KR102680357B1 - Sealant for electronic device, and method for manufacturing electronic device - Google Patents

Abstract

The purpose of the present invention is to provide a sealant for electronic devices that can be easily applied by an inkjet method and can reduce damage to inkjet devices. Additionally, the present invention aims to provide a method of manufacturing an electronic device using the electronic device sealant.
The present invention is a sealant for electronic devices that contains a curable resin, a polymerization initiator and/or a thermosetting agent, and is used for application by an inkjet method, wherein the curable resin contains a silicone compound represented by the following formula (1): It is a sealant for electronic devices. In formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and X ^{1 and} , represents a group represented by (2-3) or (2-4), and X ³ represents a group represented by the following formula (2-1), (2-2), (2-3) or (2-4) . m is an integer from 0 to 100, and n is an integer from 0 to 100. However, when n is 0, at least one of X ¹ and X ² represents a group represented by the following formula (2-1), (2-2), (2-3), or (2-4). In formulas (2-1) to (2-4), R ² represents a bond or an alkylene group having 1 to 6 carbon atoms, and in formula (2-3), R ³ represents hydrogen or an alkylene group having 1 to 6 carbon atoms. represents an alkyl group, R ⁴ represents a bond or a methylene group, and in formula (2-4), R ⁵ represents hydrogen or a methyl group.

Description

Sealant for electronic devices and method for manufacturing electronic devices {SEALANT FOR ELECTRONIC DEVICE, AND METHOD FOR MANUFACTURING ELECTRONIC DEVICE}

The present invention relates to a sealant for electronic devices that can be easily applied by an inkjet method and can reduce damage to inkjet devices. Additionally, the present invention relates to a method of manufacturing an electronic device using the electronic device sealant.

Recently, research on electronic devices using organic thin film devices, such as organic electroluminescence (hereinafter also referred to as organic EL) display devices and organic thin film solar cell devices, is in progress. Since organic thin film devices can be easily manufactured by vacuum deposition or solution application, they are also 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 opposing electrodes, and electrons are injected into this organic light-emitting material layer from one electrode and holes are injected from the other electrode. As a result, electrons and holes combine within the organic light emitting material layer to emit light. In this way, since organic EL display elements self-emit, they have the advantage of having good visibility, being able to be thinned, and being driven at low direct current voltages compared to liquid crystal display elements that require a backlight.

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

These organic thin film devices have a problem in that their performance deteriorates rapidly when the organic layer or electrode is exposed to external air. Therefore, in order to increase stability and durability, it becomes essential to seal the organic thin film element and block it from moisture and oxygen in the atmosphere. As a method of sealing an organic thin film element, a conventional method was to seal it using a sealing can with an absorbent formed inside. However, in the method of sealing with a sealing can, it becomes difficult to reduce the thickness of the electronic device. Therefore, development of methods for sealing organic thin film devices that do not use sealing cans is in progress.

Patent Document 1 discloses a method of sealing the organic luminescent material layer and 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 plays a role in preventing pressure on the organic layer or electrode due to internal stress of the silicon nitride film.

In the method of sealing with a silicon nitride film disclosed in Patent Document 1, the organic thin film element cannot be completely covered when forming the silicon nitride film due to irregularities on the surface of the organic thin film element, adhesion of foreign substances, cracks due to internal stress, etc. There are cases where this is not possible. If the covering with the silicon nitride film is incomplete, moisture penetrates into the organic layer through the silicon nitride film.

As a method for preventing moisture from entering the organic layer, Patent Document 2 discloses a method of alternately depositing an inorganic material film and a resin film, and Patent Document 3 and Patent Document 4 disclose a method of depositing a resin film on an inorganic material film. A method of forming is disclosed.

As a method of forming a resin film, there is a method of applying a liquid curable resin composition on a substrate using an inkjet method and then curing the curable resin composition. Using such an inkjet 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 substrate by an inkjet method, the viscosity of the sealant needs to be low in order to stably discharge it from a nozzle. Methods for making the sealant for electronic devices have a viscosity appropriate for the inkjet method include blending an organic solvent with the sealant for electronic devices, or using a curable resin with a low molecular weight as a blended curable resin. In the resin film produced using this, there are problems such as deterioration of the organic light-emitting material layer due to the remaining organic solvent or generation of outgassing by plasma, and when a curable resin with a low molecular weight is used, the inkjet device There was a problem of causing damage to the device, such as swelling of the adhesive or rubber material used in the head part, etc.

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

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

The purpose of the present invention is to provide a sealant for electronic devices that can be easily applied by an inkjet method and can reduce damage to inkjet devices. Additionally, the present invention aims to provide a method of manufacturing an electronic device using the electronic device sealant.

The present invention is a sealant for electronic devices that contains a curable resin, a polymerization initiator and/or a thermosetting agent, and is used for application by an inkjet method, wherein the curable resin contains a silicone compound represented by the following formula (1): It is a sealant for electronic devices.

[Formula 1]

In formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and X ^{1 and} , represents a group represented by (2-3) or (2-4), and X ³ represents a group represented by the following formula (2-1), (2-2), (2-3) or (2-4) . m is an integer from 0 to 100, and n is an integer from 0 to 100. However, when n is 0, at least one of X ¹ and X ² represents a group represented by the following formula (2-1), (2-2), (2-3), or (2-4).

[Formula 2]

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

The present invention is described in detail below.

