JPH0415623A - Colored spacer for liquid crystal display element - Google Patents
Colored spacer for liquid crystal display elementInfo
- Publication number
- JPH0415623A JPH0415623A JP12039890A JP12039890A JPH0415623A JP H0415623 A JPH0415623 A JP H0415623A JP 12039890 A JP12039890 A JP 12039890A JP 12039890 A JP12039890 A JP 12039890A JP H0415623 A JPH0415623 A JP H0415623A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- spacer
- crystal display
- particles
- display element
- 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.)
- Pending
Links
- 125000006850 spacer group Chemical group 0.000 title claims abstract description 32
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 65
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000011882 ultra-fine particle Substances 0.000 claims description 7
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 239000012798 spherical particle Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 235000019646 color tone Nutrition 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 206010024229 Leprosy Diseases 0.000 description 1
- 101150104182 MOB2 gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 235000005733 Raphanus sativus var niger Nutrition 0.000 description 1
- 244000155437 Raphanus sativus var. niger Species 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、液晶表示用パネルなどに使用される着色スペ
ーサーに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a colored spacer used in liquid crystal display panels and the like.
液晶表示素子においては、透明電極及び配向膜がそれぞ
れ形成された相対する一対の基板間に挾持される液晶層
の厚さを一定に保つために使用するスペーサーとして、
従来においては、ガラスファイバー、プラスチックビー
ズ、 Ｓｉｎ、、Ａ１□０３などが用いられてきた。そ
して最近では、大表示容量のＳＢＥあるいはＳＴＮと呼
ばれるモードの表示方式においても、高度に粒径が制御
された（真球に近い）有機高分子系球状スペーサーを用
いることにより、色ムラの低減が行なわれている。だが
、このような材料を用いて作製されたスペーサーは多く
が白色を呈しているため、光の散乱等により表示画像が
白化し、コントラスト比が低下するといった欠陥がある
。In a liquid crystal display element, a spacer is used to maintain a constant thickness of a liquid crystal layer sandwiched between a pair of opposing substrates each having a transparent electrode and an alignment film formed thereon.
Conventionally, glass fiber, plastic beads, Sin, A1□03, etc. have been used. Recently, color unevenness has been reduced by using organic polymer spherical spacers with highly controlled particle sizes (close to true spheres) in large display capacity SBE or STN mode display systems. It is being done. However, since most spacers made using such materials are white, they have defects such as whitening of the displayed image due to light scattering and a reduction in contrast ratio.
こうしたことの対策から原着スペーサーが提案され１合
成繊維を染料により着色または染色したもの（特開昭６
３−１５７１３０号公報）などが提案されているが、染
料を用いているため耐溶剤性や液晶分子との反応性等の
問題が残されている。また、有機溶剤や液晶に対して安
定であり固有の濃暗色を呈する金属酸化物も提案されて
いるが、このものは粒径を数−程度に均一に揃えること
は困難である。To solve this problem, a dope-dyed spacer was proposed.1 Synthetic fibers were colored or dyed with dyes (Japanese Unexamined Patent Publication No. 6
3-157130), but since dyes are used, problems such as solvent resistance and reactivity with liquid crystal molecules remain. Metal oxides that are stable to organic solvents and liquid crystals and exhibit a unique dark color have also been proposed, but it is difficult to uniformly arrange the particle size of these to several sizes.
本発明は上述の問題点を解消し、有機溶剤や液晶にたい
して安定で、しかも白化のない高コントラスト比、高表
示品質の液晶表示素子用着色スペーサーを提供すること
にある。The present invention solves the above-mentioned problems and provides a colored spacer for a liquid crystal display element that is stable against organic solvents and liquid crystals, has a high contrast ratio without whitening, and has high display quality.
本発明は透明電極および配向膜がそれぞれ形成された相
対する一対の基板間に挾持される液晶層の厚さを一定に
維持するのに用いられる液晶表示素子用着色スペーサー
において、そのスペーサーは５ｉｎ２及び／又は有機高
分子の球状微粒子表面に粒径が該球状微粒子より小さく
かつ０．１４以下の黒色金属酸化物超微粒子を打ち込ん
だものからなることを特徴としている。The present invention relates to a colored spacer for a liquid crystal display element used to maintain a constant thickness of a liquid crystal layer sandwiched between a pair of opposing substrates each having a transparent electrode and an alignment film formed thereon. /or It is characterized by comprising ultrafine black metal oxide particles having a particle size smaller than the spherical fine particles and 0.14 or less implanted onto the surface of the spherical fine particles of organic polymer.
