WO2017130786A1 - Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element - Google Patents

Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element Download PDF

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Publication number
WO2017130786A1
WO2017130786A1 PCT/JP2017/001347 JP2017001347W WO2017130786A1 WO 2017130786 A1 WO2017130786 A1 WO 2017130786A1 JP 2017001347 W JP2017001347 W JP 2017001347W WO 2017130786 A1 WO2017130786 A1 WO 2017130786A1
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WO
WIPO (PCT)
Prior art keywords
liquid crystal
crystal display
compound
meth
acrylate
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PCT/JP2017/001347
Other languages
French (fr)
Japanese (ja)
Inventor
大輝 山脇
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積水化学工業株式会社
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Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2017503643A priority Critical patent/JP7048314B2/en
Priority to KR1020177033055A priority patent/KR20180101166A/en
Priority to CN201780001988.5A priority patent/CN107710060B/en
Publication of WO2017130786A1 publication Critical patent/WO2017130786A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
    • 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 a liquid crystal display element that is excellent in light-shielding part curability and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
  • a liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
  • a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
  • a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
  • the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
  • Patent Document 3 discloses that a highly sensitive photopolymerization initiator is blended with a sealant. However, liquid crystal contamination could not be sufficiently suppressed in the light-shielding part only by blending a highly sensitive photopolymerization initiator.
  • An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in sclerosis
  • hardenability of light-shielding part, and can suppress liquid-crystal contamination. Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
  • the present invention relates to a sealing agent for a liquid crystal display element comprising a curable resin and a radical photopolymerization initiator, the curable resin comprising a compound having a molecular weight of 100 or more and less than 500, and a compound having a molecular weight of 500 to 3000
  • the radical photopolymerization initiator is a sealing agent for liquid crystal display elements, which is a compound having a carbazole skeleton.
  • the present inventor has examined the use of a compound having a carbazole skeleton as a particularly sensitive photoradical polymerization initiator.
  • a radical photopolymerization initiator even when such a radical photopolymerization initiator is used, there is a problem that the light-shielding part is not sufficiently cured and liquid crystal contamination is likely to occur.
  • the present inventor believes that although the compound having a carbazole skeleton used as the radical photopolymerization initiator is highly sensitive, the light-curing part curability could not be sufficiently improved due to low solubility in the curable resin. It was.
  • the present inventor not only uses a compound having a carbazole skeleton as a radical photopolymerization initiator, but also has excellent light-shielding part curability by using a combination of a compound having a specific molecular weight as a curable resin, and The present inventors have found that a sealing agent for liquid crystal display elements that can suppress liquid crystal contamination can be obtained, and have completed the present invention.
  • the sealing agent for liquid crystal display elements of this invention contains curable resin.
  • the curable resin contains a compound having a molecular weight of 100 or more and less than 500 and a compound having a molecular weight of 500 to 3000.
  • the compound having a carbazole skeleton as a radical photopolymerization initiator can be sufficiently dissolved.
  • the sealing agent for liquid crystal display elements of the present invention is excellent in light-shielding part curability and can suppress liquid crystal contamination.
  • the “molecular weight” is a molecular weight obtained from the structural formula for a compound whose molecular structure is specified, but for a compound having a wide distribution of polymerization degree and a compound whose modification site is unspecified. , Sometimes expressed using weight average molecular weight.
  • the above “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC). Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
  • the curable resin contains a compound having a molecular weight of 100 or more and less than 500.
  • the compound having a molecular weight of 100 or more and less than 500 preferably has a molecular weight of 300 or more and less than 500 from the viewpoint of the solubility of the compound having a carbazole skeleton.
  • the curable resin preferably contains a (meth) acrylic compound as the compound having a molecular weight of 100 or more and less than 500.
  • a (meth) acrylic compound for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted.
  • examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group. Of these, epoxy (meth) acrylate is preferable.
  • the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule because of its high reactivity.
  • the “(meth) acryl” means acryl or methacryl
  • the “(meth) acryl compound” means an acryloyl group or a methacryloyl group (hereinafter referred to as “(meth) acryloyl group”). Also referred to as).
  • the “(meth) acrylate” means acrylate or methacrylate.
  • the “epoxy (meth) acrylate” represents a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid.
  • Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
  • those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, penta Examples include erythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, and the like.
  • Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
  • Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol.
  • diglycidyl ether hydrogenated bisphenol E diglycidyl ether, resorcinol diglycidyl ether, biphenyl-4,4′-diylbis (glycidyl ether), 1,6-naphthalenediylbis (glycidyl ether), ethylene glycol diglycidyl ether, 1 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and the like.
  • Examples of the urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid derivative with the isocyanate compound include, for example, (meth) acrylic having a hydroxyl group with respect to 1 equivalent of an isocyanate compound having two isocyanate groups. Two equivalents of the acid derivative can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
  • isocyanate compound used as the raw material for the urethane (meth) acrylate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4.
  • Examples include '-diisocyanate (MDI), hydrogenated MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, and tetramethylxylylene diisocyanate.
  • MDI '-diisocyanate
  • XDI xylylene diisocyanate
  • XDI hydrogenated XDI
  • lysine diisocyanate lysine diisocyanate
  • tetramethylxylylene diisocyanate examples include tetramethylxylylene diisocyanate.
  • Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Divalents such as hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, etc. And mono (meth) acrylates of alcohols.
  • the curable resin preferably contains an epoxy compound as a compound having a molecular weight of 100 or more and less than 500 from the viewpoint of adhesion and solubility of the compound having a carbazole skeleton.
  • an epoxy compound the epoxy compound used as a raw material for synthesize
  • the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy compounds. Can be obtained by reacting a part of the epoxy group with (meth) acrylic acid.
  • the curable resin contains a compound having a molecular weight of 500 to 3000.
  • the preferable lower limit of the molecular weight of the compound having a molecular weight of 500 to 3000 is 600, and the preferable upper limit is 2500.
  • the molecular weight of the compound having a molecular weight of 500 to 3000 is 600 or more, the solubility of the compound having a carbazole skeleton is improved.
  • the molecular weight of the compound having a molecular weight of 500 to 3000 is 2500 or less, the obtained sealing agent for liquid crystal display elements is more excellent in low liquid crystal contamination.
  • the more preferable lower limit of the molecular weight of the compound having a molecular weight of 500 to 3000 is 1000, and the more preferable upper limit is 2000.
  • the compound having a molecular weight of 500 to 3000 is preferably an oligomer compound, and more preferably an oligomer compound having a polymerization degree of 3 to 6.
  • the compound having a molecular weight of 500 to 3000 is preferably a polyfunctional compound having two or more epoxy groups and / or (meth) acryloyl groups in one molecule, which increases the crosslinking density and further suppresses elution. Since it can do, it is more preferable that it is a polyfunctional compound which has a comb-shaped structure like a novolak-type structure.
  • the compound having a molecular weight of 500 to 3000 include, for example, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, and naphthalene phenol novolac type epoxy resins.
  • Bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type Epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadi Reaction of oligomeric epoxy resins such as ene-type epoxy resins, naphthalene-type epoxy resins, glycidylamine-type epoxy resins, alkyl polyol-type epoxy resins, rubber-modified epoxy resins, and these oligomer-type epoxy resins with (meth) acrylic acid Examples thereof include oligomer-type epoxy (meth) acrylates and oligomer-type partial (meth) acryl-modified epoxy resins. Among these, oligomer type epoxy (meth) acrylate is preferable.
  • the preferable lower limit of the content of the compound having the molecular weight of 500 to 3000 in the total of 100 parts by weight of the compound having the molecular weight of 100 or more and less than 500 and the compound having the molecular weight of 500 to 3000 is 10 parts by weight, and the preferable upper limit is 30 parts by weight. Part.
  • the content of the compound having a molecular weight of 500 to 3000 is within this range, the obtained sealing agent for liquid crystal display elements is more excellent in the light-shielding part curability and the effect of suppressing liquid crystal contamination.
  • a more preferable lower limit of the content of the compound having a molecular weight of 500 to 3000 is 12 parts by weight, and a more preferable upper limit is 20 parts by weight.
  • the sealing agent for liquid crystal display elements of this invention contains radical photopolymerization initiator.
  • the photo radical polymerization initiator is a compound having a carbazole skeleton.
  • the sealing agent for liquid crystal display elements of the present invention is excellent in light-shielding part curability.
  • the minimum with a preferable molecular weight of the compound which has the said carbazole skeleton is 300, and a preferable upper limit is 1000.
  • a preferable molecular weight of the compound having the carbazole skeleton is within this range, the solubility in the curable resin is improved.
  • the more preferable lower limit of the molecular weight of the compound having a carbazole skeleton is 400, and the more preferable upper limit is 700.
  • the compound having a carbazole skeleton preferably has an aromatic ring other than the aromatic ring contained in the carbazole skeleton from the viewpoint of solubility in the curable resin. Moreover, since the compound having the carbazole skeleton is more excellent in light-shielding part curability, it preferably has a nitrogen atom other than the nitrogen atom contained in the carbazole skeleton, and more preferably has an oxime ester bond.
