WO2013146748A1 - Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element - Google Patents

Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element Download PDF

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Publication number
WO2013146748A1
WO2013146748A1 PCT/JP2013/058713 JP2013058713W WO2013146748A1 WO 2013146748 A1 WO2013146748 A1 WO 2013146748A1 JP 2013058713 W JP2013058713 W JP 2013058713W WO 2013146748 A1 WO2013146748 A1 WO 2013146748A1
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WO
WIPO (PCT)
Prior art keywords
liquid crystal
sealing agent
crystal dropping
agent
dropping method
Prior art date
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PCT/JP2013/058713
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French (fr)
Japanese (ja)
Inventor
啓己 新井
山本　拓也
Original Assignee
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 JP2013516034A priority Critical patent/JP5374666B1/en
Priority to CN201380001372.XA priority patent/CN103562786B/en
Priority to KR1020137028658A priority patent/KR101437807B1/en
Publication of WO2013146748A1 publication Critical patent/WO2013146748A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • 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
    • G02F1/1343—Electrodes
    • 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
    • G02F1/1341—Filling or closing of cells
    • G02F1/13415—Drop filling process

Definitions

  • the present invention relates to a sealant for a liquid crystal dropping method that is excellent in drawing properties, adhesiveness, and moisture resistance of a cured product. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
  • Patent Document 1 and Patent Document 2 a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been disclosed in, for example, Patent Document 1 and Patent Document 2 from the conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used.
  • a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a liquid crystal dropping method called a dropping method using a light and heat combined curing type sealant containing a thermosetting agent are being replaced.
  • 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 with the sealant being uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays to perform temporary curing.
  • 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.
  • a sealing agent In a liquid crystal display element, a sealing agent is required to have excellent drawing performance, and at the time of manufacturing, it is required to increase the dispensing speed in order to improve the efficiency of the process.
  • the sealant when the conventional sealant is drawn at high speed, the sealant cannot be drawn stably, and there is a problem that a disconnection failure occurs or the sealant line after drawing is wavy. It was.
  • Patent Document 3 discloses a method of blending talc as an inorganic filler in a sealant for the purpose of improving the adhesiveness of the sealant, and in particular, talc is used as an inorganic filler in this way. When blended, it was difficult to stably draw the sealant.
  • An object of this invention is to provide the sealing agent for liquid crystal dropping methods excellent in drawing property, adhesiveness, and moisture resistance of hardened
  • the present invention is a sealing agent for a liquid crystal dropping method containing a curable resin, talc, and a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent.
  • This is a liquid crystal dropping method sealing agent having a total content of CaMg (CO 3 ) 2 and MgCO 3 of 0.1% by weight or less.
  • the present invention is described in detail below.
  • talc is mixed with impurities such as dolomite (CaMg (CO 3 ) 2 ) and magnesite (MgCO 3 ).
  • impurities such as dolomite (CaMg (CO 3 ) 2 ) and magnesite (MgCO 3 ).
  • CaMg (CO 3 ) 2 and MgCO 3 have a great influence on the deterioration of the drawability of the sealant. Therefore, the inventors of the present invention blended talc with a content of CaMg (CO 3 ) 2 and MgCO 3 below a specific amount into a sealing agent for liquid crystal dropping method, thereby reducing drawability, adhesiveness, and cured product. It has been found that a sealing agent for liquid crystal dropping method having excellent moisture resistance can be obtained, and the present invention has been completed.
  • the sealing agent for liquid crystal dropping method of the present invention contains talc.
  • the total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc is 0.1% by weight or less.
  • the total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc exceeds 0.1% by weight, the obtained sealing agent for liquid crystal dropping method is inferior in drawability.
  • the total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc is preferably as small as possible, and is preferably less than 0.1% by weight.
  • the substantial lower limit of the total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc is 0.0001% by weight.
  • the content of CaMg (CO 3 ) 2 in the talc can be determined from the area ratio of the peak at a diffraction angle of 30.9 ° derived from CaMg (CO 3 ) 2 in X-ray diffraction measurement ( ⁇ 0.2 An error of about ° is allowed).
  • the content of MgCO 3 in the talc can be determined from the area ratio of the peak at a diffraction angle of 32.6 ° derived from MgCO 3 in the X-ray diffraction measurement (an error of about ⁇ 0.2 ° is allowed). To do).
  • the measurement conditions of the X-ray diffraction measurement in this invention are as follows.
  • Measuring instrument X'Pert-PRO-MPD (Spectris) Target: Cu Scanning angle: 5 ° -60 ° Scanning speed: 2 ° / distributor voltage: 40 kV Tube current: 30 mA Incident side slit: 0.04 ° solar slit, automatic variable divergence slit, AS1 ° Receiving side slit: 0.04 ° The detection limit under this condition is 0.1%.
  • the total content of CaMg (CO 3 ) 2 and MgCO 3 in talc means the total content of CaMg (CO 3 ) 2 and MgCO 3 derived from talc with respect to the entire talc including impurities. Means quantity.
  • Examples of commercially available talc having a total content of CaMg (CO 3 ) 2 and MgCO 3 of 0.1% by weight or less include FG-15F and D-800F (both manufactured by Nippon Talc Co., Ltd.). ) And the like.
  • Examples of the method for reducing the total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc to 0.1% by weight or less include separation and purification by classification.
  • Examples of separation and purification methods for reducing the total content of CaMg (CO 3 ) 2 and MgCO 3 to 0.1% by weight or less include classifiers such as a forced vortex classifier and a semi-free vortex classifier And the like.
  • Examples of commercially available classifiers include turbo classifiers and eddy classifiers (both manufactured by Nisshin Engineering Co., Ltd.).
  • the talc is preferably surface-treated with a surface treatment agent.
  • the surface treatment agent include silane coupling agents, fatty acids, titanate coupling agents, and the like. Especially, since it is excellent in the effect which improves the adhesiveness of the sealing agent obtained, a silane coupling agent is preferable, and also the silane coupling agent which has an epoxy group among these is more preferable.
  • silane coupling agent used as the talc surface treatment agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxy.
  • Silane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl)- -Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-trieth
  • silane coupling agents examples include KBM-303, KBM-403, KBM-502, KBM-602, KBM-603 (all manufactured by Shin-Etsu Silicone).
  • fatty acids used as the surface treatment agent for talc include stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid, and the like.
  • titanate coupling agents used as the talc surface treatment agent include titanium acylates such as tributoxy titanium stearate, isopropoxy titanium triisostearate, mono-i-propoxy titanium tri-i-stearate, Titanium alkoxide such as titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, di-n-butoxy bis (triethanolaminato) titanium, titanium diisopropoxy bis (acetylacetate) ), Titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethylacetoacetate), etc. Over doors and the like.
  • titanium acylates such as tributoxy titanium stearate, isopropoxy titanium triisostearate, mono-i-propoxy titanium tri-i
  • titanate coupling agents examples include TAA, TOG, A-1, TOT, and B-1 (all manufactured by Nippon Soda Co., Ltd.).
  • the preferable lower limit of the average particle diameter of the talc is 0.2 ⁇ m, and the preferable upper limit is 5 ⁇ m.
  • the average particle diameter of the talc is less than 0.2 ⁇ m, viscosity and thixotropy increase, which may result in poor workability.
  • the average particle diameter of the talc exceeds 5 ⁇ m, display unevenness may occur in the liquid crystal display element due to a gap defect.
  • the more preferable lower limit of the average particle diameter of the talc is 0.6 ⁇ m, and the more preferable upper limit is 3 ⁇ m.
  • the average particle diameter means an average value of particle diameters (major diameters) of 10 particles observed at a magnification of 5000 using a scanning electron microscope. As the scanning electron microscope, S-4300 (manufactured by Hitachi High-Technologies Corporation) or the like can be used.
  • the content of the talc is preferably 0.1 parts by weight and preferably 50 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the talc is less than 0.1 part by weight, the obtained sealing agent for liquid crystal dropping method is inferior in adhesiveness and peels off, or the cured product is inferior in moisture resistance. There is. If the content of the talc exceeds 50 parts by weight, the viscosity and thixotropy of the obtained sealing agent for liquid crystal dropping method may increase, resulting in poor workability.
  • the minimum with more preferable content of the said talc is 1 weight part, and a more preferable upper limit is 40 weight part.
  • the sealing agent for liquid crystal dropping method of the present invention may contain other inorganic fillers other than the talc as long as the object of the present invention is not impaired.
  • the said other inorganic filler is not specifically limited, For example, a silica, an alumina, a titanium oxide, a calcium carbonate etc. are mentioned. Of these, silica is preferred.
  • talc and other inorganic fillers are also simply referred to as inorganic fillers.
  • the minimum with the preferable average particle diameter of the said inorganic filler is 0.01 micrometer, and a preferable upper limit is 5.0 micrometers.
  • a preferable upper limit is 5.0 micrometers.
  • the average particle diameter of the inorganic filler is less than 0.01 ⁇ m, viscosity and thixotropy increase, which may result in poor workability.
  • the average particle diameter of the inorganic filler exceeds 5.0 ⁇ m, display unevenness may occur in the liquid crystal display element due to a gap defect.
  • the minimum with a more preferable average particle diameter of the said inorganic filler is 0.1 micrometer, and a more preferable upper limit is 3.0 micrometers.
  • the minimum with preferable content of the said whole inorganic filler is 1 weight%, and a preferable upper limit is 60 weight%.
  • the content of the whole inorganic filler is less than 1% by weight, the cured product of the obtained liquid crystal dropping method sealing agent may be inferior in moisture resistance. If the total content of the inorganic filler exceeds 60% by weight, the viscosity and thixotropy of the resulting liquid crystal dropping method sealing agent may increase, resulting in poor workability.
  • a more preferable lower limit of the content of the whole inorganic filler is 10% by weight, and a more preferable upper limit is 50% by weight.
  • the sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
  • the curable resin include (meth) acrylic resins and epoxy resins.
  • the said curable resin contains the (meth) acrylate which has an isocyanur skeleton, and / or the (meth) acrylate which has a dicyclopentadiene skeleton.
  • the “(meth) acryl” means acryl or methacryl
  • the “(meth) acrylic resin” means a resin having a (meth) acryloyl group.
  • the term “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.
  • (meth) acrylate means an acrylate or a methacrylate.
  • Examples of the (meth) acrylate having the isocyanuric skeleton include ethoxylated isocyanuric triacrylate, ethoxylated isocyanuric trimethacrylate, caprolactone-modified ethoxylated isocyanuric triacrylate, caprolactone-modified ethoxylated isocyanuric trimethacrylate, and the like. Of these, ethoxylated isocyanuric triacrylate having good adhesiveness is preferable.
  • Examples of the (meth) acrylate having a dicyclopentadiene skeleton include tricyclodecane dimethanol diacrylate and tricyclodecane dimethanol dimethacrylate. Of these, tricyclodecane dimethanol diacrylate having good adhesiveness is preferable.
  • the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is preferably 0.1 parts by weight and preferably has a preferable upper limit with respect to 100 parts by weight of the entire curable resin. 30 parts by weight.
  • the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is less than 0.1 parts by weight, the moisture resistance of the cured product of the liquid crystal dropping method sealing agent is improved. The effect may not be fully exhibited.
  • the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton exceeds 30 parts by weight, liquid crystal contamination may be increased.
