JP2005258353A - Hardening resin composition for liquid crystal display element, sealing agent for liquid crystal dropping process, vertical conductive material and liquid crystal display element - Google Patents
Hardening resin composition for liquid crystal display element, sealing agent for liquid crystal dropping process, vertical conductive material and liquid crystal display element Download PDFInfo
- Publication number
- JP2005258353A JP2005258353A JP2004073422A JP2004073422A JP2005258353A JP 2005258353 A JP2005258353 A JP 2005258353A JP 2004073422 A JP2004073422 A JP 2004073422A JP 2004073422 A JP2004073422 A JP 2004073422A JP 2005258353 A JP2005258353 A JP 2005258353A
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- Prior art keywords
- liquid crystal
- crystal display
- display element
- resin composition
- curable resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000011342 resin composition Substances 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 53
- 238000007789 sealing Methods 0.000 title claims abstract description 34
- 239000004020 conductor Substances 0.000 title abstract 2
- 230000008569 process Effects 0.000 title description 3
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BLGWXSOTAXXXDE-UHFFFAOYSA-N n'-[1-(1h-imidazol-2-yl)propyl]hexanediamide Chemical compound NC(=O)CCCCC(=O)NC(CC)C1=NC=CN1 BLGWXSOTAXXXDE-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、滴下工法による液晶表示素子の製造にシール剤として用いた場合にでも、信頼
性に優れ、液晶汚染を引き起こしにくく色むらが少ない高品位な画像の液晶表示素子を製
造することができる液晶表示素子用硬化性樹脂組成物、該液晶表示素子用硬化性樹脂組成
物からなる液晶滴下工法用シール剤、上下導通材料及び液晶表示素子に関する。
Even when the present invention is used as a sealant in the production of a liquid crystal display element by a dripping method, it is possible to produce a liquid crystal display element with high reliability, which is highly reliable, hardly causes liquid crystal contamination, and has little color unevenness. The present invention relates to a curable resin composition for liquid crystal display elements, a sealing agent for liquid crystal dropping method comprising the curable resin composition for liquid crystal display elements, a vertical conduction material, and a liquid crystal display element.
従来、液晶表示セル等の液晶表示素子は、2枚の電極付き透明基板を、所定の間隔をおい
て対向させ、その周囲を液晶表示素子用硬化性樹脂組成物からなるシール剤で封着してセ
ルを形成し、その一部に設けられた液晶注入口からセル内に液晶を注入し、その液晶注入
口をシール剤又は封口剤を用いて封止することにより作製されていた。
Conventionally, a liquid crystal display element such as a liquid crystal display cell has two transparent substrates with electrodes facing each other at a predetermined interval, and the periphery thereof is sealed with a sealing agent made of a curable resin composition for a liquid crystal display element. The cell was formed, liquid crystal was injected into the cell from a liquid crystal injection port provided in a part of the cell, and the liquid crystal injection port was sealed with a sealing agent or a sealing agent.
この方法では、まず、2枚の電極付き透明基板のいずれか一方に、スクリーン印刷により
熱硬化性シール剤を用いた液晶注入口を設けたシールパターンを形成し、60〜100℃
でプリベイクを行いシール剤中の溶剤を乾燥させる。次いで、スペーサーを挟んで2枚の
基板を対向させてアライメントを行い貼り合わせ、110〜220℃で10〜90分間熱
プレスを行いシール近傍のギャップを調整した後、オーブン中で110〜220℃で10
〜120分間加熱しシール剤を本硬化させる。次いで、液晶注入口から液晶を注入し、最
後に封口剤を用いて液晶注入口を封止して、液晶表示素子を作製していた。
In this method, first, a seal pattern in which a liquid crystal injection port using a thermosetting sealant is provided by screen printing on either one of two transparent substrates with electrodes is formed at 60 to 100 ° C.
Pre-bake to dry the solvent in the sealant. Next, alignment is performed with the two substrates facing each other with a spacer interposed therebetween, and the gap in the vicinity of the seal is adjusted by performing hot pressing at 110 to 220 ° C. for 10 to 90 minutes, and then at 110 to 220 ° C. in an oven. 10
Heat for ~ 120 minutes to fully cure the sealant. Next, liquid crystal was injected from the liquid crystal injection port, and finally, the liquid crystal injection port was sealed using a sealing agent to produce a liquid crystal display element.
しかし、この作製方法によると、熱歪により位置ズレ、ギャップのバラツキ、シール剤と
基板との密着性の低下等が発生する;残留溶剤が熱膨張して気泡が発生しキャップのバラ
ツキやシールパスが発生する;シール硬化時間が長い;プリベイクプロセスが煩雑;溶剤
の揮発によりシール剤の使用可能時間が短い;液晶の注入に時間がかかる等の問題があっ
た。とりわけ、近年の大型の液晶表示装置にあっては、液晶の注入に非常に時間がかかる
ことが大きな問題となっていた。
However, according to this manufacturing method, the positional displacement, gap variation, decrease in adhesion between the sealing agent and the substrate, etc. occur due to thermal strain; residual solvent thermally expands to generate bubbles, resulting in cap variation and seal path. The seal curing time is long; the prebaking process is complicated; the usable time of the sealant is short due to the volatilization of the solvent; and it takes time to inject liquid crystal. In particular, in a large liquid crystal display device in recent years, it takes a very long time to inject liquid crystal.
これに対して、光硬化熱硬化併用型シール剤を用いた滴下工法と呼ばれる液晶表示素子の
製造方法が検討されている。滴下工法では、まず、2枚の電極付き透明基板の一方に、ス
クリーン印刷により長方形状のシールパターンを形成する。次いで、シール剤未硬化の状
態で液晶の微小滴を透明基板の枠内全面に滴下塗布し、すぐに他方の透明基板を重ねあわ
せ、シール部に紫外線を照射して仮硬化を行う。その後、液晶アニール時に加熱して本硬
化を行い、液晶表示素子を作製する。基板の貼り合わせを減圧下で行うようにすれば、極
めて高い効率で液晶表示素子を製造することができる。今後はこの滴下工法が液晶表示装
置の製造方法の主流となると期待されている。
On the other hand, a manufacturing method of a liquid crystal display element called a dripping method using a photocuring / thermosetting sealant has been studied. In the dropping method, first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by screen printing. Next, fine droplets of liquid crystal are dropped and applied to the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with ultraviolet rays for temporary curing. Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency. In the future, this dripping method is expected to become the mainstream of liquid crystal display manufacturing methods.
このような滴下工法に用いる液晶滴下工法用シール剤として、特許文献1、特許文献2及
び特許文献3には、エポキシ基の一部が(メタ)アクリル酸で変性された(メタ)アクリ
ル酸変性エポキシ樹脂からなるものが開示されている。このような(メタ)アクリル酸変
性エポキシ樹脂は、光照射、加熱のいずれによっても硬化することから、滴下工法に用い
る液晶滴下工法用シール剤として好適である。しかしながら、(メタ)アクリル酸変成エ
ポキシ樹脂等の光熱硬化性樹脂は、従来の液晶表示素子の製造に用いられていたエポキシ
樹脂等の硬化性樹脂に比べて接着力に劣り、これをシール剤として用いて製造した液晶表
示素子は信頼性に劣るという問題点があった。また、滴下工法は、その工程上、未硬化の
状態のシール剤が液晶に直接触れてしまうことから、極性の低い添加物を配合した場合に
は、これが液晶に溶出して液晶を汚染してしまい、液晶の配向乱れによると思われる色む
ら等の表示不良が生じやすいという問題点もあった。
As a sealing agent for a liquid crystal dropping method used in such a dropping method, Patent Document 1, Patent Document 2 and Patent Document 3 describe (meth) acrylic acid modification in which a part of an epoxy group is modified with (meth) acrylic acid. An epoxy resin is disclosed. Such a (meth) acrylic acid-modified epoxy resin is suitable as a sealing agent for a liquid crystal dropping method used for the dropping method because it is cured by either light irradiation or heating. However, photothermosetting resins such as (meth) acrylic acid modified epoxy resins are inferior in adhesive strength to curable resins such as epoxy resins used in the production of conventional liquid crystal display elements, and this is used as a sealing agent. The liquid crystal display element manufactured by using it has a problem that it is inferior in reliability. In addition, since the uncured sealant directly touches the liquid crystal during the process, the dripping method dissolves into the liquid crystal and contaminates the liquid crystal when an additive with low polarity is blended. As a result, there has been a problem that display defects such as color unevenness, which are thought to be caused by disordered alignment of the liquid crystal, are likely to occur.
