Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1339—Gaskets; Spacers; Sealing of cells
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
  • C08L63/10—Epoxy resins modified by unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133509—Filters, e.g. light shielding masks
  • G02F1/133514—Colour filters
• • 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
  • G02F2202/00—Materials and properties
  • G02F2202/02—Materials and properties organic material
  • G02F2202/022—Materials and properties organic material polymeric
  • G02F2202/023—Materials and properties organic material polymeric curable

Definitions

• the present invention relates to a liquid crystal sealant used for adhering a TFT (Thin film Transistor) substrate and a CF (Color Filter) substrate and enclosing liquid crystal inside, and a liquid crystal display cell using the same.
• TFT Thin film Transistor
• CF Color Filter
• a seal pattern made of a rectangular uncured sealant is formed on one of two transparent substrates with electrodes by dispensing.
• fine droplets of liquid crystal are dropped onto the entire surface of the seal pattern of the transparent substrate while the sealant is uncured, and the other transparent substrate is immediately bonded to produce a liquid crystal cell.
• Photocuring temporary curing
• Photocuring is performed by irradiating the seal pattern portion of the liquid crystal cell with ultraviolet rays. Then, it heats as needed and performs thermosetting (main curing), and produces a liquid crystal display cell.
• talc which contains very little (usually about 0.2 to 0.3%) in talc, has an influence. That is, since talc is generally obtained by grinding naturally occurring ore, it contains various impurities such as dolomite, magnesite, and crystalline silica.
• the present invention eliminates the disconnection of the wiring sealant provided on the cell substrate while using talc as an inorganic filler, reduces liquid crystal contamination, and provides adhesion to a glass substrate and moisture resistance after curing. It is another object of the present invention to provide a liquid crystal sealant that is also excellent and a liquid crystal display cell using the same.
• the present invention relates to the following (1) to (11).
• An ultraviolet curable liquid crystal sealant comprising (a) a crystalline silica-free talc, (b) a (meth) acrylated epoxy resin, and (c) a photopolymerization initiator.
• Talc (a) is 1 to 40% by weight based on the total amount of the liquid crystal sealant, and (meth) acrylated epoxy resin (b) is 30 to 90% by weight based on the total amount of the liquid crystal sealant, and photopolymerization is started.
• the ultraviolet curable liquid crystal sealant according to any one of the above.
• the liquid crystal sealant of the present invention is excellent in adhesiveness and can prevent disconnection of wiring on the substrate. Further, the liquid crystal sealing agent has little liquid crystal contamination and is excellent in adhesive strength and moisture-resistant adhesive strength. Therefore, by using this sealant, a liquid crystal display panel having excellent reliability can be easily manufactured.
• the sealing agent composition for liquid crystal display elements of the present invention contains crystalline silica-free talc (a), (meth) acrylated epoxy resin (b), and photopolymerization initiator (c) as essential components.
• Talc consists of magnesium hydroxide and silicate, and is obtained by pulverizing talc. For this reason, talc usually contains crystalline silica as an impurity.
• the crystalline silica-free talc (a) in the present invention (hereinafter also simply referred to as “talc (a)”) is, for example, a normal X-ray diffraction measurement, and the content of crystalline silica is below the detection limit (specifically Talc of 0.1% by weight or less), more preferably talc having a crystalline silica content of less than 0.1% by weight. Such talc is generally available from the market.
• the crystalline silica content in talc is determined from the area ratio of the peak at a diffraction angle of 26.8 ° derived from crystalline silica in the X-ray diffraction measurement (an error of about ⁇ 0.2 ° is allowed). To do).
• Specific examples of measurement conditions for the X-ray diffraction measurement are as follows.
• Measuring instrument X'Pert-PRO-MPD (Spectris Co., Ltd.) Target: Cu Scan angle: 5 ° -60 ° Scanning speed: 2 ° / min Tube voltage: 40 kV Tube current: 30 mA Incident side slit: 0.04 ° solar slit, automatic variable divergence slit, AS1 ° Light receiving side slit; 0.04 ° Note that the detection limit of the content of crystalline silica in talc under this measurement condition is 0.1%.