The present inventors have found that a silicone compound having a specific structure is difficult to swell a rubber material or adhesive, and has weak intermolecular forces, so the viscosity does not become excessively high even if the molecular weight is somewhat large. Therefore, by mixing a silicone compound with a specific structure as a curable resin, the present inventors were able to obtain a sealant for electronic devices that can be easily applied by an inkjet method and can reduce damage to inkjet devices. was discovered and the present invention was completed.

In addition, since the silicone compound having the specific structure has a low surface tension, the obtained sealant for electronic devices has excellent wet and spreadability, and can be easily reduced into a thin film by the inkjet method.

The sealant for electronic devices of the present invention contains a curable resin.

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

By containing the silicone compound represented by the above formula (1), the sealant for electronic devices of the present invention has a viscosity suitable for application by the inkjet method and can reduce device damage.

In the above formula (1), the preferable lower limit of m is 1, and the preferable upper limit is 10. When m is 1 or more, the effect of suppressing swelling of the rubber material or adhesive becomes more excellent. When m is 10 or less, inkjet coating properties and low outgassing properties become more excellent, and the cured product has more desirable hardness. A more preferable upper limit of m is 5.

Moreover, in the above formula (1), the preferable upper limit of n is 10. When n is 10 or less, inkjet coating properties and low outgassing properties become more excellent, and the cured product has more desirable hardness. A more preferable upper limit of n is 5.

As the silicone compound represented by the formula (1), at least ^one of X ¹ , X ² and It is preferable that it is a compound, and it is more preferable that it is at least one type selected from the group consisting of a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3). desirable.

[Formula 3]

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

From the viewpoint of anti-swelling properties of rubber materials, inkjet applicability, low outgassing properties, and flexibility (hardness) of the cured product, o in formula (3-1), p in formula (3-2), and formula (3- It is preferable that q in 3) is an integer of 1 to 6, respectively.

In addition to the silicone compound represented by the formula (1), the curable resin may contain other curable resins for purposes such as improving adhesiveness.

Examples of the other curable resins include epoxy compounds not having the structure represented by the formula (1) (hereinafter also referred to as “other epoxy compounds”), and oxetane compounds not having the structure represented by the formula (1) (hereinafter referred to as “other epoxy compounds”). , “other oxetane compounds”), (meth)acrylic compounds not having the structure represented by the above formula (1) (hereinafter also referred to as “other (meth)acrylic compounds”), and vinyl ether compounds. At least one species selected from the group is preferred.

In addition, in this specification, the “(meth)acryl” means acrylic or methacryl, the “(meth)acrylic compound” means a compound having a (meth)acryloyl group, and the “(meth)acrylic compound” means a compound having a (meth)acryloyl group. “Loyl” means acryloyl or methacryloyl.

Examples of the other epoxy compounds include bisphenol A-type epoxy resin, bisphenol E-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol O-type epoxy resin, and 2,2'-diallylbisphenol. A-type epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol-type epoxy resin, propylene oxide-added bisphenol A-type epoxy resin, resorcinol-type epoxy resin, biphenyl-type epoxy resin, sulfide-type epoxy resin, diphenyl ether-type epoxy resin. , dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol epoxy resin. Examples include rockfish-type epoxy resins, glycidylamine-type epoxy resins, alkyl polyol-type epoxy resins, rubber-modified epoxy resins, and glycidyl ester compounds. Among them, alicyclic epoxy resin is preferable.

Among the above-mentioned alicyclic epoxy resins, commercially available ones include, for example, Celoxide 2000, Celoxide 2021P, Celoxide 2081, Celoxide 3000, Celoxide 8000, Cyclomer M-100 (all manufactured by Daicel), and Oxygen Low EPS (manufactured by Nippon Ewha Industry Co., Ltd.), etc. can be mentioned.

Among the above-described alicyclic epoxy resins, those that do not have ether bonds or ester bonds 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 that do not have ether bonds or ester bonds other than those contained in the epoxy group include Celoxide 2000, Celoxide 3000, and Celoxide 8000.

These other epoxy compounds may be used individually, or two or more types may be used in combination.

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, phenolnovolakoxetane, 1,4-bis(((3-ethyl-3-oxetanyl ) methoxy) methyl) benzene, etc.

These other oxetane compounds may be used individually, or two or more types may be used in combination.

Examples of the other (meth)acrylic compounds include glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)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, etc. are mentioned.

These other (meth)acrylic compounds may be used individually, or two or more types may be used in combination.

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, and diethylene glycol. Divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, etc. are mentioned.

These vinyl ether compounds may be used individually, or two or more types may be used in combination.

Among them, because of their high reactivity at low viscosity, the other curable resins mentioned above include alicyclic epoxy resin, 3-(allyloxy)oxetane, and 3-ethyl-3-((2-ethylhexyloxy)methyl)oxetane. , and 3-ethyl-3(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane.

When containing the other curable resins, the preferred lower limit of the content of the silicone compound represented by the formula (1) is 5 parts by weight based on 100 parts by weight of the total curable resin. When the content of the silicone compound represented by the above formula (1) is 5 parts by weight or more, both the effect of excellent applicability by the inkjet method and the effect of reducing damage to the inkjet device are more excellent. A more preferable lower limit of the content of the silicone compound represented by the above formula (1) is 10 parts by weight.

In addition, the other curable resins do not need to be contained, but when the other curable resins are contained, the content of the silicone compound represented by the formula (1) has a preferable upper limit of 90 parts by weight relative to 100 parts by weight of the total curable resin. am. When the content of the silicone compound represented by the formula (1) is 90 parts by weight or less, the other curable resins can further exert effects such as improving adhesion.

