Classifications

• • 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
• • 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

Definitions

• the present invention relates to a sealant for liquid crystal display elements that has excellent adhesion to alignment films and moisture resistance, and can suppress peeling after photocuring even when applied to large substrates.
• liquid crystal display elements are manufactured by forming a plurality of cells on a mother glass at once, and then cutting each of them.
• mother glass and displays have become larger, and peeling of the substrate is likely to occur during the manufacturing process of liquid crystal display elements.
• (meth)acrylic compounds and the like have been used as a curable resin to be mixed into a sealant, and this is photocured, but peeling of the substrate sometimes occurs, particularly due to vibrations during transportation after the photocuring process.
• An object of the present invention is to provide a sealant for liquid crystal display elements which has excellent adhesion to an alignment film and moisture permeability prevention properties, and which can suppress peeling after photocuring even when applied to a large substrate.
• Disclosure 1 relates to a sealant for liquid crystal display elements, the sealant containing a curable resin and a photopolymerization initiator, the curable resin containing a compound represented by the following formula (1), the sealant for liquid crystal display elements having a thickness of 5.0 ⁇ m obtained by irradiating the sealant for liquid crystal display elements with 3000 mJ/ cm2 of ultraviolet light having a wavelength of 365 nm, has a compressive shear adhesive strength to polyimide of 15 kgf/cm2 or more, as measured in accordance with JIS K 6852 under conditions of 25 °C and a shear rate of 1 mm/sec.
• the present disclosure 2 is the sealant for liquid crystal display elements of the present disclosure 1, further comprising an organic filler, the content of the organic filler being 5 parts by mass or more per 100 parts by mass of the curable resin.
• the present disclosure 3 is the sealant for liquid crystal display elements according to the present disclosure 1 or 2, in which, when PE is the ratio of the number of epoxy groups in one molecule of a compound contained in the curable resin to the total number of epoxy groups and (meth)acryloyl groups in the compound, the epoxy functional group ratio expressed as the mass average value of PE in the entire curable resin is 30% or more.
• the present disclosure 4 is the sealant for liquid crystal display elements according to the present disclosure 1, 2 or 3, further comprising an inorganic filler, the content of the inorganic filler being 5 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the curable resin.
• the present disclosure 5 is a sealant for liquid crystal display elements according to the present disclosure 1, 2, 3, or 4, in which a cured product having a thickness of 300 ⁇ m obtained by irradiating the product with 3,000 mJ/ cm2 of ultraviolet light having a wavelength of 365 nm and then heating the product at 120°C for 1 hour has a moisture permeability of 75 g/ m2 ⁇ 24 hr or less in an environment of 80°C and 90% RH, as measured in accordance with JIS Z 0208.
• the present disclosure 6 is a sealant for liquid crystal display elements according to the present disclosure 1, 2, 3, 4, or 5, in which a storage modulus at 25°C of a cured product obtained by irradiating with ultraviolet light having a wavelength of 365 nm at 3000 mJ/cm2 is 3.5 GPa or less.
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents a group represented by the following formula (2-1), (2-2), or (2-3)
• R 3 represents a methylene group, a methylmethylene group, a dimethylmethylene group, or a sulfonyl group
• X represents a lactone ring-open structure
• n is 1 or more and 5 or less.
• * represents a bonding position; in formula (2-2), a is an integer of 1 or more and 8 or less; in formula (2-3), b is an integer of 1 or more and 8 or less; c is an integer of 1 or more and 3 or less; and d is an integer of 1 or more and 8 or less.
• the inventors have investigated adjusting the peel adhesion strength of the sealant after photocuring by using a (meth)acrylic compound having a specific flexible backbone in order to suppress peeling after photocuring while obtaining excellent adhesion and moisture permeability prevention properties to the alignment film.
• the peel adhesion strength was adjusted, the effect of suppressing peeling after photocuring could not be reproduced. Therefore, the inventors have investigated adjusting the low-speed compressive shear adhesive strength of the sealant after photocuring at a shear rate of 1 mm/sec to a specific value or more.
• the sealant for liquid crystal display elements of the present invention has a compressive shear adhesive strength to a glass substrate measured at 25 °C and a shear rate of 1 mm/sec according to JIS K 6852 for a 5.0 ⁇ m thick cured product of the sealant for liquid crystal display elements obtained by irradiating the sealant with 3000 mJ/cm2 of ultraviolet light having a wavelength of 365 nm (hereinafter also referred to as "low-speed compressive shear adhesive strength after photocuring") of 15 kgf/ cm2 in lower limit.
• the sealant for liquid crystal display elements of the present invention can suppress peeling after photocuring.