  • the more preferable lower limit of the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is 1 part by weight, and the more preferable upper limit is 20 parts by weight.
  • the curable resin preferably contains an epoxy (meth) acrylate.
  • the said "epoxy (meth) acrylate” represents the compound which made all the epoxy groups in an epoxy resin react with (meth) acrylic acid.
  • the epoxy (meth) acrylate is not particularly limited, and examples thereof include those obtained by reacting (meth) acrylic acid and an epoxy resin in the presence of a basic catalyst according to a conventional method. Among these, an epoxy methacrylate resin is preferable because the cured product has excellent moisture resistance.
  • the epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate is not particularly limited.
  • bisphenol A type epoxy resin bisphenol F 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, dicyclopentadiene type epoxy resin, naphthalene type epoxy Resin, phenol novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin Naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.
  • Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.). Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA). Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like. Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC). Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
  • epiclone HP7200 made by DIC
  • examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
  • examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Tohto Kasei Co., Ltd.).
  • Examples of commercially available glycidylamine epoxy resins include Epicoat 630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
  • alkyl polyol type epoxy resins examples include ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epicron 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611 ( Nagase ChemteX Corporation).
  • Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Tohto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical Industries, Ltd.), and the like.
  • Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
  • Examples of commercially available bisphenol A type episulfide resins include Epicoat YL-7000 (manufactured by Mitsubishi Chemical Corporation).
  • Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032 ( These include Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation), and the like.
  • Examples of commercially available epoxy (meth) acrylates include, for example, Evecryl 860, Evekril 3200, Evekril 3201, Evekryl 3412, Evekril 3600, Evekril 3700, Evekrill 3703, Evekril 3703, Evekril 3800, Evekril 6040.
  • Evacryl RDX63182 (all manufactured by Daicel Cytec), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Epoxy ester M- 600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 30 2A, epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 (Both manufactured by Nagase ChemteX Corporation).
  • the sealing agent for liquid crystal dropping method of the present invention may contain an epoxy resin as a curable resin.
  • said epoxy resin if it is resin to which the epoxy group was provided, it can be used without a limitation, The epoxy resin used as a raw material for synthesize
  • the “partially (meth) acryl-modified epoxy resin” means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule.
  • the above (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.
  • the partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy group of a part of an epoxy resin having two or more epoxy groups with (meth) acrylic acid.
  • the upper limit with the preferable ratio of the epoxy group with respect to the total amount of the (meth) acryloyloxy group and an epoxy group in the said whole curable resin is 50 mol%.
  • the ratio of the epoxy group exceeds 50 mol%, the resulting liquid crystal dropping method sealing agent is highly soluble in liquid crystals, causing liquid crystal contamination, and the resulting liquid crystal display element may be inferior in display performance. is there.
  • a more preferable upper limit of the ratio of the epoxy group is 20 mol%.
  • the sealing agent for liquid crystal dropping method of the present invention contains a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent.
  • a radical polymerization initiator or a thermosetting agent or both a radical polymerization initiator and a thermosetting agent.
  • the above-mentioned “containing a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent” means at least one of a radical polymerization initiator and a thermosetting agent. Is contained.
  • the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator.
  • examples of the photo radical polymerization initiator that generates radicals when irradiated with light include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, and oxime esters.
  • a compound, a benzoin ether compound, thioxanthone, or the like can be preferably used.
  • photo radical polymerization initiators examples include Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE01, and Lucyrin TPO (all of which are BASF). Japan), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
  • Irgacure 651, Irgacure 907, benzoin isopropyl ether, and Lucillin TPO are preferable because of their wide absorption wavelength range.
  • These radical photopolymerization initiators may be used alone or in combination of two or more.
  • thermal radical polymerization initiators that generate radicals by heat are not particularly limited, and examples thereof include peroxides and azo compounds.
  • examples of commercially available ones include perbutyl O and perhexyl O.
  • Perbutyl PV all manufactured by NOF Corporation
  • V-30, V-501, V-601, VPE-0201 all manufactured by Wako Pure Chemical Industries, Ltd.
  • a preferable minimum is 0.1 weight part and a preferable upper limit is 30 weight part with respect to 100 weight part of said curable resins.
  • the content of the radical polymerization initiator is less than 0.1 parts by weight, the polymerization of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed.
  • the content of the radical polymerization initiator exceeds 30 parts by weight, a large amount of unreacted radical polymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealing agent may deteriorate.
  • the minimum with more preferable content of the said radical polymerization initiator is 1 weight part, and a more preferable upper limit is 10 weight part.
  • thermosetting agent is not specifically limited, For example, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned. Among these, solid organic acid hydrazide is preferably used.
  • the solid organic acid hydrazide is not particularly limited, and examples thereof include 1,3-bis [hydrazinocarboethyl-5-isopropylhydantoin], sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
  • Examples of commercially available products include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), and the like.
  • thermosetting agent is not specifically limited, A preferable minimum is 2 weight part with respect to 100 weight part of curable resin, and a preferable upper limit is 50 weight part.
  • content of the thermosetting agent is less than 2 parts by weight, the obtained sealing agent for liquid crystal dropping method may be inferior in curability.
  • content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability
  • the minimum with more preferable content of the said thermosetting agent is 5 weight part, A more preferable upper limit is 20 weight part, Furthermore, a preferable upper limit is 15 weight part.
  • the sealing agent for liquid crystal dropping method of the present invention may contain a cationic polymerization initiator.
  • the cationic polymerization initiator include a photocationic polymerization initiator and a thermal cationic polymerization initiator.
  • the photocationic polymerization initiator is not particularly limited, and examples thereof include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.
  • examples of commercially available photocationic polymerization initiators include optomer SP-150, optomer SP-151, optomer SP-170, optomer SP-171 (all manufactured by ADEKA), UVE-1014 (general).
  • Irgacure 261 (BASF Japan), Sun-Aid SI-60L, Sun-Aid SI-80L, UVI-6990 (all from Union Carbide), BBI-103, MPI-103, TPS-103, MDS- 103, DTS-103, NAT-103, NDS-103 (all manufactured by Midori Chemical Co., Ltd.), Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2064, CI-2639, CI-2624, CI-2481 (Both made by Nippon Soda Co., Ltd.), RHODO RSIL PHOTOINITIATOR 2074 (manufactured by Rhone-Poulenc), CD-1012 (manufactured by Sartomer) and the like.
  • These cationic photopolymerization initiators may be used alone or in combination of two or more. Moreover, you may use together sensitizers, such as anthracene type and a thioxan
  • the thermal cationic polymerization initiator is not particularly limited, and examples thereof include various onium salts such as a quaternary ammonium salt, a phosphonium salt, and a sulfonium salt.
  • Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N-dimethyl.
  • N-N-benzylanilinium hexafluoroantimonate N, N-dimethyl-N-benzylanilinium tetrafluoroborate
  • N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate N, N-diethyl-N-benzyl Trifluoromethanesulfonate
  • N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate N, N-die -N- (4- methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.
  • Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
  • Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, and diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.
  • thermal cationic polymerization initiators examples include, for example, Adeka Opton CP-66, Adeka Opton CP-77 (all manufactured by ADEKA), Sun Aid SI-60L, Sun Aid SI-80L, Sun Aid SI-100L ( All of them are manufactured by Sanshin Chemical Industry Co., Ltd.) and CI series (manufactured by Nippon Soda Co., Ltd.).
  • content of the said cationic polymerization initiator is not specifically limited, A preferable minimum is 0.1 weight part with respect to 100 weight part of whole curable resin, and a preferable upper limit is 10 weight part. If the content of the cationic polymerization initiator is less than 0.1 parts by weight, the sealing agent for liquid crystal display elements of the present invention may not be sufficiently cured. If the content of the cationic polymerization initiator exceeds 10 parts by weight, the storage stability may be lowered.
  • the sealing agent for liquid crystal dropping method of the present invention preferably 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.
  • the silane coupling agent is not particularly limited, it is excellent in the effect of improving adhesiveness with a substrate and the like, and it can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin.
  • ⁇ -aminopropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane and the like are preferably used.
  • These silane coupling agents may be used alone or in combination of two or more.
  • the content of the silane coupling agent is such that the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the liquid crystal dropping method sealing agent of the present invention.
  • the content of the silane coupling agent is less than 0.1 parts by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited.
  • content of the said silane coupling agent exceeds 20 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid-crystal contamination.
  • the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.
  • the sealing agent for liquid crystal dropping method of the present invention may contain a light shielding agent.
  • the sealing compound for liquid crystal dropping methods of this invention can be used suitably as a light shielding sealing agent.
  • 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 preferable.
  • Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing light shielding properties to the sealing agent for liquid crystal dropping method of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
  • a shading agent Therefore, by using the photo radical polymerization initiator or the photo cationic polymerization initiator that can start the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black is high, the liquid crystal of the present invention is used.
  • the photocurability of the sealing agent for the dripping method can be further increased.
  • the light shielding agent contained in the liquid crystal dropping method sealing agent of the present invention is preferably a highly insulating material, and titanium black is also suitable as the highly insulating light shielding agent.
  • the titanium black has an optical density (OD value) per ⁇ m of preferably 0.1 or more, and more preferably 0.2 or more. The higher the light-shielding property of titanium black, the better. There is no particular upper limit for the OD value of titanium black, but it is usually 3.0 or less.
  • 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 one 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 device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus 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 (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.
  • the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
  • the 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.
  • the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated.
  • the primary particle diameter of the light-shielding agent exceeds 5 ⁇ m, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated.
  • 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 preferable lower limit of the content of the light-shielding agent is 5% by weight and the preferable upper limit is 80% by weight with respect to the entire sealing agent for liquid crystal dropping method of the present invention. If the content of the light shielding agent is less than 5% by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent is more than 80% by weight, the adhesion of the obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered.
  • the more preferable lower limit of the content of the light shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.
  • the sealing agent for liquid crystal dropping method of the present invention further comprises a reactive diluent for adjusting the viscosity, a spacer such as polymer beads for adjusting the panel gap, 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, and a polymerization inhibitor.
  • a reactive diluent for adjusting the viscosity
  • a spacer such as polymer beads for adjusting the panel gap
  • 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, and a polymerization inhibitor.
  • the method for producing the sealing agent for liquid crystal dropping method of the present invention is not particularly limited.
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, or a three roll, a curable resin
  • examples include a method of mixing talc and a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent, and an additive such as a silane coupling agent to be added as necessary. It is done.
  • a vertical conduction material can be manufactured by mix
  • the vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
  • the conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
  • the liquid crystal display element which uses the sealing compound for liquid crystal dropping methods of this invention or the vertical conduction material of this invention is also one of this invention.
  • the sealing compound for liquid crystal dropping methods which is excellent in drawing property, adhesiveness, and moisture resistance of hardened
  • the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.
  • Examples 1 to 17, Comparative Examples 1 to 3 According to the blending ratios described in Tables 1 to 3, each material was mixed using a planetary stirrer (“Shinky Co., Ltd.“ Awatori Netaro ”), and then mixed using three rolls. The sealing agents for liquid crystal dropping method of Examples 1 to 17 and Comparative Examples 1 to 3 were prepared. Note that “SG-2000” in Tables 1 to 3 is a talc in which the total content of CaMg (CO 3 ) 2 and MgCO 3 measured using an X-ray diffractometer under the conditions described above is greater than 0.2% by weight.
