WO2019082828A1 - Sealing material composition, sealing material, and electronic substrate - Google Patents

Sealing material composition, sealing material, and electronic substrate

Info

Publication number
WO2019082828A1
WO2019082828A1 PCT/JP2018/039101 JP2018039101W WO2019082828A1 WO 2019082828 A1 WO2019082828 A1 WO 2019082828A1 JP 2018039101 W JP2018039101 W JP 2018039101W WO 2019082828 A1 WO2019082828 A1 WO 2019082828A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy
sealing material
group
diene rubber
composition
Prior art date
Application number
PCT/JP2018/039101
Other languages
French (fr)
Japanese (ja)
Inventor
眸 愛澤
Original Assignee
積水ポリマテック株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 積水ポリマテック株式会社 filed Critical 積水ポリマテック株式会社
Priority to CN201880060909.2A priority Critical patent/CN111164119B/en
Priority to JP2019509573A priority patent/JP6653801B2/en
Publication of WO2019082828A1 publication Critical patent/WO2019082828A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00Compositions of rubber derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention is a sealing material composition and sealing material which are attached to an electronic device or metal exposed portion provided on an electronic substrate or the like to protect an adherend such as an electronic device from moisture and foreign matter and the like, and It relates to an electronic substrate to be used.
  • a sealing material which uses an epoxy resin as a raw material is known conventionally.
  • This sealing material is used for coating and protection of an electronic element etc. by apply
  • Patent Document 1 JP-A-2012-087292
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2015-196783
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2012-087292
  • it is necessary to heat and soften the sheet-like sealing material composition in order to fill in the gap between the unevenness of the electronic element and the like of the substrate.
  • it takes a predetermined time for heating and time for manufacturing the product.
  • the viscosity of the sealing material composition changes with temperature, if the heating can not be performed sufficiently, the softening of the sealing material composition may be insufficient, and the unevenness may not be sufficiently filled.
  • the viscosity is too low due to excessive heating, there is a risk that the ink will flow out of the predetermined range. Furthermore, it may not be applicable to an electronic device with low heat resistance.
  • the present invention has been made to solve the above-mentioned problems. That is, it is an object of the present invention to provide a flexible and fixed sealing material composition and sealing material which does not require heating after coating an electronic element or the like.
  • the encapsulant composition of the present invention is configured as follows. That is, according to the present invention, a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, a liquid diene-based rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and an epoxy compound having two or more epoxy groups. And a photopolymerization initiator to form a sealant composition having a fixed shape.
  • the reaction product of the liquid diene-based rubber forms a sealant composition which imparts shape and flexibility. Therefore, the sealing material composition of the present invention adheres by pressing with a relatively small load when adhering to a substrate having irregularities, and easily adheres to the concave portion.
  • the term “formality” refers to the property of maintaining the shape when a predetermined operation or external force is applied.
  • the encapsulant composition of the present invention can be cured by photopolymerization when irradiated with light. Therefore, regardless of heating, the sealant composition can be cured to a sealant to seal an adherend such as an electronic element.
  • liquid diene rubber has a large molecular weight, and a part thereof forms a reaction product with an epoxy compound having at least two epoxy groups or a polyamine to form a matrix that holds unreacted products. It is difficult to cause the problem of liquid component soaking.
  • the liquid diene rubber imparts flexibility, and the encapsulant composition and the encapsulant that is a photocured product thereof are also flexible.
  • the reaction product of an epoxy compound having an epoxy group and a polyamine, wherein the reactive group to the epoxy group is a carboxyl group, and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, and a liquid diene rubber having a (meth) acryloyl group and a carboxyl group A reaction product of a reaction product of an epoxy compound having two or more epoxy groups, a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine, and a photopolymerization initiator It can be used as a stopper composition.
  • the reaction product of an epoxy compound having an epoxy group and a polyamine, wherein the reactive group for the epoxy group is a carboxyl group and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, a liquid diene rubber and epoxy having a (meth) acryloyl group and a carboxyl group.
  • An encapsulant composition which imparts shape and flexibility to a reaction product of an epoxy compound having two or more groups and a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine Become. Therefore, the sealing material composition of the present invention adheres by pressing with a relatively small load when adhering to a substrate having irregularities, and easily adheres to the concave portion.
  • the present invention is a liquid composition
  • a liquid composition comprising an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator.
  • It can be constructed as a mixture of As a mixture of a liquid composition containing an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator, A reaction product of a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber, and a reaction product of a polyamine and a liquid diene rubber
  • the polymer composition becomes a gel-like or rubber-like material by covalent bonding, ionic interaction, other intermolecular interaction or the like. Therefore, it is possible to obtain a sealant composition which gives fixed shape and flexibility and adheres to a concave and convex substrate by pressing with a relatively small load so that it adheres easily to the concave portion.
  • the liquid composition can be configured as a sealing material composition including 100 to 2000 parts by mass of the liquid diene rubber with respect to a total of 100 parts by mass of the epoxy compound having two or more epoxy groups and the polyamine. Since the liquid composition contains 100 to 2000 parts by mass of the liquid diene rubber with respect to a total of 100 parts by mass of the epoxy compound having two or more epoxy groups and the polyamine, a sealing material having excellent formability It can be a composition.
  • the present invention also includes a reaction product of a polyamine including a reaction product of an epoxy compound having two or more epoxy groups, a reactive group for the epoxy group, and a liquid diene rubber having a (meth) acryloyl group, and a photopolymerization initiator. It can be configured as having regularity without containing the product.
  • a reaction of a polyamine includes a reaction product of an epoxy compound having two or more epoxy groups, a reactive group for the epoxy group and a liquid diene rubber having a (meth) acryloyl group, and a photopolymerization initiator. Since it is configured as having formality without containing a product, a reaction product of an epoxy compound having two or more epoxy groups and the liquid diene rubber is formed to form a covalent bond, an ionic interaction, and other molecules. It becomes a polymer composition which forms a gel-like thing or a rubber-like thing by interaction etc. Therefore, it is possible to obtain a sealant composition which gives fixed shape and flexibility and adheres to a concave and convex substrate by pressing with a relatively small load so that it adheres easily to the concave portion.
  • the said invention can be set as the sealing material composition whose reactive group with respect to the said epoxy group is a carboxyl group.
  • the present invention includes a reaction product of a polyamine including a reaction product of an epoxy compound having two or more epoxy groups, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator. Since the composition has the formability without being formed, the reaction product of the epoxy compound having two or more epoxy groups and the liquid diene rubber is the encapsulant composition which provides formability and flexibility. Therefore, the sealing material composition of the present invention adheres by pressing with a relatively small load when adhering to a substrate having irregularities, and easily adheres to the concave portion.
  • the present invention can be cured by photopolymerization when irradiated with light. Therefore, the sealing material composition of the present invention can cure the sealing material composition to a sealing material regardless of heating to seal an adherend such as an electronic element.
  • the sealing material composition of the present invention can cure the sealing material composition to a sealing material regardless of heating to seal an adherend such as an electronic element.
  • liquid diene rubber has a large molecular weight, and a part thereof forms a reaction product with an epoxy compound having two or more epoxy groups to form a matrix that holds unreacted components, the liquid component It is hard to cause the problem of Furthermore, the liquid diene rubber imparts flexibility, and the encapsulant composition and the encapsulant that is a photocured product thereof are also flexible.
  • the present invention is a liquid which contains an epoxy compound having two or more epoxy groups, a liquid diene-based rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator and does not contain a polyamine. It can be configured as a mixture of compositions.
  • the liquid composition may be configured as a sealing material composition including 100 to 2600 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups. Since the liquid composition contains 100 to 2600 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups, it is possible to obtain an encapsulant composition excellent in formability. Can.
  • the liquid composition can be configured as a sealant composition further containing an epoxy resin curing agent other than a polyamine. Since it is set as the sealing material composition which further contains epoxy resin hardening
  • the said invention can be set as the sealing material composition which does not have a (meth) acryloyl group, and also has a liquid diene type rubber which has a reactive group with respect to an epoxy group. Since the present invention further includes a liquid diene rubber not having a (meth) acryloyl group and having a reactive group to an epoxy group, the rubber has good handleability, and further increases the maximum tensile stress to make it difficult to break at elongation. be able to. And the follow-up property which covers an electronic element can be improved, the unevenness
  • a liquid diene rubber having a reactive group for an epoxy group and a (meth) acryloyl group has a (meth) acryloyl group and a first liquid diene rubber having no reactive group for an epoxy group
  • the encapsulant composition may be a mixture of a second liquid diene rubber having a reactive group to an epoxy group and no (meth) acryloyl group.
  • the liquid diene rubber having a reactive group to epoxy group and a (meth) acryloyl group has a (meth) acryloyl group and a first liquid diene rubber having no reactive group to epoxy group And the (meth) acryloyl group with respect to the epoxy group in one molecule, since it is a mixture of the second liquid diene rubber having the reactive group to the epoxy group and not the (meth) acryloyl group. It is possible to use a liquid diene rubber which does not contain both reactive groups.
  • the present invention includes a reaction product of an epoxy compound containing a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine, and a photopolymerization initiator and having two or more epoxy groups. It can be comprised as a sealing material composition provided with a fixed shape.
  • the present invention includes a reaction product of an epoxy compound containing a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine, and a photopolymerization initiator and having two or more epoxy groups. Since the composition is made to have a formability without any reaction, the reaction product of the polyamine and the liquid diene rubber becomes an encapsulant composition giving formability and flexibility. Therefore, the sealing material composition of the present invention adheres by pressing with a relatively small load when adhering to a substrate having irregularities, and easily adheres to the concave portion.
  • the encapsulant composition of the present invention can be cured by photopolymerization when irradiated with light. Therefore, regardless of heating, the sealant composition can be cured to a sealant to seal an adherend such as an electronic element.
  • liquid diene rubber has a large molecular weight, and a part thereof forms a reaction product with a polyamine to form a matrix that holds unreacted components, causing a problem of liquid component leaching. hard.
  • the liquid diene rubber imparts flexibility, and the encapsulant composition and the encapsulant that is a photocured product thereof are also flexible.
  • the present invention is a mixture of a liquid composition containing a polyamine, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator and not containing an epoxy compound having two or more epoxy groups. It can be configured as a certain encapsulant composition. Because it is a mixture of a liquid composition containing a polyamine, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator and no epoxy compound having two or more epoxy groups, A reaction product of a polyamine and a liquid diene rubber is formed to form a polymer composition which forms a gel or rubber. Therefore, it is possible to obtain a sealant composition which gives fixed shape and flexibility and adheres to a concave and convex substrate by pressing with a relatively small load so that it adheres easily to the concave portion.
  • the liquid composition can be configured as a sealing material composition including 100 to 2000 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the polyamine. Since the liquid composition contains 100 to 2000 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the polyamine, it is possible to obtain an encapsulant composition excellent in formability.
  • the present invention is a sealing material which is excellent in airtightness with respect to the adherend and has an excellent sealing effect.
  • the sealing material composition is flexible, the unevenness of the electronic elements can be filled only by pressure bonding the sealing material composition formed in a sheet shape to the electronic elements to be sealed. Further, even in the case of covering a large electronic element, the electronic element can be covered while adhering closely along the surface of the electronic element while the sealing material composition is extended.
  • the sealing material can be configured as a sealing material having a storage elastic modulus of 0.7 to 5.4 MPa. Since the storage elastic modulus is configured to be 0.7 to 5.4 MPa, a sealing material having high strength and excellent flexibility can be obtained.
  • the present invention can be an electronic substrate in which an electronic element is sealed by any one of the sealing materials. Since the present invention is an electronic substrate in which the electronic element is sealed with any of the sealing materials, the electronic element is an electronic substrate suitably protected from moisture, foreign matter, and the like.
  • the height T 2 of the said electronic element to the thickness T 1 of the sealing material, together with a T 1> T 2 is substantially smooth sealing material surface filling the unevenness of the electronic device It can be an electronic substrate.
  • the height T 2 of the said electronic element to the thickness T 1 of the sealing material, together with a T 1> T 2 is substantially smooth sealing material surface filling the unevenness of the electronic device Since the substrate is an electronic substrate, even in the case of an electronic substrate having a plurality of electronic elements with different heights, the sealing material can cover the surface to form a substantially smooth flat surface. Therefore, these electronic devices can not only be sealed from external air and sealed, but also can be stably held.
  • the height T 2 of the said electronic element to the thickness T 1 of the sealing material, together with a T 1 ⁇ T 2, the sealing member along an outer surface of the electronic element is in contact It can be an electronic substrate.
  • the height T 2 of the said electronic element to the thickness T 1 of the sealing material, together with a T 1 ⁇ T 2, the sealing member along an outer surface of the electronic element is in close contact Therefore, the sealing material can cover at least the side surface of the electronic substrate having electronic elements with different heights. Therefore, the side surfaces of these electronic devices can be sealed and held stably.
  • the present invention can be an electronic substrate provided with a flexible substrate having a storage elastic modulus of 0.7 to 50 MPa. Since the present invention is an electronic substrate provided with a flexible base material having a storage elastic modulus of 0.7 to 50 MPa, the sealing material is laminated with the flexible base material to prevent excessive elongation of the sealing material. It is an electronic substrate which is hard to break the sealing material.
  • the sealing material composition and sealing material of this invention has a fixed form and flexibility, and is excellent in the handleability.
  • the electronic substrate of the present invention the electronic device is an electronic substrate suitably protected from moisture, foreign matter and the like.
  • sealing material composition of the present invention and the sealing material which is a cured product thereof will be described in detail based on the embodiment. Duplicate descriptions of materials, materials, manufacturing methods, effects, functions, and the like that overlap in each embodiment will be omitted.
  • the sealing material composition of the present invention is attached to an electronic substrate (also referred to as a "substrate") or the like on which an electronic element is disposed, and is crimped to cover and adhere the electronic element.
  • an electronic substrate also referred to as a "substrate”
  • the adhesion to the electronic device is enhanced to protect the electronic device from moisture, foreign matter and the like.
  • the encapsulant composition according to the first embodiment comprises an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and photopolymerization initiation It is a gel composition or a rubber composition obtained by heating a liquid mixture containing an agent as an essential component.
  • Liquid diene rubber having reactive group to epoxy group and (meth) acryloyl group Liquid diene rubber having reactive group to epoxy group and (meth) acryloyl group:
  • a liquid diene rubber having a reactive group for an epoxy group and a (meth) acryloyl group is a photocurable component contained in a sealant composition, and is used as a sealant. It is a component that imparts rubber elasticity (flexibility), low moisture permeability, waterproofness, and adhesion to an adherend. In addition, the mechanical strength of the sealing material is improved, and the stretchability of the sealing material is enhanced.
  • Liquid diene rubbers having a reactive group to epoxy group and a (meth) acryloyl group are not only to have both a reactive group to epoxy group and a (meth) acryloyl group in a single molecule, but also to epoxy group
  • a mixture of a liquid diene rubber having a reactive group but not having a (meth) acryloyl group and a liquid diene rubber having a (meth) acryloyl group but not having a reactive group to an epoxy group may also be used.
  • the liquid diene rubber may have a reactive group for epoxy groups and a (meth) acryloyl group in the liquid diene rubber as a mixture.
  • the liquid diene rubber is liquid at normal temperature, and in the encapsulant composition, a part thereof forms a reaction product with an epoxy compound or polyimide having two or more epoxy groups, and an unreacted liquid diene rubber.
  • the rubber is held by a matrix consisting of the reaction product and an epoxy resin cured product.
  • the viscosity of the liquid diene rubber is preferably 1 to 1000 Pa ⁇ s. In the case of less than 1 Pa ⁇ s, the crosslinked structure becomes too dense in three dimensions, and the sealing material after curing may become brittle. On the other hand, if it exceeds 1000 Pa ⁇ s, the adhesion to the adherend may be reduced.
  • the number of (meth) acryloyl groups contained in one liquid diene rubber is preferably 2 to 3.
  • the number of functional groups is 1, the crosslinked structure does not develop and the strength of the sealing material may be lowered.
  • the sealing material may become brittle because the cross-linked structure is too dense in three dimensions.
  • an acid anhydride group for example, an acid anhydride group, a carboxy group, a hydroxyl group, an amino group, an imide group, an imidazole group and a mercapto group can be exemplified, but the reactivity with the epoxy group is appropriate.
  • Carboxyl groups and acid anhydride groups are preferred because they are readily available.
  • the liquid diene rubber is preferably a component having a storage elastic modulus E ′ of 0.01 to 10 MPa when cured alone. If the storage elastic modulus is less than 0.01 MPa, the toughness of the sealing material becomes extremely weak, and there is a possibility that the object to be sealed can not be sufficiently protected. When the storage elastic modulus exceeds 10 MPa, the sealing material may become harder than necessary.
  • liquid diene rubber liquid polyisoprene, liquid polybutadiene, liquid polyisobutylene and the like can be exemplified.
  • Epoxy compound having two or more epoxy groups having two or more epoxy groups:
  • an epoxy compound having two or more epoxy groups is formed as an essential raw material, and in the sealing material composition, mainly an epoxy compound having two or more epoxy groups and a liquid It is contained as a reaction product of a diene rubber and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine. Furthermore, when the below-mentioned epoxy resin curing agent is included, it is also included as an epoxy resin cured body in which an epoxy compound having two or more epoxy groups and a curing agent of epoxy resin have reacted. An epoxy component having an unreacted epoxy group may be included.
  • epoxy compound having two or more epoxy groups epoxy monomers and oligomers having two or more epoxy groups in one molecule can be used.
  • a molecule having a flexible skeleton such as polyethylene glycol skeleton, polypropylene glycol skeleton, polyether skeleton, urethane skeleton, polybutadiene skeleton, nitrile rubber skeleton, etc. is used in part of the molecule, It is preferable in that the hardness can be made more flexible.
  • epoxy compound having two or more epoxy groups include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, glycidyl amine epoxy resin, naphthalene type Epoxy resin, triphenol alkane type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like can be mentioned.
  • an aromatic dihydroxy compound such as bisphenol A is reacted with an alkylene oxide such as ethylene oxide or propylene oxide to synthesize a compound having a polyalkylene glycol skeleton, and the terminal of the compound having a polyalkylene glycol skeleton Is obtained by further epoxidizing “an epoxy compound having an aromatic dihydroxy compound and a polyalkylene glycol bonded to each other and having an epoxy group at an end”, an alkanediol such as propanediol and butanediol, or a polyalkylene glycol such as diethylene glycol and polypropylene glycol Epoxidized, further reacted with an aromatic dihydroxy compound such as bisphenol A, and epoxidized the product to obtain “alkanediol or polyalkyl” “Epoxy compounds having an epoxy group at the end by bonding of an glycol and an aromatic dihydroxy compound”, aliphatic, aromatic hydrocarbon compounds, alkaned
  • an aliphatic skeleton, an aromatic skeleton, or an epoxy compound having an epoxy group at the end by combining an alkanediol or polyalkylene glycol with an aromatic dihydroxy compound is preferred to use.
  • epoxy compounds having two or more epoxy groups may be used alone or in combination of two or more.
  • the epoxy compound having two or more epoxy groups may be liquid or solid at normal temperature.
  • the state of 25 degreeC shall be said.
  • a polyamine is formed as an essential raw material, and in the sealant composition, mainly, a reaction product of a polyamine and a liquid diene rubber and two polyamines and an epoxy group It is contained as a reaction product with the epoxy compound which has the above.
  • Polyamine is a general curing agent for epoxy compounds having two or more epoxy groups, and is also contained in the skeleton of the epoxy resin cured product in which an epoxy compound having two or more epoxy groups and a polyamine react with each other. It will be. An unreacted polyamine component may be contained.
  • a polyamine refers to a compound having a molecular weight of at least 100 and containing two or more amino groups.
  • aliphatic polyamines polyether polyamines, alicyclic amines, aromatic amines, polyamidoamines, amine adducts and the like can be mentioned.
  • the polyamine may be liquid or solid, but since it contains an epoxy compound having two or more epoxy groups as an essential component of the encapsulant composition, it is preferable to use a polyamine called a so-called latent curing agent. If a latent curing agent is used, it does not cure immediately after mixing, and therefore, it is possible to suppress an increase in viscosity when mixed with an epoxy compound having two or more epoxy groups and a liquid diene rubber. Since the sealing material formed by curing the sealing material composition protects the adherend from water and water vapor, the presence of air bubbles in the sealing material will deteriorate the characteristics of the sealing material.
  • the latent curing agent is, for example, solid at normal temperature, but may be one having a property of melting and activating at a predetermined temperature.
  • polyamines aromatic amines activated at a temperature of 60 ° C. to 120 ° C., and amine adducts are particularly preferable.
  • hexamethylenediamine 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylene Hexamine, N-hydroxyethyl ethylenediamine, tetra (hydroxyethyl) ethylene diamine and the like can be mentioned.
  • polyether polyamines examples include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines and the like.
  • Alicyclic amines include isophorone diamine, metacene diamine, N-aminoethyl piperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino And propyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, norbornene diamine and the like.
  • aromatic amines tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2, 4-Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone , M-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, ⁇ - (m-aminophenyl) ethylamine,
  • aliphatic amines, polyether polyamines and alicyclic amines are preferably used in consideration of the compatibility with other raw materials and the flexibility of the sealing material.
  • the total content of the epoxy compound having two or more epoxy groups and the polyamine is preferably 5 to 50% by mass in the encapsulant composition and the encapsulant. If the amount is less than 5% by mass, the encapsulant composition may not be able to have a predetermined shape. On the other hand, if it exceeds 50% by mass, the sealing material may be too hard. Further, since the content of the liquid diene rubber which is a light curing component is relatively decreased, the adhesion may be lowered.
  • the curing agent of the below-mentioned epoxy resin when it contains the curing agent of the below-mentioned epoxy resin as an arbitrary component further, it adds to the epoxy compound and polyamine which have 2 or more of epoxy groups, and the content which united the curing agent of this epoxy resin is sealing material composition It is preferable that 5 to 50% by mass be contained in the product and the sealing material. The reason is the same as above.
  • the compounding amount of the liquid diene rubber is preferably 100 to 2000 parts by mass, and 400 to 1600 parts by mass with respect to a total of 100 parts by mass of the epoxy compound having two or more epoxy groups and the polyamine. More preferable. If the liquid diene rubber is less than 100 parts by mass, the sealant composition and the sealant may become hard. In addition, the adhesion of the sealing material may be reduced. On the other hand, when the amount of the liquid diene rubber exceeds 2000 parts by mass, the shapeability of the sealing material composition is impaired, and the handleability may be impaired, for example, the sticking operation becomes difficult.
  • reaction product of epoxy compound having two or more epoxy groups and liquid diene rubber reaction product of epoxy compound having two or more epoxy groups and polyamine:
  • the sealant composition contains the reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber. More specifically, this reaction product is produced by the reaction of the epoxy group with the reactive group for the epoxy group contained in the liquid diene rubber. In addition to this, the reaction product of an epoxy compound having two or more epoxy groups and a polyamine is included. Furthermore, when the reactive group to the epoxy group possessed by the liquid diene rubber is a carboxyl group, the reaction product of a polyamine and a liquid diene rubber having a (meth) acryloyl group and a carboxyl group is included.
  • the reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber, the reaction product of a polyamine and a liquid diene rubber, and the reaction product of an epoxy compound having two or more epoxy groups and a polyamine have a covalent bond. It forms, forms an interaction between ions, and forms other interactions. That is, the liquid diene rubber itself is liquid, and if contained in a large amount, there is a possibility that the shape of the encapsulant composition may be impaired, but the content of the liquid diene rubber is reduced by forming a reaction product. At the same time, it is considered that the amount of the reaction product that holds the resin increases to provide the encapsulant composition with a fixed shape and to maintain appropriate softness.
  • reaction products become relatively high viscosity compared with each component before reaction, or become solid. Therefore, specifically, the tensile elongation at break is greatly improved, and when the sealant composition is stretched, it can be made difficult to break. Therefore, when a flat sealing material composition is applied to a sealing object having irregularities, the portion stretched along the irregularities becomes less likely to break, and the occurrence of defects due to breakage of the sealing material is suppressed. In addition, in other words, this can be applied to a highly uneven sealing target.
  • the temperature change of the storage elastic modulus is observed for the temperature characteristic of the dynamic viscoelasticity measurement.
  • Heat-resistant sealing material composition which is small in size and excellent in formability.
  • the storage elastic modulus measured by dynamic viscoelasticity measurement is a seal excellent in thermoplasticity in which the storage elastic modulus significantly decreases as the temperature increases.
  • a sealant composition can be obtained which becomes an anchor composition and whose flexibility increases with increasing temperature.
  • Such a sealing material composition can adhere a sealing material composition to every corner of unevenness by heating auxiliary
  • the photo radical polymerization initiator is to cause a liquid diene rubber to photo react and cure.
  • photopolymerization initiators such as benzophenone type, thioxanthone type, acetophenone type, and acyl phosphine type can be used.
