Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
  • C09J163/10—Epoxy resins modified by unsaturated compounds
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1339—Gaskets; Spacers; Sealing of cells
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

• the present invention relates to a sealant for a display element capable of obtaining a display element having excellent reliability in a high temperature and high humidity environment.
• the present invention also relates to a vertically conductive material and a display element using the sealant for the display element.
• liquid crystal display elements organic EL display elements, and the like have been widely used as display elements having features such as thinness, light weight, and low power consumption.
• the liquid crystal, the light emitting layer, and the like are usually sealed with a sealing agent made of a curable resin composition.
• a liquid crystal display element a liquid crystal display element using a light-heat combined curing type sealant as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used. It is disclosed.
• the display element is also required to have a performance corresponding to a pressure cooker test (PCT) under the conditions of 121 ° C., 100% RH, and 2 atm as high reliability in driving in a high temperature and high humidity environment.
• PCT pressure cooker test
• the sealant excellent in moisture and heat resistance.
• the present invention contains a curable resin, a polymerization initiator and / or a thermosetting agent, and has a polar component term of 6.0 or less in the surface free energy formula of the cured product by the Owns-Wendt method, and the cured product.
• the present inventor makes sure that the polar component term in the formula of the surface free energy by the Owns-Wendt method of the cured product of the sealant for a display element is equal to or less than a specific value, and the storage elastic modulus of the cured product at 121 ° C. was considered to be greater than or equal to a specific value.
• the effect of being able to obtain a display element having excellent reliability in a high temperature and high humidity environment in the sealant for a display element of the present invention is that when the sealant for a display element of the present invention is used as a sealant for a liquid crystal display element. It is especially noticeable.
• the sealant for a display element of the present invention has a polar component term (hereinafter, also simply referred to as “polar component term”) of 6.0 or less in the formula of surface free energy according to the Owns-Wendt method of the cured product. Since the polar component term is 6.0 or less and the storage elastic modulus of the cured product at 121 ° C. is 50 MPa or more, the sealant for a display element of the present invention has the invasion of air bubbles in a high temperature and high humidity environment. It becomes excellent in the effect of suppressing.
• the preferred upper limit of the polar component term is 5.7, and the more preferable upper limit is 5.3. Further, although there is no particular preferable lower limit of the polar component term, the actual lower limit is 4.5.
• the contact angle of the cured product with water and methylene iodide was measured at 25 ° C. using a contact angle meter, and the following formula was used. Can be calculated.
• the sealant is applied to one of the two non-alkali glasses, the other non-alkali glass is overlaid on the applied sealant, and 100 mW / cm 2 ultraviolet rays (wavelength 365 nm) are applied using a metal halide lamp. After irradiating for 30 seconds, one of the non-alkali glasses is peeled off and heated at 120 ° C. for 1 hour to heat-cure the sealant.
• the non-alkali glass OA-10G (manufactured by Nippon Electric Glass Co., Ltd., thickness 0.7 mm, surface roughness 0.2 nm Ra) is used.
• the contact angle meter for example, a fully automatic contact angle meter DMo-701 (manufactured by Kyowa Interface Science Co., Ltd.) and the like can be mentioned.
• the storage elastic modulus of the cured product described later at 121 ° C. is 50 MPa or more and the polar component term is 6.0 or less, the cured product itself is not only excellent in moisture resistance but also excellent in moisture resistance. It is presumed that the affinity with the alignment film and the like is increased and the interfacial adhesion is improved, and as a result, the infiltration of water that causes bubbles is suppressed.
• the sealant for a display element of the present invention has a lower limit of the storage elastic modulus of the cured product at 121 ° C. of 50 MPa.
• the storage elastic modulus of the cured product at 121 ° C. is 50 MPa or more and the polar component term is 6.0 or less
• the sealant for a display element of the present invention can be used for air bubbles in a high temperature and high humidity environment. The effect of suppressing invasion is excellent.