The sealant 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 preferably used.

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

As the ionic photoacid generating type photocation polymerization initiator, for example, the anion moiety is BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (provided that X is at least 2) aromatic sulfonium salt, aromatic iodonium salt, aromatic diazonium salt, aromatic ammonium salt, (2,4-cyclopentadien-1-yl)(( 1-methylethyl)benzene)-Fe salt, etc. may be mentioned.

Examples of the aromatic sulfonium salt include bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate. Roantimonate, bis(4-(diphenylsulfonio)phenyl)sulfide bistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfide tetrakis(pentafluorophenyl)borate , diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetra Fluoroborate, diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium Tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfide bishexafluoro Phosphate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfidebishexafluoroantimonate, bis(4-(di(4-(2-hyde) Roxyethoxy))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, etc. are mentioned.

Examples of the aromatic iodonium salt include diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetrafluoroborate, and diphenyl iodonium tetrakis (pentafluorocarbonate). Phenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium hexafluoroantimonate )Iodium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate Roantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, etc. can be mentioned.

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

Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, and 1-benzyl-2-cyano. Pyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naph Tylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium Tetrakis(pentafluorophenyl)borate, etc. can be mentioned.

The (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt includes, 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(pentafluorophenyl)borate, etc.

Examples of the nonionic photo acid generating type photo cation polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimide sulfonate, etc. there is.

Among the above-mentioned photocationic polymerization initiators, commercially available ones include, for example, DTS-200 (manufactured by Midori Chemical Co., Ltd.), UVI6990, UVI6974 (all manufactured by Union Carbide Co., Ltd.), SP-150, and SP-170 (all manufactured by ADEKA Co., Ltd.) , FC-508, FC-512 (all manufactured by 3M), IRGACURE 261, IRGACURE 290 (manufactured by BASF), and PI2074 (manufactured by Rhodia).

As the thermal cationic polymerization initiator, the anion moiety is BF ₄ ^- , PF ₆ ^- , SbF ₆ ^- , or (BX ₄ ) ^- (provided that X is substituted with at least two fluorine or trifluoromethyl groups) phenyl group), sulfonium salts, phosphonium salts, ammonium salts, etc. can be mentioned. Among them, sulfonium salts and ammonium salts are preferable.

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

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

Examples of the ammonium salt include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, and dimethylphenyl (4-methoxybenzyl). Ammonium tetrakis(pentafluorophenyl)borate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methylbenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methylbenzyl)ammonium Hexafluorotetrakis(pentafluorophenyl)borate, methylphenyldibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammoniumtetrakis(pentafluorophenyl)borate, phenyltribenzyl Ammonium tetrakis(pentafluorophenyl)borate, dimethylphenyl(3,4-dimethylbenzyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-diethyl-N-benzylaniliniumtetrafluoroborate, N,N-dimethyl-N-benzylpyridiniumhexafluoroantimonate, N,N-diethyl-N-benzylpyridiniumtrifluoro Methanesulfonic acid, etc. can be mentioned.

Among the thermal cationic polymerization initiators, commercially available ones include, for example, San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, and San-Aid SI-B4 (all from Sanshin Chemical) (manufactured by Kogyo Industries), CXC1612, and CXC1821 (all manufactured by King Industries).

Examples of the photo radical polymerization 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. Compounds, etc. can be mentioned.

Among the photo radical polymerization initiators, commercially available ones include, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF), Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.

Examples of the thermal radical polymerization initiator include those made of azo compounds, organic peroxides, etc.

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

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

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

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 better 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, workability is improved, and the cured product can be made more uniform. The more preferable lower limit of the content of the polymerization initiator is 0.05 parts by weight, and the 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 compounds include 1,3-bis(hydrazinocarbonoethyl-5-isopropylhydantoin), sebacic acid dihydrazide, isophthalic acid dihydrazide, and adipic acid dihydrazide. Drazide, malonic acid dihydrazide, etc. can be mentioned.

The imidazole derivatives include, for example, 1-cyanoethyl-2-phenylimidazole, N-(2-(2-methyl-1-imidazolyl)ethyl)urea, and 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-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. I can hear it.

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

These thermosetting agents may be used individually, or two or more types may be used in combination.

Examples of commercially available thermosetting agents include SDH, ADH (all manufactured by Otsuka Chemicals), Amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Finetechno). .

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 sealant for electronic devices 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 even more excellent storage stability, and the cured product has even more excellent moisture resistance. The more preferable lower limit of the content of the thermosetting agent is 1 part by weight, and the more preferable upper limit is 15 parts by weight.

The sealant for electronic devices of the present invention may contain a sensitizer. The sensitizer has a role in further improving the polymerization initiation efficiency of the polymerization initiator and further promoting the curing reaction of the sealant for electronic devices of the present invention.

Examples of the sensitizer include thioxanthone-based compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 2 , 4-dichlorobenzophenone, o-benzoylmethyl benzoate, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, etc.

The content of the sensitizer has a preferable lower limit of 0.01 parts by weight and a preferable 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 part by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to the deep part without excessive absorption. The more preferable lower limit of the content of the sensitizer is 0.1 part by weight, and the more preferable upper limit is 1 part by weight.

It is preferable that the sealant for electronic devices of the present invention further contains a silane coupling agent. The silane coupling agent has a role in improving the adhesion between the sealant for electronic devices of the present invention and a substrate.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, etc. can be mentioned. These silane compounds may be used individually, or two or more types may be used together.