  • the compounding amount of the photo radical polymerization initiator is preferably 0.1 to 10 parts by weight, and more preferably 1 to 8 parts by weight with respect to 100 parts by weight of the liquid diene rubber.
  • a liquid diene rubber containing no (meth) acryloyl group and having a reactive group to an epoxy group can be further included. If a liquid diene rubber having a (meth) acryloyl group and not having a reactive group to an epoxy group is further contained, the handleability of the plug composition is improved, and the maximum tensile stress is further increased to elongate the product. Can be made less likely to occur. Therefore, the followability to cover the electronic element can be enhanced, the unevenness of the electronic element can be filled with low load and the surface can be made to follow the surface of the electronic element, and the defect is less likely to occur due to the extension of the sealing material. Can. Further, by reducing the crosslink density derived from the (meth) acryloyl group, the stretchability after curing can be enhanced, and a sealing material suitable for a flexible substrate and an extension base material can be obtained.
  • a curing agent of epoxy resin can be included.
  • the curing agent of the epoxy resin is other than the above-mentioned polyamine and an epoxy group
  • An epoxy resin cured product obtained by thermally curing an epoxy compound having two or more epoxy groups and a curing agent for epoxy resin is a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber, a polyamine and Together with the reaction product with liquid diene rubber, it is a component that imparts shape to the encapsulant composition and the encapsulant. Moreover, it contributes to improving the low moisture permeability and waterproofness of the sealing material.
  • an epoxy resin having a flexible skeleton is used as the epoxy compound having two or more epoxy groups, the flexibility of the encapsulant composition and the encapsulant can be enhanced.
  • epoxy resin curing agents among epoxy resin curing agents generally used, ones other than the above-mentioned polyamine can be used.
  • the curing agent include imidazole curing agents, acid anhydride curing agents, phenol curing agents, polymercaptan curing agents, isocyanates, and blocked isocyanates.
  • These epoxy resin curing agents may be used alone or in combination of two or more.
  • the compounding ratio of the hardening agent of the epoxy resin with respect to the epoxy compound which has 2 or more epoxy groups can be made the same as the compounding ratio in the case of being generally used as a main agent of an epoxy resin, and a hardening agent.
  • the content of the curing agent of the epoxy resin is, as described above, the total content of the epoxy compound having two or more epoxy groups, the polyamine and the curing agent of the epoxy resin in the sealing material composition and the sealing material It is preferable to be%. If the amount is less than 5% by mass, the encapsulant composition may not be able to have a predetermined shape. On the other hand, if it exceeds 50% by mass, the sealing material may be too hard. Further, since the content of the liquid diene rubber which is a light curing component is relatively decreased, the adhesion may be lowered.
  • various additives can be appropriately blended without departing from the scope of the present invention.
  • silane coupling agents polymerization inhibitors, antifoaming agents, light stabilizers, antioxidants, antistatic agents, plasticizers such as polyisoprene or polybutadiene, tackifiers, curing accelerators and the like can be mentioned.
  • plasticizers such as polyisoprene or polybutadiene, tackifiers, curing accelerators and the like
  • the functional group that reacts with the epoxy group is an acid anhydride group
  • the function according to a use can also be provided with various fillers, such as insulating fillers, such as a silica and a clay, an electroconductive filler, a soft magnetic body filler, and a thermally conductive filler, for example.
  • the sealing material composition as the second embodiment comprises an epoxy compound having two or more epoxy groups, a liquid diene rubber having a reactive group for epoxy groups and a (meth) acryloyl group, and a photopolymerization initiator. It is included as an essential component and does not contain polyamine. These raw materials are the same as those described in the first embodiment.
  • the optional components are also the same as in the first embodiment, and can include, for example, an epoxy resin curing agent.
  • the epoxy compound having two or more epoxy groups is mainly contained as a reaction product of the epoxy compound having two or more epoxy groups and the liquid diene rubber.
  • a reaction product of the epoxy compound having two or more epoxy groups and the liquid diene rubber By containing such a reaction product, it is possible to obtain a heat-resistant sealing material composition having excellent formability. More specifically, with regard to the temperature characteristics of the dynamic viscoelasticity measurement, it is possible to obtain an encapsulant composition with a small change in storage elastic modulus temperature.
  • the content of the epoxy compound having two or more epoxy groups is preferably 5 to 50% by mass in the sealing material composition and the sealing material. If the amount is less than 5% by mass, the encapsulant composition may not be able to have a predetermined shape. On the other hand, if it exceeds 50% by mass, the sealing material may be too hard. Further, since the content of the liquid diene rubber which is a light curing component is relatively decreased, the adhesion may be lowered.
  • the content which united the epoxy agent which has 2 or more of epoxy groups, and the hardening agent of this epoxy resin is a sealing material composition and sealing It is preferable that 5 to 50% by mass be contained in the material. The reason is the same as above.
  • the amount of the liquid diene rubber is preferably 100 to 2600 parts by mass, and more preferably 400 to 1600 parts by mass with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups. If the liquid diene rubber is less than 100 parts by mass, the sealant composition and the sealant may become hard. In addition, the adhesion of the sealing material may be reduced. On the other hand, when the liquid diene rubber exceeds 2600 parts by mass, the formability of the sealing material composition is impaired, and there is a possibility that the handleability may be impaired, for example, the sticking operation becomes difficult.
  • the sealing material composition of this embodiment does not contain a polyamine, storage stability can be improved. Moreover, since it does not contain the bridge
  • the sealant composition as the third embodiment contains, as essential components, a polyamine, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator, and two epoxy groups are contained. It does not contain the epoxy compound possessed above. These raw materials are the same as those described in the first embodiment.
  • the optional components can be the same as in the first embodiment, but even if the curing agent of the epoxy resin is contained, the epoxy resin is cured because it does not contain an epoxy compound having two or more epoxy groups to be reacted. It is hard to come out of the characteristic by having included the agent.
  • the polyamine is mainly contained as a reaction product of the polyamine and the liquid diene rubber.
  • an encapsulant composition excellent in thermoplasticity can be obtained.
  • the temperature characteristics of the sealing material composition it is possible to obtain a sealing material composition in which the storage elastic modulus measured by dynamic viscoelasticity measurement significantly decreases as the temperature increases. That is, it is possible to obtain an encapsulant composition that increases in flexibility as the temperature increases.
  • Such a sealing material composition can adhere a sealing material composition to every corner of unevenness by heating auxiliary
  • the content of the polyamine is preferably 5 to 50% by mass in the encapsulant composition and the encapsulant. If the amount is less than 5% by mass, the encapsulant composition may not be able to have a predetermined shape. On the other hand, if it exceeds 50% by mass, the sealing material may be too hard. Further, since the content of the liquid diene rubber which is a light curing component is relatively decreased, the adhesion may be lowered.
  • the amount of the liquid diene rubber is preferably 100 to 2000 parts by mass, and more preferably 400 to 1600 parts by mass with respect to 100 parts by mass of the polyamine. If the liquid diene rubber is less than 100 parts by mass, the sealant composition and the sealant may become hard. In addition, the adhesion of the sealing material may be reduced. On the other hand, when the amount of the liquid diene rubber exceeds 2000 parts by mass, the shapeability of the sealing material composition is impaired, and the handleability may be impaired, for example, the sticking operation becomes difficult.
  • liquid composition which is a raw material used in each embodiment is prepared. Then, the liquid composition is heated.
  • a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber is generated, and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine.
  • An epoxy resin cured product is produced.
  • a curing agent of an epoxy resin is contained, a cured epoxy resin body is formed which is a reaction product of an epoxy compound having two or more epoxy groups and a curing agent of the epoxy resin. Then, the liquid composition is solidified by these reactions, and a solid encapsulant composition is obtained.
  • a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber is generated. Furthermore, when a curing agent of an epoxy resin is contained, a cured epoxy resin body is formed which is a reaction product of an epoxy compound having two or more epoxy groups and a curing agent of the epoxy resin. Then, the liquid composition is solidified by these reactions, and a solid encapsulant composition is obtained.
  • a reaction product of a polyamine and a liquid diene rubber is produced. Then, the liquid composition is solidified by this reaction, and a solid encapsulant composition is obtained.
  • the sealant composition of any of the first to third embodiments has a predetermined shape. Therefore, when sticking to the object to be sealed, it can be reliably stuck within the target range, and there is no risk of flowing out of the predetermined range.
  • these sealant compositions can have a storage elastic modulus E ′ at 23 ° C. in the range of 0.004 to 0.75 MPa. Since the storage elastic modulus E ′ is extremely flexible by setting the storage elastic modulus E ′ to 0.004 to 0.75 MPa, an excessive stress is given to the electronic substrate when the sealing material composition is pressed to be in close contact with the electronic substrate. It can be made to flexibly follow the unevenness of the electronic device with an extremely low load.
  • the electronic substrate can be closely attached without any gap and sealed reliably without applying a load to the electronic substrate.
  • the strength of the sealing material composition is weak, and when it is attached to a sealing target having irregularities, there is a possibility that the part stretched along the irregularities tends to break easily.
  • it exceeds 0.75 MPa it becomes hard more than necessary, and when sticking a sealing material composition to sealing object, there exists a possibility that big pressure may be needed.
  • the storage elastic modulus E ' is preferably in the range of 0.01 to 0.60 MPa.
  • the electronic substrate includes a resin substrate, a flexible substrate, an extension substrate, and the like.
  • the sealant composition may or may not have tackiness, but preferably has predetermined tackiness. If the sealant composition has adhesiveness, it does not shift due to vibration and impact after disposing the sealant composition on the object to be adhered, and it is easy to perform sticking and sealing work. is there.
  • the adhesive strength is not necessarily strong, it is preferable to have an adhesive property to such an extent that it does not shift due to vibration and impact after disposing the sealing material composition on the adherend. Specifically, after sticking the sealing material composition on a substrate provided with a protrusion having a height of 25% of the thickness of the sealing material composition and adhering the substrate, adhesion of such a degree that a gap does not occur for about 30 seconds Preferably,
  • the thickness of the encapsulant composition is preferably 0.2 to 2.0 mm. If it is less than 0.2 mm, handling of the encapsulant composition may be difficult. On the other hand, if it exceeds 2.0 mm, ultraviolet rays may not sufficiently penetrate to the deep portion of the encapsulant composition, and curing may be insufficient.
  • the sealing material of the present invention is flexible, it is preferable to set the thickness of the sealing material composition to 0.5 to 2.0 mm because the shock absorbing effect of protecting the electronic element from impact is enhanced.
  • the encapsulant composition preferably has some degree of transparency. Although the encapsulant composition can be cured even if it is turbid to a certain extent, if the transparency is largely impaired, the curability of the deep portion may be impaired when the encapsulant composition is photocured.
  • the sealing materials of the first to third embodiments can be manufactured. More specifically, an electronic element provided with a sealing material composition on an electronic substrate or the like and a portion where metal is exposed to cover an adherend such as an electronic element and the like, and then liquid diene rubber by light irradiation It can be used as a sealing material by hardening by photo radical polymerization reaction. At this time, in the case where the sealing material composition has an adhesive force, pressure is applied to the adherend with a jig or the like, and the sealing material is brought into close contact with the unevenness of the adherend while being crushed.
  • the jig is lifted and light is irradiated rapidly, so that the sealing material composition can be cured in a state in which the sealing material composition is in close contact with the adherend.
  • the sealing material composition does not have adhesive strength, the sealing material is brought into close contact with the unevenness of the adherend while being crushed using a light transmissive jig. Then, by irradiating light through the jig in this state, it is possible to cure the sealing material composition in a state in which the sealing material composition is in close contact with the adherend.
  • transmits the light of the wavelength to be used, such as an acrylic resin, glass, sapphire, can be used, for example.
  • any of the sealing materials of the first to third embodiments formed by irradiating and curing the sealing material composition of the first to third embodiments is also a flexible rubber-like elastic body. It has the flexibility to follow the flexible substrate.
  • the storage elastic modulus E ′ at 23 ° C. measured by a dynamic viscoelasticity measuring device can be in the range of 0.5 to 10 MPa, and is preferably 0.7 to 5.4 MPa. Since it is set as such a range, even if it uses for the use which deform
  • the strength of the sealing material may be reduced, and if the storage elastic modulus E' exceeds 10 MPa, it may not be suitable for applications requiring flexibility. is there.
  • the pressure is 0.7 to 5.4 MPa, a sealing material having high strength and excellent flexibility can be obtained.
  • the sealing material also has a predetermined adhesive property and a waterproof performance satisfying IPX7 defined in JIS C0920. Therefore, the object to be sealed can be reliably protected from water. Furthermore, the water vapor permeability of the sealing material is 50 g / m 2 ⁇ 24 h or less. Therefore, the object to be sealed can be protected from moisture even in a high humidity environment.
  • the encapsulant composition Since the encapsulant composition has a fixed shape and flexibility, the encapsulant composition is brought into close contact by pressing the encapsulant composition against the uneven electronic substrate with a relatively small load, and it is easy to penetrate into the recesses of the electronic substrate.
  • the storage elastic modulus of the sealing material is small and flexible, residual stress is unlikely to remain even if it is cured in a state where the unevenness of the electronic substrate is buried, and the electronic element is stably sealed for a long period of time Is possible.
  • the sealing material composition of the present invention is often capable of elongation of about 400%, while it is likely to be broken when trying to follow it, and it is easy to make an electronic element that is hard to break and has a high height. It can be covered.
  • the height T 2 of the electronic element is made smaller (T 1 > T 2 ) with respect to the thickness T 1 of the sealing material, and the unevenness of the electronic element is filled with the sealing material to make the surface substantially smooth, Even an electronic substrate having electronic elements of different heights can be held stably as well as separated and sealed from the outside air because the surface is smooth. Also, if the height T 2 of the electronic element is made higher (T 1 ⁇ T 2 ) with respect to the thickness T 1 of the sealing material, and the sealing material is adhered along the outer surface of the electronic element Even in the case of an electronic substrate having electronic elements different in size, since the sealing material covers at least the side surface, these electronic elements can be stably held.
  • a sealing material composition and a sealing material to be sample 1 were produced.
  • an epoxy compound having two or more epoxy groups 41.3 parts by mass of a liquid epoxy resin having a flexible skeleton ("EP-4000S" manufactured by ADEKA Co., Ltd.) (hereinafter, epoxy resin 1) is modified as a polyamine Liquid polyisoprene rubber having a carboxyl group and a methacryloyl group (30 Pa ⁇ s, 38 g of 15.9 parts by mass of aliphatic polyamine (“EH-4357S” manufactured by ADEKA Co., Ltd.) (hereinafter referred to as “polyamine 1”) as liquid diene rubber ° C, molecular weight 17000, number of functional groups carboxyl group: 2, methacryloyl group: 2 (hereinafter, liquid diene rubber 1): 42.8 parts by mass, and 1.3 mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator The parts were mixed to obtain a
  • the liquid composition is heated at 120 ° C. for 60 minutes in a state of being sandwiched between a pair of release films so as to have a thickness of 1.0 mm, thereby reacting an epoxy compound having two or more epoxy groups.
  • the sheet-like sealing material composition was prepared, and this was used as the sealing material composition of sample 1.
  • the sealing material compositions and the sealing materials of Samples 2 to 26 were also produced under the same conditions except that the respective raw materials and the blending amounts of Sample 1 were changed to the respective raw materials and blending amounts shown in the table.
  • the mass part number of each raw material is described by making into 100 mass parts the sum total of the epoxy compound which has 2 or more of epoxy groups, a polyamine, and a liquid diene rubber.
  • Epoxy resin 2 Bisphenol F type epoxy resin (DIC Corporation "EPICLON EXA-835LV”)
  • Epoxy resin 3 Liquid epoxy resin having two or more epoxy groups and having a flexible skeleton (DIC Corporation "EXA-4850-150")
  • Polyamine 2 Epoxy amine adduct (Ajinomoto Fine Techno Co., Ltd.
  • Liquid diene rubber 2 Liquid polyisoprene rubber having neither (meth) acryloyl group nor reactive group to epoxy group (70 Pa ⁇ s, 38 ° C., molecular weight 28000, no functional group)
  • Liquid diene rubber 5 Liquid polybutadiene rubber having a methacryloyl group and having no reactive group to an epoxy group (100
  • sealing material composition and sealing material of each said sample it tested from various viewpoints shown below, observed, and evaluated.
  • the sealing material composition formed by applying the liquid composition on the release film and curing it may be evaluated from the state of the sealing material composition when peeled off from the release film. it can.
  • those which could be peeled off the sealing material composition while maintaining the shape were taken as “o”, and those which could be peeled off but which were deformed such as being stretched were made “ ⁇ ”.
  • those which did not solidify those in which the encapsulant composition had flowed out of the release film, and those in which the cohesive force was extremely weak and it was difficult to detach the encapsulant composition from the release film were regarded as “x”.
  • delta)” can be evaluated as what can be utilized as a sealing material composition, and has a fixed shape.
  • the thing of "x” has a possibility that it may be difficult to stick within the predetermined range of sealing object, or it may flow out of the predetermined range, and does not have a fixed shape.
  • the evaluation results of the sealing material compositions of Samples 1 to 26 are shown in the table.
  • a sealing material composition is cut into a size of width 5.0 mm ⁇ length 30.0 mm (thickness is 1.0 mm) to prepare a test piece for measurement, and a dynamic viscoelasticity measuring apparatus (Seiko Instruments Co., Ltd.
  • a storage elastic modulus E ′ was measured in a tension mode with a distance between chucks of 8 mm, a frequency of 1 Hz, using “DMS 6100” manufactured in Japan.
  • the storage elastic modulus measured under the above conditions is preferably in the range of 0.1 to 0.6 MPa.
  • the storage modulus values of the sealing material compositions of Samples 1 to 26 are shown in the table.
  • the encapsulant composition having a predetermined weight W1 is allowed to stand in toluene for 24 hours at normal temperature, the encapsulant composition not dissolved in toluene is taken out, and the weight after evaporating the toluene contained in the encapsulant composition W2 was measured.
  • the ratio of the weight W2 of the toluene insoluble component to the initial weight W1 of the encapsulant composition is defined as the gel fraction.
  • the insoluble component includes a three-dimensionally crosslinked epoxy resin cured product and a reaction product.
  • an elution component to toluene in addition to epoxy compounds having two or more epoxy groups, polyamines, liquid diene rubbers, reaction products bonded by weak interaction, not cross-linked three-dimensionally Reaction products (hereinafter referred to as elutable reaction products) can be mentioned. Therefore, when the gel fraction is small, the sealant composition contains at least one of an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber, and an elution reaction product. Further, when the gel fraction is 100%, it can be seen that such a leachable does not remain.
  • the above-mentioned gel fraction may become small in the closure agent composition constituted with polyamine and liquid diene system rubber.
  • the reaction product of the polyamine and the liquid diene rubber is either a reaction product due to a weak interaction or a reaction product which does not have a three-dimensional structure sufficient to maintain the structure in toluene. It is considered to be solidified by formation.
  • an acid-base interaction will work.
  • maximum tensile stress also referred to as tensile strength
  • elongation at break also referred to as tensile breaking elongation
  • 100% elongation tensile stress were measured according to JIS K 6251.
  • the sheet-like sealing material composition was cut into a dumbbell shape No. 1 using a punching die, and two mark lines were attached to the rod-like portion of the dumbbell-shaped sample at an interval of 10 mm.
  • tensile force was applied to both ends of the sample under certain conditions, and the maximum tensile force until the sample broke and the elongation between the marked lines were measured.
  • TS F m / S equation (1)
  • E b (L 1 -L 0 ) / L 0 ⁇ 100
  • TS 100 F 100 / S formula (3)
  • TS Maximum tensile stress (MPa)
  • F m Maximum tensile force (N)
  • S Initial cross-sectional area of test piece (mm 2 )
  • E b Elongation at cutting (%)
  • L 0 Initial mark line distance (mm)
  • L 1 Distance between marked lines at break (mm)
  • TS 100 100% elongation tensile stress (MPa)
  • F 100 100% elongation tensile force (N)
  • a change in hardness occurs with the curing, so the degree of curing was evaluated by the change in storage elastic modulus.
  • storage elastic modulus E ′ a sealing material is cut out to a size of width 5.0 mm ⁇ length 30.0 mm (thickness 1.0 mm) to prepare a test specimen for measurement, and dynamic viscoelasticity measurement Using a device (“DMS 6100” manufactured by Seiko Instruments Inc.), the distance between chucks was 8 mm, the frequency was 1 Hz, and the measurement temperature was 23 ° C. in a tensile mode.
  • the storage elastic modulus is approximately 0.01 to 0.60 MPa in the sealing material composition, whereas the storage elastic modulus of the sealing material is in the range of 0.5 to 10 MPa.
  • the rate of change of at least 200% Preferably, the thing of 200% or more of change rate of storage elastic modulus was evaluated as "(circle)" and less than 200% as "x". The evaluation results and the values of the change in storage modulus before and after curing from the sealing material composition to the sealing material are shown in the table.
  • the waterproofness of the sealing material was evaluated by the test of the IPX7 standard defined in JIS C0920. Specifically, a 5 mm ⁇ 5 mm submersion detection seal is attached to an epoxy resin substrate having a thickness of 1 mm, and a 10 mm ⁇ 10 mm ⁇ 1 mm sealing material composition is attached to cover the submersion detection seal. By irradiating ultraviolet light, a test piece in which the submersion detection seal on the epoxy resin substrate was covered with the sealing material was produced. The test piece was placed on the bottom of water at a depth of 1 m in a stationary state for 30 minutes and then taken out, and it was evaluated whether the submersion detection seal detected water or not. The case where water was not detected was evaluated as "o", and the case where water was detected was evaluated as "x". The evaluation results are shown in the table.
  • the sealing material does not necessarily have to have strong adhesion, but needs to have adhesion to a degree that does not impair the waterproofness.
  • the adhesion state after the test of the IPX 7 was confirmed, and those with the sealing material adhered even after the test were evaluated as “ ⁇ ”, and those with the sealing material peeled off after the test were evaluated as “X”. did.
  • the evaluation results are shown in the table.
  • the sealing material is preferably capable of blocking not only liquid water but also gaseous water, that is, water vapor.
  • the water vapor permeability can be evaluated by the cup method defined in JIS Z0208, and the water vapor permeability is preferably 50 g / m 2 ⁇ 24 h or less.
  • the water vapor transmission rate test was performed by preparing a test piece made of a sealing material having a thickness of 1 mm and measuring the water vapor transmission rate under the conditions of 40 ° C. and 90% RH. The measured values are shown in the table.
  • Samples 1 to 6 are samples in which the ratio of the total mass of the epoxy resin 1 to the polyamine 1 to a constant ratio and the mass of the liquid diene rubber 1 was changed.
  • the samples 1 to 4 are excellent in formability, the formability of the sample 5 is in a usable range but is slightly deteriorated. This is considered to be the deterioration of the shaping property due to the increase in the proportion of the liquid diene rubber which becomes unreacted in the sealant composition and the decrease in the crosslink density of the reaction product. From this, the proportion of the liquid diene rubber with respect to the total amount of the epoxy compound having two or more epoxy groups, the polyamine, and the liquid diene rubber is 95.3% by mass or less, and has usable formability.
  • sample 6 in which the proportion of the liquid diene rubber is as low as 35.0% by mass, a uniform liquid composition can be obtained when an epoxy compound having two or more epoxy groups, a polyamine and a liquid diene rubber is mixed. It was not possible, and even after heating, some components flowed out in the form of liquid, and since the formability was "x", the total of the epoxy compound having two or more epoxy groups, the polyamine and the liquid diene rubber The ratio of the liquid diene rubber to the amount is required to exceed 35% by mass, and it was confirmed from the results of Sample 1 that the inclusion of 42.8% by mass or more results in excellent formability.
  • the gel fraction of the sealant compositions of Samples 1 to 5 was in the range of 69.2 to 79.7%.
  • the unreacted liquid diene rubber dissolves in toluene, which suggests the presence of a component which has become insoluble in toluene.
  • more than half of the blended liquid diene rubber forms some reaction product, and from the result of temperature dependency of storage elastic modulus, it is possible to use epoxy group of epoxy compound and liquid diene rubber. It was suggested that the carboxyl group was reacted to form a reaction product.
  • the elongation at break of the sealing material compositions of Samples 1 to 5 was 186 to 512%, and they had the property of being easy to stretch and hard to break. In particular, when the proportion of the liquid diene rubber is 50.0 to 94.2%, the elongation at break is 200% or more and the maximum tensile stress is 0.1 MPa or more. It was excellent.
  • each encapsulant composition was also excellent in photocurability.
  • the storage elastic modulus of the sealing material after curing was 0.8 to 5.4 MPa.
  • those having a liquid diene rubber ratio of 50.0% or more had a storage elastic modulus of 4 MPa or less, and became a flexible sealing material.
  • the ratio of the liquid diene rubber is 88.9% or less
  • the storage elastic modulus is 1 MPa or more, and a certain degree of rigidity is provided.