本発明は、上記現状に鑑み、滴下工法による液晶表示素子の製造にシール剤として用いた
場合にでも信頼性に優れ、液晶汚染を引き起こしにくく色むらが少ない高品位な画像の液
晶表示素子を製造することができる液晶表示素子用硬化性樹脂組成物、該液晶表示素子用
硬化性樹脂組成物からなる液晶滴下工法用シール剤、上下導通材料及び液晶表示素子を提
供することを目的とする。
In view of the above situation, the present invention manufactures a liquid crystal display element with high image quality, which is excellent in reliability even when used as a sealant in the manufacture of liquid crystal display elements by a dropping method, hardly causes liquid crystal contamination, and has little color unevenness. An object of the present invention is to provide a curable resin composition for a liquid crystal display element, a sealing agent for a liquid crystal dropping method comprising the curable resin composition for a liquid crystal display element, a vertical conduction material, and a liquid crystal display element.
本発明は、反応性不飽和基を有し、分子量1000〜6000、ガラス転移温度が−20
℃以下である反応性不飽和化合物、熱硬化剤及び充填剤を含有する液晶表示素子用硬化性
樹脂組成物である。
以下に本発明を詳述する。
The present invention has a reactive unsaturated group, has a molecular weight of 1000 to 6000, and a glass transition temperature of −20.
It is the curable resin composition for liquid crystal display elements containing the reactive unsaturated compound which is below (degreeC), a thermosetting agent, and a filler.
The present invention is described in detail below.
本発明者らは、鋭意検討の結果、特定の分子量を有し、かつ、ガラス転移温度が一定以下
である反応性不飽和化合物を含有する硬化性樹脂組成物を用いれば、液晶滴下工法用シー
ル剤として用いた場合に、高い接着信頼性が得られ、かつ、液晶に対する汚染を抑制する
ことができることを見出し、本発明を完成するに至った。
As a result of intensive studies, the present inventors have used a curable resin composition containing a reactive unsaturated compound having a specific molecular weight and having a glass transition temperature of a certain value or less, and a liquid crystal dropping method seal. When used as an agent, it has been found that high adhesion reliability can be obtained and contamination to the liquid crystal can be suppressed, and the present invention has been completed.
本発明の液晶表示素子用硬化性樹脂組成物は、反応性不飽和基を有し、分子量1000〜
6000、ガラス転移温度が−20℃以下である反応性不飽和化合物を含有する。このよ
うな反応性不飽和化合物を含有することにより、本発明の液晶表示素子用硬化性樹脂組成
物を液晶滴下工法用シール剤として用いた場合に、高い接着信頼性が得られ、かつ、液晶
に対する汚染を抑制することができる。
The curable resin composition for a liquid crystal display element of the present invention has a reactive unsaturated group and has a molecular weight of 1000 to 1000.
6000, containing a reactive unsaturated compound having a glass transition temperature of −20 ° C. or lower. By containing such a reactive unsaturated compound, when the curable resin composition for a liquid crystal display element of the present invention is used as a sealing agent for a liquid crystal dropping method, high adhesion reliability is obtained, and liquid crystal Contamination against can be suppressed.
上記反応性不飽和化合物の分子量の下限は1000、上限は6000である。1000未
満であると、本発明の液晶表示素子用硬化性樹脂組成物を液晶滴下工法用シール剤として
用いた場合に液晶を汚染してしまい、6000を超えると、粘度が高くなりすぎてシール
剤として用いることが困難となる。好ましい下限は2000、好ましい上限は5000で
ある。
The lower limit of the molecular weight of the reactive unsaturated compound is 1000, and the upper limit is 6000. If it is less than 1000, the liquid crystal is contaminated when the curable resin composition for a liquid crystal display element of the present invention is used as a sealant for a liquid crystal dropping method, and if it exceeds 6000, the viscosity becomes too high and the sealant. It becomes difficult to use as. A preferable lower limit is 2000, and a preferable upper limit is 5000.
上記反応性不飽和化合物のガラス転移温度の上限は−20℃である。−20℃を超えると
、硬化収縮緩和性が得られず、本発明の液晶表示素子用硬化性樹脂組成物を液晶滴下工法
用シール剤として用いた場合に、接着信頼性が劣る。好ましい上限は−25℃である。下
限については特に限定されないが、好ましい下限は−70℃である。
The upper limit of the glass transition temperature of the reactive unsaturated compound is −20 ° C. When it exceeds −20 ° C., the curing shrinkage relaxation property cannot be obtained, and when the curable resin composition for a liquid crystal display element of the present invention is used as a sealing agent for a liquid crystal dropping method, the adhesion reliability is inferior. A preferred upper limit is −25 ° C. Although it does not specifically limit about a minimum, A preferable minimum is -70 degreeC.
上記反応性不飽和化合物は、反応性不飽和基を有する。反応性不飽和基を有することによ
り、加熱することにより硬化させることができる。また、後述するように1分子内に(メ
タ)アクリル基とエポキシ基とをそれぞれ少なくとも1つ以上有する化合物と併用したと
きに、これと反応して硬化物中に取り込まれることから、液晶表示素子に製造においてシ
ール剤として用いたときにも、液晶に溶出して汚染することがない。
上記反応性不飽和基としては特に限定されず、例えば、ビニル基、(メタ)アクリル基等
が挙げられる。
The reactive unsaturated compound has a reactive unsaturated group. By having a reactive unsaturated group, it can be cured by heating. Further, as will be described later, when used in combination with a compound having at least one (meth) acryl group and epoxy group in one molecule, it reacts with this and is taken into the cured product. In addition, when used as a sealant in manufacturing, it does not elute into the liquid crystal and become contaminated.
The reactive unsaturated group is not particularly limited, and examples thereof include a vinyl group and a (meth) acryl group.
上記反応性不飽和化合物としては、ブタジエン−アクリロニトリル共重合体骨格を有する
化合物及び/又はウレタンアクリレート化合物が好適である。ブタジエン−アクリロニト
リル共重合体骨格を有する化合物は、伸縮性に優れたブタジエンを含有することから、こ
のような反応性不飽和化合物を含有する本発明の液晶表示素子用硬化性樹脂組成物は、硬
化させたときの硬化収縮により発生する応力を緩和することができ、高い接着力を発現す
る。また、ウレタンアクリレート化合物は、弾性体骨格を有するウレタンを含有すること
から、ブタジエン−アクリロニトリル骨格を有する化合物と同様に、硬化収縮による応力
を緩和することができ、高い接着力を発現する。
As the reactive unsaturated compound, a compound having a butadiene-acrylonitrile copolymer skeleton and / or a urethane acrylate compound is preferable. Since the compound having a butadiene-acrylonitrile copolymer skeleton contains butadiene having excellent stretchability, the curable resin composition for a liquid crystal display element of the present invention containing such a reactive unsaturated compound is cured. It is possible to relieve the stress generated by curing shrinkage when it is made to develop and to exhibit high adhesive strength. In addition, since the urethane acrylate compound contains urethane having an elastic skeleton, the stress due to curing shrinkage can be relieved and high adhesive strength can be exhibited in the same manner as the compound having a butadiene-acrylonitrile skeleton.
上記ブタジエン−アクリロニトリル共重合骨格を有する化合物は、ブタジエン比の好まし
い下限が50重量%、好ましい上限が90重量%である。60重量%未満であると、硬化
収縮を緩和するのに充分な伸縮性が得られないことがあり、90重量%を超えると、上記
1分子内に(メタ)アクリル基とエポキシ基とをそれぞれ少なくとも1つ以上有する化合
物等との相溶性が劣り、充分に混合できないことがある。より好ましい下限は60重量%
、より好ましい上限は80重量%である。
The compound having the butadiene-acrylonitrile copolymer skeleton has a preferred lower limit of butadiene ratio of 50% by weight and a preferred upper limit of 90% by weight. If it is less than 60% by weight, sufficient stretchability to alleviate curing shrinkage may not be obtained, and if it exceeds 90% by weight, each of the (meth) acryl group and epoxy group is contained in one molecule. The compatibility with the compound having at least one or more may be inferior and may not be sufficiently mixed. A more preferred lower limit is 60% by weight.
