WO2018110552A1 - Polymerizable compound, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents
Polymerizable compound, sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element Download PDFInfo
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- WO2018110552A1 WO2018110552A1 PCT/JP2017/044574 JP2017044574W WO2018110552A1 WO 2018110552 A1 WO2018110552 A1 WO 2018110552A1 JP 2017044574 W JP2017044574 W JP 2017044574W WO 2018110552 A1 WO2018110552 A1 WO 2018110552A1
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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
- 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
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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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
- 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
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- 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
Definitions
- Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of divalent alcohol, mono (meth) acrylate or di (meth) acrylate of trivalent alcohol. And epoxy (meth) acrylate.
- Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Can be mentioned.
- the preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight.
- the sealing agent for liquid crystal display elements of the present invention can exhibit more excellent light shielding properties.
- the sealing agent for liquid crystal display elements of the present invention is superior in adhesiveness, strength after curing, and applicability.
- the minimum with more preferable content of the said light-shielding agent is 10 weight part, and a more preferable upper limit is 70 weight part.
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- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Liquid Crystal (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
液晶滴下工法では、まず、2枚の電極付き基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を基板のシール枠内に滴下し、真空下で他方の基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、加熱して本硬化を行い、液晶表示素子を作製する。現在この滴下工法が液晶表示素子の製造方法の主流となっている。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A method called a liquid crystal dropping method using a photothermal combined curing type sealant containing a polymerization initiator and a thermosetting agent is used.
In the liquid crystal dropping method, first, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, liquid crystal microdrops are dropped into the sealing frame of the substrate in a state where the sealing agent is uncured, the other substrate is superposed under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Thereafter, heating is performed to perform main curing, and a liquid crystal display element is manufactured. At present, this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
このような狭額縁設計ではシール剤自体も細く描画されるため、従来のシール剤では接着性や透湿防止性が充分でなく、液晶汚染等により液晶表示素子の表示不良が生じやすいという問題があった。 By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a technique for miniaturization, there is a narrow frame of the liquid crystal display unit, and for example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as “narrow frame design”).
In such a narrow frame design, since the sealing agent itself is drawn finely, the conventional sealing agent does not have sufficient adhesion and moisture permeation prevention, and the liquid crystal display element is liable to cause a display defect due to liquid crystal contamination. there were.
以下に本発明を詳述する。 In formula (2-1) and formula (2-2), * represents a bonding position, and in formula (2-1), R represents a hydrogen atom or a methyl group.
The present invention is described in detail below.
本発明の重合性化合物は、液晶に対する汚染性が低く、かつ、接着性及び透湿防止性に優れるため、液晶表示素子用シール剤の硬化性樹脂として好適に用いられる。 The polymerizable compound of the present invention 1 (hereinafter simply referred to as “polymerizable compound of the present invention”) is represented by the above formula (1).
The polymerizable compound of the present invention is suitably used as a curable resin for a sealing agent for liquid crystal display elements because it has low contamination to liquid crystals and is excellent in adhesion and moisture permeation resistance.
上記硬化性樹脂は、上記式(1)で表される重合性化合物(即ち、本発明の重合性化合物)を含有する。上記硬化性樹脂として本発明の重合性化合物を含有することにより、本発明の液晶表示素子用シール剤は、接着性、透湿防止性、及び、低液晶汚染性に優れるものとなる。 The sealing agent for liquid crystal display elements of the present invention 2 (hereinafter also simply referred to as “sealing agent for liquid crystal display elements of the present invention”) contains a curable resin.
The said curable resin contains the polymeric compound (namely, polymeric compound of this invention) represented by the said Formula (1). By containing the polymerizable compound of the present invention as the curable resin, the sealing agent for liquid crystal display elements of the present invention is excellent in adhesiveness, moisture permeation preventive property, and low liquid crystal contamination.
なお、本明細書において、上記「(メタ)アクリロイル」とは、アクリロイル又はメタクリロイルを意味する。 In the above formula (1), Y 1 and Y 2 each independently represent a group represented by the above formula (2-1) or (2-2), and at least one of Y 1 and Y 2 Is a group represented by the above formula (2-1). That is, the polymerizable compound of the present invention may have a (meth) acryloyl group at both ends, a (meth) acryloyl group at one end, and an epoxy group at the other end. It may be.
In the present specification, the “(meth) acryloyl” means acryloyl or methacryloyl.