  • each sample had a favorable result of the water immersion test, and had predetermined
  • the water vapor transmission rate was 20 g / m 2 ⁇ 24 h or less in all cases, and the film had a predetermined low moisture permeability.
  • Sample 7 did not contain a liquid diene rubber, and although cured after heating, a cured product which was extremely hard and poor in flexibility was obtained. About this sample 7, it did not have adhesiveness and photocurability.
  • the sample 8 did not mix
  • Sample 9 and Sample 10 are samples in which the blending amounts of the epoxy compound having two or more epoxy groups and the polyamine are changed.
  • the compounding amount of the epoxy compound having two or more epoxy groups and the polyamine was such that the epoxy equivalent and the active hydrogen equivalent become 1: 1, but the sample 9 is an epoxy having two or more epoxy groups
  • the compound was in excess and sample 10 was in excess of polyamine.
  • the sample 9 and the sample 10 both had predetermined properties as a sealant composition and a sealant.
  • the sample 11 is a sample using a bisphenol F epoxy resin having no flexible skeleton as an epoxy compound having two or more epoxy groups.
  • the sample 11 also has almost the same test results as the samples 3 and 4.
  • the proportion of the liquid diene rubber is high, similar properties are obtained even if the type of epoxy compound having two or more epoxy groups is changed. It was found that the encapsulant composition and the encapsulant of the present invention can be obtained.
  • Samples 12 and 13 are samples characterized in that no polyamine was blended. That is, it is a sample in which a liquid composition mainly composed of an epoxy compound having two or more epoxy groups and a liquid diene rubber is prepared and heated to form a sealing material composition.
  • the sealant compositions of Sample 12 and Sample 13 all had a fixed shape. From this, the epoxy compound having two or more epoxy groups does not necessarily react with the curing agent of the polyamine and the epoxy resin to form a matrix, but the epoxy compound having two or more epoxy groups and the liquid diene system It has been found that the reaction product of rubber also solidifies and gives shape. Moreover, it was suggested that this is due to the reaction of the epoxy group of the epoxy compound and the carboxyl group of the liquid diene rubber from the test results of the sample described later.
  • the sealing material compositions of Samples 12 and 13 both had properties equivalent to those of Samples 3 and 4, and the temperature dependency of the storage elastic modulus was also small.
  • the sealing materials of Samples 12 and 13 have the same properties as Samples 3 and 4, and even when polyamine is not blended, predetermined sealing material compositions and sealing materials are obtained. Was found to be
  • Samples 14 and 15 are samples characterized in that the epoxy compound having two or more epoxy groups was not blended. That is, it is a sample in which a liquid composition mainly composed of a polyamine and a liquid diene rubber is prepared and heated to form a sealing material composition.
  • the samples 14 and 15 both had a fixed shape. From this, it was found that, even when the epoxy compound having two or more epoxy groups is not contained, it is solidified by the reaction product of the polyamine and the liquid diene rubber and is provided with the formability.
  • the sealing material compositions of Sample 14 and Sample 15 have a relatively large storage elastic modulus at 23 ° C., it was found that the temperature dependence of the storage elastic modulus was large unlike the conventional samples. That is, the storage elastic modulus is greatly reduced by heating. Specifically, the storage modulus value at 60 ° C. is 4.3% for sample 14 and 41% for sample 15 as compared to 23 ° C. In addition, the storage modulus at 120 ° C. can not be calculated for sample 14 (at least less than 4.3%) compared to 23 ° C., and is 5.1% for sample 15. Such a sample is excellent in that it can follow finer irregularities by heating.
  • the polyamine and the liquid diene rubber may form a reaction product which is interacted by a weak bond which is separated by the influence of toluene.
  • the acid-base interaction of a carboxyl group and an amino group and the reaction of a (meth) acryloyl group and an amino group are considered.
  • the gel fraction of the sample 14 was 0%, and the gel fraction of the sample 15 was 82%, with a large difference. was. Therefore, it was found that the storage material modulus obtained by heating can significantly decrease the storage elastic modulus regardless of the gel fraction when the polyamine is contained as the main component.
  • the sealing materials of the samples 14 and 15 have the same property as the samples 3 and 4 although they have a slightly high water vapor transmission rate, and do not contain an epoxy compound having two or more epoxy groups. Even in the case, it was found that the properties of the encapsulant did not change significantly.
  • Samples 16 to 19 are samples in which the type of liquid diene rubber is changed. Specifically, sample 16 used liquid diene rubber having no functional group. Sample 17 used was a liquid diene rubber having an acid anhydride group and no (meth) acryloyl group. Sample 18 used was a liquid diene rubber having a carboxyl group and no (meth) acryloyl group. Sample 19 uses a liquid diene rubber having a carboxyl group and a (meth) acryloyl group.
  • sample 18 was “ ⁇ ⁇ ” and sample 17 was “ ⁇ ”.
  • the remaining samples had an "x" shape. From this, it was found that the carboxyl group plays a large role in providing the formality. In addition, it was found that although the effect of enhancing the formability of the carboxyl group is greatly reduced when it becomes an anhydride, the effect of providing the formability of the compound of the anhydride still remains to some extent.
  • liquid diene rubber needs to have both a carboxyl group and a (meth) acryloyl group.
  • Samples 20 to 22 are also samples in which the compounding amounts of the epoxy resin and the liquid diene rubber are changed while the polyamine is not blended as in the samples 12 and 13, and any of these are shaped. Had sex. However, it was found that the proportion of the liquid diene rubber was preferably smaller than 96.2 because the sample of the sample 22 had a formability of “ ⁇ ”.
  • Samples 23 and 24 are, in addition to the samples 12, 13, 20 to 22, a diene system containing a functional group (such as a carboxyl group, an acid anhydride group or a hydroxyl group) which does not contain a (meth) acryloyl group and reacts with an epoxy group. It contains rubber. Since the sealing material compositions of Sample 23 and Sample 24 had a breaking elongation of 200% or more and a maximum tensile stress of 0.2 MPa or more, they were found to be very easy to handle and to be resistant to breakage due to elongation. Moreover, the sealing materials of the samples 23 and 24 were also excellent in flexibility and stretchability.
  • a functional group such as a carboxyl group, an acid anhydride group or a hydroxyl group
  • Samples 25 and 26 are samples using a liquid polyisoprene rubber having a carboxyl group and a liquid polybutadiene rubber having a methacryloyl group, both of the samples having the formability of “ ⁇ ”, the results of the other tests are “ Yes.

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Abstract

[Problem] To provide a sealing material composition and a sealing material with which it is not necessary to perform heating after coating an electronic element, etc., and which is flexible and has fixed-shape properties. [Solution] A sealing material composition comprising fixed-shape properties, the sealing material composition including: a reaction product of a polyamine and an epoxy compound having two or more epoxy groups; a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber, which has a (meth)acryloyl group and a group that reacts with the epoxy groups; and a photopolymerization initiator. Also, a sealing material that is a photo-cured article of the sealing material composition.

Description

封止材組成物、封止材及び電子基板Sealant composition, sealer and electronic substrate
 本発明は、電子基板等に設けた電子素子又は金属が露出した部分に貼付して、電子素子などの被着物を水分及び異物等から保護する封止材組成物及び封止材、そしてこれらを利用する電子基板に関する。 The present invention is a sealing material composition and sealing material which are attached to an electronic device or metal exposed portion provided on an electronic substrate or the like to protect an adherend such as an electronic device from moisture and foreign matter and the like, and It relates to an electronic substrate to be used.
 従来からエポキシ樹脂を原料とする封止材が知られている。この封止材は、エポキシ樹脂を硬化する前の液状の封止材組成物を基板等に塗布した後、硬化することで電子素子等の被覆、保護に用いられる。液状のものを硬化するこうしたタイプの封止材は、液状であるため電子素子の隙間に流し込み易く、電子素子を確実に覆うことできるというメリットがある一方で、所望の範囲から外に流れ出し易いことから、露出させたい部分までをも覆うおそれがあることが問題となっている。また、液状の封止材組成物では、硬化前に異物が付着し易いことや、他の部材に付着して汚すおそれがあるなど、取扱い性の悪さが懸念されている。このような問題に対して、固形のシート状封止材組成物が開発されており、例えば特開2012-087292号公報(特許文献1)などにシート状封止材組成物に関する技術が記載されている。また、特開2015-196783号公報(特許文献2)には、光硬化型のシート状封止材に関する技術が記載されている。 A sealing material which uses an epoxy resin as a raw material is known conventionally. This sealing material is used for coating and protection of an electronic element etc. by apply | coating the liquid sealing material composition before hardening an epoxy resin on a board | substrate etc., and hardening it. Since these types of sealants that cure liquid are liquid, they are easy to pour into the gaps of the electronic device and have the advantage of being able to reliably cover the electronic device, but they also easily flow out of the desired range. There is a problem that there is a risk of covering even the portion to be exposed. In addition, in the case of a liquid sealing material composition, there is a concern that the handling property may be poor because foreign substances may easily adhere to the liquid before curing, or may adhere to other members to cause contamination. With respect to such problems, a solid sheet-like sealing material composition has been developed, and a technology relating to the sheet-like sealing material composition is described, for example, in JP-A-2012-087292 (Patent Document 1). ing. Further, Japanese Patent Application Laid-Open No. 2015-196783 (Patent Document 2) describes a technology relating to a photocurable sheet-like sealing material.
特開2012-087292号公報JP 2012-087292 特開2015-196783号公報JP, 2015-196783, A
 ところが、特開2012-087292号公報(特許文献1)に記載された技術によれば、基板の電子素子等の凹凸間を埋めるために、シート状の封止材組成物を加熱、軟化する必要があり、加熱に所定の時間を要し、製品の製造に時間がかかるという問題がある。また、封止材組成物の粘度が温度によって変化するため、充分に加熱できないと、封止材組成物の軟化が不十分となり、凹凸を十分に埋めることができないおそれがある。一方、加熱しすぎて低粘度になると、所定の範囲外に流れ出てしまうおそれがある。さらに耐熱性の低い電子素子には、適用できない場合がある。 However, according to the technique described in Japanese Patent Application Laid-Open No. 2012-087292 (Patent Document 1), it is necessary to heat and soften the sheet-like sealing material composition in order to fill in the gap between the unevenness of the electronic element and the like of the substrate. There is a problem that it takes a predetermined time for heating and time for manufacturing the product. Moreover, since the viscosity of the sealing material composition changes with temperature, if the heating can not be performed sufficiently, the softening of the sealing material composition may be insufficient, and the unevenness may not be sufficiently filled. On the other hand, if the viscosity is too low due to excessive heating, there is a risk that the ink will flow out of the predetermined range. Furthermore, it may not be applicable to an electronic device with low heat resistance.
 また、特開2015-196783号公報に記載された光硬化型の封止材組成物は、シート状でありながら、依然として硬い組成物であるため、そのまま電子素子等へ密着させると過大な圧力がかかってしまい破損させるおそれがある。したがって、封止材組成物を凹凸へ密着させるときには加熱する必要があり、特許文献1と同じ課題を有している。 In addition, since the photocurable sealing material composition described in JP-A-2015-196783 is still a sheet-like, still hard composition, excessive pressure may result if it is adhered to an electronic element or the like as it is. There is a risk of damage and damage. Therefore, when the sealing material composition is brought into close contact with the asperities, it is necessary to heat and has the same problem as that of Patent Document 1.
 そこで本発明は、上記課題を解決するためになされたものである。即ち、電子素子等を被覆してからの加熱が不要で、柔軟で定形性のある封止材組成物及び封止材を提供することを目的とする。 Therefore, the present invention has been made to solve the above-mentioned problems. That is, it is an object of the present invention to provide a flexible and fixed sealing material composition and sealing material which does not require heating after coating an electronic element or the like.
 上記目的を達成するため本発明の封止材組成物は以下のとおり構成される。即ち、本発明はエポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物と、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムとエポキシ基を2個以上有するエポキシ化合物の反応生成物と、光重合開始剤と、を含み定形性を備える封止材組成物とした。 In order to achieve the above object, the encapsulant composition of the present invention is configured as follows. That is, according to the present invention, a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, a liquid diene-based rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and an epoxy compound having two or more epoxy groups. And a photopolymerization initiator to form a sealant composition having a fixed shape.
 エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物と、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムとエポキシ基を2個以上有するエポキシ化合物の反応生成物と、光重合開始剤と、を含み定形性を備える封止材組成物としたため、前記エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物と、前記エポキシ基を2個以上有するエポキシ化合物と前記液状ジエン系ゴムの反応生成物と、が定形性と柔軟性を与える封止材組成物となる。したがって、本発明の封止材組成物は、凹凸のある基板に貼着するとき、比較的小さな荷重で押しつけることで密着し、凹部へ密着させ易い。なお、定形性とは、所定の作業又は外力が加わったときに形状を維持する性質である。 The reaction product of an epoxy compound having two or more epoxy groups and a polyamine, the reaction product of a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and an epoxy compound having two or more epoxy groups And a photopolymerization initiator to form a sealant composition having a fixed shape, the reaction product of the epoxy compound having two or more epoxy groups and a polyamine, and the epoxy compound having two or more epoxy groups. The reaction product of the liquid diene-based rubber forms a sealant composition which imparts shape and flexibility. Therefore, the sealing material composition of the present invention adheres by pressing with a relatively small load when adhering to a substrate having irregularities, and easily adheres to the concave portion. The term “formality” refers to the property of maintaining the shape when a predetermined operation or external force is applied.
 加えて、本発明の封止材組成物は、光を照射したときに、光重合によって硬化させることができる。したがって、加熱によらず封止材組成物を封止材に硬化して電子素子等の被着物を封止することができる。また、液状ジエン系ゴムは分子量が大きく、またその一部はエポキシ基を2個以上有するエポキシ化合物又はポリアミンとの間で反応生成物を形成して未反応成物を保持するマトリクスとなるため、液状成分の浸み出しの問題が生じ難い。さらに、液状ジエン系ゴムが柔軟性を付与し、封止材組成物及びその光硬化物である封止材も柔軟である。 In addition, the encapsulant composition of the present invention can be cured by photopolymerization when irradiated with light. Therefore, regardless of heating, the sealant composition can be cured to a sealant to seal an adherend such as an electronic element. In addition, liquid diene rubber has a large molecular weight, and a part thereof forms a reaction product with an epoxy compound having at least two epoxy groups or a polyamine to form a matrix that holds unreacted products. It is difficult to cause the problem of liquid component soaking. Furthermore, the liquid diene rubber imparts flexibility, and the encapsulant composition and the encapsulant that is a photocured product thereof are also flexible.
 前記本発明は、前記エポキシ基に対する反応性基がカルボキシル基であり、エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物と、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとエポキシ基を2個以上有するエポキシ化合物の反応生成物と、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとポリアミンの反応生成物と、光重合開始剤と、を含み定形性を備える封止材組成物とすることができる。 In the present invention, the reaction product of an epoxy compound having an epoxy group and a polyamine, wherein the reactive group to the epoxy group is a carboxyl group, and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, and a liquid diene rubber having a (meth) acryloyl group and a carboxyl group A reaction product of a reaction product of an epoxy compound having two or more epoxy groups, a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine, and a photopolymerization initiator It can be used as a stopper composition.
 本発明は、前記エポキシ基に対する反応性基がカルボキシル基であり、エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物と、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとエポキシ基を2個以上有するエポキシ化合物の反応生成物と、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとポリアミンの反応生成物と、が定形性と柔軟性を与える封止材組成物となる。したがって、本発明の封止材組成物は、凹凸のある基板に貼着するとき、比較的小さな荷重で押しつけることで密着し、凹部へ密着させ易い。 In the present invention, the reaction product of an epoxy compound having an epoxy group and a polyamine, wherein the reactive group for the epoxy group is a carboxyl group, and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, a liquid diene rubber and epoxy having a (meth) acryloyl group and a carboxyl group. An encapsulant composition which imparts shape and flexibility to a reaction product of an epoxy compound having two or more groups and a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine Become. Therefore, the sealing material composition of the present invention adheres by pressing with a relatively small load when adhering to a substrate having irregularities, and easily adheres to the concave portion.
 前記本発明は、エポキシ基を2個以上有するエポキシ化合物と、ポリアミンと、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムと、光重合開始剤と、を含む液状組成物の混合物として構成できる。エポキシ基を2個以上有するエポキシ化合物と、ポリアミンと、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムと、光重合開始剤と、を含む液状組成物の混合物としたため、エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物と、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムの反応生成物と、ポリアミンと液状ジエン系ゴムの反応生成物が形成されて、共有結合、イオン間相互作用、その他の分子間相互作用等によってゲル状物又はゴム状物を形成するような高分子組成物となる。そのため、定形性と柔軟性を与え、凹凸のある基板に貼着するとき、比較的小さな荷重で押しつけることで密着し、凹部へ密着させ易い封止材組成物とすることができる。 The present invention is a liquid composition comprising an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator. It can be constructed as a mixture of As a mixture of a liquid composition containing an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator, A reaction product of a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber, and a reaction product of a polyamine and a liquid diene rubber Thus, the polymer composition becomes a gel-like or rubber-like material by covalent bonding, ionic interaction, other intermolecular interaction or the like. Therefore, it is possible to obtain a sealant composition which gives fixed shape and flexibility and adheres to a concave and convex substrate by pressing with a relatively small load so that it adheres easily to the concave portion.
 前記液状組成物が、前記エポキシ基を2個以上有するエポキシ化合物及び前記ポリアミンの合計100質量部に対して、前記液状ジエン系ゴムを100~2000質量部含む封止材組成物として構成できる。前記液状組成物が、前記エポキシ基を2個以上有するエポキシ化合物及び前記ポリアミンの合計100質量部に対して、前記液状ジエン系ゴムを100~2000質量部含むため、定形性に優れた封止材組成物とすることができる。 The liquid composition can be configured as a sealing material composition including 100 to 2000 parts by mass of the liquid diene rubber with respect to a total of 100 parts by mass of the epoxy compound having two or more epoxy groups and the polyamine. Since the liquid composition contains 100 to 2000 parts by mass of the liquid diene rubber with respect to a total of 100 parts by mass of the epoxy compound having two or more epoxy groups and the polyamine, a sealing material having excellent formability It can be a composition.
 本発明はまた、エポキシ基を2個以上有するエポキシ化合物とエポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムの反応生成物と、光重合開始剤と、を含みポリアミンの反応生成物を含まずに定形性を備えるものとして構成できる。 The present invention also includes a reaction product of a polyamine including a reaction product of an epoxy compound having two or more epoxy groups, a reactive group for the epoxy group, and a liquid diene rubber having a (meth) acryloyl group, and a photopolymerization initiator. It can be configured as having regularity without containing the product.
 前記本発明を、エポキシ基を2個以上有するエポキシ化合物とエポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムの反応生成物と、光重合開始剤と、を含みポリアミンの反応生成物を含まずに定形性を備えるものとして構成したため、エポキシ基を2個以上有するエポキシ化合物と前記液状ジエン系ゴムの反応生成物が形成されて、共有結合、イオン間相互作用、その他の分子間相互作用等によってゲル状物又はゴム状物を形成するような高分子組成物となる。そのため、定形性と柔軟性を与え、凹凸のある基板に貼着するとき、比較的小さな荷重で押しつけることで密着し、凹部へ密着させ易い封止材組成物とすることができる。 In the present invention, a reaction of a polyamine includes a reaction product of an epoxy compound having two or more epoxy groups, a reactive group for the epoxy group and a liquid diene rubber having a (meth) acryloyl group, and a photopolymerization initiator. Since it is configured as having formality without containing a product, a reaction product of an epoxy compound having two or more epoxy groups and the liquid diene rubber is formed to form a covalent bond, an ionic interaction, and other molecules. It becomes a polymer composition which forms a gel-like thing or a rubber-like thing by interaction etc. Therefore, it is possible to obtain a sealant composition which gives fixed shape and flexibility and adheres to a concave and convex substrate by pressing with a relatively small load so that it adheres easily to the concave portion.
 前記本発明は、前記エポキシ基に対する反応性基がカルボキシル基である封止材組成物とすることができる。前記本発明は、エポキシ基を2個以上有するエポキシ化合物と(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムの反応生成物と、光重合開始剤と、を含みポリアミンの反応生成物を含まずに定形性を備える構成としたため、前記エポキシ基を2個以上有するエポキシ化合物と前記液状ジエン系ゴムの反応生成物が定形性と柔軟性を与える封止材組成物となる。したがって、本発明の封止材組成物は、凹凸のある基板に貼着するとき、比較的小さな荷重で押しつけることで密着し、凹部へ密着させ易い。 The said invention can be set as the sealing material composition whose reactive group with respect to the said epoxy group is a carboxyl group. The present invention includes a reaction product of a polyamine including a reaction product of an epoxy compound having two or more epoxy groups, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator. Since the composition has the formability without being formed, the reaction product of the epoxy compound having two or more epoxy groups and the liquid diene rubber is the encapsulant composition which provides formability and flexibility. Therefore, the sealing material composition of the present invention adheres by pressing with a relatively small load when adhering to a substrate having irregularities, and easily adheres to the concave portion.
 加えて、前記本発明は、光を照射したときに、光重合によって硬化させることができる。したがって、本発明の封止材組成物は、加熱によらず封止材組成物を封止材に硬化して電子素子等の被着物を封止することができる。また、液状ジエン系ゴムは分子量が大きく、またその一部はエポキシ基を2個以上有するエポキシ化合物との間で反応生成物を形成して未反応成物を保持するマトリクスとなるため、液状成分の浸み出しの問題が生じ難い。さらに、液状ジエン系ゴムが柔軟性を付与し、封止材組成物及びその光硬化物である封止材も柔軟である。 In addition, the present invention can be cured by photopolymerization when irradiated with light. Therefore, the sealing material composition of the present invention can cure the sealing material composition to a sealing material regardless of heating to seal an adherend such as an electronic element. In addition, since liquid diene rubber has a large molecular weight, and a part thereof forms a reaction product with an epoxy compound having two or more epoxy groups to form a matrix that holds unreacted components, the liquid component It is hard to cause the problem of Furthermore, the liquid diene rubber imparts flexibility, and the encapsulant composition and the encapsulant that is a photocured product thereof are also flexible.
 前記本発明は、エポキシ基を2個以上有するエポキシ化合物と、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムと、光重合開始剤と、を含みポリアミンが含まれない液状組成物の混合物として構成できる。エポキシ基を2個以上有するエポキシ化合物と、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムと、光重合開始剤と、を含みポリアミンが含まれない液状組成物の混合物として構成したため、エポキシ基を2個以上有するエポキシ化合物と前記液状ジエン系ゴムの反応生成物が形成されて、ゲル状物又はゴム状物を形成するような高分子組成物となる。そのため、定形性と柔軟性を与え、凹凸のある基板に貼着するとき、比較的小さな荷重で押しつけることで密着し、凹部へ密着させ易い封止材組成物とすることができる。 The present invention is a liquid which contains an epoxy compound having two or more epoxy groups, a liquid diene-based rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator and does not contain a polyamine. It can be configured as a mixture of compositions. As a mixture of a liquid composition containing an epoxy compound having two or more epoxy groups, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator and containing no polyamine Since it comprised, the reaction product of the epoxy compound which has 2 or more of epoxy groups, and the said liquid diene rubber is formed, and it becomes a polymer composition which forms a gel-like thing or a rubber-like thing. Therefore, it is possible to obtain a sealant composition which gives fixed shape and flexibility and adheres to a concave and convex substrate by pressing with a relatively small load so that it adheres easily to the concave portion.
 前記液状組成物が、前記エポキシ基を2個以上有するエポキシ化合物100質量部に対して、前記液状ジエン系ゴムを100~2600質量部含む封止材組成物として構成できる。前記液状組成物が、前記エポキシ基を2個以上有するエポキシ化合物100質量部に対して、前記液状ジエン系ゴムを100~2600質量部含むため、定形性に優れた封止材組成物とすることができる。 The liquid composition may be configured as a sealing material composition including 100 to 2600 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups. Since the liquid composition contains 100 to 2600 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups, it is possible to obtain an encapsulant composition excellent in formability. Can.
 前記液状組成物にさらにポリアミン以外のエポキシ樹脂硬化剤を含む封止材組成物として構成できる。前記液状組成物にさらにポリアミン以外のエポキシ樹脂硬化剤を含む封止材組成物としたため、封止材としたときの低透湿性、防水性を高めることができる。 The liquid composition can be configured as a sealant composition further containing an epoxy resin curing agent other than a polyamine. Since it is set as the sealing material composition which further contains epoxy resin hardening | curing agents other than a polyamine in the said liquid composition, the low moisture permeability and waterproofness when setting it as a sealing material can be improved.
