JP3479285B2 - Liquid crystal display element spacer, liquid crystal display device, and method of manufacturing liquid crystal display element spacer - Google Patents
Liquid crystal display element spacer, liquid crystal display device, and method of manufacturing liquid crystal display element spacerInfo
- Publication number
- JP3479285B2 JP3479285B2 JP2001025544A JP2001025544A JP3479285B2 JP 3479285 B2 JP3479285 B2 JP 3479285B2 JP 2001025544 A JP2001025544 A JP 2001025544A JP 2001025544 A JP2001025544 A JP 2001025544A JP 3479285 B2 JP3479285 B2 JP 3479285B2
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- fine particles
- crystal display
- spacer
- core
- 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.)
- Expired - Fee Related
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims description 82
- 125000006850 spacer group Chemical group 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000010419 fine particle Substances 0.000 claims description 117
- 229920000642 polymer Polymers 0.000 claims description 32
- 238000010559 graft polymerization reaction Methods 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 26
- 239000010410 layer Substances 0.000 claims description 25
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 229910001872 inorganic gas Inorganic materials 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 238000009832 plasma treatment Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 11
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000011247 coating layer Substances 0.000 claims description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000007771 core particle Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims 1
- 239000011859 microparticle Substances 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 43
- 239000002245 particle Substances 0.000 description 31
- 230000002159 abnormal effect Effects 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 210000002858 crystal cell Anatomy 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 229920000592 inorganic polymer Polymers 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000013626 chemical specie Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- ACOGMWBDRJJKNB-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.CC(O)=O ACOGMWBDRJJKNB-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Graft Or Block Polymers (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液晶セル内に配置
される液晶表示素子用スペーサ、液晶表装置及び液晶表
示素子用スペーサの製造方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a liquid crystal display device spacer disposed within the liquid crystal cell, liquid crystal display devices and liquid crystal display
The present invention relates to a method for manufacturing a spacer for a display element .
【０００２】[0002]
【従来の技術】液晶表示素子は、パソコン、携帯型電子
機器等に広く用いられている。かかる液晶表示素子等の
液晶表示装置には、貼合わされた２枚の透明電極基板間
の間隙を一定に保持するため、スペーサが用いられてい
る。2. Description of the Related Art Liquid crystal display devices are widely used in personal computers, portable electronic devices and the like. In a liquid crystal display device such as the liquid crystal display element, a spacer is used in order to maintain a constant gap between the two bonded transparent electrode substrates.
【０００３】[0003]
【発明が解決しようとする課題】かかる液晶表示素子に
おいて、液晶とスペーサとの界面で、液晶分子の配向が
変則的になり、表示品質を低下させることが知られてい
る。特に、最近盛んに用いられているスーパーツイステ
ッドネマチック液晶（ＳＴＮ液晶）や薄膜トランジスタ
（ＴＦＴ）を用いた液晶表示素子においては、かかる液
晶の異常配向現象が問題として取り上げられることが多
い。In such a liquid crystal display device, it is known that the alignment of liquid crystal molecules becomes irregular at the interface between the liquid crystal and the spacer, which deteriorates the display quality. In particular, in a liquid crystal display element using a super twisted nematic liquid crystal (STN liquid crystal) or a thin film transistor (TFT) which has been widely used recently, such an abnormal alignment phenomenon of the liquid crystal is often taken up as a problem.
【０００４】かかる液晶の異常配向が起こると、スペー
サの周囲に光抜けと呼ばれる明るく光る領域が観察され
る。かかる光抜けの面積が大きくかつその個数が多い
と、本来黒地であるべき画面の広範な部分で白地の光抜
けが混在することとなり、液晶表示画面のコントラスト
が低下し、表示品質を著しく低下させる。When such abnormal orientation of the liquid crystal occurs, brightly shining regions called light leakage are observed around the spacers. When the area of such light leakage is large and the number thereof is large, light leakage of white background is mixed in a wide area of the screen which should originally be a black background, and the contrast of the liquid crystal display screen is deteriorated, and the display quality is remarkably deteriorated. .
【０００５】また、ノーマリーブラックモードの液晶表
示素子においては、電圧がＯＦＦ状態で黒（暗）色で表
示されるべき部分の特定のスペーサが、外部からの入射
光により光り、液晶表示画面のコントラストが低下し、
表示品質を著しく低下させることがある。Further, in a normally black mode liquid crystal display element, a specific spacer in a portion which is to be displayed in black (dark) color when the voltage is OFF is illuminated by an incident light from the outside, and a liquid crystal display screen is displayed. The contrast is reduced,
Display quality may be significantly reduced.
【０００６】さらに、近年、モバイル用途やタッチパネ
ル用途向けの液晶表示素子が増えている。かかる液晶表
示素子には、パネルに振動が伝わったり、大きい衝撃力
がかかったりする。この際、ガラス基板に歪みが生じ、
液晶層のギャップを均一に保つべく組み込まれているス
ペーサが移動してしまい、液晶表示面全体に均一に配置
されていたスペーサが不均一になり、表示品質が著しく
低下する。Further, in recent years, liquid crystal display elements for mobile applications and touch panel applications have been increasing. Vibrations are transmitted to the panel and a large impact force is applied to the liquid crystal display element. At this time, distortion occurs in the glass substrate,
The spacers incorporated to keep the gap of the liquid crystal layer uniform move, and the spacers arranged uniformly on the entire liquid crystal display surface become non-uniform, resulting in a significant deterioration in display quality.
【０００７】本発明は、かかる液晶表示素子の異常配向
や白抜け、固着不良を抑えることができる、スペーサと
して有用な、新規な微粒子を得ることを課題とする。It is an object of the present invention to obtain novel fine particles useful as a spacer, which can suppress such abnormal alignment, white spots and defective fixation of the liquid crystal display element.
【０００８】[0008]
【課題を解決するための手段】本発明は、液晶表示セル
内に配置される液晶表示素子用スペーサであって、前記
液晶表示素子用スペーサが、コア微粒子と前記コア微粒
子の表面の被覆層とから形成されている微粒子からな
り、前記コア微粒子が重合体からなり、前記被覆層が、
前記コア微粒子の非重合性無機ガス雰囲気中での低温プ
ラズマ処理によって活性化された前記コア微粒子の表面
のラジカルとビニルモノマーとの結合によるグラフト重
合層から形成されている、液晶表示素子用スペーサ及び
かかる液晶表示素子用スペーサを用いる液晶表示装置に
係るものである。The present invention is a liquid crystal display cell.
A spacer for a liquid crystal display element arranged in
The liquid crystal display element spacer is made of fine particles formed of core fine particles and a coating layer on the surface of the core fine particles .
Ri, wherein the core fine particles are made of a polymer, said coating layer,
A spacer for a liquid crystal display device, which is formed of a graft polymerization layer formed by bonding radicals and vinyl monomers on the surface of the core fine particles activated by low-temperature plasma treatment of the core fine particles in a non-polymerizable inorganic gas atmosphere, and The present invention relates to a liquid crystal display device using the spacer for a liquid crystal display element.
【０００９】また、本発明は、液晶表示セル内に配置さ
れる、液晶表示素子用スペーサを得るにあたり、前記液
晶表示素子用スペーサが、コア微粒子と前記コア微粒子
の表面の被覆層とから形成されている微粒子からなり、
前記コア微粒子が重合体から形成されており、前記コア
微粒子を非重合性の無機ガス雰囲気中で低温プラズマ処
理して、前記コア微粒子の表面を活性化し、前記コア微
粒子の表面のラジカルとビニルモノマーとを結合させ、
前記コア微粒子の表面にグラフト重合層からなる前記被
覆層を形成する、液晶表示素子用スペーサの製造方法に
係るものである。Further, the present invention is arranged in a liquid crystal display cell.