• the preferable lower limit of the storage elastic modulus of the cured product at 121 ° C. is 60 MPa, and the more preferable lower limit is 80 MPa.
• a sealant that has been irradiated with ultraviolet rays of 100 mW / cm 2 for 30 seconds and then heated at 120 ° C. for 1 hour to be cured is used.
• the storage elastic modulus can be measured using a dynamic viscoelasticity measuring device under the conditions of a test piece width of 5 mm, a thickness of 0.35 mm, a grip width of 25 mm, a heating rate of 10 ° C./min, and a frequency of 5 Hz. ..
• Examples of the dynamic viscoelasticity measuring device include DVA-200 (manufactured by IT Measurement Control Co., Ltd.) and the like.
• the type of each component contained in the sealant for a display element and the type of each component are used.
• a method of adjusting the content ratio is preferable.
• the sealant for a display element of the present invention contains a curable resin.
• the curable resin preferably contains a compound having an epoxy group.
• the obtained sealant for a display element becomes more excellent in the effect of suppressing the invasion of air bubbles in a high temperature and high humidity environment.
• Examples of the compound having an epoxy group include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2,2'-diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, and propylene oxide.
• Examples thereof include compounds, dicyclopentadiene novolac type epoxy compounds, biphenylnovolac type epoxy compounds, naphthalenephenol novolac type epoxy compounds, glycidylamine type epoxy compounds, alkyl polyol type epoxy compounds, rubber-modified epoxy compounds, and glycidyl ester compounds.
• Examples of commercially available bisphenol A type epoxy compounds include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), and the like.
• Examples of commercially available bisphenol F type epoxy compounds include jER806, jER4004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-830CRP (manufactured by DIC Corporation), and the like.
• Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA1514 (manufactured by DIC Corporation) and the like.
• 2,2'-diallyl bisphenol A type epoxy compounds commercially available ones include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
• Examples of commercially available hydrogenated bisphenol type epoxy compounds include EPICLON EXA7015 (manufactured by DIC Corporation) and the like.
• Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA Corporation) and the like.
• Examples of commercially available resorcinol-type epoxy compounds include EX-201 (manufactured by Nagase ChemteX Corporation) and the like.
• Examples of commercially available biphenyl type epoxy compounds include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.
• Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
• Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) and the like.
• Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA Corporation) and the like.
• Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
• Examples of commercially available phenol novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation) and the like.
• Examples of commercially available orthocresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like.
• Examples of commercially available dicyclopentadiene novolac type epoxy compounds include EPICLON HP7200 (manufactured by DIC Corporation) and the like.
• Examples of commercially available biphenyl novolac type epoxy compounds include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
• Examples of commercially available naphthalene phenol novolac type epoxy compounds include ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
• Examples of commercially available glycidylamine type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.) and the like.
• alkyl polyol type epoxy compounds include, for example, ZX-1542 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoei Co., Ltd.), and Denacol EX. -611 (manufactured by Nagase ChemteX Corporation) and the like.
• Examples of commercially available rubber-modified epoxy compounds include YR-450, YR-207 (all manufactured by Nippon Steel Chemical & Materials Co., Ltd.), and Epolide PB (manufactured by Daicel Co., Ltd.).
• Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation) and the like.
• Other commercially available compounds having an epoxy group include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Materials), XAC4151 (manufactured by Asahi Kasei Corporation), and the like.
• Examples thereof include jER1031 and jER1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Industries, Ltd.).
• the compound having an epoxy group a partially (meth) acrylic-modified epoxy compound is also preferably used.
• the partial (meth) acrylic-modified epoxy compound can be obtained by reacting a partial epoxy group of a compound having two or more epoxy groups with (meth) acrylic acid to obtain one molecule. It means a compound having one or more epoxy groups and one or more (meth) acryloyl groups therein.
• the said "(meth) acryloyl” means acryloyl or methacryloyl.
• Examples of commercially available partial (meth) acrylic-modified epoxy compounds include UVACURE1561, KRM8287 (all manufactured by Daicel Ornex), and MEM-5000H (manufactured by Neochemical).
