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WO2019194041A1 - Composition de résine époxy en forme de feuille et son produit durci, et feuille d'étanchéité - Google Patents

Composition de résine époxy en forme de feuille et son produit durci, et feuille d'étanchéité Download PDF

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Publication number
WO2019194041A1
WO2019194041A1 PCT/JP2019/013183 JP2019013183W WO2019194041A1 WO 2019194041 A1 WO2019194041 A1 WO 2019194041A1 JP 2019013183 W JP2019013183 W JP 2019013183W WO 2019194041 A1 WO2019194041 A1 WO 2019194041A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
sheet
resin composition
epoxy
sealing
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2019/013183
Other languages
English (en)
Japanese (ja)
Inventor
高木　正利
裕介 富田
祐五 山本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
Original Assignee
Mitsui Chemicals Inc
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 Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to CN201980023888.1A priority Critical patent/CN111936543B/zh
Priority to JP2020511716A priority patent/JP7084472B2/ja
Priority to KR1020207027243A priority patent/KR102439370B1/ko
Publication of WO2019194041A1 publication Critical patent/WO2019194041A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the present invention relates to a sheet-like epoxy resin composition, a cured product thereof, and a sealing sheet.
  • Organic EL (Electro-Luminescence) elements have recently been widely used in displays and lighting devices because of their low power consumption. Since organic EL elements are easily deteriorated by moisture and oxygen in the air, they are generally used after being sealed with a sealing material or the like.
  • a sheet-like resin composition containing an epoxy resin has been proposed as a sealing sheet for sealing an organic EL element.
  • a low molecular weight epoxy resin, a high molecular weight epoxy resin, and a latent imidazole series A sheet-like epoxy resin composition containing a compound and a silane coupling agent has been proposed (for example, Patent Document 1 and Patent Document 2).
  • Patent Document 3 a composition containing dicyclopentadienediol diglycidyl ether, a compound having an oxetane ring, and a photocationic polymerization initiator has been proposed ( Patent Document 3).
  • a sealing sheet such as an organic EL element is usually used after being in close contact with a display element and then curing the sealing sheet.
  • a sealing sheet such as an organic EL element is usually used after being in close contact with a display element and then curing the sealing sheet.
  • the temperature at which the sealing sheet is cured is too high, there is a problem that the organic EL element is affected by the heat at the time of curing or the productivity of the display device is reduced.
  • the sealing sheet when the curability of the sealing sheet is too high, the sealing sheet is cured during storage of the sealing sheet, which causes a problem that the sealing element cannot be sufficiently bonded.
  • the sealing sheet needs to be processed into a sheet shape or set in an apparatus for bonding to a display element, and the exposure time to the manufacturing environment temperature is longer than that of a liquid sealing material. Therefore, higher storage stability is required as compared with a liquid sealing material.
  • an object is to provide a sheet-like epoxy resin composition that can be cured at a relatively low temperature and that is excellent in storage stability.
  • the first of the present invention relates to the following sheet-like epoxy resin composition.
  • A an epoxy compound represented by the following general formula (1)
  • B an epoxy resin having an aromatic ring and having a weight average molecular weight of 3000 to 100,000
  • C And a cationic polymerization initiator represented by formula (2), wherein the content of the epoxy resin (B) is 45% by mass or more.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms or a naphthylmethyl group
  • R 2 represents an alkyl group having 1 to 4 carbon atoms
  • the second aspect of the present invention relates to the following sealing sheet and cured product.
  • a sealing sheet comprising a layer made of the sheet-like epoxy resin composition according to any one of [1] to [5].
  • the sealing sheet according to [6] having a protective film on at least one surface of the layer made of the sheet-like epoxy resin composition.
  • the sealing sheet according to [6] or [7] which is used for surface sealing of the display element.
  • the sheet-like epoxy resin composition of the present invention can be cured at a relatively low temperature, while having high storage stability. Therefore, it is suitable for a sealing material for sealing various display elements.