• the average particle diameter of talc (a) used in the present invention is preferably 1 ⁇ m or less. If the average particle size of talc is too large, there may be a problem when a gap is formed by laminating the upper and lower substrates when manufacturing a liquid crystal cell. Moreover, the minimum of the average particle diameter of the talc (a) used by this invention is about 0.3 micrometer normally.
• the average particle size of talc (a) is preferably about 0.3 to 1 ⁇ m, more preferably about 0.4 to 0.9 ⁇ m.
• the average particle diameter means a median diameter measured by a laser diffraction particle size distribution analyzer (SALD-2000J, manufactured by Shimadzu Corporation).
• the talc (a) used in the present invention may be a talc (a) surface-treated in advance with a silane coupling agent.
• a silane coupling agent By the surface treatment, compatibility with the (meth) acrylated epoxy resin (b) is improved, and the moisture resistance reliability is also improved. Therefore, talc (a) which has been surface-treated with a silane coupling agent in advance is more preferable.
• Examples of commercially available talc (a) used in the present invention include NANO ACE RTM D-600F (manufactured by Nippon Talc Co., Ltd.).
• Examples of commercially available talc (a) surface-treated with a silane coupling agent in advance include NANO ACE RTM D-600FC3BM43, NANO ACE RTM D-600FC3BM63 (all manufactured by Nippon Talc Co., Ltd.) and the like.
• the superscript “RTM” indicates a registered trademark.
• silane coupling agent (d) for surface-treating the talc (a) of the present invention is a silane used for surface modification of inorganic fillers. Any coupling agent can be used as long as the effects of the present invention are not hindered.
• the silane coupling agent (d) include epoxy such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
• Silane coupling agent having a group N-phenyl-3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxy Silane coupling agents having amino groups such as silane and 3-aminopropyltriethoxysilane; Silane coupling agents having mercapto groups such as 3-mercaptopropyltrimethoxysilane; Vinyltrimethoxysilane, N- (2- (vinyl Benzylamino) ethyl) 3-amino Silane coupling agents having a vinyl group such as propyltrimethoxysilane hydrochloride; Silane coupling agents having a (meth) acryloxy group such as 3-methacryloxypropyltrimethoxysilane; 3-chloropropylmethyldimethoxysilane, 3- Examples thereof include silane
• silane coupling agents (d) may be used alone or in combination of two or more. Of these, a silane coupling agent having an amino group and a silane coupling agent having an epoxy group are preferred. Of these, silane coupling agents having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are more preferable.
• talc (a) treated with the silane coupling agent the sealing agent of the present invention can obtain better moisture resistance reliability.
• the surface treatment of talc (a) with a silane coupling agent involves coating the surface of talc (a) with a silane coupling agent by spraying the silane coupling agent onto the powder of talc (a). Is done.
• the amount of the silane coupling agent (d) used is usually 0.1 with respect to 100 parts by weight of talc (a). About 10 parts by weight, preferably 1 to 5 parts by weight.
• the content of talc (a) used in the present invention in the liquid crystal sealant is usually 1 to 40% by weight, preferably 3 to 20% by weight.
• Talc (a) is used as an inorganic filler in the sealant of the present invention.
• the inorganic filler the talc (a) alone or another inorganic filler may be used in combination. Usually, it is preferable to use other inorganic fillers in combination.
• the other inorganic filler (h) any inorganic filler other than talc generally used for liquid crystal sealants can be used.
• Examples of such other inorganic fillers (h) include silica (fused silica and the like), silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, alumina, aluminum hydroxide, calcium silicate and silica. An aluminum acid etc. are mentioned. Of these, silica is preferred, fused silica (amorphous silica) is more preferred, and spherical amorphous silica (fused spherical silica) is even more preferred.
• the average particle diameter of the other inorganic filler (h) is preferably 1 ⁇ m or less, more preferably 0.9 ⁇ m or less.
• the content of the inorganic filler including talc (a) is about 5 to 40% by weight, preferably about 10 to 40% by weight, based on the total amount of the sealing agent. Preferably, it is about 15 to 30% by weight.
• the content of talc (a) is usually about 5 to 90% by weight, preferably 26 to 80% by weight, based on the total amount of inorganic filler. %, More preferably about 41 to 80% by weight, most preferably about 41 to 60% by weight, and the other inorganic filler (h) is usually about 10 to 95% by weight, preferably 20 to 74% by weight. %, More preferably about 20 to 59% by weight, and most preferably about 40 to 59% by weight.