• the preferable lower limit of the content of the compound having an epoxy group in 100 parts by weight of the curable resin is 10 parts by weight, and the preferable upper limit is 60 parts by weight.
• the content of the compound having an epoxy group is 10 parts by weight or more, the obtained sealant for a display element is more excellent in the effect of suppressing the invasion of air bubbles in a high temperature and high humidity environment.
• the content of the compound having an epoxy group is 60 parts by weight or less, the obtained sealant for a display element is excellent in low liquid crystal contamination when used as a sealant for a liquid crystal display element.
• the more preferable lower limit of the content of the compound having an epoxy group is 20 parts by weight, and the more preferable upper limit is 40 parts by weight.
• the curable resin preferably contains a (meth) acrylic compound.
• the (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable.
• the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
• the above-mentioned "(meth) acrylic” means acrylic or methacrylic
• the above-mentioned "(meth) acrylic compound” means a compound having a (meth) acryloyl group.
• (meth) acrylate means acrylate or methacrylate
• epoxy (meth) acrylate refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid. Represent.
• the curable resin may contain a compound having a methacryloyl group as the (meth) acrylic compound because the glass transition temperature of the cured product of the obtained sealant for a display element can be easily set in the range described later.
• the methacrylic ratio represented by the following formula (I) is preferably 0.3 or more.
• the methacrylic ratio is more preferably 0.5 or more, and further preferably 0.6 or more.
• Methacrylic Ratio (W M / E M) / (W A / E A + W M / E M) (I)
• E A is an acryloyl group equivalent of the compound having an acryloyl group (g / mol)
• E M is the methacryloyl group equivalent of the compound having a methacryloyl group (g / mol)
• W A is the content of the compound having an acryloyl group (parts by weight)
• W M is the content of the compound having a methacryloyl group (parts by weight).
• the "acryloyl group equivalent” is a value obtained by dividing the weight (g) of the compound having an acryloyl group by the number of moles (mol) of the acryloyl group contained in the compound having an acryloyl group.
• Compound the curable resin has a plurality of the acryloyl group (A1, A2, ⁇ ⁇ ⁇ ) if it contains "W A / E A" in the above formula (I), for compounds having the acryloyl group, It means the total of the values obtained by dividing the content of the compound having an acryloyl group by the acryloyl group equivalent ( WA1 / E A1 + WA2 / E A2 + ).
• the "methacryloyl group equivalent” is a value obtained by dividing the weight (g) of the compound having a methacryloyl group by the number of moles (mol) of the methacryloyl groups contained in the compound having a methacryloyl group.
• the curable resin has a plurality of the methacryloyl group (M1, M2, ⁇ ⁇ ⁇ ) if it contains the above formula (I) in the "W M / E M” is the compound having the methacryloyl group, It means the total of the values ( WM1 / E M1 + W M2 / E M2 + ...) obtained by dividing the content of the compound having a methacryloyl group by the methacryloyl group equivalent.
• monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
• bifunctional ones include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
• those having trifunctionality or higher include, for example, trimetyl propanetri (meth) acrylate, ethylene oxide-added trimethyl propanetri (meth) acrylate, and propylene oxide-added trimethyl propanetri (meth) acrylate.
• Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
• Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, and a 2,2'-diallyl bisphenol A type epoxy compound.
• Hydrogenated bisphenol type epoxy compound Hydrogenated bisphenol type epoxy compound, propylene oxide added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol Novolac type epoxy compound, orthocresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenylnovolac type epoxy compound, naphthalenephenol novolac type epoxy compound, glycidylamine type epoxy compound, alkyl polyol type epoxy compound, rubber modified epoxy compound , Glysidyl ester compound and the like.
• epoxy (meth) acrylates commercially available ones include, for example, epoxy (meth) acrylate manufactured by Daicel Ornex, epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and epoxy (meth) acrylate manufactured by Kyoei Co., Ltd. Examples thereof include meta) acrylate, epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation, and epoxy (meth) acrylate manufactured by KSM.