  • Sheet-like epoxy resin composition of the present invention is used for, for example, a sealing sheet (surface sealing sheet), a transparent coating sheet, and the like, and particularly a sealing sheet (surface sealing sheet). ).
  • a sheet-like epoxy resin composition is used for the sheet
  • seat for transparent coatings means the material for which the transparency which fills between image display apparatuses, such as board
  • the sheet-like epoxy resin composition for surface-sealing display elements, etc. can be softened at a relatively low temperature so as not to affect the display elements, and can be cured at a relatively low temperature. It is required to be. On the other hand, the sheet-like epoxy resin composition is also required to be difficult to be deformed or cured before being attached to the display element, that is, storage stability. However, the conventional sheet-like epoxy resin composition has a problem that it is difficult to achieve both good curability and storage stability before bonding.
  • the present inventors have intensively studied (A) an epoxy compound having a specific structure, (B) an epoxy resin having an aromatic ring and a weight average molecular weight of 3000 to 100,000, C) By combining with a cationic polymerization initiator having a specific structure, it can be bonded to a display element at an appropriate temperature (for example, about 60 ° C.), and further relatively low temperature (for example, 90 ° C. or lower). ) And the storage stability before bonding to the display element was found to be very good.
  • the sheet-like epoxy resin composition of the present invention combines these is considered as follows. Since a certain amount of the (B) epoxy resin is contained in the sheet-like epoxy resin composition, the sheet-like epoxy resin composition is hardly softened or melted during storage, and the shape can be maintained. In addition, when only (B) an epoxy resin is used, the curing temperature tends to be high, but since (A) an epoxy compound is included, the epoxy group tends to react even at a relatively low temperature (eg, 90 ° C. or less). The curability of the sheet-like epoxy resin composition is improved.
  • Epoxy compound (A) is a compound having a structure represented by the following general formula (1) and has a dicyclopentadiene skeleton.
  • the bonding position of the group bonded to the dicyclopentadiene skeleton is not particularly limited.
  • the sheet-like epoxy resin composition only one type of compound having a structure represented by the following general formula (1) may be included, or two or more types may be included.
  • the above (A) epoxy compound is liquid at 23 ° C. Since the (A) epoxy compound has a dicyclopentadiene structure, the reactivity of the epoxy group is likely to be good, and as described above, the sheet-like epoxy resin composition is easily cured even at a relatively low temperature.
  • the epoxy compound may be prepared by a known method, but may be a commercially available product.
  • Examples of commercially available epoxy compounds include EP-4088L and EP-4088S manufactured by ADEKA.
  • the amount of the (A) epoxy compound contained in 100 parts by mass of the sheet-like epoxy resin composition is preferably 10 to 50 parts by mass, more preferably 10 to 40 parts by mass, More preferably, it is 30 parts by mass.
  • the amount of the (A) epoxy compound is 10 parts by mass or more, the (A) epoxy compound and the (B) epoxy resin are likely to react at 90 ° C. or less, and the curability of the sheet-like epoxy resin composition is good. Prone.
  • the amount of (A) the epoxy compound is 50 parts by mass or less, the amount of (B) the epoxy resin is relatively sufficient, and the storage stability of the sheet-like epoxy resin composition is likely to be increased.
  • Epoxy resin (B)
  • the epoxy resin is not particularly limited as long as it has at least one aromatic ring and one epoxy group in the molecule and has a weight average molecular weight of 3000 to 100,000.
  • the sheet-like epoxy resin composition may contain only one type of (B) epoxy resin, or may contain two or more types.
  • the epoxy resin composition is usually solid at normal temperature (23 ° C.).
  • the weight average molecular weight of the epoxy resin is preferably 6000 to 60000, and more preferably 7000 to 40000. When the molecular weight of the (B) epoxy resin is 3000 or more, the (B) epoxy resin tends to be solid at room temperature. On the other hand, when the weight average molecular weight of the (B) epoxy resin is 1000000 or less, the fluidity of the sheet-like epoxy resin composition can be improved when the sheet-like epoxy resin composition is bonded to a display element or the like. It becomes easy to adhere to an element or the like.