  • the compound having the carbazole skeleton preferably has an absorption coefficient of 50 mL / g ⁇ cm or more at a wavelength of 365 nm measured in acetonitrile mixed with the compound having the carbazole skeleton so that the concentration becomes 0.1 mg / mL.
  • the compound having the carbazole skeleton has an extinction coefficient of 50 mL / g ⁇ cm or more, the obtained sealing agent for liquid crystal display elements is more excellent in light-shielding part curability.
  • the light absorption coefficient of the compound having a carbazole skeleton is more preferably 100 mL / g ⁇ cm or more. Further, there is no particular upper limit of the light absorption coefficient of the compound having a carbazole skeleton, but the substantial upper limit is 1000 mL / g ⁇ cm.
  • the compound having the carbazole skeleton include, for example, O-acetyl-1- (6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl) ethanone oxime, 3,6 -Bis- (2methyl-2morpholino-propionyl) -9-N-octylcarbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-benzoylcarbazole, 3,6-bis (2-methyl) -2-morpholinopropionyl) -9-n-butylcarbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 2- (Nn-butyl-3′-carbazolyl) ) -4,6-bis (trichloromethyl) -s-triazine and the like.
  • Examples of commercially available compounds having the carbazole skeleton include IRGACURE OXE02 (manufactured by BASF).
  • the content of the compound having a carbazole skeleton is preferably 0.5 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the compound having the carbazole skeleton is within this range, the obtained sealing agent for liquid crystal display elements is excellent in light-shielding part curability, weather resistance, storage stability, and the effect of suppressing liquid crystal contamination.
  • the more preferable lower limit of the content of the compound having a carbazole skeleton is 1 part by weight, and the more preferable upper limit is 3 parts by weight.
  • the sealing agent for liquid crystal display elements of the present invention may contain other photoradical polymerization initiator as the photoradical polymerization initiator in addition to the compound having the carbazole skeleton, but the light-shielding part curability and the liquid crystal From the viewpoint of achieving both the effect of suppressing contamination, it is preferable that no other radical photopolymerization initiator is contained.
  • the sealing agent for liquid crystal display elements of the present invention may contain a sensitizer.
  • the sealing agent for liquid crystal display elements of this invention can obtain the sealing agent for liquid crystal display elements which is more sensitive and is excellent in light-shielding part curability by containing the said sensitizer.
  • the sensitizer preferably has a sufficient light absorption band in the ultraviolet / visible region, a compound having a benzophenone skeleton, a compound having an anthracene skeleton, a compound having an anthraquinone skeleton, a compound having a coumarin skeleton, a thioxanthone skeleton And at least one compound selected from the group consisting of compounds having a phthalocyanine skeleton, and a group consisting of a compound having an anthracene skeleton, a compound having an anthraquinone skeleton, and a compound having a thioxanthone skeleton More preferably, it is at least one compound selected.
  • Examples of the compound having a benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.
  • Examples of the compound having an anthracene skeleton include 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene.
  • Examples of the compound having an anthraquinone skeleton include 1-methylanthraquinone, 2-ethylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) anthraquinone and the like.
  • Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
  • Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
  • Examples of the compound having a phthalocyanine skeleton include phthalocyanine.
  • phthalocyanine examples include phthalocyanine.
  • 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis ( At least one of diethylamino) benzophenone is preferred.
  • the content of the sensitizer is such that a preferred lower limit is 2 parts by weight and a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the radical photopolymerization initiator.
  • a preferred lower limit is 2 parts by weight
  • a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the radical photopolymerization initiator.
  • the content of the sensitizer is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in light-shielding part curability while suppressing liquid crystal contamination.
  • the minimum with more preferable content of the said sensitizer is 5 weight part, and a more preferable upper limit is 40 weight part.
  • the sealing agent for liquid crystal display elements of the present invention may contain a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
  • an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
  • the polymer azo compound means a compound having an azo group and generating a radical by heat and having a number average molecular weight of 300 or more.
  • the preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000.
  • the more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
  • the said number average molecular weight is a value calculated
  • polymer azo initiator examples include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
  • polymer azo initiator 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.
  • Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
  • Examples of azo compounds that are not a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
  • organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
  • the content of the thermal radical polymerization initiator is preferably 0.05 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
  • the thermal radical polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination.
  • the minimum with more preferable content of the said thermal radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
  • the sealing agent for liquid crystal display elements of the present invention may contain a thermosetting agent.
  • thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
  • organic acid hydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
  • organic acid hydrazides examples include, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
  • the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
  • the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
  • the sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, and further improving the moisture resistance of the cured product. preferable.
  • the filler 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,
  • Organic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned.
  • the preferable lower limit of the content of the filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
  • the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
  • the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent.
  • the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
  • silane coupling agent since it is excellent in the effect which improves adhesiveness with a board
  • -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used.
  • These silane coupling agents may be used alone or in combination of two or more.
  • the minimum with preferable content of the said silane coupling agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part.
  • a preferable upper limit is 10 weight part.
  • the minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.
  • the sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent.
  • the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.
  • the light-shielding agent examples include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferred because of its high insulating properties.
  • the above-mentioned titanium black exhibits 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, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
  • the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage A liquid crystal display element having excellent image display quality can be realized.
  • titanium black examples include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. 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 preferred lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferred lower limit is 1 ⁇ ⁇ cm, and the more preferred upper limit is 2.5 ⁇ ⁇ cm.
  • the primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more 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 5 ⁇ m. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements.
  • 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 still more preferable lower limit is 10 nm
  • the still more preferable upper limit is 100 nm.
  • the primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
  • the preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements 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 liquid crystal display element sealant can exhibit better light-shielding properties without reducing the adhesion to the substrate, the strength after curing, and the drawability. it can.
  • the more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
  • a method for producing the sealing agent for liquid crystal display elements of the present invention for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
  • a method for producing the sealing agent for liquid crystal display elements of the present invention for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin,
  • a vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention.
  • Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
  • the conductive fine particles a metal ball, a resin fine particle formed with a conductive metal layer on the surface, 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 conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
  • the liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
  • a liquid crystal dropping method is preferably used.
  • the liquid crystal display element sealant of the present invention is applied to one of two substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate by screen printing, dispenser application, or the like.
  • Examples of the method include a step of combining, and a step of irradiating light such as ultraviolet rays to the seal pattern portion of the sealant for liquid crystal display element of the present invention to photocur the sealant.
  • a step of heating and thermosetting the sealant may be performed.
  • the sealing compound for liquid crystal display elements which is excellent in light-shielding part curability and can suppress liquid-crystal contamination can be provided.
  • the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
  • Examples 1 to 9, Comparative Examples 1 to 5 According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary stirrer ("Shinky”, “Awatori Nertaro”), and then mixed by using three rolls. Sealants for liquid crystal display elements of Examples 1 to 9 and Comparative Examples 1 to 5 were prepared.
  • the obtained sealant is applied to the central part of the substrate A (boundary between the chromium vapor deposition part and the non-deposition part), and after the substrate B is bonded, the sealant is sufficiently applied.
  • 100 mW / cm 2 ultraviolet rays were irradiated from the substrate A side using a metal halide lamp for 30 seconds.
  • the substrates A and B are peeled off using a cutter, and the spectrum is measured by a microscopic IR method for the sealant on a point 50 ⁇ m away from the direct ultraviolet irradiation part (the part shielded from light by chromium vapor deposition).
  • the conversion rate of the inside (meth) acryloyl group was calculated
  • the conversion rate was 90% or more, “ ⁇ ”, 70% or more, but less than 90%, “ ⁇ ”, 50% or more, less than 70%, “ ⁇ ”, less than 50%.
  • the curability of the light-shielding part was evaluated with “ ⁇ ” as the sample.
  • TN liquid crystal manufactured by Chisso Corporation, “JC-5001LA”
  • JC-5001LA fine droplets of TN liquid crystal
  • the other transparent electrode substrate is 5 Pa with a vacuum bonding device. Bonding was performed under vacuum to obtain a cell.
  • the obtained cell was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant to obtain a liquid crystal display element.
  • the display unevenness generated in the liquid crystal (especially the corner portion) around the seal portion was visually observed, and when the display unevenness was not confirmed, “ ⁇ ”, slight display unevenness was confirmed.
  • the display performance (low liquid crystal contamination) of the liquid crystal display element was evaluated with “ ⁇ ” as the case, “ ⁇ ” when the display unevenness was clearly confirmed, and “X” when the severe display unevenness was confirmed. Note that the liquid crystal display elements evaluated as “ ⁇ ” and “ ⁇ ” are at a level that causes no problem in practical use.
  • the sealing compound for liquid crystal display elements which is excellent in light-shielding part curability and can suppress liquid-crystal contamination can be provided.
  • the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.

Abstract

One purpose of the present invention is to provide a sealing agent for liquid crystal display elements, which is capable of suppressing contamination of liquid crystals, while exhibiting excellent curability in a light-blocked part. Another purpose of the present invention is to provide: a vertically conducting material which is obtained using this sealing agent for liquid crystal display elements; and a liquid crystal display element. A sealing agent for liquid crystal display elements, which contains a curable resin and a radical photopolymerization initiator, and wherein: the curable resin contains a compound having a molecular weight of 100 or more but less than 500 and a compound having a molecular weight of 500-3,000; and the radical photopolymerization initiator is a compound having a carbazole skeleton.

