WO2010143569A1 - Visible light-curable liquid crystal sealing material and liquid crystal display cell using same - Google Patents

Visible light-curable liquid crystal sealing material and liquid crystal display cell using same Download PDF

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Publication number
WO2010143569A1
WO2010143569A1 PCT/JP2010/059335 JP2010059335W WO2010143569A1 WO 2010143569 A1 WO2010143569 A1 WO 2010143569A1 JP 2010059335 W JP2010059335 W JP 2010059335W WO 2010143569 A1 WO2010143569 A1 WO 2010143569A1
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WO
WIPO (PCT)
Prior art keywords
liquid crystal
epoxy resin
visible light
sealing material
sealant
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PCT/JP2010/059335
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French (fr)
Japanese (ja)
Inventor
直之 落
早紀 吉田
務 並木
広明 三輪
英之 太田
昌博 木田
栄一 西原
貴公男 今澄
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日本化薬株式会社
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Priority to CN201080025697.8A priority Critical patent/CN102804045B/en
Publication of WO2010143569A1 publication Critical patent/WO2010143569A1/en

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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)

Abstract

Disclosed are a liquid crystal sealing material having excellent display quality and reliability, which is composed of a sealing material that is sufficiently photo-cured by visible light of 400 nm or longer, and a liquid crystal display cell using the liquid crystal sealing material. Specifically disclosed is a visible light-curable liquid crystal sealing material which is characterized by containing (a) a photoinitiator having a carbazole skeleton, (b) a hydrogen abstraction type photosensitizer and (c) a (meth)acrylated epoxy resin that serves as a curable resin. The visible light-curable liquid crystal sealing material may additionally contain (d) an epoxy resin and (e) a thermosetting agent.

Description

可視光硬化性液晶シール剤及びそれを用いた液晶表示セルVisible light curable liquid crystal sealant and liquid crystal display cell using the same
　本発明は、４００ｎｍ以上の可視光により充分な光硬化性を有し、かつ低液晶汚染性に優れる液晶シール剤及びそれを用いた液晶表示セルに関する。 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.
　近年の液晶表示セルはテレビなどの大型表示画面への応用展開もなされ、多用途で需要が伸びている。このため、液晶パネル製造に関して、より量産性を高めるため、液晶注入方式に代わり、液晶滴下方式が主流となっている（特許文献１参照）。 In recent years, 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).
　液晶滴下方式では、まず２枚の電極付き透明基盤の一方にディスペンスにより長方形の未硬化シール剤からなるシールパターンを形成する。ついで、シール剤が未硬化の状態で液晶の微小滴を透明基盤のシールパターンの枠内全面に滴下塗布し、すぐに他方の透明基盤を貼り合わせて、液晶セルを作製し、シールパターン部に紫外線を照射して仮硬化を行う。その後、必要に応じて加熱して本硬化を行い、液晶表示セルを作製する。 In the 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.
　この液晶滴下方式では未硬化のシール剤と液晶が直接接触する為、シール剤の硬化が遅い場合には液晶にシール剤成分が溶出し、液晶を汚染する。従って、液晶滴下方式では紫外線によるシール速硬化が必須工程である。 In this liquid crystal dropping method, since the uncured sealant and the liquid crystal are in direct contact, the sealant component is eluted into the liquid crystal and contaminates the liquid crystal when the curing of the sealant is slow. Therefore, in the liquid crystal dropping method, the rapid sealing with ultraviolet rays is an essential process.
　しかしながら、液晶滴下方式による液晶表示素子の製造ではシール剤を硬化する為に照射される紫外線が液晶にも少なからず照射される。したがって、波長が短く高エネルギーの紫外線により液晶の劣化が発生し、液晶表示素子の表示品位を著しく低下させ、信頼性を低下させるという問題があった。 However, in the production of the liquid crystal display element by the liquid crystal dropping method, 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.