上記nの好ましい上限は3である。上記nが3以下であることにより、得られる液晶表示素子用シール剤の粘度が高くなり過ぎず、塗布性や取り扱い性により優れるものとなる。 In said formula (1), n is 1 or more and 5 or less (average value).
A preferable upper limit of n is 3. When n is 3 or less, the viscosity of the obtained liquid crystal display element sealing agent does not become too high, and the coating properties and handling properties are excellent.
上記ジエポキシ化合物を製造する方法としては、例えば、ビスフェノールA等のビスフェノール類とトリエチレングリコールジビニルエーテル等の上記式(1)のXに相当する構造を有するジビニルエーテル化合物とを反応させて得られる、両末端にフェノール性水酸基を有する化合物を、更にエピクロロヒドリンと反応させる方法等が挙げられる。
また、上記ジエポキシ化合物のうち市販されているものとしては、例えば、エピクロンEXA4850シリーズ(DIC社製)等が挙げられる。 Examples of the method for producing the polymerizable compound of the present invention include a diepoxy compound in which the portions corresponding to Y 1 and Y 2 in the formula (1) are both groups represented by the formula (2-2). Examples include a method in which a part or all of the epoxy groups are reacted with (meth) acrylic acid.
As a method for producing the diepoxy compound, for example, it is obtained by reacting a bisphenol such as bisphenol A with a divinyl ether compound having a structure corresponding to X of the above formula (1) such as triethylene glycol divinyl ether. Examples thereof include a method in which a compound having a phenolic hydroxyl group at both ends is further reacted with epichlorohydrin.
Moreover, as what is marketed among the said diepoxy compounds, epiclone EXA4850 series (made by DIC Corporation) etc. are mentioned, for example.
上記その他の重合性化合物としては、本発明の重合性化合物に含まれるもの以外の、その他の(メタ)アクリル化合物やその他のエポキシ化合物等が挙げられる。
なお、本明細書において、上記「(メタ)アクリル」とは、アクリル又はメタクリルを意味し、上記「(メタ)アクリル化合物」とは、(メタ)アクリロイル基を有する化合物を意味する。 The curable resin preferably contains another polymerizable compound other than the polymerizable compound of the present invention.
As said other polymeric compound, other (meth) acrylic compounds other than what is contained in the polymeric compound of this invention, another epoxy compound, etc. are mentioned.
In the present specification, the “(meth) acryl” means acryl or methacryl, and the “(meth) acryl compound” means a compound having a (meth) acryloyl group.
なお、本明細書において上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味し、上記「エポキシ(メタ)アクリレート」とは、エポキシ化合物中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを表す。 Examples of the other (meth) acrylic compounds include epoxy (meth) acrylates, (meth) acrylic acid ester compounds, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable. The other (meth) acrylic compounds are preferably those having two or more (meth) acryloyl groups in the molecule because of their high reactivity.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” means that all epoxy groups in the epoxy compound react with (meth) acrylic acid. Represents the compound.
上記ビスフェノールF型エポキシ樹脂のうち市販されているものとしては、例えば、jER806、jER4004(いずれも三菱化学社製)等が挙げられる。
上記ビスフェノールE型エポキシ樹脂のうち市販されているものとしては、例えば、R710(プリンテック社製)等が挙げられる。
上記ビスフェノールS型エポキシ樹脂のうち市販されているものとしては、例えば、EPICLON EXA-1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、EPICLON EXA-7015(DIC社製)等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、jER YX-4000H(三菱化学社製)等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-50TE(新日鉄住金化学社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-80DE(新日鉄住金化学社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、EPICLON HP4032、EPICLON EXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、EPICLON N-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、EPICLON N-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、EPICLON HP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ESN-165S(新日鉄住金化学社製)等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、jER630(三菱化学社製)、EPICLON430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも新日鉄住金化学社製)、エポリードPB(ダイセル社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。 Examples of commercially available bisphenol A type epoxy resins include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), and the like.
As what is marketed among the said bisphenol F-type epoxy resins, jER806, jER4004 (all are the Mitsubishi Chemical company make) etc. are mentioned, for example.
As what is marketed among the said bisphenol E-type epoxy resins, R710 (made by Printec Co., Ltd.) etc. are mentioned, for example.
Examples of commercially available bisphenol S-type epoxy resins include EPICLON EXA-1514 (manufactured by DIC).