Description

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Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element
本発明は、遮光部硬化性に優れ、かつ、液晶汚染を抑制することができる液晶表示素子用シール剤に関する。また、本発明は、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子に関する。 The present invention relates to a sealant for a liquid crystal display element that is excellent in light-shielding part curability and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
近年、液晶表示セル等の液晶表示素子の製造方法としては、タクトタイム短縮、使用液晶量の最適化といった観点から、特許文献１、特許文献２に開示されているような、硬化性樹脂と光重合開始剤と熱硬化剤とを含有する光熱併用硬化型のシール剤を用いた滴下工法と呼ばれる液晶滴下方式が用いられている。
滴下工法では、まず、２枚の電極付き透明基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を透明基板の枠内全面に滴下し、すぐに他方の透明基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、液晶アニール時に加熱して本硬化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極めて高い効率で液晶表示素子を製造することができ、現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
ところで、携帯電話、携帯ゲーム機等、各種液晶パネル付きモバイル機器が普及している現代において、装置の小型化は最も求められている課題である。装置の小型化の手法としては、液晶表示部の狭額縁化が挙げられ、例えば、シール部の位置をブラックマトリックス下に配置することが行われている（以下、狭額縁設計ともいう）。 By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a method for reducing the size of the apparatus, there is a narrow frame of the liquid crystal display unit. For example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
しかしながら、狭額縁設計ではシール剤がブラックマトリックスの直下に配置されるため、滴下工法を行うと、シール剤を光硬化させる際に照射した光が遮られ、シール剤の内部まで光が到達せず硬化が不充分となるという問題があった。このようにシール剤の硬化が不充分となると、未硬化のシール剤成分が液晶中に溶出し、溶出したシール剤成分による硬化反応が液晶中において進行することで液晶汚染が発生するという問題があった。
液晶汚染を抑制する方法として、特許文献３には、シール剤に高感度の光重合開始剤を配合することが開示されている。しかしながら、高感度の光重合開始剤を配合しただけでは、遮光部において充分に液晶汚染を抑制することができなかった。 However, in the narrow frame design, the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
As a method for suppressing liquid crystal contamination, Patent Document 3 discloses that a highly sensitive photopolymerization initiator is blended with a sealant. However, liquid crystal contamination could not be sufficiently suppressed in the light-shielding part only by blending a highly sensitive photopolymerization initiator.
特開２００１－１３３７９４号公報JP 2001-133794 A 国際公開第０２／０９２７１８号International Publication No. 02/092718 国際公開第２０１２／００２０２８号International Publication No. 2012/002028
本発明は、遮光部硬化性に優れ、かつ、液晶汚染を抑制することができる液晶表示素子用シール剤を提供することを目的とする。また、本発明は、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することを目的とする。 An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in sclerosis | hardenability of light-shielding part, and can suppress liquid-crystal contamination. Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
本発明は、硬化性樹脂と光ラジカル重合開始剤とを含有する液晶表示素子用シール剤であって、上記硬化性樹脂は、分子量が１００以上５００未満の化合物と、分子量が５００～３０００の化合物とを含有し、上記光ラジカル重合開始剤は、カルバゾール骨格を有する化合物である液晶表示素子用シール剤である。
以下に本発明を詳述する。 The present invention relates to a sealing agent for a liquid crystal display element comprising a curable resin and a radical photopolymerization initiator, the curable resin comprising a compound having a molecular weight of 100 or more and less than 500, and a compound having a molecular weight of 500 to 3000 The radical photopolymerization initiator is a sealing agent for liquid crystal display elements, which is a compound having a carbazole skeleton.
The present invention is described in detail below.
本発明者は、シール剤の遮光部硬化性を向上させるため、特に高感度である光ラジカル重合開始剤としてカルバゾール骨格を有する化合物を用いることを検討した。しかしながら、このような光ラジカル重合開始剤を用いても、遮光部硬化性が充分でなく、液晶汚染が生じやすいという問題があった。
本発明者は、光ラジカル重合開始剤として用いたカルバゾール骨格を有する化合物は高感度であるものの、硬化性樹脂に対する溶解性が低かったために遮光部硬化性を充分に向上させることができなかったと考えた。そこで本発明者は、光ラジカル重合開始剤としてカルバゾール骨格を有する化合物を用いるだけでなく、更に、硬化性樹脂として特定の分子量の化合物を組み合わせて用いることにより、遮光部硬化性に優れ、かつ、液晶汚染を抑制することができる液晶表示素子用シール剤を得ることができることを見出し、本発明を完成させるに至った。 In order to improve the light-shielding part curability of the sealant, the present inventor has examined the use of a compound having a carbazole skeleton as a particularly sensitive photoradical polymerization initiator. However, even when such a radical photopolymerization initiator is used, there is a problem that the light-shielding part is not sufficiently cured and liquid crystal contamination is likely to occur.
The present inventor believes that although the compound having a carbazole skeleton used as the radical photopolymerization initiator is highly sensitive, the light-curing part curability could not be sufficiently improved due to low solubility in the curable resin. It was. Therefore, the present inventor not only uses a compound having a carbazole skeleton as a radical photopolymerization initiator, but also has excellent light-shielding part curability by using a combination of a compound having a specific molecular weight as a curable resin, and The present inventors have found that a sealing agent for liquid crystal display elements that can suppress liquid crystal contamination can be obtained, and have completed the present invention.
本発明の液晶表示素子用シール剤は、硬化性樹脂を含有する。
上記硬化性樹脂は、分子量が１００以上５００未満の化合物と、分子量が５００～３０００の化合物とを含有する。上記分子量が１００以上５００未満の化合物と、上記分子量が５００～３０００の化合物とを組み合わせて用いることにより、光ラジカル重合開始剤であるカルバゾール骨格を有する化合物を充分に溶解させることができ、その結果、本発明の液晶表示素子用シール剤が遮光部硬化性に優れ、かつ、液晶汚染を抑制することができるものとなる。
なお、本明細書において、上記「分子量」は、分子構造が特定される化合物については、構造式から求められる分子量であるが、重合度の分布が広い化合物及び変性部位が不特定な化合物については、重量平均分子量を用いて表す場合がある。本明細書において、上記「重量平均分子量」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による重量平均分子量を測定する際に用いるカラムとしては、例えば、Ｓｈｏｄｅｘ　ＬＦ－８０４（昭和電工社製）等が挙げられる。 The sealing agent for liquid crystal display elements of this invention contains curable resin.
The curable resin contains a compound having a molecular weight of 100 or more and less than 500 and a compound having a molecular weight of 500 to 3000. By using a combination of the compound having a molecular weight of 100 or more and less than 500 and the compound having a molecular weight of 500 to 3000, the compound having a carbazole skeleton as a radical photopolymerization initiator can be sufficiently dissolved. The sealing agent for liquid crystal display elements of the present invention is excellent in light-shielding part curability and can suppress liquid crystal contamination.
In the present specification, the “molecular weight” is a molecular weight obtained from the structural formula for a compound whose molecular structure is specified, but for a compound having a wide distribution of polymerization degree and a compound whose modification site is unspecified. , Sometimes expressed using weight average molecular weight. In the present specification, the above “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC). Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
上記硬化性樹脂は、上記分子量が１００以上５００未満の化合物を含有する。
上記分子量が１００以上５００未満の化合物は、カルバゾール骨格を有する化合物の溶解性の観点から、分子量が３００以上５００未満であることが好ましい。 The curable resin contains a compound having a molecular weight of 100 or more and less than 500.
The compound having a molecular weight of 100 or more and less than 500 preferably has a molecular weight of 300 or more and less than 500 from the viewpoint of the solubility of the compound having a carbazole skeleton.
上記硬化性樹脂は、上記分子量が１００以上５００未満の化合物として、（メタ）アクリル化合物を含有することが好ましい。
上記（メタ）アクリル化合物としては、例えば、（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られる（メタ）アクリル酸エステル化合物、（メタ）アクリル酸とエポキシ化合物とを反応させることにより得られるエポキシ（メタ）アクリレート、イソシアネート化合物に水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレート等が挙げられる。なかでも、エポキシ（メタ）アクリレートが好ましい。また、上記（メタ）アクリル化合物は、反応性の高さから１分子中に（メタ）アクリロイル基を２個以上有するものが好ましい。
なお、本明細書において、上記「（メタ）アクリル」とは、アクリル又はメタクリルを意味し、上記「（メタ）アクリル化合物」とは、アクリロイル基又はメタクリロイル基（以下、「（メタ）アクリロイル基」ともいう）を有する化合物を意味する。また、上記「（メタ）アクリレート」とは、アクリレート又はメタクリレートを意味する。更に、上記「エポキシ（メタ）アクリレート」とは、エポキシ化合物中の全てのエポキシ基を（メタ）アクリル酸と反応させた化合物のことを表す。 The curable resin preferably contains a (meth) acrylic compound as the compound having a molecular weight of 100 or more and less than 500.
