3), both X ³ and X ⁴ in the above formula (3) are represented by the above formulas (4-1), (4-2), (4-3), Alternatively, it is preferably a compound represented by (4-4).

In the above formula (3), the above X ³ and the above X ⁴ when they are groups represented by the above formulas (4-1), (4-2), (4-3), or (4-4) In, the group represented by the formula (4-1), (4-2), (4-3), or (4-4) is a polymerizable group. The polymerizable group is preferably a group represented by formula (4-1), (4-2), or (4-3).

A preferable lower limit of the polymerizable group equivalent of the silicone compound represented by the formula (3) is 300 g/mol, and a preferable upper limit thereof is 5000 g/mol. When the polymerizable group equivalent of the silicone compound represented by the above formula (3) is within this range, the obtained sealant for electronic devices is superior in low outgassing properties and in wetting and spreading properties with respect to a substrate or an inorganic material film. Become. A more preferable lower limit of the polymerizable group equivalent weight of the silicone compound represented by the above formula (3) is 400 g/mol, and a more preferable upper limit thereof is 2000 g/mol.
In addition, the polymerizable group equivalent of the silicone compound represented by the above formula (3) is obtained by adding the weight (g) of the silicone compound represented by the above formula (3) to the silicone compound represented by the above formula (3). It is a value obtained by dividing by the number of moles (mol) of the polymerizable groups contained.

In the above formula (3), n is an integer of 1 or more and 1000 or less. When n in the above formula (3) is within this range, the resulting sealant for electronic devices has low outgassing properties, wet-spreadability with respect to a substrate or an inorganic material film, and excellent transparency. The preferable lower limit of n in the formula (3) is 5, the preferable upper limit is 20, the more preferable lower limit is 7, and the more preferable upper limit is 18.

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

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

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

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

The preferable lower limit of the content of the silicone compound represented by the formula (3) in 100 parts by weight of the curable resin is 0.01 parts by weight, and the preferable upper limit is 20 parts by weight. When the content of the silicone compound represented by the above formula (3) is within this range, the resulting sealant for electronic devices is excellent in low outgassing properties and wet spreadability with respect to 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 curable resin A preferable lower limit of is 0.01 parts by weight, and a 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 curable resin A preferable lower limit of is 0.1 parts by weight, and a preferable upper limit is 20 parts by weight. In addition, when the curable resin contains a plurality of types of compounds as the silicone compound represented by the formula (3), the polymerizable group equivalent of the silicone compound represented by the 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 curable resin contains other curable resins for the purpose of improving adhesion. You may
Examples of the other curable resins include epoxy compounds (hereinafter also referred to as "other epoxy compounds") having no structure represented by the above formula (1) and the above formula (3), the above formula (1) and Oxetane compounds not having the structure represented by the above formula (3) (hereinafter also referred to as "other oxetane compounds"), not having the structures represented by the above formulas (1) and (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 the present specification, the above-mentioned "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylic 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, 2,2'-diallyl bisphenol A type epoxy resin. 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, ortho-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkylpolyol type epoxy resin Examples thereof include resins, rubber-modified epoxy resins, glycidyl ester compounds, and the like. Among them, alicyclic epoxy resins are preferred.
Examples of commercially available alicyclic epoxy resins include alicyclic epoxy resins manufactured by Daicel Corporation, alicyclic epoxy resins manufactured by Shin Nihon Rika Kogyo Co., Ltd., and the like.
Examples of the alicyclic epoxy resins manufactured by Daicel include Celoxide 2000, Celoxide 2021P, Celoxide 2081, Celoxide 3000, Celoxide 8000, and Cychromer M-100.
Examples of the alicyclic epoxy resin manufactured by Shin Nihon Rika Kogyo Co., Ltd. include Sansocizer EPS.
Among the above alicyclic epoxy resins, those having no ether bond or ester bond other than those contained in the epoxy group are preferable from the viewpoint of suppressing the generation of outgassing. Examples of commercially available alicyclic epoxy resins having no ether bond or ester bond other than those contained in epoxy groups 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 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 novolac 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 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 ) acrylates and the like.
These other (meth)acrylic compounds may be used alone, or two or more of them may be used in combination.
In addition, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate.

