JP2009259656A - Sealer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealer which has transparency that does not obstruct light emission and reception of an electronic device and damp-proofness necessary for achieving a long life of the electronic device, a cured object of the sealer, and an electronic device having a long life sealed by the sealer, in particular, the electronic device of the long life superior in light emission and reception. <P>SOLUTION: The sealer contains a solid drying agent particle and a curing resin and the average particle size of the solid drying agent particle is 100 nm or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a sealant used for sealing for protecting an electronic device from an external environment, a method for manufacturing a cured sealant, and a method for manufacturing an electronic device sealed with the sealant. The sealing agent of the present invention includes semiconductor electronic components such as diodes, transistors, and ICs, liquid crystal panels, plasma display panels, display elements such as electroluminescence (hereinafter, EL) elements, and high-density recording media such as magneto-optical disks. It can be used for sealing solar cells, optical waveguides and the like.

  Since electronic devices are greatly affected by ambient temperature changes and humidity changes, it is well known that they are used in a state of being sealed with a liquid resin or the like.

For example, many proposals have been made to seal a light emitting diode with a resin. In particular, white light emitting diodes are attracting attention as illumination light sources that can achieve significant energy savings. Therefore, it is important how efficiently the emitted light from the light-emitting diode element (LED chip) is extracted, and the LED chip sealant is required to be non-colored and highly transparent.

  On the other hand, an organic electroluminescence element (organic EL element) has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and electrons are injected into the organic light emitting material layer from one electrode. In addition, when holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to emit light. As described above, since the organic EL element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. It has advantages and is attracting attention as a next-generation display.

  In addition, the organic EL element has a problem in that the organic light emitting material and the electrodes constituting the laminate are easily oxidized due to moisture and the like, so that the characteristics are easily deteriorated. Therefore, a general organic EL element has a structure in which moisture is prevented from entering by covering a laminated body with a lid made of glass or metal on which a desiccant is placed and sealing the periphery with a sealant. It has been. In this method, light emitted from the laminated body is taken out from the opposite side of the lid, that is, from the bottom side of the organic EL element, so that it is also called a bottom emission method (Patent Document 1).

  On the other hand, in recent years, attention has been paid to a top emission type organic EL element that takes out light emitted from a laminate from the upper surface side, instead of a conventional bottom emission type organic EL element. This method has an advantage that it has a high aperture ratio and is driven at a low voltage, which is advantageous for extending the life. In such a top emission type organic EL device, usually, the laminate is sandwiched between two moisture-proof substrates made of a transparent material such as glass, and the space between the moisture-proof substrates is filled with a sealant. (Patent Document 2).

  In the above-mentioned bottom emission type and top emission type organic EL devices, a method of filling with a sealant made of a curable resin composition such as a photocurable resin composition or a thermosetting resin composition, etc. Was being considered. However, the sealing agent made of the resin composition is not sufficiently moisture-proof, and there has been a problem that moisture entering from the outside diffuses into the sealing agent and enters the element, thereby deteriorating the organic EL element.

  Therefore, for example, the organic EL element formed on the substrate is covered with a protective film, and further through a sealing agent (consisting of a curable resin composition such as a photocurable resin composition or a thermosetting resin composition). A completely solid sealing structure in which an organic electroluminescent element is sealed in a sealing agent by bonding a sealing substrate has been proposed. In such a structure, a gap that causes intrusion of moisture or the like does not remain between the substrates on which the organic electroluminescent elements are sandwiched, so that the effect of preventing the above-described deterioration of the elements is high.

  However, the above-mentioned protective film is caused by a foreign matter on the substrate or a difference in thermal expansion coefficient between the substrate and the protective film. May occur. As a result, there is a problem that moisture or the like enters the organic EL element through them to deteriorate the organic EL element.

  The protective film is made of a highly transparent material (metal oxide such as silicon oxide or silicon nitride, organic material such as polymer, or a mixture or laminate thereof). In particular, silicon nitride or a mixture and laminate containing silicon nitride are generally used because of its high moisture resistance, but silicon nitride is not completely transparent, and the transmittance of the protective film is sufficient. It is necessary to make the protective film thin. However, when the protective film is thinned, the ability to prevent the entry of moisture and the like is lowered, and as a result, there is a problem that moisture and the like enter the organic EL element to deteriorate the organic EL element.

  As described above, it cannot be said that the sealant and the protective film are sufficiently effective in preventing the entry of moisture and the like, and it is desired that the sealant further enhance the effect of preventing the entry of moisture and the like.

  As one of means for enhancing the effect of the sealing agent to prevent moisture from entering, it has been studied to disperse a solid desiccant in the sealing agent and to mix a polymer having high water absorption.

  However, it is difficult to achieve sufficient moisture resistance by mixing a polymer with high water absorption. When solid desiccant particles are dispersed, the solid desiccant particles absorb or scatter light and seal. Since the transparency of the agent is impaired, there is a problem that the light extraction efficiency is impaired in the complete solid sealing of the top emission method.

Japanese Patent Laid-Open No. 9-148066 JP 2001-375773 A

  An object of the present invention is to provide a sealant that has both transparency that does not hinder light emission and light reception of an electronic device and moisture resistance necessary to achieve a long life of the electronic device. Furthermore, it is providing the hardened | cured material of the sealing agent, and the long-life electronic device sealed with the sealing agent, especially the long-life electronic device excellent in light emission and light reception.

  As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.

  That is, the present invention relates to a sealant containing solid desiccant particles and a curable resin, wherein the solid desiccant particles have an average particle size of 100 nm or less.

  The present invention also relates to the above-mentioned sealant, wherein the solid desiccant particles do not contain particles larger than 100 nm.

  In the present invention, the solid desiccant particles are barium oxide, strontium oxide, calcium oxide, magnesium oxide, calcium sulfate, calcium chloride, lithium chloride, calcium bromide, potassium carbonate, copper sulfate, sodium sulfate, zinc chloride, The present invention relates to the above-mentioned sealant characterized by containing at least one of zinc bromide, cobalt chloride, diphosphorus pentoxide, silica gel, aluminum oxide, and zeolite.

  The present invention also relates to the above-mentioned sealing agent, wherein the curable resin is a curable resin containing a photocationic polymerization initiator and a cationically polymerizable compound.

  Moreover, this invention relates to said sealing agent in which a photocationic polymerization initiator contains a borate anion.

  The present invention also relates to the above-described sealant in which the borate anion is represented by the following general formula (1).

General formula (1)

Wherein Y is a fluorine or chlorine atom, Z is a phenyl group substituted with two or more groups selected from fluorine atom, cyano group, nitro group and trifluoromethyl group, m is an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4.)

  The present invention also relates to the above-described sealing agent, wherein the cationic photopolymerization initiator comprises a sulfonium cation.

  Moreover, this invention relates to said sealing agent with a sulfonium cation represented by following General formula (2).