As the (meth) acrylic compound, for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted. Examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group. Of these, epoxy (meth) acrylate is preferable. The (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule because of its high reactivity.
In the present specification, the “(meth) acryl” means acryl or methacryl, and the “(meth) acryl compound” means an acryloyl group or a methacryloyl group (hereinafter referred to as “(meth) acryloyl group”). Also referred to as). The “(meth) acrylate” means acrylate or methacrylate. Furthermore, the “epoxy (meth) acrylate” represents a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid.
上記（メタ）アクリル酸エステル化合物のうち単官能のものとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ビシクロペンテニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、イミド（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチル２－ヒドロキシプロピルフタレート、２－（メタ）アクリロイロキシエチルホスフェート、グリシジル（メタ）アクリレート等が挙げられる。 Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 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, iso Myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Til (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 -Butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, 2, 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
また、上記（メタ）アクリル酸エステル化合物のうち２官能のものとしては、例えば、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、２－ｎ－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジメチロールジシクロペンタジエニルジ（メタ）アクリレート、エチレンオキシド変性イソシアヌル酸ジ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、カーボネートジオールジ（メタ）アクリレート等が挙げられる。 Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane. Diol 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, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, dimethyl Roll dicyclopentadienyl di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, etc. It is done.
また、上記（メタ）アクリル酸エステル化合物のうち３官能以上のものとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、ペンタエリスリトールテトラ（メタ）アクリレート等が挙げられる。 Further, among the above (meth) acrylic acid ester compounds, those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, penta Examples include erythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, and the like.
上記エポキシ（メタ）アクリレートとしては、例えば、エポキシ化合物と（メタ）アクリル酸とを、常法に従って塩基性触媒の存在下で反応することにより得られるもの等が挙げられる。 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.
上記エポキシ（メタ）アクリレートを合成するための原料となるエポキシ化合物としては、例えば、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ビスフェノールＥジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル、水添ビスフェノールＦジグリシジルエーテル、水添ビスフェノールＥジグリシジルエーテル、レゾルシノールジグリシジルエーテル、ビフェニル－４，４’－ジイルビス（グリシジルエーテル）、１，６－ナフタレンジイルビス（グリシジルエーテル）、エチレングリコールジグリシジルエーテル、１，３－プロパンジオールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル等が挙げられる。 Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol. F diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, resorcinol diglycidyl ether, biphenyl-4,4′-diylbis (glycidyl ether), 1,6-naphthalenediylbis (glycidyl ether), ethylene glycol diglycidyl ether, 1 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and the like.
上記イソシアネート化合物に水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレートとしては、例えば、２つのイソシアネート基を有するイソシアネート化合物１当量に対して水酸基を有する（メタ）アクリル酸誘導体２当量を、触媒量のスズ系化合物存在下で反応させることによって得ることができる。 Examples of the urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid derivative with the isocyanate compound include, for example, (meth) acrylic having a hydroxyl group with respect to 1 equivalent of an isocyanate compound having two isocyanate groups. Two equivalents of the acid derivative can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
上記ウレタン（メタ）アクリレートの原料となるイソシアネート化合物としては、例えば、イソホロンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート（ＭＤＩ）、水添ＭＤＩ、１，５－ナフタレンジイソシアネート、ノルボルナンジイソシアネート、トリジンジイソシアネート、キシリレンジイソシアネート（ＸＤＩ）、水添ＸＤＩ、リジンジイソシアネート、テトラメチルキシリレンジイソシアネート等が挙げられる。 Examples of the isocyanate compound used as the raw material for the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4. Examples include '-diisocyanate (MDI), hydrogenated MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, and tetramethylxylylene diisocyanate.
上記ウレタン（メタ）アクリレートの原料となる、水酸基を有する（メタ）アクリル酸誘導体としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレートや、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール等の二価のアルコールのモノ（メタ）アクリレート等が挙げられる。 Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Divalents such as hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, etc. And mono (meth) acrylates of alcohols.
上記硬化性樹脂は、上記分子量が１００以上５００未満の化合物として、接着性及びカルバゾール骨格を有する化合物の溶解性の観点から、エポキシ化合物を含有することが好ましい。
上記エポキシ化合物としては、例えば、上記エポキシ（メタ）アクリレートを合成するための原料となるエポキシ化合物や、部分（メタ）アクリル変性エポキシ樹脂等が挙げられる。
なお、本明細書において上記部分（メタ）アクリル変性エポキシ樹脂とは、１分子中にエポキシ基と（メタ）アクリロイル基とをそれぞれ１つ以上有する化合物を意味し、例えば、２つ以上のエポキシ化合物の一部分のエポキシ基を（メタ）アクリル酸と反応させることによって得ることができる。 The curable resin preferably contains an epoxy compound as a compound having a molecular weight of 100 or more and less than 500 from the viewpoint of adhesion and solubility of the compound having a carbazole skeleton.
As said epoxy compound, the epoxy compound used as a raw material for synthesize | combining the said epoxy (meth) acrylate, a partial (meth) acryl modified epoxy resin, etc. are mentioned, for example.
In the present specification, the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy compounds. Can be obtained by reacting a part of the epoxy group with (meth) acrylic acid.
上記硬化性樹脂は、上記分子量が５００～３０００の化合物を含有する。
上記分子量が５００～３０００の化合物の分子量の好ましい下限は６００、好ましい上限は２５００である。上記分子量が５００～３０００の化合物の分子量が６００以上であることにより、カルバゾール骨格を有する化合物の溶解性により優れるものとなる。上記分子量が５００～３０００の化合物の分子量が２５００以下であることにより、得られる液晶表示素子用シール剤が低液晶汚染性により優れるものとなる。上記分子量が５００～３０００の化合物の分子量のより好ましい下限は１０００、より好ましい上限は２０００である。 The curable resin contains a compound having a molecular weight of 500 to 3000.
The preferable lower limit of the molecular weight of the compound having a molecular weight of 500 to 3000 is 600, and the preferable upper limit is 2500. When the molecular weight of the compound having a molecular weight of 500 to 3000 is 600 or more, the solubility of the compound having a carbazole skeleton is improved. When the molecular weight of the compound having a molecular weight of 500 to 3000 is 2500 or less, the obtained sealing agent for liquid crystal display elements is more excellent in low liquid crystal contamination. The more preferable lower limit of the molecular weight of the compound having a molecular weight of 500 to 3000 is 1000, and the more preferable upper limit is 2000.
上記分子量が５００～３０００の化合物としては、オリゴマー化合物が好ましく、重合度が３～６のオリゴマー化合物であることがより好ましい。
また、上記分子量が５００～３０００の化合物は、エポキシ基及び／又は（メタ）アクリロイル基を１分子中に合計２個以上有する多官能化合物であることが好ましく、架橋密度が高まり、溶出をより抑制できることから、ノボラック型構造のような櫛形構造を有する多官能化合物であることがより好ましい。 The compound having a molecular weight of 500 to 3000 is preferably an oligomer compound, and more preferably an oligomer compound having a polymerization degree of 3 to 6.
In addition, the compound having a molecular weight of 500 to 3000 is preferably a polyfunctional compound having two or more epoxy groups and / or (meth) acryloyl groups in one molecule, which increases the crosslinking density and further suppresses elution. Since it can do, it is more preferable that it is a polyfunctional compound which has a comb-shaped structure like a novolak-type structure.
上記分子量が５００～３０００の化合物としては、具体的には例えば、フェノールノボラック型エポキシ樹脂、オルトクレゾールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンフェノールノボラック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＥ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、２，２'－ジアリルビスフェノールＡ型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂、レゾルシノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、スルフィド型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、アルキルポリオール型エポキシ樹脂、ゴム変性型エポキシ樹脂等のオリゴマー型エポキシ樹脂や、これらのオリゴマー型エポキシ樹脂と（メタ）アクリル酸とを反応させてなるオリゴマー型エポキシ（メタ）アクリレートやオリゴマー型部分（メタ）アクリル変性エポキシ樹脂等が挙げられる。なかでも、オリゴマー型エポキシ（メタ）アクリレートが好ましい。 Specific examples of the compound having a molecular weight of 500 to 3000 include, for example, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, and naphthalene phenol novolac type epoxy resins. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type Epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadi Reaction of oligomeric epoxy resins such as ene-type epoxy resins, naphthalene-type epoxy resins, glycidylamine-type epoxy resins, alkyl polyol-type epoxy resins, rubber-modified epoxy resins, and these oligomer-type epoxy resins with (meth) acrylic acid Examples thereof include oligomer-type epoxy (meth) acrylates and oligomer-type partial (meth) acryl-modified epoxy resins. Among these, oligomer type epoxy (meth) acrylate is preferable.