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

Among them, alicyclic epoxy resins, 3-(allyloxy)oxetane, 3-ethyl-3-((2-ethylhexyloxy)methyl)oxetane are used as the other curable resins because of their low viscosity and high reactivity. , and 3-ethyl-3-(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane.

A preferable 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 a preferable upper limit thereof is 90 parts by weight. When the content of the other curable resin is within this range, the effect of improving the adhesiveness, etc., is excellent without deteriorating the applicability, etc. A more preferable lower limit for the content of the other curable resin is 10 parts by weight. The upper limit of the content of the other curable resin is more preferably 70 parts by weight, more preferably 60 parts by weight, and particularly preferably 40 parts by weight.

The electronic device sealant 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 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

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

Examples of the aromatic sulfonium salts include bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate, bis(4-( 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)sulfide tetrakis(pentafluorophenyl)borate, tris(4-(4-acetylphenyl)thiophenyl) sulfonium tetrakis(pentafluorophenyl)borate and the like.

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)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexa fluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylphenyl-4-( 1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate and the like.

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

Examples of the aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -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.

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-cyclopentadien-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 esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, and N-hydroxyimide sulfonates.

Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, A photocationic polymerization initiator manufactured by 3M, a photocationic polymerization initiator manufactured by BASF, a photocationic polymerization initiator manufactured by Rhodia, and the like can be mentioned.
Examples of the photocationic polymerization initiator manufactured by Midori Kagaku Co., Ltd. include DTS-200 and the like.
Examples of photo cationic polymerization initiators manufactured by Union Carbide include UVI6990 and UVI6974.
Examples of photo cationic polymerization initiators manufactured by ADEKA include SP-150 and SP-170.
Examples of photo cationic polymerization initiators manufactured by 3M include FC-508 and FC-512.
Examples of photo cationic polymerization initiators manufactured by BASF include IRGACURE261 and IRGACURE290.
Examples of the photo cationic polymerization initiator manufactured by Rhodia include PI2074.

The thermal cationic polymerization initiator has an anion moiety of BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or (BX ₄ ) ⁻ (where X is substituted with at least two fluorine or trifluoromethyl groups). sulfonium salts, phosphonium salts, ammonium salts, etc., composed of a phenyl group represented by a phenyl group. Among them, sulfonium salts and ammonium salts are preferred.

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

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

Examples of the ammonium salts 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- benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid and the like.

Examples of commercially available thermal cationic polymerization initiators include thermal cationic polymerization initiators manufactured by Sanshin Chemical Industry Co., Ltd., and thermal cationic polymerization initiators manufactured by King Industries.
Examples of the thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry include San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, and San-Aid SI-B4.
Examples of the thermal cationic polymerization initiator manufactured by King Industries include CXC1612 and CXC1821.

Examples of the radical photopolymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, benzyl, and thioxanthone-based compounds.

Examples of commercially available radical photopolymerization initiators include radical photopolymerization initiators manufactured by BASF Corporation and radical photopolymerization initiators manufactured by Tokyo Chemical Industry Co., Ltd.
Examples of photoradical polymerization initiators manufactured by BASF include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, and Lucirin TPO.
Examples of the radical photopolymerization initiator manufactured by Tokyo Kasei Kogyo Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

Examples of the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides, and the like.
Examples of the azo compounds include 2,2′-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile and the like.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, 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 of which are manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). made) and the like.

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 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 sealant for electronic devices has excellent curability. When the content of the polymerization initiator is 10 parts by weight or less, the curing reaction of the resulting sealant for electronic devices does not become too fast, the workability is improved, and the cured product becomes more uniform. be able to. A more preferable lower limit to 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 heat curing agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamide, 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, dihydrazide sebacate, dihydrazide isophthalate, dihydrazide adipic acid, and dihydrazide malonate.
Examples of the imidazole derivative 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- phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.
Examples of the acid anhydride include tetrahydrophthalic anhydride and ethylene glycol bis(anhydrotrimellitate).
These thermosetting agents may be used alone or in combination of two or more.

Examples of commercially available thermosetting agents include thermosetting agents manufactured by Otsuka Chemical Co., Ltd., and thermosetting agents manufactured by Ajinomoto Fine-Techno Co., Ltd.
Examples of the thermosetting agent manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the thermosetting agent manufactured by Ajinomoto Fine-Techno Co., Inc. include Amicure VDH, Amicure VDH-J, and Amicure UDH.