General formula (2)

(Wherein R ₁ is a group selected from a substituted benzyl group, a substituted phenacyl group, a substituted allyl group, a substituted alkoxyl group, and a substituted aryloxy group; R ₂ and R ₃ are each Independently, a benzyl group which may have a substituent, a phenacyl group which may have a substituent, an allyl group which may have a substituent, an alkoxyl group which may have a substituent, a substituent A group selected from an aryloxy group that may have, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl group that may have a substituent; ₄ represents an oxygen atom or a lone pair, and R ₁ , R _2, and R ₃ may be combined with two or more groups to form a cyclic structure.

  Moreover, this invention relates to the manufacturing method of the sealing agent hardened | cured material obtained by irradiating active energy ray to said sealing agent, heating, or performing both.

  The present invention also relates to a method for producing the cured encapsulant described above, wherein the active energy ray is light including ultraviolet light, visible light, or both.

  Moreover, this invention relates to the sealing agent hardened | cured material obtained by said manufacturing method.

  Moreover, this invention relates to the manufacturing method of the sealed electronic device characterized by sealing an electronic device using said sealing agent.

  The present invention also relates to a sealed electronic device manufactured by the above manufacturing method.

  The effective point of the present invention is that the desiccant particles having an average particle diameter of 100 nm or less are dispersed in the curable resin, thereby allowing the sealant to have moisture adsorbability while maintaining transparency. The water adsorbability is particularly excellent due to the large surface area of the desiccant particles.

  Thereby, the electronic device can be effectively prevented from external moisture, and the quality of the sealed electronic device can be maintained over a long period of time. Furthermore, it is possible to effectively prevent moisture from entering the element without impairing the light extraction efficiency of the top emission type organic EL element or light emitting diode element, and to obtain a highly efficient and long-lasting element. .

  Hereinafter, the present invention will be described in detail.

  The solid desiccant particles used in the present invention include all shapes such as a spherical shape, a needle shape, and other irregular shapes having no fixed shape.

  The average particle diameter of the solid desiccant particles used in the present invention will be described. Using a transmission electron microscope (TEM), a total of 50 or more primary particles were observed by observing at least 3 or more different observation points, and 20 randomly selected from the observed primary particles. The distance between the two most distant points of the outer shape of the primary particle is measured based on the length of the micron marker on the observation image, and is an average value.

  Solid desiccant particles preferably used in the present invention include barium oxide, strontium oxide, calcium oxide, magnesium oxide, calcium sulfate, calcium chloride, lithium chloride, calcium bromide, potassium carbonate, copper sulfate, sodium sulfate, and zinc chloride. , Zinc bromide, cobalt chloride, diphosphorus pentoxide, silica gel, aluminum oxide, and zeolite, and further, particles made of a mixture thereof, particles made of a solid solution formed by mixing these, It is not limited to these. These particles may be used alone or in combination of two or more. Further, for the purpose of improving the dispersibility in the curable resin, the particle surface of the solid desiccant particles may be chemically or physically modified.

Zeolite is a general term for the hydrous metal salts of aluminosilicates, and some are produced as natural minerals and others are artificially synthesized. Specifically, silicon (Si) and aluminum (Al) are bonded via oxygen (O), and aluminum (+ trivalent) and silicon (+ tetravalent) in the skeleton structure are oxygen (−2). Value). Therefore, silicon is electrically neutral and aluminum is −1, and in order to compensate for this negative charge, cations (for example, Li ⁺ , Na ⁺ , K ⁺ , Na ⁺ , Ca ²⁺ , etc.) are incorporated. When the water of crystallization of the zeolite crystals is removed by heating, micropores remain in the traces of the water of crystallization, and water molecules are adsorbed in the micropores.

  The solid desiccant particles used in the present invention are a chemical desiccant that utilizes the intrinsic properties of chemical substances (chemical reaction and deliquescence), and a physical desiccant that utilizes the property that water molecules are easily adsorbed on the porous surface. Yes, not all desiccants work with the same mechanism. In addition, the amount of moisture absorbed at the same mass varies depending on the material. However, any solid desiccant particles can supplement the moisture that enters the cured sealant.

Examples of the method for producing solid desiccant particles having an average particle size of 100 nm or less used in the present invention include the following, but are not limited thereto.
Vapor phase method: A method in which a raw material in a gas phase state by gasification or the like is converted into particles by reaction, aggregation, and crystallization. For example, there is a CVD method.
Liquid phase method: A method in which a raw material in a liquid phase state by dissolution or the like is converted into particles by reaction, dispersion, and solidification. For example, there are a spray method, an alkoxide method, a micelle method and the like.
Solid phase method: A method of forming particles from raw materials in a solid state by nucleation by reaction or pulverization. For example, there are methods such as jet mill wet grinding and bead mill grinding.
(2005 Patent Distribution Support Chart General 18 Nanoparticle Manufacturing Technology)
A system in which particles with a size of about 1 nm to 100 nm are dispersed in a matrix such as an organic polymer is called a nanocomposite, and various functions that cannot be seen in a system in which particles with a size of about μm are dispersed are expressed. It has been attracting attention.

Specifically, the following can be cited as expression of the function.
1. Improvement of mechanical properties such as improvement of tensile strength, improvement of bending strength, and improvement of impact strength.
2. Despite the system in which the solid content is dispersed in the matrix, the transmittance of visible light is almost unchanged.
3. Improves barrier properties against water vapor, oxygen, etc. by dispersing fine particles in the matrix.
4). Improvement of the function of the particles by increasing the surface area of the particles because the particles dispersed in the matrix are fine.

  Various functions other than those described above are known.

  The average particle size of the solid desiccant particles used in the present invention is preferably 100 nm or less, and more preferably 50 nm or less, from the viewpoint of transparency and hygroscopicity of the cured product of the sealant.

  As the curable resin that can be used in the present invention, a photocurable resin, an electron beam curable resin, a thermosetting resin, or a mixture thereof can be used, but is not limited thereto. Since it is difficult to damage the sealing object due to heat, a photo-curing resin can be preferably used.

  As the thermosetting resin, those which are hard to be damaged by heat to the object to be sealed are preferable, and those cured at 100 ° C. or less are preferable, for example, an adhesive resin mainly composed of an epoxy resin, and a curability mainly composed of a urethane resin. Examples thereof include a resin, a curable resin mainly composed of an acrylic resin, and a curable resin mainly composed of an oxetane compound.

  The thermosetting resin may contain a curing agent and a curing accelerator or a curing catalyst. For example, in room temperature curing resins mainly composed of epoxy resins, amine curing agents, imidazole curing accelerators, amine adduct type curing accelerators, phosphorus curing accelerators, organometallic complexes, polyamine ureates ( Curing accelerators such as urea-modified polyamines) can be used.

  Examples of the photocurable resin include a curable resin mainly composed of an epoxy resin, a curable resin mainly composed of an acrylic resin, a curable resin mainly composed of a mixture of an epoxy resin and an acrylic resin, and a curing mainly composed of an oxetane compound. Curable resins mainly composed of a mixture of an epoxy resin and an oxetane compound, and curable resins mainly composed of a mixture of an acrylic resin and an oxetane compound.