　この問題に対し、様々な検討がなされており、紫外線に対し高感度であるシール剤の提案がなされている（特許文献２、特許文献３参照）。しかしこれら発明においても、照射される紫外線のエネルギーは高く、液晶の劣化対策としては充分でない。 Various studies have been made on this problem, and a sealant having high sensitivity to ultraviolet rays has been proposed (see Patent Document 2 and Patent Document 3). However, even in these inventions, the energy of the irradiated ultraviolet rays is high, and it is not sufficient as a countermeasure against deterioration of the liquid crystal.
　本発明は、上記現状に鑑み、液晶滴下方式による液晶表示素子の製造において、短波長の紫外線を使用するのではなく、４００ｎｍ以上の低エネルギーである可視光を使用する事を可能とする為に、４００ｎｍ以上の可視光により充分な光硬化性を有し、かつ低液晶汚染性に優れる液晶シール剤を提供する事を目的とする。 In view of the above-mentioned present situation, 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.
特開２００１－１３３７９４号公報JP 2001-133794 A 特開２００７－３９１１号公報JP 2007-3911 A 特開２００８－１７９７９７号公報JP 2008-179797 A
　本発明は、液晶シール剤及びそれを用いた液晶表示セルに関するものであり、詳しくは４００ｎｍ以上の可視光により充分な光硬化性を有し、かつ低液晶汚染性に優れる液晶シール剤及びそれを用いた液晶表示セルを提案することを目的とする。 TECHNICAL FIELD 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.
　本発明者らは、鋭意検討の結果、カルバゾール骨格を有する光開始剤の液晶汚染性が低い事、更に水素引き抜き型の光増感剤を併用することで、硬化性が向上し、４００ｎｍ以上の可視光により充分な光硬化性を有する事を見出し、本発明を完成させた。 As a result of intensive studies, 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.
　即ち本発明は、次の（１）～（６）に関するものである。 That is, the present invention relates to the following (1) to (6).
（１）（ａ）カルバゾール骨格を有する光開始剤、（ｂ）水素引き抜き型光増感剤及び（ｃ）（メタ）アクリル化エポキシ樹脂を硬化性樹脂として含有することを特徴とする可視光硬化性液晶シール剤。 (1) 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.
（２）（ａ）カルバゾール骨格を有する光開始剤がその分子中にオキシムエステル骨格を併存する開始剤である（１）に記載の液晶シール剤。 (2) The liquid crystal sealant according to (1), wherein (a) the photoinitiator having a carbazole skeleton is an initiator having an oxime ester skeleton in its molecule.
（３）（ｃ）（メタ）アクリル化エポキシ樹脂がレゾルシンジグリシジルエーテルの（メタ）アクリル化エポキシ樹脂である（１）又は（２）に記載の液晶シール剤。 (3) The liquid crystal sealing agent according to (1) or (2), wherein (c) (meth) acrylated epoxy resin is a (meth) acrylated epoxy resin of resorcin diglycidyl ether.
（４）更に（ｄ）エポキシ樹脂及び（ｅ）熱硬化剤を含有する（１）乃至（３）の何れか一項に記載の液晶シール剤。 (4) The liquid crystal sealing agent according to any one of (1) to (3), further comprising (d) an epoxy resin and (e) a thermosetting agent.
（５）４００ｎｍ以上の可視光により充分な光硬化性を有する（１）乃至（４）の何れか一項に記載の液晶シール剤。 (5) The liquid crystal sealant according to any one of (1) to (4), which has sufficient photocurability with visible light of 400 nm or more.
（６）前記（１）乃至（５）の何れか一項に記載の液晶シール剤を硬化して得られる硬化物でシールされた液晶表示セル。 (6) A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent according to any one of (1) to (5).
　本発明により、液晶滴下方式による液晶表示素子の製造において、４００ｎｍ以上の低エネルギーである可視光を使用する事を可能とし、液晶の汚染および劣化を低減し、高信頼性の液晶表示素子を作成することができる。 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.