A more preferred upper limit is 80% by weight.
上記ブタジエン−アクリロニトリル共重合体骨格を有する化合物を製造する方法としては
特に限定されないが、例えば、アミノ基又はカルボキシル基とブタジエン−アクリロニト
リル共重合体骨格とを有する化合物と、少なくとも1つの(メタ)アクリル基とエポキシ基
とを有する化合物とを反応させることにより得ることができる。
The method for producing the compound having a butadiene-acrylonitrile copolymer skeleton is not particularly limited. For example, the compound having an amino group or a carboxyl group and a butadiene-acrylonitrile copolymer skeleton and at least one (meth) acrylic are used. It can be obtained by reacting a compound having a group and an epoxy group.
上記アミノ基又はカルボキシル基とブタジエン−アクリロニトリル共重合体骨格とを有す
る化合物としては特に限定されず、例えば、アミノ基末端ブタジエン−アクリロニトリル
共重合体等が挙げられる。これらのアミノ基又はカルボキシル基とブタジエン−アクリロ
ニトリル共重合体骨格とを有する化合物のうち市販されているものとしては、ATBN、
CTBN(以上、宇部興産社製)等が挙げられる。
The compound having an amino group or carboxyl group and a butadiene-acrylonitrile copolymer skeleton is not particularly limited, and examples thereof include an amino group-terminated butadiene-acrylonitrile copolymer. Of those compounds having an amino group or carboxyl group and a butadiene-acrylonitrile copolymer skeleton, those commercially available include ATBN,
CTBN (above, Ube Industries, Ltd.) etc. are mentioned.
上記少なくとも1つの(メタ)アクリル基とエポキシ基とを有する化合物としては特に限定
されず、例えば、2官能以上のエポキシ樹脂を(メタ)アクリル酸変性した化合物等が挙
げられる。
上記原料となる2官能以上のエポキシ樹脂としては、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;フェノールノボラック型、クレゾールノボラ
ック型、ビフェニルノボラック型、トリスフェノールノボラック型、ジシクロペンタジエ
ンノボラック型等のノボラック型エポキシ樹脂等が挙げられる。これらのエポキシ樹脂の
うち市販されているものとしては、例えば、ビスフェノールA型では、エピコート828
、エピコート834、エピコート1001、エピコート1004(以上、油化シェルエポ
キシ社製)、エピクロン850、エピクロン860、エピクロン4055(以上、大日本
インキ化学工業社製)等が挙げられ、ビスフェノールF型エポキシ樹脂では、エピコート
807(油化シェルエポキシ樹脂社製)、エピクロン830(大日本インキ化学工業社製
)が挙げられる。これらは、単独で用いてもよく、2種以上を併用してもよい。
また、上記少なくとも1つの(メタ)アクリル基とエポキシ基とを有する化合物としては、
例えば、グリシジルメタクリレート、4−ヒドロキシブチルアクリレートグリシジル、脂
環式エポキシ基を有する(メタ)アクリレート等も用いることができる。
The compound having at least one (meth) acrylic group and an epoxy group is not particularly limited, and examples thereof include a compound obtained by modifying a bifunctional or higher functional epoxy resin with (meth) acrylic acid.
Examples of the bifunctional or higher functional epoxy resin as the raw material include bisphenol A type epoxy resin, bisphenol F type epoxy resin; phenol novolak type, cresol novolak type, biphenyl novolak type, trisphenol novolak type, dicyclopentadiene novolak type, and the like. Novolak type epoxy resin and the like. Among these epoxy resins, those commercially available include, for example, Epicoat 828 for bisphenol A type.
, Epicote 834, Epicote 1001, Epicote 1004 (manufactured by Yuka Shell Epoxy), Epicron 850, Epicron 860, Epicron 4055 (manufactured by Dainippon Ink and Chemicals, Inc.), etc. , Epicoat 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) and Epicron 830 (manufactured by Dainippon Ink & Chemicals, Inc.). These may be used alone or in combination of two or more.
Further, as the compound having at least one (meth) acryl group and an epoxy group,
For example, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl, (meth) acrylate having an alicyclic epoxy group, or the like can also be used.
上記ブタジエン−アクリロニトリル共重合体骨格を有する化合物のうち、反応性不飽和基
がビニル基であるものとしては、例えば、宇部興産社製のVTBNX等の市販品も用いる
ことができる。
Among the compounds having the butadiene-acrylonitrile copolymer skeleton, as the reactive unsaturated group is a vinyl group, for example, a commercial product such as VTBNX manufactured by Ube Industries, Ltd. can be used.
上記ウレタンアクリレート化合物のうち市販されているものとしては、例えば、ダイセル
UCB社製のEB230、EB8804等が挙げられる。
Examples of commercially available urethane acrylate compounds include EB230 and EB8804 manufactured by Daicel UCB.
本発明の液晶表示素子用硬化性樹脂組成物を液晶滴下工法用シール剤として用いる場合に
は、更に、樹脂成分として1分子内に(メタ)アクリル基とエポキシ基とをそれぞれ少な
くとも1つ以上有する化合物を併用することが好ましい。このような化合物は、光照射、
加熱のいずれによっても硬化することから、滴下工法に用いる液晶滴下工法用シール剤に
好適である。
上記1分子内に(メタ)アクリル基とエポキシ基とをそれぞれ少なくとも1つ以上有する
化合物としては特に限定されず、例えば、(メタ)アクリル酸変性エポキシ樹脂、ウレタ
ン変性(メタ)アクリルエポキシ樹脂等が挙げられる。
When the curable resin composition for a liquid crystal display element of the present invention is used as a sealing agent for a liquid crystal dropping method, it further has at least one (meth) acryl group and epoxy group in one molecule as a resin component. It is preferable to use a compound in combination. Such compounds are light irradiated,
Since it hardens | cures by any of heating, it is suitable for the sealing compound for liquid crystal dropping methods used for a dropping method.
The compound having at least one (meth) acryl group and epoxy group in one molecule is not particularly limited, and examples thereof include (meth) acrylic acid-modified epoxy resins and urethane-modified (meth) acryl epoxy resins. Can be mentioned.
上記(メタ)アクリル酸変性エポキシ樹脂としては、例えば、ノボラック型エポキシ樹脂
、ビスフェノール型エポキシ樹脂等を部分(メタ)アクリル化したもの; ビフェニル型
エポキシ樹脂、ナフタレン型エポキシ樹脂、トリス(ヒドロキシフェニル)アルキル型エ
ポキシ樹脂、テトラキス(ヒドロキシフェニル)アルキル型エポキシ樹脂等が好適である
。
Examples of the (meth) acrylic acid-modified epoxy resin include, for example, partially (meth) acrylated novolac type epoxy resin, bisphenol type epoxy resin, etc .; biphenyl type epoxy resin, naphthalene type epoxy resin, tris (hydroxyphenyl) alkyl Type epoxy resin, tetrakis (hydroxyphenyl) alkyl type epoxy resin and the like are suitable.
上記(メタ)アクリル酸変性エポキシ樹脂の原料となるエポキシ樹脂としては、例えば、
ノボラック型としてはフェノールノボラック型、クレゾールノボラック型、ビフェニルノ
ボラック型、トリスフェノールノボラック型、ジシクロペンタジエンノボラック型等が挙
げられ、また、ビスフェノール型としてはビスフェノールA型、ビスフェノールF型、2
,2’−ジアリルビスフェノールA型、ビスフェノールS型、水添ビスフェノール型、ポ
リオキシプロピレンビスフェノールA型等が挙げられる。
As an epoxy resin that is a raw material of the (meth) acrylic acid-modified epoxy resin, for example,
Examples of the novolak type include a phenol novolak type, a cresol novolak type, a biphenyl novolak type, a trisphenol novolak type, a dicyclopentadiene novolak type, and the bisphenol type includes a bisphenol A type, a bisphenol F type, 2
2,2'-diallyl bisphenol A type, bisphenol S type, hydrogenated bisphenol type, polyoxypropylene bisphenol A type and the like.