In order to obtain a spacer for a liquid crystal display element,
The crystal display element spacer comprises fine particles formed of core fine particles and a coating layer on the surface of the core fine particles ,
The core fine particles are formed of a polymer, and the core fine particles are subjected to low-temperature plasma treatment in a non-polymerizable inorganic gas atmosphere to activate the surface of the core fine particles, radicals and vinyl monomers on the surface of the core fine particles. Combine and
The present invention relates to a method for manufacturing a spacer for a liquid crystal display device , which comprises forming the coating layer made of a graft polymerization layer on the surface of the core fine particles.
【００１０】本発明者は、液晶表示素子のスペーサとし
て有用な微粒子を得るため、種々の微粒子を試作し、検
討した。The present inventor made various kinds of fine particles as trials and studied in order to obtain fine particles useful as a spacer for a liquid crystal display device.
【００１１】その結果、本発明者は、重合体から形成さ
れたコア微粒子を、非重合性の無機ガス雰囲気中で低温
プラズマ処理することにより、かかるコア微粒子の表面
が活性化され、かかるコア微粒子の表面とビニルモノマ
ーとを反応させることで、かかるコア微粒子の表面がグ
ラフト重合層で被覆された微粒子が得られることを見出
した。As a result, the inventors of the present invention activated the surface of the core fine particles by subjecting the core fine particles formed of the polymer to low temperature plasma treatment in a non-polymerizable inorganic gas atmosphere. It was found that by reacting the surface of the above with the vinyl monomer, fine particles in which the surface of such core fine particles is covered with a graft polymerization layer can be obtained.
【００１２】また、本発明者は、かかる微粒子が、液晶
表示素子の異常配向を抑え、液晶表示素子用スペーサと
して極めて有用であることを突き止め、本発明に到達し
た。Further, the present inventor found out that such fine particles are extremely useful as a spacer for a liquid crystal display element by suppressing abnormal orientation of the liquid crystal display element, and arrived at the present invention.
【００１３】本発明では、所定のコア微粒子の表面が、
非重合性の無機ガス雰囲気中での低温プラズマ処理によ
って、活性化される。In the present invention, the surface of the predetermined core fine particles is
It is activated by a low temperature plasma treatment in a non-polymerizable inorganic gas atmosphere.
【００１４】かかる活性化は、非重合性の無機ガスが低
温プラズマ処理によって励起されたりイオン化して化学
的活性種となり、かかる化学的活性種が通常の熱励起で
は困難な化学反応を所定のコア微粒子の表面に起こすこ
とによる。In the activation, the non-polymerizable inorganic gas is excited by a low temperature plasma treatment or ionized to become a chemically active species, and the chemically active species causes a chemical reaction which is difficult by ordinary thermal excitation to a predetermined core. It is caused on the surface of fine particles.
【００１５】本発明では、かかる活性化されたコア微粒
子の表面には、コア微粒子の素材に由来するラジカルが
生じ、かかるラジカルとビニルモノマーとの間で、グラ
フト重合が開始される。In the present invention, radicals derived from the material of the core fine particles are generated on the surface of the activated core fine particles, and the graft polymerization is initiated between the radicals and the vinyl monomer.
【００１６】結果として、本発明では、かかるグラフト
重合によって、所定のコア微粒子の表面が、グラフト重
合層からなる被覆層で覆われる。As a result, in the present invention, the surface of the predetermined core fine particles is covered with the coating layer composed of the graft polymerization layer by such graft polymerization.
【００１７】本発明にかかる微粒子によれば、所定のコ
ア微粒子の表面が、通常の熱励起では困難な化学反応に
よるグラフト重合層で覆われるので、かかるコア微粒子
とグラフト重合層との密着性に優れ、グラフト重合層の
被覆率に優れる。According to the fine particles of the present invention , the surface of the predetermined core fine particles is covered with the graft polymerization layer due to a chemical reaction which is difficult by ordinary thermal excitation, so that the adhesion between the core fine particles and the graft polymerization layer is improved. Excellent and excellent coverage of the graft polymerization layer.
【００１８】また、本発明にかかる微粒子によれば、所
定のコア微粒子の表面にある水酸基等の活性基が十分に
被覆されるほどにグラフト重合層が形成されるので、ス
ペーサとして用いると、液晶表示素子の異常配向を抑え
たり、ポリイミド膜との固着性に優れる。Further, according to the fine particles of the present invention , the graft polymerization layer is formed to such an extent that the active groups such as hydroxyl groups on the surface of the predetermined core fine particles are sufficiently covered. It suppresses abnormal orientation of the display element and has excellent adhesion to the polyimide film.
【００１９】[0019]
【発明の実施の形態】本発明の実施の形態を説明する。
本発明で用いるプラズマとは、原子や分子が電子とイオ
ンに電離した気体を言い、低温プラズマは、低圧下にお
ける気体の放電現象である。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described.
The plasma used in the present invention is a gas in which atoms and molecules are ionized into electrons and ions, and low temperature plasma is a gas discharge phenomenon under low pressure.
【００２０】低温プラズマでは、内部の気体分子はイオ
ン化や解離、あるいは励起失活を繰り返しており、イオ
ンと同数の自由電子を含み、電気的には全体として中性
になっている。In the low temperature plasma, the gas molecules inside are repeatedly ionized, dissociated, or excited and deactivated, contain the same number of free electrons as the ions, and are electrically neutral as a whole.
【００２１】これらの化学種が衝突することにより、コ
ア微粒子の表面にさまざまな化学変化が起こる。これを
利用して、コア微粒子の表面をプラズマ処理することが
できる。低温と呼ばれるが、運動エネルギーによって定
義される自由電子の温度は、２〜３万Ｋ程度が典型的な
値である。The collision of these chemical species causes various chemical changes on the surface of the core fine particles. By utilizing this, the surface of the core fine particles can be plasma-treated. Although called low temperature, the temperature of free electrons defined by kinetic energy is typically about 20,000 to 30,000K.
【００２２】一方、イオン、ラジカル等の化学種の温度
は、これに比べると数百℃のオーダーであって、しかも
低圧力下であるので、処理物の温度は事実上常温であ
り、好ましい処理が行える。On the other hand, the temperature of chemical species such as ions and radicals is on the order of several hundreds of degrees Celsius in comparison with this, and under a low pressure, the temperature of the treated material is practically room temperature, which is a preferable treatment. Can be done.
【００２３】本発明では、プラズマ処理を施す基になる
微粒子をコア微粒子と称する。コア微粒子としては、重
合体から形成されていれば特に制限はないが、プラズマ
で表面が活性になるものを用いる。かかるコア微粒子
は、有機質重合体微粒子又は無機質重合体微粒子を問わ
ず用いることができる。In the present invention, the fine particles serving as a base for plasma treatment are called core fine particles. The core fine particles are not particularly limited as long as they are formed of a polymer, but those whose surface is activated by plasma are used. Such core fine particles can be used regardless of whether they are organic polymer fine particles or inorganic polymer fine particles.
【００２４】有機質重合体のコア微粒子は、アクリル酸
エステル系重合体、スチレン系重合体、ナイロン系重合
体、ウレタン系重合体、ポリエチレン系重合体、ポリエ
ステル系重合体及びポリ酢酸ビニルエチレン系重合体か
らなる群より選ばれる少なくとも１種の重合体から形成
することができる。Core fine particles of an organic polymer include acrylic acid ester-based polymers, styrene-based polymers, nylon-based polymers, urethane-based polymers, polyethylene-based polymers, polyester-based polymers and polyvinyl acetate-ethylene-based polymers. It can be formed from at least one polymer selected from the group consisting of
【００２５】これらの重合体から形成されるコア微粒子
は、３次元網目構造を有し、熱可塑性でなく、有機溶剤
に不溶である。かかるコア微粒子から形成される微粒子
は、液晶セル組み立て工程時のポリイミド焼付け（２５
０℃）において、ギャップ制御性が損なわれる可能性が
低い。Core fine particles formed of these polymers have a three-dimensional network structure, are not thermoplastic, and are insoluble in organic solvents. The fine particles formed from such core fine particles are printed by polyimide baking (25
At 0 ° C.), the gap controllability is unlikely to be impaired.