上記分子量が１００以上５００未満の化合物と上記分子量が５００～３０００の化合物との合計１００重量部中における上記分子量が５００～３０００の化合物の含有量の好ましい下限は１０重量部、好ましい上限は３０重量部である。上記分子量が５００～３０００の化合物の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤が遮光部硬化性及び液晶汚染を抑制する効果により優れるものとなる。上記分子量が５００～３０００の化合物の含有量のより好ましい下限は１２重量部、より好ましい上限は２０重量部である。 The preferable lower limit of the content of the compound having the molecular weight of 500 to 3000 in the total of 100 parts by weight of the compound having the molecular weight of 100 or more and less than 500 and the compound having the molecular weight of 500 to 3000 is 10 parts by weight, and the preferable upper limit is 30 parts by weight. Part. When the content of the compound having a molecular weight of 500 to 3000 is within this range, the obtained sealing agent for liquid crystal display elements is more excellent in the light-shielding part curability and the effect of suppressing liquid crystal contamination. A more preferable lower limit of the content of the compound having a molecular weight of 500 to 3000 is 12 parts by weight, and a more preferable upper limit is 20 parts by weight.
本発明の液晶表示素子用シール剤は、光ラジカル重合開始剤を含有する。
上記光ラジカル重合開始剤は、カルバゾール骨格を有する化合物である。上記光ラジカル重合開始剤として上記カルバゾール骨格を有する化合物を用いることにより、本発明の液晶表示素子用シール剤は遮光部硬化性に優れるものとなる。 The sealing agent for liquid crystal display elements of this invention contains radical photopolymerization initiator.
The photo radical polymerization initiator is a compound having a carbazole skeleton. By using the compound having the carbazole skeleton as the photoradical polymerization initiator, the sealing agent for liquid crystal display elements of the present invention is excellent in light-shielding part curability.
上記カルバゾール骨格を有する化合物の分子量の好ましい下限は３００、好ましい上限は１０００である。上記カルバゾール骨格を有する化合物の分子量がこの範囲であることにより、上記硬化性樹脂に対する溶解性により優れるものとなる。上記カルバゾール骨格を有する化合物の分子量のより好ましい下限は４００、より好ましい上限は７００である。 The minimum with a preferable molecular weight of the compound which has the said carbazole skeleton is 300, and a preferable upper limit is 1000. When the molecular weight of the compound having the carbazole skeleton is within this range, the solubility in the curable resin is improved. The more preferable lower limit of the molecular weight of the compound having a carbazole skeleton is 400, and the more preferable upper limit is 700.
上記カルバゾール骨格を有する化合物は、上記硬化性樹脂に対する溶解性の観点から、カルバゾール骨格に含まれる芳香環以外の芳香環を有することが好ましい。
また、上記カルバゾール骨格を有する化合物は、遮光部硬化性により優れることから、カルバゾール骨格に含まれる窒素原子以外の窒素原子を有することが好ましく、オキシムエステル結合を有することがより好ましい。 The compound having a carbazole skeleton preferably has an aromatic ring other than the aromatic ring contained in the carbazole skeleton from the viewpoint of solubility in the curable resin.
Moreover, since the compound having the carbazole skeleton is more excellent in light-shielding part curability, it preferably has a nitrogen atom other than the nitrogen atom contained in the carbazole skeleton, and more preferably has an oxime ester bond.
上記カルバゾール骨格を有する化合物は、濃度が０．１ｍｇ／ｍＬとなるように該カルバゾール骨格を有する化合物混合したアセトニトリル中で測定した波長３６５ｎｍにおける吸光係数が５０ｍＬ／ｇ・ｃｍ以上であることが好ましい。上記カルバゾール骨格を有する化合物の吸光係数が５０ｍＬ／ｇ・ｃｍ以上であることにより、得られる液晶表示素子用シール剤が遮光部硬化性により優れるものとなる。上記カルバゾール骨格を有する化合物の吸光係数は、１００ｍＬ／ｇ・ｃｍ以上であることがより好ましい。
また、上記カルバゾール骨格を有する化合物の吸光係数の好ましい上限は特にないが、実質的な上限は１０００ｍＬ／ｇ・ｃｍである。 The compound having the carbazole skeleton preferably has an absorption coefficient of 50 mL / g · cm or more at a wavelength of 365 nm measured in acetonitrile mixed with the compound having the carbazole skeleton so that the concentration becomes 0.1 mg / mL. When the compound having the carbazole skeleton has an extinction coefficient of 50 mL / g · cm or more, the obtained sealing agent for liquid crystal display elements is more excellent in light-shielding part curability. The light absorption coefficient of the compound having a carbazole skeleton is more preferably 100 mL / g · cm or more.
Further, there is no particular upper limit of the light absorption coefficient of the compound having a carbazole skeleton, but the substantial upper limit is 1000 mL / g · cm.
上記カルバゾール骨格を有する化合物としては、具体的には例えば、Ｏ－アセチル－１－（６－（２－メチルベンゾイル）－９－エチル－９Ｈ－カルバゾール－３－イル）エタノンオキシム、３，６－ビス－（２メチル－２モルホリノ－プロピオニル）－９－Ｎ－オクチルカルバゾール、３，６－ビス（２－メチル－２－モルホリノプロピオニル）－９－ベンゾイルカルバゾール、３，６－ビス（２－メチル－２－モルホリノプロピオニル）－９－ｎ－ブチルカルバゾール、３，６－ビス（２－メチル－２－モルホリノプロピオニル）－９－ｎ－ドデシルカルバゾール、２－（Ｎ－ｎ－ブチル－３’－カルバゾリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン等が挙げられる。 Specific examples of the compound having the carbazole skeleton include, for example, O-acetyl-1- (6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl) ethanone oxime, 3,6 -Bis- (2methyl-2morpholino-propionyl) -9-N-octylcarbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-benzoylcarbazole, 3,6-bis (2-methyl) -2-morpholinopropionyl) -9-n-butylcarbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 2- (Nn-butyl-3′-carbazolyl) ) -4,6-bis (trichloromethyl) -s-triazine and the like.
上記カルバゾール骨格を有する化合物のうち市販されているものとしては、例えば、ＩＲＧＡＣＵＲＥ　ＯＸＥ０２（ＢＡＳＦ社製）等が挙げられる。 Examples of commercially available compounds having the carbazole skeleton include IRGACURE OXE02 (manufactured by BASF).
上記カルバゾール骨格を有する化合物の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が０．５重量部、好ましい上限が１０重量部である。上記カルバゾール骨格を有する化合物の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤が遮光部硬化性、耐候性、保存安定性、及び、液晶汚染を抑制する効果により優れるものとなる。上記カルバゾール骨格を有する化合物の含有量のより好ましい下限は１重量部、より好ましい上限は３重量部である。 The content of the compound having a carbazole skeleton is preferably 0.5 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the compound having the carbazole skeleton is within this range, the obtained sealing agent for liquid crystal display elements is excellent in light-shielding part curability, weather resistance, storage stability, and the effect of suppressing liquid crystal contamination. Become. The more preferable lower limit of the content of the compound having a carbazole skeleton is 1 part by weight, and the more preferable upper limit is 3 parts by weight.
本発明の液晶表示素子用シール剤は、上記光ラジカル重合開始剤として、上記カルバゾール骨格を有する化合物に加えて、その他の光ラジカル重合開始剤を含有してもよいが、遮光部硬化性と液晶汚染を抑制する効果とを両立する観点から、その他の光ラジカル重合開始剤は含有しないことが好ましい。 The sealing agent for liquid crystal display elements of the present invention may contain other photoradical polymerization initiator as the photoradical polymerization initiator in addition to the compound having the carbazole skeleton, but the light-shielding part curability and the liquid crystal From the viewpoint of achieving both the effect of suppressing contamination, it is preferable that no other radical photopolymerization initiator is contained.
本発明の液晶表示素子用シール剤は、増感剤を含有してもよい。
本発明の液晶表示素子用シール剤は、上記増感剤を含有することにより、より高感度で遮光部硬化性に優れる液晶表示素子用シール剤を得ることができる。 The sealing agent for liquid crystal display elements of the present invention may contain a sensitizer.
The sealing agent for liquid crystal display elements of this invention can obtain the sealing agent for liquid crystal display elements which is more sensitive and is excellent in light-shielding part curability by containing the said sensitizer.
上記増感剤は、紫外・可視領域に充分な光吸収帯を有することが好ましいことから、ベンゾフェノン骨格を有する化合物、アントラセン骨格を有する化合物、アントラキノン骨格を有する化合物、クマリン骨格を有する化合物、チオキサントン骨格を有する化合物、及び、フタロシアニン骨格を有する化合物からなる群より選択される少なくとも一種の化合物であることが好ましく、アントラセン骨格を有する化合物、アントラキノン骨格を有する化合物、及び、チオキサントン骨格を有する化合物からなる群より選択される少なくとも一種の化合物であることがより好ましい。 Since the sensitizer preferably has a sufficient light absorption band in the ultraviolet / visible region, a compound having a benzophenone skeleton, a compound having an anthracene skeleton, a compound having an anthraquinone skeleton, a compound having a coumarin skeleton, a thioxanthone skeleton And at least one compound selected from the group consisting of compounds having a phthalocyanine skeleton, and a group consisting of a compound having an anthracene skeleton, a compound having an anthraquinone skeleton, and a compound having a thioxanthone skeleton More preferably, it is at least one compound selected.