  As the photo-curing resin, a photo-curing resin containing a photo-cationic polymerization initiator and a cationically polymerizable compound is particularly preferable since the curing shrinkage is small.

  A cationically polymerizable compound may be used independently and may be used together 2 or more types. As the cationic polymerizable compound, a compound having an epoxy group, an oxetane group, or a vinyl ether group is preferably used. Particularly preferably, a compound having an epoxy group or an oxetanyl group is used. Since the polymerization of these functional groups is relatively highly reactive and the curing time is short, the sealing process can be shortened.

  Examples of the compound having an epoxy group include bisphenol A type epoxy resin, glycidyl ether type epoxy resin, phenol novolac type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolac type epoxy resin, glycidyl amine type epoxy resin, Alcohols such as naphthalene type epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, polyfunctional epoxy resin, biphenyl type epoxy resin, glycidyl ester type epoxy resin, hydrogenated bisphenol A type epoxy resin Epoxy resin, halogenated epoxy resin such as brominated epoxy resin, rubber modified epoxy resin, urethane modified epoxy resin, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene Block copolymer, epoxy group-containing polyester resin, epoxy group-containing polyurethane resins, and epoxy group-containing acrylic resin. These epoxy resins may be liquid at room temperature or solid. Epoxy group-containing oligomers can also be preferably used, and examples thereof include bisphenol A type epoxy oligomers (for example, Epicoat 1001, 1002 manufactured by Yuka Shell Epoxy Co., Ltd.). Furthermore, addition polymers of the above epoxy group-containing monomers and oligomers may be used, and examples thereof include glycidylated polyester, glycidylated polyurethane, and glycidylated acrylic.

Among them, photocationic polymerization is higher, and photocuring proceeds more efficiently even with a small amount of light. Therefore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, alicyclic epoxy resin, fat A group epoxy resin or the like is preferably used. These compounds having an epoxy group may be used alone or in combination of two or more.

  Specific examples of the alicyclic epoxy resin include, for example, 1,2: 8,9-diepoxy limonene, 4-vinylcyclohexene monoepoxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, (3,4- Epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, bis- (3,4-epoxycyclohexyl) adipate, norbornene monoepoxide, limonene monoepoxide, 2- (3,4-epoxycyclohexyl-5,5-spiro- 3,4-epoxy) cyclohexanone-meta-dioxane, bis- (3,4-epoxycyclohexylmethylene) adipate, bis- (2,3-epoxycyclopentyl) ether, (2,3-epoxy-6-methylcyclohexylmethyl) ) Adipate, dicyclopentadiene dioxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, 2,2-bis [4- (2,3- Epoxypropoxy) cyclohexyl] hexafluoropropane, BHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin (softening point 71 ° C.), and the like, but are not limited thereto.

  Specific examples of the aliphatic epoxy resin include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, and propylene. Glycol monoglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl Ether, trimethylolpropane monoglycidyl ether, trimethylolpropane triglyceride Jill ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, 2-but-ethylhexyl glycidyl ether and the like, but is not limited thereto.

  Examples of the compound having an oxetanyl group include phenoxymethyl oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3- Ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, oxetanyl Silsesquioxane, phenol novolac oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene and the like can be mentioned, but are not limited thereto.

  Examples of the cationic photopolymerization initiator include, but are not limited to, onium salts, metallocene compounds, silicon compounds / aluminum complexes, and the like.

  As the cationic photopolymerization initiator, an onium salt can be suitably used because of its excellent curability. Examples thereof include sulfonium salt-based, iodonium salt-based, phosphonium salt-based, diazonium salt-based, pyridinium salt-based, benzothiazolium salt-based, sulfoxonium salt-based compounds, and ferrocene-based compounds. These structures are not particularly limited, and may have a polyvalent cation structure such as a dication, and known counter anions can be appropriately selected and used. In addition, photocationic polymerization initiators other than onium salts include nitrobenzyl sulfonates, alkyl or aryl-N-sulfonyloxyimides, optionally halogenated alkyl sulfonate esters, and 1,2-disulfones. , Oxime sulfonates, benzoin tosylates, β-ketosulfones, β-sulfonylsulfones, bis (alkylsulfonyl) diazomethanes, iminosulfonates, imidosulfonates, trihalomethyltriazines, etc. However, it is not limited to these. These cationic photopolymerization initiators may be used alone or in combination of two or more.

  In addition, since it is particularly excellent in curability, the onium salt is preferably an onium salt composed of a sulfonium cation and a counter anion, or an onium salt composed of a borate anion and a counter cation. Both the curability and the transparency of the cured product are preferable. In particular, an onium salt composed of a sulfonium cation and a borate anion is particularly preferable.

  The amount of the photocationic polymerization initiator used in the present invention is preferably in the range of 0.01 to 20 parts by weight, particularly preferably 0.5 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. Parts to 10 parts by weight. When the addition amount of the photocationic polymerization initiator is less than 0.01 parts by weight, polymerization or crosslinking by cationic polymerization may not proceed sufficiently. Further, when the amount of the cationic photopolymerization initiator added is more than 20 parts by weight, there are too many low molecular components in the sealing composition, and sufficient adhesiveness may not be obtained. High transparency after curing may not be obtained due to coloring derived from the initiator.

  In view of curability and transparency of the cured product, the borate anion is preferably one represented by the following general formula (1).

General formula (1)

Wherein Y is a fluorine or chlorine atom, Z is a phenyl group substituted with two or more groups selected from fluorine atom, cyano group, nitro group and trifluoromethyl group, m is an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4.) As the substituent Z in the general formula (1), 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2, 3,4,6-tetrafluorophenyl group, pentafluorophenyl group, 2,4-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-trifluoro −3,5-bis (trifluoromethyl) phenyl group, 3,5-dinitrophenyl group, 2,4,6-trifluoro-3,5-dinitrophenyl group, 2,4-dicyanophenyl group, 4-cyano 3,5-dinitrophenyl group, 4-cyano-2,6-bis although (trifluoromethyl) phenyl group and the like, but is not limited thereto.

  Therefore, as the structure of the borate anion represented by the general formula (1), specifically, pentafluorophenyl trifluoroborate, 3,5-bis (trifluoromethyl) phenyl trifluoroborate, bis (pentafluorophenyl) ) Difluoroborate, bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, tris (pentafluorophenyl) fluoroborate, tris [3,5-bis (trifluoromethyl) phenyl] fluoroborate, tetrakis (penta Fluorophenyl) borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

  Among these, tetrakis (pentafluorophenyl) borate and tetrakis [3,5-bis (trifluoromethyl) phenyl] borate are particularly preferable as the anion represented by the general formula (1). The reason is that it can be synthesized relatively easily, the acid generated is very strong, has high solubility and high safety and health.

  From the viewpoint of curability and transparency of the cured product, a particularly preferred sulfonium cation structure is a sulfonium cation represented by the general formula (2).