【００２６】本発明ではまた、有機質重合体及び無機質
重合体の少なくとも一方の材料を用いた、コアシェル型
のハイブリッド微粒子をコア微粒子として用いることも
できる。かかる場合、コアシェル型のコア部分やシェル
部分には、有機質重合体及び無機質重合体の少なくとも
一方の材料を用いることができる。In the present invention, core-shell type hybrid fine particles using at least one material of organic polymers and inorganic polymers can also be used as core fine particles. In such a case, at least one of an organic polymer and an inorganic polymer can be used for the core-shell type core portion or shell portion.
【００２７】本発明にかかる無機ガスは、非重合性であ
れば特に制限されることはなく、常温等で気体の無機ガ
スを用いることができ、無機物をガス化したものも用い
ることができる。The inorganic gas according to the present invention is not particularly limited as long as it is non-polymerizable, and an inorganic gas that is a gas at room temperature or the like can be used, and a gasified inorganic material can also be used.
【００２８】かかる無機ガスとしては、例えば、酸素、
アルゴン及び窒素からなる群より選ばれる少なくとも1
種のガスを用いることができる。Examples of such an inorganic gas include oxygen,
At least one selected from the group consisting of argon and nitrogen
Seed gases can be used.
【００２９】本発明にかかるビニルモノマーは、特に制
限はないが、通常の減圧下でモノマー蒸気として、もし
くは、水溶液や水中乳化液として用いることができるも
のが好ましい。The vinyl monomer according to the present invention is not particularly limited, but those which can be used as a monomer vapor under ordinary reduced pressure, or as an aqueous solution or an emulsion in water are preferable.
【００３０】かかるビニルモノマーとしては、例えば、
アクリルアミド等のアクリルアミド系モノマー、アクリ
ル酸エチル等のアクリル酸エステル、メタクリル酸メチ
ルやメタクリル酸等のメタクリル酸エステル系モノマ
ー、スチレンやジビニルベンゼン等のスチレン系ビニル
モノマー、１−オクテンや１，４−ブタジエン等の不飽
和ビニルモノマー等からなる群より選ばれる１種か又は
それらの２種以上を併用して用いることができる。Examples of such vinyl monomers include
Acrylamide-based monomers such as acrylamide, acrylic acid esters such as ethyl acrylate, methacrylic acid ester-based monomers such as methyl methacrylate and methacrylic acid, styrene-based vinyl monomers such as styrene and divinylbenzene, 1-octene and 1,4-butadiene. These can be used alone or in combination of two or more selected from the group consisting of unsaturated vinyl monomers and the like.
【００３１】本発明では、かかるビニルモノマーのグラ
フト重合層を、従来の化学修飾法とは異なり、プラズマ
開始グラフト重合法によって、活性化されたコア微粒子
の表面のラジカルとビニルモノマーとを反応させて形成
する。In the present invention, unlike the conventional chemical modification method, the graft polymerization layer of the vinyl monomer is prepared by reacting the radicals on the surface of the activated core fine particles with the vinyl monomer by the plasma initiation graft polymerization method. Form.
【００３２】プラズマグラフト重合法は、以前より、繊
維や特定の粉体の表面処理方法（カーボンブラックの親
水性を高める等）として知られている（例えば、色材協
会誌１９９０年，６３巻，３号，１６３〜１７０頁，近
畿大学，伊藤征司郎著）。The plasma graft polymerization method has long been known as a surface treatment method for fibers and specific powders (for example, increasing the hydrophilicity of carbon black) (see, for example, Coloring Materials Society, Vol. 63, Vol. 3, pp. 163-170, Kinki University, Seijiro Ito).
【００３３】しかし、本発明で用いる反応は、プラズマ
開始グラフト重合法で、かかる反応では、所定のコア微
粒子をプラズマ照射で活性化した後、減圧等の条件下、
気相又は溶液中で、かかる活性化されたコア微粒子とビ
ニルモノマーとを反応させ、ビニルモノマーをグラフト
重合させる。However, the reaction used in the present invention is a plasma-initiated graft polymerization method. In such a reaction, after activating predetermined core fine particles by plasma irradiation, the reaction is carried out under reduced pressure or the like.
The activated core fine particles are reacted with a vinyl monomer in a gas phase or in a solution to graft polymerize the vinyl monomer.
【００３４】プラズマ開始グラフト重合は、２段階の操
作によって行う。１段階目では、酸素、アルゴン等の非
重合性の無機ガス中で、コア微粒子にプラズマ照射を行
い、コア微粒子の表面を活性化させ、コア微粒子の表面
にラジカルを形成する。Plasma-initiated graft polymerization is carried out in a two-step operation. In the first stage, the core fine particles are irradiated with plasma in a non-polymerizable inorganic gas such as oxygen or argon to activate the surface of the core fine particles and form radicals on the surface of the core fine particles.
【００３５】２段階目は、その状態もしくは不活性ガス
等を入れ、空気を遮断した系でグラフト化反応を進行さ
せる。これは、プラズマ照射によって生成したコア微粒
子の表面のラジカルが、酸素等によって失活しないよう
にして、グラフト重合反応が阻害されないようにするた
めである。In the second stage, the grafting reaction is allowed to proceed in that state or with an inert gas or the like being introduced and the system in which air is shut off. This is to prevent the radicals on the surface of the core fine particles generated by the plasma irradiation from being deactivated by oxygen or the like so that the graft polymerization reaction is not hindered.
【００３６】例えば、かかるプラズマ開始グラフト重合
は、以下のように行う。
１段階目：コア微粒子１００ｇを１０００ｍｌ容の反応
容器に入れ、系を０．０３トール（４Ｐａ、以下１ｔｏ
ｒｒ≒１３３Ｐａで換算）以下に脱気する。For example, such plasma-initiated graft polymerization is carried out as follows. First stage: 100 g of the core fine particles are put into a reaction container of 1000 ml capacity, and the system is set to 0.03 torr (4 Pa, 1 ton below).
Degas to below rr ≈ 133 Pa).
【００３７】次いで、プラズマ照射のための酸素又はア
ルゴンガスを流し、流量を調節しながら、反応容器内が
０．５トール（６７Ｐａ）程度の圧力で安定したところ
で、反応容器を回転させながら、出力と処理時間を変え
てプラズマ照射を行う。Then, oxygen or argon gas for plasma irradiation is flown, the flow rate is adjusted, and when the inside of the reaction vessel is stabilized at a pressure of about 0.5 Torr (67 Pa), the reaction vessel is rotated and output is performed. Plasma irradiation is performed by changing the processing time.
【００３８】２段階目：プラズマ照射後、重合性ガスを
反応容器内に流したり、予め脱気して装置に接続させて
おいた重合性モノマー水溶液（または、水中乳化液）３
００ｍｌを反応容器内の減圧を利用して吸引させる。Second stage: After the plasma irradiation, the polymerizable gas is flown into the reaction vessel or the polymerizable monomer aqueous solution (or emulsion in water) which is degassed in advance and connected to the apparatus 3
00 ml is aspirated using the vacuum in the reaction vessel.