  • “FG-15F” is talc having a total content of CaMg (CO 3 ) 2 and MgCO 3 measured by using an X-ray diffractometer under the above-described conditions of 0.1% by weight or less.
  • “stearic acid-treated FG-15F” is a surface-treated talc obtained by dry-treating 100 parts by weight of “FG-15F” and 10 parts by weight of stearic acid.
  • “KBM-403 treated FG-15F” was prepared by dry-drying 100 parts by weight of “FG-15F” and 10 parts by weight of ⁇ -glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone).
  • “KBM-603 treated FG-15F” is composed of 100 parts by weight of “FG-15F” and N-2- (aminoethyl) -3-aminopropyltrimethoxy.
  • the cells after pasting were irradiated with 3000 mJ / cm 2 ultraviolet rays with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent, and five liquid crystal cells were prepared for each sealing agent. Observe the sealing agent in this liquid crystal cell, and if the sealing agent had a clean line with no disconnection and no waviness at the end, “ ⁇ ”, no disconnection but a slight waviness at the end of the sealing agent. Evaluated as “ ⁇ ” if it occurred, “ ⁇ ” if there was a clear swell at the end of the sealant, but “ ⁇ ” if it was broken did.
  • the value obtained by dividing the measured value (kgf) by the cross-sectional area (cm 2 ) applied to the seal is 30 kgf / cm 2 or more, “ ⁇ ”, if it is 20 kgf / cm 2 or more and less than 30 kgf / cm 2 was evaluated as “ ⁇ ” when “O” was 10 kgf / cm 2 or more and less than 20 kgf / cm 2 , and “X” when it was less than 10 kgf / cm 2 .
  • the sealants obtained in the examples and comparative examples were applied to a smooth release film with a coater to a thickness of 200 to 300 ⁇ m, irradiated with 3000 mJ / cm 2 of ultraviolet rays with a metal halide lamp, and then 120 ° C. For 60 minutes to obtain a cured film for measuring moisture permeability.
  • a moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture proof packaging materials (cup method), and the obtained cured film for moisture permeability measurement was attached, and the temperature was 80 ° C. and the humidity was 90% RH. The moisture permeability was measured by putting it in a high-temperature and high-humidity oven.
  • the case where it was 2 ⁇ 24 hr or more and less than 80 g / m 2 ⁇ 24 hr was evaluated as “ ⁇ ”, and the case where it was 80 g / m 2 ⁇ 24 hr or more was evaluated as “x”.
  • the sealing compound for liquid crystal dropping methods which is excellent in drawing property, adhesiveness, and moisture resistance of hardened
  • the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

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Abstract

The purpose of the present invention is to provide a sealing agent for a liquid crystal dropping method with excellent rendering, adhesion, and moisture resistance of the cured product. The further purpose of the present invention is to provide a vertical conduction material and a liquid crystal display element produced using said sealing agent for the liquid crystal dropping method. This sealing agent for a liquid crystal dropping method contains a curable resin, talc, and a radical polymerization initiator or a heat curing agent, or both a radical polymerization initiator and a heat curing agent, wherein the content of the total of CaMg(CO3)2 and MgCO3 in the talc is less than or equal to 0.1 wt%.

Description

液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element
本発明は、描画性、接着性、及び、硬化物の耐湿性に優れる液晶滴下工法用シール剤に関する。また、本発明は、該液晶滴下工法用シール剤を用いて製造され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 dropping method that is excellent in drawing properties, adhesiveness, and moisture resistance of a cured product. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
近年、液晶表示セル等の液晶表示素子の製造方法は、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、従来の真空注入方式から、例えば、特許文献１、特許文献２に開示されているような光硬化性樹脂、光重合開始剤、熱硬化性樹脂、及び、熱硬化剤を含有する光、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にかわりつつある。 In recent years, a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been disclosed in, for example, Patent Document 1 and Patent Document 2 from the conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. Such a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a liquid crystal dropping method called a dropping method using a light and heat combined curing type sealant containing a thermosetting agent are being replaced.
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あわせ、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 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 with the sealant being uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays to perform 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.
液晶表示素子において、シール剤には描画性に優れることが求められており、また、製造時には工程の効率化の為にディスペンスを高速化することが求められている。しかしながら、従来のシール剤を高速に描画した場合、シール剤を安定的に描画することができず、断線不良が発生したり、描画後のシール剤のラインにうねりが生じたりするという問題があった。シール剤には通常、無機充填剤が配合されており、描画性を向上させるためには、シール剤に配合する無機充填剤の量を減らすことが考えられるが、無機充填剤の量を減らすと、シール剤が基板や配向膜に対する接着性が低下したり、シール剤の耐湿性が低下したりするといった問題があった。
特許文献３には、シール剤の接着性を向上させること等を目的として、シール剤に無機充填剤としてタルクを配合する方法が開示されているが、特に、このように無機充填剤としてタルクを配合した場合に、シール剤を安定的に描画することが困難であった。 In a liquid crystal display element, a sealing agent is required to have excellent drawing performance, and at the time of manufacturing, it is required to increase the dispensing speed in order to improve the efficiency of the process. However, when the conventional sealant is drawn at high speed, the sealant cannot be drawn stably, and there is a problem that a disconnection failure occurs or the sealant line after drawing is wavy. It was. Normally, an inorganic filler is blended in the sealing agent, and in order to improve the drawability, it is conceivable to reduce the amount of the inorganic filler to be blended in the sealing agent, but if the amount of the inorganic filler is reduced, In addition, there is a problem that the adhesion of the sealing agent to the substrate or the alignment film is lowered, or the moisture resistance of the sealing agent is lowered.
Patent Document 3 discloses a method of blending talc as an inorganic filler in a sealant for the purpose of improving the adhesiveness of the sealant, and in particular, talc is used as an inorganic filler in this way. When blended, it was difficult to stably draw the sealant.
特開２００１－１３３７９４号公報JP 2001-133794 A 国際公開第０２／０９２７１８号パンフレットInternational Publication No. 02/092718 Pamphlet 特開２００８－４００１５号公報JP 2008-40015 A
本発明は、描画性、接着性、及び、硬化物の耐湿性に優れる液晶滴下工法用シール剤を提供することを目的とする。また、本発明は、該液晶滴下工法用シール剤を用いて製造され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 agent for liquid crystal dropping methods excellent in drawing property, adhesiveness, and moisture resistance of hardened | cured material. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
本発明は、硬化性樹脂、タルク、及び、ラジカル重合開始剤若しくは熱硬化剤、又は、ラジカル重合開始剤と熱硬化剤との両方を含有する液晶滴下工法用シール剤であって、上記タルクにおけるＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量が０．１重量％以下である液晶滴下工法用シール剤である。
以下に本発明を詳述する。 The present invention is a sealing agent for a liquid crystal dropping method containing a curable resin, talc, and a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent. This is a liquid crystal dropping method sealing agent having a total content of CaMg (CO 3 ) 2 and MgCO 3 of 0.1% by weight or less.
The present invention is described in detail below.
一般的に、タルクにはドロマイト（ＣａＭｇ（ＣＯ３）２）、マグネサイト（ＭｇＣＯ３）等の不純物が混入している。本発明者らは鋭意検討した結果、驚くべきことに、このＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３がシール剤の描画性の悪化に大きく影響していることを見出した。
そこで本発明者らは、ＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の含有量を特定量以下としたタルクを液晶滴下工法用シール剤に配合することにより、描画性、接着性、及び、硬化物の耐湿性に優れる液晶滴下工法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。 Generally, talc is mixed with impurities such as dolomite (CaMg (CO 3 ) 2 ) and magnesite (MgCO 3 ). As a result of intensive studies, the present inventors have surprisingly found that CaMg (CO 3 ) 2 and MgCO 3 have a great influence on the deterioration of the drawability of the sealant.
Therefore, the inventors of the present invention blended talc with a content of CaMg (CO 3 ) 2 and MgCO 3 below a specific amount into a sealing agent for liquid crystal dropping method, thereby reducing drawability, adhesiveness, and cured product. It has been found that a sealing agent for liquid crystal dropping method having excellent moisture resistance can be obtained, and the present invention has been completed.
本発明の液晶滴下工法用シール剤は、タルクを含有する。
上記タルクにおけるＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量は、０．１重量％以下である。上記タルクにおけるＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量が０．１重量％を超えると、得られる液晶滴下工法用シール剤が描画性に劣るものとなる。上記タルクにおけるＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量は、少ないほどよく、０．１重量％未満であることが好ましい。上記タルクにおけるＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量の実質的な下限は０．０００１重量％である。
なお、上記タルクにおけるＣａＭｇ（ＣＯ３）２の含有量は、Ｘ線回折測定においてＣａＭｇ（ＣＯ３）２由来の回折角３０．９°のピークの面積比から求めることができる（±０．２°程度の誤差は許容されるものとする）。
上記タルクにおけるＭｇＣＯ３の含有量は、Ｘ線回折測定においてＭｇＣＯ３由来の回折角３２．６°のピークの面積比から求めることができる（±０．２°程度の誤差は許容されるものとする）。
なお、本発明におけるＸ線回折測定の測定条件は次の通りである。
測定機器：Ｘ’Ｐｅｒｔ－ＰＲＯ－ＭＰＤ（スペクトリス社製）
ターゲット：Ｃｕ
走査角度：５°－６０°
走査速度：２°／分
管電圧：４０ｋＶ
管電流：３０ｍＡ
入射側スリット：０．０４°ソーラースリット、自動可変型ダイバージェンススリット、ＡＳ１°
受光側スリット：０．０４°
なお、この条件における検出限界は０．１％である。
なお、本明細書において、「タルクにおけるＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量」とは、不純物を含むタルク全体に対するタルク由来のＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量を意味する。 The sealing agent for liquid crystal dropping method of the present invention contains talc.
The total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc is 0.1% by weight or less. When the total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc exceeds 0.1% by weight, the obtained sealing agent for liquid crystal dropping method is inferior in drawability. The total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc is preferably as small as possible, and is preferably less than 0.1% by weight. The substantial lower limit of the total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc is 0.0001% by weight.
The content of CaMg (CO 3 ) 2 in the talc can be determined from the area ratio of the peak at a diffraction angle of 30.9 ° derived from CaMg (CO 3 ) 2 in X-ray diffraction measurement (± 0.2 An error of about ° is allowed).
The content of MgCO 3 in the talc can be determined from the area ratio of the peak at a diffraction angle of 32.6 ° derived from MgCO 3 in the X-ray diffraction measurement (an error of about ± 0.2 ° is allowed). To do).
In addition, the measurement conditions of the X-ray diffraction measurement in this invention are as follows.
Measuring instrument: X'Pert-PRO-MPD (Spectris)
Target: Cu
Scanning angle: 5 ° -60 °
Scanning speed: 2 ° / distributor voltage: 40 kV
Tube current: 30 mA
Incident side slit: 0.04 ° solar slit, automatic variable divergence slit, AS1 °
Receiving side slit: 0.04 °
The detection limit under this condition is 0.1%.
In this specification, “the total content of CaMg (CO 3 ) 2 and MgCO 3 in talc” means the total content of CaMg (CO 3 ) 2 and MgCO 3 derived from talc with respect to the entire talc including impurities. Means quantity.
ＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量が０．１重量％以下であるタルクのうち市販されているものとしては、例えば、ＦＧ－１５Ｆ、Ｄ－８００Ｆ（いずれも日本タルク社製）等が挙げられる。 Examples of commercially available talc having a total content of CaMg (CO 3 ) 2 and MgCO 3 of 0.1% by weight or less include FG-15F and D-800F (both manufactured by Nippon Talc Co., Ltd.). ) And the like.
上記タルクにおけるＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量を０．１重量％以下にする方法としては、例えば、分級による分離精製等が挙げられる。
ＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量を０．１重量％以下にするための分離精製法としては、例えば、強制渦式分級機、半自由渦式分級機のような分級装置を用いて分級する方法等が挙げられる。このような分級装置のうち市販されているものとしては、例えば、ターボクラシファイア、エディクラシファイア（いずれも日清エンジニアリング社製）等が挙げられる。 Examples of the method for reducing the total content of CaMg (CO 3 ) 2 and MgCO 3 in the talc to 0.1% by weight or less include separation and purification by classification.
Examples of separation and purification methods for reducing the total content of CaMg (CO 3 ) 2 and MgCO 3 to 0.1% by weight or less include classifiers such as a forced vortex classifier and a semi-free vortex classifier And the like. Examples of commercially available classifiers include turbo classifiers and eddy classifiers (both manufactured by Nisshin Engineering Co., Ltd.).
上記タルクは表面処理剤によって表面処理されたものであることが好ましい。
上記表面処理剤としては、例えば、シランカップリング剤、脂肪酸、チタネートカップリング剤等が挙げられる。なかでも、得られるシール剤の接着性を向上させる効果に優れることから、シランカップリング剤が好ましく、更にその中でもエポキシ基を有するシランカップリング剤がより好ましい。 The talc is preferably surface-treated with a surface treatment agent.
Examples of the surface treatment agent include silane coupling agents, fatty acids, titanate coupling agents, and the like. Especially, since it is excellent in the effect which improves the adhesiveness of the sealing agent obtained, a silane coupling agent is preferable, and also the silane coupling agent which has an epoxy group among these is more preferable.
上記タルクの表面処理剤として用いるシランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチルブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、デシルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン等が挙げられる。 Examples of the silane coupling agent used as the talc surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxy. Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl)- -Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1 , 3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane Dimethyl diethoxy silane, phenyl triethoxy silane, hexyl trimethoxy silane, hexyl triethoxysilane, decyl trimethoxysilane, trifluoropropyl trimethoxysilane, and the like.
上記シランカップリング剤のうち市販されているものとしては、例えば、ＫＢＭ－３０３、ＫＢＭ－４０３、ＫＢＭ－５０２、ＫＢＭ－６０２、ＫＢＭ－６０３（いずれも信越シリコーン社製）等が挙げられる。 Examples of commercially available silane coupling agents include KBM-303, KBM-403, KBM-502, KBM-602, KBM-603 (all manufactured by Shin-Etsu Silicone).
上記タルクの表面処理剤として用いる脂肪酸としては、例えば、ステアリン酸、パルミチン酸、ラウリン酸、オレイン酸、リノール酸等が挙げられる。 Examples of fatty acids used as the surface treatment agent for talc include stearic acid, palmitic acid, lauric acid, oleic acid, linoleic acid, and the like.
上記タルクの表面処理剤として用いるチタネートカップリング剤としては、例えば、トリブトキシチタンステアレート、イソプロポキシチタントリイソステアレート、モノ－ｉ－プロポキシチタントリ－ｉ－ステアレート等のチタンアシレートや、チタンテトラエトキシド、チタンテトラプロポキシド、チタンテトラブトキシド、テトラシクロヘキシルチタネート、テトラベンジルチタネート等のチタンアルコキシドや、ジ－ｎ－ブトキシ・ビス（トリエタノールアミナト）チタン、チタンジイソプロポキシビス（アセチルアセトネート）、チタンテトラアセチルアセトネート、チタニウムジ－２－エチルヘキソキシビス（２－エチル－３－ヒドロキシヘキソキシド）、チタンジイソプロポキシビス（エチルアセトアセテート）等のチタンキレート等が挙げられる。 Examples of titanate coupling agents used as the talc surface treatment agent include titanium acylates such as tributoxy titanium stearate, isopropoxy titanium triisostearate, mono-i-propoxy titanium tri-i-stearate, Titanium alkoxide such as titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, di-n-butoxy bis (triethanolaminato) titanium, titanium diisopropoxy bis (acetylacetate) ), Titanium tetraacetylacetonate, titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide), titanium diisopropoxybis (ethylacetoacetate), etc. Over doors and the like.
上記チタネートカップリング剤のうち市販されているものとしては、例えば、ＴＡＡ、ＴＯＧ、Ａ－１、ＴＯＴ、Ｂ－１（いずれも日本曹達社製）等が挙げられる。 Examples of commercially available titanate coupling agents include TAA, TOG, A-1, TOT, and B-1 (all manufactured by Nippon Soda Co., Ltd.).
上記タルクの平均粒子径の好ましい下限は０．２μｍ、好ましい上限は５μｍである。上記タルクの平均粒子径が０．２μｍ未満であると、粘度、チクソトロピーが増大してしまい、作業性に劣るものとなることがある。上記タルクの平均粒子径が５μｍを超えると、ギャップ不良から液晶表示素子に表示むらが生じることがある。上記タルクの平均粒子径のより好ましい下限は０．６μｍ、より好ましい上限は３μｍである。
なお、本明細書において上記平均粒子径は、走査型電子顕微鏡を用いて、５０００倍の倍率で観察した粒子１０個の粒子径（長径）の平均値を意味する。また、上記走査型電子顕微鏡としては、Ｓ－４３００（日立ハイテクノロジーズ社製）等を用いることができる。 The preferable lower limit of the average particle diameter of the talc is 0.2 μm, and the preferable upper limit is 5 μm. When the average particle diameter of the talc is less than 0.2 μm, viscosity and thixotropy increase, which may result in poor workability. When the average particle diameter of the talc exceeds 5 μm, display unevenness may occur in the liquid crystal display element due to a gap defect. The more preferable lower limit of the average particle diameter of the talc is 0.6 μm, and the more preferable upper limit is 3 μm.
In the present specification, the average particle diameter means an average value of particle diameters (major diameters) of 10 particles observed at a magnification of 5000 using a scanning electron microscope. As the scanning electron microscope, S-4300 (manufactured by Hitachi High-Technologies Corporation) or the like can be used.
上記タルクの含有量は、硬化性樹脂１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が５０重量部である。上記タルクの含有量が０．１重量部未満であると、得られる液晶滴下工法用シール剤が接着性に劣るものとなって剥離したり、硬化物が耐湿性に劣るものとなったりすることがある。上記タルクの含有量が５０重量部を超えると、得られる液晶滴下工法用シール剤の粘度、チクソトロピーが増大してしまい、作業性に劣るものとなることがある。上記タルク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４０重量部である。 The content of the talc is preferably 0.1 parts by weight and preferably 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the talc is less than 0.1 part by weight, the obtained sealing agent for liquid crystal dropping method is inferior in adhesiveness and peels off, or the cured product is inferior in moisture resistance. There is. If the content of the talc exceeds 50 parts by weight, the viscosity and thixotropy of the obtained sealing agent for liquid crystal dropping method may increase, resulting in poor workability. The minimum with more preferable content of the said talc is 1 weight part, and a more preferable upper limit is 40 weight part.
本発明の液晶滴下工法用シール剤は、本発明の目的を阻害しない範囲において、上記タルク以外のその他の無機充填剤を含有してもよい。
上記その他の無機充填剤は特に限定されず、例えば、シリカ、アルミナ、酸化チタン、炭酸カルシウム等が挙げられる。なかでも、シリカが好適である。
以下、タルク及びその他の無機充填剤を併せて単に無機充填剤ともいう。 The sealing agent for liquid crystal dropping method of the present invention may contain other inorganic fillers other than the talc as long as the object of the present invention is not impaired.
The said other inorganic filler is not specifically limited, For example, a silica, an alumina, a titanium oxide, a calcium carbonate etc. are mentioned. Of these, silica is preferred.
Hereinafter, talc and other inorganic fillers are also simply referred to as inorganic fillers.
上記無機充填剤の平均粒子径の好ましい下限は０．０１μｍ、好ましい上限は５．０μｍである。上記無機充填剤の平均粒子径が０．０１μｍ未満であると、粘度、チクソトロピーが増大してしまい、作業性に劣るものとなることがある。上記無機充填剤の平均粒子径が５．０μｍを超えると、ギャップ不良から液晶表示素子に表示むらが生じることがある。上記無機充填剤の平均粒子径のより好ましい下限は０．１μｍ、より好ましい上限は３．０μｍである。 The minimum with the preferable average particle diameter of the said inorganic filler is 0.01 micrometer, and a preferable upper limit is 5.0 micrometers. When the average particle diameter of the inorganic filler is less than 0.01 μm, viscosity and thixotropy increase, which may result in poor workability. When the average particle diameter of the inorganic filler exceeds 5.0 μm, display unevenness may occur in the liquid crystal display element due to a gap defect. The minimum with a more preferable average particle diameter of the said inorganic filler is 0.1 micrometer, and a more preferable upper limit is 3.0 micrometers.
上記その他の無機充填剤を含有する場合、上記無機充填剤全体の含有量の好ましい下限は１重量％、好ましい上限は６０重量％である。上記無機充填剤全体の含有量が１重量％未満であると、得られる液晶滴下工法用シール剤の硬化物が耐湿性に劣るものとなることがある。上記無機充填剤全体の含有量が６０重量％を超えると、得られる液晶滴下工法用シール剤の粘度やチクソトロピーが増大してしまい、作業性が悪くなることがある。上記無機充填剤全体の含有量のより好ましい下限は１０重量％、より好ましい上限は５０重量％である。 When it contains the said other inorganic filler, the minimum with preferable content of the said whole inorganic filler is 1 weight%, and a preferable upper limit is 60 weight%. When the content of the whole inorganic filler is less than 1% by weight, the cured product of the obtained liquid crystal dropping method sealing agent may be inferior in moisture resistance. If the total content of the inorganic filler exceeds 60% by weight, the viscosity and thixotropy of the resulting liquid crystal dropping method sealing agent may increase, resulting in poor workability. A more preferable lower limit of the content of the whole inorganic filler is 10% by weight, and a more preferable upper limit is 50% by weight.
本発明の液晶滴下工法用シール剤は、硬化性樹脂を含有する。
上記硬化性樹脂としては、（メタ）アクリル樹脂やエポキシ樹脂等が挙げられる。
なかでも、上記硬化性樹脂は、イソシアヌル骨格を有する（メタ）アクリレート及び／又はジシクロペンタジエン骨格を有する（メタ）アクリレートを含有することが好ましい。上記イソシアヌル骨格を有する（メタ）アクリレート及び／又は上記ジシクロペンタジエン骨格を有する（メタ）アクリレートを含有することにより、本発明の液晶滴下工法用シール剤は、硬化物の耐湿性に特に優れるものとなる。
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）アクリル樹脂」とは、（メタ）アクリロイル基を有する樹脂を意味し、上記「（メタ）アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味する。また、本明細書において、（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。 The sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
Examples of the curable resin include (meth) acrylic resins and epoxy resins.