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available hydrogenated bisphenol epoxy resins include EPICLON EXA-7015 (manufactured by DIC).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include EPICLON HP4032, EPICLON EXA-4700 (both manufactured by DIC), and the like.
Examples of commercially available phenol novolac epoxy resins include EPICLON N-770 (manufactured by DIC).
Examples of commercially available ortho cresol novolac type epoxy resins include EPICLON N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, EPICLON HP7200 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company), and the like.
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
上記ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、グリセリン、ソルビトール、トリメチロールプロパン、カーボネートジオール、ポリエーテルジオール、ポリエステルジオール、ポリカプロラクトンジオール等が挙げられる。 As the isocyanate compound, a chain-extended isocyanate compound obtained by a reaction between a polyol and an excess of an isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
上記ヒドロキシアルキルモノ(メタ)アクリレートとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等が挙げられる。
上記二価のアルコールとしては、例えば、エチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ポリエチレングリコール等が挙げられる。
上記三価のアルコールとしては、例えば、トリメチロールエタン、トリメチロールプロパン、グリセリン等が挙げられる。
上記エポキシ(メタ)アクリレートとしては、例えば、ビスフェノールA型エポキシアクリレート等が挙げられる。 Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of divalent alcohol, mono (meth) acrylate or di (meth) acrylate of trivalent alcohol. And epoxy (meth) acrylate.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Can be mentioned.
Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.
Examples of the trivalent alcohol include trimethylolethane, trimethylolpropane, and glycerin.
Examples of the epoxy (meth) acrylate include bisphenol A type epoxy acrylate.
上記東亞合成社製のウレタン(メタ)アクリレートとしては、例えば、M-1100、M-1200、M-1210、M-1600等が挙げられる。
上記ダイセル・オルネクス社製のウレタン(メタ)アクリレートとしては、例えば、EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260等が挙げられる。
上記根上工業社製のウレタン(メタ)アクリレートとしては、例えば、アートレジンUN-330、アートレジンSH-500B、アートレジンUN-1200TPK、アートレジンUN-1255、アートレジンUN-3320HB、アートレジンUN-7100、アートレジンUN-9000A、アートレジンUN-9000H等が挙げられる。
上記新中村化学工業社製のウレタン(メタ)アクリレートとしては、例えば、U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A等が挙げられる。
上記共栄社化学社製のウレタン(メタ)アクリレートとしては、例えば、AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等が挙げられる。 Examples of commercially available urethane (meth) acrylates include, for example, urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Ornex, and urethane (meth) manufactured by Negami Kogyo Co., Ltd. Examples thereof include acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
Examples of the urethane (meth) acrylate manufactured by Toagosei include M-1100, M-1200, M-1210, and M-1600.
The urethane (meth) acrylate manufactured by the Daicel Orunekusu Inc., for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc. Can be mentioned.
Examples of the urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN- 7100, Art Resin UN-9000A, Art Resin UN-9000H, and the like.
Examples of the urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA- 4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, and the like.
Examples of the urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T. It is done.
上記重合開始剤としては、ラジカル重合開始剤が好適に用いられる。
上記ラジカル重合開始剤としては、光照射によりラジカルを発生する光ラジカル重合開始剤や、加熱によりラジカルを発生する熱ラジカル重合開始剤等が挙げられる。 The sealing agent for liquid crystal display elements of the present invention may contain a polymerization initiator.
As the polymerization initiator, a radical polymerization initiator is preferably used.
Examples of the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.
上記BASF社製の光ラジカル重合開始剤としては、例えば、IRGACURE 184、IRGACURE 369、IRGACURE 379、IRGACURE 651、IRGACURE 819、IRGACURE 907、IRGACURE 2959、IRGACURE OXE01、ルシリンTPO等が挙げられる。
上記東京化成工業社製の光ラジカル重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等が挙げられる。 As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF, the radical photopolymerization initiator by Tokyo Chemical Industry, etc. are mentioned, for example.
Examples of the radical photopolymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucillin TPO.
Examples of the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
なお、本明細書において高分子アゾ化合物とは、アゾ基を有し、熱によって(メタ)アクリロイル基を硬化させることができるラジカルを生成する、数平均分子量が300以上の化合物を意味する。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
In the present specification, the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat and having a number average molecular weight of 300 or more.