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 adhesion of the resulting sealant for electronic devices is more excellent while suppressing bleed-out due to excess silane coupling agent. The more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and the more preferable upper limit is 5 parts by weight.

The sealant for electronic devices of the present invention may contain a curing retardant. By containing the curing retardant, the pot life of the obtained sealant for electronic devices can be prolonged.

Examples of the curing retardant include polyether compounds.

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

The content of the curing retardant 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 retardant is within this range, the retarding effect can be further exerted while suppressing the generation of outgassing when curing the obtained sealant for electronic devices. The more preferable lower limit of the content of the curing retardant is 0.1 part by weight, and the more preferable upper limit is 3.0 parts by weight.

The sealant for electronic devices of the present invention may further contain a surface modifier within a range that does not impair the purpose of the present invention. By containing the surface modifier, flatness of the coating film can be imparted to the sealant for electronic devices of the present invention.

Examples of the surface modifier include surfactants and leveling agents.

Examples of the surfactant and the leveling agent include silicone-based, acrylic-based, and fluorine-based agents.

Examples of commercially available surfactants and leveling agents include BYK-340, BYK-345 (all manufactured by Big Chemi Japan), Surfron S-611 (manufactured by AGC Semichemical), etc. You can.

The sealant for electronic devices of the present invention may contain 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 the range that does not impair the transparency of the cured product.

Compounds that react with the generated acid include substances that neutralize the acid, for example, carbonates or hydrogen carbonates of alkali metals or alkaline earth metals. Specifically, for example, calcium carbonate, calcium bicarbonate, sodium carbonate, sodium bicarbonate, etc. are used.

As the ion exchange resin, cation exchange type, anion exchange type, and both ion exchange type can be used. In particular, cation exchange type or both ion exchange type that can adsorb chloride ions are preferred.

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

As a method of manufacturing the sealant for electronic devices of the present invention, for example, a curable resin is polymerized using a mixer such as a homodisper, homomixer, universal mixer, planetary mixer, kneader, or 3 roll. A method of mixing an initiator and/or a thermosetting agent and additives such as a silane coupling agent added as needed can be mentioned.

The sealant for electronic devices of the present invention has a preferable lower limit of viscosity of 5 mPa·s and a preferable upper limit of 200 mPa·s when measured using an E-type viscometer under conditions of 25°C and 100 rpm. When the viscosity is within this range, the sealant for electronic devices of the present invention has better inkjet applicability and shape retention after application. The more preferable lower limit of the viscosity of the electronic device sealant is 10 mPa·s, and the more preferable upper limit is 80 mPa·s.

Additionally, when applying by inkjet, the sealant for electronic devices of the present invention may be heated to reduce the viscosity and applied.

The preferable lower limit of the total light transmittance of the cured product of the sealant for electronic devices of the present invention at a wavelength of 380 to 800 nm is 80%. When the total light transmittance is 80% or more, it can be more preferably used in 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, for example, using a spectrometer such as AUTOMATIC HAZE MATER MODEL TC=III DPK (manufactured by Tokyo Denshoku Corporation).

The sealant for electronic devices of the present invention preferably has a transmittance of 85% or more at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours with an optical path length of 20 μm. When the transmittance after irradiating the above-mentioned ultraviolet rays for 100 hours is 85% or more, transparency becomes more excellent, loss of luminescence is small, and color reproducibility becomes more excellent. The more preferable lower limit of the transmittance after irradiating the above ultraviolet rays for 100 hours is 90%, and the more preferable lower limit is 95%.

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

The sealant for electronic devices of the present invention preferably has a moisture permeability of 100 g/m2 or less at a thickness of 100 μm, as measured by exposing the cured product to an environment of 85°C and 85%RH for 24 hours in accordance with JIS Z 0208. . When the moisture permeability is 100 g/m 2 or less, for example, when used in the manufacture of an organic EL display element as an electronic device, the effect of suppressing the occurrence of dark spots due to moisture reaching the organic luminescent material layer is more excellent. It becomes a thing.

In addition, the sealant for electronic devices of the present invention preferably has a water content of less than 0.5% when the cured product is exposed to an environment of 85°C and 85%RH for 24 hours. When the moisture content of the cured product is less than 0.5%, for example, when used in 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 is more excellent. A more preferable upper limit of the water content of the cured product is 0.3%.

Examples of the method for measuring the water content include a method of determining the moisture content by the Karl Fischer method based on JIS K 7251, and a method of determining the weight increment after absorption based on JIS K 7209-2.

The sealant for electronic devices of the present invention is used for application by the inkjet method.

A process of applying the sealant for an electronic device of the present invention to at least one of two substrates by an inkjet method, a process of curing the applied sealant for an electronic device by light irradiation and/or heating, and A method of manufacturing an electronic device including a step of bonding substrates is also one of the present inventions.

In the process of applying the sealant for an electronic device of the present invention to at least one of two substrates, the sealant for an electronic device of the present invention may be applied to the entire surface of the substrate or to a part of the substrate. For example, when manufacturing an organic EL display element as an electronic device, the shape of the sealing portion of the sealant for electronic devices of the present invention formed by application can protect the laminate having the organic light-emitting material layer from external air. There is no particular limitation as long as it has a shape, and it may be a shape that completely covers the laminate, a closed pattern may be formed on the periphery of the laminate, or a pattern with some openings may be formed on the periphery of the laminate. It's okay too.