Especially, it is preferable that the said curable resin contains the (meth) acrylate which has an isocyanur skeleton, and / or the (meth) acrylate which has a dicyclopentadiene skeleton. By containing the (meth) acrylate having the isocyanuric skeleton and / or the (meth) acrylate having the dicyclopentadiene skeleton, the sealing agent for liquid crystal dropping method of the present invention is particularly excellent in moisture resistance of the cured product. Become.
In the present specification, the “(meth) acryl” means acryl or methacryl, and the “(meth) acrylic resin” means a resin having a (meth) acryloyl group. The term “(meth) acryloyl group” means an acryloyl group or a methacryloyl group. Moreover, in this specification, (meth) acrylate means an acrylate or a methacrylate.
上記イソシアヌル骨格を有する（メタ）アクリレートとしては、例えば、エトキシ化イソシアヌルトリアクリレート、エトキシ化イソシアヌルトリメタクリレート、カプロラクトン変性エトキシ化イソシアヌルトリアクリレート、カプロラクトン変性エトキシ化イソシアヌルトリメタクリレート等が挙げられる。なかでも、接着性が良好であるエトキシ化イソシアヌルトリアクリレートが好ましい。 Examples of the (meth) acrylate having the isocyanuric skeleton include ethoxylated isocyanuric triacrylate, ethoxylated isocyanuric trimethacrylate, caprolactone-modified ethoxylated isocyanuric triacrylate, caprolactone-modified ethoxylated isocyanuric trimethacrylate, and the like. Of these, ethoxylated isocyanuric triacrylate having good adhesiveness is preferable.
上記ジシクロペンタジエン骨格を有する（メタ）アクリレートとしては、例えば、トリシクロデカンジメタノールジアクリレート、トリシクロデカンジメタノールジメタクリレート等が挙げられる。なかでも、接着性が良好であるトリシクロデカンジメタノールジアクリレートが好ましい。 Examples of the (meth) acrylate having a dicyclopentadiene skeleton include tricyclodecane dimethanol diacrylate and tricyclodecane dimethanol dimethacrylate. Of these, tricyclodecane dimethanol diacrylate having good adhesiveness is preferable.
上記イソシアヌル骨格を有する（メタ）アクリレート及び上記ジシクロペンタジエン骨格を有する（メタ）アクリレートの含有量は、上記硬化性樹脂全体１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が３０重量部である。上記イソシアヌル骨格を有する（メタ）アクリレート及び上記ジシクロペンタジエン骨格を有する（メタ）アクリレートの含有量が０．１重量部未満であると、液晶滴下工法用シール剤の硬化物の耐湿性を向上させる効果が充分に発揮されないことがある。上記イソシアヌル骨格を有する（メタ）アクリレート及び上記ジシクロペンタジエン骨格を有する（メタ）アクリレートの含有量が３０重量部を超えると、液晶汚染性が増大することがある。上記イソシアヌル骨格を有する（メタ）アクリレート及び上記ジシクロペンタジエン骨格を有する（メタ）アクリレート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２０重量部である。 The content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is preferably 0.1 parts by weight and preferably has a preferable upper limit with respect to 100 parts by weight of the entire curable resin. 30 parts by weight. When the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is less than 0.1 parts by weight, the moisture resistance of the cured product of the liquid crystal dropping method sealing agent is improved. The effect may not be fully exhibited. When the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton exceeds 30 parts by weight, liquid crystal contamination may be increased. The more preferable lower limit of the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is 1 part by weight, and the more preferable upper limit is 20 parts by weight.
上記硬化性樹脂は、エポキシ（メタ）アクリレートを含有することが好ましい。
なお、本明細書において、上記「エポキシ（メタ）アクリレート」とは、エポキシ樹脂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。
上記エポキシ（メタ）アクリレートは特に限定されず、例えば、（メタ）アクリル酸とエポキシ樹脂とを、常法に従って塩基性触媒の存在下で反応させることにより得られるものが挙げられる。なかでも、硬化物の耐湿性に優れることからエポキシメタクリレート樹脂が好適である。 The curable resin preferably contains an epoxy (meth) acrylate.
In addition, in this specification, the said "epoxy (meth) acrylate" represents the compound which made all the epoxy groups in an epoxy resin react with (meth) acrylic acid.
The epoxy (meth) acrylate is not particularly limited, and examples thereof include those obtained by reacting (meth) acrylic acid and an epoxy resin in the presence of a basic catalyst according to a conventional method. Among these, an epoxy methacrylate resin is preferable because the cured product has excellent moisture resistance.
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樹脂は特に限定されず、例えば、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、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、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、グリシジルエステル化合物、ビスフェノールＡ型エピスルフィド樹脂等が挙げられる。 The epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F 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, dicyclopentadiene type epoxy resin, naphthalene type epoxy Resin, phenol novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin Naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.
上記ビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、エピコート８２８ＥＬ、エピコート１００４（いずれも三菱化学社製）、エピクロン８５０（ＤＩＣ社製）等が挙げられる。
上記ビスフェノールＦ型エポキシ樹脂のうち市販されているものとしては、例えば、エピコート８０６、エピコート４００４（いずれも三菱化学社製）等が挙げられる。
上記ビスフェノールＳ型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ１５１４（ＤＩＣ社製）等が挙げられる。
上記２，２’－ジアリルビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＲＥ－８１０ＮＭ（日本化薬社製）等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＥＸＡ７０１５（ＤＩＣ社製）等が挙げられる。
上記プロピレンオキシド付加ビスフェノールＡ型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０００Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＸ－２０１（ナガセケムテックス社製）等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、エピコートＹＸ－４０００Ｈ（三菱化学社製）等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－５０ＴＥ（東都化成社製）等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＳＬＶ－８０ＤＥ（東都化成社製）等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＰ－４０８８Ｓ（ＡＤＥＫＡ社製）等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ４０３２、エピクロンＥＸＡ－４７００（いずれもＤＩＣ社製）等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－７７０（ＤＩＣ社製）等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＮ－６７０－ＥＸＰ－Ｓ（ＤＩＣ社製）等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンＨＰ７２００（ＤＩＣ社製）等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＮＣ－３０００Ｐ（日本化薬社製）等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ＥＳＮ－１６５Ｓ（東都化成社製）等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、エピコート６３０（三菱化学社製）、エピクロン４３０（ＤＩＣ社製）、ＴＥＴＲＡＤ－Ｘ（三菱ガス化学社製）等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ＺＸ－１５４２（東都化成社製）、エピクロン７２６（ＤＩＣ社製）、エポライト８０ＭＦＡ（共栄社化学社製）、デナコールＥＸ－６１１（ナガセケムテックス社製）等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、ＹＲ－４５０、ＹＲ－２０７（いずれも東都化成社製）、エポリードＰＢ（ダイセル化学工業社製）等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールＥＸ－１４７（ナガセケムテックス社製）等が挙げられる。
上記ビスフェノールＡ型エピスルフィド樹脂のうち市販されているものとしては、例えば、エピコートＹＬ－７０００（三菱化学社製）等が挙げられる。
上記エポキシ樹脂のうちその他に市販されているものとしては、例えば、ＹＤＣ－１３１２、ＹＳＬＶ－８０ＸＹ、ＹＳＬＶ－９０ＣＲ（いずれも東都化成社製）、ＸＡＣ４１５１（旭化成社製）、エピコート１０３１、エピコート１０３２（いずれも三菱化学社製）、ＥＸＡ－７１２０（ＤＩＣ社製）、ＴＥＰＩＣ（日産化学社製）等が挙げられる。 As what is marketed among the said bisphenol A type epoxy resin, Epicoat 828EL, Epicoat 1004 (all are the Mitsubishi Chemical company make), Epiklon 850 (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F type epoxy resins, Epicoat 806, Epicoat 4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include Epicoat YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Tohto Kasei Co., Ltd.).
Examples of commercially available glycidylamine epoxy resins include Epicoat 630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epicron 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611 ( Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Tohto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical Industries, Ltd.), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available bisphenol A type episulfide resins include Epicoat YL-7000 (manufactured by Mitsubishi Chemical Corporation).
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032 ( These include Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation), and the like.
上記エポキシ（メタ）アクリレートのうち市販されているものとしては、例えば、エベクリル８６０、エベクリル３２００、エベクリル３２０１、エベクリル３４１２、エベクリル３６００、エベクリル３７００、エベクリル３７０１、エベクリル３７０２、エベクリル３７０３、エベクリル３８００、エベクリル６０４０、エベクリルＲＤＸ６３１８２（いずれもダイセルサイテック社製）、ＥＡ－１０１０、ＥＡ－１０２０、ＥＡ－５３２３、ＥＡ－５５２０、ＥＡ－ＣＨＤ、ＥＭＡ－１０２０（いずれも新中村化学工業社製）、エポキシエステルＭ－６００Ａ、エポキシエステル４０ＥＭ、エポキシエステル７０ＰＡ、エポキシエステル２００ＰＡ、エポキシエステル８０ＭＦＡ、エポキシエステル３００２Ｍ、エポキシエステル３００２Ａ、エポキシエステル１６００Ａ、エポキシエステル３０００Ｍ、エポキシエステル３０００Ａ、エポキシエステル２００ＥＡ、エポキシエステル４００ＥＡ（いずれも共栄社化学社製）、デナコールアクリレートＤＡ－１４１、デナコールアクリレートＤＡ－３１４、デナコールアクリレートＤＡ－９１１（いずれもナガセケムテックス社製）等が挙げられる。 Examples of commercially available epoxy (meth) acrylates include, for example, Evecryl 860, Evekril 3200, Evekril 3201, Evekryl 3412, Evekril 3600, Evekril 3700, Evekrill 3703, Evekril 3703, Evekril 3800, Evekril 6040. , Evacryl RDX63182 (all manufactured by Daicel Cytec), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Epoxy ester M- 600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 30 2A, epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 (Both manufactured by Nagase ChemteX Corporation).
本発明の液晶滴下工法用シール剤は、硬化性樹脂として、エポキシ樹脂を含有してもよい。
上記エポキシ樹脂としては、エポキシ基が付与した樹脂なら特に限定無く使用することができ、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樹脂等が使用できる。 The sealing agent for liquid crystal dropping method of the present invention may contain an epoxy resin as a curable resin.
As said epoxy resin, if it is resin to which the epoxy group was provided, it can be used without a limitation, The epoxy resin used as a raw material for synthesize | combining the said epoxy (meth) acrylate etc. can be used.
また、上記エポキシ樹脂として、部分（メタ）アクリル変性エポキシ樹脂を含有してもよい。
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）アクリロイルオキシ基とをそれぞれ１つ以上有する樹脂を意味する。また、本明細書において上記（メタ）アクリロイルオキシ基とは、アクリロイルオキシ基又はメタクリロイルオキシ基を意味する。
上記部分（メタ）アクリル変性エポキシ樹脂は、例えば、２つ以上のエポキシ基を有するエポキシ樹脂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。 Moreover, you may contain a partial (meth) acryl modified epoxy resin as said epoxy resin.
In the present specification, the “partially (meth) acryl-modified epoxy resin” means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule. In the present specification, the above (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.
The partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy group of a part of an epoxy resin having two or more epoxy groups with (meth) acrylic acid.