The content of the thermosetting agent has a preferable lower limit of 0.5 parts by weight and a preferable upper limit of 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 sealing agent for electronic devices has excellent thermosetting properties. When the content of the thermosetting agent is 30 parts by weight or less, the obtained sealant for electronic devices has excellent storage stability, and the cured product has excellent moisture resistance. A more preferable lower limit to the content of the thermosetting agent is 1 part by weight, and a more preferable upper limit is 15 parts by weight.

The electronic device sealant of the present invention may contain a sensitizer. The sensitizer serves to further improve the polymerization initiation efficiency of the polymerization initiator and further accelerate the curing reaction of the electronic device sealant 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 content of the sensitizer has a preferred lower limit of 0.01 parts by weight and a preferred upper limit of 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 exhibited more. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep portion without excessive 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 electronic device sealant of the present invention may further contain a silane coupling agent. The silane coupling agent serves to improve the adhesiveness between the electronic device sealant of the present invention and a substrate or the like.

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

The content of the silane coupling agent has a preferable lower limit of 0.1 parts by weight and a preferable upper limit of 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 resulting electronic device sealant while suppressing bleed-out due to excess silane coupling agent is excellent. . A more preferable lower limit to 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 electronic device sealant of the present invention may contain a curing retardant. By containing the curing retarder, the pot life of the resulting electronic device sealant can be lengthened.

Examples of the curing retarder include polyether compounds.
Examples of the polyether compounds include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, crown ether compounds, and the like. Among them, 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 with respect to 100 parts by weight of the curable resin. When the content of the curing retarder is within this range, the retarding effect can be exhibited more while suppressing the generation of outgassing when curing the obtained sealant for electronic devices. A more preferred lower limit to the content of the curing retarder is 0.1 parts by weight, and a more preferred upper limit is 3.0 parts by weight.

The electronic device sealant of the present invention may further contain a surface modifier within a range that does not impair the object of the present invention. By containing the above surface modifier, it is possible to impart flatness to the coating film of the electronic device sealant of the present invention.
Examples of the surface modifier include surfactants and leveling agents.

Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based agents.
Examples of commercially available surface modifiers include surface modifiers manufactured by BYK-Chemie Japan and surface modifiers manufactured by AGC Seimi Chemical.
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 Co., Ltd. include Surflon S-611.

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

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

As the ion exchange resin, any of a cation exchange type, an anion exchange type, and an amphoteric ion exchange type can be used. is preferred.

In addition, the sealant for electronic devices of the present invention may optionally contain various known additives such as reinforcing agents, softening agents, plasticizers, viscosity modifiers, ultraviolet absorbers, and antioxidants. good.

As a method for producing the sealant for an electronic device of the present invention, for example, a curable resin and a polymerizing A method of mixing an initiator and/or a thermosetting agent with an additive such as a silane coupling agent to be added as necessary.

The upper limit of the haze of the sealant for electronic devices of the present invention is 10%. When the haze is 10% or less, the transparency is excellent and can be suitably used for an organic EL display element or the like. A preferable upper limit of the haze is 5%, and a more preferable upper limit is 1%.
The haze means the ratio of diffuse transmitted light to total transmitted light, and can be measured using a spectrometer such as AUTOMATIC HAZE METER MODEL TC-III DPK (manufactured by Tokyo Denshoku Co., Ltd.).
As a sample for measuring the haze, a sealant is coated on a transparent substrate such as glass by a method such as spin coating to a thickness that is practically used, and then cured. The haze of the sealant for electronic devices is determined, for example, by applying the sealant to a glass plate to a thickness of 10 μm by a method such as spin coating, and then curing the sealant to obtain a cured product. Obtained by measuring haze.
Moreover, the haze of the sealant for electronic devices can be adjusted by adjusting the types and content ratios of the respective components contained.

The sealant for electronic devices of the present invention preferably has a lower limit of 5 mPa·s and a preferred upper limit of viscosity measured at 25° C. and 100 rpm using an E-type viscometer. When the viscosity is within this range, the sealant for electronic devices of the present invention is superior in ink jet applicability and shape retention after application. A more preferable lower limit of the viscosity of the electronic device sealant is 10 mPa·s, and a more preferable upper limit thereof is 80 mPa·s.
It should be noted that the electronic device sealant of the present invention may be heated at the time of coating by inkjet to reduce the viscosity before coating.