【００３９】この時点では、反応容器内の圧力は、大気
圧に達していないので、反応容器内への空気の侵入を防
ぐために、窒素ガスのような不活性ガスによって反応容
器内をほぼ大気圧等の環境圧にするか、環境圧よりも高
い圧力の下で、所定の時間、グラフト反応を進行させ
る。At this point in time, the pressure in the reaction vessel has not reached atmospheric pressure. Therefore, in order to prevent the invasion of air into the reaction vessel, the pressure in the reaction vessel is reduced to almost atmospheric pressure by an inert gas such as nitrogen gas. The graft reaction is allowed to proceed for a predetermined time under an environmental pressure such as the above or under a pressure higher than the environmental pressure.
【００４０】得られたグラフト重合物のグラフト率は、
反応後試料を適当な溶剤で濾過洗浄して、未反応物やホ
モポリマーを除去した後、乾燥し反応前後の重量比を調
べたり、処理前後のコア微粒子の粒子径から変化量を算
出して知ることができる。The graft ratio of the obtained graft polymer is
After the reaction, the sample is filtered and washed with an appropriate solvent to remove unreacted substances and homopolymers, and then dried to check the weight ratio before and after the reaction, and to calculate the amount of change from the particle size of the core fine particles before and after the treatment. I can know.
【００４１】本発明にかかる微粒子は、一対の液晶表示
セル内に配置される、液晶表示素子用スペーサとして用
いることができ、また、一対の基板とかかる各基板の間
を所定の間隔に維持するスペーサとかかる各基板の間に
介在する液晶とを備える、液晶表示装置において、スペ
ーサとして用いることができる。Particles in accordance with the [0041] present invention is placed within a pair of liquid crystal display cells, can be used as a spacer for a liquid crystal display device, also maintains between the substrate according a pair of substrates a predetermined distance It can be used as a spacer in a liquid crystal display device including a spacer and liquid crystal interposed between the substrates.
【００４２】本発明にかかる微粒子を、かかる液晶表示
素子用スペーサ、すなわち液晶セルスペーサとする場
合、かかる微粒子は、真球状の形状であるのがよく、１
〜１５μｍの平均粒径がよい。その理由は、薄い液晶層
を得るには、平均粒径のなるべく小さな液晶表示素子用
スペーサを用いるのが好ましいが、この範囲の平均粒径
の微粒子を用いると、液晶のカイラルピッチ（螺旋階段
状に３６０°回転するピッチ）に基づき、鮮明な画像が
得られるからである。また、更に好ましくは、かかる微
粒子の平均粒径は、３〜１０μｍである。When the fine particles according to the present invention are used as such a spacer for a liquid crystal display element, that is, a liquid crystal cell spacer, it is preferable that the fine particles have a spherical shape.
An average particle size of ˜15 μm is good. The reason is that in order to obtain a thin liquid crystal layer, it is preferable to use a spacer for a liquid crystal display element having an average particle diameter as small as possible. However, when fine particles having an average particle diameter in this range are used, the chiral pitch (spiral step shape) of the liquid crystal is used. This is because a clear image can be obtained based on the pitch of 360 ° rotation). Moreover, more preferably, the average particle diameter of the fine particles is 3 to 10 μm.
【００４３】本発明にかかる微粒子は、基となるコア微
粒子（内核）にプラズマ処理を施し、その活性化した表
面にビニルモノマーをグラフト反応させ、グラフト重合
層（外殻：シェル）を形成する。In the fine particles according to the present invention , the core fine particles (inner core) serving as a base are subjected to plasma treatment, and a vinyl monomer is graft-reacted on the activated surface to form a graft polymerization layer (outer shell: shell).
【００４４】形成するシェルの厚みは、目的によって異
なり、特に限定されるものではないが、例えば、液晶表
示素子用スペーサとして、異常配向防止処理や固着性向
上を目的とした場合、コア微粒子の直径の１／１００〜
１／１０が好ましい。シェルの厚さがコア微粒子の直径
の１／１００未満では、シェルによって覆う効果が得ら
れ難く、１／１０を超えると、液晶表示素子用スペーサ
としての十分な圧縮物性が得られ難くなる。The thickness of the shell to be formed varies depending on the purpose and is not particularly limited. For example, in the case of a spacer for a liquid crystal display element for the purpose of preventing abnormal alignment or improving stickiness, the diameter of the core fine particles is 1/100 of
1/10 is preferable. If the thickness of the shell is less than 1/100 of the diameter of the core fine particles, it is difficult to obtain the effect of covering with the shell, and if it exceeds 1/10, it becomes difficult to obtain sufficient compression properties as a spacer for a liquid crystal display device.
【００４５】液晶表示素子での異常配向を抑えるために
は、従来のスペーサの表面に存在する水酸基等を反応性
のモノマーで化学修飾したり、水酸基を利用して、アセ
タール化、ウレタン化及びエステル化より選ばれる化学
反応により修飾したり、種々のモノマーの重合体により
被覆したりして、スペーサ表面の液晶規制力を弱め、液
晶の異常配向を防止することが考えられる。[0045] In order to suppress the abnormal alignment of the liquid crystal display device, a hydroxyl group present on the surface of the conventional spacer or chemically modified with reactive monomers, by utilizing a hydroxyl group, acetalization, urethanization and It is conceivable that modification by a chemical reaction selected from esterification or coating with a polymer of various monomers is performed to weaken the liquid crystal regulating force on the spacer surface and prevent abnormal alignment of liquid crystals.
【００４６】しかしながら、本発明者の検討によると、
かかる技術では、スペーサの表面に存在する水酸基等の
割合を特定することが難しく、結果的に液晶の規制力が
不安定になることがわかった。However, according to the study by the present inventor,
It has been found that with such a technique, it is difficult to specify the proportion of hydroxyl groups and the like existing on the surface of the spacer, and as a result, the regulation force of the liquid crystal becomes unstable.
【００４７】すなわち、かかる技術では、水酸基は、合
成樹脂製スペーサの場合、分散媒として用いられるポリ
ビニルアルコール由来のものであったり、又はシリカ製
スペーサの場合、シラノール結合に由来するものであ
り、いずれも副次的に形成されるものであり、水酸基の
数を制御できるものではない。That is, in this technique, the hydroxyl group is derived from polyvinyl alcohol used as a dispersion medium in the case of a spacer made of synthetic resin, or is derived from a silanol bond in the case of a spacer made of silica. Is also formed secondarily, and the number of hydroxyl groups cannot be controlled.
【００４８】本発明にかかる微粒子及びスペーサは、従
来の化学修飾法では得ることのできない、ビニルモノマ
ー等のグラフト重合層が被覆層としてコア微粒子表面に
形成されており、水酸基等の液晶規制力を抑制すること
ができる。In the fine particles and spacers according to the present invention , a graft polymerization layer of vinyl monomer or the like, which cannot be obtained by the conventional chemical modification method, is formed on the surface of the core fine particles as a coating layer, and the liquid crystal regulating force such as hydroxyl group is exerted. Can be suppressed.
【００４９】本発明では、コア微粒子から微粒子を形成
するために、微粒子製造装置を用いることができる。こ
の微粒子製造装置は、反応容器とこの反応容器を回転さ
せる回転機と減圧機と高周波発生機とを備えている。In the present invention, an apparatus for producing fine particles can be used to form fine particles from core fine particles. This fine particle manufacturing apparatus includes a reaction container, a rotating machine for rotating the reaction container, a decompressor, and a high-frequency generator.
【００５０】かかる微粒子製造装置では、コア微粒子が
反応容器内に投入され、反応容器内が減圧機によって減
圧にされる。また、かかる装置では、反応容器内に非重
合性の無機ガスが導入され、高周波発生機からの高周波
によって反応容器内にプラズマが発生する。さらに、か
かる装置では、反応容器の回転によるコア微粒子の転動
及びコア微粒子の非重合性無機ガス雰囲気中での低温プ
ラズマ処理によって、コア微粒子の表面が活性化され
る。In such an apparatus for producing fine particles, core fine particles are put into a reaction vessel, and the inside of the reaction vessel is decompressed by a decompressor. Further, in such an apparatus, a non-polymerizable inorganic gas is introduced into the reaction container, and plasma is generated in the reaction container by the high frequency wave from the high frequency generator. Further, in such an apparatus, the surface of the core fine particles is activated by rolling of the core fine particles due to rotation of the reaction vessel and low-temperature plasma treatment of the core fine particles in a non-polymerizable inorganic gas atmosphere.