　以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明で用いられる液晶シール材は、（ａ）カルバゾール骨格（下記一般式（１））を有する光開始剤を含有する。この骨格を有する開始剤は光吸収によりラジカルを発生でき、また他の光増感剤からのエネルギーによっても効率的にラジカルを発生できる。また、分子中に窒素原子を有する為、一般的にラジカル硬化で問題とされる酸素阻害に対しても効果を有し、効率的に硬化を進行させられる。更には、カルバゾール骨格を有する開始剤は、液晶汚染性が低く、開始剤自体の液晶への溶解も低く抑えられる。 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.
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒは炭素原子数１～２０のアルキル基、水素原子、水酸基、炭素原子数１～２０のアルコキシル基、（メタ）アクリル基、又はフェニル基を表す。）
Figure JPOXMLDOC01-appb-C000001
 (Wherein 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.)
　式（１）において、Ｒとしての炭素原子数１～２０のアルキル基とは、直鎖でも分岐してもよいものであって、例えばメチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｔ－ブチル基等を示す。また、炭素原子数１～２０のアルコキシル基とは直鎖でも分岐してもよいものであって、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｔ－ブトキシ基等を示す。 In the formula (1), 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.
　具体的に、この（ａ）開始剤としては、Ｎ－１４１４（カルバゾール骨格含有光開始剤；３，６－ビス（２－メチル－２－モルホリノプロピオニル）－９－ｎ－オクチルカルバゾール；旭電化工業（株）社製）、Ｎ－１９１９（カルバゾール・オキシムエステル骨格含有光開始剤；アデカ（登録商標）オプトマーＮ－１９１９；旭電化工業（株）社製）、イルガキュアＯＸＥ０２（カルバゾール・オキシムエステル骨格含有光開始剤（エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）；チバ・スペシャリティーケミカルズ（株）社製）等が挙げられる。 Specifically, 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. N-1919 (carbazole oxime ester skeleton-containing photoinitiator; Adeka (registered trademark) Optomer N-1919; manufactured by Asahi Denka Kogyo KK), 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. Manufactured) and the like.
　また、反応性の観点から（ａ）成分は、その分子中にオキシムエステル骨格を併存するものである事が好ましい。オキシムエステル骨格は光に対し高感度であり、シール剤の光反応を補足する為、添加量も少なく抑えられる。具体的には、前記した、Ｎ－１９１９、イルガキュアＯＸＥ０２が好適である。 Further, from the viewpoint of reactivity, 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.
　また、（ａ）光開始剤の液晶シール剤中に占める含有率としては、０．０１～３質量％の範囲内である事が好ましく、更に好ましくは０．１～０．５質量％程度である。０．０１質量％より少ないと、充分な硬化性能が得られず液晶の汚染を発生し、また、３質量％より多いと開始剤自体の液晶汚染性が問題となる。 Further, (a) 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.
　本発明で用いられる液晶シール剤は、（ｂ）水素引き抜き型光増感剤を必須成分として含有する。前記した（ａ）カルバゾール骨格光開始剤だけでは４００ｎｍ以上の可視光で吸収する液晶シール剤は可能とならない。即ち、本発明においては、（ａ）カルバゾール骨格光開始剤と（ｂ）水素引き抜き型光増感剤を併用することで、初めて４００ｎｍ以上の可視光、通常は４００～６００ｎｍの範囲の可視光で吸収する液晶シール剤が可能となる。従って、充分な可視光硬化性を実現する為（ｂ）成分が必須となる。この水素引き抜き型光増感剤は、単独で使用した場合には充分な可視光硬化性を有さない。従って、（ａ）
成分および（ｂ）成分との併用によってのみ、本発明は実現される。 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 | achieved only by combined use with a component and (b) component.