上記(メタ)アクリル酸変性エポキシ樹脂の原料のうち市販されているものとしては、例
えば、フェノールノボラック型としては、エピクロンN−740、エピクロンN−770
、エピクロンN−775(以上、大日本インキ化学社製)、エピコート152、エピコー
ト154(以上、ジャパンエポキシレジン社製)が挙げられ、クレゾールノボラック型と
しては、エピクロンN−660、エピクロンN−665、エピクロンN−670、エピク
ロンN−673、エピクロンN−680、エピクロンN−695、エピクロンN−665
−EXP、エピクロンN−672−EXP(以上、大日本インキ化学社製)等が挙げられ
る。
Examples of commercially available raw materials for the (meth) acrylic acid-modified epoxy resin include, for example, phenol novolak type, Epicron N-740, Epicron N-770.
, Epicron N-775 (manufactured by Dainippon Ink Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (manufactured by Japan Epoxy Resin Co., Ltd.), and cresol novolac types include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, Epicron N-665
-EXP, Epicron N-672-EXP (above, Dainippon Ink & Chemicals) etc. are mentioned.
上記エポキシ樹脂の部分(メタ)アクリル化物は、例えば、エポキシ樹脂と(メタ)アク
リル酸とを、常法に従って塩基性触媒の存在下で反応することにより得られる。エポキシ
樹脂と(メタ)アクリル酸との配合量を適宜変更する事により所望のアクリル化率のエポ
キシ樹脂を得る事が可能である。
The partially (meth) acrylated product of the epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It is possible to obtain an epoxy resin having a desired acrylation rate by appropriately changing the blending amount of the epoxy resin and (meth) acrylic acid.
上記ウレタン変性(メタ)アクリルエポキシ樹脂は、例えば、以下の方法によって得られ
るものである。すなわち、ポリオールと2官能以上のイソシアネートとを反応させ、更に
これに水酸基を有する(メタ)アクリルモノマー及びグリシドールを反応させる方法;ポ
リオールを用いずに2官能以上のイソシアネートに水酸基を有する(メタ)アクリルモノ
マーやグリシドールを反応させる方法;イソシアネート基を有する(メタ)アクリレート
にグリシドールを反応させる方法等により作製することができる。具体的には、例えば、
まずトリメチロールプロパン1モルとイソホロンジイソシアネート3モルとをスズ系触媒
下で反応させ、得られた化合物中に残るイソシアネート基と、水酸基を有するアクリルモ
ノマーであるヒドロキシエチルアクリレート及び水酸基を有するエポキシであるグリシド
ールとを反応させることにより作製することができる。
The urethane-modified (meth) acrylic epoxy resin is obtained by the following method, for example. That is, a method of reacting a polyol with a bifunctional or higher isocyanate, and further reacting this with a (meth) acrylic monomer having a hydroxyl group and glycidol; (meth) acrylic having a hydroxyl group with a bifunctional or higher isocyanate without using a polyol It can be produced by a method in which a monomer or glycidol is reacted; a method in which glycidol is reacted with a (meth) acrylate having an isocyanate group. Specifically, for example,
First, 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate are reacted under a tin-based catalyst, and the isocyanate group remaining in the resulting compound, hydroxyethyl acrylate which is an acrylic monomer having a hydroxyl group, and glycidol which is an epoxy having a hydroxyl group. Can be made to react.
上記ポリオールとしては特に限定されず、例えば、エチレングリコール、グリセリン、ソ
ルビトール、トリメチロールプロパン、(ポリ)プロピレングリコール等が挙げられる。
上記イソシアネートとしては、2官能以上であれば特に限定されず、例えば、イソホロ
ンジイソシアネート、2,4−トリレンジイソシアネート、2,6−トリレンジイソシア
ネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート
、ジフェニルメタン−4,4’−ジイソシアネート(MDI)、水添MDI、ポリメリッ
クMDI、1,5−ナフタレンジイソシアネート、ノルボルナンジイソシネート、トリジ
ンジイソシアネート、キシリレンジイオシアネート(XDI)、水添XDI、リジンジイ
ソシアネート、トリフェニルメタントリイソシアネート、トリス(イソシアネートフェニ
ル)チオフォスフェート、テトラメチルキシレンジイソシアネート、1,6,10−ウン
デカントリイソシアネート等が挙げられる。
It does not specifically limit as said polyol, For example, ethylene glycol, glycerol, sorbitol, a trimethylol propane, (poly) propylene glycol etc. are mentioned.
The isocyanate is not particularly limited as long as it is bifunctional or higher. For example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate , Tris (isocyanatephenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate, etc. I can get lost.
上記水酸基を有する(メタ)アクリルモノマーとしては特に限定されず、例えば、分子内
に水酸基を1つ有するモノマーとしては、ヒドロキシエチル(メタ)アクリレート、ヒド
ロキシプロピル(メタ)アクリレート、ヒドロキシブチル(メタ)アクリレート等が挙げ
られ、分子内に水酸基を2つ以上有するモノマーとしては、ビスフェノールA変性エポキ
シ(メタ)アクリレート等のエポキシ(メタ)アクリレートが挙げられる。これらは、単
独で用いても、2種以上を併用してもよい。
The (meth) acrylic monomer having a hydroxyl group is not particularly limited, and examples of the monomer having one hydroxyl group in the molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Examples of the monomer having two or more hydroxyl groups in the molecule include epoxy (meth) acrylates such as bisphenol A-modified epoxy (meth) acrylate. These may be used alone or in combination of two or more.
本発明の液晶表示素子用硬化性樹脂組成物は、熱硬化剤を含有する。
上記熱硬化剤は、加熱により液晶表示素子用硬化性樹脂組成物中のエポキシ基や(メタ)
アクリル基を反応させ、架橋させるためのものであり、硬化後の液晶表示素子用硬化性樹
脂組成物の接着性、耐湿性を向上させる役割を有する。上記熱硬化剤としては、融点が1
00℃以上の潜在性熱硬化剤が好適に用いられる。融点が100℃以下の熱硬化剤を使用
すると保存安定性が著しく悪くなることがある。
The curable resin composition for a liquid crystal display element of the present invention contains a thermosetting agent.
The thermosetting agent is an epoxy group or (meta) in the curable resin composition for liquid crystal display elements by heating.
It is for reacting and crosslinking an acrylic group, and has a role of improving the adhesion and moisture resistance of the curable resin composition for a liquid crystal display element after curing. The thermosetting agent has a melting point of 1
A latent thermosetting agent of 00 ° C. or higher is preferably used. When a thermosetting agent having a melting point of 100 ° C. or lower is used, the storage stability may be remarkably deteriorated.
このような熱硬化剤としては、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]等のヒドラジド化合物、ジシアンジアミド、グアニジン誘導体、1−
シアノエチル−2−フェニルイミダゾール、N−[2−(2−メチル−1−イミダゾリル
)エチル]尿素、2,4−ジアミノ−6−[2’−メチルイミダゾリル−(1’)]−エ
チル−s−トリアジン、N,N’−ビス(2−メチル−1−イミダゾリルエチル)尿素、
N,N’−(2−メチル−1−イミダゾリルエチル)−アジポアミド、2−フェニル−4
−メチル−5−ヒドロキシメチルイミダゾール、2−フェニル−4,5−ジヒドロキシメ
チルイミダゾール等のイミダゾール誘導体、変性脂肪族ポリアミン、テトラヒドロ無水フ
タル酸、エチレングリコールービス(アンヒドロトリメリテート)等の酸無水物、各種ア
ミンとエポキシ樹脂との付加生成物等が挙げられる。これらは、単独で用いても、2種類
以上が用いられてもよい。
Examples of such thermosetting agents include hydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], dicyandiamide, guanidine derivatives, 1-
Cyanoethyl-2-phenylimidazole, N- [2- (2-methyl-1-imidazolyl) ethyl] urea, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s— Triazine, N, N′-bis (2-methyl-1-imidazolylethyl) urea,
N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4
-Acid anhydrides such as methyl-5-hydroxymethylimidazole, imidazole derivatives such as 2-phenyl-4,5-dihydroxymethylimidazole, modified aliphatic polyamines, tetrahydrophthalic anhydride, ethylene glycol-bis (anhydrotrimellitate) Products, addition products of various amines and epoxy resins, and the like. These may be used alone or in combination of two or more.
上記熱硬化剤としては、固体熱硬化剤粒子の表面が微粒子により被覆されている被覆熱硬
化剤も好適である。このような被覆熱硬化剤を用いれば、予め熱硬化剤を配合していても
高い保存安定性を有する液晶表示素子用硬化性樹脂組成物が得られる。
As the thermosetting agent, a coated thermosetting agent in which the surface of solid thermosetting agent particles is coated with fine particles is also suitable. When such a coating thermosetting agent is used, a curable resin composition for a liquid crystal display element having high storage stability can be obtained even if a thermosetting agent is blended in advance.