• Examples of the epoxy (meth) acrylate manufactured by Daicel Ornex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3701, EBECRYL3701
• Examples of the epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.
• Examples of the epoxy (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, and epoxy ester 1600A. Examples thereof include epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, and epoxy ester 400EA. Examples of the epoxy (meth) acrylate manufactured by Nagase ChemteX include Denacol acrylate DA-141, Denacol acrylate DA-314, and Denacol acrylate DA-911. Examples of the epoxy (meth) acrylate manufactured by KSM Co., Ltd. include BAEM-100 and the like.
• the urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with a polyfunctional isocyanate compound in the presence of a catalytic amount of a tin-based compound.
• polyfunctional isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), and the like.
• Hydrogenated MDI Polymeric MDI, 1,5-naphthalenediocyanate, Norbornan diisocyanate, Trizine diisocyanate, Xylylene diisocyanate (XDI), Hydrogenated XDI, Lysine diisocyanate, Triphenylmethane triisocyanate, Tris (isocyanatephenyl) thiophosphate, Tetramethyl Examples thereof include xylylene diisocyanate and 1,6,11-undecantry isocyanate.
• polyfunctional isocyanate compound a chain-extended polyfunctional isocyanate compound obtained by reacting a polyol with an excess polyfunctional isocyanate compound can also be used.
• the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
• Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of dihydric alcohol, mono (meth) acrylate of trihydric alcohol, and di (meth) acrylate. , Epoxy (meth) acrylate and the like.
• Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Can be mentioned.
• Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like.
• Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.
• Examples of the epoxy (meth) acrylate include bisphenol A type epoxy acrylate and the like.
• urethane (meth) acrylates commercially available ones include, for example, urethane (meth) acrylate manufactured by Toa Synthetic Co., Ltd., urethane (meth) acrylate manufactured by Daicel Ornex, and urethane (meth) manufactured by Negami Kogyo Co., Ltd. Examples thereof include acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. Examples of the urethane (meth) acrylate manufactured by Toagosei Co., Ltd.
• the urethane (meth) acrylate manufactured by the Daicel Orunekusu Inc. for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc. Can be mentioned.
• Examples of the urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, and Art Resin UN-. 7100, Art Resin UN-9000A, Art Resin UN-9000H and the like can be mentioned.
• Examples of the urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, and the like.
• Examples of the urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T. Be done.
• the curable resin preferably contains a compound having a flexible skeleton, and more preferably contains an epoxy compound having a flexible skeleton and / or a (meth) acrylic compound having a flexible skeleton.
• a compound having such a flexible skeleton it becomes easier to set the storage elastic modulus of the cured product at 121 ° C. in the above range.
• the flexible skeleton is preferably at least one selected from the group consisting of a lactone ring-opening structure, an alkylene oxide structure, and a rubber structure, and a lactone ring-opening structure is more preferable.
• the above-mentioned "rubber structure” refers to a vulcanized rubber structure formed by adding sulfur to raw rubber, a synthetic rubber structure formed in a molecular main chain by addition polymerization, and a peroxide. It means a structure that exhibits rubber elasticity, such as a silicone rubber structure formed by cross-linking polymethyl siloxane with.
• lactone examples include ⁇ -undecalactone, ⁇ -caprolactone, ⁇ -decalactone, ⁇ -dodecalactone, ⁇ -nononalactone, ⁇ -nonanolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -butyrolactone, and ⁇ -.
• examples thereof include butyrolactone, ⁇ -propiolactone, ⁇ -hexanolactone, 7-butyl-2-oxepanone and the like. Of these, those having 5 to 7 carbon atoms in the linear portion of the main skeleton when the ring is opened are preferable.
• alkylene oxide structure examples include an ethylene oxide structure, a propylene oxide structure, and a butylene oxide structure.