 前記本発明は、(メタ)アクリロイル基を有せずエポキシ基に対する反応性基を有する液状ジエン系ゴムをさらに含む封止材組成物とすることができる。前記本発明を(メタ)アクリロイル基を有せずエポキシ基に対する反応性基を有する液状ジエン系ゴムをさらに含むものとしたため、取扱い性が良く、さらに最大引張応力を高めて伸長時に破断し難くすることができる。そして、電子素子を覆う追従性を高めることができ、低荷重で電子素子の凹凸を埋めたり、電子素子の表面に沿わせたりすることができ、伸長時に欠陥が生じ難くすることができる。さらに、(メタ)アクリロイル基由来の架橋密度を減らすことで、硬化後の伸縮性を高めることができ、フレキシブル基板及び伸長基材に対して好適な封止材とすることができる。 The said invention can be set as the sealing material composition which does not have a (meth) acryloyl group, and also has a liquid diene type rubber which has a reactive group with respect to an epoxy group. Since the present invention further includes a liquid diene rubber not having a (meth) acryloyl group and having a reactive group to an epoxy group, the rubber has good handleability, and further increases the maximum tensile stress to make it difficult to break at elongation. be able to. And the follow-up property which covers an electronic element can be improved, the unevenness | corrugation of an electronic element can be filled with low load, it can be made to follow the surface of an electronic element, and a defect can be made hard to produce at the time of expansion. Furthermore, by reducing the crosslink density derived from the (meth) acryloyl group, stretchability after curing can be enhanced, and a sealing material suitable for a flexible substrate and an extension substrate can be obtained.
 前記本発明は、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムが、(メタ)アクリロイル基を有しエポキシ基に対する反応性基を有しない第1の液状ジエン系ゴムと、エポキシ基に対する反応性基を有し(メタ)アクリロイル基を有しない第2の液状ジエン系ゴムの混合物である封止材組成物とすることができる。前記本発明を、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムが、(メタ)アクリロイル基を有しエポキシ基に対する反応性基を有しない第1の液状ジエン系ゴムと、エポキシ基に対する反応性基を有し(メタ)アクリロイル基を有しない第2の液状ジエン系ゴムの混合物であるものとしたため、1分子中にエポキシ基に対する反応性基と(メタ)アクリロイル基との両方の反応性基を含まない液状ジエン系ゴムを用いることができる。 In the present invention, a liquid diene rubber having a reactive group for an epoxy group and a (meth) acryloyl group has a (meth) acryloyl group and a first liquid diene rubber having no reactive group for an epoxy group The encapsulant composition may be a mixture of a second liquid diene rubber having a reactive group to an epoxy group and no (meth) acryloyl group. In the present invention, the liquid diene rubber having a reactive group to epoxy group and a (meth) acryloyl group has a (meth) acryloyl group and a first liquid diene rubber having no reactive group to epoxy group And the (meth) acryloyl group with respect to the epoxy group in one molecule, since it is a mixture of the second liquid diene rubber having the reactive group to the epoxy group and not the (meth) acryloyl group. It is possible to use a liquid diene rubber which does not contain both reactive groups.
 前記本発明は、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとポリアミンの反応生成物と、光重合開始剤と、を含みエポキシ基を2個以上有するエポキシ化合物の反応生成物を含まずに定形性を備える封止材組成物として構成できる。 The present invention includes a reaction product of an epoxy compound containing a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine, and a photopolymerization initiator and having two or more epoxy groups. It can be comprised as a sealing material composition provided with a fixed shape.
 前記本発明は、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとポリアミンの反応生成物と、光重合開始剤と、を含みエポキシ基を2個以上有するエポキシ化合物の反応生成物を含まずに定形性を備える構成としたため、前記ポリアミンと前記液状ジエン系ゴムの反応生成物が定形性と柔軟性を与える封止材組成物となる。したがって、本発明の封止材組成物は、凹凸のある基板に貼着するとき、比較的小さな荷重で押しつけることで密着し、凹部へ密着させ易い。 The present invention includes a reaction product of an epoxy compound containing a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine, and a photopolymerization initiator and having two or more epoxy groups. Since the composition is made to have a formability without any reaction, the reaction product of the polyamine and the liquid diene rubber becomes an encapsulant composition giving formability and flexibility. Therefore, the sealing material composition of the present invention adheres by pressing with a relatively small load when adhering to a substrate having irregularities, and easily adheres to the concave portion.
 加えて、本発明の封止材組成物は、光を照射したときに、光重合によって硬化させることができる。したがって、加熱によらず封止材組成物を封止材に硬化して電子素子等の被着物を封止することができる。また、液状ジエン系ゴムは分子量が大きく、またその一部はポリアミンとの間で反応生成物を形成して未反応成物を保持するマトリクスとなるため、液状成分の浸み出しの問題が生じ難い。さらに、液状ジエン系ゴムが柔軟性を付与し、封止材組成物及びその光硬化物である封止材も柔軟である。 In addition, the encapsulant composition of the present invention can be cured by photopolymerization when irradiated with light. Therefore, regardless of heating, the sealant composition can be cured to a sealant to seal an adherend such as an electronic element. In addition, liquid diene rubber has a large molecular weight, and a part thereof forms a reaction product with a polyamine to form a matrix that holds unreacted components, causing a problem of liquid component leaching. hard. Furthermore, the liquid diene rubber imparts flexibility, and the encapsulant composition and the encapsulant that is a photocured product thereof are also flexible.
 前記本発明は、ポリアミンと、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムと、光重合開始剤と、を含みエポキシ基を2個以上有するエポキシ化合物を含まない液状組成物の混合物である封止材組成物として構成できる。ポリアミンと、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムと、光重合開始剤と、を含みエポキシ基を2個以上有するエポキシ化合物を含まない液状組成物の混合物である構成としたため、ポリアミンと液状ジエン系ゴムの反応生成物が形成されて、ゲル状物又はゴム状物を形成するような高分子組成物となる。そのため、定形性と柔軟性を与え、凹凸のある基板に貼着するとき、比較的小さな荷重で押しつけることで密着し、凹部へ密着させ易い封止材組成物とすることができる。 The present invention is a mixture of a liquid composition containing a polyamine, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator and not containing an epoxy compound having two or more epoxy groups. It can be configured as a certain encapsulant composition. Because it is a mixture of a liquid composition containing a polyamine, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator and no epoxy compound having two or more epoxy groups, A reaction product of a polyamine and a liquid diene rubber is formed to form a polymer composition which forms a gel or rubber. Therefore, it is possible to obtain a sealant composition which gives fixed shape and flexibility and adheres to a concave and convex substrate by pressing with a relatively small load so that it adheres easily to the concave portion.
 前記液状組成物が、前記ポリアミン100質量部に対して、前記液状ジエン系ゴムを100~2000質量部含む封止材組成物として構成できる。前記液状組成物が、前記ポリアミン100質量部に対して、前記液状ジエン系ゴムを100~2000質量部含むため、定形性に優れた封止材組成物とすることができる。 The liquid composition can be configured as a sealing material composition including 100 to 2000 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the polyamine. Since the liquid composition contains 100 to 2000 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the polyamine, it is possible to obtain an encapsulant composition excellent in formability.
 そして、前記何れかの封止材組成物の光硬化体である封止材として構成することができる。前記何れかの封止材組成物の光硬化体である封止材としたため、この封止材もまた柔軟性を有し、好適な接着性を備えている。したがって、本発明は被着体に対する気密性に優れ、優れた封止効果を備えた封止材である。換言すれば、封止材組成物が柔軟なため、封止する電子素子にシート状に形成した封止材組成物を圧着するだけでそれらの電子素子の凹凸を埋めることができる。また、大きな電子素子を覆う場合であっても、封止材組成物が伸長しながら電子素子の表面に沿って密着しながら電子素子を覆うことができる。 And it can comprise as a sealing material which is a photocuring body of the above-mentioned any sealing material composition. Since it is set as the sealing material which is a photocuring body of the said any sealing material composition, this sealing material also has a softness | flexibility and has suitable adhesiveness. Therefore, the present invention is a sealing material which is excellent in airtightness with respect to the adherend and has an excellent sealing effect. In other words, since the sealing material composition is flexible, the unevenness of the electronic elements can be filled only by pressure bonding the sealing material composition formed in a sheet shape to the electronic elements to be sealed. Further, even in the case of covering a large electronic element, the electronic element can be covered while adhering closely along the surface of the electronic element while the sealing material composition is extended.
 そしてまた、貯蔵弾性率が0.7~5.4MPaである封止材として構成することができる。貯蔵弾性率が0.7~5.4MPaであるように構成したため、強度が大きくフレキシブル性にも優れた封止材とすることができる。 In addition, it can be configured as a sealing material having a storage elastic modulus of 0.7 to 5.4 MPa. Since the storage elastic modulus is configured to be 0.7 to 5.4 MPa, a sealing material having high strength and excellent flexibility can be obtained.
 前記本発明は、前記何れかの封止材で電子素子が封止された電子基板とすることができる。前記本発明を前記何れかの封止材で電子素子が封止された電子基板としたため、電子素子が水分及び異物等から好適に保護された電子基板である。 The present invention can be an electronic substrate in which an electronic element is sealed by any one of the sealing materials. Since the present invention is an electronic substrate in which the electronic element is sealed with any of the sealing materials, the electronic element is an electronic substrate suitably protected from moisture, foreign matter, and the like.
 前記本発明は、封止材の厚さTに対する前記電子素子の高さTが、T>Tであるとともに、前記電子素子の凹凸を埋めた封止材表面が略平滑である電子基板とすることができる。前記本発明を、封止材の厚さTに対する前記電子素子の高さTが、T>Tであるとともに、前記電子素子の凹凸を埋めた封止材表面が略平滑である電子基板としたため、複数の高さの異なる電子素子を有する電子基板であっても、封止材がその表面を覆って略平滑な平面を形成することができる。そのため、これらの電子素子を外気から隔離して封止するだけでなく、安定的に保持することもできる。 The present invention, the height T 2 of the said electronic element to the thickness T 1 of the sealing material, together with a T 1> T 2, is substantially smooth sealing material surface filling the unevenness of the electronic device It can be an electronic substrate. The present invention, the height T 2 of the said electronic element to the thickness T 1 of the sealing material, together with a T 1> T 2, is substantially smooth sealing material surface filling the unevenness of the electronic device Since the substrate is an electronic substrate, even in the case of an electronic substrate having a plurality of electronic elements with different heights, the sealing material can cover the surface to form a substantially smooth flat surface. Therefore, these electronic devices can not only be sealed from external air and sealed, but also can be stably held.
 前記本発明は、封止材の厚さTに対する前記電子素子の高さTが、T≦Tであるとともに、前記電子素子の外面に沿って前記封止材が密着している電子基板とすることができる。前記本発明を、封止材の厚さTに対する前記電子素子の高さTが、T≦Tであるとともに、前記電子素子の外面に沿って前記封止材が密着しているものとしたため、複数の高さの異なる電子素子を有する電子基板であっても、封止材が少なくともその側面を覆うことができる。そのため、これらの電子素子の側面を封止して安定的に保持することもできる。 The present invention, the height T 2 of the said electronic element to the thickness T 1 of the sealing material, together with a T 1 ≦ T 2, the sealing member along an outer surface of the electronic element is in contact It can be an electronic substrate. The present invention, the height T 2 of the said electronic element to the thickness T 1 of the sealing material, together with a T 1 ≦ T 2, the sealing member along an outer surface of the electronic element is in close contact Therefore, the sealing material can cover at least the side surface of the electronic substrate having electronic elements with different heights. Therefore, the side surfaces of these electronic devices can be sealed and held stably.
 前記本発明は、貯蔵弾性率が0.7~50MPaであるフレキシブル基材を備える電子基板とすることができる。前記本発明を、貯蔵弾性率が0.7~50MPaであるフレキシブル基材を備える電子基板としたため、前記封止材がこのフレキシブル基材と積層することで、封止材の過度な伸びを防止でき封止材の破損がし難い電子基板である。 The present invention can be an electronic substrate provided with a flexible substrate having a storage elastic modulus of 0.7 to 50 MPa. Since the present invention is an electronic substrate provided with a flexible base material having a storage elastic modulus of 0.7 to 50 MPa, the sealing material is laminated with the flexible base material to prevent excessive elongation of the sealing material. It is an electronic substrate which is hard to break the sealing material.
 本発明の封止材組成物及び封止材によれば、定形性と柔軟性を有し、取扱い性に優れる。また、本発明の電子基板によれば、電子素子が水分及び異物等から好適に保護された電子基板である。 ADVANTAGE OF THE INVENTION According to the sealing material composition and sealing material of this invention, it has a fixed form and flexibility, and is excellent in the handleability. Further, according to the electronic substrate of the present invention, the electronic device is an electronic substrate suitably protected from moisture, foreign matter and the like.
 本発明の封止材組成物及びその硬化体である封止材について実施形態に基づいて詳しく説明する。各実施形態において重複する材料、材質、製造方法、作用効果、機能等については重複説明を省略する。 The sealing material composition of the present invention and the sealing material which is a cured product thereof will be described in detail based on the embodiment. Duplicate descriptions of materials, materials, manufacturing methods, effects, functions, and the like that overlap in each embodiment will be omitted.
<封止材組成物> <Sealing material composition>
 本発明の封止材組成物は、電子素子を配置した電子基板(「基板」ともいう)等に貼付し、圧着して電子素子を覆うとともに密着させた後、光を照射し硬化して封止材とし、電子素子に対する接着性を高めて、電子素子を水分及び異物等から保護するものである。 The sealing material composition of the present invention is attached to an electronic substrate (also referred to as a "substrate") or the like on which an electronic element is disposed, and is crimped to cover and adhere the electronic element. As a stopper, the adhesion to the electronic device is enhanced to protect the electronic device from moisture, foreign matter and the like.
 (1)第1実施形態: (1) First Embodiment:
 第1実施形態としての封止材組成物は、エポキシ基を2個以上有するエポキシ化合物と、ポリアミンと、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムと、光重合開始剤とを必須成分とする液状混合物を加熱して得られるゲル状組成物又はゴム状組成物である。以下、これらの成分から説明する。 The encapsulant composition according to the first embodiment comprises an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and photopolymerization initiation It is a gel composition or a rubber composition obtained by heating a liquid mixture containing an agent as an essential component. Hereinafter, these components will be described.
 エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴム: Liquid diene rubber having reactive group to epoxy group and (meth) acryloyl group:
 エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴム(以下、単に液状ジエン系ゴムともいう)は、封止材組成物中に含まれる光硬化成分であり、封止材にゴム弾性(柔軟性)、低透湿性、防水性、被着体に対する密着性を付与する成分である。また、封止材の機械的強度を向上させ、封止材の伸縮性を高める効果がある。 A liquid diene rubber having a reactive group for an epoxy group and a (meth) acryloyl group (hereinafter, also simply referred to as a liquid diene rubber) is a photocurable component contained in a sealant composition, and is used as a sealant. It is a component that imparts rubber elasticity (flexibility), low moisture permeability, waterproofness, and adhesion to an adherend. In addition, the mechanical strength of the sealing material is improved, and the stretchability of the sealing material is enhanced.
 エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムは、単一の分子内にエポキシ基に対する反応性基と(メタ)アクリロイル基の両方を有する場合だけでなく、エポキシ基に対する反応性基を有するが(メタ)アクリロイル基を有しない液状ジエン系ゴムと、(メタ)アクリロイル基を有するがエポキシ基に対する反応性基を有しない液状ジエン系ゴムとの混合物とすることもできる。したがって、前記液状ジエン系ゴムは、混合物としての液状ジエン系ゴム中にエポキシ基に対する反応性基と(メタ)アクリロイル基を有していれば良い。 Liquid diene rubbers having a reactive group to epoxy group and a (meth) acryloyl group are not only to have both a reactive group to epoxy group and a (meth) acryloyl group in a single molecule, but also to epoxy group A mixture of a liquid diene rubber having a reactive group but not having a (meth) acryloyl group and a liquid diene rubber having a (meth) acryloyl group but not having a reactive group to an epoxy group may also be used. Accordingly, the liquid diene rubber may have a reactive group for epoxy groups and a (meth) acryloyl group in the liquid diene rubber as a mixture.
 液状ジエン系ゴムは、常温で液状であり、封止材組成物中では、その一部がエポキシ基を2個以上有するエポキシ化合物又はポリミアンと反応生成物を形成するとともに、未反応の液状ジエン系ゴムは、この反応生成物及びエポキシ樹脂硬化体でなるマトリクスによって保持されている。 The liquid diene rubber is liquid at normal temperature, and in the encapsulant composition, a part thereof forms a reaction product with an epoxy compound or polyimide having two or more epoxy groups, and an unreacted liquid diene rubber. The rubber is held by a matrix consisting of the reaction product and an epoxy resin cured product.
 液状ジエン系ゴムの粘度は、1~1000Pa・sであることが好ましい。1Pa・s未満の場合には、架橋構造が3次元的に密になりすぎ、硬化後の封止材が脆くなるおそれがある。一方、1000Pa・sを超えると、被着体への接着力が低下するおそれがある。 The viscosity of the liquid diene rubber is preferably 1 to 1000 Pa · s. In the case of less than 1 Pa · s, the crosslinked structure becomes too dense in three dimensions, and the sealing material after curing may become brittle. On the other hand, if it exceeds 1000 Pa · s, the adhesion to the adherend may be reduced.
 液状ジエン系ゴム1分子中に含まれる(メタ)アクリロイル基の数は、2~3であることが好ましい。官能基数が1の場合には、架橋構造が発達せず、封止材の強度が低くなるおそれがある。一方、官能基数が4を超えると、架橋構造が3次元的に密になりすぎることで、封止材が脆くなるおそれがある。 The number of (meth) acryloyl groups contained in one liquid diene rubber is preferably 2 to 3. When the number of functional groups is 1, the crosslinked structure does not develop and the strength of the sealing material may be lowered. On the other hand, if the number of functional groups is more than 4, the sealing material may become brittle because the cross-linked structure is too dense in three dimensions.
 エポキシ基に対する反応性基としては、例えば酸無水物基、カルボキシ基、水酸基、アミノ基、イミド基、イミダゾール基、メルカプト基を例示できるが、エポキシ基との反応性が適度であることや、材料の入手性が良いことからカルボキシル基及び酸無水物基が好ましい。 As the reactive group for the epoxy group, for example, an acid anhydride group, a carboxy group, a hydroxyl group, an amino group, an imide group, an imidazole group and a mercapto group can be exemplified, but the reactivity with the epoxy group is appropriate. Carboxyl groups and acid anhydride groups are preferred because they are readily available.
 液状ジエン系ゴムは、単独で硬化したときに、貯蔵弾性率E’が0.01~10MPaとなる成分であることが好ましい。貯蔵弾性率が0.01MPa未満の場合には、封止材の強靭性が極度に弱くなり、封止対象を充分に保護できなくなるおそれがある。貯蔵弾性率が10MPaを超える場合には、封止材が必要以上に硬くなるおそれがある。 The liquid diene rubber is preferably a component having a storage elastic modulus E ′ of 0.01 to 10 MPa when cured alone. If the storage elastic modulus is less than 0.01 MPa, the toughness of the sealing material becomes extremely weak, and there is a possibility that the object to be sealed can not be sufficiently protected. When the storage elastic modulus exceeds 10 MPa, the sealing material may become harder than necessary.
 なお液状ジエン系ゴムの具体例としては、液状ポリイソプレン、液状ポリブタジエン、液状ポリイソブチレンなどを例示することができる。 As specific examples of the liquid diene rubber, liquid polyisoprene, liquid polybutadiene, liquid polyisobutylene and the like can be exemplified.
 エポキシ基を2個以上有するエポキシ化合物: Epoxy compound having two or more epoxy groups:
 第1実施形態の封止材組成物では、エポキシ基を2個以上有するエポキシ化合物を必須の原材料として形成され、封止材組成物中では主に、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムとの反応生成物及びエポキシ基を2個以上有するエポキシ化合物とポリアミンとの反応生成物として含有される。さらに後述のエポキシ樹脂の硬化剤を含むときはエポキシ基を2個以上有するエポキシ化合物とエポキシ樹脂の硬化剤とが反応したエポキシ樹脂硬化体としても含まれる。未反応のエポキシ基を有するエポキシ成分が含まれていても良い。 In the sealing material composition of the first embodiment, an epoxy compound having two or more epoxy groups is formed as an essential raw material, and in the sealing material composition, mainly an epoxy compound having two or more epoxy groups and a liquid It is contained as a reaction product of a diene rubber and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine. Furthermore, when the below-mentioned epoxy resin curing agent is included, it is also included as an epoxy resin cured body in which an epoxy compound having two or more epoxy groups and a curing agent of epoxy resin have reacted. An epoxy component having an unreacted epoxy group may be included.
 エポキシ基を2個以上有するエポキシ化合物には、1分子中に2個以上のエポキシ基を有するエポキシモノマー及びオリゴマーを用いることができる。また、分子の一部に、ポリエチレングリコール骨格、ポリプロレピレングリコール骨格、ポリエーテル骨格、ウレタン骨格、ポリブタジエン骨格、ニトリルゴム骨格等の柔軟骨格を含んでいるものを用いると、封止材組成物の硬さをより柔軟にできる点で好ましい。 As the epoxy compound having two or more epoxy groups, epoxy monomers and oligomers having two or more epoxy groups in one molecule can be used. In addition, when a molecule having a flexible skeleton such as polyethylene glycol skeleton, polypropylene glycol skeleton, polyether skeleton, urethane skeleton, polybutadiene skeleton, nitrile rubber skeleton, etc. is used in part of the molecule, It is preferable in that the hardness can be made more flexible.
 上記エポキシ基を2個以上有するエポキシ化合物として、具体的にはビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノール・ノボラック型エポキシ樹脂、クレゾール・ノボラック型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ナフタレン型エポキシ樹脂、トリフェノールアルカン型エポキシ樹脂、ビフェニル型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族エポキシ樹脂などが挙げられる。 Specific examples of the epoxy compound having two or more epoxy groups include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, glycidyl amine epoxy resin, naphthalene type Epoxy resin, triphenol alkane type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin and the like can be mentioned.
 また、柔軟骨格を有するエポキシ樹脂として、ビスフェノールA等の芳香族ジヒドロキシ化合物とエチレンオキシド、プロピレンオキシド等のアルキレンオキシドを反応させポリアルキレングリコール骨格を有する化合物を合成し、ポリアルキレングリコール骨格を有する化合物の末端をさらにエポキシ化して得られる「芳香族ジヒドロキシ化合物とポリアルキレングリコールが結合し、末端にエポキシ基を有するエポキシ化合物」、プロパンジオール、ブタンジオール等のアルカンジオール又はジエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコールをエポキシ化し、さらにビスフェノールA等の芳香族ジヒドロキシ化合物と反応させ、その生成物をエポキシ化して得られる「アルカンジオール又はポリアルキレングリコールと芳香族ジヒドロキシ化合物が結合し、末端にエポキシ基を有するエポキシ化合物」、脂肪族、芳香族炭化水素化合物、プロパンジオール、ブタンジオール等のアルカンジオール又はジエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコールをジビニルエーテル化し、さらにビスフェノールA等の芳香族ジヒドロキシ化合物と反応させ、その生成物をエポキシ化して得られる「脂肪族骨格、芳香族骨格、又はアルカンジオール、ポリアルキレングリコールと芳香族ジヒドロキシ化合物が結合し、末端にエポキシ基を有するエポキシ化合物」、ダイマー酸又はセバシン酸等の脂肪族ジカルボン酸とビスフェノールAエポキシ樹脂、その他のエポキシ化剤を反応させることで得られる「脂肪族骨格を有するエポキシ化合物」、プロピレンオキシド等のポリアルキレングリコーンの末端をエポキシ化して得られる「末端にエポキシ基を有するポリアルキレングリコール構造を有するエポキシ化合物」等を挙げることができる。 Further, as an epoxy resin having a flexible skeleton, an aromatic dihydroxy compound such as bisphenol A is reacted with an alkylene oxide such as ethylene oxide or propylene oxide to synthesize a compound having a polyalkylene glycol skeleton, and the terminal of the compound having a polyalkylene glycol skeleton Is obtained by further epoxidizing “an epoxy compound having an aromatic dihydroxy compound and a polyalkylene glycol bonded to each other and having an epoxy group at an end”, an alkanediol such as propanediol and butanediol, or a polyalkylene glycol such as diethylene glycol and polypropylene glycol Epoxidized, further reacted with an aromatic dihydroxy compound such as bisphenol A, and epoxidized the product to obtain “alkanediol or polyalkyl” “Epoxy compounds having an epoxy group at the end by bonding of an glycol and an aromatic dihydroxy compound”, aliphatic, aromatic hydrocarbon compounds, alkanediols such as propanediol and butanediol, or polyalkylene glycols such as diethylene glycol and polypropylene glycol It is divinylated, further reacted with an aromatic dihydroxy compound such as bisphenol A, and epoxidized with the product “aliphatic skeleton, aromatic skeleton or alkanediol, polyalkylene glycol and aromatic dihydroxy compound are bonded. , An epoxy compound having an epoxy group at the terminal, a dimer acid or an aliphatic dicarboxylic acid such as sebacic acid, which is obtained by reacting a bisphenol A epoxy resin, and other epoxidizing agents Epoxy compound ", and epoxy compounds" or the like having a polyalkylene glycol structure having the polyalkylene ring epoxy group terminal to the "end obtained by epoxidation of recone and propylene oxide.