本発明者は、前記課題を解決するために、液晶表示素子
用着色スペーサーについているいろ検討した結果、Ｓｉ
Ｏ□又は有機高分子球状微粒子（以降「母粒子」と称す
ることがある）の表面にこれよりも更に粒径が小さくて
黒色（黒褐色を含む）の金属酸化物超微粒子（以降「子
粒子」と称することがある）を打ち込んで得られたもの
が着色スペーサーとして有用であることを確めた。本発
明はこれによりなされたものである。In order to solve the above problem, the inventors of the present invention investigated various aspects of colored spacers for liquid crystal display elements, and found that Si
On the surface of O□ or organic polymer spherical fine particles (hereinafter sometimes referred to as ``mother particles''), ultrafine metal oxide particles (hereinafter referred to as ``child particles'') with a smaller particle size and black (including blackish brown) are formed. It has been confirmed that the product obtained by implanting the spacer (sometimes referred to as ``spacer'') is useful as a colored spacer. The present invention has been achieved thereby.
以下に本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
前記のように、本発明に係る着色スペーサーは母粒子表
面に、粒径が母粒子より小さくかつ０．１閥以下の黒色
子粒子を打ち込んだものからなっている。このものは特
に、一般的によく用いられているグレー系の偏光板を使
用した液晶表示素子において、高コントラスト比を得る
うえで、また、耐有機溶媒・液晶性に有効である。加え
て、黒色又はグレー系の偏光板を使用した液晶表示素子
においては、より見やすい高品質の表示が可能になる。As described above, the colored spacer according to the present invention is made of a matrix particle having a particle size smaller than that of the matrix particle and 0.1 μg or less implanted into the surface of the matrix particle. This material is particularly effective in obtaining a high contrast ratio and in improving resistance to organic solvents and liquid crystallinity in liquid crystal display devices using commonly used gray polarizing plates. In addition, a liquid crystal display element using a black or gray polarizing plate can provide a higher quality display that is easier to see.
母粒子の材料としては、子粒子を打ち込む必要から極度
に硬くないものであることと、均一な粒径の球状粒子が
作製しやすいものであることという条件により、ＳｉＯ
□や有機高分子等が選択される。As the material for the mother particles, SiO
□ and organic polymers are selected.
有機高分子としては例えばポリエチレン、ポリスチレン
、ベンゾグアナミン、ジビニルベンゼン誘導体などがあ
げられる。母粒子の粒径は、液晶表示素子において設定
した液晶層の厚さに応じて選ばれてよく、通常、一般的
な表示方式（Ｔ〜、５ＴＩＩＩなと）において用いられ
る液晶層厚から１〜２０癖程度が好ましい。Examples of organic polymers include polyethylene, polystyrene, benzoguanamine, and divinylbenzene derivatives. The particle size of the base particles may be selected depending on the thickness of the liquid crystal layer set in the liquid crystal display element, and is usually 1 to 1 from the liquid crystal layer thickness used in general display systems (T~, 5TIII, etc.). Approximately 20 habits are preferable.
子粒子としては、その粒径が小さいほど良好である。こ
れは打ち込み後のスペーサー粒子表面は子粒子の粒径が
小さいほど凹凸が小さく滑らかなものとなり、また粒径
分布の変化も小さくなるので、液晶層厚のバラツキによ
る表示ムラも低減することになるためである。従って、
子粒子は、具体的には、粒径が母粒子より小さく、かつ
、その粒径はＯ，ｌｐ８以下、好ましくは０．０８．以
下、さらに好ましくはＯ，ＯＳ、以下の超微粒子である
。更には、子粒子は母粒子表面を被覆するように打だ込
まれることから、子粒子の粒径は母粒子の粒径の１７１
０〜１／１０００ ＜らいに設定されているのが望まし
い。子粒子は超微粒子化が可能であること、有機溶剤や
液晶に対して安定であること等から黒色（黒褐色を含む
）の金属酸化物が選ばれる。As for child particles, the smaller the particle size, the better. This is because the surface of the spacer particle after implantation becomes smoother with fewer irregularities as the particle size of the child particle becomes smaller, and changes in particle size distribution are also smaller, which reduces display unevenness due to variations in the liquid crystal layer thickness. It's for a reason. Therefore,
Specifically, the child particles have a particle size smaller than the mother particle, and the particle size is 0.1p8 or less, preferably 0.08. More preferred are O, OS, and the following ultrafine particles. Furthermore, since the child particles are implanted so as to cover the surface of the mother particle, the particle size of the child particles is 171 times smaller than that of the mother particle.