• the rubber structure is preferably a structure having an unsaturated bond in the main chain or a structure having a polysiloxane skeleton in the main chain.
• the structure having an unsaturated bond in the main chain include a structure having a skeleton in the main chain by polymerization of a conjugated diene.
• the skeleton obtained by polymerizing the conjugated diene include an acrylonitrile-butadiene skeleton, a polybutadiene skeleton, a polyisoprene skeleton, a styrene-butadiene skeleton, a polyisobutylene skeleton, and a polychloroprene skeleton.
• the preferable lower limit of the content of the compound having a flexible skeleton in 100 parts by weight of the curable resin is 5 parts by weight, and the preferable upper limit is 30 parts by weight.
• the content of the compound having the flexible skeleton is in this range, it becomes easier to set the storage elastic modulus of the obtained cured product of the sealant for a display element at 121 ° C. in the above range.
• the more preferable lower limit of the content of the compound having a flexible skeleton is 10 parts by weight, and the more preferable upper limit is 20 parts by weight.
• the sealant for a display element of the present invention contains a polymerization initiator and / or a thermosetting agent.
• the polymerization initiator include radical polymerization initiators, cationic polymerization initiators and the like.
• radical polymerization initiator examples include a photoradical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.
• photoradical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like.
• Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2- (dimethylamino).
• thermal radical polymerization initiator examples include those composed of an azo compound, an organic peroxide and the like. Of these, a polymer azo initiator composed of a polymer azo compound is preferable.
• the polymer azo compound means a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of curing the (meth) acryloyloxy group by heat.
• the preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000.
• the number average molecular weight of the polymer azo compound is in this range, it can be easily mixed with the curable resin, and when the obtained sealant for a display element is used for a liquid crystal display element, it adversely affects the liquid crystal. Can be prevented.
• the more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the further preferable lower limit is 10,000, and the further preferable upper limit is 90,000.
• the number average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene.
• GPC gel permeation chromatography
• Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.
• Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
• the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group those having a polyethylene oxide structure are preferable.
• Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group and the like.
• Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Be done. Examples of commercially available azo compounds that are not polymers include V-65 and V-501 (both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
• organic peroxide examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates and the like.
• a photocationic polymerization initiator can be preferably used as the cationic polymerization initiator.
• the photocationic polymerization initiator is not particularly limited as long as it generates protonic acid or Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type. It may be.
• Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salt, aromatic halonium salt and aromatic sulfonium salt, and organic metal complexes such as iron-allene complex, titanosen complex and arylsilanol-aluminum complex. Can be mentioned.
• photocationic polymerization initiators examples include ADEKA PUTMER SP-150 and ADEKA PTOMER SP-170 (both manufactured by ADEKA).
• the above-mentioned polymerization initiator may be used alone or in combination of two or more.
• the content of the polymerization initiator is preferably 0.1 part by weight and a preferable upper limit is 30 parts by weight with respect to 100 parts by weight of the curable resin.
• a preferable upper limit is 30 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the polymerization initiator is 0.1 parts by weight or more, the obtained sealant for a display element becomes more excellent in curability.
• the content of the polymerization initiator is 30 parts by weight or less, the obtained sealant for a display element becomes more excellent in storage stability.
• the more preferable lower limit of the content of the polymerization initiator is 1 part by weight, the more preferable upper limit is 10 parts by weight, and the more preferable upper limit is 5 parts by weight.
• thermosetting agent examples include organic acid hydrazide, imidazole derivative, amine compound, polyhydric phenol compound, acid anhydride and the like. Of these, solid organic acid hydrazide is preferably used.
• the above thermosetting agent may be used alone or in combination of two or more.
• Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydrandin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.
• Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Japan Finechem Co., Ltd., and organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Ltd.
• Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
• Examples of the organic acid hydrazide manufactured by Japan Finechem Co., Ltd. include MDH and the like.
• Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, and Amicure UDH.