【００５１】また、かかる装置では、反応容器内にビニ
ルモノマーが導入され、活性化したコア微粒子の表面と
ビニルモノマーとの重合によるグラフト重合層が、コア
微粒子の表面に形成され、微粒子が製造される。Further, in such an apparatus, a vinyl monomer is introduced into the reaction vessel, and a graft polymerization layer formed by polymerization of the surface of the activated core fine particles and the vinyl monomer is formed on the surface of the core fine particles to produce fine particles. It
【００５２】かかる装置は、ロータリーエバポレーター
を改造して作製することができる。また、かかる装置
は、反応容器をガラス製のボールミルとし、適切な減圧
機及び高周波発生機を設けることによって作製すること
ができる。Such a device can be manufactured by modifying a rotary evaporator. Further, such an apparatus can be produced by using a glass ball mill as a reaction container and providing an appropriate pressure reducer and high frequency generator.
【００５３】かかる装置では、本発明にかかるコア微粒
子の非重合性無機ガス雰囲気中での低温プラズマ処理の
際、コア微粒子を転動させることができ、処理されるコ
ア微粒子の表面が絶えず入れ代わるので、コア微粒子の
表面が均一に低温プラズマ処理され、コア微粒子同士の
合着が防止され、コア微粒子の表面が均一に活性化され
る。In such an apparatus, the core fine particles can be tumbled during the low temperature plasma treatment of the core fine particles according to the present invention in the non-polymerizable inorganic gas atmosphere, and the surfaces of the core fine particles to be treated are constantly replaced. The surface of the core fine particles is uniformly subjected to the low temperature plasma treatment, the coalescence of the core fine particles is prevented, and the surface of the core fine particles is uniformly activated.
【００５４】また、かかる装置では、１３．５６ＭＨｚ
等の高周波でプラズマを発生させることができ、コア微
粒子にプラズマを均一に照射することができる。なお、
かかる装置のリーク量は、５×１０ｍｌ／分−３（ＳＴ
Ｐ：標準状態）以下とすることができる。Further, in such a device, 13.56 MHz
Plasma can be generated at a high frequency such as, and the core fine particles can be uniformly irradiated with plasma. In addition,
The leak rate of such a device is 5 × 10 ml / min −3 (ST
P: standard state) can be the following.
【００５５】本発明では、実際のプラズマ処理による微
粒子の製造には、コア微粒子のプラズマ照射をより一層
効率よくさせるために、コア微粒子の転動及び撹拌効率
を上げた、ボールミル方式のプラズマ照射装置によって
行うのがよい。In the present invention, in the production of fine particles by the actual plasma treatment, in order to make the plasma irradiation of the core fine particles more efficient, the rolling and stirring efficiency of the core fine particles is increased, and the plasma irradiation apparatus of the ball mill system is used. Good to do by.
【００５６】[0056]
【実施例】以下、実施例及び比較例に基づいて、本発明
を更に詳述する。
〔コア微粒子の作製〕ポリビニルアルコール〔日本合成
化学（株）製ＧＨ−１７、ケン化度８７％）の５％水溶
液８５００ｇ中に、予めモノメトキシハイドロキノン１
ｇと過酸化ベンゾイル（日本油脂製、アセトンで再結
晶）２０ｇと、ペンタエリスリトールテトラアクリレー
ト１５００ｇとを４０〜４３℃で空気下に十分攪拌しな
がら混合した後、投入し、攪拌により微小粒子に分散さ
せた。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. [Production of core fine particles] Monomethoxyhydroquinone 1 was previously added to 8500 g of a 5% aqueous solution of polyvinyl alcohol [GH-17 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 87%].
g, 20 g of benzoyl peroxide (manufactured by NOF CORPORATION, recrystallized with acetone), and 1500 g of pentaerythritol tetraacrylate were thoroughly mixed in the air at 40 to 43 ° C. with thorough stirring, then added, and dispersed into fine particles by stirring. Let
【００５７】その後、これらを窒素下に、８０℃で５時
間重合した。得られた重合体微粒子を十分水洗した後、
分級操作を施した。平均粒子径６．０μｍ、標準偏差
０．３μｍの粒子を分取し、乾燥して、コア微粒子とし
た。Thereafter, these were polymerized under nitrogen at 80 ° C. for 5 hours. After sufficiently washing the obtained polymer fine particles with water,
A classification operation was performed. Particles having an average particle diameter of 6.0 μm and a standard deviation of 0.3 μm were collected and dried to obtain core fine particles.
【００５８】〔微粒子の作製〕
（実施例１）（異常配向防止＋固着機能型の液晶セルス
ペーサ、その１）
前述した反応容器とこの反応容器を回転させる回転機と
減圧機と高周波発生機とを備えている、微粒子製造装置
を用いて実験した。なお、反応容器には、ガラス製ボー
ルミルを使用した。また、高周波発生装置（サムコ株式
会社製、グラフト重合装置Ｍｏｄｅｌ ＰＴ−５０１）
の高周波（１３．５６ＭＨｚ）によりプラズマを発生さ
せる。装置のリーク量は、５×１０−３ｍｌ／分（ＳＴ
Ｐ：標準状態）である。[Production of Fine Particles] (Example 1) (Liquid Crystal Cell Spacer of Abnormal Alignment Prevention + Fixing Function Type, Part 1) The above-mentioned reaction vessel, a rotating machine for rotating the reaction vessel, a decompressor and a high frequency generator. Experiments were carried out using a fine particle manufacturing apparatus equipped with. A glass ball mill was used as the reaction vessel. In addition, a high frequency generator (Samco Co., Ltd., graft polymerization device Model PT-501)
Plasma is generated by the high frequency (13.56 MHz). The leak amount of the device is 5 × 10 −3 ml / min (ST
P: standard state).
【００５９】１Ｌ容のガラス製フラスコ内に、前述した
コア微粒子５０ｇと２ｍｍと１５ｍｍのガラスボール混
合物（混合重量比１：１）３５０ｇを入れて、反応槽内
の真空度を０．０３トール（４Ｐａ）まで減圧し、５０
ＲＰＭの回転速度でフラスコを１２時間保った。In a 1 L glass flask, 50 g of the core fine particles and 350 g of a glass ball mixture of 2 mm and 15 mm (mixing weight ratio 1: 1) were placed, and the degree of vacuum in the reaction tank was 0.03 torr ( Decompress to 4 Pa), 50
The flask was kept at RPM for 12 hours.
【００６０】続いて、非重合性無機ガスとして、アルゴ
ンガスを供給し、反応槽内の真空度が０．５トール（６
７Ｐａ）で一定になるようにバルブ調整し、プラズマ発
生装置に電圧をかけ、電力値を５０Ｗにして２０分間プ
ラズマ処理を行った。プラズマ状態の発光色は、白色で
あった。Subsequently, argon gas was supplied as the non-polymerizable inorganic gas, and the degree of vacuum in the reaction vessel was 0.5 torr (6
The valve was adjusted so as to be constant at 7 Pa), a voltage was applied to the plasma generator, the power value was set to 50 W, and the plasma treatment was performed for 20 minutes. The emission color in the plasma state was white.