• the lower limit of the low-speed compressive shear adhesive strength after photocuring is preferably 20 kgf/ cm2 , more preferably 25 kgf/ cm2 . Although there is no particular upper limit to the low-speed compressive shear adhesive strength after photocuring, the substantial upper limit is 100 kgf/cm 2 .
• the low-speed compressive shear adhesive strength after photocuring can be measured by the following method.
• a polyimide solution is applied to an ITO substrate having a length of 45 mm, a width of 25 mm, and a thickness of 0.7 mm in a thickness of about 100 nm, and two substrates (polyimide substrates) obtained by processing are prepared, and a sealant is dotted on one of them so that the diameter when bonded is 3 mm.
• the other polyimide substrate is overlapped on the polyimide substrate dotted with the sealant through the sealant so as to be shifted 10 mm in the longitudinal direction.
• the sealant is cured by irradiating ultraviolet light having a wavelength of 365 nm at 3000 mJ/ cm2 using a metal halide lamp or the like, and a test piece having a cured product of the sealant having a thickness of 5.0 ⁇ m is obtained.
• the obtained test piece can be measured for low-speed compression shear adhesive strength after photocuring under conditions of 25 ° C. and a shear rate of 1 mm/sec in accordance with JIS K 6852.
• the sealant for liquid crystal display elements of the present invention is irradiated with 3000 mJ/ cm2 of ultraviolet light having a wavelength of 365 nm, and then heated at 120°C for 1 hour to obtain a cured product having a thickness of 300 ⁇ m.
• the upper limit of the moisture permeability measured in accordance with JIS Z 0208 in an environment of 80°C and 90% RH is preferably 75 g/ m2 ⁇ 24 hr. When the moisture permeability is 75 g/ m2 ⁇ 24 hr or less, the obtained liquid crystal display element has better reliability.
• the more preferable upper limit of the moisture permeability is 65 g/ m2 ⁇ 24 hr. Further, there is no particular preferred lower limit for the moisture permeability, but the substantial lower limit is 35 g/m 2 ⁇ 24 hr.
• the sealant for liquid crystal display elements of the present invention has a storage modulus at 25°C of a cured product obtained by irradiating the cured product with 3000 mJ/ cm2 of ultraviolet light having a wavelength of 365 nm (hereinafter also referred to as "storage modulus after photocuring") of preferably 3.5 GPa.
• storage modulus after photocuring is 3.5 GPa or less
• the sealant for liquid crystal display elements of the present invention has a superior effect of suppressing peeling after photocuring.
• a more preferable upper limit of the storage modulus after photocuring is 3.0 GPa.
• the lower limit of the storage modulus after photocuring is preferably 0.1 GPa, and more preferably 1.0 GPa.
• the storage modulus can be measured using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Measurement & Control Co., Ltd.) under the conditions of a tensile mode, 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.
• a dynamic viscoelasticity measuring device for example, "DVA-200" manufactured by IT Measurement & Control Co., Ltd.
• the low-speed compressive shear adhesive strength after photocuring, the moisture permeability, and the storage modulus after photocuring can be set within the above-mentioned ranges by selecting the types and adjusting the content ratios of the curable resin, photopolymerization initiator, and other components such as organic fillers and inorganic fillers, which will be described later.
• the sealing agent for a liquid crystal display element of the present invention contains a curable resin.
• the curable resin contains a compound represented by the formula (1).
• the sealant for liquid crystal display elements of the present invention has excellent adhesion to an alignment film and moisture permeability prevention properties, and it is easy to set the low-speed compressive shear adhesive strength after photocuring and the storage modulus after photocuring in the above-mentioned ranges.
• R 2 represents a group represented by the above formula (2-1), (2-2), or (2-3).
• R 2 is preferably a group represented by the above formula (2-2), and more preferably a group in which a in the above formula (2-2) is 2 (ethylene group).
• the bonding position on the methylene group side is the bonding position with the (meth)acryloyloxy group in the above formula (1).
• (meth)acryloyl means acryloyl or methacryloyl.
• R3 represents a methylene group, a methylmethylene group, a dimethylmethylene group, or a sulfonyl group.
• R3 is preferably a methylene group, a methylmethylene group, or a dimethylmethylene group.
• X represents a ring-opened lactone structure.
• the lactone include ⁇ -undecalactone, ⁇ -caprolactone, ⁇ -decalactone, ⁇ -dodecalactone, ⁇ -nonanolactone, ⁇ -heptanolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -propiolactone, ⁇ -hexanolactone, 7-butyl-2-oxepanone, etc.
• those having a linear portion of the main skeleton with 5 or more and 7 or less carbon atoms when ring-opened are preferred.