• the content of the thermosetting agent is preferably 1 part by weight and a preferable upper limit of 50 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the thermosetting agent is 1 part by weight or more, the obtained sealant for a display element becomes more excellent in thermosetting property.
• the content of the thermosetting agent is 50 parts by weight or less, the obtained sealant for a display element is excellent in coatability and storage stability.
• a more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
• the sealant for a display element of the present invention preferably contains a filler for the purpose of adjusting the viscosity, improving the adhesiveness by the stress dispersion effect, improving the coefficient of linear expansion, improving the moisture resistance of the cured product, and the like.
• an inorganic filler or an organic filler can be used as the filler.
• the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide.
• the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like.
• the preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a display element of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
• the more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.
• the sealant for a display element of the present invention preferably contains a silane coupling agent.
• the silane coupling agent mainly has a role as an adhesive auxiliary for satisfactorily adhering the sealant and the substrate or the like.
• silane coupling agent for example, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like are preferably used. Be done. These silane coupling agents are excellent in the effect of improving the adhesiveness with a substrate or the like, and when the obtained sealant for a display element is used for a liquid crystal display element, the outflow of the curable resin into the liquid crystal is suppressed. Can be done.
• the silane coupling agent may be used alone or in combination of two or more.
• the preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a display element of the present invention is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight.
• the content of the silane coupling agent is in this range, the obtained sealant for a display element becomes more excellent in adhesiveness, and when the obtained sealant for a display element is used for a liquid crystal display element, it causes liquid crystal contamination. The occurrence can be suppressed.
• the more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.
• the sealant for a display element of the present invention may contain the above-mentioned light-shielding agent.
• the sealant for a display element of the present invention can be suitably used as a light-shielding sealant.
• the light-shielding agent examples include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black and the like. Of these, titanium black is preferable.
• the light-shielding agent may be used alone or in combination of two or more.
• the titanium black is a substance having a higher transmittance for light in the ultraviolet region, particularly for light having a wavelength of 370 nm or more and 450 nm or less, as compared with the average transmittance for light having a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting light-shielding property to the sealant for a display element of the present invention by sufficiently blocking light having a wavelength in the visible light region, while transmitting light having a wavelength near the ultraviolet region. It is a light-shielding agent.
• the light-shielding agent contained in the sealant for a display element of the present invention a substance having a high insulating property is preferable, and titanium black is also preferable as a light-shielding agent having a high insulating property.
• the above titanium black exerts a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, or oxidation.
• an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, or oxidation.
• Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide, can also be used. Among them, those treated with an organic component are preferable in that the insulating property can be further improved.
• the display element manufactured by using the sealant for a display element of the present invention containing the titanium black as a light-shielding agent has a sufficient light-shielding property, so that there is no light leakage and a high contrast is obtained, which is excellent. A display element having image display quality can be realized.
• Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd. Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13RN, 14MC and the like. Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilak D and the like.
• the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
• the preferable lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferable lower limit is 1 ⁇ ⁇ cm, and the more preferable upper limit is 2.5 ⁇ ⁇ cm.
• the primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the display element, but the preferable lower limit is 1 nm and the preferable upper limit is 5000 nm. When the primary particle size of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the drawing property of the obtained sealant for a display element.
• the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm
• the more preferable upper limit is 200 nm
• the further preferable lower limit is 10 nm
• the further preferable upper limit is 100 nm.
• the primary particle size of the light-shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS) and dispersing the light-shielding agent in a solvent (water, organic solvent, etc.).
• the preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight.
• the content of the light-shielding agent is within this range, it is more excellent in the effect of improving the light-shielding property while suppressing the deterioration of the adhesiveness, the strength after curing, and the drawing property of the obtained sealant for the display element. It becomes.
• the more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the further preferable upper limit is 60 parts by weight.
• the sealant for a display element of the present invention further contains additives such as a reactive diluent, a spacer, a curing accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor, and other coupling agents, if necessary. You may.