It is desirable to set it to 0 to 1/1000 < leprosy. A black (including blackish brown) metal oxide is selected as the child particle because it can be made into ultrafine particles and is stable against organic solvents and liquid crystals.
超微粒子の製法は数多くあるが、例えばガス中蒸発法の
ような乾式法においても、沈殿法のような湿式法におい
ても、金属酸化物は最も作製しやすいものであり、殊に
、粒径が０．０５癖以下で粒度が均一な超微粒子の作製
が可能である。There are many methods for producing ultrafine particles, but metal oxides are the easiest to produce, whether by dry methods such as evaporation in gas or wet methods such as precipitation. It is possible to produce ultrafine particles with a uniform particle size of 0.05 or less.
黒色及び黒褐色を呈する代表的な酸化物として次のもの
があげられ、適宜選ばれてよい。Typical oxides exhibiting black and blackish brown colors include the following, which may be selected as appropriate.
Ａｇｏ、Ｃｒｙ、Ｃｒｙ□、Ｃｒ２Ｏ，、ＧｅＯ，Ｃｏ
２０゜Ｃｏ、 ０４． ＦｅＯ、Ｆｅ、 ０４． Ｔｅ
Ｏ、ＣｕＯ、Ｐｂ０２ＮｂＯ，Ｐｔ、０４．ＰｔＯ２，
Ｖ２Ｃ１３，ＢｉＯ，Ｍｎ、０゜ＭｎｚＯ，、ＭｎＯ，
、Ｍｏｂ、Ｍｏｂ２実際に、本発明に係る着色スペーサ
ーをつくるには、母粒子表面が子粒子で被覆されるくら
いの量、即ち、大略母粒子に対し１〜３０重量％重量％
子粒子を例えばハイブリダイザ−〇型を用いて打ち込む
ようにすればよい。Ago, Cry, Cry□, Cr2O,, GeO, Co
20°Co, 04. FeO, Fe, 04. Te
O, CuO, Pb02NbO, Pt, 04. PtO2,
V2C13, BiO, Mn, 0°MnzO,, MnO,
, Mob, Mob2 Actually, in order to make the colored spacer according to the present invention, the amount of the mother particle is such that the surface of the mother particle is covered with child particles, that is, approximately 1 to 30% by weight based on the mother particle.
The child particles may be implanted using, for example, a hybridizer type O.
実施例１ 母粒子として平均粒径約８．２癖の５ｉｎ２球状粒子。 Example 1 The base particles are 5in2 spherical particles with an average particle diameter of approximately 8.2cm.
子粒子として平均粒径約０．１ＭのＦｅ、 ０４超微粒
子を用い、母粒子にだいし子粒子約５重量２をハイブリ
ダイザ−〇型を用いて打ち込みを行い、充分な色調の黒
色を呈した粉末（スペーサー粒子）を得た。Fe, 04 ultrafine particles with an average particle size of about 0.1M were used as child particles, and about 5 weight 2 of diamond particles were implanted into the mother particles using a hybridizer type ○, resulting in a powder with a sufficient black color tone. (Spacer particles) were obtained.
これを電子顕微鏡で観察したところ、母粒子の表面が子
粒子によりほぼ均一に被覆されているのが確認され、平
均粒径は約８．３．であった。この得られたスペーサー
粒子は、アルコール系などの有機溶媒および液晶との反
応を示さなかった。When this was observed using an electron microscope, it was confirmed that the surface of the mother particle was almost uniformly covered with child particles, and the average particle size was about 8.3. Met. The obtained spacer particles showed no reaction with organic solvents such as alcohols and liquid crystals.
このスペーサー粒子及び黒色偏光板などを用いて液晶表
示素子を作製したところ、高コントラストや色調におい
て、従来の白色スペーサーや黒色スペーサーを用いた場
合に比べ高い表示品質を示した。When a liquid crystal display element was manufactured using these spacer particles and a black polarizing plate, it showed higher display quality in terms of contrast and color tone than when conventional white spacers or black spacers were used.