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo compound is within this range, it can be easily mixed with a curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ化合物としては、ポリエチレンオキサイド構造を有するものが好ましい。
上記高分子アゾ化合物としては、具体的には例えば、4,4’-アゾビス(4-シアノペンタン酸)とポリアルキレングリコールの重縮合物や、4,4’-アゾビス(4-シアノペンタン酸)と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられる。
上記高分子アゾ化合物のうち市販されているものとしては、例えば、VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(いずれも和光純薬工業社製)等が挙げられる。
また、高分子ではないアゾ化合物として市販されているものとしては、例えば、V-65、V-501(いずれも和光純薬工業社製)等が挙げられる。 Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable.
Specific examples of the polymer azo compound include, for example, a polycondensate of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group.
Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). .
Examples of commercially available azo compounds that are not polymers include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
上記熱硬化剤としては、例えば、有機酸ヒドラジド、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。 The sealing agent for liquid crystal display elements of the present invention may contain a thermosetting agent.
As said thermosetting agent, organic acid hydrazide, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned, for example. Of these, organic acid hydrazide is preferably used.
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、大塚化学社製の有機酸ヒドラジド、味の素ファインテクノ社製の有機酸ヒドラジド等が挙げられる。
上記大塚化学社製の有機酸ヒドラジドとしては、例えば、SDH、ADH等が挙げられる。
上記味の素ファインテクノ社製の有機酸ヒドラジドとしては、例えば、アミキュアVDH、アミキュアVDH-J、アミキュアUDH、アミキュアUDH-J等が挙げられる。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, and the like.
Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., and the like.
Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno Co. include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, and the like.
上記無機充填剤としては、例えば、シリカ、タルク、ガラスビーズ、石綿、石膏、珪藻土、スメクタイト、ベントナイト、モンモリロナイト、セリサイト、活性白土、アルミナ、酸化亜鉛、酸化鉄、酸化マグネシウム、酸化錫、酸化チタン、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、水酸化アルミニウム、窒化アルミニウム、窒化珪素、硫酸バリウム、珪酸カルシウム等が挙げられる。
上記有機充填剤としては、例えば、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等が挙げられる。 As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
また、遮光剤として上記チタンブラックを含有する本発明の液晶表示素子用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has a sufficient light-shielding property, and thus has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
上記三菱マテリアル社製のチタンブラックとしては、例えば、12S、13M、13M-C、13R-N、14M-C等が挙げられる。
上記赤穂化成社製のチタンブラックとしては、例えば、ティラックD等が挙げられる。 Examples of commercially available titanium black include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd.
Examples of the titanium black manufactured by Mitsubishi Materials include 12S, 13M, 13M-C, 13R-N, and 14M-C.
Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilac D.
また、上記チタンブラックの体積抵抗の好ましい下限は0.5Ω・cm、好ましい上限は3Ω・cmであり、より好ましい下限は1Ω・cm、より好ましい上限は2.5Ω・cmである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
なお、上記遮光剤の一次粒子径は、NICOMP 380ZLS(PARTICLE SIZING SYSTEMS社製)を用いて、上記遮光剤を溶媒(水、有機溶媒等)に分散させて測定することができる。 Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board | substrates of a liquid crystal display element, a preferable minimum is 1 nm and a preferable upper limit is 5000 nm. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the drawability of the obtained sealing agent for liquid crystal display elements. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
まず、ITO薄膜等の電極付きのガラス基板やポリエチレンテレフタレート基板等の2枚の基板の一方に、本発明の液晶表示素子用シール剤を、スクリーン印刷、ディスペンサー塗布等により塗布して枠状のシールパターンを形成する工程を行う。次いで、本発明の液晶表示素子用シール剤が未硬化の状態で液晶の微小滴を基板のシールパターンの枠内に滴下塗布し、真空下で別の基板を重ね合わせる工程を行う。その後、本発明の液晶表示素子用シール剤のシールパターン部分に紫外線等の光を照射してシール剤を仮硬化させる工程、及び、仮硬化させたシール剤を加熱して本硬化させる工程を行う方法により、液晶表示素子を得ることができる。 As a method for producing the liquid crystal display element of the present invention, a liquid crystal dropping method is suitably used, and specific examples include the following methods.
