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
• • 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 
  • G02F1/0102—Constructional details, not otherwise provided for in this subclass
  • G02F1/0107—Gaskets, spacers or sealing of cells; Filling and closing of cells
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • 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
  • 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 having sufficient photocurability with visible light of 400 nm or more and excellent in low liquid crystal contamination, and a liquid crystal display cell using the same.
• liquid crystal display cells have been applied to large display screens such as televisions, and demand for them is increasing. For this reason, a liquid crystal dropping method is the mainstream in place of the liquid crystal injection method in order to further increase the mass productivity in manufacturing the liquid crystal panel (see Patent Document 1).
• liquid crystal dropping method first, a seal pattern made of a rectangular uncured sealant is formed on one of two transparent substrates with electrodes by dispensing. Next, with the sealant in an uncured state, liquid crystal microdrops are dropped onto the entire surface of the transparent substrate seal pattern, and the other transparent substrate is immediately bonded to produce a liquid crystal cell. Temporary curing is performed by irradiating with ultraviolet rays. Thereafter, heating is performed as necessary to perform main curing, and a liquid crystal display cell is manufactured.
• the ultraviolet rays irradiated to cure the sealing agent are also irradiated to the liquid crystal in a considerable amount. Accordingly, there has been a problem that the liquid crystal is deteriorated by ultraviolet rays having a short wavelength and high energy, the display quality of the liquid crystal display element is remarkably lowered, and the reliability is lowered.
• the present invention makes it possible to use visible light having a low energy of 400 nm or more, instead of using ultraviolet light having a short wavelength, in the production of a liquid crystal display element by a liquid crystal dropping method.
• An object of the present invention is to provide a liquid crystal sealing agent that has sufficient photocurability with visible light of 400 nm or more and that is excellent in low liquid crystal contamination.
• the present invention relates to a liquid crystal sealant and a liquid crystal display cell using the same, and more specifically, a liquid crystal sealant having sufficient photocurability with visible light of 400 nm or more and excellent in low liquid crystal contamination, and the same. It aims at proposing the used liquid crystal display cell.
• the present inventors have found that the photoinitiator having a carbazole skeleton has a low liquid crystal contamination property, and further, by using a hydrogen abstraction type photosensitizer in combination, the curability is improved, and the photoinitiator is 400 nm or more.
• the present invention was completed by finding that it has sufficient photocurability by visible light.
• the present invention relates to the following (1) to (6).
• a visible light curing comprising (a) a photoinitiator having a carbazole skeleton, (b) a hydrogen abstraction type photosensitizer and (c) a (meth) acrylated epoxy resin as a curable resin Liquid crystal sealant.
• liquid crystal sealing agent according to any one of (1) to (3), further comprising (d) an epoxy resin and (e) a thermosetting agent.
• liquid crystal sealant according to any one of (1) to (4), which has sufficient photocurability with visible light of 400 nm or more.
• the present invention makes it possible to use visible light having a low energy of 400 nm or more in the production of a liquid crystal display device by a liquid crystal dropping method, to reduce the contamination and deterioration of the liquid crystal, and to produce a highly reliable liquid crystal display device. can do.
• the liquid crystal sealing material used in the present invention contains (a) a photoinitiator having a carbazole skeleton (the following general formula (1)).
• An initiator having this skeleton can generate radicals by light absorption, and can also generate radicals efficiently by energy from other photosensitizers. Moreover, since it has a nitrogen atom in the molecule, it has an effect on oxygen inhibition, which is generally a problem in radical curing, and curing can proceed efficiently. Furthermore, an initiator having a carbazole skeleton has low liquid crystal contamination, and dissolution of the initiator itself in the liquid crystal can be suppressed to a low level.
• R represents an alkyl group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a (meth) acryl group, or a phenyl group.
• the alkyl group having 1 to 20 carbon atoms as R may be linear or branched, and includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group. N-butyl group, t-butyl group and the like.
• the alkoxy group having 1 to 20 carbon atoms may be linear or branched, and includes, for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, t -Represents a butoxy group or the like.