上記ベンゾフェノン骨格を有する化合物としては、例えば、ベンゾフェノン、２，４－ジクロロベンゾフェノン、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン等が挙げられる。
上記アントラセン骨格を有する化合物としては、例えば、９，１０－ジエトキシアントラセン、９，１０－ジプロポキシアントラセン、９，１０－ジブトキシアントラセン等が挙げられる。
上記アントラキノン骨格を有する化合物としては、例えば、１－メチルアントラキノン、２－エチルアントラキノン、１，４－ジヒドロキシアントラキノン、２－（２－ヒドロキシエトキシ）アントラキノン等が挙げられる。
上記クマリン骨格を有する化合物としては、例えば、７－ジエチルアミノ－４－メチルクマリン等が挙げられる。
上記チオキサントン骨格を有する化合物としては、例えば、２，４－ジエチルチオキサントン、２－クロロチオキサントン、４－イソプロピルチオキサントン、１－クロロ－４－プロピルチオキサントン等が挙げられる。
上記フタロシアニン骨格を有する化合物としては、例えば、フタロシアニン等が挙げられる。
これらの増感剤のなかでも、得られる液晶表示素子用シール剤が遮光部硬化性に特に優れるものとなることから、４，４’－ビス（ジメチルアミノ）ベンゾフェノン及び４，４’－ビス（ジエチルアミノ）ベンゾフェノンの少なくともいずれかが好ましい。 Examples of the compound having a benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.
Examples of the compound having an anthracene skeleton include 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene.
Examples of the compound having an anthraquinone skeleton include 1-methylanthraquinone, 2-ethylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) anthraquinone and the like.
Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
Examples of the compound having a phthalocyanine skeleton include phthalocyanine.
Among these sensitizers, since the obtained sealant for liquid crystal display elements is particularly excellent in light-shielding part curability, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis ( At least one of diethylamino) benzophenone is preferred.
上記増感剤の含有量は、上記光ラジカル重合開始剤１００重量部に対して、好ましい下限が２重量部、好ましい上限が５０重量部である。上記増感剤の含有量がこの範囲であることにより、液晶汚染を抑制しつつ、得られる液晶表示素子用シール剤が遮光部硬化性により優れるものとなる。上記増感剤の含有量のより好ましい下限は５重量部、より好ましい上限は４０重量部である。 The content of the sensitizer is such that a preferred lower limit is 2 parts by weight and a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the radical photopolymerization initiator. When the content of the sensitizer is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in light-shielding part curability while suppressing liquid crystal contamination. The minimum with more preferable content of the said sensitizer is 5 weight part, and a more preferable upper limit is 40 weight part.
本発明の液晶表示素子用シール剤は、熱ラジカル重合開始剤を含有してもよい。
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。なかでも、高分子アゾ化合物からなる開始剤（以下、「高分子アゾ開始剤」ともいう）が好ましい。
なお、本明細書において高分子アゾ化合物とは、アゾ基を有し、熱によってラジカルを生成する、数平均分子量が３００以上の化合物を意味する。 The sealing agent for liquid crystal display elements of the present invention may contain a thermal radical polymerization initiator.
As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and generating a radical by heat and having a number average molecular weight of 300 or more.
上記高分子アゾ開始剤の数平均分子量の好ましい下限は１０００、好ましい上限は３０万である。上記高分子アゾ開始剤の数平均分子量がこの範囲であることにより、液晶汚染を抑制しつつ、硬化性樹脂と容易に混合することができる。上記高分子アゾ開始剤の数平均分子量のより好ましい下限は５０００、より好ましい上限は１０万であり、更に好ましい下限は１万、更に好ましい上限は９万である。
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ　ＬＦ－８０４（昭和電工社製）等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymeric azo initiator is within this range, it can be easily mixed with a curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記高分子アゾ開始剤としては、例えば、アゾ基を介してポリアルキレンオキサイドやポリジメチルシロキサン等のユニットが複数結合した構造を有するものが挙げられる。
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、４，４’－アゾビス（４－シアノペンタン酸）とポリアルキレングリコールの重縮合物や、４，４’－アゾビス（４－シアノペンタン酸）と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、ＶＰＥ－０２０１、ＶＰＥ－０４０１、ＶＰＥ－０６０１、ＶＰＳ－０５０１、ＶＰＳ－１００１（いずれも和光純薬工業社製）等が挙げられる。
また、高分子ではないアゾ化合物の例としてはＶ－６５、Ｖ－５０１（いずれも和光純薬工業社製）等が挙げられる。 Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator 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. Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
Examples of azo compounds that are not a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記有機過酸化物としては、例えば、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネート等が挙げられる。 Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
上記熱ラジカル重合開始剤の含有量は、硬化性樹脂１００重量部に対して、好ましい下限が０．０５重量部、好ましい上限が１０重量部である。上記熱ラジカル重合開始剤この範囲であることにより、得られる液晶表示素子用シール剤が液晶汚染を抑制しつつ、保存安定性や硬化性により優れるものとなる。上記熱ラジカル重合開始剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は５重量部である。 The content of the thermal radical polymerization initiator is preferably 0.05 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the thermal radical polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination. The minimum with more preferable content of the said thermal radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
本発明の液晶表示素子用シール剤は、熱硬化剤を含有してもよい。
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。 The sealing agent for liquid crystal display elements of the present invention may contain a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
上記有機酸ヒドラジドとしては、例えば、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド、アジピン酸ジヒドラジド、マロン酸ジヒドラジド等が挙げられる。
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、ＳＤＨ、ＡＤＨ（いずれも大塚化学社製）、アミキュアＶＤＨ、アミキュアＶＤＨ－Ｊ、アミキュアＵＤＨ、アミキュアＵＤＨ－Ｊ（いずれも味の素ファインテクノ社製）等が挙げられる。 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, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
上記熱硬化剤の含有量は、上記硬化性樹脂１００重量部に対して、好ましい下限が１重量部、好ましい上限が５０重量部である。上記熱硬化剤の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤の塗布性等を悪化させることなく、より熱硬化性に優れるものとすることができる。上記熱硬化剤の含有量のより好ましい上限は３０重量部である。 The content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit. When the content of the thermosetting agent is within this range, the thermosetting property can be further improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. The upper limit with more preferable content of the said thermosetting agent is 30 weight part.
本発明の液晶表示素子用シール剤は、粘度の向上、応力分散効果による接着性の改善、線膨張率の改善、硬化物の耐湿性の更なる向上等を目的として充填剤を含有することが好ましい。 The sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, and further improving the moisture resistance of the cured product. preferable.
上記充填剤としては、例えば、シリカ、タルク、ガラスビーズ、石綿、石膏、珪藻土、スメクタイト、ベントナイト、モンモリロナイト、セリサイト、活性白土、アルミナ、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、水酸化アルミニウム、窒化アルミニウム、窒化珪素、硫酸バリウム、珪酸カルシウム等の無機充填剤や、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機充填剤が挙げられる。 Examples of the filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, Organic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned.
本発明の液晶表示素子用シール剤１００重量部中における上記充填剤の含有量の好ましい下限は１０重量部、好ましい上限は７０重量部である。上記充填剤の含有量がこの範囲であることにより、塗布性等を悪化させることなく、接着性の改善等の効果により優れるものとなる。上記充填剤の含有量のより好ましい下限は２０重量部、より好ましい上限は６０重量部である。 The preferable lower limit of the content of the filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. When the content of the filler is within this range, the effect of improving adhesiveness and the like is improved without deteriorating applicability and the like. The minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
本発明の液晶表示素子用シール剤は、シランカップリング剤を含有することが好ましい。上記シランカップリング剤は、主にシール剤と基板等とを良好に接着するための接着助剤としての役割を有する。 It is preferable that the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
上記シランカップリング剤としては、基板等との接着性を向上させる効果に優れ、硬化性樹脂と化学結合することにより液晶中への硬化性樹脂の流出を抑制することができることから、例えば、３－アミノプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－イソシアネートプロピルトリメトキシシラン等が好適に用いられる。これらのシランカップリング剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 As said silane coupling agent, since it is excellent in the effect which improves adhesiveness with a board | substrate etc. and it can suppress the outflow of curable resin in a liquid crystal by chemically bonding with curable resin, it is 3 for example. -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.
本発明の液晶表示素子用シール剤１００重量部中における上記シランカップリング剤の含有量の好ましい下限は０．１重量部、好ましい上限は１０重量部である。上記シランカップリング剤の含有量がこの範囲であることにより、液晶汚染の発生を抑制しつつ、接着性を向上させる効果により優れるものとなる。上記シランカップリング剤の含有量のより好ましい下限は０．３重量部、より好ましい上限は５重量部である。 The minimum with preferable content of the said silane coupling agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the occurrence of liquid crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.
本発明の液晶表示素子用シール剤は、遮光剤を含有してもよい。上記遮光剤を含有することにより、本発明の液晶表示素子用シール剤は、遮光シール剤として好適に用いることができる。 The sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.
上記遮光剤としては、例えば、酸化鉄、チタンブラック、アニリンブラック、シアニンブラック、フラーレン、カーボンブラック、樹脂被覆型カーボンブラック等が挙げられる。なかでも、絶縁性が高いことから、チタンブラックが好ましい。 Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferred because of its high insulating properties.