本発明の液晶表示素子用硬化性樹脂組成物は、応力分散効果による接着性の改善、線膨張
率の改善等の目的で充填剤を含有する。上記充填剤としては特に限定されず、例えば、シ
リカ、珪藻土、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、
水酸化マグネシウム、水酸化アルミニウム、炭酸マグネシウム、硫酸バリウム、石膏、珪
酸カルシウム、タルク、ガラスビーズ、セリサイト活性白土、ベントナイト、窒化アルミ
ニウム、窒化珪素等の無機フィラー等が挙げられる。
The curable resin composition for a liquid crystal display element of the present invention contains a filler for the purpose of improving the adhesiveness due to the stress dispersion effect and improving the linear expansion coefficient. The filler is not particularly limited. For example, silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide,
Examples thereof include inorganic fillers such as magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride.
本発明の液晶表示素子用硬化性樹脂組成物は、更に、光ラジカル重合開始剤を含有しても
よい。
上記光ラジカル重合開始剤としては特に限定されないが、反応性二重結合と光反応開始部
とを有するものが好適である。このような光ラジカル重合開始剤を用いれば、本発明の液
晶表示素子用硬化性樹脂組成物に充分な反応性を付与することができるとともに、液晶中
に溶出して液晶を汚染することがない。なかでも、反応性二重結合と水酸基及び/又はウ
レタン結合とを有するベンゾイン(エーテル)類化合物が好適である。なお、ベンゾイン
(エーテル)類化合物とは、ベンゾイン類及びベンゾインエーテル類を表す。
The curable resin composition for a liquid crystal display element of the present invention may further contain a radical photopolymerization initiator.
Although it does not specifically limit as said radical photopolymerization initiator, What has a reactive double bond and a photoreaction start part is suitable. If such a radical photopolymerization initiator is used, sufficient reactivity can be imparted to the curable resin composition for a liquid crystal display element of the present invention, and it does not elute into the liquid crystal and contaminate the liquid crystal. . Of these, benzoin (ether) compounds having a reactive double bond and a hydroxyl group and / or a urethane bond are preferred. The benzoin (ether) compounds represent benzoins and benzoin ethers.
上記反応性二重結合としては、アリル基、ビニルエーテル基、(メタ)アクリル基等の残
基が挙げられるが、反応性の高さから(メタ)アクリル残基が好適である。このような反
応性二重結合を有することにより、本発明の液晶表示素子用液晶表示素子用硬化性樹脂組
成物の耐候性が向上する。
Examples of the reactive double bond include residues such as an allyl group, a vinyl ether group, and a (meth) acryl group, and a (meth) acryl residue is preferable because of its high reactivity. By having such a reactive double bond, the weather resistance of the curable resin composition for a liquid crystal display element of the present invention is improved.
上記ベンゾイン(エーテル)類化合物は、水酸基とウレタン結合とのどちらか1つを有し
ていればよく、両方を有していてもよい。上記ベンゾイン(エーテル)類化合物が水酸基
とウレタン結合のいずれも有していない場合には、液晶に溶出してしまうことがある。
The said benzoin (ether) type compound should just have any one of a hydroxyl group and a urethane bond, and may have both. If the benzoin (ether) compound has neither a hydroxyl group nor a urethane bond, it may elute into the liquid crystal.
上記ベンゾイン(エーテル)類化合物において、上記反応性二重結合及び水酸基及び/又
はウレタン結合は、ベンゾイン(エーテル)骨格のどの部分に位置していてもよいが、下
記一般式(1)で表される分子骨格を有するものが好適である。かかる分子骨格を有する
化合物を、光ラジカル重合開始剤として用いれば、残存物が少なくなり、アウトガスの量
を少なくすることができる。
In the benzoin (ether) compound, the reactive double bond and the hydroxyl group and / or the urethane bond may be located at any part of the benzoin (ether) skeleton, and are represented by the following general formula (1). Those having a molecular skeleton are preferred. If a compound having such a molecular skeleton is used as a radical photopolymerization initiator, the amount of residue is reduced and the amount of outgas can be reduced.
族炭化水素残鎖であると、光ラジカル重合開始剤を配合したときの保存安定性は増加する
ものの、置換基の立体障害により反応性が低下することがある。
一般式(1)で表される分子骨格を有するベンゾイン(エーテル)類化合物としては、例
えば、下記一般式(2)で表される化合物が挙げられる。
Examples of benzoin (ether) compounds having a molecular skeleton represented by general formula (1) include compounds represented by the following general formula (2).
官能イソシアネート誘導体の残基を表し、Yは炭素数4以下の脂肪族炭化水素残基又は残
基を構成する炭素と酸素の原子数比が3以下の残基を表す。Xが炭素数13を超える2官
能イソシアネート誘導体の残基であると、液晶に溶解しやすくなることがあり、Yが炭素
数4を超える脂肪族炭化水素基又は炭素と酸素の原子数比が3を超える残基であると、液
晶に溶解しやすくなることがある。
Y represents a residue of a functional isocyanate derivative, and Y represents an aliphatic hydrocarbon residue having 4 or less carbon atoms or a residue having an atomic ratio of carbon to oxygen constituting the residue of 3 or less. When X is a residue of a bifunctional isocyanate derivative having more than 13 carbon atoms, it may be easily dissolved in the liquid crystal, and Y may be an aliphatic hydrocarbon group having more than 4 carbon atoms or an atomic ratio of carbon to oxygen of 3 If the residue exceeds 50, it may be easily dissolved in the liquid crystal.
上記光ラジカル重合開始剤としては、他にも例えば、ベンゾフェノン、2,2−ジエトキ
シアセトフェノン、ベンジル、ベンゾイルイソプロピルエーテル、ベンジルジメチルケタ
ール、1−ヒドロキシシクロヘキシルフェニルケトン、チオキサントン等を用いることが
できる。これらの光ラジカル重合開始剤は単独で用いてもよく、2種以上を併用してもよ
い。
Other examples of the photo radical polymerization initiator include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. These radical photopolymerization initiators may be used alone or in combination of two or more.
本発明の液晶表示素子用硬化性樹脂組成物は、シランカップリング剤を含有していてもよ
い。シランカップリング剤を含有することにより、本発明の液晶表示素子用硬化性樹脂組
成物を液晶滴下工法用シール剤として用いた場合に、シール剤と基板との接着性を向上さ
せることができる。
上記シランカップリング剤としては特に限定されないが、基板等との接着性向上効果に優
れ、硬化性樹脂と化学結合することにより液晶材料中への流出を防止するとができること
から、例えば、γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメ
トキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−イソシアネートプロ
ピルトリメトキシシラン等や、スペーサー基を介してイミダゾール骨格とアルコキシシリ
ル基とが結合した構造を有するイミダゾールシラン化合物からなるもの等が好適に用いら
れる。これらのシランカップリング剤は単独で用いてもよく、2種以上を併用してもよい
。
The curable resin composition for a liquid crystal display element of the present invention may contain a silane coupling agent. By containing the silane coupling agent, when the curable resin composition for a liquid crystal display element of the present invention is used as a sealing agent for a liquid crystal dropping method, the adhesion between the sealing agent and the substrate can be improved.
The silane coupling agent is not particularly limited, but is excellent in the effect of improving adhesion to a substrate and the like, and can be prevented from flowing into the liquid crystal material by chemically bonding with a curable resin. Propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, etc., and a structure in which the imidazole skeleton and alkoxysilyl group are bonded via a spacer group What consists of the imidazole silane compound which has is used suitably. These silane coupling agents may be used alone or in combination of two or more.
本発明の液晶表示素子用硬化性樹脂組成物を製造する方法としては特に限定されず、上記
反応性不飽和化合物、熱硬化剤、充填剤、及び、必要に応じて添加する添加剤等を、従来
公知の方法により混合する方法等が挙げられる。このとき、イオン性の不純物を除去する
ために層状珪酸塩鉱物等のイオン吸着性固体と接触させてもよい。
The method for producing the curable resin composition for a liquid crystal display element of the present invention is not particularly limited, and the reactive unsaturated compound, the thermosetting agent, the filler, and an additive added as necessary, The method of mixing by a conventionally well-known method etc. are mentioned. At this time, in order to remove ionic impurities, it may be brought into contact with an ion-adsorbing solid such as a layered silicate mineral.