【００６１】プラズマ停止後、アルゴンガスの供給を止
め、予め準備してある１％アクリルアミド水溶液２００
ｇを、減圧状態を利用して、ゆっくりと反応容器内に吸
引させ、プラズマ処理粉体をその水溶液中に浸した。そ
して、反応層を回転数７０ｒｐｍで１０分間回して、粉
体を水溶液中に均一に分散させた。そして、反応層をウ
ォーターバスで５０℃に保った。After the plasma was stopped, the supply of argon gas was stopped and the 1% acrylamide aqueous solution 200 prepared in advance was used.
g was slowly sucked into the reaction vessel by utilizing a reduced pressure state, and the plasma-treated powder was immersed in the aqueous solution. Then, the reaction layer was rotated at 70 rpm for 10 minutes to uniformly disperse the powder in the aqueous solution. Then, the reaction layer was kept at 50 ° C. in a water bath.
【００６２】その後、反応液を取り出し、水洗濾過して
アクリルアミド水溶液を除去した。得られた粉体は、白
色であった。コールターカウンター（コールター社製、
粒子径測定装置）で粒子径分布を測定したところ、平均
粒子径６．１μｍ、標準偏差０．３２μｍであり、０．
１μｍの厚さのアクリルアミド重合物が被覆されている
ことが判った。Then, the reaction solution was taken out, washed with water and filtered to remove the aqueous acrylamide solution. The obtained powder was white. Coulter counter (manufactured by Coulter,
The particle size distribution was measured with a particle size measuring device) to find that the average particle size was 6.1 μm and the standard deviation was 0.32 μm.
It was found to be coated with a 1 μm thick acrylamide polymer.
【００６３】（実施例２）（異常配向防止＋固着機能型
の液晶セルスペーサ、その２）
１Ｌ容のガラス製フラスコ内に、前述したコア微粒子５
０ｇと２ｍｍと１５ｍｍのガラスボール混合物（混合重
量比１：１）３５０ｇを入れて、反応槽内の真空度を
０．０３トール（４Ｐａ）まで減圧し、５０ｒｐｍの回
転速度でフラスコを１２時間保った。(Example 2) (Liquid Crystal Cell Spacer of Abnormal Alignment Prevention + Fixing Function Type, Part 2) In a 1 L glass flask, the above-mentioned core fine particles 5 were added.
350 g of a glass ball mixture of 0 g, 2 mm, and 15 mm (mixing weight ratio 1: 1) was added, the vacuum degree in the reaction tank was reduced to 0.03 Torr (4 Pa), and the flask was kept at a rotation speed of 50 rpm for 12 hours. It was
【００６４】続いて、非重合性無機ガスとしてアルゴン
ガスを供給し、反応槽内の真空度が０．５トール（６７
Ｐａ）で一定になるようにバルブ調整し、プラズマ発生
装置に電圧をかけ、電力値を５０Ｗにして２０分間プラ
ズマ処理を行った。プラズマ状態の発光色は、白色であ
った。Subsequently, argon gas was supplied as the non-polymerizable inorganic gas, and the degree of vacuum in the reaction tank was 0.5 Torr (67 tons).
The valve was adjusted to be constant at Pa), a voltage was applied to the plasma generator, the power value was set to 50 W, and the plasma treatment was performed for 20 minutes. The emission color in the plasma state was white.
【００６５】プラズマ停止後、アルゴンガスを止め、予
め準備してある１％アクリル酸エチル乳化液（ドデシル
硫酸ナトリウム０．１重量部を溶かした純水１００重量
部に１重量部のアクリル酸エチルを加えて、ホモジナイ
ザーで乳化させたもの）２００ｇを、減圧状態を利用し
て、ゆっくりと反応容器内に吸引させ、プラズマ処理粉
体をその水溶液中に浸した。そして、反応層を回転数７
０ｒｐｍで１０分間回して、粉体を水溶液中に均一に分
散させた。そして、反応層をウォーターバスで５０℃に
保った。After the plasma was stopped, the argon gas was stopped, and a 1% ethyl acrylate emulsion prepared in advance (1 part by weight of ethyl acrylate was added to 100 parts by weight of pure water in which 0.1 part by weight of sodium dodecyl sulfate was dissolved). In addition, 200 g of what was emulsified with a homogenizer) was slowly sucked into the reaction vessel by utilizing a reduced pressure state, and the plasma-treated powder was immersed in the aqueous solution. Then, the reaction layer is rotated at a rotational speed of 7
The powder was uniformly dispersed in the aqueous solution by rotating at 0 rpm for 10 minutes. Then, the reaction layer was kept at 50 ° C. in a water bath.
【００６６】その後、反応液を取り出し、水洗濾過して
アクリル酸エチル乳化液を除去した。得られた粉体は、
白色であった。コールターカウンター（コールター社
製，粒子系測定装置）で粒子径分布を測定した所、平均
粒子径６．１μｍ、標準偏差０．３２μｍであり、０．
１μｍの厚さのアクリル酸エチル重合物が被覆されてい
ることが判った。Then, the reaction solution was taken out, washed with water and filtered to remove the ethyl acrylate emulsion. The obtained powder is
It was white. When the particle size distribution was measured with a Coulter counter (manufactured by Coulter Inc., particle system measuring device), the average particle size was 6.1 μm and the standard deviation was 0.32 μm.
It was found to be coated with a 1 μm thick ethyl acrylate polymer.
【００６７】（実施例３）（異常配向防止＋固着機能型
の液晶セルスペーサ、その３）
実施例２で使用したアクリル酸エチルをスチレンに変え
て、同様にプラズマグラフト処理を行った。(Example 3) (Liquid Crystal Cell Spacer for Preventing Abnormal Alignment + Fixing Function, Part 3) The ethyl acrylate used in Example 2 was changed to styrene, and the same plasma graft treatment was carried out.
【００６８】水洗濾過後、得られた粉体は、白色であっ
た。コールターカウンター（コールター社製、粒子径測
定装置）で粒子径分布を測定したところ、平均粒子径
６．１μｍ、標準偏差０．３２μｍであり、０．１μｍ
の厚さのスチレン重合物が被覆されていることが判っ
た。The powder obtained after washing with water was white. When the particle size distribution was measured with a Coulter counter (manufactured by Coulter, particle size measuring device), the average particle size was 6.1 μm and the standard deviation was 0.32 μm.
It was found that a styrene polymer having a thickness of about 100 μm was coated.
【００６９】（実施例４）（異常配向防止機能型の液晶
セルスペーサ、その１）
実施例２で使用したアクリル酸エチルをジビニルベンゼ
ンに変えて、同様にプラズマグラフト処理を行った。(Example 4) (Liquid Crystal Cell Spacer of Abnormal Alignment Prevention Function, Part 1) The ethyl acrylate used in Example 2 was changed to divinylbenzene and the same plasma graft treatment was carried out.
【００７０】水洗濾過後、得られた粉体は、白色であっ
た。コールターカウンター（コールター社製、粒子径測
定装置）で粒子径分布を測定したところ、平均粒子径
６．１μｍ、標準偏差０．３２μｍであり、０．１μｍ
の厚さのジビニルベンゼン重合物が被覆されていること
が判った。The powder obtained after washing with water was white in color. When the particle size distribution was measured with a Coulter counter (manufactured by Coulter, particle size measuring device), the average particle size was 6.1 μm and the standard deviation was 0.32 μm.
It was found that a divinylbenzene polymer having a thickness of about 100 μm was coated.
【００７１】（実施例５）（異常配向防止＋固着機能型
の液晶セルスペーサ、その４）
実施例２で使用したアクリル酸エチルをメタクリル酸メ
チルに変えて、同様にプラズマグラフト処理を行った。(Example 5) (Abnormal alignment prevention / fixing function type liquid crystal cell spacer, No. 4) The ethyl acrylate used in Example 2 was changed to methyl methacrylate and the same plasma graft treatment was carried out.