• Examples of methods for producing the compound represented by the above formula (1) include the following methods. That is, first, a (meth)acrylic compound having a hydroxyl group and a group corresponding to the above R2 is reacted with a lactone in the presence of a polymerization inhibitor by heating and stirring, etc., and then the above phthalic acid or phthalic anhydride is added and reacted by heating and stirring, etc. Next, an epoxy compound having a bisphenol skeleton, such as bisphenol A diglycidyl ether, is added to the resulting reaction product and heated and stirred, etc., to react some of the epoxy groups of the epoxy compound having a bisphenol skeleton.
• the term "(meth)acrylic” means acrylic or methacrylic.
• the curable resin preferably contains a curable resin other than the compound represented by formula (1) for the purpose of adjusting the low-speed compressive shear adhesive strength after photocuring, the moisture permeability, and the storage modulus after photocuring, or for the purpose of improving low liquid crystal contamination properties.
• the preferred lower limit of the content of the compound represented by the formula (1) in 100 parts by mass of the curable resin is 10 parts by mass, and the preferred upper limit is 70 parts by mass.
• the more preferred lower limit of the content of the compound represented by the formula (1) is 15 parts by mass, and the more preferred upper limit is 50 parts by mass.
• Examples of the other curable resins include epoxy compounds and (meth)acrylic compounds.
• the above-mentioned epoxy compounds include, for example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, 2,2'-diallyl bisphenol A type epoxy compounds, hydrogenated bisphenol type epoxy compounds, propylene oxide-added bisphenol A type epoxy compounds, resorcinol type epoxy compounds, biphenyl type epoxy compounds, sulfide type epoxy compounds, diphenyl ether type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds, phenol novolac type epoxy compounds, orthocresol novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds, biphenyl novolac type epoxy compounds, naphthalene phenol novolac type epoxy compounds, glycidyl amine type epoxy compounds, alkyl polyol type epoxy compounds, rubber modified type epoxy compounds, glycidyl ester compounds, etc.
• the above bisphenol A type epoxy compounds commercially available ones include, for example, jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), and the like.
• the above bisphenol F type epoxy compounds commercially available ones include, for example, jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
• the above bisphenol S type epoxy compounds commercially available ones include, for example, EPICLON EXA1514 (manufactured by DIC Corporation).
• RE-810NM manufactured by Nippon Kayaku Co., Ltd.
• examples of the above hydrogenated bisphenol type epoxy compounds include EPICLON EXA7015 (manufactured by DIC Corporation).
• propylene oxide-added bisphenol A type epoxy compounds commercially available ones include, for example, EP-4000S (manufactured by ADEKA Corporation).
• resorcinol type epoxy compounds a commercially available example is EX-201 (manufactured by Nagase Chemtex Corporation).
• examples of commercially available compounds include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
• a commercially available example is YSLV-50TE (manufactured by Nippon Steel Chemical & Material Co., Ltd.).
• a commercially available example is YSLV-80DE (manufactured by Nippon Steel Chemical & Material Co., Ltd.).
• commercially available ones include, for example, EP-4088S (manufactured by ADEKA Corporation).
• naphthalene type epoxy compounds commercially available ones include, for example, EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
• phenol novolac type epoxy compounds commercially available ones include, for example, EPICLON N-770 (manufactured by DIC Corporation).
• ortho-cresol novolac type epoxy compounds commercially available ones include, for example, EPICLON N-670-EXP-S (manufactured by DIC Corporation).
• EPICLON HP7200 manufactured by DIC Corporation.
• biphenyl novolac type epoxy compounds a commercially available example is NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
• naphthalenephenol novolac type epoxy compounds a commercially available example is ESN-165S (manufactured by Nippon Steel Chemical & Material Co., Ltd.).
• ESN-165S manufactured by Nippon Steel Chemical & Material Co., Ltd.
• glycidylamine type epoxy compounds commercially available ones include, for example, jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.).
• alkyl polyol type epoxy compounds commercially available ones include, for example, ZX-1542 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-611 (manufactured by Nagase ChemteX Corporation).
• commercially available ones include, for example, YR-450, YR-207 (both manufactured by Nippon Steel Chemical & Material Co., Ltd.), Epolead PB (manufactured by Daicel Corporation), and the like.
• glycidyl ester compounds include, for example, Denacol EX-147 (manufactured by Nagase Chemtex Corporation).
• Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Material Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Industries, Ltd.).
• the curable resin may also contain a compound having an epoxy group and a (meth)acryloyl group in one molecule other than the compound represented by formula (1) above as the other curable resin.
• examples of such compounds include partially (meth)acrylic modified epoxy compounds obtained by reacting a portion of the epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.
• the (meth)acrylic compound examples include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. Among these, epoxy (meth)acrylates are preferred. From the viewpoint of reactivity, the (meth)acrylic compound is preferably one having two or more (meth)acryloyl groups in one molecule.