実施例２
母粒子として平均粒径的７．５μｓのジビニルベンゼン
誘導体の球状粒子、子粒子として平均粒径的０．０５４
のＣｕＯ超微粒子を用い、母粒子にだいし子粒子１０重
量２をハイブリダイザ−〇型を用いて打ち込みを行ない
、充分な色調の黒色を呈した粉末（スペーサー粒子）を
得た。これを電子顕微鏡で観察したところ、母粒子の表
面が子粒子によりほぼ均一に被覆されているのが確認さ
れ、平均粒径は約７．６癖であった。この得られたスペ
ーサー粒子は、アルコール系などの有機溶媒および液晶
との反応を示さなかった。Example 2 Spherical particles of divinylbenzene derivative with an average particle diameter of 7.5 μs as the mother particles, and 0.054 in average particle diameter as the child particles
Using CuO ultrafine particles, 10 parts by weight of 2 parts by weight of daikon particles were implanted into the base particles using a hybridizer type O to obtain a powder (spacer particles) exhibiting a sufficient black color tone. When this was observed using an electron microscope, it was confirmed that the surface of the mother particles was almost uniformly covered with child particles, and the average particle size was about 7.6 mm. The obtained spacer particles showed no reaction with organic solvents such as alcohols and liquid crystals.
このスペーサー粒子及び黒色偏光板などを用いて液晶表
示素子を作製したところ、コントラストや色調において
、従来の白色スペーサーや黒色スペーサーを用いた場合
に比べ高い表示品質を示した。When a liquid crystal display element was manufactured using these spacer particles and a black polarizing plate, it showed higher display quality in terms of contrast and color tone than when conventional white spacers or black spacers were used.
実施例から明らかなように、本発明によれば充分な色調
の黒色を呈し、かつ、有機溶媒や液晶に対し安定な球状
のスペーサーが提供されるので、グレー系の偏光板を用
いた場合においても、白化がなく、コントラストや色調
の点においても優れた液晶表示素子を提供できる。As is clear from the examples, the present invention provides a spherical spacer that exhibits a sufficient black tone and is stable against organic solvents and liquid crystals. Also, it is possible to provide a liquid crystal display element that does not cause whitening and has excellent contrast and color tone.
特許出願人 株式会社 リ コPatent applicant Rico Co., Ltd.
Claims (1)
する一対の基板間に挾持される液晶層の厚さを一定に維
持するのに用いられる液晶表示素子用スペーサーにおい
て、該スペーサーはＳｉＯ＿２及び／又は有機高分子球
状微粒子の表面に該球状微粒子の粒径より小さく、かつ
、粒径０．１μｍ以下の黒色の金属酸化物超微粒子が打
ち込まれたものであることを特徴とする液晶表示素子用
着色スペーサー。(1) In a spacer for a liquid crystal display element used to maintain a constant thickness of a liquid crystal layer sandwiched between a pair of opposing substrates on which transparent electrodes and alignment films are respectively formed, the spacer is made of SiO_2 and/or Or for a liquid crystal display device, characterized in that black metal oxide ultrafine particles smaller than the particle size of the spherical particles and having a particle size of 0.1 μm or less are implanted onto the surface of the spherical particles of organic polymer. colored spacers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12039890A JPH0415623A (en) | 1990-05-09 | 1990-05-09 | Colored spacer for liquid crystal display element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12039890A JPH0415623A (en) | 1990-05-09 | 1990-05-09 | Colored spacer for liquid crystal display element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0415623A true JPH0415623A (en) | 1992-01-21 |
Family
ID=14785224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12039890A Pending JPH0415623A (en) | 1990-05-09 | 1990-05-09 | Colored spacer for liquid crystal display element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0415623A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5559621A (en) * | 1993-07-22 | 1996-09-24 | Toppan Printing Co., Ltd. | Liquid crystal having a plurality of rectilinear barrier members |
| US6246456B1 (en) * | 1993-12-27 | 2001-06-12 | Matsushita Electric Industrial Co., Ltd. | Liquid-crystal panel of polymer dispersed type, method of manufacturing the same, and liquid-crystal display apparatus |
| JP2004046205A (en) * | 2003-07-31 | 2004-02-12 | Hayakawa Rubber Co Ltd | Spacer for electro-optic panel, spacer for laminated glass and filler for coating material |
-
1990
- 1990-05-09 JP JP12039890A patent/JPH0415623A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5559621A (en) * | 1993-07-22 | 1996-09-24 | Toppan Printing Co., Ltd. | Liquid crystal having a plurality of rectilinear barrier members |
| US6246456B1 (en) * | 1993-12-27 | 2001-06-12 | Matsushita Electric Industrial Co., Ltd. | Liquid-crystal panel of polymer dispersed type, method of manufacturing the same, and liquid-crystal display apparatus |
| JP2004046205A (en) * | 2003-07-31 | 2004-02-12 | Hayakawa Rubber Co Ltd | Spacer for electro-optic panel, spacer for laminated glass and filler for coating material |
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