First, the sealant for liquid crystal display element of the present invention is applied to one of two substrates such as a glass substrate with an electrode such as an ITO thin film or a polyethylene terephthalate substrate by screen printing, dispenser application, etc. A step of forming a pattern is performed. Next, in a state where the sealant for a liquid crystal display element of the present invention is uncured, a step of applying droplets of liquid crystals into the frame of the seal pattern of the substrate and superimposing another substrate under vacuum is performed. Thereafter, a step of irradiating the seal pattern portion of the sealant for the liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily cure the sealant and a step of heating and temporarily curing the temporarily cured sealant are performed. A liquid crystal display element can be obtained by the method.
フラスコにビスフェノールA456重量部とトリエチレングリコールジビニルエーテル202重量部とを入れ、120℃で6時間撹拌することにより反応させて中間体フェノール化合物を得た。
液温を常温に戻した後、エピクロロヒドリン925重量部及びn-ブタノール150重量部を加えて均一な溶液とし、60℃に昇温した。次いで、40%水酸化ナトリウム水溶液220重量部を5時間かけて滴下し、更に60℃で1時間反応させた。反応終了後、残存エピクロルヒドリンを減圧蒸留で留去し、粗エポキシ化合物を得た。得られた粗エポキシ化合物にメチルイソブチルケトン600重量部とn-ブタノール100重量部とを加えて溶液とし、該溶液に10%水酸化ナトリウム水溶液30重量部を添加して80℃で2時間反応させた後、水200重量部での水洗を3回繰り返して洗浄液のpHを測定し、中性となったのを確認した。次いで、共沸脱水を実施し、更に溶媒を留去して中間体エポキシ化合物(A-1)を得た。 (Synthesis of Intermediate Epoxy Compound (A-1))
456 parts by weight of bisphenol A and 202 parts by weight of triethylene glycol divinyl ether were placed in a flask and reacted by stirring at 120 ° C. for 6 hours to obtain an intermediate phenol compound.
After returning the liquid temperature to room temperature, 925 parts by weight of epichlorohydrin and 150 parts by weight of n-butanol were added to obtain a uniform solution, and the temperature was raised to 60 ° C. Next, 220 parts by weight of 40% aqueous sodium hydroxide solution was added dropwise over 5 hours, and the reaction was further carried out at 60 ° C. for 1 hour. After completion of the reaction, the remaining epichlorohydrin was distilled off under reduced pressure to obtain a crude epoxy compound. To the obtained crude epoxy compound, 600 parts by weight of methyl isobutyl ketone and 100 parts by weight of n-butanol were added to form a solution, and 30 parts by weight of 10% aqueous sodium hydroxide solution was added to the solution and reacted at 80 ° C. for 2 hours. After that, washing with 200 parts by weight of water was repeated three times, and the pH of the washing solution was measured to confirm that it became neutral. Next, azeotropic dehydration was carried out, and the solvent was distilled off to obtain an intermediate epoxy compound (A-1).
フラスコに中間体エポキシ化合物(A-1)を404重量部、アクリル酸36重量部、トリフェニルホスフィン0.5重量部、及び、ジブチルヒドロキシトルエン0.05重量部を入れ、100℃で6時間撹拌することにより反応させた。得られた反応物を純水1000重量部で3回洗浄した後、減圧蒸留で水を除去し、本発明の重合性化合物(B-1)を得た。
なお、得られた本発明の重合性化合物(B-1)は、1H-NMR、13C-NMR、及び、FT-IR分析により、式(1)におけるAがジメチルメチレン基であり、Xがジ(エチレンオキシ)エチル基であり、Y1及びY2のうち、一方が式(2-1)で表される基(Rが水素原子)であり、他方が式(2-2)で表される基であることを確認した。また、本発明の重合性化合物(B-1)は、式(1)におけるn(平均値)が1.3である化合物であることを確認した。 (Synthesis of the polymerizable compound (B-1) of the present invention)
404 parts by weight of the intermediate epoxy compound (A-1), 36 parts by weight of acrylic acid, 0.5 parts by weight of triphenylphosphine, and 0.05 parts by weight of dibutylhydroxytoluene are placed in a flask and stirred at 100 ° C. for 6 hours. To react. The obtained reaction product was washed three times with 1000 parts by weight of pure water, and then water was removed by distillation under reduced pressure to obtain the polymerizable compound (B-1) of the present invention.
The obtained polymerizable compound (B-1) of the present invention was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis, wherein A in Formula (1) is a dimethylmethylene group, and X Is a di (ethyleneoxy) ethyl group, and one of Y 1 and Y 2 is a group represented by formula (2-1) (R is a hydrogen atom), and the other is represented by formula (2-2) It was confirmed that the group was represented. Further, it was confirmed that the polymerizable compound (B-1) of the present invention was a compound having n (average value) of 1.3 in the formula (1).