【００７２】水洗濾過後、得られた粉体は、白色であっ
た。コールターカウンター（コールター社製、粒子径測
定装置）で粒子径分布を測定したところ、平均粒子径
６．１μｍ、標準偏差０．３２μｍであり、０．１μｍ
の厚さのメタクリル酸メチル重合物が被覆されているこ
とが判った。The powder obtained after washing with water and filtration was white. When the particle size distribution was measured with a Coulter counter (manufactured by Coulter, particle size measuring device), the average particle size was 6.1 μm and the standard deviation was 0.32 μm.
Was found to be coated with a methyl methacrylate polymer of
【００７３】（実施例６）（異常配向防止＋固着機能型
の液晶セルスペーサ、その５）
実施例２で使用したアクリル酸エチルをメタクリル酸に
変えて、同様にプラズマグラフト処理を行った。(Example 6) (Liquid Crystal Cell Spacer for Preventing Abnormal Alignment + Fixing Function, Part 5) The ethyl acrylate used in Example 2 was replaced with methacrylic acid, and the same plasma graft treatment was carried out.
【００７４】水洗濾過後、得られた粉体は、白色であっ
た。コールターカウンター（コールター社製、粒子径測
定装置）で粒子径分布を測定したところ、平均粒子径
６．１μｍ、標準偏差０．３２μｍであり、０．１μｍ
の厚さのメタクリル酸重合物が被覆されていることが判
った。The powder obtained after washing with water was white in color. When the particle size distribution was measured with a Coulter counter (manufactured by Coulter, particle size measuring device), the average particle size was 6.1 μm and the standard deviation was 0.32 μm.
It was found that a methacrylic acid polymer having a thickness of about 100 μm was coated.
【００７５】（実施例７）（異常配向防止機能型の液晶
セルスペーサ、その２）
実施例２で使用したアクリル酸エチルを１−オクテンに
変えて、同様にプラズマグラフト処理を行った。(Example 7) (Liquid Crystal Cell Spacer of Abnormal Alignment Prevention Function, Part 2) The ethyl acrylate used in Example 2 was changed to 1-octene, and the same plasma graft treatment was carried out.
【００７６】水洗濾過後、得られた粉体は、白色であっ
た。コールターカウンター（コールター社製、粒子径測
定装置）で粒子径分布を測定したところ、平均粒子径
６．１μｍ、標準偏差０．３２μｍであり、０．１μｍ
の厚さの１−オクテン重合物が被覆されていることが判
った。The powder obtained after washing with water was white. When the particle size distribution was measured with a Coulter counter (manufactured by Coulter, particle size measuring device), the average particle size was 6.1 μm and the standard deviation was 0.32 μm.
It was found that a 1-octene polymer having a thickness of 1 to 3 was coated.
【００７７】（比較例１）前述したコア微粒子をそのま
ま用いた。Comparative Example 1 The above core fine particles were used as they were.
【００７８】〔微粒子の評価〕実施例１〜７の微粒子及
び比較例のコア微粒子について、異常配向及び固着性を
評価した。評価方法を以下に示し、評価結果を表１に示
す。[Evaluation of Fine Particles] The fine particles of Examples 1 to 7 and the core fine particles of Comparative Example were evaluated for abnormal orientation and adhesion. The evaluation methods are shown below, and the evaluation results are shown in Table 1.
【００７９】（液晶表示素子での異常配向の評価）微粒
子を用いて、基板サイズ５０ｍｍ×５０ｍｍ、セルギャ
ップ６．０μｍのＳＴＮ型液晶表示素子を作製し、以下
のようにしてセル評価を行った。(Evaluation of Abnormal Alignment in Liquid Crystal Display Element) Using fine particles, an STN type liquid crystal display element having a substrate size of 50 mm × 50 mm and a cell gap of 6.0 μm was prepared, and cell evaluation was performed as follows. .
【００８０】まず、液晶表示素子にＡＣ２Ｖの電圧を印
荷し、初期状態のセル表示特性を評価し（異常配向
１）、次いで、液晶表示素子に２０Ｖの電圧を印荷した
後に、更に２Ｖの電圧を印荷して、電圧印荷状態でのセ
ル表示特性を評価した（異常配向２）。First, a voltage of AC2V was applied to the liquid crystal display element to evaluate the cell display characteristics in the initial state (abnormal orientation 1). Then, a voltage of 20V was applied to the liquid crystal display element, and then a further 2V was applied. The voltage was applied, and the cell display characteristics in the voltage applied state were evaluated (abnormal orientation 2).
【００８１】（固着性の評価）３０ｍｍ角、０．９ｍｍ
厚のＩＴＯ（インジウム・錫酸化物）成膜ガラス基板に
ポリイミド成膜用の溶液（日産化学製、ＳＥ−３５１
０）をスピンコーターで均一に塗布し、乾燥後、２５０
℃で１時間焼付けをした。(Evaluation of adhesiveness) 30 mm square, 0.9 mm
Thick ITO (indium tin oxide) film-forming glass substrate solution for polyimide film formation (NISSAN SE-351
0) is evenly coated with a spin coater, dried and then 250
Baking was carried out at ℃ for 1 hour.
【００８２】そのポリイミド面に、試験微粒子の０．１
重量％のイソプロピルアルコール分散液を、スポイトで
滴下し、自然乾燥後、１６０℃、１時間の焼付けを行っ
て試料を作成した。On the polyimide surface, 0.1 of the test fine particles was
A wt% isopropyl alcohol dispersion was dropped with a dropper, naturally dried and then baked at 160 ° C. for 1 hour to prepare a sample.
【００８３】固着力の評価は、試料に、空気吹き付け
〔空気吹き付け条件：乾燥空気４ｋｇｆ／ｃｍ２（３９
２ｋＰａ、１ｋｇｆ／ｃｍ２≒９８ｋＰａで換算）圧、
吹き付け時間６０秒、ノズル−基板間距離１ｃｍ、吹き
付け角度４５°〕を行って、吹き付け前後の粒子数の残
存率を調べて表した。The adhesion strength was evaluated by blowing air onto the sample [air blowing conditions: dry air 4 kgf / cm 2 (39
2kPa, converted to 1kgf / cm 2 ≈98kPa) pressure,
The spraying time was 60 seconds, the nozzle-substrate distance was 1 cm, and the spraying angle was 45 °], and the residual rate of the number of particles before and after spraying was examined and expressed.
【００８４】[0084]
【表１】 [Table 1]
【００８５】表１に示すように、実施例１〜７の微粒子
は、いずれも、液晶表示素子用スペーサとして用いる場
合、異常配向を示さない。また、実施例１〜３、５及び
６の微粒子は、固着率にも優れている。一方、比較例の
プラズマ未処理のグラフト重合層を有していない微粒子
は、異常配向が生じ、固着率も低かった。As shown in Table 1, all the fine particles of Examples 1 to 7 do not show abnormal alignment when used as spacers for liquid crystal display elements. Further, the fine particles of Examples 1 to 3, 5 and 6 are also excellent in the sticking rate. On the other hand, the fine particles not having the graft-polymerized layer that was not treated with the plasma of Comparative Example had an abnormal orientation and a low sticking rate.
【００８６】[0086]
【発明の効果】本発明にかかる微粒子は、所定のコア微
粒子の表面が、通常の熱励起では困難な化学反応による
グラフト重合層で覆われるので、かかるコア微粒子とグ
ラフト重合層との密着性に優れ、グラフト重合層の被覆
率に優れる。INDUSTRIAL APPLICABILITY In the fine particles according to the present invention , the surface of the predetermined core fine particles is covered with the graft polymerization layer by a chemical reaction which is difficult by ordinary thermal excitation, and therefore the adhesion between the core fine particles and the graft polymerization layer is improved. Excellent and excellent coverage of the graft polymerization layer.