• (meth)acrylate means acrylate or methacrylate
• epoxy (meth)acrylate means a compound in which all epoxy groups in an epoxy compound have been reacted with (meth)acrylic acid.
• Examples of monofunctional (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, Isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, iso
• examples of the bifunctional (meth)acrylic acid ester compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, Examples of such di(meth)acrylates include butyl di(meth)acrylate,
• examples of the (meth)acrylic acid ester compounds having three or more functional groups include trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythri
• the epoxy (meth)acrylate may be, for example, one obtained by reacting an epoxy compound with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.
• Epoxy compounds that serve as raw materials for the epoxy (meth)acrylate may be the epoxy compounds listed above as other curable resins.
• epoxy (meth)acrylates examples of commercially available ones include epoxy (meth)acrylate manufactured by Daicel Allnex Corporation, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., and epoxy (meth)acrylate manufactured by Nagase ChemteX Corporation.
• Examples of the epoxy (meth)acrylates manufactured by Daicel-Allnex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, and EBECRYL RDX63182.
• Examples of the epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.
• Examples of the epoxy (meth)acrylates 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, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, and Epoxy Ester 400EA.
• Examples of the epoxy (meth)acrylates manufactured by Nagase ChemteX Corporation include Denacol Acrylate DA-141, Denacol Acrylate DA-314, and Denacol Acrylate DA-911.
• the above 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 compounds include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.
• MDI diphenylmethane-4,4'-diisocyanate
• XDI xylylene di
• polyfunctional isocyanate compound a chain-extended polyfunctional isocyanate compound obtained by reacting a polyol with an excess of the 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)acrylates, mono(meth)acrylates of dihydric alcohols, mono(meth)acrylates or di(meth)acrylates of trihydric alcohols, and epoxy (meth)acrylates.
• 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.
• Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
• Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.
• the epoxy (meth)acrylate may, for example, be bisphenol A type epoxy acrylate.
• urethane (meth)acrylates commercially available ones include, for example, urethane (meth)acrylate manufactured by Toagosei Co., Ltd., urethane (meth)acrylate manufactured by Daicel-Allnex Corporation, urethane (meth)acrylate manufactured by Negami Chemical Industries Co., Ltd., urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., and urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd.
• Examples of the urethane (meth)acrylates manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210, and M-1600.
• Examples of the urethane (meth)acrylates manufactured by Daicel-Allnex include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, and EBECRYL9260.
• urethane (meth)acrylates manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T.
• the preferred lower limit of the epoxy functional group ratio expressed as the mass average value of PE in the entire curable resin is 30%.
• the epoxy functional group ratio is 30% or more, it becomes easier to set the low-speed compressive shear adhesive strength after photocuring and the storage modulus after photocuring in the above-mentioned ranges.
• the more preferred lower limit of the epoxy functional group ratio is 35%.
• the upper limit of the epoxy functional group ratio is preferably 50%, and more preferably 45%.
• the sealing agent for liquid crystal display elements of the present invention contains a photopolymerization initiator.
• the photopolymerization initiator include a benzophenone compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, an oxime ester compound, a benzoin ether compound, and a thioxanthone compound.
• photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)- ...
• the content of the photopolymerization initiator is preferably 0.01 parts by mass at the lower limit and 10 parts by mass at the upper limit relative to 100 parts by mass of the curable resin. When the content of the photopolymerization initiator is within this range, the resulting sealant for liquid crystal display elements has better storage stability and photocurability.
• a more preferred lower limit of the content of the photopolymerization initiator is 0.1 parts by mass, and a more preferred upper limit is 5 parts by mass.
• the sealing agent for a liquid crystal display element of the present invention may contain a thermal polymerization initiator.
• the thermal polymerization initiator include those composed of an azo compound, an organic peroxide, etc. Among them, a polymeric azo initiator composed of a polymeric azo compound is preferred.
• the thermal polymerization initiators may be used alone or in combination of two or more kinds.
• the term "polymeric azo compound” refers to a compound that has an azo group, generates radicals by heat, and has a number average molecular weight of 300 or more.
• the preferred lower limit of the number average molecular weight of the polymeric azo compound is 1,000, and the preferred upper limit is 300,000. By having the number average molecular weight of the polymeric azo compound within this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination.
• a more preferred lower limit of the number average molecular weight of the polymeric azo compound is 5,000, and a more preferred upper limit is 100,000, and an even more preferred lower limit is 10,000, and an even more preferred upper limit is 90,000.
• polymeric azo compound examples include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via azo groups.
• polymeric 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 preferred.
• Specific examples of the polymeric azo compound include a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polydimethylsiloxane having a terminal amino group.