General formula (2)

(Wherein R ₁ is a group selected from a substituted benzyl group, a substituted phenacyl group, a substituted allyl group, a substituted alkoxyl group, and a substituted aryloxy group; R ₂ and R ₃ are each Independently, a benzyl group which may have a substituent, a phenacyl group which may have a substituent, an allyl group which may have a substituent, an alkoxyl group which may have a substituent, a substituent A group selected from an aryloxy group that may have, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl group that may have a substituent; ₄ represents an oxygen atom or a lone pair, and R ₁ , R _2, and R ₃ may be combined with two or more groups to form a cyclic structure.

The substituent R ₁ in the general formula (2) is a substituted benzyl group, a substituted phenacyl group, a substituted allyl group, a substituted alkoxyl group, or a substituted aryloxy group. It is a structure selected from Formula (3) to General Formula (6).

(In the formula, R ₅ is a monocyclic or condensed polycyclic aryl group having 4 to 24 carbon atoms which may contain a hetero atom, and a substituted hetero atom, which is common to the general formulas (3) to (6). the which may include monocyclic or condensed polycyclic aryl group having a carbon number of 4 to 24, represents an alkyl group (for general formula (6)), (for the general formula (6)) an alkyl group substituted .R ₆ And R ₇ are common to the general formula (3) to the general formula (5), and each independently represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxyl group, a substituted group. Represents an alkoxyl group, an aryloxy group, a substituted aryloxy group, an alkenyl group or a substituted alkenyl group.
However, R ₅ , R ₆ and R ₇ may be combined to form a ring. )

The substituent in the sulfonium cation represented by the general formula (2) will be described below. First, in the substituent R ₅ in the sulfonium cation represented by the general formula (3) to the general formula (6) constituting the sulfonium cation represented by the general formula (2),

Examples of the monocyclic or condensed polycyclic aryl group having 4 to 24 carbon atoms that may contain a hetero atom include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 9-anthryl group, a 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-indenyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, 2-furyl group, 2-thienyl group, 2-indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-acridinyl group, 2-thianthrenyl group, 2-carbazolyl group, 3-carbazolyl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxy group Satiynyl group, 3-phenixazinyl group, 3-thianthenyl group, 3-coumarinyl group and the like can be mentioned, Not limited to these, also, these aryl groups may be bonded to the carbon atom at the substitution position other than the above, they also included in the scope of the substituents denoted by R ₅ of the present invention It is.

Among these, carbon which may contain a more preferred hetero atom in the substituent R ₅ in the sulfonium cation represented by the general formula (3) to the general formula (6) constituting the sulfonium cation represented by the general formula (2) Examples of the monocyclic or condensed polycyclic aryl group of Formula 4 to 24 include structures selected from General Formula (7) to General Formula (10).

(In the formula, each R ₈ independently represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, an acyl group, an alkoxyl group, an aryloxy group, or a halogen atom. R ₉ represents an alkyl group, an aryl group, or an acyl group. R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, or a halogen atom, and R (R _j , R _k , R _l , R _p ) is represented by the general formula In common with (8) to general formula (10), each independently represents an alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyloxy group, or halogen atom. J, k, l and p represent the number of substituents R substituted, and j represents an integer of 1 to 5. k is common to the general formulas (8) to (10). And represents an integer of 0 to 3. l represents an integer of 0 to 3. p represents an integer of 0 to 3. However, k + l is always 1 or more. ₈ or R and R ₉ , or R and R ₁₀ may form a ring structure by a covalent bond to each other, and in the general formulas (8) to (10), substitution positions other than those described above. And may be bonded to a carbon atom of general formula (3) to general formula (5) or an oxygen atom of general formula (6).

  Moreover, as a substituent introduce | transduced in order to improve curability of the sulfonium cation represented by General formula (2), an aryl group, an alkylthio group, an arylthio group, an alkoxyl group, an aryloxy group, and an acyl group are preferable. Can be mentioned.

Substituents R ₂ and R ₃ in the sulfonium cation represented by formula (2), substituents R ₆ and R ₇ in formulas (3) to (5), substituent R ₈ in formula (7) , the substituents R ₉ in the general formula (9), the substituents R ₁₀ in the general formula (10), the alkyl group in the substituents R in the general formula (7) to the general formula (10), 1 to 18 carbon atoms Examples include linear, branched, monocyclic or condensed polycyclic alkyl groups. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. Group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, t-butyl group, sec-pentyl group, t-pentyl group, t-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group, 4-decyl cyclohexyl group and the like, but is not limited thereto.

Substituents R ₂ and R _{3 in} the sulfonium cation represented by the general formula (2), the substituent R ₆ in the general formula (3) to the general formula (5) constituting the sulfonium cation represented by the general formula (2) substituted in R _7, the substituents R ₈ in the general formula (7), the substituent R ₉ in the general formula (9), the substituents R ₁₀ in the general formula (10), the general formula (7) to the general formula (10) and Examples of the aryl group in the group R include the same substituents as those exemplified as the aryl group in the substituent R ₅ , but are not limited thereto. In the substituent R ₉ in the general formula (9), these aryl groups may be bonded to a nitrogen atom at a substitution position other than those described above, and they are also included in the category of the substituent represented by R ₉ in the present invention. include.

Substituents R ₂ and R ₃ constituting the sulfonium cation represented by general formula (2), substituents R ₆ and R ₇ in general formula (3) to general formula (5), general formula (7) to general formula Examples of the alkenyl group in the substituent R in (10) include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, and these include a plurality of carbon-carbon dicarbon groups in the structure. Specific examples include a vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2- Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3- A butadienyl group, a cyclohexadienyl group, a cyclopentadienyl group, and the like can be given, but the invention is not limited thereto.

Substituents R ₂ and R ₃ constituting the sulfonium cation represented by formula (2), substituents R ₆ and R ₇ in formulas (3) to (5), and substituents in formula (7) Examples of R ₈ , substituent R ₁₀ in general formula (10), and alkoxyl group in substituent R in general formula (7) to general formula (10) include straight chain, branched chain, Examples thereof include cyclic or condensed polycyclic alkoxyl groups, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, Dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyl Xyl group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group , 4-decylcyclohexyloxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, and the like, but are not limited thereto.

Substituents R ₂ and R ₃ constituting the sulfonium cation represented by formula (2), substituents R ₆ and R ₇ in formulas (3) to (5), and substituents in formula (7) R ₈ , the substituent R _{10 in} the general formula (10), and the aryloxy group in the substituent R in the general formula (7) to the general formula (10) are monocyclic rings having 4 to 18 carbon atoms that may contain a hetero atom. Or a condensed polycyclic aryloxy group is mentioned, As a specific example, a phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5 -Naphthenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyloxy group Group, 9-acridinyloxy group and the like, but are not limited thereto.