本発明の液晶表示素子用硬化性樹脂組成物は、上述の構成よりなることから、液晶滴下工
法用シール剤として用いた場合に、極めて信頼性に優れ、また、液晶汚染を引き起こしに
くく、色むらが少ない高品位な画像の液晶表示素子を製造することができる。
本発明の液晶表示素子用硬化性樹脂組成物からなる液晶滴下工法用シール剤もまた、本発
明の1つである。
Since the curable resin composition for a liquid crystal display element of the present invention has the above-described configuration, when used as a sealing agent for a liquid crystal dropping method, it is extremely reliable, hardly causes liquid crystal contamination, and has uneven color. It is possible to manufacture a liquid crystal display element having a high quality image with a small amount of image data.
The sealing agent for a liquid crystal dropping method comprising the curable resin composition for a liquid crystal display element of the present invention is also one aspect of the present invention.
本発明の液晶滴下工法用シール剤は、硬化後おけるガラス転移温度の好ましい下限が80
℃、好ましい上限が150℃である。80℃未満であると、本発明の液晶滴下工法用シー
ル剤を用いて液晶表示素子を製造した場合に、耐湿性(耐高温高湿性)に劣ることがあり
、150℃を超えると、剛直に過ぎ基板との密着性に劣ることがある。
なお、上記ガラス転移温度は、DMA法により昇温速度5℃/分、周波数10Hzの条件
で測定した値である。ただし、DMA法によるガラス転移点温度の測定には大量の試料を
要することから、少量の試料しか得られない場合にはDSC法により昇温速度10℃/分
の条件で測定を行うことが好ましい。一般に、DSC法によって測定したガラス転移点温
度は、DMA法によって測定したガラス転移点温度よりも30℃程度低くなる。したがっ
て、DSC法によってガラス転移点温度を測定する場合には、本発明の液晶滴下工法用シ
ール剤は、硬化後におけるガラス転移温度の好ましい下限が50℃、好ましい上限が12
0℃である。
The lower limit of the glass transition temperature after curing of the sealing agent for liquid crystal dropping method of the present invention is preferably 80.
The preferred upper limit is 150 ° C. When it is less than 80 ° C., when the liquid crystal display element is produced using the liquid crystal dropping method sealing agent of the present invention, it may be inferior in moisture resistance (high temperature and high humidity resistance). It may be inferior in adhesion to the substrate.
In addition, the said glass transition temperature is the value measured on conditions with a temperature increase rate of 5 degree-C / min and a frequency of 10 Hz by DMA method. However, since measurement of the glass transition temperature by the DMA method requires a large amount of sample, when only a small amount of sample is obtained, it is preferable to perform the measurement at a temperature increase rate of 10 ° C./min by the DSC method. . In general, the glass transition temperature measured by the DSC method is about 30 ° C. lower than the glass transition temperature measured by the DMA method. Accordingly, when the glass transition temperature is measured by the DSC method, the sealing agent for liquid crystal dropping method of the present invention has a preferable lower limit of 50 ° C. and a preferable upper limit of 12 for the glass transition temperature after curing.
0 ° C.
本発明の液晶表示素子用硬化性樹脂組成物に、導電性微粒子を配合することにより、上下
導通材料を製造することができる。このような上下導通材料を用いれば、液晶を汚染する
ことなく透明基板の電極を導電接続することができる。
本発明の液晶表示素子用硬化性樹脂組成物と、導電性微粒子とを含有する上下導通材料も
また、本発明の1つである。
A vertical conduction material can be manufactured by mix | blending electroconductive fine particles with the curable resin composition for liquid crystal display elements of this invention. By using such a vertical conduction material, the electrodes of the transparent substrate can be conductively connected without contaminating the liquid crystal.
The vertical conduction material containing the curable resin composition for a liquid crystal display element of the present invention and conductive fine particles is also one aspect of the present invention.
上記導電性微粒子としては特に限定されず、金属ボール、樹脂微粒子の表面に導電金属層
を形成したもの等を用いることができる。なかでも、樹脂微粒子の表面に導電金属層を形
成したものは、樹脂微粒子の優れた弾性により、透明基板等を損傷することなく導電接続
が可能であることから好適である。
The conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
本発明の液晶滴下工法用シール剤及び/又は本発明の上下導通材料を用いてなる液晶表示
素子もまた、本発明の1つである。
The liquid crystal display element using the sealing compound for liquid crystal dropping method of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.
本発明によれば、滴下工法による液晶表示素子の製造にシール剤として用いた場合にでも
、信頼性に優れ、液晶汚染を引き起こしにくく色むらが少ない高品位な画像の液晶表示素
子を製造することができる液晶表示素子用硬化性樹脂組成物、該液晶表示素子用硬化性樹
脂組成物からなる液晶滴下工法用シール剤、上下導通材料及び液晶表示素子を提供するこ
とができる。
According to the present invention, even when used as a sealant in the production of a liquid crystal display element by a dropping method, a liquid crystal display element with high reliability and excellent image quality that hardly causes liquid crystal contamination and has little color unevenness is produced. It is possible to provide a curable resin composition for liquid crystal display elements, a sealing agent for liquid crystal dropping method comprising the curable resin composition for liquid crystal display elements, a vertical conduction material, and a liquid crystal display element.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定
されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
(実施例1)
ビスフェノールA型エポキシアクリレート(ダイセルUCB社製、EB3700)60重
量部に、ブタジエン−アクリロニトリル共重合体骨格とビニル基とを有する化合物(宇部
興産社製、VTBNX)15重量部、光ラジカル重合開始剤(チバ・スペシャリティ・ケ
ミカルズ社製、イルガキュア907)2重量部を加え80℃で15分加熱して光ラジカル
開始剤を溶解した後、更に攪拌した。更に、カップリング剤としてエポキシシラン(チッ
ソ社製、S−510)2重量部、充填剤として球状シリカ(アドマテック社製、SO−C
1)18重量部、及び、熱硬化剤として有機酸ジヒドラジド(味の素FT社製、VDH)
3重量部を加え、均一な液となるように三本ロールを用いて充分に混合して液晶表示素子
用硬化性樹脂組成物を得た。
(Example 1)
60 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel UCB, EB3700), 15 parts by weight of a compound having a butadiene-acrylonitrile copolymer skeleton and a vinyl group (manufactured by Ube Industries, VTBNX), a radical photopolymerization initiator ( 2 parts by weight of Ciba Specialty Chemicals, Inc., Irgacure 907) was added and heated at 80 ° C. for 15 minutes to dissolve the photoradical initiator, followed by further stirring. Furthermore, 2 parts by weight of epoxysilane (S-510, manufactured by Chisso Corporation) as a coupling agent, and spherical silica (manufactured by Admatech, SO-C) as a filler.
1) 18 parts by weight, and organic acid dihydrazide (manufactured by Ajinomoto FT, VDH) as a thermosetting agent
3 parts by weight was added and mixed thoroughly using a three roll so as to obtain a uniform liquid to obtain a curable resin composition for a liquid crystal display element.
(実施例2)
アミノ酸末端ブタジエン−アクリロニトリル共重合体(宇部興産社製、ATBN 130
0X16)15重量部とビスフェノールA型エポキシアクリレート(ダイセルUCB社製
、EB3700)60重量部とを120℃、3時間反応させて、アクリル変性ブタジエン
−アクリロニトリル共重合体を得た。
得られたアクリル変性ブタジエン−アクリロニトリル共重合体70重量部に光ラジカル重
合開始剤2重量部を加え80℃で15分加熱して光ラジカル開始剤を溶解した後、更に攪
拌した。更に、カップリング剤としてエポキシシラン(チッソ社製、S−510)2重量
部、充填剤として球状シリカ(アドマテック社製、SO−C1)18重量部、及び、熱硬
化剤として有機酸ジヒドラジド(味の素FT社製、VDH)3重量部を加え、均一な液と
なるように三本ロールを用いて充分に混合して液晶表示素子用硬化性樹脂組成物を得た。
(Example 2)
Amino acid-terminated butadiene-acrylonitrile copolymer (manufactured by Ube Industries, ATBN 130
0X16) 15 parts by weight and 60 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel UCB, EB3700) were reacted at 120 ° C. for 3 hours to obtain an acryl-modified butadiene-acrylonitrile copolymer.