• polymeric azo compounds commercially available ones include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
• non-polymeric azo compounds include V-65 and V-501 (both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
• organic peroxides examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxy esters, diacyl peroxides, and peroxydicarbonates.
• the content of the thermal polymerization initiator is preferably 0.05 parts by mass at the lower limit and 10 parts by mass at the upper limit relative to 100 parts by mass of the curable resin.
• the sealant for liquid crystal display elements of the present invention has superior thermosetting properties.
• the sealant for liquid crystal display elements of the present invention has superior low liquid crystal contamination properties and storage stability.
• a more preferred lower limit of the content of the thermal polymerization initiator is 0.1 parts by mass, and a more preferred upper limit is 5 parts by mass.
• the sealing agent for liquid crystal display elements of the present invention preferably contains a heat curing agent.
• the heat curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, etc. Among these, organic acid hydrazides are preferably used.
• Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.
• examples of commercially available ones include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Ltd., and organic acid hydrazides manufactured by Nippon Finechem Co., Ltd.
• Examples of the organic acid hydrazides available from Otsuka Chemical Co., Ltd. include SDH and ADH.
• Examples of the organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Inc. include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.
• the organic acid hydrazide manufactured by Japan Finechem Co., Ltd. is, for example, MDH.
• the content of the heat curing agent is preferably 1 part by mass at the lower limit and 50 parts by mass at the upper limit relative to 100 parts by mass of the curable resin.
• the resulting sealant for liquid crystal display elements has excellent heat curing properties while maintaining storage stability and coatability.
• a more preferred upper limit of the content of the heat curing agent is 30 parts by mass.
• the sealant for liquid crystal display elements of the present invention preferably contains an organic filler.
• an organic filler By containing the organic filler, it becomes easier to set the low-speed compressive shear adhesive strength after photocuring and the storage modulus after photocuring to the above-mentioned ranges.
• organic filler examples include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and (meth)acrylic polymer fine particles.
• the organic filler may have a core-shell structure. Among these, (meth)acrylic polymer fine particles having a core-shell structure are preferred.
• the preferred lower limit of the average particle size of the organic filler is 0.1 ⁇ m, and the preferred upper limit is 0.8 ⁇ m.
• the more preferred upper limit of the average particle size of the organic filler is 0.5 ⁇ m.
• the average particle size of the organic filler can be measured by dispersing the organic filler in a solvent (water, organic solvent, etc.) using a particle size distribution measuring device. Examples of the particle size distribution measuring device include NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
• the content of the organic filler is preferably 5 parts by mass relative to 100 parts by mass of the curable resin. By making the content of the organic filler 5 parts by mass or more, it becomes easier to make the low-speed compression shear adhesive strength after photocuring and the storage modulus after photocuring fall within the above-mentioned range.
• the more preferable lower limit of the content of the organic filler is 10 parts by mass.
• the upper limit of the content of the organic filler is preferably 40 parts by mass, and more preferably 30 parts by mass.
• the sealant for liquid crystal display elements of the present invention preferably contains the above-mentioned inorganic filler for the purposes of improving moisture permeability prevention, increasing viscosity, improving adhesion due to stress dispersion effect, improving linear expansion coefficient, etc.
• the above-mentioned inorganic filler if a large amount is contained, it becomes difficult to set the low-speed compression shear adhesive strength after photocuring and the storage modulus after photocuring to the above-mentioned ranges.
• inorganic fillers examples include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.
• the content of the inorganic filler is preferably 5 parts by mass at the lower limit and 30 parts by mass at the upper limit relative to 100 parts by mass of the curable resin.
• the content of the inorganic filler is 5 parts by mass or more, the effect of improving moisture permeability prevention is superior.
• the content of the inorganic filler is 30 parts by mass or less, it becomes easier to set the low-speed compression shear adhesive strength after photocuring and the storage modulus after photocuring to the above-mentioned range.
• a more preferable lower limit of the content of the inorganic filler is 10 parts by mass, and a more preferable upper limit is 25 parts by mass.
• the sealant for liquid crystal display elements of the present invention preferably contains a silane coupling agent.
• the silane coupling agent mainly serves as an adhesion aid for providing good adhesion between the sealant for liquid crystal display elements and a substrate or the like.
• the silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. are suitably used.
• the preferred lower limit of the content of the silane coupling agent in 100 parts by mass of the sealant for liquid crystal display elements of the present invention is 0.1 parts by mass, and the preferred upper limit is 10 parts by mass.
• the more preferred lower limit of the content of the silane coupling agent is 0.3 parts by mass, and the more preferred upper limit is 5 parts by mass.
• the sealant for liquid crystal display elements of the present invention may contain a light-shielding agent.
• the sealant for liquid crystal display elements of the present invention can be suitably used as a light-shielding sealant.