上記硬化性樹脂全体における（メタ）アクリロイルオキシ基とエポキシ基との合計量に対するエポキシ基の比率の好ましい上限は５０モル％である。上記エポキシ基の比率が５０モル％を超えると、得られる液晶滴下工法用シール剤の液晶に対する溶解性が高くなって液晶汚染を引き起こし、得られる液晶表示素子が表示性能に劣るものとなることがある。上記エポキシ基の比率のより好ましい上限は２０モル％である。 The upper limit with the preferable ratio of the epoxy group with respect to the total amount of the (meth) acryloyloxy group and an epoxy group in the said whole curable resin is 50 mol%. When the ratio of the epoxy group exceeds 50 mol%, the resulting liquid crystal dropping method sealing agent is highly soluble in liquid crystals, causing liquid crystal contamination, and the resulting liquid crystal display element may be inferior in display performance. is there. A more preferable upper limit of the ratio of the epoxy group is 20 mol%.
本発明の液晶滴下工法用シール剤は、ラジカル重合開始剤若しくは熱硬化剤、又は、ラジカル重合開始剤と熱硬化剤との両方を含有する。
なお、本明細書において、上記「ラジカル重合開始剤若しくは熱硬化剤、又は、ラジカル重合開始剤と熱硬化剤との両方を含有する」とは、ラジカル重合開始剤及び熱硬化剤の少なくともいずれかを含有することを意味する。
上記ラジカル重合開始剤としては、光ラジカル重合開始剤、熱ラジカル重合開始剤が挙げられる。 The sealing agent for liquid crystal dropping method of the present invention contains a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent.
In the present specification, the above-mentioned “containing a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent” means at least one of a radical polymerization initiator and a thermosetting agent. Is contained.
Examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator.
上記ラジカル重合開始剤のうち、光が照射されることでラジカルを生成する光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、チオキサントン等を好適に用いることができる。
また、上記光ラジカル重合開始剤のうち市販されているものとしては、例えば、イルガキュア１８４、イルガキュア３６９、イルガキュア３７９、イルガキュア６５１、イルガキュア８１９、イルガキュア９０７、イルガキュア２９５９、イルガキュアＯＸＥ０１、ルシリンＴＰＯ（いずれもＢＡＳＦ　Ｊａｐａｎ社製）、ベンソインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル（いずれも東京化成工業社製）等が挙げられる。なかでも吸収波長域が広いことから、イルガキュア６５１、イルガキュア９０７、ベンゾインイソプロピルエーテル、及び、ルシリンＴＰＯが好適である。これらの光ラジカル重合開始剤は単独で用いてもよく、２種以上を併用してもよい。 Among the radical polymerization initiators, examples of the photo radical polymerization initiator that generates radicals when irradiated with light include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, and oxime esters. A compound, a benzoin ether compound, thioxanthone, or the like can be preferably used.
Examples of commercially available photo radical polymerization initiators include Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE01, and Lucyrin TPO (all of which are BASF). Japan), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like. Among these, Irgacure 651, Irgacure 907, benzoin isopropyl ether, and Lucillin TPO are preferable because of their wide absorption wavelength range. These radical photopolymerization initiators may be used alone or in combination of two or more.
上記ラジカル重合開始剤のうち、熱によりラジカルを発生する熱ラジカル重合開始剤は特に限定されず、過酸化物やアゾ化合物が挙げられ、市販されているものとしては、例えば、パーブチルＯ、パーヘキシルＯ、パーブチルＰＶ（いずれも日油社製）、Ｖ－３０、Ｖ－５０１、Ｖ－６０１、ＶＰＥ－０２０１（いずれも和光純薬工業社製）等が挙げられる。 Among the above radical polymerization initiators, thermal radical polymerization initiators that generate radicals by heat are not particularly limited, and examples thereof include peroxides and azo compounds. Examples of commercially available ones include perbutyl O and perhexyl O. Perbutyl PV (all manufactured by NOF Corporation), V-30, V-501, V-601, VPE-0201 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
上記ラジカル重合開始剤の含有量は特に限定されないが、上記硬化性樹脂１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が３０重量部である。上記ラジカル重合開始剤の含有量が０．１重量部未満であると、得られる液晶滴下工法用シール剤の重合が充分に進行しないことがある。上記ラジカル重合開始剤の含有量が３０重量部を超えると、未反応のラジカル重合開始剤が多く残り、得られる液晶滴下工法用シール剤の耐候性が悪くなることがある。上記ラジカル重合開始剤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１０重量部である。 Although content of the said radical polymerization initiator is not specifically limited, A preferable minimum is 0.1 weight part and a preferable upper limit is 30 weight part with respect to 100 weight part of said curable resins. When the content of the radical polymerization initiator is less than 0.1 parts by weight, the polymerization of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed. When the content of the radical polymerization initiator exceeds 30 parts by weight, a large amount of unreacted radical polymerization initiator remains, and the weather resistance of the obtained liquid crystal dropping method sealing agent may deteriorate. The minimum with more preferable content of the said radical polymerization initiator is 1 weight part, and a more preferable upper limit is 10 weight part.
上記熱硬化剤は特に限定されず、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、固形の有機酸ヒドラジドが好適に用いられる。 The said thermosetting agent is not specifically limited, For example, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned. Among these, solid organic acid hydrazide is preferably used.
上記固形の有機酸ヒドラジドは特に限定されず、例えば、１，３－ビス［ヒドラジノカルボエチル－５－イソプロピルヒダントイン］、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、市販されているものとしては、例えば、アミキュアＶＤＨ、アミキュアＵＤＨ（いずれも、味の素ファインテクノ社製）、ＳＤＨ、ＩＤＨ、ＡＤＨ（いずれも、大塚化学社製）等が挙げられる。 The solid organic acid hydrazide is not particularly limited, and examples thereof include 1,3-bis [hydrazinocarboethyl-5-isopropylhydantoin], sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like. Examples of commercially available products include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), and the like.
上記熱硬化剤の含有量は特に限定されないが、硬化性樹脂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。上記熱硬化剤の含有量が２重量部未満であると、得られる液晶滴下工法用シール剤が硬化性に劣るものとなることがある。上記熱硬化剤の含有量が５０重量部を超えると、得られる液晶滴下工法用シール剤の粘度が高くなり、塗布性が悪くなることがある。上記熱硬化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２０重量部、更に好ましい上限は１５重量部である。 Although content of the said thermosetting agent is not specifically limited, A preferable minimum is 2 weight part with respect to 100 weight part of curable resin, and a preferable upper limit is 50 weight part. When the content of the thermosetting agent is less than 2 parts by weight, the obtained sealing agent for liquid crystal dropping method may be inferior in curability. When content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability | paintability may worsen. The minimum with more preferable content of the said thermosetting agent is 5 weight part, A more preferable upper limit is 20 weight part, Furthermore, a preferable upper limit is 15 weight part.
本発明の液晶滴下工法用シール剤は、カチオン重合開始剤を含有してもよい。
上記カチオン重合開始剤としては、光カチオン重合開始剤、熱カチオン重合開始剤が挙げられる。 The sealing agent for liquid crystal dropping method of the present invention may contain a cationic polymerization initiator.
Examples of the cationic polymerization initiator include a photocationic polymerization initiator and a thermal cationic polymerization initiator.
上記光カチオン重合開始剤は特に限定されず、例えば、芳香族ジアゾニウム塩、芳香族ヨードニウム塩、芳香族スルホニウム塩等が挙げられる。
上記光カチオン重合開始剤のうち市販されているものとしては、例えば、オプトマーＳＰ－１５０、オプトマーＳＰ－１５１、オプトマーＳＰ－１７０、オプトマーＳＰ－１７１（いずれもＡＤＥＫＡ社製）、ＵＶＥ－１０１４（ゼネラルエレクトロニクス社製）、イルガキュア２６１（ＢＡＳＦ　Ｊａｐａｎ社製）、サンエイドＳＩ－６０Ｌ、サンエイドＳＩ－８０Ｌ、ＵＶＩ－６９９０（いずれもユニオンカーバイド社製）、ＢＢＩ－１０３、ＭＰＩ－１０３、ＴＰＳ－１０３、ＭＤＳ－１０３、ＤＴＳ－１０３、ＮＡＴ－１０３、ＮＤＳ－１０３（いずれもミドリ化学社製）、サンエイドＳＩ－１００Ｌ（三新化学工業社製）、ＣＩ－２０６４、ＣＩ－２６３９、ＣＩ－２６２４、ＣＩ－２４８１（いずれも日本曹達社製）、ＲＨＯＤＯＲＳＩＬ　ＰＨＯＴＯＩＮＩＴＩＡＴＯＲ　２０７４（ローヌ・プーラン社製）、ＣＤ－１０１２（サートマー社製）等が挙げられる。これらの光カチオン重合開始剤は単独で用いてもよいし、２種以上を併用してもよい。また、必要に応じてアントラセン系、チオキサントン系等の増感剤を併用しても良い。 The photocationic polymerization initiator is not particularly limited, and examples thereof include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.
Examples of commercially available photocationic polymerization initiators include optomer SP-150, optomer SP-151, optomer SP-170, optomer SP-171 (all manufactured by ADEKA), UVE-1014 (general). Electronics), Irgacure 261 (BASF Japan), Sun-Aid SI-60L, Sun-Aid SI-80L, UVI-6990 (all from Union Carbide), BBI-103, MPI-103, TPS-103, MDS- 103, DTS-103, NAT-103, NDS-103 (all manufactured by Midori Chemical Co., Ltd.), Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2064, CI-2639, CI-2624, CI-2481 (Both made by Nippon Soda Co., Ltd.), RHODO RSIL PHOTOINITIATOR 2074 (manufactured by Rhone-Poulenc), CD-1012 (manufactured by Sartomer) and the like. These cationic photopolymerization initiators may be used alone or in combination of two or more. Moreover, you may use together sensitizers, such as anthracene type and a thioxanthone type, as needed.
上記熱カチオン重合開始剤は特に限定されず、例えば、第四級アンモニウム塩、ホスホニウム塩、スルホニウム塩等の各種オニウム塩類が例示される。 The thermal cationic polymerization initiator is not particularly limited, and examples thereof include various onium salts such as a quaternary ammonium salt, a phosphonium salt, and a sulfonium salt.
上記第四級アンモニウム塩としては、例えば、テトラブチルアンモニウムテトラフルオロボレート、テトラブチルアンモニウムヘキサフルオロホスフェート、テトラブチルアンモニウムハイドロジェンサルフェート、テトラエチルアンモニウムテトラフルオロボレート、テトラエチルアンモニウムｐ－トルエンスルホネート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルアニリニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルアニリニウムテトラフルオロボレート、Ｎ，Ｎ－ジメチル－Ｎ－ベンジルピリジニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジエチル－Ｎ－ベンジルトリフルオロメタンスルホネート、Ｎ，Ｎ－ジメチル－Ｎ－（４－メトキシベンジル）ピリジニウムヘキサフルオロアンチモネート、Ｎ，Ｎ－ジエチル－Ｎ－（４－メトキシベンジル）トルイジニウムヘキサフルオロアンチモネート等が挙げられる。 Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N-dimethyl. -N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyl Trifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-die -N- (4- methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.
上記ホスホニウム塩としては、例えば、エチルトリフェニルホスホニウムヘキサフルオロアンチモネート、テトラブチルホスホニウムヘキサフルオロアンチモネート等が挙げられる。
上記スルホニウム塩は、例えば、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムヘキサフルオロアルシネート、トリス（４－メトキシフェニル）スルホニウムヘキサフルオロアルシネート、ジフェニル（４－フェニルチオフェニル）スルホニウムヘキサフルオロアルシネート等が挙げられる。 Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, and diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.
