WO2022071116A1 - チオキサントン化合物、光重合開始剤、硬化性樹脂組成物、表示素子用組成物、液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子 - Google Patents

チオキサントン化合物、光重合開始剤、硬化性樹脂組成物、表示素子用組成物、液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子 Download PDF

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Publication number
WO2022071116A1
WO2022071116A1 PCT/JP2021/035089 JP2021035089W WO2022071116A1 WO 2022071116 A1 WO2022071116 A1 WO 2022071116A1 JP 2021035089 W JP2021035089 W JP 2021035089W WO 2022071116 A1 WO2022071116 A1 WO 2022071116A1
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Prior art keywords
liquid crystal
display element
meth
curable resin
crystal display
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PCT/JP2021/035089
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English (en)
French (fr)
Japanese (ja)
Inventor
信烈 梁
大輝 山脇
剛 大浦
秀幸 林
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to CN202180043468.7A priority Critical patent/CN115996959B/zh
Priority to KR1020227038335A priority patent/KR20230078950A/ko
Priority to JP2021559819A priority patent/JP7144627B2/ja
Publication of WO2022071116A1 publication Critical patent/WO2022071116A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • 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 thioxanthone compounds. Further, the present invention comprises a photopolymerization initiator composed of the thioxanthone compound, a curable resin composition containing the photopolymerization initiator, a composition for a display element using the curable resin composition, and the curing.
  • the present invention relates to a sealant for a liquid crystal display element using a sex resin composition. Further, the present invention relates to a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
  • a liquid crystal display dropping method called a dropping method using a sex resin composition as a sealing agent is used.
  • a frame-shaped seal pattern is formed on one of the two transparent substrates with electrodes by dispensing.
  • a narrowing of the frame of the liquid crystal display unit is mentioned.
  • the position of the seal portion is arranged under the black matrix (hereinafter, also referred to as a narrow frame design).
  • the sealant In the narrow frame design, the sealant is placed directly under the black matrix, so if the dropping method is used, the light emitted when the sealant is photocured will be blocked. In the future, if the frame is narrowed or the liquid crystal material is changed, there is a risk that liquid crystal contamination will occur due to the elution of the uncured sealant component into the liquid crystal, even if the sealant has no problem in the past. There is. Therefore, there has been a demand for a sealant having a lower liquid crystal contamination property.
  • ultraviolet irradiation is usually performed as a method of photocuring the sealant, but especially in the liquid crystal dropping method, since the sealant is cured after the liquid crystal is dropped, the liquid crystal is exposed to ultraviolet rays. There was a problem that it was easily deteriorated. Therefore, in order to prevent deterioration of the liquid crystal display due to ultraviolet rays, photo-curing is performed by light having a long wavelength in the visible light region through a cut filter or the like.
  • a method of photocuring the sealant with long-wavelength light a method of using a sensitizer having high sensitivity to long-wavelength light in combination with a photopolymerization initiator can be considered.
  • Patent Document 3 and Patent Document 4 disclose a curable resin composition in which a photopolymerization initiator and a sensitizer are combined and blended.
  • these curable resin compositions are used as a sealant for a liquid crystal display element, the total amount of the photopolymerization initiator and the sensitizer becomes large in order to sufficiently photo-cure with light having a long wavelength. This may cause liquid crystal contamination or reduce storage stability.
  • An object of the present invention is to provide a thioxanthone compound having excellent reactivity with light having a long wavelength. Further, the present invention uses a photopolymerization initiator composed of the thioxanthone compound, a curable resin composition containing the photopolymerization initiator and excellent storage stability and curability of a light-shielding portion, and the curable resin composition. It is an object of the present invention to provide a sealant for a liquid crystal display element, which comprises a composition for a display element and the curable resin composition, which is excellent in low liquid crystal contamination. Further, an object of the present invention is to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
  • the present invention is a thioxanthone compound represented by the following formula (1).
  • X represents a structure represented by the following formula (2-1), (2-2), or (2-3), and R 1 is an independent hydrogen atom. Represents a methyl group, an ethyl group, or a nitro group, and R 2 independently represents a hydrogen atom, a methyl group, an ethyl group, or a nitro group.
  • R3 represents a structure containing a heteroatom and containing an aromatic ring
  • * represents a bond position
  • the present inventors have studied to improve the curability of a light-shielding portion by adding a photopolymerization initiator having excellent reactivity to long-wavelength light to a curable resin composition.