 これらの中でも、硬化後の柔軟性と脆さ改善の点から、脂肪族骨格、芳香族骨格、若しくはアルカンジオール又はポリアルキレングリコールと芳香族ジヒドロキシ化合物が結合し、末端にエポキシ基を有するエポキシ化合物を用いることが好ましい。 Among these, from the viewpoint of improving flexibility and brittleness after curing, an aliphatic skeleton, an aromatic skeleton, or an epoxy compound having an epoxy group at the end by combining an alkanediol or polyalkylene glycol with an aromatic dihydroxy compound. It is preferred to use.
 これらのエポキシ基を2個以上有するエポキシ化合物は、単独で用いても、二種類以上を組み合わせて用いてもかまわない。また、上記エポキシ基を2個以上有するエポキシ化合物は、常温で液体であっても固体であっても良い。なお、本発明で常温という場合は25℃の状態をいうものとする。 These epoxy compounds having two or more epoxy groups may be used alone or in combination of two or more. The epoxy compound having two or more epoxy groups may be liquid or solid at normal temperature. In addition, when calling it normal temperature by this invention, the state of 25 degreeC shall be said.
 ポリアミン: Polyamine:
 第1実施形態の封止材組成物では、ポリアミンを必須の原材料として形成され、封止材組成物中では主に、ポリアミンと液状ジエン系ゴムとの反応生成物及びポリアミンとエポキシ基を2個以上有するエポキシ化合物との反応生成物として含有される。またポリアミンは、エポキシ基を2個以上有するエポキシ化合物に対して一般的な硬化剤であり、エポキシ基を2個以上有するエポキシ化合物とポリアミンとが反応したエポキシ樹脂硬化体の骨格中にも含まれることになる。未反応のポリアミン成分が含まれていても良い。 In the sealant composition of the first embodiment, a polyamine is formed as an essential raw material, and in the sealant composition, mainly, a reaction product of a polyamine and a liquid diene rubber and two polyamines and an epoxy group It is contained as a reaction product with the epoxy compound which has the above. Polyamine is a general curing agent for epoxy compounds having two or more epoxy groups, and is also contained in the skeleton of the epoxy resin cured product in which an epoxy compound having two or more epoxy groups and a polyamine react with each other. It will be. An unreacted polyamine component may be contained.
 本発明においてポリアミンとは、少なくとも分子量100を超え、アミノ基を2つ以上含む化合物を指すものとする。例えば脂肪族ポリアミン、ポリエーテルポリアミン類、脂環式アミン類、芳香族アミン、ポリアミドアミン、アミンアダクトなどを挙げることができる。 In the present invention, a polyamine refers to a compound having a molecular weight of at least 100 and containing two or more amino groups. For example, aliphatic polyamines, polyether polyamines, alicyclic amines, aromatic amines, polyamidoamines, amine adducts and the like can be mentioned.
 ポリアミンは液状でも固形であっても良いが、封止材組成物の必須成分としてエポキシ基を2個以上有するエポキシ化合物を含んでいるため、いわゆる潜在性硬化剤といわれるポリアミンを用いることが好ましい。潜在性硬化剤を用いれば、混合後に直ちに硬化することがないため、エポキシ基を2個以上有するエポキシ化合物及び液状ジエン系ゴムとの混合時の粘度上昇を抑制することができるからである。封止材組成物を硬化してなる封止材は、水及び水蒸気から被着体を保護するため、封止材中に気泡が存在すると封止材の特性を悪化させることになる。そのため、封止材組成物の製造過程で気泡を除去する必要があるが、原材料を混合した直後の粘度上昇が急激であると気泡の除去が困難になるおそれがある。しかしながら、製造時の粘度上昇を抑えることができれば封止材中の気泡も確実に脱泡することができるため、潜在性硬化剤を用いれば気泡に起因する特性の悪化を防ぐことができる。 The polyamine may be liquid or solid, but since it contains an epoxy compound having two or more epoxy groups as an essential component of the encapsulant composition, it is preferable to use a polyamine called a so-called latent curing agent. If a latent curing agent is used, it does not cure immediately after mixing, and therefore, it is possible to suppress an increase in viscosity when mixed with an epoxy compound having two or more epoxy groups and a liquid diene rubber. Since the sealing material formed by curing the sealing material composition protects the adherend from water and water vapor, the presence of air bubbles in the sealing material will deteriorate the characteristics of the sealing material. Therefore, although it is necessary to remove air bubbles in the manufacturing process of a sealing material composition, there is a possibility that removal of air bubbles may become difficult if the viscosity rise immediately after mixing raw materials is rapid. However, if the viscosity increase at the time of production can be suppressed, the air bubbles in the sealing material can be defoamed with certainty, and the use of the latent curing agent can prevent the deterioration of the characteristics due to the air bubbles.
 上記潜在性硬化剤は、一例として常温で固形であるが、所定の温度で溶融して活性化する性質を有するものを例示できる。前記ポリアミンの中では、特に60℃~120℃の範囲で活性化する芳香族アミン、アミンアダクトが好適である。 The latent curing agent is, for example, solid at normal temperature, but may be one having a property of melting and activating at a predetermined temperature. Among the above-mentioned polyamines, aromatic amines activated at a temperature of 60 ° C. to 120 ° C., and amine adducts are particularly preferable.
 脂肪族アミン類としては、ヘキサメチレンジアミン、2,5‐ジメチルヘキサメチレンジアミン、トリメチルヘキサメチレンジアミン、ジエチレントリアミン、イミノビスプロピルアミン、ビス(ヘキサメチレン)トリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、N‐ヒドロキシエチルエチレンジアミン、テトラ(ヒドロキシエチル)エチレンジアミン等が挙げられる。 As aliphatic amines, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylene Hexamine, N-hydroxyethyl ethylenediamine, tetra (hydroxyethyl) ethylene diamine and the like can be mentioned.
 ポリエーテルポリアミン類としては、トリエチレングリコールジアミン、テトラエチレングリコールジアミン、ジエチレングリコールビス(プロピルアミン)、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン類等が挙げられる。脂環式アミン類としては、イソホロンジアミン、メタセンジアミン、N‐アミノエチルピペラジン、ビス(4‐アミノ‐3‐メチルジシクロヘキシル)メタン、ビス(アミノメチル)シクロヘキサン、3,9‐ビス(3‐アミノプロピル)2,4,8,10‐テトラオキサスピロ(5,5)ウンデカン、ノルボルネンジアミン等が挙げられる。 Examples of polyether polyamines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines and the like. Alicyclic amines include isophorone diamine, metacene diamine, N-aminoethyl piperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino And propyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, norbornene diamine and the like.
 芳香族アミン類としては、テトラクロロ‐p‐キシレンジアミン、m‐キシレンジアミン、p‐キシレンジアミン、m‐フェニレンジアミン、o‐フェニレンジアミン、p‐フェニレンジアミン、2,4‐ジアミノアニゾール、2,4‐トルエンジアミン、2,4‐ジアミノジフェニルメタン、4,4’‐ジアミノジフェニルメタン、4,4’‐ジアミノ‐1,2‐ジフェニルエタン、2,4‐ジアミノジフェニルスルホン、4,4’‐ジアミノジフェニルスルホン、m‐アミノフェノール、m‐アミノベンジルアミン、ベンジルジメチルアミン、2‐(ジメチルアミノメチル)フェノール、トリエタノールアミン、メチルベンジルアミン、α‐(m‐アミノフェニル)エチルアミン、α‐(p‐アミノフェニル)エチルアミン、ジアミノジエチルジメチルジフェニルメタン、α,α’‐ビス(4‐アミノフェニル)‐p‐ジイソプロピルベンゼン等が挙げられる。 As aromatic amines, tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2, 4-Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone , M-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl ) Ethylamine, diamino di Ethyldimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene and the like can be mentioned.
 上記具体例の中でも、他の原材料との相溶性及び封止材の柔軟性を考慮すると、脂肪族アミン類、ポリエーテルポリアミン類、脂環式アミン類を用いることが好ましい。 Among the above specific examples, aliphatic amines, polyether polyamines and alicyclic amines are preferably used in consideration of the compatibility with other raw materials and the flexibility of the sealing material.
 エポキシ基を2個以上有するエポキシ化合物とポリアミンを合わせた含有量は、封止材組成物及び封止材中に5~50質量%含まれることが好ましい。5質量%未満では、封止材組成物が所定の定形性を有することができないおそれがある。一方、50質量%を超えると、封止材が硬くなりすぎるおそれがある。また、相対的に光硬化成分である液状ジエン系ゴムの含有量が少なくなるため、密着性が低下するおそれがある。なお、任意成分としての後述のエポキシ樹脂の硬化剤をさらに含む場合には、エポキシ基を2個以上有するエポキシ化合物とポリアミンに加え、このエポキシ樹脂の硬化剤を合わせた含有量が封止材組成物及び封止材中に5~50質量%含まれることが好ましい。その理由は前記同様である。 The total content of the epoxy compound having two or more epoxy groups and the polyamine is preferably 5 to 50% by mass in the encapsulant composition and the encapsulant. If the amount is less than 5% by mass, the encapsulant composition may not be able to have a predetermined shape. On the other hand, if it exceeds 50% by mass, the sealing material may be too hard. Further, since the content of the liquid diene rubber which is a light curing component is relatively decreased, the adhesion may be lowered. In addition, when it contains the curing agent of the below-mentioned epoxy resin as an arbitrary component further, it adds to the epoxy compound and polyamine which have 2 or more of epoxy groups, and the content which united the curing agent of this epoxy resin is sealing material composition It is preferable that 5 to 50% by mass be contained in the product and the sealing material. The reason is the same as above.
 また、エポキシ基を2個以上有するエポキシ化合物とポリアミンの合計100質量部に対して、液状ジエン系ゴムの配合量は100~2000質量部であることが好ましく、400~1600質量部であることがより好ましい。液状ジエン系ゴムが100質量部未満である場合には、封止材組成物及び封止材が硬くなるおそれがある。また、封止材の密着性が低下するおそれがある。一方、液状ジエン系ゴムが2000質量部を超えると、封止材組成物の定形性が損なわれ、貼着作業が難しくなるなど取扱い性が損なわれるおそれがある。 In addition, the compounding amount of the liquid diene rubber is preferably 100 to 2000 parts by mass, and 400 to 1600 parts by mass with respect to a total of 100 parts by mass of the epoxy compound having two or more epoxy groups and the polyamine. More preferable. If the liquid diene rubber is less than 100 parts by mass, the sealant composition and the sealant may become hard. In addition, the adhesion of the sealing material may be reduced. On the other hand, when the amount of the liquid diene rubber exceeds 2000 parts by mass, the shapeability of the sealing material composition is impaired, and the handleability may be impaired, for example, the sticking operation becomes difficult.
 エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムの反応生成物、エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物: Reaction product of epoxy compound having two or more epoxy groups and liquid diene rubber, reaction product of epoxy compound having two or more epoxy groups and polyamine:
 封止材組成物には上記のように、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムの反応生成物が含まれる。この反応生成物は、より詳しくは、液状ジエン系ゴムが備えるエポキシ基に対する反応性基と、エポキシ基が反応することで生じるものである。また、これに加え、エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物を含む。さらに液状ジエン系ゴムの有するエポキシ基に対する反応性基がカルボキシル基の場合には、ポリアミンと、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムの反応生成物を含む As described above, the sealant composition contains the reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber. More specifically, this reaction product is produced by the reaction of the epoxy group with the reactive group for the epoxy group contained in the liquid diene rubber. In addition to this, the reaction product of an epoxy compound having two or more epoxy groups and a polyamine is included. Furthermore, when the reactive group to the epoxy group possessed by the liquid diene rubber is a carboxyl group, the reaction product of a polyamine and a liquid diene rubber having a (meth) acryloyl group and a carboxyl group is included.
 エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムの反応生成物、ポリアミンと液状ジエン系ゴムの反応生成物、エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物は、共有結合を形成したり、イオン間相互作用を形成したり、その他の相互作用を形成している。即ち、液状ジエン系ゴム自体は液状であり多量に含まれると封止材組成物の定形性が損なわれるおそれがあるが、反応生成物を形成することで液状ジエン系ゴムの含有量が減少するとともに、これを保持する反応性生物が増加して封止材組成物に定形性を与えるとともに適度な柔らかさを維持していると考えられる。 The reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber, the reaction product of a polyamine and a liquid diene rubber, and the reaction product of an epoxy compound having two or more epoxy groups and a polyamine have a covalent bond. It forms, forms an interaction between ions, and forms other interactions. That is, the liquid diene rubber itself is liquid, and if contained in a large amount, there is a possibility that the shape of the encapsulant composition may be impaired, but the content of the liquid diene rubber is reduced by forming a reaction product. At the same time, it is considered that the amount of the reaction product that holds the resin increases to provide the encapsulant composition with a fixed shape and to maintain appropriate softness.
 そして、これらの反応生成物は、反応前の各成分と比較して相対的に高粘度となるか、又は固体となる。したがって、具体的には、引張り破断伸びが大きく向上し、封止材組成物を伸ばしたときに、千切れ難くさせることができる。したがって、平坦な封止材組成物を凹凸のある封止対象に貼付するとき、凹凸に沿って伸ばされた部分が破断し難くなり、封止材が破断することに起因する不具合の発生を抑えることができる、また、このことは換言すれば、凹凸の大きい封止対象に対して適用することができるようになる。 And these reaction products become relatively high viscosity compared with each component before reaction, or become solid. Therefore, specifically, the tensile elongation at break is greatly improved, and when the sealant composition is stretched, it can be made difficult to break. Therefore, when a flat sealing material composition is applied to a sealing object having irregularities, the portion stretched along the irregularities becomes less likely to break, and the occurrence of defects due to breakage of the sealing material is suppressed. In addition, in other words, this can be applied to a highly uneven sealing target.
 反応生成物について個別的にみると、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムの反応生成物を含む場合には、動的粘弾性測定の温度特性について、貯蔵弾性率の温度変化が小さく、定形性に優れた耐熱性のある封止材組成物となる。一方、ポリアミンと液状ジエン系ゴムの反応生成物によって定形性を有する場合には、動的粘弾性測定で測定される貯蔵弾性率が、温度が高くなるにしたがって著しく低下する熱可塑性に優れた封止材組成物となり、温度が高くなると柔軟性が増す封止材組成物を得ることができる。こうした封止材組成物は、被着対象が微細な凹凸を有するときに補助的に加熱することで凹凸の隅々まで封止材組成物を密着させることができる。そして、この両者の特徴は、エポキシ基を2個以上有するエポキシ化合物とポリアミンの双方の割合を変更することで調整することができる。 In the case of the reaction product individually, when the reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber is contained, the temperature change of the storage elastic modulus is observed for the temperature characteristic of the dynamic viscoelasticity measurement. Heat-resistant sealing material composition which is small in size and excellent in formability. On the other hand, in the case where the reaction product of a polyamine and a liquid diene rubber has a fixed shape, the storage elastic modulus measured by dynamic viscoelasticity measurement is a seal excellent in thermoplasticity in which the storage elastic modulus significantly decreases as the temperature increases. A sealant composition can be obtained which becomes an anchor composition and whose flexibility increases with increasing temperature. Such a sealing material composition can adhere a sealing material composition to every corner of unevenness by heating auxiliary | assistant, when a deposition object has fine unevenness | corrugation. And these characteristics can be adjusted by changing the ratio of both the epoxy compound which has 2 or more epoxy groups, and a polyamine.
 なお、液状ジエン系ゴムの(メタ)アクリロイル基とポリアミンのアミノ基が反応して反応生成物を形成する場合に、全ての(メタ)アクリロイル基が反応に寄与してしまうと、封止材組成物の光反応性が失われるおそれがあるが、発明者らが鋭意検討したところ、ポリアミンを過剰に添加した場合であっても、未反応の(メタ)アクリロイル基を残存させることができることを確認しており、ポリアミンと液状ジエン系ゴムとの反応生成物の生成に起因して封止材組成物の光硬化の不具合が生じることは確認されなかった。 In the case where the (meth) acryloyl group of the liquid diene rubber and the amino group of the polyamine react to form a reaction product, if all the (meth) acryloyl groups contribute to the reaction, the sealant composition There is a risk that the photoreactivity of the product may be lost, but as a result of intensive investigations by the inventors, it is confirmed that unreacted (meth) acryloyl group can be left even when polyamine is added in excess. It was not confirmed that the photocuring failure of the encapsulant composition occurred due to the formation of the reaction product of the polyamine and the liquid diene rubber.
 光ラジカル重合開始剤: Photo radical polymerization initiator:
 光ラジカル重合開始剤は、液状ジエン系ゴムを光反応させて硬化させるものである。具体的には、ベンゾフェノン系、チオキサントン系、アセトフェノン系、アシルフォスフィン系等の光重合開始剤を用いることができる。光ラジカル重合開始剤の配合量は、液状ジエン系ゴムの配合量100重量部に対して、0.1~10重量部が好ましく、1~8重量部がより好ましい。 The photo radical polymerization initiator is to cause a liquid diene rubber to photo react and cure. Specifically, photopolymerization initiators such as benzophenone type, thioxanthone type, acetophenone type, and acyl phosphine type can be used. The compounding amount of the photo radical polymerization initiator is preferably 0.1 to 10 parts by weight, and more preferably 1 to 8 parts by weight with respect to 100 parts by weight of the liquid diene rubber.
 その他の成分: Other ingredients:
 (メタ)アクリロイル基を有せずエポキシ基に対する反応性基を有する液状ジエン系ゴムをさらに含むものとすることができる。(メタ)アクリロイル基を有せずエポキシ基に対する反応性基を有する液状ジエン系ゴムをさらに含むものとすれば、封止材組成物の取扱い性を良いものとし、さらに最大引張応力を高めて伸長による破断を生じ難くすることができる。そのため、電子素子を覆う追従性を高めることができ、低荷重で電子素子の凹凸を埋めたり、電子素子の表面に沿わせたりすることができ、封止材の伸長で欠陥を生じ難くすることができる。また、(メタ)アクリロイル基由来の架橋密度を減らすことで、硬化後の伸縮性を高めることができ、フレキシブル基板及び伸長基材に対して好適な封止材とすることができる。 A liquid diene rubber containing no (meth) acryloyl group and having a reactive group to an epoxy group can be further included. If a liquid diene rubber having a (meth) acryloyl group and not having a reactive group to an epoxy group is further contained, the handleability of the plug composition is improved, and the maximum tensile stress is further increased to elongate the product. Can be made less likely to occur. Therefore, the followability to cover the electronic element can be enhanced, the unevenness of the electronic element can be filled with low load and the surface can be made to follow the surface of the electronic element, and the defect is less likely to occur due to the extension of the sealing material. Can. Further, by reducing the crosslink density derived from the (meth) acryloyl group, the stretchability after curing can be enhanced, and a sealing material suitable for a flexible substrate and an extension base material can be obtained.
 任意成分の例として、エポキシ樹脂の硬化剤を含むことができる。上記必須成分であるポリアミンとここでのエポキシ樹脂の硬化剤とを区別するために、本明細書及び請求の範囲においてエポキシ樹脂の硬化剤という場合には、上記のポリアミン以外であって、エポキシ基を2個以上有するエポキシ化合物との間で硬化反応を起こし得るものをいうものとする。 As an example of the optional component, a curing agent of epoxy resin can be included. In order to distinguish the polyamine which is the above-mentioned essential component from the curing agent of the epoxy resin here, in the present specification and claims, when the curing agent of the epoxy resin is referred to, it is other than the above-mentioned polyamine and an epoxy group These compounds are those which can cause a curing reaction with an epoxy compound having two or more.
 エポキシ基を2個以上有するエポキシ化合物とエポキシ樹脂の硬化剤とを熱硬化させて得るエポキシ樹脂硬化体は、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムとの反応生成物、ポリアミンと液状ジエン系ゴムとの反応生成物と共に、封止材組成物及び封止材に定形性を与える成分である。また、封止材の低透湿性、防水性を高めることに寄与している。エポキシ基を2個以上有するエポキシ化合物として柔軟骨格を有するエポキシ樹脂を用いたときは、封止材組成物及び封止材の柔軟性を高めることができる。 An epoxy resin cured product obtained by thermally curing an epoxy compound having two or more epoxy groups and a curing agent for epoxy resin is a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber, a polyamine and Together with the reaction product with liquid diene rubber, it is a component that imparts shape to the encapsulant composition and the encapsulant. Moreover, it contributes to improving the low moisture permeability and waterproofness of the sealing material. When an epoxy resin having a flexible skeleton is used as the epoxy compound having two or more epoxy groups, the flexibility of the encapsulant composition and the encapsulant can be enhanced.
 エポキシ樹脂の硬化剤としては、一般的に使われているエポキシ樹脂硬化剤の中で前述のポリアミン以外のものを用いることができる。例えば、イミダゾール系硬化剤、酸無水物系硬化剤、フェノール系硬化剤、ポリメルカプタン系硬化剤、イソシアネート類、ブロックイソシアネート等を挙げることができる。これらのエポキシ樹脂の硬化剤は単独で使用してもよいし、2種以上混合して使用してもよい。また、エポキシ基を2個以上有するエポキシ化合物に対するエポキシ樹脂の硬化剤の配合割合は、一般的にエポキシ樹脂の主剤と硬化剤として用いられる場合の配合割合と同じとすることができる。 As a curing agent for epoxy resin, among epoxy resin curing agents generally used, ones other than the above-mentioned polyamine can be used. Examples of the curing agent include imidazole curing agents, acid anhydride curing agents, phenol curing agents, polymercaptan curing agents, isocyanates, and blocked isocyanates. These epoxy resin curing agents may be used alone or in combination of two or more. Moreover, the compounding ratio of the hardening agent of the epoxy resin with respect to the epoxy compound which has 2 or more epoxy groups can be made the same as the compounding ratio in the case of being generally used as a main agent of an epoxy resin, and a hardening agent.
 エポキシ樹脂の硬化剤の含有量は、上記のとおり、エポキシ基を2個以上有するエポキシ化合物とポリアミンとエポキシ樹脂の硬化剤の合計含量が封止材組成物及び封止材中に5~50質量%となることが好ましい。5質量%未満では、封止材組成物が所定の定形性を有することができないおそれがある。一方、50質量%を超えると、封止材が硬くなりすぎるおそれがある。また、相対的に光硬化成分である液状ジエン系ゴムの含有量が少なくなるため、密着性が低下するおそれがある。 The content of the curing agent of the epoxy resin is, as described above, the total content of the epoxy compound having two or more epoxy groups, the polyamine and the curing agent of the epoxy resin in the sealing material composition and the sealing material It is preferable to be%. If the amount is less than 5% by mass, the encapsulant composition may not be able to have a predetermined shape. On the other hand, if it exceeds 50% by mass, the sealing material may be too hard. Further, since the content of the liquid diene rubber which is a light curing component is relatively decreased, the adhesion may be lowered.
 エポキシ樹脂の硬化剤以外にも本発明の趣旨を逸脱しない範囲で各種添加剤を適宜配合することができる。例えば、シランカップリング剤、重合禁止剤、消泡剤、光安定剤、酸化防止剤、帯電防止剤、ポリイソプレン又はポリブタジエン等の可塑剤、粘着付与剤、硬化促進剤等が挙げられる。例えばエポキシ基と反応する官能基が酸無水物基である場合は、反応を促進するために前記硬化促進剤として、三級アミンを含むクレイを添加することが好ましい。また、例えば、シリカ、クレイ等の絶縁性フィラー、導電性フィラー、軟磁性体フィラー及び熱伝導性フィラーなど種々の充填剤により、用途に応じた機能を付与することもできる。 In addition to the curing agent for epoxy resin, various additives can be appropriately blended without departing from the scope of the present invention. For example, silane coupling agents, polymerization inhibitors, antifoaming agents, light stabilizers, antioxidants, antistatic agents, plasticizers such as polyisoprene or polybutadiene, tackifiers, curing accelerators and the like can be mentioned. For example, when the functional group that reacts with the epoxy group is an acid anhydride group, it is preferable to add a clay containing a tertiary amine as the above-mentioned curing accelerator to accelerate the reaction. Moreover, the function according to a use can also be provided with various fillers, such as insulating fillers, such as a silica and a clay, an electroconductive filler, a soft magnetic body filler, and a thermally conductive filler, for example.