When manufacturing an organic EL display element as the electronic device, the substrate to which the sealant for electronic devices of the present invention is applied (hereinafter also referred to as one substrate) may be a substrate on which a laminate having an organic luminescent material layer is formed. , it may be a base material on which the laminated body is not formed.

When one of the substrates is a substrate on which the laminate is not formed, the sealant for electronic devices of the present invention is applied to the one substrate so that the laminate can be protected from external air when bonding the other substrate. do. That is, it is applied entirely to the location of the laminate when bonding the other base material, or is formed into a closed pattern that completely enters the location of the laminate when bonding the other base material. A sealant portion may be formed.

Additionally, the laminate may be covered with an inorganic material film.

As the inorganic material constituting the inorganic material film, conventionally known materials can be used, and examples include silicon nitride (SiN _x ) and silicon oxide (SiO _x ). The inorganic material film may be composed of one layer, or may be a laminate of multiple types of layers. Additionally, the laminate may be alternately covered with the inorganic material film and the resin film made of the electronic device sealant of the present invention.

The step of curing the electronic device sealant by light irradiation and/or heating may be performed before the step of bonding the two substrates together, or may be performed after the step of bonding the two substrates together.

When the process of curing the electronic device sealant by light irradiation and/or heating is performed before the process of bonding the two substrates, the electronic device sealant of the present invention is cured by light irradiation and/or heating. It is preferable that the pot life from when the curing reaction proceeds until 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 higher.

When the sealant for electronic devices is cured by irradiation with light, the sealant for electronic devices of the present invention is preferably cured by irradiating light with a wavelength of 300 nm to 400 nm and an accumulated light amount of 300 to 3000 mJ/cm2. You can do it.

Light sources for irradiating light to the sealant for electronic devices of the present invention include, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, and a metal lamp. Examples include halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, solar lights, and electron beam irradiation devices. These light sources may be used individually, or two or more types may be used together.

These light sources are appropriately selected according to the absorption wavelength of the photocationic polymerization initiator or the photoradical polymerization initiator.

Examples of means for irradiating light to the sealant for electronic devices of the present invention include simultaneous irradiation from various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc., which irradiation means may be used. You may use it.

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

In the step of bonding the two substrates, the method of bonding the two substrates is not particularly limited, but bonding in a reduced pressure atmosphere is preferable.

The lower limit of the vacuum degree in the reduced pressure atmosphere is 0.01 kPa, and the upper limit is 10 kPa. Since the degree of vacuum in the reduced pressure atmosphere is within this range, it does not take a long time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump, and the sealing for electronic devices of the present invention when joining two substrates together Air bubbles can be removed more efficiently.

According to the present invention, it is possible to provide a sealant for electronic devices that can be easily applied by an inkjet method and can reduce device damage. Additionally, according to the present invention, a method for manufacturing an electronic device using the electronic device sealant can be provided.

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

(Production Example 1)

20 ml of toluene was added to a four-necked flask equipped with a dropping funnel, stirrer, thermometer, and septum. Additionally, a mixed solution of 45.7 g (0.4 mol) of 3-(allyloxy)oxetane and 76 g (0.15 mol) of hydrogen-terminated tridimethylsiloxane (manufactured by Gelest, “DMS-03H”) was added dropwise to the dropping funnel. 3 ml of the mixed solution was added dropwise to the toluene in the flask from the funnel, and the temperature in the flask was raised to 80°C.

Next, 800 μl of a benzonitrile solution of chloroplatinic acid hexahydrate (H ₂ PtCl ₆ ·6H ₂ O) as a catalyst (chloroplatinic acid concentration: 0.1% by weight) was added into the flask from the septum using a syringe. After that, a mixed solution of 3-(allyloxy)oxetane and hydrogen-terminated tridimethylsiloxane was additionally added dropwise from the dropping funnel over 40 minutes. After the dropwise addition was completed, the inside of the flask was heated at 80°C to 85°C for 2 hours to react 3-(allyloxy)oxetane and hydrogen-terminated tridimethylsiloxane. After completion of the reaction, volatile compounds such as toluene were removed by distillation under reduced pressure. In this way, a compound with q of 2 in the above formula (3-3) with a purity of 95% was obtained.

(Example 1)

100 parts by weight of a silicone compound represented by the above formula (1) where o is 1 in the above formula (3-1) (manufactured by Shin-Etsu Chemical Co., Ltd., “X-22-163”), and tris ( 1 part by weight of 4-(4-acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate (manufactured by BASF, “IRGACURE 290”) was added to a homodisper type stirring mixer (manufactured by Primix, “Homo Disper L type") was used to uniformly stir and mix at a stirring speed of 3000 rpm to produce a sealant for electronic devices.

(Example 2)

The compounding amount of the compound in which o is 1 in the above formula (3-1) (“X-22-163” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 50 parts by weight, and 3, 4, 3', 4' was used as the other curable resin. -A sealant for electronic devices was produced in the same manner as in Example 1, except that 50 parts by weight of diepoxybicyclohexane (“Celoxide 8000” manufactured by Daicel) was added.

(Example 3)

As another curable resin, instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane ("Celoxide 8000" manufactured by Daicel), 1,2-epoxy-4-vinylcyclohexane (Diepoxy-4-vinylcyclohexane) A sealant for electronic devices was produced in the same manner as in Example 2, except that 50 parts by weight of "Celoxide 2000" manufactured by Cell Corporation was added.