  • the said weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography (GPC).
  • the epoxy equivalent of the (B) epoxy resin is preferably 900 g / eq or more and 20000 g / eq or less, and more preferably 1000 g / eq or more and 200000 g / eq or less.
  • the epoxy equivalent of the epoxy resin is 900 g / eq or more, the tackiness at room temperature of the sheet-like epoxy resin composition is reduced. As a result, the handleability when the sheet-shaped epoxy resin composition is bonded to the display element is likely to be good, and the sheet-like epoxy resin composition is easily bonded accurately on the display element.
  • the epoxy equivalent of the (B) epoxy resin is preferably 20000 g / eq or less.
  • the epoxy equivalent of an epoxy resin is the said range, the melting temperature of a sheet-like epoxy resin composition will become a moderate range, and it will become possible to bond together with a display element at desired temperature.
  • the said (B) epoxy resin contains a some epoxy resin, it is preferable that the epoxy equivalent of each epoxy resin is the said range.
  • the epoxy resin may contain one or more epoxy groups in the molecule, but preferably contains a plurality of epoxy groups so as to satisfy the above-mentioned epoxy equivalent. Moreover, (B) epoxy resin should just contain one or more aromatic rings in a molecule
  • epoxy resins include bisphenol A type, bisphenol F type, bisphenol E type, bisphenol S type, bisphenol AD type, and mixed types thereof, such as bisphenol type epoxy resins; diphenyl ether type epoxy resins; phenol novolac type, Cresol novolak type, biphenyl novolak type, bisphenol novolak type, naphthol novolak type, trisphenol novolak type, dicyclopentadiene novolak type, etc. novolac type epoxy resin; biphenyl type epoxy resin; naphthyl type epoxy resin; triphenolmethane type, triphenol Ethane type, triphenolalkane type epoxy resin such as triphenolpropane type; and the like.
  • the epoxy resin is preferably a bisphenol type epoxy resin or a biphenyl type epoxy resin among the above.
  • the amount of the bisphenol F skeleton in the epoxy resin increases, the softening point of the (B) epoxy resin tends to decrease. Therefore, when the melting temperature of the sheet-like epoxy resin composition is set to a relatively high temperature, it is preferable to use an epoxy resin having a small bisphenol F skeleton.
  • the amount of (B) epoxy resin contained in 100 parts by mass of the sheet-like epoxy resin composition is 45 parts by mass or more, preferably 50 to 85 parts by mass, and more preferably 60 to 75 parts by mass. .
  • (B) When the amount of the epoxy resin is 50 parts by mass or more, the storage stability of the sheet-like epoxy resin composition is likely to be increased, and further, the bonding temperature of the sheet-like epoxy resin composition is likely to be within an appropriate range. .
  • C Cationic polymerization initiator
  • the cationic polymerization initiator is a compound represented by the following general formula (2). Only 1 type (C) cationic polymerization initiator may be contained in the sheet-like epoxy resin composition, and 2 or more types may be contained.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms or a naphthylmethyl group, and a naphthylmethyl group is particularly preferable.
  • R 2 represents an alkyl group having 1 to 4 carbon atoms, and a methyl group is particularly preferable.
  • (C) the cationic polymerization initiator is particularly preferably a compound represented by the following formula (2a).
  • the cationic polymerization initiator may be prepared by a known method or may be a commercially available product. Examples of commercially available products include trade name SI-60 manufactured by Sanshin Chemical Industry Co., Ltd.
  • the amount of the cationic polymerization initiator (C) contained in 100 parts by mass of the sheet-like epoxy resin composition is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass. More preferably, it is a part.
  • (C) When the amount of the cationic polymerization initiator is 1 part by mass or more, the curability of the sheet-like epoxy resin composition tends to be good. On the other hand, when the amount of (C) the cationic polymerization initiator is 10 parts by mass or less, the storage stability of the sheet-like epoxy resin composition is likely to be increased.
  • Examples of other components include other resins, fillers, modifiers, stabilizers, and the like.
