JP2635224B2 - Method for producing crosslinked polymer fine particles - Google Patents
Method for producing crosslinked polymer fine particlesInfo
- Publication number
- JP2635224B2 JP2635224B2 JP3011989A JP1198991A JP2635224B2 JP 2635224 B2 JP2635224 B2 JP 2635224B2 JP 3011989 A JP3011989 A JP 3011989A JP 1198991 A JP1198991 A JP 1198991A JP 2635224 B2 JP2635224 B2 JP 2635224B2
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- JP
- Japan
- Prior art keywords
- fine particles
- polymer fine
- crosslinked polymer
- meth
- acrylate
- 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 - Lifetime
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- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は液晶パネル用スペーサ等
に好適な高弾性率の架橋重合体微粒子の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing high elastic modulus crosslinked polymer fine particles suitable for a liquid crystal panel spacer or the like.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】一般
に、液晶表示パネルでは液晶物質を間隙に有する二枚の
ガラス基板を一定の間隙に保持することが必要とされて
おり、そのためにガラス基板の間にスペーサを介在さ
せ、両ガラス基板を所望のセルギャップになるまで押圧
し、固定する方法がとられている。2. Description of the Related Art In general, in a liquid crystal display panel, it is necessary to hold two glass substrates having a liquid crystal substance in a gap at a constant gap. A method is employed in which both glass substrates are pressed until a desired cell gap is reached, with a spacer interposed therebetween, and fixed.
【０００３】このようなスペーサとして、従来よりスチ
レン系単量体等を懸濁重合させて得られるポリマー微粒
子が用いられている。As such a spacer, polymer fine particles obtained by subjecting a styrene-based monomer or the like to suspension polymerization have been conventionally used.
【０００４】しかしながら、スチレン系のポリマー微粒
子は一般に機械的強度が低く、押圧時の圧力によりスペ
ーサが破壊もしくは変形し、適正なセルギャップが得ら
れず、また耐溶剤性に乏しく液晶を汚染する等の問題が
生じる。これらの問題を解決する手段として、架橋性単
量体を用いた架橋ポリマービーズが提案されているが、
満足のいくものが得られていない。However, styrene-based polymer fine particles generally have low mechanical strength, the spacer is broken or deformed by the pressure at the time of pressing, an appropriate cell gap cannot be obtained, and the solvent resistance is poor, contaminating the liquid crystal. Problem arises. As a means for solving these problems, crosslinked polymer beads using a crosslinkable monomer have been proposed,
Satisfaction has not been obtained.
【０００５】[0005]
【課題を解決するための手段】このような現状に鑑み、
本発明者らは鋭意検討を重ねた結果、架橋性単量体を主
構成成分とする重合性単量体に、常法に比べて非常に多
くの有機過酸化物系ラジカル重合開始剤を加えて水系懸
濁重合することにより高強度の架橋重合体微粒子が得ら
れることを見出し、本発明を完成させるに至った。In view of the above situation,
The present inventors have conducted intensive studies, and as a result, added a much larger amount of an organic peroxide-based radical polymerization initiator to a polymerizable monomer having a crosslinkable monomer as a main component compared to a conventional method. It has been found that high-strength crosslinked polymer fine particles can be obtained by aqueous suspension polymerization, thereby completing the present invention.
【０００６】即ち、本発明は、架橋性単量体を50重量％
以上含む重合性単量体に対し３〜10重量％の有機過酸化
物系ラジカル重合開始剤を用い、水系媒体中で重合させ
ることを特徴とする架橋重合体微粒子の製造方法を提供
するものである。That is, according to the present invention, the crosslinking monomer is added in an amount of 50% by weight.
The present invention provides a method for producing crosslinked polymer fine particles, characterized in that polymerization is carried out in an aqueous medium by using an organic peroxide-based radical polymerization initiator in an amount of 3 to 10% by weight based on the polymerizable monomer contained above. is there.