(Example 4)

As another curable resin, 3-ethyl-3(((3-ethyloxetane) instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane ("Celoxide 8000" manufactured by Daicel Corporation) A sealant for electronic devices was produced in the same manner as in Example 2, except that 50 parts by weight of -3-yl)methoxy)methyl)oxetane (“Aronoxetane OXT-221”, manufactured by Toa Synthetics) was added.

(Example 5)

As another curable resin, instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane (manufactured by Daicel Corporation, "Celoxide 8000"), 3-allyloxyoxetane (manufactured by Yokkaichi Synthetic Corporation, "Celoxide 8000") A sealant for electronic devices was produced in the same manner as in Example 2, except that 50 parts by weight of "AL-OX") was added.

(Example 6)

As another curable resin, instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane (manufactured by Daicel, "Celoxide 8000"), cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide) was used. A sealant for electronic devices was produced in the same manner as in Example 2, except that 50 parts by weight of "CHDVE") was added.

(Example 7)

A silicone compound represented by the formula (1) above, where o is 1 in the formula (3-1) (“X-22-163” manufactured by Shin-Etsu Chemical Co., Ltd.) instead of 50 parts by weight of R in the formula (1) ¹ is ^{a methyl} group, X ^{1 and} A sealant for electronic devices was produced in the same manner as in Example 2, except that 50 parts by weight of "-22-343") was added.

(Example 8)

As another curable resin, 3-ethyl-3(((3-ethyloxetane) instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane ("Celoxide 8000" manufactured by Daicel Corporation) A sealant for electronic devices was produced in the same manner as in Example 7, except that 50 parts by weight of -3-yl)methoxy)methyl)oxetane (“Aronoxetane OXT-221”, manufactured by Toa Synthetics) was added.

(Example 9)

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

(Example 10)

The compounding amount of the compound (“DMS-EC13”, manufactured by Gelest) in which p in the above formula (3-2) is 9 was changed to 50 parts by weight, and 3,4,3',4'-diepoxy was used as the other curable resin. A sealant for electronic devices was produced in the same manner as in Example 9, except that 50 parts by weight of bicyclohexane (“Celoxide 8000” manufactured by Daicel) was added.

(Example 11)

As another curable resin, 3-ethyl-3(((3-ethyloxetane) instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane ("Celoxide 8000" manufactured by Daicel Corporation) A sealant for electronic devices was produced in the same manner as in Example 10, except that 50 parts by weight of -3-yl)methoxy)methyl)oxetane (“Aronoxetane OXT-221”, manufactured by Toa Synthetics) was added.

(Example 12)

Instead of the photo cation polymerization initiator, 1 part by weight of dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate (manufactured by King Industries, “CXC-1612”) was added as a thermal cation polymerization initiator. A sealant for electronic devices was produced in the same manner as in Example 11.

(Example 13)

The silicone compound represented by the formula (1) above, where o is 1 in the formula (3-1) (manufactured by Shin-Etsu Chemical Co., Ltd., “X-22-163”), is replaced with 50 parts by weight of the above formula obtained in Production Example 1. A sealant for electronic devices was produced in the same manner as in Example 4, except that 50 parts by weight of the compound in (3-3) with q of 2 was mixed.

(Example 14)

^A silicone compound represented by the above formula (1) ^, wherein R ¹ in the above formula ( ¹ ) is a methyl group, X ¹ and ), 50 parts by weight of a compound in which m is 1 and n is 0 (“X-22-164” manufactured by Shin-Etsu Chemical Co., Ltd.), 50 parts by weight of 1,6-hexanediol diacrylate as another curable resin, and light As a radical polymerization initiator, 2 parts by weight of diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide (manufactured by BASF, “Lucirin TPO”) was added to a homodisper type stirring mixer (manufactured by Primix, “Homodis”). A sealant for electronic devices was produced by uniformly stirring and mixing at a stirring speed of 3000 rpm using a "Per L type").

(Example 15)

100 parts by weight of a silicone compound represented by the above formula (1) where p in the above formula (3-2) is 1 (manufactured by Gelest, “SIB1092.0”), and tris (4-() as a photocationic polymerization initiator. 1 part by weight of 4-acetylphenyl)thiophenyl)sulfonium tetrakis(pentafluorophenyl)borate (manufactured by BASF, “IRGACURE 290”), mixed with a homodisper type stirring mixer (manufactured by Primix, “Homodisper L type”) ") was used to uniformly stir and mix at a stirring speed of 3000 rpm to produce a sealant for electronic devices.

(Example 16)

The compounding amount of the compound in which p in the above formula (3-2) is 1 (“SIB1092.0” manufactured by Gelest) was changed to 50 parts by weight, and 3,4,3',4'-diepoxy was used as the other curable resin. A sealant for electronic devices was produced in the same manner as in Example 15, except that 50 parts by weight of bicyclohexane (“Celoxide 8000” manufactured by Daicel) was added.

(Example 17)

The compounding amount of the compound in which p in the above formula (3-2) is 1 (“SIB1092.0” manufactured by Gelest) was changed to 40 parts by weight, and 3,4,3',4'-diepoxybicyclohexane (diepoxybicyclohexane) Except that the blending amount of "Celoxide 8000" manufactured by Cell Corporation was changed to 30 parts by weight, and 20 parts by weight of 3-allyloxyoxetane ("AL-OX" manufactured by Yokkaichi Synthetic Co., Ltd.) was additionally added as other curable resin. , a sealant for electronic devices was produced in the same manner as in Example 16.