  • Examples of other resins include (A) epoxy compound and (B) epoxy resin not corresponding to epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene-styrene block Copolymers, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, silicon-based oligomers, polysulfide-based oligomers and the like are included.
  • the sheet-like epoxy resin composition may contain only one kind or two or more kinds.
  • the filler examples include glass beads, styrene polymer particles, methacrylate polymer particles, ethylene polymer particles, propylene polymer particles, and the like.
  • the sheet-like epoxy resin composition may contain only one type of filler, or may contain two or more types.
  • the modifier include a polymerization initiator, an anti-aging agent, a leveling agent, a wettability improver, a surfactant, a plasticizer, a solvent, a silane coupling agent, and the like.
  • a polymerization initiator an anti-aging agent, a leveling agent, a wettability improver, a surfactant, a plasticizer, a solvent, a silane coupling agent, and the like.
  • One of these modifiers may be included, or two or more thereof may be included.
  • the sheet-like epoxy resin composition may contain only one kind or two or more kinds.
  • the above-mentioned sheet-like epoxy resin composition can be manufactured by arbitrary methods, unless the effect of this invention is impaired.
  • the sheet-like epoxy resin composition of the present invention is prepared by, for example, dissolving a resin composition containing (A) an epoxy compound, (B) an epoxy resin, and (C) a cationic polymerization initiator in various solvents at 30 ° C. or lower.
  • the varnish can be applied to the base material in the form of a sheet and dried.
  • solvents examples include aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether Ethers such as propylene glycol or dialkyl ether; aprotic polar solvents such as N-methylpyrrolidone, dimethylimidazolidinone and dimethylformaldehyde; esters such as ethyl acetate and butyl acetate.
  • aromatic solvents such as toluene and xylene
  • ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • ethers dibutyl ether, tetrahydrofuran, dioxane,
  • the (A) epoxy compound, (B) epoxy resin, (C) cationic polymerization initiator, and solvent may be mixed at one time. After the (B) epoxy resin or the like is dissolved in the solvent, other components are mixed. May be added. Examples of the mixing method include a known stirring method and a kneading method using three rolls.
  • the varnish application method is not particularly limited, and examples thereof include screen printing, dispenser application, various roll methods, and the like. Moreover, it does not restrict
  • the drying temperature and drying time of the varnish are the temperature and time at which (A) the epoxy compound and (B) the epoxy resin are not cured.
  • the drying temperature is 20 to 100 ° C.
  • the drying time can be about 1 minute to 3 hours, for example.
  • the drying method is not particularly limited, and examples thereof include hot air drying and vacuum drying.
  • the thickness of the sheet-like epoxy resin composition is appropriately selected depending on the application, but is, for example, 1 to 100 ⁇ m when used as a sealing material for display elements. It is preferably 5 to 50 ⁇ m, more preferably 10 to 30 ⁇ m.
  • the melting temperature of the sheet-like epoxy resin composition is preferably 35 ° C. or more and 60 ° C. or less, and is 40 to 56 ° C. when the tackiness at the time of working the sheet-like epoxy resin composition is lowered. Is preferred.
  • the sheet-like epoxy resin composition and the display element are bonded together, the sheet-like epoxy resin composition is softened (melted) so that a gap with the display element is hardly generated and can be adhered.
  • the melting temperature of the sheet-like epoxy resin composition is 60 ° C. or less, the sheet-like epoxy resin composition can be bonded to the display element at a relatively low temperature (60 ° C. or less).
  • the melting temperature of the sheet-like epoxy resin composition is 35 ° C.
  • the tackiness at the time of working the sheet-like epoxy resin composition is low, and the workability tends to be good. Further, when the sheet-like epoxy resin composition is stored, the sheet-like epoxy resin composition is hardly deformed, and the shape can be maintained.
  • the melting temperature can be measured as follows.
  • the sheet-like epoxy resin composition is cut into a length of about 30 mm and a width of about 5 mm to produce a strip-shaped test piece.
  • the test piece is brought into close contact with a glass plate heated on a hot plate. Thereafter, the test piece is gradually peeled from the glass plate in the 180 ° direction.