• the initiator (a) includes N-1414 (carbazole skeleton-containing photoinitiator; 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole; Asahi Denka Kogyo Co., Ltd.
• the component (a) preferably has an oxime ester skeleton in the molecule. Since the oxime ester skeleton is highly sensitive to light and supplements the photoreaction of the sealant, the amount added can be reduced. Specifically, N-1919 and Irgacure OXE02 described above are preferable.
• the content of the photoinitiator in the liquid crystal sealant is preferably within a range of 0.01 to 3% by mass, and more preferably about 0.1 to 0.5% by mass. is there. If the amount is less than 0.01% by mass, sufficient curing performance cannot be obtained and the liquid crystal is contaminated. If the amount is more than 3% by mass, the liquid crystal contamination of the initiator itself becomes a problem.
• the liquid crystal sealant used in the present invention contains (b) a hydrogen abstraction type photosensitizer as an essential component.
• the liquid crystal sealant that absorbs visible light of 400 nm or more is not possible with the above-mentioned (a) carbazole skeleton photoinitiator alone. That is, in the present invention, (a) a carbazole skeleton photoinitiator and (b) a hydrogen abstraction type photosensitizer are used together for the first time in visible light of 400 nm or more, usually in the range of 400 to 600 nm. An absorbing liquid crystal sealant is possible. Therefore, the component (b) is essential for realizing sufficient visible light curability. This hydrogen abstraction type photosensitizer does not have sufficient visible light curability when used alone. Therefore, (a) This invention is implement
• component (b) examples include benzophenone, acridone, 2-ethylanthraquinone, 2-chlorothioxanthone, 2-isopropylanthraquinone, 2,4-diethylthioxanthone, and 2,4-diethylthioxanthone is particularly preferable. It is.
• the content of the photosensitizer in the liquid crystal sealant is preferably in the range of 0.01 to 3% by mass, more preferably about 0.1 to 0.5% by mass. is there.
• the present invention contains a (meth) acrylated epoxy resin as the curable resin component (c).
• (meth) acryl means “acryl” and / or “methacryl”. The same shall apply hereinafter.
• (Meth) acryloylated epoxy resin can be obtained by a known method by reaction of epoxy resin and (meth) acrylic acid.
• An epoxy resin more than bifunctional is preferable, 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, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin , Isocyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenolmethane skeleton, and other difunctional phenolic diglycidyl esters such as catechol and resorcinol Ether compound, bi-functional alcohol diglycidyl ethers of, and their halides, and
• resorcin diglycidyl ether is more preferred from the viewpoint of liquid crystal contamination.
• the ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination.
• the content of (c) (meth) acrylated epoxy resin in the liquid crystal sealant is preferably in the range of 30 to 80% by mass, and more preferably about 40 to 70% by mass.
• an epoxy resin can be used to improve the adhesive strength.
• the epoxy resin (d) that can be used is not particularly limited, but is preferably a bifunctional or higher epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac.
• bisphenol type epoxy resin and novolac type epoxy resin are preferable from the viewpoint of liquid crystal contamination.
• the content of the (d) epoxy resin in the liquid crystal sealant is preferably about 5 to 50% by mass.
• thermosetting agent as component (e) that can be used in the liquid crystal sealant of the present invention is not particularly limited, and solid organic acid hydrazide is preferably used.
• the aromatic hydrazide salicylic acid hydrazide, benzoic acid hydrazide, 1-naphthoic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzene Examples include trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide, and the like.
• Examples of the aliphatic hydrazide compound include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, 1,4- Cyclohexane dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis (hydrazinocarbono Examples thereof include dihydrazides having a valine hydantoin skeleton such as ethyl) -5-isopropy
• a dihydrazide is a two-functional, particularly preferably can be exemplified isophthalic acid dihydrazide.
• the amount used is 0.5 to 2.0 equivalents, preferably 0 when the epoxy equivalent of the epoxy group of the epoxy resin of component (d) is 1. .8 to 1.2 equivalents.