　上記（ｂ）成分の具体例としては、ベンゾフェノン、アクリドン、２－エチルアントラキノン、２－クロロチオキサントン、２－イソプロピルアントラキノン、２，４－ジエチルチオキサントン等が挙げられ、特に２，４－ジエチルチオキサントンが好適である。 Specific examples of the component (b) include benzophenone, acridone, 2-ethylanthraquinone, 2-chlorothioxanthone, 2-isopropylanthraquinone, 2,4-diethylthioxanthone, and 2,4-diethylthioxanthone is particularly preferable. It is.
　また、（ｂ）光増感剤の液晶シール剤に占める含有率としては、０．０１～３質量％の範囲内である事が好ましく、更に好ましくは０．１～０．５質量％程度である。 Further, (b) 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.
　本発明は硬化性樹脂成分（ｃ）として、（メタ）アクリル化エポキシ樹脂を含有する。（ここで「（メタ）アクリル」とは「アクリル」及び／又は「メタクリル」を意味する。以下同様。） The present invention contains a (meth) acrylated epoxy resin as the curable resin component (c). (Here, “(meth) acryl” means “acryl” and / or “methacryl”. The same shall apply hereinafter.)
　（メタ）アクリロイル化エポキシ樹脂は、エポキシ樹脂と（メタ）アクリル酸の反応により公知の方法で得られる。原料となるエポキシ樹脂としては、特に限定されるものではないが、２官能以上のエポキシ樹脂が好ましく、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、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、トリフェノールメタン骨格を有するフェノールノボラック型エポキシ樹脂、その他、カテコール、レゾルシノール等の二官能フェノール類のジグリシジルエーテル化物、二官能アルコール類のジグリシジルエーテル化物、およびそれらのハロゲン化物、水素添加物などが挙げられる。これらのうち液晶汚染性の観点から、より好ましいものはレゾルシンジグリシジルエーテルである。また、エポキシ基と（メタ）アクリロイル基との比率は限定されるものではなく、工程適合性及び液晶汚染性の観点から適切に選択される。 (Meth) acryloylated epoxy resin can be obtained by a known method by reaction of epoxy resin and (meth) acrylic acid. Although it does not specifically limit as an epoxy resin used as a raw material, 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 the like hydrogenated product. Of these, resorcin diglycidyl ether is more preferred from the viewpoint of liquid crystal contamination. Further, 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.
　また、（ｃ）（メタ）アクリル化エポキシ樹脂の液晶シール剤中に占める含有率としては、３０～８０質量％の範囲内である事が好ましく、更に好ましくは４０～７０質量％程度である。 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.
　本発明の液晶シール剤では（ｄ）エポキシ樹脂を用い、接着強度向上を図る事ができる。用いられうるエポキシ樹脂（ｄ）としては、特に限定されるものではないが、２官能以上のエポキシ樹脂が好ましく、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、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、トリフェノールメタン骨格を有するフェノールノボラック型エポキシ樹脂、その他、二官能フェノール類のジグリシジルエーテル化物、二官能アルコール類のジグリシジルエーテル化物、およびそれらのハロゲン化物、水素添加物などがある。これらのうち液晶汚染性の観点より好ましいのはビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂である。 In the liquid crystal sealant of the present invention, (d) 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. Epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, hydantoin Type epoxy resin, isocyanurate type epoxy resin, phenol novolac type epoxy resin having triphenolmethane skeleton, other diglycidyl ethers of bifunctional phenols, bifunctional al Diglycidyl ethers of Lumpur acids, and their halides, and the like hydrogenated product. Among these, bisphenol type epoxy resin and novolac type epoxy resin are preferable from the viewpoint of liquid crystal contamination.
　かかる（ｄ）エポキシ樹脂の液晶シール剤に占める含有量は、５～５０質量％程度であるのが好ましい。 The content of the (d) epoxy resin in the liquid crystal sealant is preferably about 5 to 50% by mass.