• Examples of the light-blocking agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black.
• titanium black is preferred.
• the titanium black is a substance that has a higher transmittance for light near the ultraviolet region, particularly light with a wavelength of 370 nm to 450 nm, compared to the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the titanium black is a light-shielding agent that imparts light-shielding properties to the sealant for liquid crystal display elements of the present invention by sufficiently blocking light with wavelengths in the visible light region, while allowing light with wavelengths near the ultraviolet region to pass through.
• the photopolymerization initiator a substance that can initiate a reaction with light of a wavelength (370 nm to 450 nm) at which the transmittance of the titanium black is high, the photocuring property of the sealant for liquid crystal display elements of the present invention can be further increased.
• the light-shielding agent contained in the sealant for liquid crystal display elements of the present invention is preferably a substance with high insulating properties, and titanium black is also suitable as a light-shielding agent with high insulating properties.
• the titanium black preferably has an optical density (OD value) per 1 ⁇ m of 3 or more, and more preferably has an OD value of 4 or more. The higher the light-shielding ability of the titanium black, the better. There is no particular upper limit to the OD value of the titanium black, but it is usually 5 or less.
• titanium black exhibits sufficient effects even when not surface-treated, it is also possible to use titanium black whose surface has been treated with an organic component such as a coupling agent, or titanium black whose surface has been coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc.
• titanium black treated with an organic component is preferred in that it can further improve insulation properties.
• a liquid crystal display element manufactured using the sealing agent for liquid crystal display elements of the present invention, which contains the above-mentioned titanium black as a light-blocking agent has sufficient light-blocking properties, so that it is possible to realize a liquid crystal display element with no light leakage, high contrast, and excellent image display quality.
• titanium blacks mentioned above commercially available titanium blacks include, for example, 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, 13R-N, and 14M-C.
• An example of the titanium black manufactured by Ako Kasei Co., Ltd. is Tilac D.
• the specific surface area of the titanium black has a preferred lower limit of 13 m 2 /g and a preferred upper limit of 30 m 2 /g, a more preferred lower limit of 15 m 2 /g and a more preferred upper limit of 25 m 2 /g.
• the volume resistivity of the titanium black is preferably 0.5 ⁇ cm in lower limit and 3 ⁇ cm in upper limit, more preferably 1 ⁇ cm in lower limit and 2.5 ⁇ cm in upper limit.
• the primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or smaller than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm, and the preferred upper limit is 5000 nm.
• the primary particle diameter of the light-shielding agent is in this range, the obtained sealant for liquid crystal display elements can have excellent light-shielding properties without deteriorating the coatability, etc. of the sealant.
• the more preferred lower limit of the primary particle diameter of the light-shielding agent is 5 nm, the more preferred upper limit is 200 nm, the even more preferred lower limit is 10 nm, and the even more preferred upper limit is 100 nm.
• the primary particle size of the light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using a NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
• the preferred lower limit of the content of the light-shielding agent in 100 parts by mass of the sealant for liquid crystal display elements of the present invention is 5 parts by mass, and the preferred upper limit is 80 parts by mass.
• the adhesiveness, post-curing strength, and drawability of the resulting sealant for liquid crystal display elements can be improved without decreasing, and the effect of improving the light-shielding properties can be more effectively achieved.
• a more preferred lower limit of the content of the light-shielding agent is 10 parts by mass, a more preferred upper limit is 70 parts by mass, an even more preferred lower limit is 30 parts by mass, and an even more preferred upper limit is 60 parts by mass.
• the sealant for liquid crystal display elements of the present invention may further contain additives such as stress relaxation agents, reactive diluents, curing accelerators, defoamers, leveling agents, and polymerization inhibitors, as necessary.
• the method for producing the sealing agent for liquid crystal display elements of the present invention may, for example, be a method in which a curable resin, a photopolymerization initiator, and other components such as an organic filler or an inorganic filler are mixed using a mixer.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mixer.
• a vertically conductive material can be produced.
• the conductive fine particles may be metal balls, fine resin particles having a conductive metal layer formed on the surface thereof, etc. Among them, fine resin particles having a conductive metal layer formed on the surface thereof are preferred because they have excellent elasticity and can provide conductive connection without damaging a transparent substrate or the like.
• a liquid crystal dropping method is suitably used, and specifically, for example, a method having the following steps can be mentioned.
• a process is performed in which the sealant for liquid crystal display elements of the present invention is applied by screen printing, dispenser application, or the like onto one of two transparent substrates having an electrode such as an ITO thin film and an alignment film, thereby forming a frame-shaped seal pattern.
• a process is performed in which minute droplets of liquid crystal are dropwise applied onto the entire surface within the frame of the seal pattern, and the other transparent substrate is superimposed under vacuum.