(Example 18)

As another curable resin, instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane ("Celoxide 8000" manufactured by Daicel), 1,2-epoxy-4-vinylcyclohexane (Diepoxy-4-vinylcyclohexane) A sealant for electronic devices was produced in the same manner as in Example 16, except that 50 parts by weight of "Celoxide 2000" manufactured by Cell Corporation was added.

(Example 19)

As another curable resin, 3-ethyl-3(((3-ethyloxetane) instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane ("Celoxide 8000" manufactured by Daicel Corporation) A sealant for electronic devices was produced in the same manner as in Example 16, except that 50 parts by weight of -3-yl)methoxy)methyl)oxetane (“Aronoxetane OXT-221” manufactured by Toa Synthetics) was added.

(Example 20)

As another curable resin, instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane (manufactured by Daicel Corporation, "Celoxide 8000"), 3-allyloxyoxetane (manufactured by Yokkaichi Synthetic Corporation, "Celoxide 8000") A sealant for electronic devices was produced in the same manner as in Example 16, except that 50 parts by weight of "AL-OX") was added.

(Example 21)

As another curable resin, instead of 50 parts by weight of 3,4,3',4'-diepoxybicyclohexane (manufactured by Daicel, "Celoxide 8000"), cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide) was used. A sealant for electronic devices was produced in the same manner as in Example 16, except that 50 parts by weight of "CHDVE") was added.

(Comparative Example 1)

The silicone compound represented by the above formula (1) was not blended, and 100 parts by weight of 3,4,3',4'-diepoxybicyclohexane (manufactured by Daicel Corporation, "Celoxide 8000") was blended as another curable resin. Except that, a sealant for electronic devices was produced in the same manner as in Example 1.

(Comparative Example 2)

The silicone compound represented by the above formula (1) is not blended, and as another curable resin, 3-ethyl-3(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane (manufactured by Toa Synthetic Co., Ltd.) A sealant for electronic devices was produced in the same manner as in Example 1, except that 100 parts by weight of "Aronoxetane OXT-221") was added.

(Comparative Example 3)

Without blending the silicone compound represented by the above formula (1), another curable resin, 3-ethyl-3(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane (manufactured by Toa Synthetic Co., Ltd., A sealant for electronic devices was produced in the same manner as in Example 12, except that the mixing amount of "Aronoxetane OXT-221") was changed to 100 parts by weight.

(Comparative Example 4)

Sealing for electronic devices was carried out in the same manner as in Example 14, except that the silicone compound represented by the above formula (1) was not mixed and the mixing amount of 1,6-hexanediol diacrylate, which is another curable resin, was changed to 100 parts by weight. A ritual was made.

<Evaluation>

The following evaluation was performed on each of the sealants for electronic devices obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(viscosity)

For each electronic device sealant obtained in the examples and comparative examples, the viscosity was measured at 25°C and 100 rpm using an E-type viscometer (“VISCOMETER TV-22”, manufactured by Toki Sangyo Co., Ltd.).

(Wet Spreadability)

The sealants for each electronic device obtained in the examples and comparative examples were alkali-cleaned with a droplet volume of 80 picoliters using an inkjet ejection device (“NanoPrinter300”, manufactured by Microjet Co., Ltd.) to alkali-free glass (manufactured by Asahi Glass Co., Ltd.) “AN100”), and the diameter of the droplet on the alkali-free glass was measured 10 minutes later.

(adhesiveness)

Each of the sealants for electronic devices obtained in the Examples and Comparative Examples was applied to a thickness of 10 μm on alkali-free glass (“AN100”, manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then Examples 1 to 11. , 13 to 21 and Comparative Examples 1, 2, and 4 were irradiated with 3000 mJ/cm2 of ultraviolet rays with a wavelength of 365 nm using an LED lamp to obtain the electronic device sealants obtained in Example 12 and Comparative Example 3. The sealant for devices was heated at 100°C for 30 minutes to cure the sealant for electronic devices, and a resin film was obtained.

The formed resin film was subjected to a crosscut test with a cutting interval of 1 mm according to JIS K 5600-5-6.

When performing the crosscut test, “◎” indicates peeling of 5% or less, “○” indicates that peeling exceeds 5% and does not exceed 35%, and “△” indicates that peeling exceeds 35% and does not exceed 65%. , adhesion was evaluated by setting the case where peeling exceeded 65% to “×”.

(Swelling properties of adhesive pieces (device damage))

Approximately 0.15 g of an epoxy adhesive (“Araldite AR-S30” manufactured by Nichiban Corporation) was cured to produce an adhesive piece, and the weight (W ₁ ) was measured. After that, the sealant for each electronic device obtained in the examples and comparative examples was placed in a brown screw tube, the prepared adhesive piece was immersed in it, the lid was closed, and the adhesive piece was left still at 60° C. for 7 days, and then the adhesive piece was taken out. After wiping the surface with a waste cloth, the weight (W ₂ ) was measured, and the weight change rate of the adhesive piece was calculated using the following formula.

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

The case where the weight change rate was less than 1% was set to “◎”, the case where it was 1% to less than 10% was set to “○”, the case where it was 10% to less than 20% was set to “△”, and the case where it was 20% or more was set to “×”. The swelling properties (device damage) of the adhesive pieces were evaluated.

(Display performance of organic EL display element)

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

An ITO electrode was formed to a thickness of 1000 Å on a glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm), which was used as a substrate. The 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 again washed with UV-ozone cleaner (Nippon Laser Electronics Co., Ltd., “NL”). -UV253”) was immediately treated.