  • a photopolymerization initiator having excellent reactivity to long-wavelength light
  • the obtained curable resin composition becomes inferior in storage stability, or when the obtained curable resin composition is used as a sealing agent for a liquid crystal display element. May cause liquid crystal contamination. Therefore, the present inventors have studied the use of a thioxanthone compound having a specific structure as a photopolymerization initiator.
  • the above-mentioned "long wavelength” means light having a wavelength of 400 nm or more.
  • the thioxanthone compound of the present invention is represented by the above formula (1).
  • X represents a structure represented by the above formula (2-1), (2-2), or (2-3), and the above formulas (2-1) and (2-2).
  • R3 represents a structure containing a heteroatom and containing an aromatic ring.
  • the thioxanthone compound of the present invention has excellent reactivity to long-wavelength light because the conjugation of the thioxanthone skeleton is extended by the structure in which R 3 contains a hetero atom and contains an aromatic ring. ..
  • the curable resin composition has excellent curability in a light-shielding portion.
  • the above R 3 has the following formulas (3-1), (3-2), (3-3), (3-4), (3). -5), (3-6), (3-7), or (3-8) is preferable, and the structure is preferably used as a sealing agent for a liquid crystal display element due to a high electron density. Since it is more excellent in low liquid crystal contamination, it is represented by the following formula (3-1), (3-2), (3-3), (3-4), or (3-5). The structure is more preferable, and the structure represented by the following formula (3-1) is further preferable.
  • R 1 independently represents a hydrogen atom, a methyl group, an ethyl group, or a nitro group
  • R 2 independently represents a hydrogen atom, a methyl group, an ethyl group, and the like. Alternatively, it represents a nitro group.
  • at least one R 1 in the formula (1) is a methyl group or an ethyl group
  • at least one R 2 in the above formula (1) is from the viewpoint of solubility in a curable resin described later. It is preferably a methyl group or an ethyl group.
  • the preferred lower limit of the molecular weight of the thioxanthone compound of the present invention is 500, and the preferred upper limit is 1000.
  • the molecular weight is in this range, and the low liquid crystal contamination property becomes more excellent.
  • the more preferable lower limit of the molecular weight of the thioxanthone compound of the present invention is 550, and the more preferable upper limit is 800.
  • the above-mentioned "molecular weight” is the molecular weight obtained from the structural formula for a compound whose molecular structure is specified, but for a compound having a wide distribution of degree of polymerization and a compound having an unspecified modification site. It may be expressed using a number average molecular weight.
  • the above-mentioned "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. Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.
  • the thioxanthone compound of the present invention is suitably used as a photopolymerization initiator.
  • a photopolymerization initiator composed of the thioxanthone compound of the present invention is also one of the present inventions.
  • a curable resin composition containing a curable resin and the photopolymerization initiator of the present invention is also one of the present inventions.
  • the present invention is in the range in which the curability of the light-shielding portion can be maintained when the curable resin composition of the present invention is used as a sealant for a liquid crystal display element.
  • the sealant for a liquid crystal display element can be made more excellent in low liquid crystal contamination.
  • the content of the photopolymerization initiator of the present invention in the curable resin composition of the present invention is preferably 0.05 parts by weight and a preferable upper limit of 3 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the photopolymerization initiator of the present invention When the content of the photopolymerization initiator of the present invention is 0.05 parts by weight or more, the obtained curable resin composition becomes more excellent in the light-shielding portion curability. When the content of the photopolymerization initiator of the present invention is 3 parts by weight or less, the obtained curable resin composition becomes more excellent in storage stability, and the curable resin composition is sealed for a liquid crystal display element. When used as an agent, it is superior in low liquid crystal contamination.
  • the more preferable lower limit of the content of the photopolymerization initiator of the present invention is 0.1 parts by weight, and the more preferable upper limit is 2 parts by weight.
  • the curable resin composition of the present invention may contain other photopolymerization initiators other than the photopolymerization initiator of the present invention as long as the object of the present invention is not impaired.
  • the other photopolymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, and other thioxanthone compounds other than the photopolymerization initiator of the present invention. Can be mentioned.
  • photopolymerization initiator examples include 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and 1,2- (dimethylamino).
  • the curable resin composition of the present invention contains a curable resin.