　本発明の液晶シール剤で用いられ得る（ｅ）成分である熱硬化剤は特に限定されるものではなく、固形の有機酸ヒドラジドが好適に用いられる。例えば、芳香族ヒドラジドであるサリチル酸ヒドラジド、安息香酸ヒドラジド、１－ナフトエ酸ヒドラジド、テレフタル酸ジヒドラジド、イソフタル酸ジヒドラジド、２，６－ナフトエ酸ジヒドラジド、２，６－ピリジンジヒドラジド、１，２，４－ベンゼントリヒドラジド、１，４，５，８－ナフトエ酸テトラヒドラジド、ピロメリット酸テトラヒドラジド等をあげることが出来る。また、脂肪族ヒドラジド化合物であれば、例えば、ホルムヒドラジド、アセトヒドラジド、プロピオン酸ヒドラジド、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、ピメリン酸ジヒドラジド、１，４－シクロヘキサンジヒドラジド、酒石酸ジヒドラジド、リンゴ酸ジヒドラジド、イミノジ酢酸ジヒドラジド、Ｎ，Ｎ’－ヘキサメチレンビスセミカルバジド、クエン酸トリヒドラジド、ニトリロ酢酸トリヒドラジド、シクロヘキサントリカルボン酸トリヒドラジド、１，３－ビス（ヒドラジノカルボノエチル）－５－イソプロピルヒダントイン等のバリンヒダントイン骨格を有するジヒドラジド類等をあげることができるが、硬化反応性と潜在性のバランスから好ましくは２官能であるジヒドラジドであり、特に好ましくはイソフタル酸ジヒドラジドを挙げる事が出来る。かかる（ｅ）熱硬化剤を使用する場合の使用量としては、成分(ｄ)のエポキシ樹脂のエポキシ基のエポキシ当量を１とした場合、０．５～２．０当量であり、好ましくは０．８～１．２当量である。 The 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. For example, 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-isopropylhydantoin, which are preferable from the balance of curing reactivity and potential. Properly is a dihydrazide is a two-functional, particularly preferably can be exemplified isophthalic acid dihydrazide. When (e) the thermosetting agent is used, 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.
　本発明にかかる液晶シール剤には、接着強度向上及び耐湿信頼性向上を目的として無機充填剤、カップリング剤を配合しても良く、さらに必要に応じて、有機充填剤ならびに顔料、レベリング剤、消泡剤、有機溶剤などの添加剤を配合することができる。 In the liquid crystal sealing agent according to the present invention, 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.
　本発明の液晶シール剤は、まず成分（ｃ）に必要に応じ、成分（ｄ）を溶解混合し、次いでこの混合物に成分（ａ）及び成分（ｂ）を溶解し、更に必要に応じシランカップリング剤、無機充填剤、有機充填剤、消泡剤、及びレベリング剤等の所定量を添加し、必要に応じて成分（ｅ）を混合し、公知の混合装置、例えば３本ロール、サンドミル、ボールミル等により均一に混合し、金属メッシュにて濾過することにより得られる。 In the liquid crystal sealing agent of the present invention, 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.