上記チタンブラックは、表面処理されていないものでも充分な効果を発揮するが、表面がカップリング剤等の有機成分で処理されているものや、酸化ケイ素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化ジルコニウム、酸化マグネシウム等の無機成分で被覆されているもの等、表面処理されたチタンブラックを用いることもできる。なかでも、有機成分で処理されているものは、より絶縁性を向上できる点で好ましい。
また、遮光剤として上記チタンブラックを含有する本発明の液晶表示素子用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned titanium black exhibits 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, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage A liquid crystal display element having excellent image display quality can be realized.
上記チタンブラックのうち市販されているものとしては、例えば、１２Ｓ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ－Ｎ、１４Ｍ－Ｃ（いずれも三菱マテリアル社製）、ティラックＤ（赤穂化成社製）等が挙げられる。 Examples of commercially available titanium black include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. Can be mentioned.
上記チタンブラックの比表面積の好ましい下限は１３ｍ２／ｇ、好ましい上限は３０ｍ２／ｇであり、より好ましい下限は１５ｍ２／ｇ、より好ましい上限は２５ｍ２／ｇである。
また、上記チタンブラックの体積抵抗の好ましい下限は０．５Ω・ｃｍ、好ましい上限は３Ω・ｃｍであり、より好ましい下限は１Ω・ｃｍ、より好ましい上限は２．５Ω・ｃｍである。 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.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
上記遮光剤の一次粒子径は、液晶表示素子の基板間の距離以下であれば特に限定されないが、好ましい下限は１ｎｍ、好ましい上限は５μｍである。上記遮光剤の一次粒子径がこの範囲であることにより、得られる液晶表示素子用シール剤の塗布性等を悪化させることなく遮光性により優れるものとすることができる。上記遮光剤の一次粒子径のより好ましい下限は５ｎｍ、より好ましい上限は２００ｎｍ、更に好ましい下限は１０ｎｍ、更に好ましい上限は１００ｎｍである。
なお、上記遮光剤の一次粒子径は、ＮＩＣＯＭＰ　３８０ＺＬＳ（ＰＡＲＴＩＣＬＥ　ＳＩＺＩＮＧ　ＳＹＳＴＥＭＳ社製）を用いて、上記遮光剤を溶媒（水、有機溶媒等）に分散させて測定することができる。 The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more 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 5 μm. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. 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 still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
本発明の液晶表示素子用シール剤１００重量部中における上記遮光剤の含有量の好ましい下限は５重量部、好ましい上限は８０重量部である。上記遮光剤の含有量がこの範囲であることにより、得られる液晶表示素子用シール剤の基板に対する密着性や硬化後の強度や描画性を低下させることなくより優れた遮光性を発揮することができる。上記遮光剤の含有量のより好ましい下限は１０重量部、より好ましい上限は７０重量部であり、更に好ましい下限は３０重量部、更に好ましい上限は６０重量部である。 The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, the liquid crystal display element sealant can exhibit better light-shielding properties without reducing the adhesion to the substrate, the strength after curing, and the drawability. it can. The more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
本発明の液晶表示素子用シール剤を製造する方法としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、硬化性樹脂と、光ラジカル重合開始剤と、必要に応じて添加するシランカップリング剤等の添加剤とを混合する方法等が挙げられる。 As a method for producing the sealing agent for liquid crystal display elements of the present invention, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light Examples thereof include a method of mixing a radical polymerization initiator and an additive such as a silane coupling agent added as necessary.
本発明の液晶表示素子用シール剤に、導電性微粒子を配合することにより、上下導通材料を製造することができる。このような本発明の液晶表示素子用シール剤と導電性微粒子とを含有する上下導通材料もまた、本発明の１つである。 A vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention. Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子としては、金属ボール、樹脂微粒子の表面に導電金属層を形成したもの等を用いることができる。なかでも、樹脂微粒子の表面に導電金属層を形成したものは、樹脂微粒子の優れた弾性により、透明基板等を損傷することなく導電接続が可能であることから好適である。 As the conductive fine particles, a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
本発明の液晶表示素子用シール剤又は本発明の上下導通材料を用いてなる液晶表示素子もまた、本発明の１つである。 The liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
本発明の液晶表示素子を製造する方法としては、液晶滴下工法が好適に用いられる。具体的には例えば、ＩＴＯ薄膜等の電極付きのガラス基板やポリエチレンテレフタレート基板等の２枚の基板の一方に、本発明の液晶表示素子用シール剤を、スクリーン印刷、ディスペンサー塗布等により塗布して枠状のシールパターンを形成する工程、本発明の液晶表示素子用シール剤が未硬化の状態で液晶の微小滴を基板のシールパターンの枠内に滴下塗布し、真空下で別の基板を重ね合わせる工程、及び、本発明の液晶表示素子用シール剤のシールパターン部分に紫外線等の光を照射してシール剤を光硬化させる工程を有する方法等が挙げられる。また、上記シール剤を光硬化させる工程に加えて、シール剤を加熱して熱硬化させる工程を行ってもよい。 As a method for producing the liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used. Specifically, for example, the liquid crystal display element sealant of the present invention is applied to one of two substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate by screen printing, dispenser application, or the like. A step of forming a frame-shaped seal pattern, in which the liquid crystal display element sealant of the present invention is in an uncured state, droplets of liquid crystal are dropped into the frame of the substrate seal pattern, and another substrate is stacked under vacuum. Examples of the method include a step of combining, and a step of irradiating light such as ultraviolet rays to the seal pattern portion of the sealant for liquid crystal display element of the present invention to photocur the sealant. In addition to the step of photocuring the sealant, a step of heating and thermosetting the sealant may be performed.
本発明によれば、遮光部硬化性に優れ、かつ、液晶汚染を抑制することができる液晶表示素子用シール剤を提供することができる。また、本発明によれば、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in light-shielding part curability and can suppress liquid-crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（ビスフェノールＡ型エポキシアクリレートＡの合成）
ビスフェノールＡジグリシジルエーテル（ＤＩＣ社製、「ＥＰＩＣＬＯＮ　ＥＸＡ－８５０ＣＲＰ」）３４０ｇをトルエン５００ｍＬに溶解させた後、トリフェニルホスフィン０．１ｇを加え、均一な溶液とした。得られた溶液にアクリル酸１４４ｇを還流撹拌下にて２時間かけて滴下した後、更に、還流撹拌を８時間行った。次に、トルエンを除去することによって、ビスフェノールＡ型エポキシアクリレートＡを得た。
１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＬＣ－ＴＯＦ／ＭＳ、及び、ＩＲにより、得られたビスフェノールＡ型エポキシアクリレートＡは、ビスフェノールＡジグリシジルエーテルジアクリレート（分子量４８４）であることを確認した。 (Synthesis of bisphenol A type epoxy acrylate A)
After 340 g of bisphenol A diglycidyl ether (manufactured by DIC, “EPICLON EXA-850CRP”) was dissolved in 500 mL of toluene, 0.1 g of triphenylphosphine was added to obtain a uniform solution. After 144 g of acrylic acid was added dropwise to the obtained solution under reflux stirring over 2 hours, reflux stirring was further performed for 8 hours. Next, bisphenol A type epoxy acrylate A was obtained by removing toluene.
It was confirmed by 1 H-NMR, 13 C-NMR, LC-TOF / MS, and IR that the obtained bisphenol A type epoxy acrylate A was bisphenol A diglycidyl ether diacrylate (molecular weight 484).
（ビスフェノールＡ型エポキシアクリレートＢの合成）
ビスフェノールＡ型エポキシ樹脂（三菱化学社製、「ｊＥＲ８３４」）５００ｇをトルエン５００ｍＬに溶解させた後、トリフェニルホスフィン０．１ｇを加え、均一な溶液とした。得られた溶液にアクリル酸１４４ｇを還流撹拌下にて２時間かけて滴下した後、更に、還流撹拌を８時間行った。次に、トルエンを除去することによって、ビスフェノールＡ型エポキシアクリレートＢを得た。
１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＬＣ－ＴＯＦ／ＭＳ、及び、ＩＲにより、得られたビスフェノールＡ型エポキシアクリレートＢは、分子量が６４４のオリゴマー型エポキシアクリレートであることを確認した。 (Synthesis of bisphenol A type epoxy acrylate B)
After 500 g of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “jER834”) was dissolved in 500 mL of toluene, 0.1 g of triphenylphosphine was added to obtain a uniform solution. After 144 g of acrylic acid was added dropwise to the resulting solution over 2 hours under reflux stirring, the mixture was further stirred under reflux for 8 hours. Next, bisphenol A type epoxy acrylate B was obtained by removing toluene.
It was confirmed by 1 H-NMR, 13 C-NMR, LC-TOF / MS, and IR that the obtained bisphenol A type epoxy acrylate B was an oligomer type epoxy acrylate having a molecular weight of 644.