Substituent R ₈ in general formula (7) constituting the sulfonium cation represented by general formula (2), substituent R ₉ in general formula (9), substituents in general formula (7) to general formula (10) The acyl group in R may contain a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a hetero atom. Examples thereof include a carbonyl group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms is bonded, which may have an unsaturated bond in the structure. Specific examples thereof include a formyl group, an acetyl group, Propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, lauroyl, myristoyl, palmitoyl, stearoyl, cyclopentylcarbo Group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl Group, isonicotinoyl group and the like, but are not limited thereto.

The substituent R _{8 in} the general formula (7) constituting the sulfonium cation represented by the general formula (2) and the alkylthio group in the substituent R in the general formula (7) to the general formula (10) 18 linear, branched, monocyclic or condensed polycyclic alkylthio groups, and specific examples include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group , Dodecylthio group, octadecylthio group and the like, but are not limited thereto.

The substituent R _{8 in} the general formula (7) constituting the sulfonium cation represented by the general formula (2) and the arylthio group in the substituent R in the general formula (7) to the general formula (10) include a hetero atom. And a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms, and specific examples include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3-carbazolylthio group, 4-carbazolylthio group, etc. However, it is not limited to these.

  The acyloxy group in the substituent R in the general formula (7) to the general formula (10) constituting the sulfonium cation represented by the general formula (2) is a hydrogen atom or a linear or branched chain having 1 to 18 carbon atoms. A carbonyloxy group to which a monocyclic or condensed polycyclic aliphatic group is bonded, or a carbonyloxy group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms which may contain a hetero atom is bonded. Specific examples include acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group Group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group Group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3 -Furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group, etc. can be mentioned, but are not limited thereto. .

The substituent R ₁₀ in the general formula (10) constituting the sulfonium cation represented by the general formula (2), and the halogen atom in the substituent R in the general formula (7) to the general formula (10) include fluorine, chlorine, Bromine and iodine can be mentioned.

Substituents R ₂ and R ₃ constituting the sulfonium cation represented by formula (2), substituents R ₆ and R ₇ in formulas (3) to (5), and substituents in formula (7) R _8, an alkyl group in the substituents R in the substituents R ₉ in the general formula (9), the substituents R ₁₀ in the general formula (10), the general formula (7) to the general formula (10), the general formula (3) - Substituent R ₅ in General Formula (6), Substituents R ₆ and R ₇ in General Formula (3) to General Formula (5), Substituent R ₈ in General Formula (7), Substituent in General Formula (9) R ₉ , substituent R ₁₀ in general formula (10), aryl group in substituent R in general formula (7) to general formula (10), substituents R ₂ and R ₃ in general formula (2), general formula ( 3) substitutions in ~ the general formula (5) groups R ₆ and R _7, put the general formula (7) to the general formula (10) Alkenyl group in the substituents R, the general formula the substituents R ₂ in (2) and R _3, the general formula (3) substitutions in ~ the general formula (5) groups R ₆ and R _7, the substituents in the general formula (7) R ₈ , substituent R ₁₀ in general formula (10), alkoxyl group in substituent R in general formula (7) to general formula (10), substituents R ₂ and R ₃ in general formula (2), general formula (3 ) - formula (5) substituents R ₆ and R ₇ in, in the substituent R ₈ in the general formula (7), the substituent R ₁₀ in the general formula (10), the general formula (7) to the general formula (10) Aryloxy group in substituent R, substituent R ₈ in general formula (7), substituent R ₉ in general formula (9), acyl group in substituent R in general formula (7) to general formula (10), general wherein the substituents R ₈ in (7), the general formula (7) to the general formula (10) An alkylthio group in definitive substituent R, in the substituent R ₈ in the general formula (7), the general formula (7) an arylthio group in the substituents R in ~ the general formula (10), the general formula (7) to the general formula (10) The acyloxy group in the substituent R may be further substituted with other substituents. Examples of such other substituents include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom, an alkyl group, and an aryl group. Groups, acyl groups, alkoxyl groups, aryloxy groups, acyloxy groups, alkylthio groups, arylthio groups and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, t-butyl, sec-pentyl, t-pentyl, Examples include t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

  Examples of the aryl group include a monocyclic or condensed polycyclic aryl group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 9-anthryl group. , 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group, 2-furanyl group, 2-thienyl group, 2-indolyl group , 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like.

  As the acyl group, a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon atom which may contain a hetero atom is 4 carbon atoms. To 18 monocyclic or condensed polycyclic aromatic carbonyl groups, which may have an unsaturated bond in the structure. Specific examples thereof include formyl group, acetyl group, propionyl group, Butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group , Benzoyl group, 2-methylbenzoyl group, 4-methoxy Nzoiru group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-Ansuroiru group, and the like 5 Nafutasenoiru group.

  Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group , Boronyloxy group, 4-decyl Cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like.

  Examples of the aryloxy group include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms which may contain a hetero atom. Specific examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, 9 -Anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluore Nyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group , 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group and the like.

  The acyloxy group is a hydrogen atom or a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon number which may contain a hetero atom. Examples include a carbonyloxy group having 4 to 18 monocyclic or condensed polycyclic aromatics bonded thereto, and specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. Group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, Oreo Ruoxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anth A royloxy group, a 5-naphthacenoyloxy group, etc. can be mentioned.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like. Examples of the arylthio group include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3 -A carbazolylthio group, a 4-carbazolylthio group, etc. can be mentioned, However, It is not limited to these.

The substituent R ₂ may be bonded to any one of R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R via a divalent linking group to form a ring structure. The substituents R ₆ and R ₇ may be bonded to any of R ₈ , R ₉ , R ₁₀ , and R via a divalent linking group to form a ring structure. The divalent linking group here is an alkylene group which may have a substituent having 1 to 4 carbon atoms, an arylene group which may have a substituent, an arylalkylene group, or -C = C-,- O—, —S—, —NH—, —SO ₂ —, —CO—, —COO—, —OCOO—, —CONH—, —SO ₂ —O—, and substitutions having these bonds in part An alkylene group which may have a group is meant.

  Specific examples of the onium salt composed of a sulfonium cation and a borate anion are shown below, but are not limited thereto.

However, X ⁻ in the above structural formula may be any anion selected from the structures shown below.

  The sealing agent of this invention may mix | blend an inorganic filler in order to improve characteristics, such as heat resistance, adhesiveness, and hardness. Specifically, powders such as fused silica powder, crystalline silica powder, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, aluminum nitride, boron nitride, beryllium, zirconia, talc, clay, aluminum hydroxide, Alternatively, one or more kinds of spherical beads, potassium titanate, silicon carbide, silicon nitride, alumina and other single crystal fibers, glass fibers, and the like can be blended and used. Among these inorganic fillers, fused silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The amount used is preferably 0.1 to 2000 parts by weight with respect to 100 parts by weight of the sealant. In addition, it is preferable to mix the inorganic filler in advance. In addition, in order to maintain the transparency of the cured product of the sealant, the inorganic filler must be a highly transmissive material, and the refractive index of the inorganic filler must be within 0.2 of the refractive index difference of the cured product of the sealant. It is preferable to select an inorganic filler such that the inorganic filler is particulate and the average particle size is 100 nm or less.