• an inorganic filler and a coupling agent may be blended for the purpose of improving the adhesive strength and improving the moisture resistance reliability. Further, if necessary, an organic filler and a pigment, a leveling agent, Additives such as antifoaming agents and organic solvents can be blended.
• the component (d) is first dissolved and mixed in the component (c) as necessary, and then the component (a) and the component (b) are dissolved in this mixture.
• a predetermined amount such as a ring agent, an inorganic filler, an organic filler, an antifoaming agent, and a leveling agent is added, and the component (e) is mixed as necessary, and a known mixing device such as a three-roll, sand mill, It is obtained by uniformly mixing with a ball mill or the like and filtering with a metal mesh.
• the liquid crystal display cell of the present invention is a cell in which a pair of substrates having predetermined electrodes formed on a substrate are arranged opposite to each other at a predetermined interval, the periphery is sealed with the liquid crystal sealant of the present invention, and liquid crystal is sealed in the gap. is there.
• the kind of liquid crystal to be sealed is not particularly limited.
• the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties.
• a spacer such as glass fiber
• a dispenser or a screen printing device is used on one of the pair of substrates.
• the liquid crystal display cell of the present invention can be obtained by curing at 90 to 130 ° C. for 1 to 2 hours.
• the liquid crystal display cell of the present invention thus obtained has no display defects due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability.
• the spacer include glass fiber, silica beads, polymer beads and the like.
• the diameter varies depending on the purpose, but is usually 2 to 8 ⁇ m, preferably 4 to 7 ⁇ m.
• the amount used is usually 0.1 to 4 parts by weight, preferably 0.5 to 2 parts by weight, more preferably about 0.9 to 1.5 parts by weight, based on 100 parts by weight of the liquid crystal sealant of the present invention. is there.
• Parts in the table means parts by weight.
• the specific resistance value “3.00E + 12” represents “3.00 ⁇ 10 12 ”, and the same description in Table 1 also has the same meaning.
• RGEAC reaction product of resorcin diglycidyl ether and acrylic acid
• R-93100 Bisphenol A type epoxy acrylate (reaction product of Epicoat 828 (Japan Epoxy Resin Co., Ltd.) and acrylic acid)
• YD-8125 Bis phenol A type epoxy resin (product of Toto Kasei Co., Ltd.)
• Irgacure OXE02 carbazole oxime ester skeleton-containing photoinitiator (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Ciba Specialty Chemicals Co., Ltd.)
• N-1414 carbazole skeleton-containing photoinitiator (3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole; manufactured by Asahi Denka Kogyo Co., Ltd.)
• a photoinitiator having a carbazole skeleton (b) a hydrogen abstraction type photosensitizer and (c) (meth) acrylated epoxy of Examples 1 to 3 according to the present invention.
• the visible light curable liquid crystal sealing agent characterized by containing a resin as a curable resin has sufficient curability with visible light of 400 nm or more, and it is difficult to cause display unevenness of the panel. Further, the results of the panel display unevenness test of Examples 1 and 3 are particularly good, and it is shown that the carbazole skeleton and the oxime ester skeleton coexist in one molecule as the photoinitiator of (a). . Furthermore, by using resorcin diglycidyl ether as the acrylated epoxy resin of (c), it is possible to suppress a decrease in specific resistance value.

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• Physics & Mathematics (AREA)
• Nonlinear Science (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Mathematical Physics (AREA)
• Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Sealing Material Composition (AREA)
• Liquid Crystal (AREA)
• Epoxy Resins (AREA)

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• 2009
  • 2009-06-11 JP JP2009140052A patent/JP5152868B2/ja active Active
• 2010
  • 2010-06-02 KR KR1020117030570A patent/KR101634981B1/ko active IP Right Grant
  • 2010-06-02 CN CN201080025697.8A patent/CN102804045B/zh not_active Expired - Fee Related
  • 2010-06-02 WO PCT/JP2010/059335 patent/WO2010143569A1/ja active Application Filing
  • 2010-06-10 TW TW099118926A patent/TWI464188B/zh not_active IP Right Cessation

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