To 70 parts by weight of the resulting acrylic-modified butadiene-acrylonitrile copolymer, 2 parts by weight of a radical photopolymerization initiator was added and heated at 80 ° C. for 15 minutes to dissolve the radical photoinitiator, followed by further stirring. Furthermore, 2 parts by weight of epoxy silane (manufactured by Chisso, S-510) as a coupling agent, 18 parts by weight of spherical silica (manufactured by Admatech, SO-C1) as a filler, and organic acid dihydrazide (Ajinomoto) as a thermosetting agent FT Co., Ltd., VDH) 3 parts by weight was added and mixed thoroughly using a three roll so as to obtain a uniform liquid to obtain a curable resin composition for liquid crystal display elements.
(実施例3)
カルボン酸末端ブタジエン−アクリロニトリル共重合体(宇部興産社製、CTBN130
0X8)3550重量部、重合禁止剤としてp−メトキシフェノール10重量部、反応触
媒としてトリエチルアミン10重量部、及び、4−ヒドロキシブチルアクリレートグリシ
ジル(日本化成社製)400重量部を、空気を送り込みながら110℃で還流攪拌して5時
間反応させて、アクリル変性ブタジエン−アクリロニトリル共重合体を得た。
(Example 3)
Carboxylic acid-terminated butadiene-acrylonitrile copolymer (manufactured by Ube Industries, CTBN130
0X8) 3550 parts by weight, 10 parts by weight of p-methoxyphenol as a polymerization inhibitor, 10 parts by weight of triethylamine as a reaction catalyst, and 400 parts by weight of 4-hydroxybutyl acrylate glycidyl (manufactured by Nippon Kasei Co., Ltd.) while feeding air. The mixture was stirred at reflux at 5 ° C. and reacted for 5 hours to obtain an acryl-modified butadiene-acrylonitrile copolymer.
ブタジエン−アクリロニトリル共重合体骨格とビニル基とを有する化合物(宇部興産社製
、VTBNX)15重量部の代わりに、得られたアクリル変性ブタジエン−アクリロニト
リル共重合体10重量部を用いた以外は実施例1と同様にして、液晶表示素子用硬化性樹
脂組成物を得た。
Example except that 10 parts by weight of the resulting acryl-modified butadiene-acrylonitrile copolymer was used instead of 15 parts by weight of a compound having a butadiene-acrylonitrile copolymer skeleton and a vinyl group (manufactured by Ube Industries, VTBNX). In the same manner as in Example 1, a curable resin composition for a liquid crystal display element was obtained.
(実施例4)
ビスフェノールA型エポキシアクリレート(ダイセルUCB社製、EB3700)60重
量部に、ウレタンアクリレート化合物(ダイセルUCB社製、EB230)15重量部、
光ラジカル重合開始剤(チバ・スペシャリティ・ケミカルズ社製、イルガキュア907)
2重量部を加え80℃で15分加熱して光ラジカル開始剤を溶解した後、更に攪拌した。
更に、カップリング剤としてエポキシシラン(チッソ社製、S−510)2重量部、充填
剤として球状シリカ(アドマテック社製、SO−C1)18重量部、及び、熱硬化剤とし
て有機酸ジヒドラジド(味の素FT社製、VDH)3重量部を加え、均一な液となるよう
に三本ロールを用いて充分に混合して液晶表示素子用硬化性樹脂組成物を得た。
Example 4
60 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel UCB, EB3700), 15 parts by weight of urethane acrylate compound (manufactured by Daicel UCB, EB230),
Photoradical polymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals)
After adding 2 parts by weight and heating at 80 ° C. for 15 minutes to dissolve the photoradical initiator, the mixture was further stirred.
Furthermore, 2 parts by weight of epoxy silane (manufactured by Chisso, S-510) as a coupling agent, 18 parts by weight of spherical silica (manufactured by Admatech, SO-C1) as a filler, and organic acid dihydrazide (Ajinomoto) as a thermosetting agent FT Co., Ltd., VDH) 3 parts by weight was added and mixed thoroughly using a three roll so as to obtain a uniform liquid to obtain a curable resin composition for liquid crystal display elements.
(比較例1)
ビスフェノールA型エポキシアクリレート(ダイセルUCB社製、EB3700)の使用
量を75重量部とし、ブタジエン−アクリロニトリル共重合体骨格とビニル基とを有する
化合物(宇部興産社製、VTBNX)を用いなかった以外は実施例1と同様にして、液晶
表示素子用硬化性樹脂組成物を得た。
(Comparative Example 1)
The amount of bisphenol A type epoxy acrylate (manufactured by Daicel UCB, EB3700) was 75 parts by weight, and a compound having a butadiene-acrylonitrile copolymer skeleton and a vinyl group (manufactured by Ube Industries, VTBNX) was used. In the same manner as in Example 1, a curable resin composition for a liquid crystal display element was obtained.
(比較例2)
ビスフェノールA型エポキシアクリレート(ダイセルUCB社製、EB3700)60重
量部に、ラクトン変性可とう性アクリレート(ダイセルUCB社製、FA3;分子量45
8以下、ガラス転移温度−46℃)15重量部、光ラジカル重合開始剤(チバ・スペシャ
リティ・ケミカルズ社製、イルガキュア907)2重量部を加え80℃で15分加熱して
光ラジカル開始剤を溶解した後、更に攪拌した。更に、カップリング剤としてエポキシシ
ラン(チッソ社製、S−510)2重量部、充填剤として球状シリカ(アドマテック社製
、SO−C1)18重量部、及び、熱硬化剤として有機酸ジヒドラジド(味の素FT社製
、VDH)3重量部を加え、均一な液となるように三本ロールを用いて充分に混合して液
晶表示素子用硬化性樹脂組成物を得た。
(Comparative Example 2)
60 parts by weight of bisphenol A type epoxy acrylate (Daicel UCB, EB3700) and lactone-modified flexible acrylate (Daicel UCB, FA3; molecular weight 45)
8 or less, glass transition temperature -46 ° C.) 15 parts by weight, photo radical polymerization initiator (Ciba Specialty Chemicals, Irgacure 907) 2 parts by weight is added and heated at 80 ° C. for 15 minutes to dissolve the photo radical initiator And then stirred further. Furthermore, 2 parts by weight of epoxy silane (manufactured by Chisso, S-510) as a coupling agent, 18 parts by weight of spherical silica (manufactured by Admatech, SO-C1) as a filler, and organic acid dihydrazide (Ajinomoto) as a thermosetting agent FT Co., Ltd., VDH) 3 parts by weight was added and mixed thoroughly using a three roll so as to obtain a uniform liquid to obtain a curable resin composition for liquid crystal display elements.
(比較例3)
ビスフェノールA型エポキシアクリレート(ダイセルUCB社製、EB3700)60重
量部に、ウレタンアクリレート(ダイセルUCB社製、EB4849;分子量1600、
ガラス転移温度29℃)15重量部、光ラジカル重合開始剤(チバ・スペシャリティ・ケ
ミカルズ社製、イルガキュア907)2重量部を加え80℃で15分加熱して光ラジカル
開始剤を溶解した後、更に攪拌した。更に、カップリング剤としてエポキシシラン(チッ
ソ社製、S−510)2重量部、充填剤として球状シリカ(アドマテック社製、SO−C
1)18重量部、及び、熱硬化剤として有機酸ジヒドラジド(味の素FT社製、VDH)
3重量部を加え、均一な液となるように三本ロールを用いて充分に混合して液晶表示素子
用硬化性樹脂組成物を得た。
(Comparative Example 3)
60 parts by weight of bisphenol A type epoxy acrylate (manufactured by Daicel UCB, EB3700) and urethane acrylate (manufactured by Daicel UCB, EB4849; molecular weight 1600,
After adding 15 parts by weight of a glass transition temperature (29 ° C.) and 2 parts by weight of a photo radical polymerization initiator (Ciba Specialty Chemicals, Irgacure 907), heating at 80 ° C. for 15 minutes to dissolve the photo radical initiator, Stir. Furthermore, 2 parts by weight of epoxysilane (S-510, manufactured by Chisso Corporation) as a coupling agent, and spherical silica (manufactured by Admatech, SO-C) as a filler.
1) 18 parts by weight, and organic acid dihydrazide (manufactured by Ajinomoto FT, VDH) as a thermosetting agent
3 parts by weight was added and mixed thoroughly using a three roll so as to obtain a uniform liquid to obtain a curable resin composition for a liquid crystal display element.