  Furthermore, if necessary, an adhesion-imparting agent such as a silane coupling agent for further improving the adhesiveness, a viscosity adjusting agent for adjusting the viscosity, a thixotropic agent (thickening) for imparting thixotropic properties (thixotropic properties). Modification modifiers), physical property modifiers for improving tensile properties, etc., heat stabilizers, flame retardants, antistatic agents, etc. may be added.

  In the sealant of the present invention, a silane coupling agent or a titanate coupling agent can also be used as a coupling agent. By using these, the adhesiveness of the hardened | cured material and base material by the sealing agent of this invention can be improved.

  Examples of silane coupling agents include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, etc. Aminosilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ- Taku Lilo trimethoxy silane vinylsilane, further, epoxy, amino-based, can be used silane polymer type vinyl, but is not limited thereto. In particular, epoxy silane, aminosilane, and mercaptosilane are preferable.

  On the other hand, titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, etc. are used. However, it is not limited to these.

These coupling agents may be used alone or in combination of two or more. At this time, the amount of the coupling agent used is preferably in the range of 0.1 to 1 part by weight with respect to 100 parts by weight of the curable resin.

  The sealing agent of the present invention can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. As a general method, there can be mentioned a method in which raw materials having a predetermined blending amount are sufficiently mixed with a mixer or the like, then kneaded with a mixing roll, a kneader, an extruder or the like, then cooled and pulverized. Melt kneading may be performed a plurality of times using a plurality of apparatuses, or after kneading a part of the raw material with a mixing roll or the like, the whole raw material may be kneaded again with a kneader or an extruder. .

  In preparing the sealant of the present invention, it is preferable to carry out the step of uniformly dispersing and mixing various raw materials in a vacuum or in an inert gas atmosphere in order to maintain the hygroscopicity of the solid desiccant particles.

  In preparing the sealant of the present invention, in order to uniformly disperse solid desiccant particles in the sealant, a solvent as a dispersion medium, a curable resin, a resin having compatibility with the curable resin, or Alternatively, a dispersion of solid desiccant particles may be made by a method such as uniformly dispersing in the mixture, and then mixed with various raw materials of the sealant to prepare the sealant.

  As a method for obtaining a dispersion liquid of solid desiccant particles, any means may be used as long as it is a means capable of uniformly dispersing with little formation of secondary particles. For example, a method in which a solid desiccant particle is directly formed in a solvent by a sol-gel method to obtain a dispersion, or a solvent as a dispersion medium using a solid desiccant particle as a dispersion medium using a dispersant, Examples thereof include a method of uniformly dispersing in a curable resin, a resin having compatibility with the curable resin, or a mixture thereof.

  An example of a method for obtaining a dispersion of solid desiccant particles is shown below. After mixing the solid desiccant particles with a dispersant and a solvent, a dispersion treatment is performed. Examples of the dispersant include various coupling agents such as a silicon coupling agent, various polymer dispersants, and various surfactants such as anionic, nonionic, and cationic types. These dispersants can be appropriately selected according to the type of conductive oxide fine particles used and the dispersion treatment method. Even if no dispersant is used, a good dispersion state may be obtained depending on the combination of the solid desiccant particles and the solvent to be applied and the dispersion method. Since the use of a dispersant may deteriorate the transparency, moisture resistance, and stability of the sealant of the present invention, it is most preferable to disperse solid desiccant particles without using a dispersant. As the dispersion treatment, general-purpose methods such as ultrasonic treatment, homogenizer, paint shaker, and bead mill can be applied. The obtained dispersion liquid may be subjected to component adjustment such as solid desiccant particle concentration and solvent concentration by concentration by heating or dilution by adding a solvent or the like.

  The method for obtaining the above dispersion is preferably performed in a vacuum or in an inert gas atmosphere in order to maintain the hygroscopicity of the solid desiccant particles.

  The sealing agent of the present invention such as a curable resin, a curable resin raw material (photo cationic polymerization initiator, cationic polymerizable compound), solid desiccant particles, silane coupling agent, inorganic filler, and other various additives. Before using the raw material for the preparation of the sealant, heat treatment is performed in a vacuum or in an inert atmosphere, and after adding the desiccant and kneading it, the desiccant is removed by filtration, etc. It is also possible to use after removing in advance.

  The sealing agent of this invention is used in order to protect a base material from an external environment by hardening on the base material containing an electronic device or an electronic device fundamentally. The object to which the sealing composition of the present invention is applied or filled is not particularly limited, and can be used by applying to any one of a planar shape, a three-dimensional shape, and an uneven shape.

  Examples of the method for curing the sealant of the present invention include a method of curing by irradiating active energy rays or heating, or a method of curing by both. The curing method is preferably selected according to the curable resin contained in the sealant.

  Here, the base material of the present invention will be described. The base material used for applying or filling the sealant of the present invention is not particularly limited, and any known material can be used. For example, PET film, polypropylene film, cellophane, synthetic resin film represented by polyimide, various papers, cloth, non-woven fabric, metal foil represented by aluminum foil, resin plate such as acrylic plate, metal plate, wood, foam And circuit board materials such as glass and glass epoxy substrates.

  The electronic device of the present invention includes semiconductor electronic components such as diodes, transistors, and ICs, display elements such as liquid crystal panels, plasma display panels, and organic EL panels, high-density recording media such as magneto-optical disks, solar cells, and light guides. Examples include a waveguide.

  Moreover, the base material containing the electronic device of the present invention refers to a substrate in which the electronic device and a circuit incidental to the electronic device are stacked or formed on the base material described above. Moreover, the electronic device stacked or formed on the base material may be covered with a protective layer. The material of the protective layer may be any material as long as it has excellent moisture resistance. However, in the case of a top emission type organic EL element, such as silicon oxide, silicon nitride, etc. that are excellent in transparency and moisture resistance. It is preferable to form with organic materials, such as a metal oxide and a polymer, or these mixtures and laminated bodies.

  When sealing semiconductor elements, etc., the most common sealing method using the sealant of the present invention is a low-pressure transfer method, but it can also be sealed by injection molding, compression molding, casting, etc. is there. After sealing with the sealing composition, the semiconductor element is sealed by curing.

  More specifically, for example, after the sealing composition of the present invention is placed in a mold made of a material easy to pass active energy rays such as glass, ceramic, plastic, and silicone rubber, the semiconductor element is immersed and cured as it is. It is a method of demolding.

  In the case of a liquid crystal panel or an organic EL panel, sealing is basically performed by a method of bonding two substrates. The order in which the sealing composition of the present invention contacts the two substrates is not particularly limited. In the case of coating on a base material, after coating on a peeled substrate, it is transferred to another base material using a roll or laminator, and then the peeled base material is peeled off. It can exist as an adhesive sheet consisting of only one layer of the sealant of the present invention.

  The method for sealing the organic EL panel will be described in more detail.