　本発明の液晶表示セルは、基板に所定の電極を形成した一対の基板を所定の間隔に対向配置し、周囲を本発明の液晶シール剤でシールし、その間隙に液晶が封入されたものである。封入される液晶の種類は特に限定されない。ここで、基板とはガラス、石英、プラスチック、シリコン等からなる少なくとも一方に光透過性がある組み合わせの基板から構成される。その製法としては、例えば液晶滴下方式の場合、本発明の液晶シール剤に、グラスファイバー等のスペーサー（間隙制御材）を添加後、該一対の基板の一方にディスペンサー、またはスクリーン印刷装置等を用いて該液晶シール剤を塗布する。続いて該液晶シ
ール剤の堰の内側に液晶を滴下し、真空中にてもう一方のガラス基板を重ね合わせ、ギャップ出しを行う。ギャップ形成後、シール剤を光硬化させる。この時、紫外線カットフィルターを使用し、４００ｎｍ以下の光をカットする。照射量は、４０５ｎｍのセンサーを使用し、好ましくは５００ｍＪ／ｃｍ２～６０００ｍＪ／ｃｍ２、より好ましくは１０００ｍＪ／ｃｍ２～４０００ｍＪ／ｃｍ２の照射量が好ましい。その後、９０～１３０℃で１～２時間硬化することにより本発明の液晶表示セルを得ることができる。このようにして得られた本発明の液晶表示セルは、液晶汚染による表示不良が無く、接着性、耐湿信頼性に優れたものである。スペーサーとしては、例えばグラスファイバー、シリカビーズ、ポリマービーズ等があげられる。その直径は、目的に応じ異なるが、通常２～８μｍ、好ましくは４～７μｍである。その使用量は、本発明の液晶シール剤１００重量部に対し通常０．１～４重量部、好ましくは０．５～２重量部、更に、好ましくは０．９～１．５重量部程度である。 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. Here, 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. For example, in the case of the liquid crystal dropping method, after adding a spacer (gap control material) such as glass fiber to the liquid crystal sealing agent of the present invention, a dispenser or a screen printing device is used on one of the pair of substrates. Then apply the liquid crystal sealant. Subsequently, the liquid crystal is dropped inside the liquid crystal sealing agent weir, and the other glass substrate is overlaid in a vacuum to create a gap. After forming the gap, the sealant is photocured. At this time, an ultraviolet cut filter is used to cut light of 400 nm or less. The irradiation dose is 405 nm using a sensor, preferably 500 mJ / cm 2 to 6000 mJ / cm 2 , more preferably 1000 mJ / cm 2 to 4000 mJ / cm 2 . Thereafter, 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. Examples of 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 μm, preferably 4 to 7 μm. 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.
　以下実施例により本発明を更に詳細に説明する。表中の「部」は重量部を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” in the table means parts by weight.
実施例１～３、比較例１，２
（液晶滴下工法用のシール剤の調整）
　下記表１に示す割合で各樹脂成分を混合攪拌した後、光重合開始剤を加熱溶解させた。その後、充填剤等を３本ロールミルにて分散させたのち、金属メッシュで濾過し、液晶滴下工法用シール剤を調整した。 Examples 1 to 3, Comparative Examples 1 and 2
(Adjustment of sealant for liquid crystal dropping method)
Each resin component was mixed and stirred at the ratio shown in Table 1 below, and then the photopolymerization initiator was dissolved by heating. Then, after disperse | distributing a filler etc. with a 3 roll mill, it filtered with the metal mesh and adjusted the sealing compound for liquid crystal dropping methods.
（評価）
　作成した実施例１～３及び比較例１，２にかかるシール剤について以下の評価を行った。表１に結果を纏める。 (Evaluation)
The sealants according to Examples 1 to 3 and Comparative Examples 1 and 2 thus prepared were evaluated as follows. Table 1 summarizes the results.
（１）パネル表示ムラの評価
　実施例１～３及び比較例１，２のシール剤を用い、パネルを作成し、４００ｎｍ以下の光をカットするフィルターを使用し、紫外線照射装置により１０００ｍＪ／ｃｍ２の可視光照射をおこなった。その後１２０℃の熱オーブンで１時間硬化し、シール部周辺の液晶に生じる色むらを目視にて、下記基準により観察した。
◎（色ムラは全くなし）
○（コーナー部のみ色むら有り）
△（色むらの領域がシールから１ｍｍ未満）
×（色むらの領域がシールから１ｍｍ以上） (1) Evaluation of panel display unevenness Panels were prepared using the sealants of Examples 1 to 3 and Comparative Examples 1 and 2, and a filter that cuts off light of 400 nm or less was used, and 1000 mJ / cm 2 by an ultraviolet irradiation device. Was irradiated with visible light. Thereafter, it was cured in a 120 ° C. heat oven for 1 hour, and the color unevenness generated in the liquid crystal around the seal portion was visually observed according to the following criteria.