実施例1〜4及び比較例1〜3で作製した液晶表示素子用硬化性樹脂組成物について、以
下の方法により評価を行った。
結果を表1に示した。
About the curable resin composition for liquid crystal display elements produced in Examples 1-4 and Comparative Examples 1-3, evaluation was performed with the following method.
The results are shown in Table 1.
(1)接着力の評価
少量の液晶表示素子用硬化性樹脂組成物を無アルカリガラス片上に採り、同じガラス片を
十字型になるように乗せ、シール部分が直径4〜5mmとなるように加圧した。3000
mJの紫外線を照射してギャップを固定した後、120℃、1時間加熱して液晶表示素子
用硬化性樹脂組成物を硬化させて試験片を作製した。
得られた試験片について、引張試験装置を用いた引張強度を測定した。値は、比較例1で
作製した液晶表示素子用硬化性樹脂組成物の接着力を10として表した。
(1) Evaluation of adhesive strength A small amount of the curable resin composition for liquid crystal display elements is placed on a non-alkali glass piece, and the same glass piece is placed in a cross shape so that the seal portion has a diameter of 4 to 5 mm. Pressed. 3000
After the gap was fixed by irradiating mJ ultraviolet rays, the test piece was prepared by heating at 120 ° C. for 1 hour to cure the curable resin composition for liquid crystal display elements.
About the obtained test piece, the tensile strength using the tensile test apparatus was measured. The value is represented by 10 as the adhesive force of the curable resin composition for a liquid crystal display device produced in Comparative Example 1.
(2)液晶汚染性の評価
得られた液晶表示素子用硬化性樹脂組成物を液晶滴下工法用シール剤として用い、滴下工
法により液晶表示素子を作製した。
即ち、2枚の透明電極付き透明基板の一方に、得られた液晶滴下工法用シール剤を長方形
の枠を描くようにディスペンサーで塗布した。次いで、液晶(チッソ社製、JC−500
4LA)の微小滴を透明基板の枠内全面に滴下塗布し、直ちにもう一方の透明基板を重ね
合わせてシール部に高圧水銀ランプを用い紫外線を50mW/cm2で20秒照射した。
その後液晶アニールを120℃、1時間行い同時に液晶滴下工法用シール剤を熱硬化させ
て液晶表示用素子を得た。
(2) Evaluation of liquid crystal contamination The obtained curable resin composition for a liquid crystal display device was used as a sealing agent for a liquid crystal dropping method, and a liquid crystal display device was produced by the dropping method.
That is, the obtained sealing agent for liquid crystal dropping method was applied to one of two transparent substrates with a transparent electrode with a dispenser so as to draw a rectangular frame. Next, liquid crystal (manufactured by Chisso Corporation, JC-500
4LA) was applied to the entire surface of the transparent substrate by dropping, and the other transparent substrate was immediately placed on top of each other and irradiated with ultraviolet rays at 50 mW / cm 2 for 20 seconds using a high-pressure mercury lamp on the seal portion.
Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 hour, and at the same time, the sealing agent for the liquid crystal dropping method was thermally cured to obtain a liquid crystal display element.
得られた液晶表示素子のシール部周辺の液晶に生じる色むらを目視にて観察し、以下の基
準により評価した。
○:色むらがない
△:少し色むらがある
×:色むらがかなりある
Color unevenness generated in the liquid crystal around the seal portion of the obtained liquid crystal display element was visually observed and evaluated according to the following criteria.
○: No color unevenness Δ: Some color unevenness ×: There is considerable color unevenness
本発明によれば、滴下工法による液晶表示素子の製造にシール剤として用いた場合にでも
、信頼性に優れ、液晶汚染を引き起こしにくく色むらが少ない高品位な画像の液晶表示素
子を製造することができる液晶表示素子用硬化性樹脂組成物、該液晶表示素子用硬化性樹
脂組成物からなる液晶滴下工法用シール剤、上下導通材料及び液晶表示素子を提供するこ
とができる。
According to the present invention, even when used as a sealant in the production of a liquid crystal display element by a dropping method, a liquid crystal display element with high reliability and excellent image quality that hardly causes liquid crystal contamination and has little color unevenness is produced. It is possible to provide a curable resin composition for liquid crystal display elements, a sealing agent for liquid crystal dropping method comprising the curable resin composition for liquid crystal display elements, a vertical conduction material, and a liquid crystal display element.
Claims (7)
る反応性不飽和化合物、熱硬化剤及び充填剤を含有することを特徴とする液晶表示素子用
硬化性樹脂組成物。 Curing property for liquid crystal display elements, comprising a reactive unsaturated group, a reactive unsaturated compound having a molecular weight of 1000 to 6000, and a glass transition temperature of −20 ° C. or less, a thermosetting agent, and a filler. Resin composition.
/又はウレタンアクリレート化合物であることを特徴とする請求項1記載の液晶表示素子
用硬化性樹脂組成物。 The curable resin composition for a liquid crystal display device according to claim 1, wherein the reactive unsaturated compound is a compound having a butadiene-acrylonitrile copolymer skeleton and / or a urethane acrylate compound.
、かつ、分子量が1000〜5000であることを特徴とする請求項2記載の液晶表示素
子用硬化性樹脂組成物。 The curable resin composition for a liquid crystal display element according to claim 2, wherein the butadiene-acrylonitrile copolymer skeleton has a butadiene ratio of 50 to 90% by weight and a molecular weight of 1000 to 5000.
又は3記載の液晶表示素子用硬化性樹脂組成物。 The reactive unsaturated group is a vinyl group or a (meth) acryl group.
Or 3. The curable resin composition for a liquid crystal display element according to 3.
る液晶滴下工法用シール剤。 A sealing agent for a liquid crystal dropping method comprising the curable resin composition for a liquid crystal display element according to claim 1, 2, 3 or 4.
の液晶滴下工法用シール剤と、導電性微粒子とを含有することを特徴とする上下導通用材
料。 A vertical guide comprising the curable resin composition for a liquid crystal display element according to claim 1, 2, 3 or 4, and / or the sealing agent for liquid crystal dropping method according to claim 5, and conductive fine particles. Common material.
てなることを特徴とする液晶表示素子。 A liquid crystal display element comprising the sealing agent for liquid crystal dropping method according to claim 5 and / or the material for vertical conduction according to claim 6.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007225772A (en) * | 2006-02-22 | 2007-09-06 | Mitsui Chemicals Inc | Liquid crystal sealing agent and liquid crystal display panel using the same |
JP2007225774A (en) * | 2006-02-22 | 2007-09-06 | Mitsui Chemicals Inc | Liquid crystal sealing agent and liquid crystal display panel using the same |
JP2008303362A (en) * | 2007-06-11 | 2008-12-18 | Hitachi Chem Co Ltd | Photocurable moisture-proof insulating paint, electronic part moisture insulated by using the paint and method for producing the same |
JP2009168985A (en) * | 2008-01-15 | 2009-07-30 | Sekisui Chem Co Ltd | Sealant for liquid crystal dropping construction method, vertical conducting material, and liquid crystal display element |
US8196916B2 (en) | 2008-09-22 | 2012-06-12 | Fujitsu Frontech Limited | Banknote depositing unit and insert/return unit attachable to and detachable from banknote depositing unit |
-
2004
- 2004-03-15 JP JP2004073422A patent/JP4452530B2/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007225772A (en) * | 2006-02-22 | 2007-09-06 | Mitsui Chemicals Inc | Liquid crystal sealing agent and liquid crystal display panel using the same |
JP2007225774A (en) * | 2006-02-22 | 2007-09-06 | Mitsui Chemicals Inc | Liquid crystal sealing agent and liquid crystal display panel using the same |
JP2008303362A (en) * | 2007-06-11 | 2008-12-18 | Hitachi Chem Co Ltd | Photocurable moisture-proof insulating paint, electronic part moisture insulated by using the paint and method for producing the same |
JP2009168985A (en) * | 2008-01-15 | 2009-07-30 | Sekisui Chem Co Ltd | Sealant for liquid crystal dropping construction method, vertical conducting material, and liquid crystal display element |
US8196916B2 (en) | 2008-09-22 | 2012-06-12 | Fujitsu Frontech Limited | Banknote depositing unit and insert/return unit attachable to and detachable from banknote depositing unit |
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