  • the curable resin preferably contains a (meth) acrylic compound, and more preferably contains a (meth) acrylic compound and an epoxy compound.
  • (meth) acrylic means acrylic or methacrylic
  • (meth) acrylic compound means a compound having a (meth) acryloyl group
  • (meth) means acryloyl or methacryloyl.
  • the (meth) acrylic compound examples include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable. Further, the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
  • (meth) acrylate means acrylate or methacrylate
  • epoxy (meth) acrylate means that all epoxy groups in the epoxy compound are referred to as (meth) acrylic acid. It means a reacted compound.
  • 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.
  • Dimethylol dicyclopentadienyldi (meth) acrylate Dimethylol dicyclopentadienyldi (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, Examples thereof include polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and polybutadiene diol di (meth) acrylate.
  • those having trifunctionality or higher include, for example, trimethylol propanetri (meth) acrylate, ethylene oxide-added trimethylol propanetri (meth) acrylate, and propylene oxide-added trimethylol 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 above 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 Novolak type epoxy compound, orthocresol novolak type epoxy compound, dicyclopentadiene novolak type epoxy compound, biphenylnovolak type epoxy compound, naphthalenephenol novolak type epoxy compound, glycidylamine type epoxy compound, alkylpolypoly type epoxy compound, rubber-modified epoxy compound , Glysidyl ester compound and the like.
  • 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 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
  • Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA1514 (manufactured by DIC Corporation) and the like.
  • Examples of commercially available 2,2'-diallyl bisphenol A type epoxy compounds include 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 Nittetsu Chemical & Materials Co., Ltd.).
  • Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nittetsu Chemical & Materials Co., Ltd.).
  • 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 novolak type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like.
  • Examples of commercially available dicyclopentadiene novolak 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 Nittetsu 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 those commercially available include, for example, ZX-1542 (manufactured by Nittetsu 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 can be mentioned.
  • ZX-1542 manufactured by Nittetsu Chemical & Materials Co., Ltd.
  • EPICLON 726 manufactured by DIC Corporation
  • Epolite 80MFA manufactured by Kyoei Co., Ltd.
  • Denacol EX. -611 manufactured by Nagase ChemteX Corporation
  • Examples of commercially available rubber-modified epoxy compounds include YR-450, YR-207 (all manufactured by Nittetsu Chemical & Materials Co., Ltd.), Epolide PB (manufactured by Daicel Co., Ltd.), and the like.
  • Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation) and the like.
  • epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nittetsu Chemical & Materials Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031 and jER1032. (All manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.
  • epoxy (meth) acrylates commercially available ones include, for example, epoxy (meth) acrylate manufactured by Dycel Ornex, epoxy (meth) acrylate manufactured by Shin Nakamura Chemical Industry Co., Ltd., and epoxy manufactured by Kyoei Co., Ltd. Examples thereof include meta) acrylate and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
  • Examples of the epoxy (meth) acrylate manufactured by Dycel Ornex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, 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, EMA-1020 and the like.
  • 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.
  • the urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with respect to an isocyanate compound in the presence of a catalytic amount of a tin-based compound.
  • isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), and hydrogenated products.
  • MDI Polymeric MDI, 1,5-naphthalenediocyanate, norbornan diisocyanate, trizine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, tetramethylxylylene diisocyanate Examples thereof include isocyanates and 1,6,11-undecantry isocyanates.
  • isocyanate compound a chain-extended isocyanate compound obtained by reacting a polyol with an excess 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 or 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.
  • urethane (meth) acrylates commercially available ones include, for example, urethane (meth) acrylate manufactured by Toa Synthetic Co., Ltd., urethane (meth) acrylate manufactured by Dycel 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., urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like. 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, UA-306T and the like. Be done.
  • the epoxy compound examples include an epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth) acrylate, a partially (meth) acrylic-modified epoxy compound, and the like.
  • the above-mentioned partially (meth) acrylic-modified epoxy compound means, for example, reacting a part of the epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid. It means a compound having one or more epoxy groups and one or more (meth) acryloyl groups in one molecule, which can be obtained by.
  • the (meth) acrylic compound and the epoxy compound are contained as the curable resin, or when the partially (meth) acrylic-modified epoxy compound is contained, the (meth) acryloyl group and the epoxy in the curable resin are contained. It is preferable that the ratio of the (meth) acryloyl group in the total with the group is 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl group is in this range, the curable resin composition obtained is excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination when used as a sealant for a liquid crystal display element. Become.