フラスコに中間体エポキシ化合物(A-1)を404重量部、アクリル酸72重量部、トリフェニルホスフィン0.5重量部、及び、ジブチルヒドロキシトルエン0.05重量部を入れ、100℃で6時間撹拌することにより反応させた。得られた反応物を純水1000重量部で3回洗浄した後、減圧蒸留で水を除去し、本発明の重合性化合物(C-1)を得た。
なお、得られた本発明の重合性化合物(C-1)は、1H-NMR、13C-NMR、及び、FT-IR分析により、式(1)におけるAがジメチルメチレン基であり、Xがジ(エチレンオキシ)エチル基であり、Y1及びY2がともに式(2-1)で表される基(Rが水素原子)であることを確認した。また、本発明の重合性化合物(C-1)は、式(1)におけるn(平均値)が1.3である化合物であることを確認した。 (Synthesis of the polymerizable compound (C-1) of the present invention)
404 parts by weight of the intermediate epoxy compound (A-1), 72 parts by weight of acrylic acid, 0.5 parts by weight of triphenylphosphine, and 0.05 parts by weight of dibutylhydroxytoluene are placed in a flask and stirred at 100 ° C. for 6 hours. To react. The obtained reaction product was washed three times with 1000 parts by weight of pure water, and then water was removed by distillation under reduced pressure to obtain the polymerizable compound (C-1) of the present invention.
The obtained polymerizable compound (C-1) of the present invention was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis, wherein A in Formula (1) is a dimethylmethylene group, and X Was a di (ethyleneoxy) ethyl group, and both Y 1 and Y 2 were confirmed to be a group represented by the formula (2-1) (R is a hydrogen atom). Further, it was confirmed that the polymerizable compound (C-1) of the present invention was a compound having an n (average value) of 1.3 in the formula (1).
アクリル酸72重量部に代えてメタクリル酸86重量部を用いたこと以外は上記「(本発明の重合性化合物(C-1)の合成)」と同様の操作を行い、本発明の重合性化合物(C-1M)を得た。
なお、得られた本発明の重合性化合物(C-1M)は、1H-NMR、13C-NMR、及び、FT-IR分析により、式(1)におけるAがジメチルメチレン基であり、Xがジ(エチレンオキシ)エチル基であり、Y1及びY2がともに式(2-1)で表される基(Rがメチル基)であることを確認した。また、本発明の重合性化合物(C-1M)は、式(1)におけるn(平均値)が1.3である化合物であることを確認した。 (Synthesis of polymerizable compound (C-1M) of the present invention)
The polymerizable compound of the present invention was prepared in the same manner as the above “(Synthesis of the polymerizable compound (C-1) of the present invention)” except that 86 parts by weight of methacrylic acid was used instead of 72 parts by weight of acrylic acid. (C-1M) was obtained.
The obtained polymerizable compound (C-1M) of the present invention was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis, wherein A in Formula (1) is a dimethylmethylene group, and X Was a di (ethyleneoxy) ethyl group, and both Y 1 and Y 2 were confirmed to be a group represented by the formula (2-1) (R is a methyl group). Further, it was confirmed that the polymerizable compound (C-1M) of the present invention was a compound having n (average value) of 1.3 in the formula (1).
トリエチレングリコールジビニルエーテル202重量部に代えて1,6-ビス(ビニルオキシ)ヘキサン170重量部を用いたこと以外は上記「(中間体エポキシ化合物(A-1)の合成)」と同様の操作を行い、中間体エポキシ化合物(A-2)を得た。 (Synthesis of Intermediate Epoxy Compound (A-2))
The same operation as “(intermediate epoxy compound (A-1))” except that 170 parts by weight of 1,6-bis (vinyloxy) hexane was used instead of 202 parts by weight of triethylene glycol divinyl ether. The intermediate epoxy compound (A-2) was obtained.