【００８７】また、本発明にかかる微粒子は、所定のコ
ア微粒子の表面にある水酸基等の活性基が十分に被覆さ
れるほどにグラフト重合層が形成されるので、スペーサ
として用いると、液晶表示素子の異常配向を抑えたり、
ポリイミド膜との固着性に優れる。[0087] Furthermore, particles in accordance with the present invention, since the graft polymerization layer is formed as the active group such as a hydroxyl group on the surface of a given core particles are sufficiently covered, when used as a spacer, a liquid crystal display device Suppress abnormal orientation of
Excellent adhesion to polyimide film.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平９−194842（ＪＰ，Ａ) 特開 平11−202341（ＪＰ，Ａ) 特開2000−321581（ＪＰ，Ａ) 特開 平１−193313（ＪＰ，Ａ) 特開 昭59−80443（ＪＰ，Ａ) 特開 平７−278327（ＪＰ，Ａ) 特開 平６−239943（ＪＰ，Ａ) 特開 平８−225673（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 291/00 G02F 1/1339 500 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-9-194842 (JP, A) JP-A-11-202341 (JP, A) JP-A-2000-321581 (JP, A) JP-A-1-193313 (JP, A) JP 59-80443 (JP, A) JP 7-278327 (JP, A) JP 6-239943 (JP, A) JP 8-225673 (JP, A) (JP, A) 58) Fields surveyed (Int.Cl. 7 , DB name) C08F 291/00 G02F 1/1339 500
Claims (6)
子用スペーサであって、 前記液晶表示素子用スペーサが、 コア微粒子と前記コア
微粒子の表面の被覆層とから形成されている微粒子から
なり、前記コア微粒子が重合体からなり、前記被覆層
が、前記コア微粒子の非重合性無機ガス雰囲気中での低
温プラズマ処理によって活性化された前記コア微粒子の
表面のラジカルとビニルモノマーとの結合によるグラフ
ト重合層から形成されていることを特徴とする、液晶表
示素子用スペーサ。1. A liquid crystal display element arranged in a liquid crystal display cell.
A child spacer, the microparticles spacer liquid crystal display element is formed from a coating layer on the surface of the core particles and core particles
The core fine particles are made of a polymer, and the coating layer is a combination of radicals on the surface of the core fine particles activated by a low temperature plasma treatment of the core fine particles in a non-polymerizable inorganic gas atmosphere and a vinyl monomer. A liquid crystal surface characterized by being formed from a graft polymerization layer of
Display element spacer .
系重合体、スチレン系重合体、ナイロン系重合体、ウレ
タン系重合体、ポリエチレン系重合体、ポリジメチルシ
ロキサン系重合体、ポリエステル系重合体及びポリ酢酸
ビニルエチレン系重合体からなる群より選ばれる少なく
とも１種の重合体から形成されていることを特徴とす
る、請求項１記載の液晶表示素子用スペーサ。2. The core fine particles are acrylic acid ester-based polymers, styrene-based polymers, nylon-based polymers, urethane-based polymers, polyethylene-based polymers, polydimethylsiloxane-based polymers, polyester-based polymers and poly-based polymers. The spacer for a liquid crystal display element according to claim 1, which is formed of at least one polymer selected from the group consisting of vinyl acetate ethylene-based polymers.
ン及び窒素からなる群より選ばれる少なくとも１種のガ
スであることを特徴とする、請求項１又は２記載の液晶
表示素子用スペーサ。3. The liquid crystal according to claim 1 or 2, wherein the non-polymerizable inorganic gas is at least one gas selected from the group consisting of oxygen, argon and nitrogen.
Spacer for display element .
ド、アクリル酸エチル、メタクリル酸メチル、メタクリ
ル酸、スチレン、ジビニルベンゼン、１−オクテン及び
１，４−ブタジエンからなる群より選ばれる少なくとも
１種のモノマーであることを特徴とする、請求項１〜３
のいずれか一項記載の液晶表示素子用スペーサ。4. The vinyl monomer is at least one monomer selected from the group consisting of acrylic acid amide, ethyl acrylate, methyl methacrylate, methacrylic acid, styrene, divinylbenzene, 1-octene and 1,4-butadiene. It is characterized by these.
The spacer for a liquid crystal display element according to any one of items 1 to 5.
隔に維持するスペーサと前記各基板の間に介在する液晶
とを備える、液晶表示装置であって、 前記スペーサが、請求項１〜４いずれか一項記載の液晶
表示素子用スペーサであることを特徴とする、液晶表示
装置 。 5. A predetermined distance between a pair of substrates and each of the substrates.
Liquid crystal interposed between the spacers and the substrates
5. A liquid crystal display device comprising: the liquid crystal according to claim 1 , wherein the spacer is a liquid crystal display device.
Liquid crystal display characterized by being a spacer for a display element
Equipment .
素子用スペーサを得るにあたり、 前記液晶表示素子用スペーサが、コア微粒子と前記コア
微粒子の表面の被覆層とから形成されている微粒子から
なり、前記コア微粒子が重合体から形成されて おり、前
記コア微粒子を非重合性の無機ガス雰囲気中で低温プラ
ズマ処理して、前記コア微粒子の表面を活性化し、前記
コア微粒子の表面のラジカルとビニルモノマーとを結合
させ、前記コア微粒子の表面にグラフト重合層からなる
前記被覆層を形成することを特徴とする、液晶表示素子
用スペーサの製造方法 。6. A liquid crystal display arranged in a liquid crystal display cell.
In obtaining the device spacer, the liquid crystal display device spacer includes the core fine particles and the core.
From the fine particles formed with the coating layer on the surface of the fine particles
And the core fine particles are formed of a polymer ,
The core particles are placed in a non-polymerizable inorganic gas atmosphere at low temperature
Zuma treatment to activate the surface of the core fine particles,
Bonding radicals on the surface of core particles with vinyl monomers
And a graft polymerization layer is formed on the surface of the core fine particles.
Liquid crystal display device, characterized in that the coating layer is formed.
Of manufacturing spacer for car .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001025544A JP3479285B2 (en) | 2001-02-01 | 2001-02-01 | Liquid crystal display element spacer, liquid crystal display device, and method of manufacturing liquid crystal display element spacer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001025544A JP3479285B2 (en) | 2001-02-01 | 2001-02-01 | Liquid crystal display element spacer, liquid crystal display device, and method of manufacturing liquid crystal display element spacer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002226531A JP2002226531A (en) | 2002-08-14 |
| JP3479285B2 true JP3479285B2 (en) | 2003-12-15 |
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|---|---|---|---|
| JP2001025544A Expired - Fee Related JP3479285B2 (en) | 2001-02-01 | 2001-02-01 | Liquid crystal display element spacer, liquid crystal display device, and method of manufacturing liquid crystal display element spacer |
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| JP (1) | JP3479285B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4170762B2 (en) | 2001-02-09 | 2008-10-22 | 冷化工業株式会社 | Functional particles, manufacturing method thereof, and plasma processing method |
| JP5253934B2 (en) * | 2008-09-05 | 2013-07-31 | 三井化学株式会社 | Powder manufacturing method |
| JP5583446B2 (en) * | 2009-04-02 | 2014-09-03 | 三井化学株式会社 | Resin powder and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000321581A (en) | 1999-05-10 | 2000-11-24 | Sekisui Chem Co Ltd | Liquid crystal display element spacer, method of manufacturing the same, and liquid crystal display element |
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2001
- 2001-02-01 JP JP2001025544A patent/JP3479285B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000321581A (en) | 1999-05-10 | 2000-11-24 | Sekisui Chem Co Ltd | Liquid crystal display element spacer, method of manufacturing the same, and liquid crystal display element |
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| Publication number | Publication date |
|---|---|
| JP2002226531A (en) | 2002-08-14 |
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