• the content of talc (a) with respect to the total amount of the sealing agent is preferably about 3 to 35% by weight, more preferably about 3 to 20% by weight. More preferably, it is about 6 to 20% by weight.
• the content of the other inorganic filler (h) is usually 2 to 30% by weight, preferably 5 to 20% by weight, more preferably 5 to 15% by weight, based on the total amount of the liquid crystal sealant.
• the aspect which contains more talc (a) than another inorganic filler (h) is more preferable.
• the (meth) acrylated epoxy resin (b) used in the present invention is obtained by a reaction between an epoxy resin and (meth) acrylic acid. That is, (meth) acrylic acid may be ring-opened and added to the epoxy group of the epoxy resin.
• the (meth) acrylated epoxy resin (b) may be a partially (meth) acrylated epoxy resin in which an epoxy group remains partially, but preferably (meth) acrylic acid is opened to all epoxy groups.
• An added (meth) acrylated epoxy resin also referred to as epoxy (meth) acrylate
• “(meth) acryl” in “(meth) acrylation” or “(meth) acrylic acid” means “acryl” and / or “methacryl”.
• the (meth) acrylated epoxy resin (b) of the present invention preferably has low contamination and solubility in liquid crystals. Although it does not specifically limit as an epoxy resin used as a raw material of this (meth) acrylated epoxy resin (b), A bifunctional or more functional epoxy resin is preferable.
• the epoxy equivalent of the epoxy resin is not particularly limited, but is usually about 50 to 1000 g / eq, preferably about 100 to 500 g / eq.
• Specific examples of the epoxy resin include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol F.
• Novolac type epoxy resin alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenol novolac type having triphenolmethane skeleton Epoxy resins, diglycidyl etherified products of difunctional phenols, and diglycidyl etherified products of difunctional alcohols, and their halides or hydrogenated products Things and the like.
• bisphenol type epoxy resin and novolac type epoxy resin are preferable from the viewpoint of liquid crystal contamination, and more preferably bisphenol type epoxy resin (for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S). Type epoxy resin).
• Most preferred is a bisphenol A type epoxy resin.
• the preferred (meth) acrylated epoxy resin (b) is an epoxy (meth) acrylate obtained by ring-opening addition of (meth) acrylic acid to the above preferred, more preferred or most preferred epoxy resin. Specifically, bisphenol type epoxy (meth) acrylate or novolak type epoxy (meth) acrylate is preferable, bisphenol type epoxy (meth) acrylate is more preferable, and bisphenol A type epoxy (meth) acrylate is particularly preferable.
• the epoxy equivalent of the (meth) acrylated epoxy resin (b) is usually about 50 to 1000 g / eq, preferably about 100 to 500 g / eq.
• the content of the (meth) acrylated epoxy resin (b) used in the present invention in the liquid crystal sealant is 30 to 90% by weight, preferably 40 to 80% by weight, and more preferably 50%. About 80% by weight. If the content of the (meth) acrylated epoxy resin (b) is too small, the substrate may be peeled off due to insufficient curing when the liquid crystal sealant is thermally cured.
• the photopolymerization initiator (c) used in the present invention is a photoradical polymerization initiator that generates radicals by light irradiation.
• Specific examples of the photopolymerization initiator (c) include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl.
• Examples include-[4- (methylthio) phenyl] -2-morpholino-1-propane and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• photopolymerization initiators include Irgacure RTM 184, Irgacure RTM 369, Irgacure RTM 651, Irgacure RTM 2959, Irgacure RTM 819 (all of which are Ciba Specialty Chemicals shares) Company), Lucillin RTM TPO (BASF), Adeka RTM Optmer N-1414, Adeka RTM Optomer N-1717 (all manufactured by Asahi Denka Kogyo Co., Ltd.), Esacure KIP150, Esacure KK (all Nippon Sebel Hegner, Inc.) Manufactured). These may be used alone or in combination of two or more.
• the amount used is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the (meth) acrylated epoxy resin (b). If the amount used is too small, the sealing agent of the present invention may not be sufficiently cured. Moreover, when there is too much usage-amount, the contamination with respect to the liquid crystal derived from an initiator and the fall of the resin characteristic after hardening will pose a problem.