 (2)第2実施形態: (2) Second embodiment:
 第2実施形態としての封止材組成物は、エポキシ基を2個以上有するエポキシ化合物と、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムと、光重合開始剤とを必須成分として含んでおり、ポリアミンを含まないものである。これらの原材料については第1実施形態で説明したものと同じである。任意成分についても第1実施形態と同じであり、例えば、エポキシ樹脂の硬化剤を含むことができる。 The sealing material composition as the second embodiment comprises an epoxy compound having two or more epoxy groups, a liquid diene rubber having a reactive group for epoxy groups and a (meth) acryloyl group, and a photopolymerization initiator. It is included as an essential component and does not contain polyamine. These raw materials are the same as those described in the first embodiment. The optional components are also the same as in the first embodiment, and can include, for example, an epoxy resin curing agent.
 第2実施形態の封止材組成物でもエポキシ基を2個以上有するエポキシ化合物は主に、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムとの反応生成物として含有される。こうした反応生成物を含有することで、定形性に優れた耐熱性のある封止材組成物とすることができる。より具体的には、動的粘弾性測定の温度特性について、貯蔵弾性率の温度変化の小さい封止材組成物を得ることができる。 Also in the encapsulant composition of the second embodiment, the epoxy compound having two or more epoxy groups is mainly contained as a reaction product of the epoxy compound having two or more epoxy groups and the liquid diene rubber. By containing such a reaction product, it is possible to obtain a heat-resistant sealing material composition having excellent formability. More specifically, with regard to the temperature characteristics of the dynamic viscoelasticity measurement, it is possible to obtain an encapsulant composition with a small change in storage elastic modulus temperature.
 エポキシ基を2個以上有するエポキシ化合物の含有量は、封止材組成物及び封止材中に5~50質量%含まれることが好ましい。5質量%未満では、封止材組成物が所定の定形性を有することができないおそれがある。一方、50質量%を超えると、封止材が硬くなりすぎるおそれがある。また、相対的に光硬化成分である液状ジエン系ゴムの含有量が少なくなるため、密着性が低下するおそれがある。なお、任意成分としての後述のエポキシ樹脂の硬化剤をさらに含む場合には、エポキシ基を2個以上有するエポキシ化合物とこのエポキシ樹脂の硬化剤を合わせた含有量が封止材組成物及び封止材中に5~50質量%含まれることが好ましい。その理由は前記同様である。 The content of the epoxy compound having two or more epoxy groups is preferably 5 to 50% by mass in the sealing material composition and the sealing material. If the amount is less than 5% by mass, the encapsulant composition may not be able to have a predetermined shape. On the other hand, if it exceeds 50% by mass, the sealing material may be too hard. Further, since the content of the liquid diene rubber which is a light curing component is relatively decreased, the adhesion may be lowered. In addition, when it contains the hardening agent of the below-mentioned epoxy resin as an arbitrary component further, the content which united the epoxy agent which has 2 or more of epoxy groups, and the hardening agent of this epoxy resin is a sealing material composition and sealing It is preferable that 5 to 50% by mass be contained in the material. The reason is the same as above.
 また、エポキシ基を2個以上有するエポキシ化合物100質量部に対して、液状ジエン系ゴムの配合量は100~2600質量部であることが好ましく、400~1600質量部であることがより好ましい。液状ジエン系ゴムが100質量部未満である場合には、封止材組成物及び封止材が硬くなるおそれがある。また、封止材の密着性が低下するおそれがある。一方、液状ジエン系ゴムが2600質量部を超えると、封止材組成物の定形性が損なわれ、貼着作業が難しくなるなど取扱い性が損なわれるおそれがある。 The amount of the liquid diene rubber is preferably 100 to 2600 parts by mass, and more preferably 400 to 1600 parts by mass with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups. If the liquid diene rubber is less than 100 parts by mass, the sealant composition and the sealant may become hard. In addition, the adhesion of the sealing material may be reduced. On the other hand, when the liquid diene rubber exceeds 2600 parts by mass, the formability of the sealing material composition is impaired, and there is a possibility that the handleability may be impaired, for example, the sticking operation becomes difficult.
 本実施形態の封止材組成物はポリアミンを含まないため、保管安定性の向上を図ることができる。また、ポリアミンとエポキシ基の反応による架橋を含まないため硬化して封止材とした際の柔軟性及び伸縮性の向上を図ることができる。さらに封止材組成物の取扱い性に優れる。 Since the sealing material composition of this embodiment does not contain a polyamine, storage stability can be improved. Moreover, since it does not contain the bridge | crosslinking by reaction of a polyamine and an epoxy group, the softness | flexibility at the time of hardening | curing and it is set as a sealing material, and the stretchability can be improved. Furthermore, it is excellent in the handleability of a sealing material composition.
 (3)第3実施形態: (3) Third Embodiment:
 第3実施形態としての封止材組成物は、ポリアミンと、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムと、光重合開始剤とを必須成分として含んでおり、エポキシ基を2個以上有するエポキシ化合物を含まないものである。これらの原材料については第1実施形態で説明したものと同じである。任意成分については第1実施形態と同じとすることができるが、エポキシ樹脂の硬化剤を含ませても反応の対象となるエポキシ基を2個以上有するエポキシ化合物を含まないため、エポキシ樹脂の硬化剤を含有させたことによる特徴は出にくい。 The sealant composition as the third embodiment contains, as essential components, a polyamine, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator, and two epoxy groups are contained. It does not contain the epoxy compound possessed above. These raw materials are the same as those described in the first embodiment. The optional components can be the same as in the first embodiment, but even if the curing agent of the epoxy resin is contained, the epoxy resin is cured because it does not contain an epoxy compound having two or more epoxy groups to be reacted. It is hard to come out of the characteristic by having included the agent.
 第3実施形態の封止材組成物でもポリアミンは主に、ポリアミンと液状ジエン系ゴムとの反応生成物として含有される。こうした反応生成物を含有することで、熱可塑性に優れた封止材組成物とすることができる。具体的には、封止材組成物の温度特性について、動的粘弾性測定で測定される貯蔵弾性率が、温度が高くなるにしたがって著しく低下する封止材組成物を得ることができる。すなわち、温度が高くなると柔軟性を増す封止材組成物を得ることができる。こうした封止材組成物は、被着対象が微細な凹凸を有するとき、補助的に加熱することで凹凸の隅々まで封止材組成物を密着させることができる。 Also in the sealant composition of the third embodiment, the polyamine is mainly contained as a reaction product of the polyamine and the liquid diene rubber. By containing such a reaction product, an encapsulant composition excellent in thermoplasticity can be obtained. Specifically, with regard to the temperature characteristics of the sealing material composition, it is possible to obtain a sealing material composition in which the storage elastic modulus measured by dynamic viscoelasticity measurement significantly decreases as the temperature increases. That is, it is possible to obtain an encapsulant composition that increases in flexibility as the temperature increases. Such a sealing material composition can adhere a sealing material composition to every corner of unevenness by heating auxiliary | assistantly, when a deposition object has fine unevenness | corrugation.
 ポリアミンの含有量は、封止材組成物及び封止材中に5~50質量%含まれることが好ましい。5質量%未満では、封止材組成物が所定の定形性を有することができないおそれがある。一方、50質量%を超えると、封止材が硬くなりすぎるおそれがある。また、相対的に光硬化成分である液状ジエン系ゴムの含有量が少なくなるため、密着性が低下するおそれがある。 The content of the polyamine is preferably 5 to 50% by mass in the encapsulant composition and the encapsulant. If the amount is less than 5% by mass, the encapsulant composition may not be able to have a predetermined shape. On the other hand, if it exceeds 50% by mass, the sealing material may be too hard. Further, since the content of the liquid diene rubber which is a light curing component is relatively decreased, the adhesion may be lowered.
 また、ポリアミン100質量部に対して、液状ジエン系ゴムの配合量は100~2000質量部であることが好ましく、400~1600質量部であることがより好ましい。液状ジエン系ゴムが100質量部未満である場合には、封止材組成物及び封止材が硬くなるおそれがある。また、封止材の密着性が低下するおそれがある。一方、液状ジエン系ゴムが2000質量部を超えると、封止材組成物の定形性が損なわれ、貼着作業が難しくなるなど取扱い性が損なわれるおそれがある。 The amount of the liquid diene rubber is preferably 100 to 2000 parts by mass, and more preferably 400 to 1600 parts by mass with respect to 100 parts by mass of the polyamine. If the liquid diene rubber is less than 100 parts by mass, the sealant composition and the sealant may become hard. In addition, the adhesion of the sealing material may be reduced. On the other hand, when the amount of the liquid diene rubber exceeds 2000 parts by mass, the shapeability of the sealing material composition is impaired, and the handleability may be impaired, for example, the sticking operation becomes difficult.
 <封止材組成物の製造> <Production of encapsulant composition>
 第1実施形態~第3実施形態の何れの封止材組成物を製造する場合にも、それぞれの実施形態で用いる原材料である液状組成物(以下単に「液状組成物」)を準備する。そして、この液状組成物を加熱する。 When manufacturing any of the sealing material compositions of the first to third embodiments, a liquid composition (hereinafter simply referred to as "liquid composition") which is a raw material used in each embodiment is prepared. Then, the liquid composition is heated.
 第1実施形態の封止材組成物の場合は、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムとの反応生成物が生じ、エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物であるエポキシ樹脂硬化体が生じる。さらにエポキシ樹脂の硬化剤を含むときには、エポキシ基を2個以上有するエポキシ化合物とエポキシ樹脂の硬化剤の反応生成物であるエポキシ樹脂硬化体が生じる。そして、これらの反応により液状組成物は固化し、固体の封止材組成物が得られる。 In the case of the encapsulant composition of the first embodiment, a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber is generated, and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine. An epoxy resin cured product is produced. Furthermore, when a curing agent of an epoxy resin is contained, a cured epoxy resin body is formed which is a reaction product of an epoxy compound having two or more epoxy groups and a curing agent of the epoxy resin. Then, the liquid composition is solidified by these reactions, and a solid encapsulant composition is obtained.
 第2実施形態の封止材組成物の場合は、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムとの反応生成物が生じる。さらにエポキシ樹脂の硬化剤を含むときには、エポキシ基を2個以上有するエポキシ化合物とエポキシ樹脂の硬化剤の反応生成物であるエポキシ樹脂硬化体が生じる。そして、これらの反応により液状組成物は固化し、固体の封止材組成物が得られる。 In the case of the sealant composition of the second embodiment, a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber is generated. Furthermore, when a curing agent of an epoxy resin is contained, a cured epoxy resin body is formed which is a reaction product of an epoxy compound having two or more epoxy groups and a curing agent of the epoxy resin. Then, the liquid composition is solidified by these reactions, and a solid encapsulant composition is obtained.
 第3実施形態の封止材組成物の場合は、ポリアミンと液状ジエン系ゴムとの反応生成物が生じる。そして、この反応により液状組成物は固化し、固体の封止材組成物が得られる。 In the case of the sealant composition of the third embodiment, a reaction product of a polyamine and a liquid diene rubber is produced. Then, the liquid composition is solidified by this reaction, and a solid encapsulant composition is obtained.
 <封止材組成物の性質> <Properties of Sealant Composition>
 第1実施形態~第3実施形態の何れの封止材組成物も所定の定形性を有している。そのため、封止対象に貼着したとき、目的とする範囲内に確実に貼着することでき、所定の範囲外に流れ出てしまうおそれがない。また、これらの封止材組成物は、23℃における貯蔵弾性率E’を0.004~0.75MPaの範囲とすることができる。貯蔵弾性率E’を0.004~0.75MPaとすることで、極めて柔軟であることから、封止材組成物を加圧して電子基板に密着させるときに、電子基板に過大な応力を与えることのない低い荷重で電子素子の凹凸に柔軟に追従させることができる。したがって、電子基板に負荷をかけずに、電子基板との間に隙間なく密着させて確実に封止することができる。0.004MPaより低い場合には、封止材組成物の強度が弱く、凹凸のある封止対象に貼付したとき、凹凸に沿って伸ばされた部分で破断し易くなるおそれがある。一方、0.75MPaを超えると必要以上に硬くなり、封止材組成物を封止対象に貼付するとき、大きな圧力が必要となるおそれがある。また、貯蔵弾性率E’は0.01~0.60MPaの範囲とすることが好ましい。貯蔵弾性率E’が0.01以上であれば、封止材組成物を剥離フィルムから剥すときに変形し難く、貼着作業等の取扱い性に優れるためである。貯蔵弾性率E’が0.60以下であれば、電子基板への負荷を極めて小さくすることができるためである。なお、電子基板には、樹脂基板、フレキシブル基板、伸長基板等が含まれる。  The sealant composition of any of the first to third embodiments has a predetermined shape. Therefore, when sticking to the object to be sealed, it can be reliably stuck within the target range, and there is no risk of flowing out of the predetermined range. In addition, these sealant compositions can have a storage elastic modulus E ′ at 23 ° C. in the range of 0.004 to 0.75 MPa. Since the storage elastic modulus E ′ is extremely flexible by setting the storage elastic modulus E ′ to 0.004 to 0.75 MPa, an excessive stress is given to the electronic substrate when the sealing material composition is pressed to be in close contact with the electronic substrate. It can be made to flexibly follow the unevenness of the electronic device with an extremely low load. Therefore, the electronic substrate can be closely attached without any gap and sealed reliably without applying a load to the electronic substrate. When it is lower than 0.004 MPa, the strength of the sealing material composition is weak, and when it is attached to a sealing target having irregularities, there is a possibility that the part stretched along the irregularities tends to break easily. On the other hand, when it exceeds 0.75 MPa, it becomes hard more than necessary, and when sticking a sealing material composition to sealing object, there exists a possibility that big pressure may be needed. The storage elastic modulus E 'is preferably in the range of 0.01 to 0.60 MPa. If storage elastic modulus E 'is 0.01 or more, it is difficult to be deformed when peeling a sealing material composition from a peeling film, and it is because it is excellent in the handleability, such as adhesion work. If the storage elastic modulus E ′ is 0.60 or less, the load on the electronic substrate can be extremely reduced. The electronic substrate includes a resin substrate, a flexible substrate, an extension substrate, and the like.
 封止材組成物は、粘着性を有していても良いし、有していなくても良いが、所定の粘着性を有していることが好ましい。封止材組成物が粘着性を有している方が、被着対象に封止材組成物を配置した後に、振動及び衝撃によって位置ずれせず、貼着、封止作業がし易いためである。粘着力は必ずしも強い必要性はないが、被着対象に封止材組成物を配置した後に、振動及び衝撃によって位置ずれしない程度の粘着性を有していることが好ましい。具体的には、封止材組成物の厚みの25%の高さの突起を備える基板に封止材組成物を貼着して密着させた後に、30秒程度隙間を生じさせない程度の粘着性を備えることが好ましい。 The sealant composition may or may not have tackiness, but preferably has predetermined tackiness. If the sealant composition has adhesiveness, it does not shift due to vibration and impact after disposing the sealant composition on the object to be adhered, and it is easy to perform sticking and sealing work. is there. Although the adhesive strength is not necessarily strong, it is preferable to have an adhesive property to such an extent that it does not shift due to vibration and impact after disposing the sealing material composition on the adherend. Specifically, after sticking the sealing material composition on a substrate provided with a protrusion having a height of 25% of the thickness of the sealing material composition and adhering the substrate, adhesion of such a degree that a gap does not occur for about 30 seconds Preferably,
 より具体的には、封止材組成物の厚みは0.2~2.0mmであることが好ましい。0.2mm未満では封止材組成物の取扱いが難しい場合がある。一方で2.0mmを超えると封止材組成物の深部まで紫外線が充分に透過せず、硬化が不十分となるおそれがある。また、本発明の封止材は柔軟であることから、封止材組成物の厚みを0.5~2.0mmとすると、電子素子を衝撃から保護する緩衝効果が高まるため好ましい。 More specifically, the thickness of the encapsulant composition is preferably 0.2 to 2.0 mm. If it is less than 0.2 mm, handling of the encapsulant composition may be difficult. On the other hand, if it exceeds 2.0 mm, ultraviolet rays may not sufficiently penetrate to the deep portion of the encapsulant composition, and curing may be insufficient. In addition, since the sealing material of the present invention is flexible, it is preferable to set the thickness of the sealing material composition to 0.5 to 2.0 mm because the shock absorbing effect of protecting the electronic element from impact is enhanced.
 封止材組成物は、ある程度の透明性を有することが好ましい。封止材組成物がある程度白濁していても硬化可能であるものの、透明性が大きく損なわれると、封止材組成物を光硬化させるときに深部の硬化性が損なわれるおそれがある。 The encapsulant composition preferably has some degree of transparency. Although the encapsulant composition can be cured even if it is turbid to a certain extent, if the transparency is largely impaired, the curability of the deep portion may be impaired when the encapsulant composition is photocured.
 <封止材の製造> <Manufacture of sealing material>
 第1実施形態から第3実施形態の封止材組成物を光硬化させることで第1実施形態から第3実施形態それぞれの封止材を製造できる。より具体的には、封止材組成物を電子基板等に設けた電子素子及び金属が露出した部分に貼付して電子素子などの被着体を覆った後、光照射により、液状ジエン系ゴムを光ラジカル重合反応によって硬化させることで封止材とすることができる。このとき封止材組成物が粘着力を有している場合には、被着体に治具等で圧力をかけて封止材を押し潰しながら被着体の凹凸へ密着させる。その後に治具を持ち上げ、速やかに光を照射することで、被着体に封止材組成物が密着した状態のまま硬化させることができる。一方、封止材組成物が粘着力を有していない場合には、光透過性の治具を用いて、封止材を押し潰しながら被着体の凹凸へ密着させる。そして、この状態のまま、治具を介して光を照射することで、被着体に封止材組成物が密着した状態のまま硬化させることができる。なお、光透過性の治具としては、例えばアクリル樹脂、ガラス、サファイアなど、使用する波長の光を透過する材料を用いることができる。また、粘着性を有している封止材組成物について、粘着性を有していない封止材組成物と同様の方法を採用しても良い。 By photocuring the sealing material compositions of the first to third embodiments, the sealing materials of the first to third embodiments can be manufactured. More specifically, an electronic element provided with a sealing material composition on an electronic substrate or the like and a portion where metal is exposed to cover an adherend such as an electronic element and the like, and then liquid diene rubber by light irradiation It can be used as a sealing material by hardening by photo radical polymerization reaction. At this time, in the case where the sealing material composition has an adhesive force, pressure is applied to the adherend with a jig or the like, and the sealing material is brought into close contact with the unevenness of the adherend while being crushed. Thereafter, the jig is lifted and light is irradiated rapidly, so that the sealing material composition can be cured in a state in which the sealing material composition is in close contact with the adherend. On the other hand, when the sealing material composition does not have adhesive strength, the sealing material is brought into close contact with the unevenness of the adherend while being crushed using a light transmissive jig. Then, by irradiating light through the jig in this state, it is possible to cure the sealing material composition in a state in which the sealing material composition is in close contact with the adherend. In addition, as a transparent jig | tool, the material which permeate | transmits the light of the wavelength to be used, such as an acrylic resin, glass, sapphire, can be used, for example. Moreover, you may employ | adopt the method similar to the sealing material composition which does not have adhesiveness about the sealing material composition which has adhesiveness.
 <封止材の性質> <Properties of sealing material>
 第1実施形態から第3実施形態の封止材組成物を光照射して硬化させて形成した第1実施形態から第3実施形態の何れの封止材も、柔軟なゴム状弾性体でありフレキシブル基板に追従できる柔軟性を有している。具体的には動的粘弾性測定装置で測定される23℃における貯蔵弾性率E’を0.5~10MPaの範囲とすることができ、0.7~5.4MPaとすることが好ましい。こうした範囲としたため、フレキシブルに変形する用途に用いても、剥がれ又は破損のおそれがなく、封止対象を確実に封止することができる。貯蔵弾性率E’が0.5MPa未満の場合には、封止材の強度が小さくなるおそれがあり、貯蔵弾性率E’が10MPaを超えると、フレキシブル性が要求される用途に適さなくなるおそれがある。また、0.7~5.4MPaとすれば、強度が大きくフレキシブル性にも優れた封止材とすることができる。 Any of the sealing materials of the first to third embodiments formed by irradiating and curing the sealing material composition of the first to third embodiments is also a flexible rubber-like elastic body. It has the flexibility to follow the flexible substrate. Specifically, the storage elastic modulus E ′ at 23 ° C. measured by a dynamic viscoelasticity measuring device can be in the range of 0.5 to 10 MPa, and is preferably 0.7 to 5.4 MPa. Since it is set as such a range, even if it uses for the use which deform | transforms flexibly, there is no fear of peeling or a failure and it can seal the sealing object reliably. If the storage elastic modulus E 'is less than 0.5 MPa, the strength of the sealing material may be reduced, and if the storage elastic modulus E' exceeds 10 MPa, it may not be suitable for applications requiring flexibility. is there. When the pressure is 0.7 to 5.4 MPa, a sealing material having high strength and excellent flexibility can be obtained.
 封止材はまた、所定の接着性を有していると共にJIS C0920に規定されたIPX7を満たす防水性能を有している。したがって、封止対象を確実に水から保護できる。
さらに、上記封止材の水蒸気透過度は50g/m・24h以下である。したがって、高湿度環境下においても、封止対象を水分から保護できる。
The sealing material also has a predetermined adhesive property and a waterproof performance satisfying IPX7 defined in JIS C0920. Therefore, the object to be sealed can be reliably protected from water.
Furthermore, the water vapor permeability of the sealing material is 50 g / m 2 · 24 h or less. Therefore, the object to be sealed can be protected from moisture even in a high humidity environment.
 封止材組成物に定形性と柔軟性があるため、凹凸のある電子基板に比較的小さな荷重で封止材組成物を押しつけることで密着し、電子基板の凹部へしみ込ませ易い。また、封止材の貯蔵弾性率が小さく柔軟であることから、電子基板の凹凸を埋めた状態で硬化されたものであっても残留応力が残りにくく、長期にわたって安定して電子素子の封止が可能である。 Since the encapsulant composition has a fixed shape and flexibility, the encapsulant composition is brought into close contact by pressing the encapsulant composition against the uneven electronic substrate with a relatively small load, and it is easy to penetrate into the recesses of the electronic substrate. In addition, since the storage elastic modulus of the sealing material is small and flexible, residual stress is unlikely to remain even if it is cured in a state where the unevenness of the electronic substrate is buried, and the electronic element is stably sealed for a long period of time Is possible.
 例えば、ゴム状ではなく、一度加熱して軟化又は溶融させる従来タイプのシート状封止材では、ゴム弾性に乏しく、軟化又は溶融状態で伸長できたとしても特に高さが高い電子素子の表面に追従させようとすると千切れるおそれが高かったのに対し、本発明の封止材組成物は、400%程度の伸長も可能である場合が多く、千切れ難く高さが高い電子素子を容易に覆うことができる。 For example, in the case of a conventional sheet-like sealing material which is not rubbery but is once heated and softened or melted, it has poor rubber elasticity and is particularly high on the surface of the electronic element even if it can be stretched in the softened or molten state. The sealing material composition of the present invention is often capable of elongation of about 400%, while it is likely to be broken when trying to follow it, and it is easy to make an electronic element that is hard to break and has a high height. It can be covered.
 封止材の厚さTに対して電子素子の高さTを低く(T>T)し、電子素子の凹凸を封止材で埋めて表面を略平滑とすれば、複数の高さの異なる電子素子を有する電子基板であっても、その表面が平滑であるため、これらの電子素子を外気から隔離して封止するだけでなく、安定的に保持することもできる。また、封止材の厚さTに対して電子素子の高さTを高く(T≦T)し、電子素子の外面に沿って封止材を密着させれば、複数の高さの異なる電子素子を有する電子基板であっても、封止材が少なくともその側面を覆うため、これらの電子素子を安定的に保持することができる。 If the height T 2 of the electronic element is made smaller (T 1 > T 2 ) with respect to the thickness T 1 of the sealing material, and the unevenness of the electronic element is filled with the sealing material to make the surface substantially smooth, Even an electronic substrate having electronic elements of different heights can be held stably as well as separated and sealed from the outside air because the surface is smooth. Also, if the height T 2 of the electronic element is made higher (T 1 ≦ T 2 ) with respect to the thickness T 1 of the sealing material, and the sealing material is adhered along the outer surface of the electronic element Even in the case of an electronic substrate having electronic elements different in size, since the sealing material covers at least the side surface, these electronic elements can be stably held.
 実施例に基づき本発明を説明する。次に説明する試料1~試料26を作製するとともに各種試験を行った。 The invention will be described on the basis of examples. Samples 1 to 26 described below were prepared and subjected to various tests.