• a liquid crystal display element can be obtained by a process of irradiating the seal pattern portion with light such as ultraviolet light to provisionally cure the sealant (photocuring process), and a process of heating the provisionally cured sealant to fully cure it (thermal curing process).
• the present invention provides a sealant for liquid crystal display elements that has excellent adhesion to alignment films and moisture resistance, and can suppress peeling after photocuring even when applied to large substrates.
• the curable resin A contained 50 mass % of a compound represented by the following formula (3), 25 mass % of a compound represented by the following formula (4), and 25 mass % of bisphenol A diglycidyl ether (the P E of the curable resin A can be considered to be 0.5).
• Curable resin B was obtained in the same manner as in "(Preparation of curable resin A)" above, except that the blending amount of ⁇ -caprolactone was 228 parts by mass. It was confirmed by 1 H-NMR and 13 C-NMR that the curable resin B contained 50 mass % of a compound represented by the following formula (5), 25 mass % of a compound represented by the following formula (6), and 25 mass % of bisphenol A diglycidyl ether (the P E of the curable resin B can be regarded as 0.5).
• Curable resin C was obtained in the same manner as in "(Preparation of curable resin A)" above, except that the blending amount of bisphenol A diglycidyl ether was 170 parts by mass. It was confirmed by 1 H-NMR and 13 C-NMR that the curable resin C was the compound represented by the above formula (4).
• Curable resin D was obtained in the same manner as in "(Preparation of curable resin A)" above, except that the blending amount of ⁇ -caprolactone was 228 parts by mass and the blending amount of bisphenol A diglycidyl ether was 170 parts by mass. It was confirmed by 1 H-NMR and 13 C-NMR that the curable resin D was the compound represented by the above formula (6).
• Examples 1 to 13, Comparative Examples 1 to 9 According to the compounding ratios shown in Tables 1 and 2, each material was stirred with a planetary stirrer and then uniformly mixed with a ceramic triple roll to obtain sealants for liquid crystal display elements of Examples 1 to 13 and Comparative Examples 1 to 9.
• Awatori Mixer manufactured by Thinky Corporation
• the epoxy functional group ratio of the curable resin in each of the resulting sealants for liquid crystal display elements is shown in Tables 1 and 2.
• the obtained sealant for liquid crystal display devices was dotted on one of two polyimide substrates, each having a length of 45 mm, a width of 25 mm, and a thickness of 0.7 mm, so that the diameter of the dotted polyimide substrate when bonded was 3 mm.
• the other polyimide substrate was overlapped on the polyimide substrate dotted with the sealant, shifted by 10 mm in the longitudinal direction, via the sealant.
• a metal halide lamp was used to irradiate the substrate with ultraviolet light having a wavelength of 365 nm and an illuminance of 100 mW/cm 2 for 30 seconds (accumulated light quantity 3000 mJ/cm 2 ) to obtain a test piece having a cured product of the sealant having a thickness of 5.0 ⁇ m.
• an SE-1500M manufactured by Sen Special Light Source Co., Ltd.
• the ultraviolet light was irradiated through a 340 nm cut filter (manufactured by Asahi Spectroscopic Co., Ltd.).
• the compressive shear adhesive strength (low-speed compressive shear adhesive strength) of the obtained test pieces was measured using an Autograph AGX (manufactured by Shimadzu Corporation) in accordance with JIS K 6852 at 25° C. and a shear rate of 1 mm/sec. The results are shown in Tables 1 and 2.
• Each of the obtained sealants for liquid crystal display elements was irradiated with ultraviolet light having a wavelength of 365 nm and an illuminance of 100 mW/ cm2 for 30 seconds (accumulated light quantity 3000 mJ/ cm2 ) using a metal halide lamp to obtain a cured product.
• a metal halide lamp an SE-1500M (manufactured by Sen Special Light Sources Co., Ltd.) was used, and ultraviolet light was irradiated through a 340 nm cut filter (manufactured by Asahi Spectroscopic Co., Ltd.).
• the obtained cured products were subjected to dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device under the conditions of a tensile mode, 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, and the storage modulus at 25°C was measured.
• the results are shown in Tables 1 and 2.
• Adhesion to alignment film An imide resin was applied by spin coating to a glass substrate with an ITO thin film, prebaked at 80° C., and then baked at 230° C. to prepare a substrate with an alignment film.
• SE7492 manufactured by Nissan Chemical Industries, Ltd.
• the thickness of the resulting alignment film (imide alignment film) was 100 nm.
• 1 part by mass of silica spacer was uniformly dispersed by a planetary stirring device.
• SI-H055 manufactured by Sekisui Chemical Co., Ltd.
• the sealant in which the silica spacer was dispersed was dropped in small drops onto the alignment film of the substrate with the alignment film.