中間体エポキシ化合物(A-1)404重量部に代えて中間体エポキシ化合物(A-2)388重量部を用いたこと以外は上記「(本発明の重合性化合物(C-1)の合成)」と同様の操作を行い、本発明の重合性化合物(C-2)を得た。
なお、得られた本発明の重合性化合物(C-2)は、1H-NMR、13C-NMR、及び、FT-IR分析により、式(1)におけるAがジメチルメチレン基であり、Xがヘキサメチレン基であり、Y1及びY2がともに式(2-1)で表される基(Rが水素原子)であることを確認した。また、本発明の重合性化合物(C-2)は、式(1)におけるn(平均値)が1.2である化合物であることを確認した。 (Synthesis of the polymerizable compound (C-2) of the present invention)
“(Synthesis of polymerizable compound (C-1) of the present invention)” except that 388 parts by weight of the intermediate epoxy compound (A-2) was used instead of 404 parts by weight of the intermediate epoxy compound (A-1). The polymerizable compound (C-2) of the present invention was obtained in the same manner as in the above.
The obtained polymerizable compound (C-2) of the present invention was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR analysis, wherein A in Formula (1) is a dimethylmethylene group, and X Was a hexamethylene group, and both Y 1 and Y 2 were confirmed to be a group represented by the formula (2-1) (R is a hydrogen atom). Further, it was confirmed that the polymerizable compound (C-2) of the present invention was a compound having an n (average value) of 1.2 in the formula (1).
中間体エポキシ化合物(A-1)404重量部に代えてプロピレンオキサイド変性ビスフェノールA型エポキシ樹脂260重量部を用いたこと以外は上記「(本発明の重合性化合物(C-1)の合成)」と同様の操作を行い、プロピレンオキサイド変性ビスフェノールA型エポキシアクリレートを得た。上記プロピレンオキサイド変性ビスフェノールA型エポキシ樹脂としては、アデカレジン EP-4000S(ADEKA社製)を用いた。 (Synthesis of propylene oxide modified bisphenol A type epoxy acrylate)
“(Synthesis of polymerizable compound (C-1) of the present invention”) except that 260 parts by weight of propylene oxide-modified bisphenol A type epoxy resin was used instead of 404 parts by weight of the intermediate epoxy compound (A-1). The same operation was performed to obtain a propylene oxide-modified bisphenol A type epoxy acrylate. As the propylene oxide-modified bisphenol A type epoxy resin, Adeka Resin EP-4000S (manufactured by ADEKA) was used.
表1、2に記載された配合比に従い、各材料を遊星式撹拌機(シンキー社製、「あわとり練太郎」)を用いて混合した後、更に3本ロールを用いて混合することにより実施例1~11及び比較例1~3の液晶表示素子用シール剤を調製した。 (Examples 1 to 11 and Comparative Examples 1 to 3)
According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary stirrer ("Shinky", "Awatori Nertaro"), and then mixed by using three rolls. Sealants for liquid crystal display elements of Examples 1 to 11 and Comparative Examples 1 to 3 were prepared.
実施例及び比較例で得られた液晶表示素子用シール剤について以下の評価を行った。結果を表1、2に示した。 <Evaluation>
The following evaluation was performed about the sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
実施例及び比較例で得られた各液晶表示素子用シール剤100重量部にスペーサー粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を遊星式撹拌装置によって均一に分散させ、極微量をコーニングガラス1737(長さ50mm×幅20mm×厚さ0.7mm)の中央部に塗布した。同型のガラスをその上に重ね合わせて液晶表示素子用シール剤を押し広げ、メタルハライドランプを用いて100mW/cm2の紫外線を30秒照射した後、120℃で1時間加熱してシール剤を硬化させ、接着試験片を得た。
得られた接着試験片について、テンションゲージを用いて接着強度を測定した。 (Adhesiveness)
1 part by weight of spacer particles (“Micropearl SI-H050”, manufactured by Sekisui Chemical Co., Ltd.) is uniformly dispersed by 100% by weight of a sealing agent for liquid crystal display elements obtained in Examples and Comparative Examples using a planetary stirrer. A very small amount was applied to the center of Corning glass 1737 (length 50 mm × width 20 mm × thickness 0.7 mm). The same type of glass is placed on top of it to spread the sealant for liquid crystal display elements, and 100 mW / cm 2 of UV light is irradiated for 30 seconds using a metal halide lamp, followed by heating at 120 ° C. for 1 hour to cure the sealant. To obtain an adhesion test piece.
About the obtained adhesion test piece, the adhesive strength was measured using the tension gauge.