◎ (No color unevenness)
○ (There is uneven color only in the corner)
Δ (color unevenness area is less than 1mm from the seal)
× (Color uneven area is 1mm or more from the seal)
（２）シール剤の比抵抗測定
　サンプル瓶に実施例１～３及び比較例１，２のシール剤を０．１ｇ入れ、１０００ｍＪ／ｃｍ２の可視光を照射し、硬化した後液晶（メルク製、ＭＬＣ－６８６６－１００）１ｍｌを加え、１２０℃オーブンに１時間投入し、その後、０．５時間室温にて放置した。処理が終ったサンプル瓶から液晶のみを取り出し、液体電極ＬＥ２１（安藤電気製）に入れて、アドバンテスト製エレクトロメーターＲ－８３４０により測定電圧１０Ｖで４分後の液晶の比抵抗を測定して行った。下記基準により判定した。
◎（３．００Ｅ＋１２以上）
○（１．００Ｅ＋１２～２．９９Ｅ＋１２）
△（５．００Ｅ＋１１～９．９９Ｅ＋１１）
×（４．９９Ｅ＋１１以下） (2) Measurement of specific resistance of sealant 0.1 g of the sealant of Examples 1 to 3 and Comparative Examples 1 and 2 was put in a sample bottle, irradiated with 1000 mJ / cm 2 of visible light, cured, and then liquid crystal (Merck) , MLC-6866-100) 1 ml was added, and the mixture was placed in an oven at 120 ° C. for 1 hour, and then allowed to stand at room temperature for 0.5 hour. Only the liquid crystal was taken out from the sample bottle after the treatment, placed in the liquid electrode LE21 (manufactured by Ando Electric Co., Ltd.), and the specific resistance of the liquid crystal after 4 minutes was measured at a measurement voltage of 10 V with an Advantest electrometer R-8340. . Judgment was made according to the following criteria.
◎ (3.00E + 12 or more)
○ (1.00E + 12 to 2.99E + 12)
Δ (5.00E + 11 to 9.99E + 11)
× (4.99E + 11 or less)
　なお、比抵抗値の「３．００Ｅ＋１２」は「３．００ｘ１０１２」を表し、表１中における同様な記載も、同様な意味を表す。 The specific resistance value “3.00E + 12” represents “3.00 × 10 12 ”, and the same description in Table 1 also has the same meaning.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
ＲＧＥＡＣ：レゾルシンジグリシジルエーテルとアクリル酸の反応物
Ｒ－９３１００：ＢｉｓフェノールＡ型エポキシアクリレート
（エピコート８２８（ジャパンエポキシレジン株式会社製）とアクリル酸の反応物）
ＹＤ－８１２５：ＢｉｓフェノールＡ型エポキシ樹脂（東都化成（株）社品）
イルガキュアＯＸＥ０２：カルバゾール・オキシムエステル骨格含有光開始剤（エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）；チバ・スペシャリティーケミカルズ（株）社製）
Ｎ－１４１４：カルバゾール骨格含有光開始剤（３，６－ビス（２－メチル－２－モルホリノプロピオニル）－９－ｎ－オクチルカルバゾール；旭電化工業（株）社製）
ダロキュアＴＰＯ：光開始剤（２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド；チバ・スペシャリティーケミカルズ（株）社製）
ＤＥＴＸ：光増感剤（２，４－ジエチルチオキサントン；シーベルヘグナー（株）社製）
Ｓ－５１０：シランカップリング剤（チッソ（株）社製）
ＳＥＺ：シリカ（アドマテックス（株）社製） 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.)
