WO2019082828A1 - Composition de matériau d'étanchéité, matériau d'étanchéité et substrat électronique - Google Patents

Composition de matériau d'étanchéité, matériau d'étanchéité et substrat électronique

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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
English (en)
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/zh
Priority to JP2019509573A priority patent/JP6653801B2/ja
Publication of WO2019082828A1 publication Critical patent/WO2019082828A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Epoxy Resins (AREA)
  • Sealing Material Composition (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Electroluminescent Light Sources (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de pourvoir à une composition de matériau d'étanchéité, et à un matériau d'étanchéité qui élimine la nécessité de mettre en œuvre un chauffage après le revêtement d'un élément électronique, etc., et qui est souple et présente des propriétés de maintien de forme. La solution selon l'invention porte sur une composition de matériau d'étanchéité comprenant des propriétés de maintien de forme, la composition de matériau d'étanchéité comprenant : un produit de réaction d'une polyamine et d'un composé époxy ayant au moins deux groupes époxy ; un produit de réaction d'un composé époxy ayant au moins deux groupes époxy et d'un caoutchouc diénique liquide, qui possède un groupe (méth)acryloyle et un groupe qui réagit avec les groupes époxy ; et un initiateur de photopolymérisation. L'invention concerne également un matériau d'étanchéité qui est un article photo-durci de la composition de matériau d'étanchéité.
PCT/JP2018/039101 2017-10-27 2018-10-19 Composition de matériau d'étanchéité, matériau d'étanchéité et substrat électronique WO2019082828A1 (fr)

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Citations (5)

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JPH0539409A (ja) * 1991-08-02 1993-02-19 Idemitsu Petrochem Co Ltd エポキシ樹脂組成物
JPH06212138A (ja) * 1992-11-02 1994-08-02 Lord Corp 耐熱性の構造用接着剤組成物
JP2000178400A (ja) * 1998-12-17 2000-06-27 Shin Etsu Polymer Co Ltd ポリブタジエン系熱硬化性樹脂組成物
JP2009084518A (ja) * 2007-10-03 2009-04-23 Toray Fine Chemicals Co Ltd 接着剤組成物
JP2016147930A (ja) * 2015-02-10 2016-08-18 昭和電工株式会社 半導体用接着剤並びに半導体装置及びその製造方法

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JP4918962B2 (ja) * 2004-06-25 2012-04-18 株式会社スリーボンド 光硬化性組成物
JP5565588B2 (ja) * 2011-03-22 2014-08-06 スリーボンドファインケミカル株式会社 液晶滴下工法用シール剤
KR101664765B1 (ko) * 2013-12-04 2016-10-12 주식회사 쿠라레 변성 액상 디엔계 고무 및 그 제조 방법
JP5778303B2 (ja) * 2014-02-28 2015-09-16 古河電気工業株式会社 電子デバイス封止用樹脂組成物および電子デバイス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0539409A (ja) * 1991-08-02 1993-02-19 Idemitsu Petrochem Co Ltd エポキシ樹脂組成物
JPH06212138A (ja) * 1992-11-02 1994-08-02 Lord Corp 耐熱性の構造用接着剤組成物
JP2000178400A (ja) * 1998-12-17 2000-06-27 Shin Etsu Polymer Co Ltd ポリブタジエン系熱硬化性樹脂組成物
JP2009084518A (ja) * 2007-10-03 2009-04-23 Toray Fine Chemicals Co Ltd 接着剤組成物
JP2016147930A (ja) * 2015-02-10 2016-08-18 昭和電工株式会社 半導体用接着剤並びに半導体装置及びその製造方法

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JPWO2019082828A1 (ja) 2019-11-14
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CN111164119A (zh) 2020-05-15
TWI787371B (zh) 2022-12-21
TW201925335A (zh) 2019-07-01

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