The preferred lower limit of the total light transmittance of the cured product of the electronic device sealant of the present invention at a wavelength of 380 nm or more and 800 nm or less is 80%. When the total light transmittance is 80% or more, it can be preferably 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 METER MODEL TC-III DPK (manufactured by Tokyo Denshoku Co., Ltd.).
If the cured product used for measuring the total light transmittance is a photocurable sealant, for example, it is obtained by irradiating the sealant with 3000 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm with an LED lamp. If it is a thermosetting sealant, it can be obtained by heating at 80° C. for 1 hour, for example.

The electronic device sealant 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 100 hours of irradiation with ultraviolet rays is 85% or more, the transparency becomes more excellent, the loss of light emission becomes smaller, and the color reproducibility becomes more excellent. A more preferable lower limit of the transmittance after 100 hours of UV irradiation is 90%, and a more preferable lower limit is 95%.
Conventionally known light sources such as a xenon lamp and a carbon arc lamp can be used as the light source for irradiating the ultraviolet rays.
In addition, if the cured product used for measuring the transmittance after being irradiated with the ultraviolet rays for 100 hours is a photocurable sealant, for example, the sealant is irradiated with ultraviolet light having a wavelength of 365 nm at 3000 mJ/cm using an LED lamp. ² irradiation, and 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 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. The following are preferred. When the moisture permeability is 100 g/m ² or less, for example, when it is used for manufacturing an organic EL display element as an electronic device, it has the effect of suppressing the generation of dark spots due to moisture reaching the organic light-emitting material layer. become excellent.
In addition, if the cured product used for measuring the moisture permeability is a photocurable sealant, for example, it can be obtained by irradiating the sealant with 3000 mJ/cm ² of ultraviolet light having a wavelength of 365 nm with an LED lamp. A thermosetting sealant can be obtained by heating at 80° C. for 1 hour, for example.

Further, the electronic device sealant 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 water content of the cured product is less than 0.5%, for example, when it is used for the production of 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. become 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 determining by the Karl Fischer method in accordance with JIS K 7251, and a method of determining weight increase after water absorption in accordance with JIS K 7209-2.
If the cured product used for measuring the water content is a photocurable sealant, for example, it can be obtained by irradiating the sealant with 3000 mJ/cm ² of ultraviolet light having a wavelength of 365 nm using an LED lamp. A thermosetting sealant can be obtained by heating at 80° C. for 1 hour, for example.

A method for producing an electronic device using the electronic device sealant of the present invention includes, for example, a step of applying the electronic device sealant of the present invention to at least one of two substrates; A method including a step of curing the electronic device sealant by light irradiation and/or heating, and a step of bonding the two substrates together may be used.

In the step of applying the electronic device sealant of the present invention to at least one of the two base materials, the electronic device sealant of the present invention may be applied to the entire surface of the base material. It may be partially applied. For example, when manufacturing an organic EL display element as an electronic device, the shape of the sealing portion of the electronic device sealant 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. There is no particular limitation as long as the shape is flexible. That is, it may have a shape that completely covers the laminate, a closed pattern may be formed in the peripheral portion of the laminate, or a partial opening is provided in the peripheral portion of the laminate. A pattern of shapes may be formed.
Moreover, as a method of apply|coating the sealant for electronic devices of this invention, the inkjet method is preferable.

When an organic EL display element is produced as the electronic device, the substrate (hereinafter also referred to as one substrate) to which the electronic device sealant 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 having a layer formed thereon, or the base material may be a base material on which the laminate is not formed.
When the one base material is a base material on which the laminate is not formed, the composition of the present invention is attached to the one base material so that the laminate can be protected from the outside air when the other base material is attached. An electronic device sealant may be applied. That is, it is applied to the entire surface of the position of the laminate when the other base material is attached, or the position of the laminate when the other base material is attached is completely covered. A closed pattern of the encapsulant portion may be formed in a shape that fits within.