• the remainder other than the talc (a), the (meth) acrylated epoxy resin (b) and the photopolymerization initiator (c) is an optional additive component, and its content is: It is usually 0 to 60% by weight, preferably 0 to 40% by weight, based on the total amount of the liquid crystal sealant.
• optional additives include the other inorganic fillers (h), the following epoxy resin (e) and thermosetting agent (f), the (meth) acrylate monomer (g) described below, and other additives. I can do it.
• the liquid crystal sealing agent of the present invention may contain an epoxy resin (e) and a thermosetting agent (f) in order to improve the adhesive strength after thermosetting, and an embodiment including these is one of preferred embodiments. is there.
• epoxy resin (e) used in the liquid crystal sealant of the present invention can be used as long as it is an epoxy resin that can be usually used in a liquid crystal sealant. Those having low contamination and solubility are preferred.
• suitable epoxy resins (e) include (i) bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins or bisphenol S type epoxy resins, and (ii) bisphenol A novolak type epoxy resins or bisphenols.
• Bisphenol novolac epoxy resin such as F novolac epoxy resin, (iii) novolac epoxy resin such as phenol novolac epoxy resin, cresol novolac epoxy resin or phenol novolac epoxy resin having triphenolmethane skeleton, and (iv) Other epoxy resins, such as alicyclic epoxy resins, aliphatic chain epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurates Epoxy resins, diglycidyl ethers of bifunctional phenols and difunctional alcohols diglycidyl ethers of, and, like those of halides and hydrogenated product.
• the epoxy resin (e) is not necessarily limited to these.
• the epoxy resin (e) is preferably one of the above (i) to (iii), more preferably a bisphenol type epoxy resin and a novolac type epoxy resin, still more preferably a bisphenol type epoxy resin, and particularly preferably a bisphenol A type epoxy resin. preferable.
• the content is usually 1% by weight or more, preferably 3% by weight or more, and usually 50% by weight or less, based on the total amount of the liquid crystal sealing agent. Preferably it is 25 weight% or less. More preferably, it is 3 to 15% by weight with respect to the total amount of the liquid crystal sealant. If the amount of the epoxy resin (e) used is too small, the effect of improving the adhesive strength may not appear. Moreover, when there is too much usage-amount, the contamination with respect to the liquid crystal derived from an epoxy resin (e) will become a problem.
• thermosetting agent (f) is not particularly limited as long as it forms a cured product by reacting with the epoxy resin (e). However, the liquid crystal sealant uniformly does not contaminate the liquid crystal when heated. In addition, it is important that the reaction is started quickly and that the viscosity change with time at room temperature is small at the time of use.
• thermosetting condition of the thermosetting agent (f) in the case of the liquid crystal dropping method, a low temperature curing ability at about 120 ° C. for about 1 hour is generally required in order to minimize deterioration of the characteristics of the encapsulated liquid crystal. .
• polyfunctional hydrazides or polyvalent amines are preferable as the thermosetting agent (f) in the liquid crystal sealant of the present invention.
• the content is preferably about 10 to 80 parts by weight, more preferably 15 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin (e). Degree.
• the thermosetting agent (f) is used in such an amount that the reactive group with respect to the epoxy group in the thermosetting agent (f) is 0.1 to 1.5 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin (e). It is also preferable to do this. If the amount of the thermosetting agent (f) used with respect to the epoxy resin (e) is too small, the epoxy resin may not be sufficiently cured. Moreover, when there is too much this usage-amount, the moisture resistance performance of a sealing agent will become a problem.
• polyfunctional hydrazides refer to compounds having two or more hydrazide groups in the molecule.
• polyfunctional hydrazides include, for example, carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, , Hexadecanediohydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 1,4-bisbenzenedihydrazide , 4-
• thermosetting agent (f) polyfunctional hydrazides
• the average particle size at this time is preferably about 0.3 to 3 ⁇ m.
• thermosetting agent (f) polyfunctional hydrazides are preferable, and among the polyfunctional hydrazides, dihydrazide is preferable.
• thermosetting agent (f) is more preferably sebacic acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide and dihydrazides having a valine hydrantoin skeleton, and sebacic acid dihydrazide is particularly preferable.