• a curable resin for example, a curable resin, a polymerization initiator and / or a thermosetting agent, a silane coupling agent to be added as needed, and the like using a mixer are used.
• a method of mixing with and the like can be mentioned.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
• the preferable lower limit of the glass transition temperature of the cured product is 125 ° C.
• the glass transition temperature of the cured product is 125 ° C. or higher, the obtained sealant for a display element is more excellent in the effect of suppressing the invasion of air bubbles in a high temperature and high humidity environment.
• a more preferable lower limit of the glass transition temperature of the cured product is 130 ° C.
• the preferable upper limit of the glass transition temperature of the cured product is 170 ° C.
• the above-mentioned "glass transition temperature” means the temperature at which the maximum due to the Micro Brownian motion appears among the maximums of the loss tangent (tan ⁇ ) obtained by the dynamic viscoelasticity measurement.
• the glass transition temperature can be measured by a conventionally known method using a dynamic viscoelasticity measuring device or the like.
• a sealant is irradiated with ultraviolet rays of 100 mW / cm 2 for 30 seconds and then heated at 120 ° C. for 1 hour to be cured.
• the sealant for a display element of the present invention has a preferable upper limit of water absorption of 4.0% by weight after a high-temperature and high-humidity test in which a cured product is exposed to an environment of 121 ° C., 100% RH, and 2 atm for 24 hours. is there.
• the sealant for a display element of the present invention is more excellent in the effect of suppressing the invasion of air bubbles in a high temperature and high humidity environment.
• a more preferable upper limit of the water absorption rate is 3.0% by weight, and a more preferable upper limit is 2.5% by weight. Further, although there is no particular preferable lower limit of the water absorption rate, a practical lower limit is 1.0% by weight.
• the "water absorption rate” is calculated by the following formula, where W 1 is the weight before the high temperature and high humidity test and W 2 is the weight after the high temperature and high humidity test.
• Water absorption (wt%) ((W 2 -W 1) / W 1) ⁇ 100
• the cured product for measuring the water absorption rate a cured product obtained by irradiating the sealant with ultraviolet rays of 100 mW / cm 2 for 30 seconds and then heating at 120 ° C. for 1 hour is used.
• a vertically conductive material By blending conductive fine particles with the sealant for a display element of the present invention, a vertically conductive material can be produced.
• a vertically conductive material containing such a sealant for a display element and conductive fine particles of the present invention is also one of the present inventions.
• the conductive fine particles are not particularly limited, and metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.
• a display element having a cured product of the sealant for a display element of the present invention or a cured product of the vertically conductive material of the present invention is also one of the present inventions.
• a liquid crystal display element is suitable.
• a liquid crystal dropping method is preferably used, and specific examples thereof include a method having the following steps. First, a step of applying the sealant for a display element of the present invention to one of two transparent substrates having electrodes such as an ITO thin film by screen printing, dispenser application, or the like to form a frame-shaped seal pattern is performed.
• the liquid crystal display element can be obtained by a method of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily cure the sealant and a step of heating the temporarily cured sealant to perform main curing. it can.
• a sealant for a display element capable of obtaining a display element having excellent reliability in a high temperature and high humidity environment. Further, according to the present invention, it is possible to provide a vertically conductive material and a display element using the sealant for the display element.
• each material was mixed using a planetary stirrer, and then further mixed using three rolls to prepare a sealant for a display element.
• Awatori Rentaro manufactured by Shinky Co., Ltd.
• "NEM-5000H” contains about 50% by weight of the partially methacryl-modified bisphenol A type epoxy compound, about 25% by weight of the bisphenol A type epoxy methacrylate, and about 25% by weight of the bisphenol A type epoxy compound.
• the mixture to be contained (content ratio of compound having an epoxy group is about 75% by weight).
• KRM8287 contains about 50% by weight of the partially acrylic modified bisphenol E type epoxy compound, about 25% by weight of the bisphenol E type epoxy acrylate, and about 25% by weight of the bisphenol E type epoxy compound. It is a mixture (content ratio of compound having an epoxy group is about 75% by weight).