Moreover, the laminate may be coated with an inorganic material film.
As the inorganic material constituting the inorganic material film, conventionally known materials can be used, and examples thereof include silicon nitride (SiN _x ) and silicon oxide (SiO _x ). The inorganic material film may consist of one layer, or may be a laminate of a plurality of types of layers. Alternatively, the inorganic material film and the resin film made of the sealant for an electronic device of the present invention may be alternately repeated to coat the laminate.

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 together, or after the step of bonding the two substrates together. You can do it later.
When the step of curing the electronic device sealant by light irradiation and/or heating is performed before the step of bonding the two substrates together, the electronic device sealant of the present invention can be cured by light irradiation and/or heating. / Or, it is preferable that the usable time from heating to curing reaction proceeds and adhesion becomes impossible is 1 minute or more. When the pot life is 1 minute or more, the progress of curing before bonding two substrates can be suppressed, and the adhesive strength after bonding can be increased.

When the electronic device sealant is cured by light irradiation, the electronic device sealant 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 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, LED lamps, fluorescent lamps, sunlight, electron beam irradiation devices, and the like. These light sources may be used alone or in combination of two or more.
These light sources are appropriately selected according to the absorption wavelength of the photo cationic polymerization initiator and the photo radical polymerization initiator.

Examples of means for irradiating the sealant for electronic devices of the present invention with light include simultaneous irradiation with various light sources, sequential irradiation with a time lag, combined irradiation of simultaneous irradiation and sequential irradiation, and the like. Irradiation means may be used.

When the electronic device sealant is cured 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 substrates together, the method of bonding the two substrates together is not particularly limited, but it is preferable to bond the two substrates together under a reduced pressure atmosphere.
A preferable lower limit of the degree of vacuum under the reduced pressure atmosphere is 0.01 kPa, and a preferable upper limit thereof is 10 kPa. When the degree of vacuum under the reduced pressure atmosphere is within this range, it is possible to bond two substrates together without spending a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump. Air bubbles can be more efficiently removed from the sealant for electronic devices of the present invention.

The sealant for electronic devices of the present invention has low outgassing properties, excellent wettability and spreadability on a substrate or an inorganic material film, and excellent transparency, and thus can be suitably used as a sealant for organic EL display devices. A sealant for an organic EL display device using the sealant for an electronic device of the present invention is also one aspect of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the sealant for electronic devices which is excellent in low outgassing property, wettability to a board|substrate or an inorganic material film|membrane, and transparency can be provided. Moreover, according to this invention, the sealant for organic EL display elements which uses this sealant for electronic devices can be provided.

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

(Examples 1 to 16, Comparative Examples 1 to 3)
According to the blending ratios described in Tables 1 to 3, each material was uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer to obtain the electrons of Examples 1 to 16 and Comparative Examples 1 to 3. A device sealant was produced. As the homodisper type stirring mixer, Homodisper L type (manufactured by Primix) was used. Each of the obtained sealants for electronic devices was applied to a 5 cm square glass plate using a spin coater to a thickness of 10 μm, and then irradiated with 3000 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm using an LED lamp to form a cured product. Obtained. Tables 1 to 3 show the haze of the resulting cured product measured using a spectrometer. As a spectrometer, AUTOMATIC HAZE METER MODEL TC-III DPK (manufactured by Tokyo Denshoku Co., Ltd.) was used.
The silicone compound represented by formula (1) and the silicone compound represented by formula (3) in the table are described in detail below.
"SIB1092.0" is represented by formula (1) in which all R ¹ are methyl groups, and X ¹ and X ² are groups represented by formula (2-2) above (R ² is a dimethylene group) It is a silicone compound (polymerizable group equivalent weight: 191 g/mol).
"X-22-163" is a formula (1) in which all R ¹ are methyl groups, 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 represented (polymerizable group equivalent weight: 200 g/mol).
"X-22-164" is a group in which all R ¹ are methyl groups, and X ¹ and X ² are groups represented by the above formula (2-4) (R ² is a trimethylene group and R ⁵ is a methyl group); It is a silicone compound represented by formula (1) (polymerizable group equivalent: 190 g/mol).
The “silicone compound A having an oxetanyl group” has all R ¹ methyl groups, and X ¹ and X ² are groups 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) (polymerizable group equivalent: 223 g/mol) represented by the formula (1).
"X-22-169AS", all of R ⁶ are methyl groups, X ³ and X ⁴ are groups represented by the above formula (4-2) (R ⁷ is a dimethylene group), and n is 8; A silicone compound represented by formula (3) (polymerizable group equivalent: 500 g/mol).
"X-22-163A", wherein all R ⁶ are methyl groups, X ³ and X ⁴ are groups represented by the above formula (4-1) (R ⁷ is a trimethylene group), and n is 18; It is a silicone compound represented by formula (3) (polymerizable group equivalent: 1000 g/mol).
"X-22-173DX" is a group in which all R ⁶ are methyl groups, one of X ³ and X ⁴ is a methyl group, and the other is a group represented by the above formula (4-1) (R ⁷ is trimethylene group) and n is a silicone compound represented by the formula (3) in which n is 60 (polymerizable group equivalent: 4600 g/mol).
The “silicone compound B having an oxetanyl group” has all R ⁶ being methyl groups, X ³ and X ⁴ being groups represented by the above formula (4-3) (R ⁷ is a trimethylene group, R ⁸ is an ethyl group , R9 is a methylene group) and n is a silicone compound represented by the formula ( ³ ) (polymerizable group equivalent: 482 g/mol).