Darocur TPO: Photoinitiator (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; manufactured by Ciba Specialty Chemicals)
DETX: Photosensitizer (2,4-diethylthioxanthone; manufactured by Sebel Hegner)
S-510: Silane coupling agent (manufactured by Chisso Corporation)
SEZ: Silica (manufactured by Admatechs)
　上記表１に示される結果により、本発明である実施例１乃至３の（ａ）カルバゾール骨格を有する光開始剤、（ｂ）水素引き抜き型光増感剤及び（ｃ）（メタ）アクリル化エポキシ樹脂を硬化性樹脂として含有することを特徴とする可視光硬化性液晶シール剤は、４００ｎｍ以上の可視光での硬化性が充分であり、パネルの表示ムラを起こし難い結果となった。また、実施例１及び３のパネル表示ムラ試験の結果が特に良好であり、（ａ）の光開始剤として、カルバゾール骨格とオキシムエステル骨格が一分子中に併存するものが好ましい事を示している。更に、（ｃ）のアクリル化エポキシ樹脂としてレゾルシンジグリシジルエーテルを使用する事で、比抵抗値の低下も抑える事が可能である。 According to the results shown in Table 1 above, (a) 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.

Claims (6)

  1. 　（ａ）カルバゾール骨格を有する光開始剤、
    　（ｂ）水素引き抜き型光増感剤、及び
    　（ｃ）（メタ）アクリル化エポキシ樹脂
    を硬化性樹脂として含有することを特徴とする可視光硬化性液晶シール剤。     (A) a photoinitiator having a carbazole skeleton,
    A visible light curable liquid crystal sealant comprising (b) a hydrogen abstraction type photosensitizer, and (c) a (meth) acrylated epoxy resin as a curable resin.
  2. 　（ａ）カルバゾール骨格を有する光開始剤がその分子中にオキシムエステル骨格を併存する開始剤である請求項１に記載の液晶シール剤。 The liquid crystal sealant according to claim 1, wherein (a) the photoinitiator having a carbazole skeleton is an initiator having an oxime ester skeleton in its molecule.
  3. 　（ｃ）（メタ）アクリル化エポキシ樹脂がレゾルシンジグリシジルエーテルの（メタ）アクリル化エポキシ樹脂である請求項１又は２に記載の液晶シール剤。 The liquid crystal sealant according to claim 1 or 2, wherein the (c) (meth) acrylated epoxy resin is a (meth) acrylated epoxy resin of resorcin diglycidyl ether.
  4. 　更に（ｄ）エポキシ樹脂及び（ｅ）熱硬化剤を含有する請求項１乃至請求項３の何れか一項に記載の液晶シール剤。 The liquid crystal sealing agent according to any one of claims 1 to 3, further comprising (d) an epoxy resin and (e) a thermosetting agent.
  5. 　４００ｎｍ以上の可視光により充分な光硬化性を有する請求項１乃至請求項４の何れか一項に記載の液晶シール剤。 The liquid crystal sealant according to any one of claims 1 to 4, which has sufficient photocurability with visible light of 400 nm or more.
  6. 　請求項１乃至請求項５の何れか一項に記載の液晶シール剤を硬化して得られる硬化物でシールされた液晶表示セル。 A liquid crystal display cell sealed with a cured product obtained by curing the liquid crystal sealing agent according to any one of claims 1 to 5.
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JP6031215B1 (en) * 2015-06-02 2016-11-24 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element
WO2016194871A1 (en) * 2015-06-02 2016-12-08 積水化学工業株式会社 Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element
CN107111194A (en) * 2015-06-02 2017-08-29 积水化学工业株式会社 Sealing material for liquid crystal display device, up and down conductive material and liquid crystal display cells
KR20180015106A (en) * 2015-06-02 2018-02-12 세키스이가가쿠 고교가부시키가이샤 Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element
CN107111194B (en) * 2015-06-02 2020-12-11 积水化学工业株式会社 Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element
KR102588717B1 (en) 2015-06-02 2023-10-12 세키스이가가쿠 고교가부시키가이샤 Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element

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KR20120028332A (en) 2012-03-22
CN102804045A (en) 2012-11-28
TW201113304A (en) 2011-04-16
TWI464188B (en) 2014-12-11
CN102804045B (en) 2015-04-22
KR101634981B1 (en) 2016-06-30
JP5152868B2 (en) 2013-02-27

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