 <試料の作製> <Preparation of sample>
 試料1となる封止材組成物及び封止材を作製した。具体的にはエポキシ基を2個以上有するエポキシ化合物として、柔軟骨格を有する液状エポキシ樹脂(株式会社ADEKA製「EP-4000S」)(以下、エポキシ樹脂1)を41.3質量部、ポリアミンとして変性脂肪族ポリアミン(株式会社ADEKA製「EH-4357S」)(以下、ポリアミン1)を15.9質量部、液状ジエン系ゴムとして、カルボキシル基とメタクリロイル基を有する液状ポリイソプレンゴム(30Pa・s、38℃、分子量17000、官能基数 カルボキシル基:2、メタクリロイル基:2)(以下、液状ジエン系ゴム1)を42.8質量部と、光重合開始剤として1-ヒドロキシシクロヘキシルフェニルケトンを1.3質量部と、を混合して、均一な液状組成物を得た。 A sealing material composition and a sealing material to be sample 1 were produced. Specifically, as an epoxy compound having two or more epoxy groups, 41.3 parts by mass of a liquid epoxy resin having a flexible skeleton ("EP-4000S" manufactured by ADEKA Co., Ltd.) (hereinafter, epoxy resin 1) is modified as a polyamine Liquid polyisoprene rubber having a carboxyl group and a methacryloyl group (30 Pa · s, 38 g of 15.9 parts by mass of aliphatic polyamine (“EH-4357S” manufactured by ADEKA Co., Ltd.) (hereinafter referred to as “polyamine 1”) as liquid diene rubber ° C, molecular weight 17000, number of functional groups carboxyl group: 2, methacryloyl group: 2 (hereinafter, liquid diene rubber 1): 42.8 parts by mass, and 1.3 mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator The parts were mixed to obtain a uniform liquid composition.
 次に、この液状組成物を厚さ1.0mmとなるように一対の剥離フィルムの間に挟み込んだ状態で120℃、60分加熱することで、エポキシ基を2個以上有するエポキシ化合物等を反応させ、シート状の封止材組成物を作製しこれを試料1の封止材組成物とした。 Next, the liquid composition is heated at 120 ° C. for 60 minutes in a state of being sandwiched between a pair of release films so as to have a thickness of 1.0 mm, thereby reacting an epoxy compound having two or more epoxy groups. The sheet-like sealing material composition was prepared, and this was used as the sealing material composition of sample 1.
 そして、この封止材組成物の一方面の剥離フィルムを剥して、露出した封止材組成物の表面を、厚さ1mmのエポキシ樹脂基板に貼付けてから、平坦な押板で圧力0.3MPaで5秒間加圧した。その後、照度600mW/cm、積算光量5000mJ/cmの条件で紫外線を照射して封止材を作製し、これを試料1の封止材とした。 And after peeling the peeling film of one side of this sealing material composition and sticking the surface of the exposed sealing material composition on an epoxy resin substrate with a thickness of 1 mm, pressure 0.3MPa with a flat pressing plate And pressurized for 5 seconds. Thereafter, ultraviolet rays were irradiated under the conditions of illuminance 600 mW / cm 2 and integrated light amount 5000 mJ / cm 2 to prepare a sealing material, which was used as a sealing material of Sample 1.
 試料2~試料26の封止材組成物及び封止材についても、試料1の各原料と配合を表に示した各原料と配合量に変更した以外は同じ条件で作製した。なお、各試料の配合については、エポキシ基を2個以上有するエポキシ化合物とポリアミンと液状ジエン系ゴムの合計を100質量部として、各原料の質量部数を記載している。 The sealing material compositions and the sealing materials of Samples 2 to 26 were also produced under the same conditions except that the respective raw materials and the blending amounts of Sample 1 were changed to the respective raw materials and blending amounts shown in the table. In addition, about the compounding of each sample, the mass part number of each raw material is described by making into 100 mass parts the sum total of the epoxy compound which has 2 or more of epoxy groups, a polyamine, and a liquid diene rubber.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 表に示す各原料は次のとおりである。
 エポキシ樹脂2:ビスフェノールF型エポキシ樹脂(DIC株式会社「EPICLON EXA-835LV」)
 エポキシ樹脂3:エポキシ基を2個以上有し、柔軟骨格を有する液状エポキシ樹脂(DIC株式会社「EXA-4850-150」)
 ポリアミン2:エポキシアミンアダクト(味の素ファインテクノ株式会社「アミキュアMY-24」)
 液状ジエン系ゴム2:(メタ)アクリロイル基及びエポキシ基に対する反応性基の何れも有しない液状ポリイソプレンゴム(70Pa・s、38℃、分子量28000、官能基なし)
 液状ジエン系ゴム3:(メタ)アクリロイル基を有さず酸無水物基を有する液状ポリイソプレンゴム(200Pa・s、38℃、分子量34000、官能基数3=酸無水物基数3)
 液状ジエン系ゴム4:(メタ)アクリロイル基を有さずカルボキシル基を有する液状ポリイソプレンゴム(430Pa・s、38℃、分子量30000、官能基数10=カルボキシル基数10)
 液状ジエン系ゴム5:メタクリロイル基を有し、エポキシ基に対する反応性基を有しない液状ポリブタジエンゴム(100Pa・s、38℃、分子量4000、官能基数2=メタクリロイル基数2)
Each raw material shown to a table is as follows.
Epoxy resin 2: Bisphenol F type epoxy resin (DIC Corporation "EPICLON EXA-835LV")
Epoxy resin 3: Liquid epoxy resin having two or more epoxy groups and having a flexible skeleton (DIC Corporation "EXA-4850-150")
Polyamine 2: Epoxy amine adduct (Ajinomoto Fine Techno Co., Ltd. “AMICURE MY-24”)
Liquid diene rubber 2: Liquid polyisoprene rubber having neither (meth) acryloyl group nor reactive group to epoxy group (70 Pa · s, 38 ° C., molecular weight 28000, no functional group)
Liquid diene rubber 3: Liquid polyisoprene rubber not having (meth) acryloyl group but having acid anhydride group (200 Pa · s, 38 ° C., molecular weight 34000, number of functional groups 3 = number of acid anhydride groups 3)
Liquid diene rubber 4: Liquid polyisoprene rubber not having (meth) acryloyl group but having carboxyl group (430 Pa · s, 38 ° C., molecular weight 30,000, number of functional groups 10 = number of carboxyl groups 10)
Liquid diene rubber 5: Liquid polybutadiene rubber having a methacryloyl group and having no reactive group to an epoxy group (100 Pa · s, 38 ° C., molecular weight 4000, functional group number 2 = methacryloyl group number 2)
 <試験方法及び試験結果> <Test method and test result>
 上記各試料の封止材組成物及び封止材については以下に示す種々の観点から試験し、観察し、評価した。 About the sealing material composition and sealing material of each said sample, it tested from various viewpoints shown below, observed, and evaluated.
 (1)封止材組成物の定形性: (1) Formability of Sealant Composition:
 定形性については、剥離フィルム上に液状組成物を塗布して硬化することで形成した封止材組成物を、この剥離フィルムから引き剥がした際の封止材組成物の状態から評価することができる。ここでは封止材組成物を、形状を保ったまま剥がすことができたものを「○」とし、また、剥がすことができるものの伸びてしまうなど変形してしまうものを「△」とした。一方、固形に固まらず、封止材組成物が剥離フィルムから流れ出てしまったもの及び凝集力が極めて弱く、剥離フィルムから封止材組成物を剥すことが困難なものを「×」とした。「○」又は「△」のものは、封止材組成物として利用可能であり定形性を備えるものと評価できる。一方、「×」のものは、封止対象の所定の範囲内に貼着することが困難であったり、所定の範囲外に流れ出てしまったりするおそれがあり、定形性を備えるものではない。試料1~26の封止材組成物の評価結果について表に示した。 With regard to the formability, the sealing material composition formed by applying the liquid composition on the release film and curing it may be evaluated from the state of the sealing material composition when peeled off from the release film. it can. Here, those which could be peeled off the sealing material composition while maintaining the shape were taken as “o”, and those which could be peeled off but which were deformed such as being stretched were made “Δ”. On the other hand, those which did not solidify, those in which the encapsulant composition had flowed out of the release film, and those in which the cohesive force was extremely weak and it was difficult to detach the encapsulant composition from the release film were regarded as “x”. The thing of "(circle)" or "(triangle | delta)" can be evaluated as what can be utilized as a sealing material composition, and has a fixed shape. On the other hand, the thing of "x" has a possibility that it may be difficult to stick within the predetermined range of sealing object, or it may flow out of the predetermined range, and does not have a fixed shape. The evaluation results of the sealing material compositions of Samples 1 to 26 are shown in the table.
 (2)封止材組成物の貯蔵弾性率: (2) Storage Modulus of Sealant Composition:
 封止材組成物を幅5.0mm×長さ30.0mm(厚さは1.0mm)の大きさに切り出して測定用試験片を準備し、動的粘弾性測定装置(セイコーインスツル株式会社製「DMS6100」)を用いて、チャック間距離8mm、周波数1Hz、引張モードにて貯蔵弾性率E’を測定した。測定温度を23℃、60℃、120℃の3条件で測定することで、封止材組成物の温度特性を評価することができる。上記条件で測定した貯蔵弾性率は、0.1~0.6MPaの範囲となることが好ましい。試料1~26の封止材組成物の貯蔵弾性率の値について表に示した。 A sealing material composition is cut into a size of width 5.0 mm × length 30.0 mm (thickness is 1.0 mm) to prepare a test piece for measurement, and a dynamic viscoelasticity measuring apparatus (Seiko Instruments Co., Ltd. A storage elastic modulus E ′ was measured in a tension mode with a distance between chucks of 8 mm, a frequency of 1 Hz, using “DMS 6100” manufactured in Japan. By measuring the measurement temperature under three conditions of 23 ° C., 60 ° C., and 120 ° C., it is possible to evaluate the temperature characteristics of the sealing material composition. The storage elastic modulus measured under the above conditions is preferably in the range of 0.1 to 0.6 MPa. The storage modulus values of the sealing material compositions of Samples 1 to 26 are shown in the table.
 (3)封止材組成物の粘着性: (3) Tackiness of encapsulant composition:
 封止材組成物の厚みの25%の高さの突起を備える基板に封止材組成物を貼着して密着させた後に、30秒間隙間を生じさせない粘着性を備えるものを「〇」、そうした粘着性を備えないものを「×」と評価した。その評価結果について表に示した。 After sticking the sealing material composition on a substrate provided with a protrusion having a height of 25% of the thickness of the sealing material composition and adhering the substrate, “O” is one having adhesiveness not causing a gap for 30 seconds. Those having no such tackiness were evaluated as "x". The evaluation results are shown in the table.
 (4)封止材組成物のゲル分率: (4) Gel fraction of encapsulant composition:
 所定重量W1の封止材組成物をトルエン中に常温で24時間放置した後にトルエンに溶けなかった封止材組成物を取り出し、封止材組成物中に含まれるトルエンを蒸発させた後の重量W2を測定した。封止材組成物の初期重量W1に対するトルエン不溶成分の重量W2の割合をゲル分率と定義する。 After the encapsulant composition having a predetermined weight W1 is allowed to stand in toluene for 24 hours at normal temperature, the encapsulant composition not dissolved in toluene is taken out, and the weight after evaporating the toluene contained in the encapsulant composition W2 was measured. The ratio of the weight W2 of the toluene insoluble component to the initial weight W1 of the encapsulant composition is defined as the gel fraction.
  ゲル分率(%)= W2/W1 × 100
   W1:試験前の封止材組成物の重量
   W2:試験後の封止材組成物の重量
Gel fraction (%) = W2 / W1 × 100
W1: Weight of encapsulant composition before test W2: Weight of encapsulant composition after test
 封止材組成物中に含まれる成分のうち、不溶成分としては3次元的に架橋したエポキシ樹脂硬化体及び反応生成物を挙げることができる。一方、トルエンへの溶出成分としては、エポキシ基を2個以上有するエポキシ化合物、ポリアミン、液状ジエン系ゴムの他に、弱い相互作用で結合している反応生成物、3次元的に架橋していない反応生成物(以下、溶出性反応生成物)を挙げることができる。したがって、ゲル分率が小さいとき、その封止材組成物には、少なくともエポキシ基を2個以上有するエポキシ化合物、ポリアミン、液状ジエン系ゴム、溶出性反応生成物の何れかが含まる。また、ゲル分率が100%のとき、こうした溶出性物が残存していないことがわかる。 Among the components contained in the encapsulant composition, the insoluble component includes a three-dimensionally crosslinked epoxy resin cured product and a reaction product. On the other hand, as an elution component to toluene, in addition to epoxy compounds having two or more epoxy groups, polyamines, liquid diene rubbers, reaction products bonded by weak interaction, not cross-linked three-dimensionally Reaction products (hereinafter referred to as elutable reaction products) can be mentioned. Therefore, when the gel fraction is small, the sealant composition contains at least one of an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber, and an elution reaction product. Further, when the gel fraction is 100%, it can be seen that such a leachable does not remain.
 ところで、ポリアミンと液状ジエン系ゴムとで構成される封止材組成物は、上記ゲル分率が小さくなることがある。このことは、ポリアミンと液状ジエン系ゴムの反応生成物は、弱い相互作用による反応生成物の形成か、又はトルエン中で構造を保つことができるほど十分な3次元構造を有しない反応生成物の形成によって固化しているものと考えられる。ここで、官能基として、ポリアミンのアミノ基と液状ジエン系ゴムのカルボキシル基の相互作用を考えると、酸塩基相互作用が働くことが予想される。一方、ポリアミンのアミノ基と液状ジエン系ゴムの(メタ)アクリロイル基が反応する場合には、共有結合による反応生成物を形成するものと考えられる。試料1~26の封止材組成物のゲル分率(%)について表に示した。 By the way, the above-mentioned gel fraction may become small in the closure agent composition constituted with polyamine and liquid diene system rubber. This means that the reaction product of the polyamine and the liquid diene rubber is either a reaction product due to a weak interaction or a reaction product which does not have a three-dimensional structure sufficient to maintain the structure in toluene. It is considered to be solidified by formation. Here, in consideration of the interaction between the amino group of the polyamine and the carboxyl group of the liquid diene rubber as a functional group, it is expected that an acid-base interaction will work. On the other hand, when the amino group of the polyamine and the (meth) acryloyl group of the liquid diene rubber react, it is considered that a reaction product is formed by covalent bonding. The gel fraction (%) of the encapsulant composition of Samples 1 to 26 is shown in the table.
 (5)封止材組成物の機械的強度(引張り試験): (5) Mechanical strength of sealing composition (tensile test):
 封止材組成物の機械的強度については、JIS K 6251に従い最大引張応力(引張強さともいう)及び切断時伸び(引張破断伸びともいう)、100%伸び引張応力を測定した。まず、シート状の封止材組成物を、抜き型を用いてダンベル状1号形に切断し、ダンベル状試料の棒状部に、10mmの間隔を空けて2本の標線を付した。次に、試料の両端部に一定条件下で引張力を加え、試料が破断するまでの最大引張力、及び標線間の伸びを測定した。また、標線の伸びが100%(すなわち標線間が初期の2倍となった状態)になったときの引張力を測定した。そして、それぞれ下記式(1)、式(2)、式(3)に適用して最大引張応力、切断時伸び、100%伸び引張応力を算出した。これらの値を表に示した。 Regarding the mechanical strength of the sealing material composition, maximum tensile stress (also referred to as tensile strength), elongation at break (also referred to as tensile breaking elongation), and 100% elongation tensile stress were measured according to JIS K 6251. First, the sheet-like sealing material composition was cut into a dumbbell shape No. 1 using a punching die, and two mark lines were attached to the rod-like portion of the dumbbell-shaped sample at an interval of 10 mm. Next, tensile force was applied to both ends of the sample under certain conditions, and the maximum tensile force until the sample broke and the elongation between the marked lines were measured. In addition, the tensile force was measured when the elongation of the marked line reached 100% (that is, the state in which the distance between the marked lines was twice that of the initial stage). Then, maximum tensile stress, elongation at break, and 100% elongation tensile stress were calculated by applying the following expressions (1), (2), and (3), respectively. These values are shown in the table.
 TS=F/S ・・・式(1)
 E=(L-L)/L×100 ・・・式(2)
 TS100=F100/S ・・・式(3)
TS = F m / S equation (1)
E b = (L 1 -L 0 ) / L 0 × 100 Formula (2)
TS 100 = F 100 / S formula (3)
  TS:最大引張応力(MPa)
  F:最大引張力(N)
  S:試験片の初期断面積(mm
  E:切断時伸び(%)
  L:初期の標線間距離(mm)
  L:破断時の標線間距離(mm)
  TS100:100%伸び引張応力(MPa)
  F100:100%伸び引張力(N)
TS: Maximum tensile stress (MPa)
F m : Maximum tensile force (N)
S: Initial cross-sectional area of test piece (mm 2 )
E b : Elongation at cutting (%)
L 0 : Initial mark line distance (mm)
L 1 : Distance between marked lines at break (mm)
TS 100 : 100% elongation tensile stress (MPa)
F 100 : 100% elongation tensile force (N)
 (6)封止材の硬化性(貯蔵弾性率): (6) Curability of sealing material (storage modulus):
 封止材組成物に光照射して形成した封止材の硬化の程度については、硬化に伴う硬さの変化が生じるため、貯蔵弾性率の変化で硬化の程度を評価した。貯蔵弾性率E’の測定は、封止材を幅5.0mm×長さ30.0mm(厚さは1.0mm)の大きさに切り出して測定用試験片を準備し、動的粘弾性測定装置(セイコーインスツル株式会社製「DMS6100」)を用いて、チャック間距離8mm、周波数1Hz、測定温度が23℃、引張モードにて行った。貯蔵弾性率は、封止材組成物では概ね0.01~0.60MPaとなるのに対して封止材の貯蔵弾性率は0.5~10MPaの範囲となるが、このときの貯蔵弾性率の変化率が少なくとも200%以上であることが好ましい。したがって、貯蔵弾性率の変化率が200%以上のものを「○」、200%未満のものを「×」と評価した。この評価結果と、封止材組成物から封止材に硬化する前後の貯蔵弾性率の変化の値を表に示した。 With respect to the degree of curing of the sealing material formed by irradiating the sealing material composition with light, a change in hardness occurs with the curing, so the degree of curing was evaluated by the change in storage elastic modulus. For measurement of storage elastic modulus E ′, a sealing material is cut out to a size of width 5.0 mm × length 30.0 mm (thickness 1.0 mm) to prepare a test specimen for measurement, and dynamic viscoelasticity measurement Using a device (“DMS 6100” manufactured by Seiko Instruments Inc.), the distance between chucks was 8 mm, the frequency was 1 Hz, and the measurement temperature was 23 ° C. in a tensile mode. The storage elastic modulus is approximately 0.01 to 0.60 MPa in the sealing material composition, whereas the storage elastic modulus of the sealing material is in the range of 0.5 to 10 MPa. Preferably, the rate of change of at least 200%. Therefore, the thing of 200% or more of change rate of storage elastic modulus was evaluated as "(circle)" and less than 200% as "x". The evaluation results and the values of the change in storage modulus before and after curing from the sealing material composition to the sealing material are shown in the table.
 硬化性の別の評価方法として表面に粘着性を有する封止材組成物については、その粘着力が消失することで、粘着力を発現している液状ジエン系ゴムが反応して充分に硬化したものと判断することができる。 As for another evaluation method of the curability, with respect to the sealing material composition having adhesiveness on the surface, the pressure-sensitive adhesive force disappeared, and the liquid diene rubber exhibiting the adhesive force reacted and was sufficiently cured. It can be judged as a thing.
 (7)封止材の防水性(浸水試験): (7) Waterproofness of sealing material (water immersion test):
 封止材の防水性については、JIS C0920に規定されたIPX7規格の試験で評価した。具体的には、厚さ1mmのエポキシ樹脂基板に、5mm×5mmの水没検知シールを貼り、さらにその水没検知シールを覆うように10mm×10mm×1mmの封止材組成物を貼着してから紫外線を照射することで、エポキシ樹脂基板上の水没検知シールが封止材で被覆された試験片を作製した。この試験片を水深1mの水底に静止状態で30分置いた後に取り出し、水没検知シールが水を検知したか否かで評価した。水を検知しなかった場合を「〇」、水を検知した場合を「×」と評価した。この評価結果を表に示した。 The waterproofness of the sealing material was evaluated by the test of the IPX7 standard defined in JIS C0920. Specifically, a 5 mm × 5 mm submersion detection seal is attached to an epoxy resin substrate having a thickness of 1 mm, and a 10 mm × 10 mm × 1 mm sealing material composition is attached to cover the submersion detection seal. By irradiating ultraviolet light, a test piece in which the submersion detection seal on the epoxy resin substrate was covered with the sealing material was produced. The test piece was placed on the bottom of water at a depth of 1 m in a stationary state for 30 minutes and then taken out, and it was evaluated whether the submersion detection seal detected water or not. The case where water was not detected was evaluated as "o", and the case where water was detected was evaluated as "x". The evaluation results are shown in the table.
 (8)封止材の接着性: (8) Adhesiveness of sealing material:
 封止材は、必ずしも強い接着力は必要ないが、防水性を損なわない程度の接着力を備える必要がある。ここでは、前記IPX7の試験後の接着状態を確認し、試験後においても封止材が接着していたものを「○」、試験後に封止材が剥がれてしまったものを「×」と評価した。その評価結果を表に示した。 The sealing material does not necessarily have to have strong adhesion, but needs to have adhesion to a degree that does not impair the waterproofness. Here, the adhesion state after the test of the IPX 7 was confirmed, and those with the sealing material adhered even after the test were evaluated as “○”, and those with the sealing material peeled off after the test were evaluated as “X”. did. The evaluation results are shown in the table.
 (9)封止材の水蒸気透過度: (9) Water vapor permeability of sealing material:
 封止材は、液状の水を遮断するだけに留まらず、気体の水、すなわち水蒸気をも遮断できることが好ましい。この水蒸気の透過度については、JIS Z0208に規定されたカップ法で評価することができ、その水蒸気透過度は50g/m・24h以下とすることが好ましい。この水蒸気透過度試験は、厚さ1mmの封止材でなる試験片を作製して40℃、90%RHの条件で水蒸気透過度を測定することで行った。その測定値を表に示した。 The sealing material is preferably capable of blocking not only liquid water but also gaseous water, that is, water vapor. The water vapor permeability can be evaluated by the cup method defined in JIS Z0208, and the water vapor permeability is preferably 50 g / m 2 · 24 h or less. The water vapor transmission rate test was performed by preparing a test piece made of a sealing material having a thickness of 1 mm and measuring the water vapor transmission rate under the conditions of 40 ° C. and 90% RH. The measured values are shown in the table.
 <考 察> <Consideration>
 試料1~6は、エポキシ樹脂1とポリアミン1の比を一定にした合計質量と、液状ジエン系ゴム1の質量との比を変化させた試料である。これらの試料について見ると、試料1~試料4は定形性に優れているが、試料5の定形性は利用できる範囲にあるがやや悪化している。これは封止材組成物中で未反応となる液状ジエン系ゴムの割合が増えたこと及び反応生成物の架橋密度が低くなったことで定形性が悪化したものと思われる。このことから、エポキシ基を2個以上有するエポキシ化合物とポリアミンと液状ジエン系ゴムの合計量に対する液状ジエン系ゴムの割合は、95.3質量%以下であれば使用可能な程度の定形性を有し、94.2質量%以下であれば定形性が良いことがわかった。一方、液状ジエン系ゴムの割合が35.0質量%と少ない試料6では、エポキシ基を2個以上有するエポキシ化合物とポリアミンと液状ジエン系ゴムを混合したとき、均一な液状組成物を得ることができず、加熱した後も一部の成分が液状のまま流れ出る状態であり、定形性が「×」であったことから、エポキシ基を2個以上有するエポキシ化合物とポリアミンと液状ジエン系ゴムの合計量に対する液状ジエン系ゴムの割合は、35質量%を超えることが必要であり、試料1の結果から42.8質量%以上含めば定形性に優れることが確認できた。 Samples 1 to 6 are samples in which the ratio of the total mass of the epoxy resin 1 to the polyamine 1 to a constant ratio and the mass of the liquid diene rubber 1 was changed. As for these samples, although the samples 1 to 4 are excellent in formability, the formability of the sample 5 is in a usable range but is slightly deteriorated. This is considered to be the deterioration of the shaping property due to the increase in the proportion of the liquid diene rubber which becomes unreacted in the sealant composition and the decrease in the crosslink density of the reaction product. From this, the proportion of the liquid diene rubber with respect to the total amount of the epoxy compound having two or more epoxy groups, the polyamine, and the liquid diene rubber is 95.3% by mass or less, and has usable formability. It was found that if it is 94.2 mass% or less, the shape is good. On the other hand, in sample 6 in which the proportion of the liquid diene rubber is as low as 35.0% by mass, a uniform liquid composition can be obtained when an epoxy compound having two or more epoxy groups, a polyamine and a liquid diene rubber is mixed. It was not possible, and even after heating, some components flowed out in the form of liquid, and since the formability was "x", the total of the epoxy compound having two or more epoxy groups, the polyamine and the liquid diene rubber The ratio of the liquid diene rubber to the amount is required to exceed 35% by mass, and it was confirmed from the results of Sample 1 that the inclusion of 42.8% by mass or more results in excellent formability.