  Cover the substrate made of a transparent material such as glass on which the organic EL element constituting the organic EL panel is formed with a lid made of glass or metal on which a desiccant is placed so as to cover the organic EL element, and its surroundings Is sealed with the sealant of the present invention.

  In addition, in the organic EL panel using the organic EL element of the top emission method, the organic EL element is sandwiched between the base material on which the organic EL element constituting the organic EL panel is formed and the base material between the two base materials. Is sealed with the sealant of the present invention. At this time, the organic EL element may be covered with a protective layer made of silicon oxide, silicon nitride, or the like.

  The sealing method of the liquid crystal panel will be described in more detail. The sealant of the present invention is applied using a dispenser or the like, leaving one opening on the outer periphery of the flat surface of the glass substrate, and the same size as the applied glass substrate. After the glass substrates are overlapped so that the sealant layer is between the glass substrates, the sealant is cured, liquid crystal is injected from the openings, and the openings are sealed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example. In the examples, all mixing ratios are weight ratios unless otherwise specified.

Production Example 1
Calcium oxide (average particle size of 1 μm) was prepared to an average particle size of 50 nm by using a bead mill with a dry method using beads having an average particle size of 100 μm.

Production Example 2
Calcium oxide (average particle size: 1 μm) was prepared to be an average particle size of 96 nm by dry-bead milling using beads having an average particle size of 300 μm.

Production Example 3
Silica gel (average particle size 1.8 μm) was prepared to an average particle size of 75 nm by dry-bead milling using beads having an average particle size of 100 μm.

  The average particle diameters after the pulverization treatment in Production Examples 1 to 3 are all values estimated from observation results of a transmission electron microscope (scanning transmission electron microscope HD-2700, manufactured by Hitachi High-Tech).

Examples 1-6, Comparative Examples 1-3
Hereinafter, various raw materials used in each example and each comparative example are shown.

(A) Cationic polymerizable compound A1 component: Bisphenol F-type epoxy resin (trade name “Epicoat 806” manufactured by Japan Epoxy Resin Co., Ltd.). However, what was hold | maintained for 5 hours in the vacuum oven heated at 80 degreeC was used.

(B) Photocationic polymerization initiator B1 component: Compound represented by the following structural formula (manufactured by Toyo Ink Manufacturing Co., Ltd.)

  B2 component: UVI-6976 (manufactured by The Dow Chemical Company)

(C) Solid desiccant particle C1 component: calcium oxide having an average particle diameter of 50 nm. (Production Example 1)
C2 component: Calcium oxide having an average particle size of 96 nm. (Production Example 2)
C3 component: Calcium oxide having an average particle size of 1 μm.
C4 component: silica gel having an average particle size of 75 nm. (Production Example 3)
C5 component: silica gel having an average particle size of 1.8 μm.

  The above-mentioned various raw materials were blended and kneaded in parts by weight shown in Table 1 to prepare sealants corresponding to Examples 1 to 6 and Comparative Examples 1 to 3, respectively. The blending and kneading were performed in a nitrogen-substituted glove box (water content and oxygen concentration of 1 ppm or less).

  At this time, among the solid desiccant particles (C), the C1, C2, and C3 components were heated in an electric furnace at 1000 ° C. for 5 hours, and then quickly carried into the glove box for use. In addition, among the solid desiccant particles (C), the C4 component and the C5 component were held in a vacuum dryer heated to 200 ° C. for 5 hours, and then quickly carried into the glove box for use.

Table 1

Example 7
Using the sealant prepared in Example 1, a cured sealant thin film was formed on a 2 × 2 cm fused quartz substrate by the following procedure.

First, a sealant was applied onto a quartz substrate with a spin coater so as to have a film thickness of 15 μm. Thereafter, the sealing agent was cured by irradiating light of 6000 mJ / cm ² with a mercury-xenon lamp UXM-200YA manufactured by Ushio Electric Co., Ltd.

  The transmittance spectrum was measured for the thin film of the obtained encapsulant cured product, and the average transmittance with respect to light in the visible range was measured (the transmittance in the range of 400 nm to 780 nm was measured with a resolution of 1 nm and all 380 measurement points were measured. The average value of the transmittance is calculated). The measurement results are shown in Table 2.

Examples 8-12, Comparative Examples 4-6
Except that the sealant used in Example 7 was replaced with the sealant shown in Table 2, a thin film of the cured sealant was formed in the same manner as in Example 7, and the average transmission with respect to visible light The rate was measured. The average transmittance obtained is shown in Table 2.

Table 2

  As is apparent from Table 2, when solid desiccant particles having an average particle size of 100 nm or less in Examples 7 to 12 were used, compared with Comparative Example 6 in which solid desiccant particles were not included. The same average transmittance was shown. In contrast, Comparative Example 4 and Comparative Example 5 in which solid desiccant particles larger than 100 nm were used resulted in poor average transmittance. Moreover, in Examples 1-3, the sealing agent hardened | cured material did not show coloring by hardening, but in Examples 4-6, the sealing agent hardened | cured material showed coloring by hardening.

  As a result of observing the hardened | cured material of the sealing agent obtained in Examples 7-12 and Comparative Examples 4 and 5 with a transmission electron microscope, in any case, solid desiccant particles were not aggregated without aggregation. It was observed in a state dispersed in the cured product.

Example 13
On the glass substrate, Al was formed as a reflective metal by a vapor deposition method, and ITO (Indium Tin Oxide) was formed thereon by sputtering. After the film formation, the substrate was polished and patterned using a photolithography method to form a reflective electrode made of Al / ITO. Aqua regia was used as an etching solution for Al and ITO.

The substrate on which the reflective electrode was formed was cleaned and placed in a vapor deposition apparatus in which an oxygen plasma chamber, an organic film vapor deposition chamber, a metal vapor deposition chamber, and a sputtering chamber were connected. First, the substrate was placed in an oxygen plasma chamber, and a power of 100 W was applied in an atmosphere of Ar / O ₂ = 1: 1 for cleaning for 1 minute. Next, the substrate was moved to a vapor deposition chamber (pressure 5 × 10 ⁻⁵ Pa, room temperature), and α-NPD (bis ((N- (1-naphthyl-n- phenyl)) benzidine) (hole transport layer), and Alq ₃ (tris- (8-hydroxyquinolin) alminium) (electron transport light-emitting layer) having a film formation rate of 0.5 nm / s and a film thickness of 60 nm were deposited. Next, the substrate was moved to a metal vapor deposition chamber, and a 5 nm-thick MgAg alloy (Mg: Ag = 9: 1, electron injection layer) was deposited to form an organic EL layer. Then, using an opposed target sputtering method, IZO (Indium Zinc Oxide) having a film thickness of 75 nm is deposited at a film forming rate of 20 nm / min using a direct current of 100 W, and transparent To produce an organic EL element having a top emission type formed by a. Further, the light emitting area of the device to produce an organic EL element so as to be 2 mm × 2 mm.