  • the curable resin has -OH group, -NH- group, and -NH 2 groups from the viewpoint of making the obtained curable resin composition more excellent in low liquid crystal contamination property when used as a sealant for a liquid crystal display element.
  • Those having a hydrogen-bonding unit such as the above are preferable.
  • the curable resin may be used alone or in combination of two or more.
  • the curable resin composition of the present invention may contain a sensitizer.
  • the sensitizer has a role of further improving the polymerization initiation efficiency of the photopolymerization initiator and further promoting the curing reaction of the curable resin composition of the present invention.
  • sensitizer examples include ethyl 4- (dimethylamino) benzoate, 9,10-dibutoxyanthracene, 2,4-diethylthioxanthone, and 2,2-dimethoxy-1,2-diphenylethan-1-one.
  • the content of the sensitizer is preferably 0.01 part by weight and a preferable upper limit of 3 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited.
  • the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption.
  • the more preferable lower limit of the content of the sensitizer is 0.1 parts by weight, and the more preferable upper limit is 1 part by weight.
  • the curable resin composition of the present invention may contain a thermal polymerization initiator as long as the object of the present invention is not impaired.
  • the thermal polymerization initiator include those composed of an azo compound, an organic peroxide, or the like.
  • an initiator composed of an azo compound hereinafter, also referred to as “azo initiator”.
  • an initiator composed of a polymer azo compound hereinafter, also referred to as "polymer azo initiator”
  • the thermal polymerization initiator may be used alone or in combination of two or more.
  • 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) acryloyl group by heat. do.
  • 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, when the obtained curable resin composition is used as a sealing agent for a liquid crystal display element, it is easy to obtain a curable resin while preventing adverse effects on the liquid crystal. Can be mixed.
  • 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.
  • 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.
  • polymer azo initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like. Can be mentioned.
  • examples of the non-polymer azo initiator include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
  • organic peroxide examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates and the like.
  • the content of the thermal polymerization initiator has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the thermosetting initiator is in this range, the curable resin composition obtained can be used as a sealant for a liquid crystal display element to suppress liquid crystal contamination, and the storage stability and thermosetting property can be improved. It will be excellent.
  • the more preferable lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.
  • the curable resin composition of the present invention may contain a thermosetting agent.
  • the heat-curing agent include organic acid hydrazide, imidazole derivative, amine compound, polyvalent phenolic compound, acid anhydride and the like. Of these, organic acid hydrazide is preferably used.
  • the thermosetting agent may be used alone or in combination of two or more.
  • Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
  • Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., Ltd., and the like.
  • Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
  • Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J and the like.
  • 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 thermosetting resin composition can be made more excellent in thermosetting property without deteriorating the coatability and the like.
  • a more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
  • the curable resin composition of the present invention preferably contains a filler for the purpose of adjusting the viscosity, further 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 soil, smectite, bentonite, montmorillonite, sericite, active white clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide and titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
  • the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like. The filler may be used alone or in combination of two or more.
  • the preferable lower limit of the content of the filler in 100 parts by weight of the curable resin composition of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
  • the content of the filler is in this range, the effect of improving the adhesiveness and the like is excellent without deteriorating the coatability and the like.
  • 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 curable resin composition of the present invention may contain a silane coupling agent.
  • the silane coupling agent mainly has a role as an adhesive auxiliary for satisfactorily adhering the curable resin composition to an adherend such as a substrate.
  • silane coupling agent for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesiveness to the substrate and the like, and when the curable resin composition obtained by chemically bonding with the curable resin is used as a sealant for a liquid crystal display element, the curability into the liquid crystal is excellent. The outflow of resin can be suppressed.
  • 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 curable resin composition 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 within this range, the effect of improving the adhesiveness while suppressing the occurrence of liquid crystal contamination when the obtained curable resin composition is used as a sealant for a liquid crystal display element is obtained. It will be excellent.
  • 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 curable resin composition of the present invention may contain a light-shielding agent.
  • the curable resin composition of the present invention can be suitably used as a light-shielding sealant. Since the curable resin composition of the present invention contains the photopolymerization initiator of the present invention having excellent reactivity with long-wavelength light, it is considered to have excellent curability with respect to long-wavelength light even when the above-mentioned light-shielding agent is contained. Become.
  • Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, a substance having high insulating properties is preferable, and titanium black is more preferable.
  • 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, and oxidation.
  • an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, and 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 device manufactured by using the curable resin composition of the present invention containing the titanium black as a light-shielding agent has sufficient light-shielding properties, so that there is no light leakage and high contrast is obtained, which is excellent. A display element having image display quality can be realized.
  • titanium blacks for example, 12S, 13M, 13M-C, 13RN, 14M-C (all manufactured by Mitsubishi Materials), Tilak D (manufactured by Ako Kasei Co., Ltd.) and the like are commercially available. Can be mentioned.
  • 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 preferable upper limit is 3 ⁇ ⁇ cm, the more preferable lower limit is 1 ⁇ ⁇ cm, and the more preferable upper limit is 2.5 ⁇ ⁇ cm.
  • the preferable lower limit of the primary particle diameter of the light-shielding agent is 1 nm, and the preferable upper limit is 5000 nm.
  • the primary particle size of the light-shielding agent is in this range, the light-shielding property can be improved without deteriorating the drawing property of the obtained curable resin composition.
  • 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, and 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) to disperse 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 curable resin composition 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, the obtained curable resin composition has better light-shielding properties without deteriorating the adhesiveness to the adherend such as a substrate, the strength after curing, and the drawing property. Can be demonstrated.
  • a more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a further preferable lower limit is 30 parts by weight, and a further preferable upper limit is 60 parts by weight.
  • the curable resin composition of the present invention further contains additives such as a stress relaxation agent, a reactive diluent, a rocking agent, a spacer, a curing accelerator, a leveling agent, and a polymerization inhibitor, if necessary. May be good.
  • a curable resin composition of the present invention for example, a curable resin, a photopolymerization initiator, and an additive such as a silane coupling agent used as necessary are used in a mixer.
  • a method for mixing examples include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.
  • the curable resin composition of the present invention can be suitably used for a composition for a display element, and can be particularly preferably used as a sealant for a liquid crystal display element.
  • a composition for a display element and a sealant for a liquid crystal display element using the curable resin composition of the present invention are also one of the present inventions, respectively.
  • a vertically conductive material By blending conductive fine particles with the sealant for a liquid crystal display element of the present invention, a vertically conductive material can be manufactured.
  • a vertically conductive material containing a sealing agent for a liquid crystal display element of the present invention and conductive fine particles is also one of the present inventions.
  • the conductive fine particles a metal ball, a resin fine particle having a conductive metal layer formed on the surface thereof, or the like can be used.
  • 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 liquid crystal display element using the sealant for a liquid crystal display element of the present invention or the vertically conductive material of the present invention is also one of the present inventions.
  • the sealant for a liquid crystal display element of the present invention can be suitably used for manufacturing a liquid crystal display element by a liquid crystal dropping method.
  • Examples of the method for manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods. First, a step of applying the sealant for a liquid crystal display element of the present invention to a substrate to form a frame-shaped seal pattern is performed. Next, in a state where the sealant for a liquid crystal display element of the present invention is uncured, fine droplets of liquid crystal are dropped and applied on the entire surface of the frame of the seal pattern, and another substrate is immediately superimposed. After that, a liquid crystal display element can be obtained by a method of irradiating the seal pattern portion with light to photo-curing the sealant.
  • the sealant By irradiating light with a long wavelength such as visible light, damage caused by light irradiation to peripheral members can be mitigated, and even when the sealant is placed in the light-shielding portion, the sealant can be sufficiently applied. Can be photocured. Further, in addition to the step of photo-curing the sealant, a step of heating and curing the sealant may be performed.
  • a thioxanthone compound having excellent reactivity with light having a long wavelength it is possible to provide a thioxanthone compound having excellent reactivity with light having a long wavelength.
  • a curable resin composition containing the photopolymerization initiator composed of the thioxanthone compound and the photopolymerization initiator, which is excellent in storage stability and light-shielding portion curability, and the curable resin composition By using the composition for a display element to be used and the curable resin composition, it is possible to provide a sealant for a liquid crystal display element having excellent low liquid crystal contamination property. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.
  • FIG. 1 is a cross-sectional view schematically showing a liquid crystal display element manufactured by using each of the curable resin compositions obtained in Examples and Comparative Examples without a light-shielding portion.