<Evaluation>
The electronic device sealants obtained in Examples and Comparative Examples were evaluated as follows. The results are shown in Tables 1-3.

(viscosity)
The viscosity of each electronic device sealant obtained in 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)
The outgassing generated during heating of the cured product of each electronic device sealant obtained in Examples and Comparative Examples was measured by gas chromatography using a headspace method as described below.
First, 100 mg of each electronic device sealant was applied with an applicator to a thickness of 300 μm. Next, after curing the sealant by irradiating 3000 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm with an LED lamp, the cured sealant was put into a headspace vial and the vial was sealed. C. for 30 minutes, and the generated gas was measured by the headspace method. The sealant obtained in Example 15 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 generated gas was less than 300 ppm, "Δ" when it was 300 ppm or more and less than 500 ppm, and "X" when it was 500 ppm or more.

(Wet spreadability)
Each of the electronic device sealants obtained in Examples and Comparative Examples was dropped onto alkali-washed alkali-free glass in a droplet volume of 10 picoliters using an inkjet ejection device, and after 5 minutes from the dropping. The diameter of the droplet on the alkali-free glass was measured. Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.) was used as the inkjet ejection device, and AN100 (manufactured by AGC Co.) 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 was prepared by forming an ITO electrode to a thickness of 1000 Å. After ultrasonically cleaning the substrate with acetone, an alkaline aqueous solution, deionized water, and isopropyl alcohol for 15 minutes each, the substrate is cleaned with boiled isopropyl alcohol for 10 minutes, and further treated immediately before with a UV-ozone cleaner. gone. NL-UV253 (manufactured by Nippon Laser Electronics Co., Ltd.) was used as the UV-ozone cleaner.
Next, the substrate after the previous treatment was fixed to a substrate holder of a vacuum deposition apparatus, 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 in the vacuum chamber was reduced to 1×10 ⁻⁴ Pa. Then, the crucible containing α-NPD was heated to deposit α-NPD on the substrate at a deposition rate of 15 Å/s to form a hole transport layer with a film thickness of 600 Å. Next, the crucible containing Alq ₃ was heated, and an organic light-emitting material layer with a thickness of 600 Å was formed at a deposition rate of 15 Å/s. After that, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum deposition apparatus having a tungsten resistance heating boat, and lithium fluoride is transferred to one of the tungsten resistance heating boats in the vacuum deposition apparatus. 200 mg was put, and 1.0 g of aluminum wire was put into another tungsten resistance heating boat. After that, the pressure inside the vapor deposition device of the vacuum deposition apparatus was reduced to 2×10 ⁻⁴ Pa, and after lithium fluoride was deposited at a deposition rate of 0.2 Å/s to form a 5 Å film, aluminum was deposited at a rate of 20 Å/s to form a 1000 Å film. did. The inside of the evaporator 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 on the substrate on which the obtained laminate was placed, and an inorganic material film A was formed by plasma CVD so as to cover the entire laminate.
The plasma CVD method uses SiH ₄ gas and nitrogen gas as raw material gases, with flow rates of SiH ₄ gas of 10 sccm and nitrogen gas of 200 sccm, RF power of 10 W (frequency of 2.45 GHz), chamber temperature of 100 ° C., chamber It was carried out 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 sealants obtained in Examples and Comparative Examples was pattern-coated at 40° C. on the substrate coated with the inorganic material film A using an inkjet discharge apparatus. A material printer DMP-2831 (manufactured by FUJIFILM Corporation) was used as an inkjet ejection device.
Thereafter, an LED lamp was used to irradiate 3000 mJ/cm ² of ultraviolet rays having a wavelength of 365 nm to cure the electronic device sealant and form a resin protective film. The sealant obtained in Example 15 was cured by heating at 80° C. for 1 hour instead of being irradiated 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×12 mm is placed on the substrate, and an inorganic material film B is formed by plasma CVD so as to cover the entire resin protective film, thereby producing an organic EL display device. got
The plasma CVD method was performed under the same conditions as the above "(Coating with inorganic material film A)".
The thickness of the formed inorganic material film B was about 1 μm.