• Another substrate with an alignment film was laminated in a cross shape to the substrate with the alignment film on which the sealant was dropped, via the sealant, and the substrate was irradiated with ultraviolet light having a wavelength of 365 nm and an illuminance of 100 mW/cm 2 from a metal halide lamp for 30 seconds (accumulated light quantity 3000 mJ/cm 2 ), and then heated at 120°C for 1 hour to obtain an adhesive test piece.
• SE-1500M manufactured by Sen Special Light Sources Co., Ltd.
• the ultraviolet light was irradiated through a 340 nm cut filter (manufactured by Asahi Spectroscopic Co., Ltd.).
• the strength at which the panel peeled off occurred when the edge of the substrate of the prepared adhesive test piece was pressed in at a speed of 5 mm/min using a metal cylinder with a radius of 5 mm was measured.
• the adhesiveness to the alignment film was evaluated by dividing the measured value (kgf) by the seal diameter (cm) as follows: 3.0 kgf/cm or more is indicated as “ ⁇ ”, 2.5 kgf/cm or more but less than 3.0 kgf/cm is indicated as " ⁇ ", 2.0 kgf/cm or more but less than 2.5 kgf/cm is indicated as " ⁇ ”, and less than 2.0 kgf/cm is indicated as "X”.
• a moisture permeability test cup was prepared according to the moisture permeability test method for moisture-proof packaging materials (cup method) of JIS Z 0208, the obtained moisture permeability test film was attached, and the cup was placed in a constant temperature and humidity oven at a temperature of 80°C and a humidity of 90% RH to measure the moisture permeability.
• silica spacer was added to 100 parts by mass of each sealant for liquid crystal display elements obtained in the examples and comparative examples, and the mixture was uniformly dispersed by a planetary stirring device, and the bubbles in the sealant for liquid crystal display elements were removed by defoaming treatment, after which the mixture was filled into a syringe for dispensing and defoaming treatment was performed again.
• SI-H055 manufactured by Sekisui Chemical Co., Ltd.
• PSY-10E manufactured by Musashi Engineering Co., Ltd.
• the sealant for liquid crystal display elements was applied to a glass substrate so as to draw a frame using a dispenser.
• SHOTMASTER300 manufactured by Musashi Engineering Co., Ltd.
• minute droplets of FFS liquid crystal were applied dropwise into the frame of the sealant for liquid crystal display elements using a liquid crystal dropping device.
• a glass substrate coated with FFS liquid crystal was overlaid with another glass substrate via a sealant for liquid crystal display elements, and the two substrates were bonded together under a reduced pressure of 5 Pa using a vacuum bonding device to obtain a cell.
• JC-5223XX manufactured by Chisso Corporation
• the obtained cell was irradiated with ultraviolet light having a wavelength of 365 nm and an illuminance of 100 mW/cm 2 from a metal halide lamp for 30 seconds (accumulated light quantity 3000 mJ/cm 2 ) to produce a liquid crystal display element in which the sealant for liquid crystal display elements was cured by light alone.
• SE-1500M manufactured by Sen Special Light Sources Co., Ltd.
• ultraviolet light irradiation was performed through a 340 nm cut filter (manufactured by Asahi Spectroscopic Co., Ltd.).
• the obtained liquid crystal display element was exposed to an ultrasonic cleaner (manufactured by AS ONE CORPORATION, "VS-10003", 28 kH condition) for 10 minutes. After the exposure, the liquid crystal display element was observed under a microscope, and peeling prevention properties after photocuring were evaluated by rating the case where no peeling of the substrate was observed as " ⁇ ” and the case where peeling of the substrate was observed as " ⁇ ".
• an ultrasonic cleaner manufactured by AS ONE CORPORATION, "VS-10003", 28 kH condition
• the present invention provides a sealant for liquid crystal display elements that has excellent adhesion to alignment films and moisture resistance, and can suppress peeling after photocuring even when applied to large substrates.

Landscapes

• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Nonlinear Science (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Mathematical Physics (AREA)
• Crystallography & Structural Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Sealing Material Composition (AREA)
• Liquid Crystal (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=91955967

Family Applications (1)

Country Status (5)

Citations (6)

Family Cites Families (2)

• 2024
  • 2024-01-12 WO PCT/JP2024/000588 patent/WO2024154662A1/ja not_active Ceased
  • 2024-01-12 CN CN202480004641.6A patent/CN120092207A/zh active Pending
  • 2024-01-12 JP JP2024504240A patent/JP7649420B2/ja active Active
  • 2024-01-12 KR KR1020257026753A patent/KR20250135827A/ko active Pending
  • 2024-01-15 TW TW113101535A patent/TW202438631A/zh unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events