• the obtained sealant for each display element is applied to one of the two non-alkali glasses, another non-alkali glass is overlaid on the applied sealant, and 100 mW / cm 2 is used using a metal halide lamp. After irradiating with ultraviolet rays (wavelength 365 nm) for 30 seconds, the other non-alkali glass was peeled off, and the sealant was thermally cured by heating at 120 ° C. for 1 hour to obtain a cured product.
• OA-10G manufactured by Nippon Electric Glass Co., Ltd., thickness 0.7 mm, surface roughness 0.2 nm Ra
• the contact angle with water and methylene iodide (dropping amount 3 ⁇ L, 30 seconds after dropping) was measured at 25 ° C. using a contact angle meter, and the polar component term was calculated by the above formula. ..
• a fully automatic contact angle meter DMo-701 (manufactured by Kyowa Interface Science Co., Ltd.) was used. The results are shown in Tables 1 and 2. Further, each of the obtained sealants for display elements was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW / cm 2 for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to obtain a cured product.
• the obtained cured product has a storage elastic modulus at 121 ° C. under the conditions of a test piece width of 5 mm, a thickness of 0.35 mm, a grip width of 25 mm, a heating rate of 10 ° C./min, and a frequency of 5 Hz, using a dynamic viscoelasticity measuring device.
• a dynamic viscoelasticity measuring device was used.
• the temperature of the maximum value of the loss tangent (tan ⁇ ) was determined as the glass transition temperature.
• DVA-200 manufactured by IT Measurement Control Co., Ltd.
• each of the obtained sealants for display elements was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW / cm 2 for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to obtain a cured product.
• the obtained cured product was subjected to a high temperature and high humidity test in which it was exposed to an environment of 121 ° C., 100% RH, and 2 atm for 24 hours, and the water absorption rate was calculated by the above formula. The results are shown in Tables 1 and 2.
• spacer particles 1 part by weight of spacer particles was uniformly dispersed in 100 parts by weight of the sealant for each display element obtained in Examples and Comparative Examples.
• the spacer particles Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used.
• a sealant in which spacer particles were dispersed was filled in a dispenser syringe, defoamed, and then applied with a dispenser on a transparent substrate with an alignment film and an ITO thin film in a rectangular frame.
• PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used as the syringe, and SHOTMASTER 300 (manufactured by Musashi Engineering Co., Ltd.) was used as the dispenser. Subsequently, fine droplets of liquid crystal were dropped and applied to the entire surface of the sealant frame, and another transparent substrate was immediately attached. As the liquid crystal, JC-5004LA (manufactured by Chisso) was used. Immediately after the transparent substrate was bonded, the sealant portion was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW / cm 2 for 30 seconds using a metal halide lamp, and then heated at 120 ° C.
• ultraviolet rays wavelength 365 nm
• liquid crystal display element for 1 hour to obtain a liquid crystal display element. .. Twenty liquid crystal display elements were produced for each of the sealants for each display element obtained in Examples and Comparative Examples. The obtained liquid crystal display element was exposed to PCT conditions (121 ° C., 100% RH, 2 atm) for 24 hours. The presence or absence of air bubbles was confirmed by visual observation of the liquid crystal display element after being exposed to the PCT conditions. " ⁇ " when no bubbles are confirmed in all 20 liquid crystal display elements, " ⁇ " when bubbles are confirmed in 1 or more and 3 or less liquid crystal display elements, and 4 or more and 8 or less liquid crystal The reliability in a high temperature and high humidity environment was evaluated as " ⁇ " when bubbles were confirmed in the display element and "x" when bubbles were confirmed in nine or more liquid crystal display elements.
• a sealant for a display element capable of obtaining a display element having excellent reliability in a high temperature and high humidity environment. Further, according to the present invention, it is possible to provide a vertically conductive material and a display element using the sealant for the display element.

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