上記熱カチオン重合開始剤のうち市販されているものとしては、例えば、アデカオプトンＣＰ－６６、アデカオプトンＣＰ－７７（いずれもＡＤＥＫＡ社製）、サンエイドＳＩ－６０Ｌ、サンエイドＳＩ－８０Ｌ、サンエイドＳＩ－１００Ｌ（いずれも三新化学工業社製）、ＣＩシリーズ（日本曹達社製）等が挙げられる。 Examples of commercially available thermal cationic polymerization initiators include, for example, Adeka Opton CP-66, Adeka Opton CP-77 (all manufactured by ADEKA), Sun Aid SI-60L, Sun Aid SI-80L, Sun Aid SI-100L ( All of them are manufactured by Sanshin Chemical Industry Co., Ltd.) and CI series (manufactured by Nippon Soda Co., Ltd.).
上記カチオン重合開始剤の含有量は特に限定されないが、硬化性樹脂全体１００重量部に対して好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記カチオン重合開始剤の含有量が０．１重量部未満であると、本発明の液晶表示素子用シール剤を充分に硬化させることができないことがある。上記カチオン重合開始剤の含有量が１０重量部を超えると、貯蔵安定性が低下することがある。 Although content of the said cationic polymerization initiator is not specifically limited, A preferable minimum is 0.1 weight part with respect to 100 weight part of whole curable resin, and a preferable upper limit is 10 weight part. If the content of the cationic polymerization initiator is less than 0.1 parts by weight, the sealing agent for liquid crystal display elements of the present invention may not be sufficiently cured. If the content of the cationic polymerization initiator exceeds 10 parts by weight, the storage stability may be lowered.
本発明の液晶滴下工法用シール剤は、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。 The sealing agent for liquid crystal dropping method of the present invention preferably 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は特に限定されないが、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、γ－アミノプロピルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－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てもよいし、２種以上を併用してもよい。 Although the silane coupling agent is not particularly limited, it is excellent in the effect of improving adhesiveness with a substrate and the like, and it can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin. For example, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.
上記シランカップリング剤の含有量は、本発明の液晶滴下工法用シール剤１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が２０重量部である。上記シランカップリング剤の含有量が０．１重量部未満であると、シランカップリング剤を配合することによる効果が充分に発揮されないことがある。上記シランカップリング剤の含有量が２０重量部を超えると、得られる液晶滴下工法用シール剤が液晶汚染を引き起こすことがある。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０．５重量部、より好ましい上限は１０重量部である。 The content of the silane coupling agent is such that the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the liquid crystal dropping method sealing agent of the present invention. When the content of the silane coupling agent is less than 0.1 parts by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 20 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid-crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.
本発明の液晶滴下工法用シール剤は、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、本発明の液晶滴下工法用シール剤は、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 dropping method of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal dropping methods 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、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 preferable.
上記チタンブラックは、波長３００～８００ｎｍの光に対する平均透過率と比較して、紫外線領域付近、特に波長３７０～４５０ｎｍの光に対する透過率が高くなる物質である。即ち、上記チタンブラックは、可視光領域の波長の光を充分に遮蔽することで本発明の液晶滴下工法用シール剤に遮光性を付与する一方、紫外線領域付近の波長の光は透過させる性質を有する遮光剤である。従って、上記光ラジカル重合開始剤や上記光カチオン重合開始剤として、上記チタンブラックの透過率の高くなる波長（３７０～４５０ｎｍ）の光によって反応を開始可能なものを用いることで、本発明の液晶滴下工法用シール剤の光硬化性をより増大させることができる。また一方で、本発明の液晶滴下工法用シール剤に含有される遮光剤としては、絶縁性の高い物質が好ましく、絶縁性の高い遮光剤としてもチタンブラックが好適である。
上記チタンブラックは、１μｍあたりの光学濃度（ＯＤ値）が、０．１以上であることが好ましく、０．２以上であることがより好ましい。上記チタンブラックの遮光性は高ければ高いほどよく、上記チタンブラックのＯＤ値に好ましい上限は特にないが、通常は３.０以下となる。 Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing light shielding properties to the sealing agent for liquid crystal dropping method of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. Therefore, by using the photo radical polymerization initiator or the photo cationic polymerization initiator that can start the reaction with light having a wavelength (370 to 450 nm) at which the transmittance of the titanium black is high, the liquid crystal of the present invention is used. The photocurability of the sealing agent for the dripping method can be further increased. On the other hand, the light shielding agent contained in the liquid crystal dropping method sealing agent of the present invention is preferably a highly insulating material, and titanium black is also suitable as the highly insulating light shielding agent.
The titanium black has an optical density (OD value) per μm of preferably 0.1 or more, and more preferably 0.2 or more. The higher the light-shielding property of titanium black, the better. There is no particular upper limit for the OD value of titanium black, but it is usually 3.0 or less.
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滴下工法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 one 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 device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus 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（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 (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like.
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１ｎｍ未満であると、得られる液晶滴下工法用シール剤の粘度やチクソトロピーが大きく増大してしまい、作業性が悪くなることがある。上記遮光剤の一次粒子径が５μｍを超えると、得られる液晶滴下工法用シール剤の基板への塗布性が悪くなることがある。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。 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 less than 1 nm, the viscosity and thixotropy of the obtained liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated. 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.
上記遮光剤の含有量は、本発明の液晶滴下工法用シール剤全体に対して、好ましい下限が５重量％、好ましい上限が８０重量％である。上記遮光剤の含有量が５重量％未満であると、充分な遮光性が得られないことがある。上記遮光剤の含有量が８０重量％を超えると、得られる液晶滴下工法用シール剤の基板に対する密着性や硬化後の強度が低下したり、描画性が低下したりすることがある。上記遮光剤の含有量のより好ましい下限は１０重量％、より好ましい上限は７０重量％であり、更に好ましい下限は３０重量％、更に好ましい上限は６０重量％である。 The preferable lower limit of the content of the light-shielding agent is 5% by weight and the preferable upper limit is 80% by weight with respect to the entire sealing agent for liquid crystal dropping method of the present invention. If the content of the light shielding agent is less than 5% by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent is more than 80% by weight, the adhesion of the obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered. The more preferable lower limit of the content of the light shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.
本発明の液晶滴下工法用シール剤は、更に、必要に応じて、粘度調整の為の反応性希釈剤、パネルギャップ調整の為のポリマービーズ等のスペーサー、３－Ｐ－クロロフェニル－１，１－ジメチル尿素等の硬化促進剤、消泡剤、レベリング剤、重合禁止剤等の添加剤を含有してもよい。 The sealing agent for liquid crystal dropping method of the present invention further comprises a reactive diluent for adjusting the viscosity, a spacer such as polymer beads for adjusting the panel gap, 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, and a polymerization inhibitor.
本発明の液晶滴下工法用シール剤を製造する方法は特に限定されず、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリウムミキサー、ニーダー、３本ロール等の混合機を用いて、硬化性樹脂、タルク、及び、ラジカル重合開始剤若しくは熱硬化剤、又は、ラジカル重合開始剤と熱硬化剤との両方、並びに、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を混合する方法等が挙げられる。 The method for producing the sealing agent for liquid crystal dropping method of the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, or a three roll, a curable resin, Examples include a method of mixing talc and a radical polymerization initiator or a thermosetting agent, or both a radical polymerization initiator and a thermosetting agent, and an additive such as a silane coupling agent to be added as necessary. It is done.
本発明の液晶滴下工法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滴下工法用シール剤と、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 conduction material can be manufactured by mix | blending electroconductive fine particles with the sealing compound for liquid crystal dropping methods of this invention. The vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子は特に限定されず、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。 The conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
本発明の液晶滴下工法用シール剤、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 which uses the sealing compound for liquid crystal dropping methods of this invention or the vertical conduction material of this invention is also one of this invention.
本発明によれば、描画性、接着性、及び、硬化物の耐湿性に優れる液晶滴下工法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、該液晶滴下工法用シール剤を用いて製造され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 dropping methods which is excellent in drawing property, adhesiveness, and moisture resistance of hardened | cured material can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods 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.
（実施例１～１７、比較例１～３）
表１～３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１～１７、比較例１～３の液晶滴下工法用シール剤を調製した。
なお、表１～３における「ＳＧ－２０００」は、上述した条件でＸ線回折装置を用いて測定したＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量が０．２重量％より大きいタルクであり、「ＦＧ－１５Ｆ」は、上述した条件でＸ線回折装置を用いて測定したＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量が０．１重量％以下のタルクである。
また、表１～３において、「ステアリン酸処理ＦＧ－１５Ｆ」は、「ＦＧ－１５Ｆ」１００重量部と、ステアリン酸１０重量部とを、乾式表面処理することにより得られた表面処理タルクであり、「ＫＢＭ－４０３処理ＦＧ－１５Ｆ」は、「ＦＧ－１５Ｆ」１００重量部と、γ－グリシドキシプロピルトリメトキシシラン（信越シリコーン社製、「ＫＢＭ－４０３」）１０重量部とを、乾式表面処理することにより得られた表面処理タルクであり、「ＫＢＭ－６０３処理ＦＧ－１５Ｆ」は、「ＦＧ－１５Ｆ」１００重量部と、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン（信越シリコーン社製、「ＫＢＭ－６０３」）１０重量部とを、乾式表面処理することにより得られた表面処理タルクである。 (Examples 1 to 17, Comparative Examples 1 to 3)
According to the blending ratios described in Tables 1 to 3, each material was mixed using a planetary stirrer (“Shinky Co., Ltd.“ Awatori Netaro ”), and then mixed using three rolls. The sealing agents for liquid crystal dropping method of Examples 1 to 17 and Comparative Examples 1 to 3 were prepared.
Note that “SG-2000” in Tables 1 to 3 is a talc in which the total content of CaMg (CO 3 ) 2 and MgCO 3 measured using an X-ray diffractometer under the conditions described above is greater than 0.2% by weight. “FG-15F” is talc having a total content of CaMg (CO 3 ) 2 and MgCO 3 measured by using an X-ray diffractometer under the above-described conditions of 0.1% by weight or less.
In Tables 1 to 3, “stearic acid-treated FG-15F” is a surface-treated talc obtained by dry-treating 100 parts by weight of “FG-15F” and 10 parts by weight of stearic acid. , “KBM-403 treated FG-15F” was prepared by dry-drying 100 parts by weight of “FG-15F” and 10 parts by weight of γ-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone). This is a surface-treated talc obtained by surface treatment. “KBM-603 treated FG-15F” is composed of 100 parts by weight of “FG-15F” and N-2- (aminoethyl) -3-aminopropyltrimethoxy. This is a surface-treated talc obtained by dry-treating 10 parts by weight of silane (“KBM-603” manufactured by Shin-Etsu Silicone Co., Ltd.).
＜評価＞
実施例及び比較例で得られたシール剤について以下の評価を行った。結果を表１～３に示した。 <Evaluation>
The following evaluation was performed about the sealing agent obtained by the Example and the comparative example. The results are shown in Tables 1-3.