• a monomer (or an oligomer) (g) may be used for controlling reactivity and viscosity. good.
• a (meth) acrylate monomer (g) is not particularly limited as long as it has low contamination to liquid crystals.
• pentaerythritol, dipentaerythritol or caprolactone-modified dipentaerythritol and (meth) ) A reaction product with acrylic acid and the like.
• a reaction product of pentaerythritol or dipentaerythritol and (meth) acrylic acid is preferable, and more specifically, pentaerythritol mono-tetraacrylate or dipentaerythritol mono-hexaacrylate can be mentioned. More preferred is pentaerythritol di-tetraacrylate or dipentaerythritol di-hexaacrylate, and most preferred is pentaerythritol di-tetraacrylate.
• the (meth) acrylate monomer (g) may be used alone or in combination of two or more in the liquid crystal sealant of the present invention.
• the content when the (meth) acrylate monomer (g) is used is preferably 1 to 30% by weight and more preferably 5 to 20% by weight with respect to the total amount of the liquid crystal sealant.
• the liquid crystal sealant of the present invention may further contain other additives such as organic fillers, pigments, coupling agents, leveling agents, and antifoaming agents.
• the amount of the other additive used is about 0 to 10% by weight based on the total amount of the liquid crystal sealant.
• the viscosity of the liquid crystal sealant of the present invention is not particularly limited, but is preferably 10 to 500 Pa ⁇ s (25 ° C.), more preferably 100 to 300 Pa ⁇ s (25 ° C.) from the viewpoint of dispensing properties.
• liquid-crystal sealing compound of this invention is illustrated below. “%” Indicates wt%, and “part” indicates part by weight.
• III The liquid crystal sealing agent according to the above (I) or (II), which contains bisphenol type epoxy (meth) acrylate or novolac type epoxy (meth) acrylate as the (meth) acrylated epoxy resin (b).
• (XII) The liquid crystal sealant according to any one of the above (I) to (XI), which further contains another inorganic filler (h).
• (XIII) The liquid crystal sealant according to the above (XII), wherein the other inorganic filler (h) has an average particle size of 0.1 to 1 ⁇ m.
• (XIV) The liquid crystal sealant according to (XII) or (XIII), wherein the inorganic filler (h) is fused spherical silica.
• Crystalline silica-free talc (a) is 1 to 40% with respect to the total amount of the liquid crystal sealant, and (meth) acrylated epoxy resin (b) is 30 to 90% with respect to the total amount of the liquid crystal sealant.
• the photopolymerization initiator (c) is contained in an amount of 0.01 to 20 parts with respect to 100 parts of the (meth) acrylated epoxy resin (b), and the balance is any of the above optional components (I) to (XIV) Liquid crystal sealing agent as described in any one of Claims.
• (XVI) The liquid crystal sealant according to the above (XV), wherein the content of talc (a) is 3 to 20% based on the total amount of the liquid crystal sealant.
• the liquid crystal sealant further contains an epoxy resin (e) and a thermosetting agent (f), the content of the epoxy resin (e) is 3 to 50% with respect to the total amount of the liquid crystal sealant,
• (XIX) Any of (XV) to (XVIII) above, wherein the liquid crystal sealant further contains a (meth) acrylate monomer (g), and the content thereof is 1 to 30% with respect to the total amount of the liquid crystal sealant Liquid crystal sealing agent as described in any one of Claims.
• (XX) 1 to 30% of a reaction product of pentaerythritol, dipentaerythritol or caprolactone-modified dipentaerythritol and (meth) acrylic acid as a (meth) acrylate monomer (g) with respect to the total amount of the liquid crystal sealant
• the liquid crystal sealant contains another inorganic filler (h), and the total amount of inorganic filler including talc (a) is 5 to 40% with respect to the total amount of liquid crystal sealant (XV ) To (XXI).
• the liquid crystal sealant of the present invention comprises a resin component ((meth) acrylated epoxy resin (b), if necessary, epoxy resin (e) and (meth) acrylate monomer (g)) and photopolymerization initiator (c).
• a resin component ((meth) acrylated epoxy resin (b), if necessary, epoxy resin (e) and (meth) acrylate monomer (g)) and photopolymerization initiator (c).