実施例及び比較例で得られた各液晶表示素子用シール剤100重量部にスペーサー微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を分散させ、2枚のラビング済み配向膜及び透明電極付き基板の一方に、シール剤の線幅が1mmになるようにディスペンサーで塗布した。続いて液晶(チッソ社製、「JC-5004LA」)の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付き基板を貼り合わせ、シール剤部分にメタルハライドランプを用いて100mW/cm2の紫外線を30秒照射した後、120℃で1時間加熱してシール剤を硬化させ、液晶表示素子を得た。実施例及び比較例で得られた各液晶表示素子用シール剤について、低液晶汚染性及び透湿防止性の評価にかかる液晶表示素子をそれぞれ作製した。
低液晶汚染性の評価は、得られた液晶表示素子を60℃で1000時間電圧印加状態とした後、シール剤付近の液晶配向乱れの程度を目視によって確認して行った。また、透湿防止性の評価は、60℃95%RHで1000時間電圧印加状態とした後、シール剤付近の液晶配向乱れの程度を目視によって確認して行った。
液晶配向乱れは色むらにより判断しており、色むらの程度に応じて、色むらが全くなかった場合を「◎」、色むらが微かにあった場合を「○」、色むらが少しあった場合を「△」、色むらがかなりあった場合を「×」として液晶汚染性を評価した。
なお、評価が「◎」、「○」の液晶表示素子は実用に全く問題のないレベルである。 (Low liquid crystal contamination and moisture permeability prevention)
1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples, and two rubbed orientations are obtained. It applied to one side of a film | membrane and a board | substrate with a transparent electrode with a dispenser so that the line | wire width of a sealing compound might be 1 mm. Subsequently, liquid crystal (Chisso, “JC-5004LA”) microdrops are applied to the entire surface of the sealant frame of the substrate with the transparent electrode, and the other substrate with the transparent electrode is immediately bonded to the sealant part. After being irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, the sealant was cured by heating at 120 ° C. for 1 hour to obtain a liquid crystal display element. About each liquid crystal display element sealing agent obtained by the Example and the comparative example, the liquid crystal display element concerning evaluation of low liquid-crystal contamination | pollution property and moisture-proofing property was produced, respectively.
Evaluation of low liquid crystal contamination was performed by visually checking the degree of disorder of liquid crystal alignment in the vicinity of the sealant after the obtained liquid crystal display element was subjected to a voltage application state at 60 ° C. for 1000 hours. Further, the evaluation of moisture permeation prevention was performed by visually checking the degree of liquid crystal alignment disorder in the vicinity of the sealant after applying a voltage application state at 60 ° C. and 95% RH for 1000 hours.
The liquid crystal alignment disorder is judged by the color unevenness. Depending on the degree of color unevenness, “◎” indicates that there is no color unevenness, “○” indicates that there is slight color unevenness, and there is a little color unevenness. In this case, “Δ” was assigned to the case where the color was uneven, and “X” was given to the case where the color was considerably uneven.
Note that the liquid crystal display elements with the evaluations “◎” and “で” are at a level that causes no problem in practical use.
Claims (5)
- 硬化性樹脂を含有する液晶表示素子用シール剤であって、
前記硬化性樹脂は、下記式(1)で表される重合性化合物を含有することを特徴とする液晶表示素子用シール剤。
The said curable resin contains the polymeric compound represented by following formula (1), The sealing compound for liquid crystal display elements characterized by the above-mentioned.
- 硬化性樹脂100重量部中における式(1)で表される重合性化合物の含有量が5重量部以上80重量部以下であることを特徴とする請求項1記載の液晶表示素子用シール剤。 2. The sealant for a liquid crystal display element according to claim 1, wherein the content of the polymerizable compound represented by the formula (1) in 100 parts by weight of the curable resin is 5 parts by weight or more and 80 parts by weight or less.
- 請求項1又は2記載の液晶表示素子用シール剤と導電性微粒子とを含有することを特徴とする上下導通材料。 A vertical conduction material comprising the sealing agent for a liquid crystal display element according to claim 1 or 2 and conductive fine particles.
- 請求項1若しくは2記載の液晶表示素子用シール剤又は請求項3記載の上下導通材料を用いてなることを特徴とする液晶表示素子。 A liquid crystal display element comprising the sealant for a liquid crystal display element according to claim 1 or 2 or the vertical conduction material according to claim 3.
- 下記式(1)で表されることを特徴とする重合性化合物。
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JP2017566877A JP7000164B2 (en) | 2016-12-16 | 2017-12-12 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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