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 PDFInfo
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- 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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- WIPO (PCT)
- Prior art keywords
- liquid crystal
- epoxy resin
- visible light
- sealing material
- sealant
- Prior art date
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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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- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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- Chemical & Material Sciences (AREA)
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Abstract
Description
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.
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.
(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.
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.
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)
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)
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)
Claims (6)
- (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. - (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.
- (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.
- 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.
- 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.
- 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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JP (1) | JP5152868B2 (en) |
KR (1) | KR101634981B1 (en) |
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CN106405946A (en) * | 2016-11-29 | 2017-02-15 | 深圳市华星光电技术有限公司 | Sealant curing method and liquid crystal panel manufacturing method |
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Also Published As
Publication number | Publication date |
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KR101634981B1 (en) | 2016-06-30 |
TW201113304A (en) | 2011-04-16 |
CN102804045A (en) | 2012-11-28 |
TWI464188B (en) | 2014-12-11 |
CN102804045B (en) | 2015-04-22 |
KR20120028332A (en) | 2012-03-22 |
JP5152868B2 (en) | 2013-02-27 |
JP2010286640A (en) | 2010-12-24 |
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