  • This operation is started at a preset temperature of 40 ° C. of the hot plate, and each time the set temperature is raised by 1 ° C., a strip-shaped test piece is newly prepared and repeated, and the adhesive peelability of the layer made of the sheet-like epoxy resin composition at the time of peeling
  • the temperature at which becomes the largest is the melting temperature. However, at 40 ° C., those having already high adhesive peelability are measured for melting temperature from 25 ° C.
  • the melting temperature of the sheet-like epoxy resin composition after being stored at 40 ° C. for 17 hours is preferably within the range of the melting temperature ⁇ 10 ° C. of the sheet-like epoxy resin composition before storage, and within ⁇ 5 ° C. More preferably.
  • the said temperature change becomes a parameter
  • index of the storage stability of a sheet-like epoxy resin composition if a temperature change is 10 degrees C or less, it can be said that it is hard to produce a curing reaction etc. at the time of storage.
  • the melting temperature of the sheet-like epoxy resin composition changes greatly during storage, it becomes necessary to change the temperature, pressure, etc. when the sheet-like epoxy resin composition is bonded to a display element or the like in accordance with the change.
  • the heat generation starting temperature measured by a differential scanning calorimeter (DSC) of the sheet-like epoxy resin composition is preferably 60 ° C. or higher and 90 ° C. or lower, and more preferably 65 to 85 ° C.
  • the exothermic start temperature is 60 ° C. or higher
  • the (A) epoxy compound or the (B) epoxy resin is difficult to cure at the time of molding the sheet-like epoxy resin composition, at the time of storing the sheet-like epoxy resin composition, Storage stability is improved.
  • the heat generation starting temperature is 90 ° C. or lower, the sheet-like epoxy resin composition can be cured at 90 ° C. or lower, and the display element and the like are hardly affected.
  • the heat generation start temperature can be measured by the following method.
  • the epoxy reaction rate when the sheet-like epoxy resin composition is heated at 85 ° C. for 50 minutes is preferably 80% or more, and more preferably 85% or more.
  • the said epoxy reaction rate is a parameter
  • the said epoxy reaction rate is 80% or more, it can be said that a sheet-like epoxy resin composition can fully be hardened even at 90 degrees C or less.
  • the light transmittance at a wavelength of 550 nm is preferably 90% or more, more preferably 95% or more. Preferably, it is 97% or more.
  • the sheet-shaped epoxy resin composition can be used for applications requiring light transmittance.
  • the light transmittance of the cured product of the sheet-like epoxy resin composition can be measured by the following procedure.
  • a laminate comprising a base film and a sheet-like epoxy resin composition having a thickness of 20 ⁇ m prepared on the base film is cut into a length of about 60 mm and a width of about 40 mm to obtain a test piece.
  • Bubbles entered into the glass plate No. 3 made by Matsunami Glass, thickness 0.3 mm, 70 mm ⁇ 50 mm
  • a hot plate heated to 70 ° C. of the layer made of the sheet-like epoxy resin composition of this test piece. Transfer and stick together with a roll.
  • the test piece is removed from the hot plate and allowed to cool for 3 minutes.
  • the base film is peeled off, and the sheet-like epoxy resin composition on the glass plate is heated in an oven at 85 ° C. for 50 minutes to obtain a cured product.
  • the light transmittance at a wavelength of 550 nm of the glass plate on which the cured product of the sheet-like epoxy resin composition is formed is measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV-2550). In the measurement, the light transmittance of the glass plate alone is used as the baseline. In addition, you may perform the measurement of the transmittance
  • the sealing sheet of the present invention includes a layer made of the above-described sheet-like epoxy resin composition.
  • the sealing sheet of the present invention is a laminate of a base film, the above-described sheet-shaped epoxy resin composition disposed on the base film, and a protective film disposed on the sheet-shaped epoxy resin composition. It can be a body or the like.
  • the base film or the protective film examples include known release films. These films are preferably films having moisture barrier properties and gas barrier properties, such as polyethylene terephthalate films. Although depending on the film material, the thickness of the base film can be set to about 50 ⁇ m from the viewpoint of followability to a sealing material such as an organic EL element.