（実施例１～９、比較例１～５）
表１、２に記載された配合比に従い、各材料を遊星式撹拌機（シンキー社製、「あわとり練太郎」）を用いて混合した後、更に３本ロールを用いて混合することにより実施例１～９、比較例１～５の液晶表示素子用シール剤を調製した。 (Examples 1 to 9, Comparative Examples 1 to 5)
According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary stirrer ("Shinky", "Awatori Nertaro"), and then mixed by using three rolls. Sealants for liquid crystal display elements of Examples 1 to 9 and Comparative Examples 1 to 5 were prepared.
＜評価＞
実施例及び比較例で得られた各液晶表示素子用シール剤について以下の評価を行った。結果を表１、２に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
（遮光部硬化性）
まず、厚さ０．７ｍｍのコーニングガラスの半面をクロム蒸着した基板Ａと、前面をクロム蒸着した基板Ｂとを準備した。次に、実施例及び比較例で得られた各液晶表示素子用シール剤１００重量部に対して平均粒子径５μｍのスペーサー微粒子（積水化学工業社製、「ミクロパールＳＩ－Ｈ０５０」）１重量部を遊星式撹拌装置によって均一に分散させ、得られたシール剤を基板Ａの中央部（クロム蒸着部と非蒸着部との境界）に塗布し、基板Ｂを貼り合わせてからシール剤を充分に押し潰し、基板Ａ側からメタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射した。
その後、カッターを用いて基板Ａ及びＢを剥がし、紫外線直接照射部の際から５０μｍ離れた点（クロム蒸着により遮光されていた部分）上のシール剤について顕微ＩＲ法によってスペクトルを測定し、シール剤中の（メタ）アクリロイル基の転化率を以下の方法により求めた。即ち、８１５～８００ｃｍ－１のピーク面積を（メタ）アクリロイル基のピーク面積とし、８４５～８２０ｃｍ－１のピーク面積をリファレンスピーク面積として、下記式により（メタ）アクリロイル基の転化率を算出し、転化率が９０％以上であったものを「◎」、７０％以上９０％未満であったものを「○」、５０％以上７０％未満であったものを「△」、５０％未満であったものを「×」として遮光部硬化性を評価した。
（メタ）アクリロイル基の転化率＝（１－（紫外線照射後の（メタ）アクリロイル基のピーク面積／紫外線照射後のリファレンスピーク面積）／（紫外線照射前の（メタ）アクリロイル基のピーク面積／紫外線照射前のリファレンスピーク面積））×１００ (Light-shielding part curability)
First, a substrate A on which half of a Corning glass having a thickness of 0.7 mm was vapor-deposited and a substrate B on which the front surface was vapor-deposited were prepared. Next, 1 part by weight of spacer fine particles having an average particle diameter of 5 μm (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) with respect to 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples. Is uniformly dispersed by a planetary stirrer, and the obtained sealant is applied to the central part of the substrate A (boundary between the chromium vapor deposition part and the non-deposition part), and after the substrate B is bonded, the sealant is sufficiently applied. After crushing, 100 mW / cm 2 ultraviolet rays were irradiated from the substrate A side using a metal halide lamp for 30 seconds.
Thereafter, the substrates A and B are peeled off using a cutter, and the spectrum is measured by a microscopic IR method for the sealant on a point 50 μm away from the direct ultraviolet irradiation part (the part shielded from light by chromium vapor deposition). The conversion rate of the inside (meth) acryloyl group was calculated | required with the following method. That is, with the peak area of 815 to 800 cm −1 as the peak area of the (meth) acryloyl group and the peak area of 845 to 820 cm −1 as the reference peak area, the conversion ratio of the (meth) acryloyl group is calculated according to the following formula: The conversion rate was 90% or more, “◎”, 70% or more, but less than 90%, “◯”, 50% or more, less than 70%, “△”, less than 50%. The curability of the light-shielding part was evaluated with “×” as the sample.
Conversion rate of (meth) acryloyl group = (1- (peak area of (meth) acryloyl group after UV irradiation / reference peak area after UV irradiation) / (peak area of (meth) acryloyl group before UV irradiation / ultraviolet light) Reference peak area before irradiation)) x 100
（液晶表示素子の表示性能（低液晶汚染性））
実施例及び比較例で得られた各液晶表示素子用シール剤１００重量部に対して平均粒子径５μｍのスペーサー粒子（積水化学工業社製、「ミクロパールＳＩ－Ｈ０５０」）１重量部を遊星式撹拌装置によって均一に分散させ、得られたシール剤をディスペンス用のシリンジ（武蔵エンジニアリング社製、「ＰＳＹ－１０Ｅ」）に充填し、脱泡処理を行ってから、ディスペンサー（武蔵エンジニアリング社製、「ＳＨＯＴＭＡＳＴＥＲ３００」）にて、２枚のＩＴＯ薄膜付きの透明電極基板の一方にシール剤を枠状に塗布した。続いて、ＴＮ液晶（チッソ社製、「ＪＣ－５００１ＬＡ」）の微小滴を液晶滴下装置にてシール剤の枠内に滴下塗布し、他方の透明電極基板を、真空貼り合わせ装置にて５Ｐａの真空下にて貼り合わせ、セルを得た。得られたセルに、メタルハライドランプを用いて１００ｍＷ／ｃｍ２の紫外線を３０秒照射した後、１２０℃で１時間加熱してシール剤を硬化させ、液晶表示素子を得た。
得られた液晶表示素子について、シール部周辺の液晶（特にコーナー部）に生じる表示むらを目視にて観察し、表示むらが確認されなかった場合を「◎」、わずかな表示むらが確認された場合を「○」、はっきりと表示むらが確認された場合を「△」、酷い表示むらが確認された場合を「×」として液晶表示素子の表示性能（低液晶汚染性）を評価した。
なお、評価が「◎」、「○」の液晶表示素子は、実用に全く問題のないレベルである。 (Display performance of liquid crystal display elements (low liquid crystal contamination))
One part by weight of spacer particles (Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) having an average particle size of 5 μm is used for 100 parts by weight of each liquid crystal display element sealing agent obtained in Examples and Comparative Examples. After uniformly dispersing with a stirrer, the resulting sealant is filled into a dispensing syringe (Musashi Engineering, PSY-10E), defoamed, and dispenser (Musashi Engineering, The sealant was applied in a frame shape to one of the two transparent electrode substrates with an ITO thin film by using SHOTMASTER 300 "). Subsequently, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) are applied dropwise to the frame of the sealing agent with a liquid crystal dropping device, and the other transparent electrode substrate is 5 Pa with a vacuum bonding device. Bonding was performed under vacuum to obtain a cell. The obtained cell was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant to obtain a liquid crystal display element.
Regarding the obtained liquid crystal display element, the display unevenness generated in the liquid crystal (especially the corner portion) around the seal portion was visually observed, and when the display unevenness was not confirmed, “◎”, slight display unevenness was confirmed. The display performance (low liquid crystal contamination) of the liquid crystal display element was evaluated with “◯” as the case, “△” when the display unevenness was clearly confirmed, and “X” when the severe display unevenness was confirmed.
Note that the liquid crystal display elements evaluated as “◎” and “、” are at a level that causes no problem in practical use.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
本発明によれば、遮光部硬化性に優れ、かつ、液晶汚染を抑制することができる液晶表示素子用シール剤を提供することができる。また、本発明によれば、該液晶表示素子用シール剤を用いてなる上下導通材料及び液晶表示素子を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in light-shielding part curability and can suppress liquid-crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.

Claims (5)

  1. 硬化性樹脂と光ラジカル重合開始剤とを含有する液晶表示素子用シール剤であって、
    前記硬化性樹脂は、分子量が１００以上５００未満の化合物と、分子量が５００～３０００の化合物とを含有し、
    前記光ラジカル重合開始剤は、カルバゾール骨格を有する化合物である
    ことを特徴とする液晶表示素子用シール剤。     A sealing agent for a liquid crystal display element comprising a curable resin and a radical photopolymerization initiator,
    The curable resin contains a compound having a molecular weight of 100 or more and less than 500, and a compound having a molecular weight of 500 to 3000.
    The said radical photopolymerization initiator is a compound which has a carbazole skeleton, The sealing compound for liquid crystal display elements characterized by the above-mentioned.
  2. カルバゾール骨格を有する化合物は、カルバゾール骨格に含まれる芳香環以外の芳香環を有することを特徴とする請求項１記載の液晶表示素子用シール剤。 The sealing compound for liquid crystal display elements according to claim 1, wherein the compound having a carbazole skeleton has an aromatic ring other than the aromatic ring contained in the carbazole skeleton.
  3. 遮光剤を含有することを特徴とする請求項１又は２記載の液晶表示素子用シール剤。 3. The sealing agent for liquid crystal display elements according to claim 1, further comprising a light shielding agent.
  4. 請求項１、２又は３記載の液晶表示素子用シール剤と導電性微粒子とを含有することを特徴とする上下導通材料。 A vertical conduction material comprising the sealing agent for a liquid crystal display element according to claim 1, 2 or 3 and conductive fine particles.
  5. 請求項１、２若しくは３記載の液晶表示素子用シール剤又は請求項４記載の上下導通材料を用いてなることを特徴とする液晶表示素子。 A liquid crystal display element comprising the sealant for a liquid crystal display element according to claim 1, 2 or 3, or the vertical conduction material according to claim 4.
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