(Light emitting state of organic EL display element)
After exposing the resulting organic EL display device to an environment of 85° C. temperature and 85% humidity for 100 hours, a voltage of 3 V was applied to determine the light emission state of the organic EL display device (presence or absence of dark spots and peripheral quenching of pixels). was visually observed. The organic EL display element was rated as "○" when it emitted light uniformly without dark spots or peripheral quenching, "△" when dark spots or peripheral quenching was observed, and "×" when the non-light-emitting area was remarkably enlarged. Display performance was evaluated.

ADVANTAGE OF THE INVENTION According to this invention, the sealant for electronic devices which is excellent in low outgassing property, wettability to a board|substrate or an inorganic material film|membrane, and transparency can be provided. Moreover, according to this invention, the sealant for organic EL display elements which uses this sealant for electronic devices can be provided.

Claims (7)

An electronic device sealant 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),
Using an E-type viscometer, the viscosity measured at 25 ° C. and 100 rpm is 5 mPa s or more and 200 mPa s or less,
An electronic device sealant, wherein the haze of the entire electronic device sealant is 10% or less.

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 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 is hydrogen or 1 carbon atom Represents an alkyl group of 6 or less, R ⁴ represents a bond or a methylene group, and R ⁵ in formula (2-4) represents hydrogen or a methyl group.

In formula (3), R ⁶ represents an alkyl group having 1 to 10 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) Represents a group represented by n is an integer of 1 or more and 1000 or less. However, at least one of X ³ and X ⁴ represents a group represented by formula (4-1), (4-2), (4-3) or (4-4) below.

In formulas (4-1) to (4-4), R ⁷ represents a bond or an alkylene group having 1 to 6 carbon atoms, and in formula (4-3), R ⁸ is hydrogen or 1 carbon atom Represents an alkyl group of 6 or less, R ⁹ represents a bond or a methylene group, and R ¹⁰ in formula (4-4) represents hydrogen or a methyl group. In the silicone compound represented by formula (1), both X ¹ and X ² in formula (1) are represented by formulas (2-1), (2-2), (2-3), or 2. The sealant for electronic devices according to claim 1, which is a compound represented by (2-4). In the silicone compound represented by formula (3), both X ³ and X ⁴ in formula (3) are represented by formulas (4-1), (4-2), (4-3), or 3. The sealant for electronic devices according to claim 1, which is a compound represented by (4-4). 4. The electronic device encapsulant according to claim 1, wherein the content of the silicone compound represented by the formula (3) in 100 parts by weight of the curable resin is 0.01 parts by weight or more and 20 parts by weight or less. agent. The curable resin further includes, as other curable resins, an epoxy compound having no structure represented by the formula (1) or the formula (3), the formula (1) or the formula (3) At least one selected from the group consisting of an oxetane compound having no structure represented by the formula (1) and a (meth)acrylic compound having no structure represented by the formula (3), and a vinyl ether compound 5. The sealant for electronic devices according to claim 1, 2, 3 or 4, which contains seeds. 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 -(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane according to claim 5, containing at least one selected from the group consisting of oxetane. A sealant for an organic EL display element, which is obtained by using the sealant for an electronic device according to claim 1, 2, 3, 4, 5 or 6 .