（描画性）
実施例及び比較例で得られた液晶滴下工法用シール剤に、シリカスペーサー（積水化学工業社製、「ＳＩ－Ｈ０５５」）を１重量％配合し、脱泡処理をしてシール剤中の泡を取り除いた後、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、再び脱泡処理を行った。次いで、ディスペンサー（武蔵エンジニアリング社製、「ＳＨＯＴＭＡＳＴＥＲ３００」）を用いてＩＴＯ薄膜付きの透明電極基板に長方形の枠を描く様にシール剤を塗布し、他方の透明基板を、真空張り合わせ装置にて５Ｐａの減圧下にて張り合わせた。張り合わせた後のセルをメタルハライドランプにて３０００ｍＪ／ｃｍ２の紫外線を照射した後、１２０℃で６０分加熱することによってシール剤を熱硬化させ、液晶セルを各シール剤につき５枚ずつ作製した。この液晶セル内のシール剤を観察し、シール剤に断線不良も端部のうねりもなくきれいなラインが描けていた場合を「◎」、断線不良はないがシール剤の端部にわずかにうねりが生じる等していた場合を「○」、断線不良はないがシール剤の端部にはっきりとうねりが生じる等していた場合を「△」、断線不良が生じていた場合を「×」として評価した。 (Drawability)
1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) was added to the sealing agent for liquid crystal dropping method obtained in the examples and comparative examples, and the bubbles in the sealing agent were defoamed. Then, a dispensing syringe (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) was filled and defoamed again. Next, using a dispenser (“SHOTMASTER300” manufactured by Musashi Engineering Co., Ltd.), a sealing agent is applied to the transparent electrode substrate with the ITO thin film so as to draw a rectangular frame, and the other transparent substrate is coated with 5 Pa with a vacuum bonding apparatus. Bonding was performed under reduced pressure. The cells after pasting were irradiated with 3000 mJ / cm 2 ultraviolet rays with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent, and five liquid crystal cells were prepared for each sealing agent. Observe the sealing agent in this liquid crystal cell, and if the sealing agent had a clean line with no disconnection and no waviness at the end, “◎”, no disconnection but a slight waviness at the end of the sealing agent. Evaluated as “○” if it occurred, “△” if there was a clear swell at the end of the sealant, but “×” if it was broken did.
（接着性）
実施例及び比較例で得られたシール剤に、シリカスペーサー（積水化学工業社製、「ＳＩ－Ｈ０５５」）を１重量％配合し、２枚のＩＴＯ膜付きアルカリガラス試験片（３０×４０ｍｍ）のうち一方に微小滴下し、これにもう一方のガラス試験片を十字状に張り合わせたものを、メタルハライドランプにて３０００ｍＪ／ｃｍ２の紫外線を照射した後、１２０℃で６０分加熱することによって接着試験片を得た。これを上下に配したチャックにて引っ張り試験（５ｍｍ／ｓｅｃ）を行った。得られた測定値（ｋｇｆ）をシール塗布断面積（ｃｍ２）で除した値が３０ｋｇｆ／ｃｍ２以上であった場合を「◎」、２０ｋｇｆ／ｃｍ２以上３０ｋｇｆ／ｃｍ２未満であった場合を「○」、１０ｋｇｆ／ｃｍ２以上２０ｋｇｆ／ｃｍ２未満であった場合を「△」、１０ｋｇｆ／ｃｍ２未満であった場合を「×」として評価した。 (Adhesiveness)
1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) was added to the sealants obtained in the examples and comparative examples, and two alkali glass test pieces with ITO film (30 × 40 mm) Adhering a fine glass drop on one of them and pasting the other glass test piece in a cross shape onto the metal halide lamp by irradiating 3000 mJ / cm 2 with ultraviolet rays and heating at 120 ° C. for 60 minutes. A specimen was obtained. This was subjected to a tensile test (5 mm / sec) with a chuck arranged vertically. The value obtained by dividing the measured value (kgf) by the cross-sectional area (cm 2 ) applied to the seal is 30 kgf / cm 2 or more, “◎”, if it is 20 kgf / cm 2 or more and less than 30 kgf / cm 2 Was evaluated as “◯” when “O” was 10 kgf / cm 2 or more and less than 20 kgf / cm 2 , and “X” when it was less than 10 kgf / cm 2 .
（硬化物の耐湿性）
実施例及び比較例で得られたシール剤を、平滑な離型フィルム状にコーターで厚さ２００～３００μｍに塗行した後、メタルハライドランプにて３０００ｍＪ／ｃｍ２の紫外線を照射した後、１２０℃で６０分加熱することによって透湿度測定用硬化フィルムを得た。ＪＩＳ　Ｚ　０２０８の防湿包装材料の透湿度試験方法（カップ法）に準じた方法で透湿度試験用カップを作製し、得られた透湿度測定用硬化フィルムを取り付け、温度８０℃湿度９０％ＲＨの高温高湿オーブンに投入して透湿度を測定した。得られた透湿度の値が４０ｇ／ｍ２・２４ｈｒ未満であった場合を「◎」、４０ｇ／ｍ２・２４ｈｒ以上６０ｇ／ｍ２・２４ｈｒ未満であった場合を「○」、６０ｇ／ｍ２・２４ｈｒ以上８０ｇ／ｍ２・２４ｈｒ未満であった場合を「△」、８０ｇ／ｍ２・２４ｈｒ以上であった場合を「×」として評価した。 (Humidity resistance of cured product)
The sealants obtained in the examples and comparative examples were applied to a smooth release film with a coater to a thickness of 200 to 300 μm, irradiated with 3000 mJ / cm 2 of ultraviolet rays with a metal halide lamp, and then 120 ° C. For 60 minutes to obtain a cured film for measuring moisture permeability. A moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture proof packaging materials (cup method), and the obtained cured film for moisture permeability measurement was attached, and the temperature was 80 ° C. and the humidity was 90% RH. The moisture permeability was measured by putting it in a high-temperature and high-humidity oven. The case where the obtained moisture permeability value is less than 40 g / m 2 · 24 hr is “◎”, and the case where it is 40 g / m 2 · 24 hr or more and less than 60 g / m 2 · 24 hr is “◯”, 60 g / m The case where it was 2 · 24 hr or more and less than 80 g / m 2 · 24 hr was evaluated as “Δ”, and the case where it was 80 g / m 2 · 24 hr or more was evaluated as “x”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
本発明によれば、描画性、接着性、及び、硬化物の耐湿性に優れる液晶滴下工法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、該液晶滴下工法用シール剤を用いて製造され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 dropping methods which is excellent in drawing property, adhesiveness, and moisture resistance of hardened | cured material can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

Claims (12)

  1. 硬化性樹脂、タルク、及び、ラジカル重合開始剤若しくは熱硬化剤、又は、ラジカル重合開始剤と熱硬化剤との両方を含有する液晶滴下工法用シール剤であって、
    前記タルクにおけるＣａＭｇ（ＣＯ３）２及びＭｇＣＯ３の合計の含有量が０．１重量％以下である
    ことを特徴とする液晶滴下工法用シール剤。     A curable resin, talc, and a radical polymerization initiator or a thermosetting agent, or a liquid crystal dropping method sealing agent containing both a radical polymerization initiator and a thermosetting agent,
    A total amount of CaMg (CO 3 ) 2 and MgCO 3 in the talc is 0.1% by weight or less.
  2. タルクは、表面処理剤によって表面処理されたものであることを特徴とする請求項１記載の液晶滴下工法用シール剤。 The sealing agent for liquid crystal dropping method according to claim 1, wherein the talc is surface-treated with a surface treating agent.
  3. 表面処理剤は、シランカップリング剤であることを特徴とする請求項２記載の液晶滴下工法用シール剤。 The sealing agent for liquid crystal dropping method according to claim 2, wherein the surface treatment agent is a silane coupling agent.
  4. シランカップリング剤は、エポキシ基を有するシランカップリング剤であることを特徴とする請求項３記載の液晶滴下工法用シール剤。 4. The sealing agent for liquid crystal dropping method according to claim 3, wherein the silane coupling agent is a silane coupling agent having an epoxy group.
  5. タルクの含有量が、硬化性樹脂１００重量部に対して、０．１～５０重量部であることを特徴とする請求項１、２、３又は４記載の液晶滴下工法用シール剤。 5. The sealing agent for liquid crystal dropping method according to claim 1, wherein the content of talc is 0.1 to 50 parts by weight with respect to 100 parts by weight of curable resin.
  6. 硬化性樹脂は、イソシアヌル骨格を有する（メタ）アクリレート及び／又はジシクロペンタジエン骨格を有する（メタ）アクリレートを含有することを特徴とする請求項１、２、３、４又は５記載の液晶滴下工法用シール剤。 6. The liquid crystal dropping method according to claim 1, wherein the curable resin contains (meth) acrylate having an isocyanuric skeleton and / or (meth) acrylate having a dicyclopentadiene skeleton. Sealing agent.
  7. 硬化性樹脂は、イソシアヌル骨格を有する（メタ）アクリレートを含有し、
    前記イソシアヌル骨格を有する（メタ）アクリレートは、エトキシ化イソシアヌルトリアクリレートである
    ことを特徴とする請求項６記載の液晶滴下工法用シール剤。     The curable resin contains a (meth) acrylate having an isocyanuric skeleton,
    The sealing agent for liquid crystal dropping method according to claim 6, wherein the (meth) acrylate having an isocyanuric skeleton is ethoxylated isocyanuric triacrylate.
  8. 硬化性樹脂は、ジシクロペンタジエン骨格を有する（メタ）アクリレートを含有し、
    前記ジシクロペンタジエン骨格を有する（メタ）アクリレートは、トリシクロデカンジメタノールジアクリレートである
    ことを特徴とする請求項６又は７記載の液晶滴下工法用シール剤。     The curable resin contains a (meth) acrylate having a dicyclopentadiene skeleton,
    The sealing agent for liquid crystal dropping method according to claim 6 or 7, wherein the (meth) acrylate having a dicyclopentadiene skeleton is tricyclodecane dimethanol diacrylate.
  9. イソシアヌル骨格を有する（メタ）アクリレート及びジシクロペンタジエン骨格を有する（メタ）アクリレートの含有量が、硬化性樹脂全体１００重量部に対して、０．１～３０重量部であることを特徴とする請求項６、７又は８記載の液晶滴下工法用シール剤。 The content of (meth) acrylate having an isocyanuric skeleton and (meth) acrylate having a dicyclopentadiene skeleton is 0.1 to 30 parts by weight with respect to 100 parts by weight of the entire curable resin. Item 9. A sealing agent for liquid crystal dropping method according to item 6, 7 or 8.
  10. 遮光剤を含有することを特徴とする請求項１、２、３、４、５、６、７、８又は９記載の液晶滴下工法用シール剤。 The light-shielding agent is contained, The sealing agent for liquid crystal dropping methods of Claim 1, 2, 3, 4, 5, 6, 7, 8 or 9 characterized by the above-mentioned.
  11. 請求項１、２、３、４、５、６、７、８、９又は１０記載の液晶滴下工法用シール剤と、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 conducting material comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and conductive fine particles.
  12. 請求項１、２、３、４、５、６、７、８、９若しくは１０記載の液晶滴下工法用シール剤、又は、請求項１１記載の上下導通材料を用いて製造されることを特徴とする液晶表示素子。 It is manufactured using the sealing agent for liquid crystal dropping methods according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or the vertical conduction material according to claim 11. Liquid crystal display element.
PCT/JP2013/058713 2012-03-30 2013-03-26 Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element WO2013146748A1 (en)

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