Next, this substrate was fixed to the substrate folder of the vacuum evaporation device, and N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (α-NPD) was added to the crucible baked without glaze. 200 mg of tris(8-hydroxyquinoline)aluminum (Alq ₃ ) was placed in a crucible fired without applying another glaze, and the pressure inside the vacuum chamber was reduced to 1 × 10 ^-4 Pa. Afterwards, the crucible containing α-NPD was heated, α-NPD was deposited on the substrate at a deposition rate of 15 Å/s, and a hole transport layer with a film thickness of 600 Å was formed. 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. After that, the substrate on which the hole transport layer and the organic light-emitting material layer were formed was transferred to another vacuum evaporation apparatus, and 200 mg of lithium fluoride was placed in a tungsten resistance heating boat in this vacuum evaporation apparatus, and 1.0 g of aluminum wire was placed in another tungsten boat. Afterwards, the pressure inside the evaporator of the vacuum evaporation device was reduced to 2 × 10 ^-4 Pa, and 5 Å of lithium fluoride was deposited at a deposition rate of 0.2 Å/s, and then 1000 Å of aluminum was formed at a deposition rate of 20 Å/s. The inside of the evaporator was returned to normal pressure with nitrogen, and the substrate on which the laminate having a 10 mm x 10 mm organic light-emitting material layer was placed was taken out.

(Covering with inorganic material film A)

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

The plasma CVD method uses SiH ₄ gas and nitrogen gas as raw material gases, each flow rate is set to 10 sccm for SiH ₄ gas and 200 sccm for nitrogen gas, the RF power is set to 10 W (frequency 2.45 GHz), and the temperature inside the chamber is set to 10 sccm. It was carried out at 100°C and the chamber pressure was 0.9 Torr.

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

(Formation of resin protective film)

With respect to the obtained substrate, each of the sealants for electronic devices obtained in Examples and Comparative Examples was applied in a pattern to the substrate using an inkjet ejection device (“NanoPrinter300” manufactured by Microjet).

Thereafter, each of the sealants for electronic devices obtained in Examples 1 to 11, 13 to 21 and Comparative Examples 1, 2, and 4 was irradiated with 3000 mJ/cm2 of ultraviolet rays with a wavelength of 365 nm using an LED lamp. The electronic device sealant obtained in Example 12 and Comparative Example 3 was heated at 100°C for 30 minutes to cure the electronic device sealant and form a resin protective film.

(Covering with inorganic material film B)

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

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

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

(Emission state of organic EL display element)

The obtained organic EL display element was exposed to an environment with a temperature of 85°C and a humidity of 85% for 100 hours, and then a voltage of 3 V was applied to inspect the light emission state of the organic EL display element (presence or absence of dark spots and extinction around the pixel) with the naked eye. It was observed as follows. The case where light is emitted uniformly without dark spots or ambient light is set to “○”, the case where dark spots or ambient light is recognized is set to “△”, and the case where the non-light emitting area is significantly enlarged is set to “×”. Display performance was evaluated.

According to the present invention, it is possible to provide a sealant for electronic devices that can be easily applied by an inkjet method and can reduce device damage. Additionally, according to the present invention, a method for manufacturing an electronic device using the electronic device sealant can be provided.

Claims (7)

A sealant for electronic devices containing a curable resin, a polymerization initiator and/or a thermosetting agent, and used for application by an inkjet method,
The curable resin contains a silicone compound represented by the following formula (1),
In addition to the silicone compound represented by formula (1), the curable resin includes other curable resins, such as alicyclic epoxy resin, 3-(allyloxy)oxetane, 3-ethyl-3-((2-ethylhexyl oxide, Contains at least one member selected from the group consisting of methyl)oxetane, and 3-ethyl-3(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane,
The sealant for electronic devices is characterized in that the viscosity of the sealant for electronic devices is 10 mPa·s or more and 80 mPa·s or less, as measured using an E-type viscometer under conditions of 25°C and 100 rpm.
[Formula 1]

In formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, and X ^{1 and} , represents a group represented by (2-3) or (2-4), and X ³ represents a group represented by the following formula (2-1), (2-2), (2-3) or (2-4) . m is an integer from 0 to 100, and n is an integer from 0 to 100. However, when n is 0, at least one of X ¹ and X ² represents a group represented by the following formula (2-1), (2-2), (2-3), or (2-4).
[Formula 2]

In formulas (2-1) to (2-4), R ² represents a bond or an alkylene group having 1 to 6 carbon atoms, and in formula (2-3), R ³ represents hydrogen or an alkylene group having 1 to 6 carbon atoms. represents an alkyl group, R ⁴ represents a bond or a methylene group, and in formula (2-4), R ⁵ represents hydrogen or a methyl group. According to claim 1,
The silicone compound represented by formula (1) is a compound in which at least one of X ¹ , X ² and X ³ in formula (1) is a group represented by formula (2-1), (2-2) or (2-3) A sealant for electronic devices, characterized in that. The method of claim 1 or 2,
The silicone compound represented by formula (1) is at least selected from the group consisting of a compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3). A sealant for electronic devices, characterized in that it is of one type.
[Formula 3]

In formula (3-1), o is an integer from 1 to 10, in formula (3-2), p is an integer from 1 to 10, and in formula (3-3), q is an integer from 1 to 10. is the integer of delete delete A process of applying the sealant for electronic devices according to claim 1 or 2 to at least one of two substrates by an inkjet method;
A process of curing the applied sealant for electronic devices by light irradiation and/or heating;
A method of manufacturing an electronic device, comprising a step of bonding the two substrates. delete