  • the protective film is preferably laminated on a layer made of a sheet-like epoxy resin composition. Lamination can be performed at about 70 ° C. using a laminator, for example. The thickness of the protective film can also be about 20 to 40 ⁇ m depending on the film material.
  • the sealing sheet of the present invention may further include a gas barrier layer depending on the application.
  • the gas barrier layer is a layer that suppresses permeation of moisture and gas.
  • Such a gas barrier layer can be disposed adjacent to the sheet-like epoxy resin composition, for example.
  • the gas barrier layer examples include metals such as Al, Cr, Ni, Cu, Zn, Si, Fe, Ti, Ag, Au, and Co; oxides of these metals; nitrides of these metals; Oxynitrides; resins such as polyethylene terephthalate and polycarbonate are included.
  • the gas barrier layer may be composed of one kind of material or may be composed of two or more kinds of materials.
  • the gas barrier layer is preferably a layer having high light reflectance
  • the gas barrier layer can be a layer made of, for example, Al or Cu.
  • the gas barrier layer is preferably a light-transmitting layer.
  • the layer can be a layer made of, for example, polyethylene terephthalate or polycarbonate.
  • the thickness of the gas barrier layer can be about 10 to 3000 ⁇ m.
  • the method for forming the gas barrier layer is not particularly limited, and examples of the dry process include various PVD methods such as vacuum deposition, sputtering, and ion plating; and CVD methods such as plasma CVD. Examples of the wet process include a plating method and a coating method.
  • the sealing sheet of the present invention is used after a layer made of a sheet-like epoxy resin composition is brought into close contact with a desired material to be sealed and then a layer made of the sheet-like epoxy resin composition is cured.
  • the material to be sealed which is an object to be sealed, is not particularly limited, and examples thereof include an organic EL element, a liquid crystal element, and an LED element.
  • Epoxy compound EP-4088L manufactured by ADEKA dicyclopendiene type epoxy compound represented by the following general formula: epoxy equivalent 165 g / eq
  • Epoxy resin jER4005P bisphenol F type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 950 g / eq, Mw 7582 YX6954B35: Biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 10,000 g / eq, Mw36691 -JER4275: Mitsubishi Chemical Corporation bisphenol A / bisphenol F type epoxy resin, epoxy equivalent 8,400 g / eq, Mw58287
  • Example 1 30 parts by mass of EP-4088L, 50 parts by mass of jER4005P, and 20 parts by mass (in terms of solid content) of YX6954B35 were added to the flask, and 100 parts by mass of methyl ethyl ketone was added thereto and stirred and dissolved at room temperature. To this solution, 2.5 parts by weight of cationic polymerization initiator SI-60 and 1 part by weight of KBM-403 were added and stirred at room temperature to prepare a varnish.
  • the prepared varnish was coated with an applicator using a coating machine on a base film (release-treated PET film A53 (manufactured by Teijin Film Solutions Co., Ltd.) thickness 50 ⁇ m) so that the thickness after drying was about 20 ⁇ m.
  • This film was dried in a 90 ° C. inert oven for 3 minutes, and the MEK in the varnish coating film was removed by drying to form a layer made of a sheet-like epoxy resin composition on the base film.
  • the protective film Release processing PET film A31 (made by Teijin Film Solutions) thickness 38 micrometers
  • the protective film was peeled off as appropriate, and the surface of the layer made of the sheet-like epoxy resin composition was exposed for use.
  • Examples 2 to 10 and Comparative Examples 1 to 10 Varnishes were prepared in the same manner as in Example 1 with the composition ratios (mass ratios) shown in Tables 1 and 2. This was coated and dried to obtain a sealing sheet having a layer made of a sheet-like epoxy resin composition.