  The obtained organic EL element was transferred into the glove box (oxygen / water concentration 1 ppm or less) without being exposed to the atmosphere, and the sealing operation was performed according to the following procedure.

On the element side of the glass substrate, the sealant prepared in Example 1 was applied by spin coating so as to have a film thickness of 50 μm to cover the organic EL element. Further, a fused quartz glass substrate having a thickness of 0.5 mm was laminated on the sealing agent covering the organic EL element. Then, the light of mercury-xenon lamp UXM-200YA manufactured by Ushio Electric Co., Ltd. was irradiated with 6000 mJ / cm ² to cure the sealant, and a sealed organic EL device was obtained.

The sealed organic EL device was caused to emit light by driving at a constant current density of 10 mA / cm ² , and the current efficiency and luminance half life in the initial state were measured. In addition, it was confirmed whether or not dark spots were generated in the light emitting surface of the sealed organic EL element when 100 hours had elapsed after the start of luminance half-life measurement. The measurement was performed in the atmosphere at 25 ° C. The results are shown in Table 3.

Examples 14-18, Comparative Examples 7-9
Except that the sealant used in Example 13 was replaced with the sealant shown in Table 3, a sealed organic EL element was produced in the same manner as in Example 13, and the obtained organic EL element was The device was caused to emit light by driving at a constant current density of 10 mA / cm ² , and the current efficiency and luminance half life in the initial state were measured. In addition, it was confirmed whether or not dark spots were generated in the light emitting surface of the sealed organic EL element when 100 hours had elapsed after the start of luminance half-life measurement. Table 3 shows the measurement results.

Table 3

Examples 19 to 34
A sealant was prepared in the same manner as in Example 1 except that the solid desiccant particles having an average particle diameter of 100 nm or less produced by the pulverization treatment were those shown in Table 4, respectively. Next, an organic EL device sealed with the same operation as in Example 13 was produced except that each obtained sealing agent was used. When the obtained organic EL device was made to emit light by driving the device at a constant current density of 10 mA / cm ² , the current efficiency in the initial state was 2.4 (cd / A) or more in both cases, and the luminance was reduced by half. The lifetime was 5000 hours or more, and no dark spot was observed when 100 hours had elapsed after the start of luminance half-life measurement.

Table 4

Example 35 to Example 71
(B) As a photocationic polymerization initiator, the same operation as Example 1 was carried out using the compounds (1) to (24) shown in Table 5 and the commercially available photocationic polymerization initiator shown in Table 6, respectively. A sealant was prepared. Next, an organic EL element sealed with the same operation as in Example 13 was produced except that each obtained sealing agent was used. The obtained organic EL device was made to emit light by driving the device at a constant current density of 10 mA / cm ² . In Examples 35 to 57, the current efficiency in the initial state is 2.6 to 2.5 (cd / A), the luminance half-life is 5000 hours or more, and it is dark when 100 hours have elapsed after the luminance half-life measurement is started. No spots were observed. In Examples 59 to 71, the current efficiency in the initial state is 2.4 to 2.2 (cd / A), the luminance half-life is 5000 hours or more, and dark when 100 hours have elapsed after the luminance half-life measurement is started. No spots were observed. In Example 58, the current efficiency in the initial state was 2.1 (cd / A), the luminance half-life was 5000 hours or more, and no dark spot was observed when 100 hours had elapsed after the luminance half-life measurement was started. The main cause of the difference between the current efficiencies measured in Examples 35 to 57 and the current efficiencies measured in Examples 58 to 71 is considered to be due to the presence or absence of coloring of the cured sealant.

Table 5

Table 6

  As is apparent from the above results, when solid desiccant particles having an average particle diameter of 100 nm or less, which is an example of the present invention, were used, compared with Comparative Example 9 that does not include solid desiccant particles, Equivalent current efficiency was shown. This is considered due to the transparency of the sealant. On the other hand, Comparative Example 7 and Comparative Example 8 in which solid desiccant particles having an average particle size larger than 100 nm were used resulted in poor current efficiency. This is considered due to the low transmittance of the sealant. Further, when solid desiccant particles having an average particle diameter of 100 nm or less according to the present invention are used, the solid sealing agent having an average particle diameter larger than 100 nm is used as compared with Comparative Example 7 and Comparative Example 8. As a result, the luminance half-life was long. This is thought to be due to the fact that the surface area of the particles increased due to the refinement of the solid desiccant particles, thereby increasing the effect of adsorbing moisture that diffuses and enters the encapsulant resin.

Claims (13)

  An encapsulant comprising solid desiccant particles and a curable resin, wherein the mean particle size of the solid desiccant particles is 100 nm or less.   2. The sealant according to claim 1, wherein the solid desiccant particles do not contain particles larger than 100 nm.   Solid desiccant particles are barium oxide, strontium oxide, calcium oxide, magnesium oxide, calcium sulfate, calcium chloride, lithium chloride, calcium bromide, potassium carbonate, copper sulfate, sodium sulfate, zinc chloride, zinc bromide, cobalt chloride 3. The sealant according to claim 1, comprising at least one of phosphorous pentoxide, silica gel, aluminum oxide, and zeolite.   The sealing agent according to any one of claims 1 to 3, wherein the curable resin is a curable resin containing a cationic photopolymerization initiator and a cationically polymerizable compound.   The sealing agent according to claim 4, wherein the cationic photopolymerization initiator comprises a borate anion. The sealant according to claim 5, wherein the borate anion is represented by the following general formula (1).
General formula (1)

Wherein Y is a fluorine or chlorine atom, Z is a phenyl group substituted with two or more groups selected from fluorine atom, cyano group, nitro group and trifluoromethyl group, m is an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4.)   The sealing agent according to any one of claims 4 to 6, wherein the cationic photopolymerization initiator comprises a sulfonium cation. The sealing agent according to claim 7, wherein the sulfonium cation is represented by the following general formula (2).
General formula (2)

(Wherein R ₁ is a group selected from a substituted benzyl group, a substituted phenacyl group, a substituted allyl group, a substituted alkoxyl group, and a substituted aryloxy group; R ₂ and R ₃ are each Independently, a benzyl group which may have a substituent, a phenacyl group which may have a substituent, an allyl group which may have a substituent, an alkoxyl group which may have a substituent, a substituent A group selected from an aryloxy group that may have, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl group that may have a substituent; ₄ represents an oxygen atom or a lone pair, and R ₁ , R _2, and R ₃ may be combined with two or more groups to form a cyclic structure.   The manufacturing method of the sealing agent hardened | cured material obtained by irradiating active energy rays to the sealing agent in any one of Claims 1-8, or heating, or both.   The method for producing a cured sealant according to claim 9, wherein the active energy ray is light including ultraviolet light, visible light, or both.   A sealant cured product obtained by the production method according to claim 9 or 10.   The manufacturing method of the sealed electronic device characterized by sealing an electronic device using the sealing agent in any one of Claims 1-8.   An encapsulated electronic device manufactured by the manufacturing method according to claim 12.