  • FIG. 2 is a cross-sectional view schematically showing a liquid crystal display element manufactured by using each of the curable resin compositions obtained in Examples and Comparative Examples with a light-shielding portion.
  • Examples 1 to 15 Comparative Examples 1 to 4
  • a planetary stirrer manufactured by Shinky Co., Ltd., "Awatori Rentaro"
  • Curable resin compositions of Examples 1 to 15 and Comparative Examples 1 to 4 were prepared.
  • the curable resin composition portion of the bonded glass substrate was irradiated with light of 100 mW / cm 2 for 10 seconds using a metal halide lamp.
  • the light irradiation was performed through a cut filter (400 nm cut filter) that cuts light having a wavelength of 400 nm or less.
  • An FT-IR measurement of the curable resin composition was performed using an infrared spectroscope (“FTS3000” manufactured by BIORAD), and the amount of change in the (meth) acryloyl group-derived peak before and after light irradiation was measured.
  • the curable resin composition portion was irradiated with light of 100 mW / cm 2 for 30 seconds using a metal halide lamp to cure it, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
  • the light irradiation was performed through a cut filter (400 nm cut filter) that cuts light having a wavelength of 400 nm or less.
  • the liquid crystal display element controls the application position of the curable resin composition with a dispenser, and the liquid crystal display element (without a light-shielding portion) in which the curable resin composition is completely exposed to light, and the curable resin composition are the color filter substrates.
  • FIG. 1 is a cross-sectional view schematically showing a liquid crystal display element manufactured by using each of the curable resin compositions obtained in Examples and Comparative Examples without a light-shielding portion
  • FIG. 2 shows Examples and FIGS.
  • It is sectional drawing which shows typically the liquid crystal display element manufactured in the state of having the light-shielding part using each curable resin composition obtained in the comparative example.
  • the curable resin composition 1 has no light-shielding portion, the curable resin composition 1 is completely exposed to light, while the curable resin composition 1 has a light-shielding portion.
  • the curable resin composition 1 at the portion in contact with the liquid crystal 3 is shielded by the black matrix 2 and almost no light reaches it.
  • the obtained liquid crystal display element was subjected to an operation test for 100 hours, and then the liquid crystal alignment disorder (display unevenness) was visually confirmed after the voltage was applied at 80 ° C. for 1000 hours.
  • “ ⁇ ” indicates that there is no display unevenness on the liquid crystal display element
  • " ⁇ ” indicates that a slightly thin display unevenness appears near (peripheral part) of the curable resin composition of the liquid crystal display element, and clearly on the peripheral part.
  • the low liquid crystal contamination property was evaluated as " ⁇ " when there was a dark display unevenness, and as “x” when the clear dark display unevenness spread not only to the peripheral part but also to the central part.
  • the liquid crystal display elements with evaluations of " ⁇ ” and “ ⁇ ” are at a level that does not cause any problems in practical use, and the liquid crystal display elements with " ⁇ ” are at a level that may cause problems depending on the display design.
  • the liquid crystal display element of "x" is at a level that cannot withstand practical use.
  • a thioxanthone compound having excellent reactivity with light having a long wavelength it is possible to provide a thioxanthone compound having excellent reactivity with light having a long wavelength.