  • Epoxy reaction rate at a curing temperature of 85 ° C. (%) A measurement sample was prepared in the same manner as the uncured product. Curing was performed in an oven set to 85 ° C. in advance, and a measurement sample was taken out 50 minutes after the sample was put in. Then, the calorific value of the cured product was specified by DSC at a heating rate of 5 ° C./min and a measurement temperature range of 20 ° C. to 300 ° C. And the epoxy reaction rate (%) in the curing temperature of 85 degreeC was calculated
  • required from the measured calorific value from the formula shown below. Reaction rate (%) (Heat generation amount of uncured product ⁇ Heat generation amount after curing) / Heat generation amount of uncured product ⁇ 100
  • the sealing sheet obtained in the example or the comparative example was cut into a length of about 150 mm and a width of about 40 mm to obtain a strip-shaped test piece.
  • the layer made of the sheet-like epoxy resin composition of the test piece was transferred and pasted onto a glass plate heated on a hot plate heated to 70 ° C. with a roll so as not to contain bubbles.
  • the test piece was removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film was peeled off, and the transferability was evaluated as follows.
  • ⁇ Resin layer transferred to the entire glass surface
  • ⁇ Resin layer remaining on the substrate side
  • ⁇ The resin layer does not adhere to the glass
  • seat for sealing obtained by the Example or the comparative example was cut out to about 60 mm in length, and about 40 mm in width, and the test piece was obtained. Bubbles entered into the glass plate (No. 3 made by Matsunami Glass, thickness 0.3 mm, 70 mm ⁇ 50 mm) heated on a hot plate heated to 70 ° C. of the layer made of the sheet-like epoxy resin composition of this test piece. It was transferred by a roll and pasted together. The test piece was removed from the hot plate and allowed to cool for 3 minutes. Thereafter, the base film was peeled off, and the sheet-like epoxy resin composition on the glass plate was heated in an oven at 85 ° C.
  • the light transmittance at a wavelength of 550 nm of the glass plate on which the cured product of the sheet-like epoxy resin composition was formed was measured using an ultraviolet-visible light spectrophotometer (Shimadzu Corporation UV-2550). In the measurement, the light transmittance of the glass plate alone was taken as the baseline.
  • Comparative Example 1 that does not include an epoxy compound having an alicyclic structure, the epoxy reaction rate at a curing temperature of 85 ° C. is less than 80%, and the curing reaction is sufficiently performed when the temperature for curing is low. I could not proceed.
  • SI-300 an acetyl group is bonded to a phenyl group and an anion is PF 6 —
  • a heating test at 40 ° C. for 17 hours holding The later melting temperature exceeded 80 ° C.
  • the change in melting temperature before and after the heating test was 10 ° C. or more, and it can be said that the storage stability was poor.
  • the transferability after the heating test could not be bonded to the glass.
  • SI-B2A (when an acetyl group is bonded to a phenyl group and an anion is B (C 6 F 5 ) 4 — ) (Comparative Example 8) is also obtained by simply forming into a sheet shape. It has hardened. The reactivity of the cationic polymerization initiator was too high, and the storage stability was poor. Moreover, since it was not able to transfer at 70 degreeC, the light transmittance after hardening was not able to be measured.
  • SI-B7 or SI-80 other than the structure specified in the present invention was used as the cationic polymerization initiator (Comparative Examples 9 and 10), although the storage stability was good, it was at 85 ° C. The epoxy reaction rate of was low and could not be cured sufficiently at 85 ° C.
  • the sealing material for display elements of the present invention can be cured at a relatively low temperature, and further has excellent storage stability. Therefore, the present invention can be applied to sealing various display elements.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Electroluminescent Light Sources (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Le problème abordé par la présente invention consiste à fournir une composition de résine époxy en forme de feuille capable de durcir à une température relativement faible et ayant également une excellente stabilité au stockage. Une composition de résine époxy en forme de feuille qui résout le problème ci-dessus comprend (A) un composé époxy représenté par formule générale (1), (B) une résine époxy ayant un cycle aromatique et un poids moléculaire moyen en poids de 3 000 à 100 000, et (C) un initiateur de polymérisation cationique représenté par formule générale (2) ; et la teneur de la (B) résine époxy étant de 45 % en masse ou plus. (Dans la formule générale (2), R1 représente un groupe alkyle en C1 à C4 ou un groupe naphtylméthyle, et R2 représente un groupe alkyle en C1 à C4).