 試料1~5について、23℃における封止材組成物の貯蔵弾性率が0.004~0.75で、柔軟性にすぐれる封止材組成物であり、表面は粘着性を有しているものであった。ここで、液状ジエン系ゴムの割合が増えるほど貯蔵弾性率が低下する傾向が見られた。また、各試料について貯蔵弾性率の温度依存性はほとんど見られず、加熱した場合であっても、溶け出すことはなかった。 It is a sealing material composition with a storage elastic modulus of 0.004 to 0.75 of the sealing material composition at 23 ° C. and excellent in flexibility for samples 1 to 5, and the surface has adhesiveness. It was a thing. Here, the storage elastic modulus tended to decrease as the proportion of the liquid diene rubber increased. In addition, the temperature dependence of the storage elastic modulus was hardly observed for each sample, and even when heated, it did not melt out.
 また、試料1~5の封止材組成物のゲル分率は69.2~79.7%の範囲であった。ゲル分率の測定では未反応の液状ジエン系ゴムがトルエンに溶け出すため、反応してトルエンに不溶になった成分の存在が示唆される。前記ゲル分率からは、配合した液状ジエン系ゴムの半分以上が、なんらかの反応生成物を形成しており、貯蔵弾性率の温度依存性の結果から、エポキシ化合物のエポキシ基と液状ジエン系ゴムのカルボキシル基が反応して反応生成物を形成していることが示唆された。 Also, the gel fraction of the sealant compositions of Samples 1 to 5 was in the range of 69.2 to 79.7%. In the measurement of the gel fraction, the unreacted liquid diene rubber dissolves in toluene, which suggests the presence of a component which has become insoluble in toluene. From the gel fraction, more than half of the blended liquid diene rubber forms some reaction product, and from the result of temperature dependency of storage elastic modulus, it is possible to use epoxy group of epoxy compound and liquid diene rubber. It was suggested that the carboxyl group was reacted to form a reaction product.
 試料1~5の封止材組成物の切断時伸びは186~512%であり、伸び易く破れにくい性質を有するものだった。特に液状ジエン系ゴムの割合が50.0~94.2%のとき、切断時伸びが200%以上且つ最大引張応力が0.1MPa以上となるため、伸びに対する応力と千切れ難さのバランスに優れるものであった。 The elongation at break of the sealing material compositions of Samples 1 to 5 was 186 to 512%, and they had the property of being easy to stretch and hard to break. In particular, when the proportion of the liquid diene rubber is 50.0 to 94.2%, the elongation at break is 200% or more and the maximum tensile stress is 0.1 MPa or more. It was excellent.
 試料1~5について、各封止材組成物は光硬化性にも優れるものであった。硬化後の封止材の貯蔵弾性率は0.8~5.4MPaであった。この中で、特に液状ジエン系ゴムの割合が50.0%以上のものは貯蔵弾性率が4MPa以下であり、柔軟な封止材となった。また、液状ジエン系ゴム割合が88.9%以下のものは貯蔵弾性率が1MPa以上となり、ある程度の剛性を備えることがわかった。また、各試料は浸水試験の結果も良好であり、所定の接着力を有していた。また、何れも水蒸気透過度が20g/m・24h以下となり、所定の低透湿性を備えることがわかった。 For Samples 1 to 5, each encapsulant composition was also excellent in photocurability. The storage elastic modulus of the sealing material after curing was 0.8 to 5.4 MPa. Among them, in particular, those having a liquid diene rubber ratio of 50.0% or more had a storage elastic modulus of 4 MPa or less, and became a flexible sealing material. In addition, it was found that when the ratio of the liquid diene rubber is 88.9% or less, the storage elastic modulus is 1 MPa or more, and a certain degree of rigidity is provided. Moreover, each sample had a favorable result of the water immersion test, and had predetermined | prescribed adhesive force. In addition, it was found that the water vapor transmission rate was 20 g / m 2 · 24 h or less in all cases, and the film had a predetermined low moisture permeability.
 試料7は、液状ジエン系ゴムを配合しなかったものであり、加熱後に硬化したものの、極度に硬く、柔軟性に乏しい硬化物が得られた。この試料7については、粘着性、光硬化性を有しなかった。 Sample 7 did not contain a liquid diene rubber, and although cured after heating, a cured product which was extremely hard and poor in flexibility was obtained. About this sample 7, it did not have adhesiveness and photocurability.
 試料8は、エポキシ基を2個以上有するエポキシ化合物及びポリアミンを配合しなかったものであり、定形性を有する封止材組成物が得られなかった。したがって、封止材組成物に関する試験を実施できなかった。一方、紫外線を照射したのちは固形となり、封止材としての試験は実施することができた。 The sample 8 did not mix | blend the epoxy compound which has 2 or more of epoxy groups, and a polyamine, and the sealing material composition which has a fixed shape was not obtained. Therefore, the test on the encapsulant composition could not be performed. On the other hand, it became solid after irradiation with ultraviolet light, and the test as a sealing material could be carried out.
 試料9及び試料10は、エポキシ基を2個以上有するエポキシ化合物とポリアミンの配合量を変化させた試料である。試料1~6では、エポキシ基を2個以上有するエポキシ化合物とポリアミンの配合量は、エポキシ当量と活性水素当量が1:1となる配合としていたが、試料9はエポキシ基を2個以上有するエポキシ化合物が過剰、試料10はポリアミンが過剰となる配合とした。試料9及び試料10は、何れも封止材組成物及び封止材として所定の性質を有していた。 Sample 9 and Sample 10 are samples in which the blending amounts of the epoxy compound having two or more epoxy groups and the polyamine are changed. In the samples 1 to 6, the compounding amount of the epoxy compound having two or more epoxy groups and the polyamine was such that the epoxy equivalent and the active hydrogen equivalent become 1: 1, but the sample 9 is an epoxy having two or more epoxy groups The compound was in excess and sample 10 was in excess of polyamine. The sample 9 and the sample 10 both had predetermined properties as a sealant composition and a sealant.
 試料11は、エポキシ基を2個以上有するエポキシ化合物として、柔軟骨格を有しないビスフェノールFエポキシ樹脂を用いた試料である。試料11についても、試料3及び試料4とほぼ同等の試験結果であり、液状ジエン系ゴムの割合が高い場合には、エポキシ基を2個以上有するエポキシ化合物の種類を変えても、似た性質の封止材組成物及び封止材が得られることがわかった。 The sample 11 is a sample using a bisphenol F epoxy resin having no flexible skeleton as an epoxy compound having two or more epoxy groups. The sample 11 also has almost the same test results as the samples 3 and 4. When the proportion of the liquid diene rubber is high, similar properties are obtained even if the type of epoxy compound having two or more epoxy groups is changed. It was found that the encapsulant composition and the encapsulant of the present invention can be obtained.
 試料12及び試料13は、ポリアミンを配合しなかったことが特徴の試料である。すなわち、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムを主体とする液状組成物を調製し、これを加熱して封止材組成物を形成した試料である。 Samples 12 and 13 are samples characterized in that no polyamine was blended. That is, it is a sample in which a liquid composition mainly composed of an epoxy compound having two or more epoxy groups and a liquid diene rubber is prepared and heated to form a sealing material composition.
 試料12及び試料13の封止材組成物は、何れも定形性を有していた。このことから、エポキシ基を2個以上有するエポキシ化合物は、必ずしもポリアミン及びエポキシ樹脂の硬化剤と反応してマトリクスを形成しているわけではなく、エポキシ基を2個以上有するエポキシ化合物と液状ジエン系ゴムの反応生成物によっても、固化して定形性を与えることがわかった。また、このことは、後述の試料の試験結果から、エポキシ化合物のエポキシ基と液状ジエン系ゴムのカルボキシル基の反応によるものであることが示唆された。 The sealant compositions of Sample 12 and Sample 13 all had a fixed shape. From this, the epoxy compound having two or more epoxy groups does not necessarily react with the curing agent of the polyamine and the epoxy resin to form a matrix, but the epoxy compound having two or more epoxy groups and the liquid diene system It has been found that the reaction product of rubber also solidifies and gives shape. Moreover, it was suggested that this is due to the reaction of the epoxy group of the epoxy compound and the carboxyl group of the liquid diene rubber from the test results of the sample described later.
 試料12及び試料13の封止材組成物は、何れも試料3及び4と同等の性質を有しており貯蔵弾性率の温度依存性が小さいことも同じであった。試料12及び試料13の封止材についても、試料3及び試料4と同等の性質を有しており、ポリアミンを配合しない場合であっても、所定の封止材組成物及び封止材が得られることがわかった。 The sealing material compositions of Samples 12 and 13 both had properties equivalent to those of Samples 3 and 4, and the temperature dependency of the storage elastic modulus was also small. The sealing materials of Samples 12 and 13 have the same properties as Samples 3 and 4, and even when polyamine is not blended, predetermined sealing material compositions and sealing materials are obtained. Was found to be
 試料14及び試料15は、エポキシ基を2個以上有するエポキシ化合物を配合しなかったことが特徴の試料である。すなわち、ポリアミンと液状ジエン系ゴムを主体とする液状組成物を調製し、これを加熱して封止材組成物を形成した試料である。試料14及び試料15は、何れも定形性を有していた。このことから、エポキシ基を2個以上有するエポキシ化合物を含まない場合であっても、ポリアミンと液状ジエン系ゴムの反応生成物によって固化し、定形性を備えることがわかった。 Samples 14 and 15 are samples characterized in that the epoxy compound having two or more epoxy groups was not blended. That is, it is a sample in which a liquid composition mainly composed of a polyamine and a liquid diene rubber is prepared and heated to form a sealing material composition. The samples 14 and 15 both had a fixed shape. From this, it was found that, even when the epoxy compound having two or more epoxy groups is not contained, it is solidified by the reaction product of the polyamine and the liquid diene rubber and is provided with the formability.
 試料14及び試料15の封止材組成物は、23℃における貯蔵弾性率は比較的大きいものの、これまでの試料と異なり、貯蔵弾性率の温度依存性が大きいことが判明した。すなわち、加熱により貯蔵弾性率が大きく低下するのである。具体的には、60℃の貯蔵弾性率の値は23℃にくらべて試料14では4.3%、試料15では41%である。また、120℃の貯蔵弾性率は23℃にくらべて試料14では計算不能(少なくとも4.3%未満)、試料15では5.1%である。こうした試料は、加熱することで、より細かい凹凸へ追従させることができる点で優れる。このことは、ポリアミンと液状ジエン系ゴムは、3次元的な架橋構造の他に、トルエンの影響で乖離する弱い結合で相互作用した反応生成物を形成している可能性が示唆された。こうした反応としては、カルボキシル基とアミノ基の酸塩基相互作用及び(メタ)アクリロイル基とアミノ基の反応が考えられる。また、試料14及び試料15について、試料14のゲル分率は0%、試料15のゲル分率は82%と大きな差が生じたが、何れの試料も貯蔵弾性率の温度依存性は大きい結果だった。したがって、ポリアミンを主体として配合した場合には、得られた封止材組成物は、ゲル分率によらず、加熱により貯蔵弾性率を大きく低下させることができることがわかった。 Although the sealing material compositions of Sample 14 and Sample 15 have a relatively large storage elastic modulus at 23 ° C., it was found that the temperature dependence of the storage elastic modulus was large unlike the conventional samples. That is, the storage elastic modulus is greatly reduced by heating. Specifically, the storage modulus value at 60 ° C. is 4.3% for sample 14 and 41% for sample 15 as compared to 23 ° C. In addition, the storage modulus at 120 ° C. can not be calculated for sample 14 (at least less than 4.3%) compared to 23 ° C., and is 5.1% for sample 15. Such a sample is excellent in that it can follow finer irregularities by heating. This suggests that, in addition to the three-dimensional crosslinked structure, the polyamine and the liquid diene rubber may form a reaction product which is interacted by a weak bond which is separated by the influence of toluene. As such reaction, the acid-base interaction of a carboxyl group and an amino group and the reaction of a (meth) acryloyl group and an amino group are considered. In addition, for the samples 14 and 15, the gel fraction of the sample 14 was 0%, and the gel fraction of the sample 15 was 82%, with a large difference. was. Therefore, it was found that the storage material modulus obtained by heating can significantly decrease the storage elastic modulus regardless of the gel fraction when the polyamine is contained as the main component.
 一方、上記試料14及び試料15の封止材については、水蒸気透過率がやや高いものの、試料3及び試料4と同等の性質を有しており、エポキシ基を2個以上有するエポキシ化合物を配合しない場合であっても、封止材の性質は大きく変わらないことがわかった。 On the other hand, the sealing materials of the samples 14 and 15 have the same property as the samples 3 and 4 although they have a slightly high water vapor transmission rate, and do not contain an epoxy compound having two or more epoxy groups. Even in the case, it was found that the properties of the encapsulant did not change significantly.
 試料16から試料19は、液状ジエン系ゴムの種類を変更した試料である。具体的には、試料16は官能基を有しない液状ジエン系ゴムを用いた。試料17は酸無水物基を有し(メタ)アクリロイル基を有しない液状ジエン系ゴムを用いた。試料18は、カルボキシル基を有し(メタ)アクリロイル基を有しない液状ジエン系ゴムを用いた。試料19はカルボキシル基を有さず(メタ)アクリロイル基を有する液状ジエン系ゴムを用いたものである。 Samples 16 to 19 are samples in which the type of liquid diene rubber is changed. Specifically, sample 16 used liquid diene rubber having no functional group. Sample 17 used was a liquid diene rubber having an acid anhydride group and no (meth) acryloyl group. Sample 18 used was a liquid diene rubber having a carboxyl group and no (meth) acryloyl group. Sample 19 uses a liquid diene rubber having a carboxyl group and a (meth) acryloyl group.
 これらの試料について封止材組成物の定形性に注目すると、試料18は「○」、試料17は「△」であった。一方、残余の試料は定形性が「×」だった。このことから、定形性を備えるためには、カルボキシル基が大きな役割を果たしていることがわかった。また、カルボキシル基は無水物になると定形性を高める効果が大きく低下するものの、無水物の化合物であっても定形性を与える効果がやや残っていることがわかった。 When attention was paid to the formability of the encapsulant composition for these samples, sample 18 was “試 料” and sample 17 was “Δ”. On the other hand, the remaining samples had an "x" shape. From this, it was found that the carboxyl group plays a large role in providing the formality. In addition, it was found that although the effect of enhancing the formability of the carboxyl group is greatly reduced when it becomes an anhydride, the effect of providing the formability of the compound of the anhydride still remains to some extent.
 一方、封止材の光硬化性についても見ると(メタ)アクリロイル基を有する試料19は光硬化性が「○」だったが、残余の試料は光硬化性を有しないものだった。 On the other hand, when looking also at the photo-curing property of the sealing material, the sample 19 having (meth) acryloyl group was “○” in photo-curing property, but the remaining samples had no photo-curing property.
 以上の評価結果より、液状ジエン系ゴムは、カルボキシル基及び(メタ)アクリロイル基の両方を備えることが必要であることがわかった。 From the above evaluation results, it was found that the liquid diene rubber needs to have both a carboxyl group and a (meth) acryloyl group.
 試料20~試料22もまた試料12及び試料13と同様に、ポリアミンを配合しなかったことを特徴としながら、エポキシ樹脂と液状ジエン系ゴムの配合量を変えた試料であり、これらの何れも定形性を有していた。しかしながら、試料22では定形性が「△」となったことから液状ジエン系ゴムの割合は96.2よりも少ない方が好ましいことがわかった。 Samples 20 to 22 are also samples in which the compounding amounts of the epoxy resin and the liquid diene rubber are changed while the polyamine is not blended as in the samples 12 and 13, and any of these are shaped. Had sex. However, it was found that the proportion of the liquid diene rubber was preferably smaller than 96.2 because the sample of the sample 22 had a formability of “Δ”.
 試料23及び試料24は、試料12,13,20~22に加えて、(メタ)アクリロイル基を含まずエポキシ基と反応する官能基(カルボキシル基、酸無水物基、水酸基など)を含むジエン系ゴムを配合したものである。試料23及び試料24の封止材組成物は、切断伸びが200%以上且つ最大引張応力が0.2MPa以上となるため、非常に取扱い性に優れるとともに伸長による破断が生じ難いことがわかった。また、この試料23及び試料24の封止材についても柔軟性と伸縮性に優れていた。 Samples 23 and 24 are, in addition to the samples 12, 13, 20 to 22, a diene system containing a functional group (such as a carboxyl group, an acid anhydride group or a hydroxyl group) which does not contain a (meth) acryloyl group and reacts with an epoxy group. It contains rubber. Since the sealing material compositions of Sample 23 and Sample 24 had a breaking elongation of 200% or more and a maximum tensile stress of 0.2 MPa or more, they were found to be very easy to handle and to be resistant to breakage due to elongation. Moreover, the sealing materials of the samples 23 and 24 were also excellent in flexibility and stretchability.
 試料25と試料26は、カルボキシル基を有する液状ポリイソプレンゴムと、メタクリロイル基を有する液状ポリブタジエンゴムを用いた試料であり、両試料とも定形性は「△」であり、その他の試験の結果は「○」であった。 Samples 25 and 26 are samples using a liquid polyisoprene rubber having a carboxyl group and a liquid polybutadiene rubber having a methacryloyl group, both of the samples having the formability of “Δ”, the results of the other tests are “ Yes.

Claims (20)

  1. エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物と、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムとエポキシ基を2個以上有するエポキシ化合物の反応生成物と、光重合開始剤と、を含み定形性を備える封止材組成物。 The reaction product of an epoxy compound having two or more epoxy groups and a polyamine, the reaction product of a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and an epoxy compound having two or more epoxy groups And a photopolymerization initiator, and an encapsulant composition having a shape.
  2. 前記エポキシ基に対する反応性基がカルボキシル基であり、エポキシ基を2個以上有するエポキシ化合物とポリアミンの反応生成物と、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとエポキシ基を2個以上有するエポキシ化合物の反応生成物と、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとポリアミンの反応生成物と、光重合開始剤と、を含み定形性を備える請求項1記載の封止材組成物。 The reaction product of an epoxy compound having an epoxy group and a polyamine, wherein the reactive group for the epoxy group is a carboxyl group, and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine, and a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and two epoxy groups. The seal according to claim 1, comprising a reaction product of the epoxy compound possessed above, a reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine, and a photopolymerization initiator, and having a fixed shape. Stopper composition.
  3. エポキシ基を2個以上有するエポキシ化合物と、ポリアミンと、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムと、光重合開始剤と、を含む液状組成物の混合物である請求項1又は請求項2記載の封止材組成物。 It is a mixture of a liquid composition comprising an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator. The sealing material composition of Claim 1 or Claim 2.
  4. 前記液状組成物が、前記エポキシ基を2個以上有するエポキシ化合物及び前記ポリアミンの合計100質量部に対して、前記液状ジエン系ゴムを100~2000質量部含む請求項3記載の封止材組成物。 The sealing material composition according to claim 3, wherein the liquid composition contains 100 to 2000 parts by mass of the liquid diene rubber with respect to a total of 100 parts by mass of the epoxy compound having two or more epoxy groups and the polyamine. .
  5. エポキシ基を2個以上有するエポキシ化合物とエポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムの反応生成物と、光重合開始剤と、を含みポリアミンの反応生成物を含まずに定形性を備える封止材組成物。 A reaction product of an epoxy compound having two or more epoxy groups, a reaction product of a reactive group for the epoxy group and a liquid diene rubber having a (meth) acryloyl group, and a photopolymerization initiator, and a reaction product of a polyamine is not included. Sealant composition having a fixed shape.
  6. 前記エポキシ基に対する反応性基がカルボキシル基である請求項5記載の封止材組成物。 The encapsulant composition according to claim 5, wherein the reactive group for the epoxy group is a carboxyl group.
  7. エポキシ基を2個以上有するエポキシ化合物と、エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムと、光重合開始剤と、を含みポリアミンが含まれない液状組成物の混合物である請求項5又は請求項6記載の封止材組成物。 A mixture of a liquid composition containing an epoxy compound having two or more epoxy groups, a liquid diene rubber having a reactive group for the epoxy group and a (meth) acryloyl group, and a photopolymerization initiator and containing no polyamine The sealing material composition according to claim 5 or 6.
  8. 前記液状組成物が、前記エポキシ基を2個以上有するエポキシ化合物100質量部に対して、前記液状ジエン系ゴムを100~2600質量部含む請求項7記載の封止材組成物。 8. The encapsulant composition according to claim 7, wherein the liquid composition comprises 100 to 2600 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups.
  9. 前記液状組成物にさらにポリアミン以外のエポキシ樹脂の硬化剤を含む請求項3,4,7又は8何れか1項記載の封止材組成物。 The encapsulant composition according to any one of claims 3, 4, 7, and 8, further comprising a curing agent of an epoxy resin other than a polyamine in the liquid composition.
  10. (メタ)アクリロイル基を有せずエポキシ基に対する反応性基を有する液状ジエン系ゴムをさらに含む請求項1~請求項9何れか1項記載の封止材組成物。 The encapsulant composition according to any one of claims 1 to 9, further comprising a liquid diene rubber having no (meth) acryloyl group and having a reactive group to an epoxy group.
  11. エポキシ基に対する反応性基と(メタ)アクリロイル基を有する液状ジエン系ゴムが、(メタ)アクリロイル基を有しエポキシ基に対する反応性基を有しない第1の液状ジエン系ゴムと、エポキシ基に対する反応性基を有し(メタ)アクリロイル基を有しない第2の液状ジエン系ゴムの混合物である請求項1~請求項9何れか1項記載の封止材組成物。 A liquid diene rubber having a reactive group to epoxy group and a (meth) acryloyl group has a first liquid diene rubber having a (meth) acryloyl group and no reactive group to epoxy group, and a reaction to epoxy group The sealing material composition according to any one of claims 1 to 9, which is a mixture of a second liquid diene rubber having a functional group and not having a (meth) acryloyl group.
  12. (メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムとポリアミンの反応生成物と、光重合開始剤と、を含みエポキシ基を2個以上有するエポキシ化合物の反応生成物を含まずに定形性を備える封止材組成物。 It contains the reaction product of a liquid diene rubber having a (meth) acryloyl group and a carboxyl group and a polyamine, and a photopolymerization initiator, and does not contain the reaction product of an epoxy compound having two or more epoxy groups, and does not contain formability Sealant composition provided.
  13. ポリアミンと、(メタ)アクリロイル基とカルボキシル基を有する液状ジエン系ゴムと、光重合開始剤と、を含みエポキシ基を2個以上有するエポキシ化合物を含まない液状組成物の混合物である請求項12記載の封止材組成物。 A liquid composition comprising a polyamine, a liquid diene rubber having a (meth) acryloyl group and a carboxyl group, and a photopolymerization initiator, and containing no epoxy compound having two or more epoxy groups. Sealant composition.
  14. 前記液状組成物が、前記ポリアミン100質量部に対して、前記液状ジエン系ゴムを100~2000質量部含む請求項13記載の封止材組成物。 The encapsulant composition according to claim 13, wherein the liquid composition comprises 100 to 2000 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the polyamine.
  15. 請求項1~請求項14何れか1項記載の封止材組成物の光硬化体である封止材。 An encapsulant as a photocured body of the encapsulant composition according to any one of claims 1 to 14.
  16. 貯蔵弾性率が0.7~5.4MPaである請求項15記載の封止材。 The encapsulant according to claim 15, which has a storage elastic modulus of 0.7 to 5.4 MPa.
  17. 請求項15又は請求項16記載の封止材で電子素子が封止された電子基板。 The electronic board | substrate with which the electronic device was sealed by the sealing material of Claim 15 or Claim 16.
  18. 封止材の厚さTに対する前記電子素子の高さTが、T>Tであるとともに、前記電子素子の凹凸を埋めた封止材表面が略平滑である請求項17記載の電子基板。 Height T 2 of the electronic element to the thickness T 1 of the sealing material, together with a T 1> T 2, according to claim 17, wherein uneven sealing material surface filling the said electronic device is a substantially smooth Electronic substrate.
  19. 封止材の厚さTに対する前記電子素子の高さTが、T≦Tであるとともに、前記電子素子の外面に沿って前記封止材が密着している請求項17記載の電子基板。 Height T 2 of the electronic element to the thickness T 1 of the sealing material, together with a T 1 ≦ T 2, along the outer surface of the electronic element of the sealing material according to claim 17, wherein in close contact Electronic substrate.
  20. 貯蔵弾性率が0.7~50MPaであるフレキシブル基材を備える請求項17~請求項19何れか1項記載の電子基板。 The electronic substrate according to any one of claims 17 to 19, comprising a flexible substrate having a storage elastic modulus of 0.7 to 50 MPa.
PCT/JP2018/039101 2017-10-27 2018-10-19 Sealing material composition, sealing material, and electronic substrate WO2019082828A1 (en)

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