  • a curable resin composition containing the photopolymerization initiator composed of the thioxanthone compound and the photopolymerization initiator, which is excellent in storage stability and light-shielding portion curability, and the curable resin composition By using the composition for a display element to be used and the curable resin composition, it is possible to provide a sealant for a liquid crystal display element having excellent low liquid crystal contamination property. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

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PCT/JP2021/035089 2020-09-30 2021-09-24 チオキサントン化合物、光重合開始剤、硬化性樹脂組成物、表示素子用組成物、液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子 Ceased WO2022071116A1 (ja)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007284516A (ja) * 2006-04-14 2007-11-01 Toyo Ink Mfg Co Ltd 紫外線遮断性樹脂組成物及びその利用
JP2010520317A (ja) * 2007-02-28 2010-06-10 ディーエスエム アイピー アセッツ ビー．ブイ． 親水性コーティング
JP2016504274A (ja) * 2012-11-08 2016-02-12 中国科学院理化技術研究所 チオキサントンオキシド系誘導物、製造方法及びその応用
WO2017002362A1 (ja) * 2015-06-30 2017-01-05 三井化学株式会社 光硬化性樹脂組成物、表示素子シール剤、液晶シール剤、液晶表示パネル及び液晶表示パネルの製造方法
WO2020013128A1 (ja) * 2018-07-10 2020-01-16 積水化学工業株式会社 液晶素子用シール剤、上下導通材料、及び、液晶素子
WO2020084988A1 (ja) * 2018-10-26 2020-04-30 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子
JP2020097746A (ja) * 2018-04-11 2020-06-25 積水化学工業株式会社 表示素子用シール剤、上下導通材料、及び、表示素子
US20200270278A1 (en) * 2019-10-31 2020-08-27 Shanghai Tianma AM-OLED Co., Ltd. Compound, a display panel and an electronic device

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3583326B2 (ja) 1999-11-01 2004-11-04 協立化学産業株式会社 Ｌｃｄパネルの滴下工法用シール剤
WO2002092718A1 (fr) 2001-05-16 2002-11-21 Sekisui Chemical Co., Ltd. Composition de resine durcissable, mastics et matieres pour soudage en bout destines aux afficheurs
JP6120574B2 (ja) * 2012-01-31 2017-04-26 キヤノン株式会社 感光性ネガ型樹脂組成物、微細構造体、微細構造体の製造方法及び液体吐出ヘッド
WO2015083663A1 (ja) * 2013-12-05 2015-06-11 積水化学工業株式会社 重合性単量体、高分子化合物、光硬化性樹脂組成物、液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子
JP2015120779A (ja) * 2013-12-20 2015-07-02 株式会社Kri 遅延蛍光発光体及び有機ｅｌ素子
CN106278967B (zh) * 2015-06-03 2020-08-07 江苏和成新材料有限公司 用于uv固化材料的酰基肟酯类化合物及其合成方法及应用
JP6554040B2 (ja) 2016-01-25 2019-07-31 三井化学株式会社 液晶表示パネル及び液晶表示パネルの製造方法
CN108084299B (zh) * 2016-11-21 2020-11-10 中国石油化工股份有限公司 具有引发聚合反应功能的组合物及制备丙烯酰胺共聚物的方法
CN108219691A (zh) * 2016-12-22 2018-06-29 日本化药株式会社 光固化性树脂组合物和电子部件用密封剂
CN106831817B (zh) * 2016-12-30 2019-09-03 上海天马有机发光显示技术有限公司 一种有机电致发光材料以及有机光电装置
JP6190553B2 (ja) 2017-02-20 2017-08-30 協立化学産業株式会社 光重合開始剤
CN106995430A (zh) * 2017-03-15 2017-08-01 同济大学 新型硫杂蒽酮化合物及其应用
KR20200015487A (ko) * 2017-06-06 2020-02-12 닛뽄 가야쿠 가부시키가이샤 광경화성 조성물 및 전자 부품용 접착제
CN110590824B (zh) * 2019-08-28 2022-12-16 苏州欧纳克纳米科技有限公司 一种硫杂蒽酮有机锆配合物光引发剂及其制备方法和应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007284516A (ja) * 2006-04-14 2007-11-01 Toyo Ink Mfg Co Ltd 紫外線遮断性樹脂組成物及びその利用
JP2010520317A (ja) * 2007-02-28 2010-06-10 ディーエスエム アイピー アセッツ ビー．ブイ． 親水性コーティング
JP2016504274A (ja) * 2012-11-08 2016-02-12 中国科学院理化技術研究所 チオキサントンオキシド系誘導物、製造方法及びその応用
WO2017002362A1 (ja) * 2015-06-30 2017-01-05 三井化学株式会社 光硬化性樹脂組成物、表示素子シール剤、液晶シール剤、液晶表示パネル及び液晶表示パネルの製造方法
JP2020097746A (ja) * 2018-04-11 2020-06-25 積水化学工業株式会社 表示素子用シール剤、上下導通材料、及び、表示素子
WO2020013128A1 (ja) * 2018-07-10 2020-01-16 積水化学工業株式会社 液晶素子用シール剤、上下導通材料、及び、液晶素子
WO2020084988A1 (ja) * 2018-10-26 2020-04-30 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子
US20200270278A1 (en) * 2019-10-31 2020-08-27 Shanghai Tianma AM-OLED Co., Ltd. Compound, a display panel and an electronic device

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