• an inorganic filler (filler component) talc (a) and, if necessary, an inorganic filler (h)
• a thermosetting agent f
• It can be produced by uniformly mixing with a known mixing apparatus, for example, a three roll, sand mill, ball mill, planetary mixer or the like. After mixing, it is preferable to perform a filtration treatment in order to remove impurities from the obtained liquid crystal sealant.
• a pair of substrates on which predetermined electrodes are formed are arranged so as to face each other with a predetermined gap, and the periphery of the substrates is sealed with the liquid crystal sealant of the present invention, It is produced by encapsulating liquid crystal in
• the kind of the liquid crystal sealed in the liquid crystal display cell of the present invention is not particularly limited. Any substrate can be used as the substrate used in the liquid crystal display cell of the present invention as long as it can be used as the substrate of the liquid crystal display cell. For example, a commonly used substrate made of glass, quartz, plastic, silicon, or the like is used. be able to. At least one of the pair of substrates used in the liquid crystal display cell of the present invention is a substrate having optical transparency.
• the liquid crystal display cell of the present invention can be produced, for example, by the following production method. After adding a spacer (gap control material) such as glass fiber to the liquid crystal sealant of the present invention, the liquid crystal sealant is applied to one of the pair of substrates in a dam shape by a dispenser or the like. Thereafter, liquid crystal is dropped inside the weir made of the liquid crystal sealant, and the other glass substrate is overlaid in a vacuum to form a gap. After the gap is formed, the liquid crystal sealant is photocured by irradiating the liquid crystal seal part with ultraviolet rays by an ultraviolet irradiator.
• a spacer space control material
• the liquid crystal sealant is applied to one of the pair of substrates in a dam shape by a dispenser or the like. Thereafter, liquid crystal is dropped inside the weir made of the liquid crystal sealant, and the other glass substrate is overlaid in a vacuum to form a gap. After the gap is formed, the liquid crystal sealant is photocured by irradiating
• the amount of ultraviolet irradiation at this time is an integrated light quantity, and is usually 200 mJ / cm 2 to 6000 mJ / cm 2 , preferably 500 mJ / cm 2 to 4000 mJ / cm 2 .
• the liquid crystal sealing agent is thermally cured at 90 to 140 ° C. for 1 to 2 hours, whereby the liquid crystal display cell of the present invention can be obtained.
• the spacer used for manufacturing the liquid crystal display cell of the present invention include glass fiber, silica beads, polymer beads and the like.
• the diameter varies depending on the purpose of the liquid crystal display cell, but is usually 2 to 8 ⁇ m, preferably 4 to 7 ⁇ m.
• the amount used is usually about 0.1 to 4 parts by weight, preferably about 0.5 to 2 parts by weight with respect to 100 parts by weight of the liquid crystal sealant of the present invention.
• the present invention will be described in more detail with reference to examples.
• the present invention is not limited to the following examples.
• the viscosity of the liquid crystal sealing agent of an Example and a comparative example was measured with the R-type viscosity meter (made by Toki Sangyo Co., Ltd.).
• Example 1 As the (meth) acrylated epoxy resin (b), 58.4 parts by weight of KAYARAD RTM R-93100 (manufactured by Nippon Kayaku Co., Ltd., epoxy acrylate obtained by reaction of bisphenol A type epoxy resin and acrylic acid), ) 10.0 parts by weight of KAYARAD RTM PET-30 (Nippon Kayaku Co., Ltd., pentaerythritol triacrylate) as the acrylate monomer (g), YD-8125 (Toto Kasei Co., Ltd .: epoxy equivalent) as the epoxy resin (e) 175 g / eq, bisphenol A type epoxy resin) 5.5 parts by weight, 3.7 parts by weight of Irgacure RTM 2959 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator (c) is heated and dissolved at 90 ° C.
• KAYARAD RTM R-93100 manufactured by Nippon Kayaku Co., Ltd., epoxy
• a resin composition was obtained. After the obtained resin composition was cooled to room temperature, SDH (trade name, manufactured by Nippon Finechem Co., Ltd .: pulverized sebacic acid dihydrazide with a jet mill) as a thermosetting agent (f) 1 .8 parts by weight, 9.6 parts by weight of SO-C2 (manufactured by Admatechs, fused spherical silica, average particle size 0.5 ⁇ m) as other inorganic filler (h), NANO ACE RTM D as talc (a) -11.0 parts by weight of 600FC3BM43 (trade name: manufactured by Nippon Talc Co., Ltd.) was added.