PCT/JP2019/013183 2018-04-02 2019-03-27 Composition de résine époxy en forme de feuille et son produit durci, et feuille d'étanchéité Ceased WO2019194041A1 (fr)

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JP2020511716A JP7084472B2 (ja) 2018-04-02 2019-03-27 シート状エポキシ樹脂組成物およびその硬化物、ならびに封止用シート
KR1020207027243A KR102439370B1 (ko) 2018-04-02 2019-03-27 시트상 에폭시 수지 조성물 및 그의 경화물, 및 봉지용 시트

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013227420A (ja) * 2012-04-25 2013-11-07 Hitachi Chemical Co Ltd 回路接続材料、回路接続構造体、接着フィルム及び巻重体。
JP2014031465A (ja) * 2012-08-06 2014-02-20 Dexerials Corp 回路接続材料
WO2015129670A1 (fr) * 2014-02-27 2015-09-03 積水化学工業株式会社 Composition de résine durcissable pour sceller un élément d'affichage électroluminescent organique, feuille de résine durcissable pour sceller un élément d'affichage électroluminescent organique, et élément d'affichage électroluminescent organique
JP2016179564A (ja) * 2015-03-23 2016-10-13 味の素株式会社 樹脂シート
WO2017014037A1 (fr) * 2015-07-21 2017-01-26 古河電気工業株式会社 Composition de résine hygroscopique durcissable pour l'étanchéité d'un dispositif électronique, produit durci en résine, et dispositif électronique
WO2018235824A1 (fr) * 2017-06-23 2018-12-27 三井化学株式会社 Matériau d'étanchéité pour dispositif d'affichage d'image et feuille d'étanchéité pour dispositif d'affichage d'image

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003327951A (ja) 2002-05-10 2003-11-19 Mitsui Chemicals Inc シール材用光硬化型樹脂組成物
JP4816863B2 (ja) 2004-12-22 2011-11-16 株式会社スリーボンド 有機ｅｌ素子封止用熱硬化型組成物
JP5288150B2 (ja) 2005-10-24 2013-09-11 株式会社スリーボンド 有機ｅｌ素子封止用熱硬化型組成物
CN105916937B (zh) * 2014-01-23 2018-11-16 电化株式会社 树脂组合物
WO2019065455A1 (fr) 2017-09-29 2019-04-04 三井化学株式会社 Matériau d'étanchéité pour dispositif d'affichage d'images et feuille d'étanchéité pour dispositif d'affichage d'images

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013227420A (ja) * 2012-04-25 2013-11-07 Hitachi Chemical Co Ltd 回路接続材料、回路接続構造体、接着フィルム及び巻重体。
JP2014031465A (ja) * 2012-08-06 2014-02-20 Dexerials Corp 回路接続材料
WO2015129670A1 (fr) * 2014-02-27 2015-09-03 積水化学工業株式会社 Composition de résine durcissable pour sceller un élément d'affichage électroluminescent organique, feuille de résine durcissable pour sceller un élément d'affichage électroluminescent organique, et élément d'affichage électroluminescent organique
JP2016179564A (ja) * 2015-03-23 2016-10-13 味の素株式会社 樹脂シート
WO2017014037A1 (fr) * 2015-07-21 2017-01-26 古河電気工業株式会社 Composition de résine hygroscopique durcissable pour l'étanchéité d'un dispositif électronique, produit durci en résine, et dispositif électronique
WO2018235824A1 (fr) * 2017-06-23 2018-12-27 三井化学株式会社 Matériau d'étanchéité pour dispositif d'affichage d'image et feuille d'étanchéité pour dispositif d'affichage d'image

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TW201942180A (zh) 2019-11-01
KR20200125649A (ko) 2020-11-04
CN111936543A (zh) 2020-11-13
TWI853808B (zh) 2024-09-01

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