• SDH trade name, manufactured by Nippon Finechem Co., Ltd .: pulverized sebacic acid dihydrazide with a jet mill
• f 1 .8 parts by weight
• SO-C2 manufactured by Admatechs, fused spherical silica, average particle size 0.5 ⁇ m
• the obtained resin composition was kneaded with three rolls to obtain the liquid crystal sealant of the present invention.
• the obtained liquid crystal sealant had a viscosity (25 ° C.) of 230 Pa ⁇ s.
• NANO ACE RTM D-600FC3BM43 used in this example was obtained by adding NANO ACE RTM D-600F (talc not containing crystalline silica) (trade name: manufactured by Nippon Talc Co., Ltd.) to 3% by weight with respect to talc.
• a silane coupling agent-treated talc having an average particle size of 0.6 ⁇ m obtained by surface treatment with 3-glycidoxypropyltrimethoxysilane.
• Example 2 The liquid crystal sealant of the present invention was obtained in exactly the same manner as in Example 1 except that NANO ACE RTM D-600FC3BM63 was used instead of talc (a) NANO ACE RTM D-600FC3BM43 added in Example 1. .
• the obtained liquid crystal sealant had a viscosity (25 ° C.) of 230 Pa ⁇ s.
• NANO ACE RTM D-600FC3BM63 used in this example is NANO ACE RTM D-600F (manufactured by Nippon Talc Co., Ltd.) (talc that does not contain crystalline silica).
• a silane coupling agent-treated talc having an average particle size of 0.6 ⁇ m obtained by surface treatment with (2-aminoethyl) 3-aminopropyltrimethoxysilane.
• Example 3 In place of talc (a) NANO ACE RTM D-600FC3BM43 used in Example 1, NANO ACE RTM D-600F (trade name, manufactured by Nippon Talc Co., Ltd .; untreated silane coupling agent, average particle size 0.6 ⁇ m, A liquid crystal sealant of the present invention was obtained in the same manner as in Example 1 except that no crystalline silica was used. The obtained liquid crystal sealant had a viscosity (25 ° C.) of 250 Pa ⁇ s.
• the sealing agent was applied so that the application cross-sectional area was 3800 to 4200 ⁇ m 2 .
• a glass substrate having no slit pattern was superimposed on a glass substrate coated with a sealing agent to form a gap.
• an ultraviolet ray irradiator was used to irradiate the seal portion with ultraviolet rays having an integrated light amount of 3000 mJ / cm 2 to photocur the sealant.
• the obtained cell was observed with a microscope, and the number of slit patterns in which the aluminum slits were cut was confirmed.
• Example 1 has 0 breaks
• Example 2 has 1 breaks
• Example 3 has 0 breaks
• Comparative 1 has 7 breaks
• Comparative 2 has The number of disconnections was 12, and the one of Comparative Example 3 had 13 disconnections.
• the disconnection of the aluminum wiring was determined together with the comparative example according to the following criteria, and the results are shown in Table 1. ⁇ (1 or less) ⁇ (2-4) ⁇ (5 or more)
• the shear adhesive strength of the glass piece was measured at 10 mm / sec using a bond tester SS-30WD (manufactured by Seishin Enterprise Co., Ltd.).
• Comparative Example 2 shear The adhesive strength was 43 MPa
• the shear adhesive strength of the comparative example 3 was 62 MPa. From the measured values, the adhesive strength of each liquid crystal sealant was determined according to the following criteria, and was determined together with the comparative example. The results are shown in Table 1. ⁇ (60 MPa or more) ⁇ (59 MPa to 40 MPa) ⁇ (39 MPa or less)
• the sealing agent of the present invention has excellent adhesive strength to the glass substrate and eliminates disconnection of the substrate wiring. Moreover, it was excellent also in liquid-crystal contamination, an adhesive agent, and moisture-proof adhesive strength, and the characteristic as a liquid-crystal sealing agent was excellent. Furthermore, the liquid crystal sealant of Example 1 using talc surface-treated with a silane coupling agent having an epoxy group as talc (a) was particularly excellent in moisture-resistant adhesive strength.

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• 2011
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