【０００７】本発明において用いられる架橋性単量体と
しては、ラジカル重合可能な不飽和二重結合を２個以上
有する架橋性単量体であれば特に限定されるものでな
い。例えば、ジビニルベンゼン、1,4 −ジビニロキシブ
タン、ジビニルスルホン等のビニル化合物；ジアリルフ
タレート、ジアリルアクリルアミド、トリアリル(イソ)
シアヌレート、トリアリルトリメリテート等のアリル化
合物；（ポリ) エチレングリコールジ（メタ）アクリレ
ート、（ポリ）プロピレングリコールジ（メタ）アクリ
レート等の（ポリ）オキシアルキレングリコールジ（メ
タ）アクリレート；ペンタエリスリトールテトラ（メ
タ）アクリレート、ペンタエリスリトールトリ（メタ）
アクリレート、ペンタエリスリトールジ（メタ）アクリ
レート、トリメチロールプロパントリ（メタ）アクリレ
ート、ジペンタエリスリトールヘキサ（メタ）アクリレ
ート、ジペンタエリスリトールペンタ（メタ）アクリレ
ート及びグリセロールトリ（メタ）アクリレート、グリ
セロールジ（メタ）アクリレート等が挙げられる。これ
らの架橋性単量体は単独又は２種以上混合して用いるこ
とができる。本発明においては、特にジビニルベンゼン
が好ましい。通常市販のジビニルベンゼンは55〜80重量
％程度の純度でエチルスチレン等の不純物をかなり含ん
でおり、また、主成分であるジビニルベンゼン自体もパ
ラ体とメタ体との混合物（パラ体60〜70重量％）であ
る。ジビニルベンゼンを用いる場合、純度はより高い方
が好ましいが、特にメタ体の高純度品を用いた場合によ
り高弾性率の架橋重合体微粒子が得られる。The crosslinking monomer used in the present invention is not particularly limited as long as it is a crosslinking monomer having two or more radically polymerizable unsaturated double bonds. For example, vinyl compounds such as divinylbenzene, 1,4-divinyloxybutane, and divinylsulfone; diallyl phthalate, diallyl acrylamide, triallyl (iso)
Allyl compounds such as cyanurate and triallyl trimellitate; (poly) oxyalkylene glycol di (meth) acrylates such as (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di (meth) acrylate; pentaerythritol tetra (Meth) acrylate, pentaerythritol tri (meth)
Acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and glycerol tri (meth) acrylate, glycerol di (meth) acrylate And the like. These crosslinkable monomers can be used alone or in combination of two or more. In the present invention, divinylbenzene is particularly preferred. Usually, commercially available divinylbenzene has a purity of about 55 to 80% by weight and contains a considerable amount of impurities such as ethylstyrene, and the main component, divinylbenzene itself, is a mixture of para- and meta-forms (para-form 60 to 70). % By weight). When divinylbenzene is used, the higher the purity, the better. However, when a highly pure meta-form is used, crosslinked polymer fine particles having a higher elastic modulus can be obtained.
【０００８】又、本発明において用いられる非架橋性単
量体としては、ラジカル重合可能な、架橋性単量体以外
の全ての単量体を用いることができるが、例えばスチレ
ン、ｐ−(m−）メチルスチレン、ｐ−(m−) エチルスチ
レン、ｐ−(m−) クロロスチレン、ｐ−(m−）クロロメ
チルスチレン、スチレンスルホン酸、ｐ−(m−)t−ブト
キシスチレン、α−メチル−ｐ−t −アミロキシスチレ
ン、ｐ−t −アミロキシスチレン等のスチレン系モノマ
ー；（メタ）アクリル酸エチル、（メタ）アクリル酸２
−エチルヘキシル、（メタ）アクリル酸ラウリル、ジメ
チルアミノエチル（メタ）アクリレート、ジエチルアミ
ノエチル（メタ）アクリレート、ヒドロキシエチル（メ
タ）アクリレート、ジエチレングリコールモノ（メタ）
アクリレート、グリセロールモノ(メタ）アクリレー
ト、ポリエチレングリコールモノ(メタ）アクリレー
ト、ブタンジオールモノ（メタ）アクリレート等の（メ
タ）アクリル酸エステル系モノマー；（メタ）アクリル
酸、マレイン酸等の不飽和カルボン酸系モノマー；メチ
ルビニルエーテル、エチルビニルエーテル等のアルキル
ビニルエーテル；酢酸ビニル、酪酸ビニル等のビニルエ
ステル系モノマー；N −メチル（メタ）アクリルアミ
ド、N −エチル（メタ）アクリルアミド等のN −アルキ
ル置換（メタ）アクリルアミド；（メタ）アクリロニト
リル等のニトリル系モノマーが挙げられる。これらの非
架橋性単量体は単独又は２種以上混合して用いることが
できる。As the non-crosslinkable monomer used in the present invention, any monomer other than a crosslinkable monomer which can be radically polymerized can be used. For example, styrene, p- (m -) Methylstyrene, p- (m-) ethylstyrene, p- (m-) chlorostyrene, p- (m-) chloromethylstyrene, styrenesulfonic acid, p- (m-) t-butoxystyrene, α- Styrene monomers such as methyl-pt-amyloxystyrene and pt-amyloxystyrene; ethyl (meth) acrylate, (meth) acrylic acid 2
-Ethylhexyl, lauryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, diethylene glycol mono (meth)
(Meth) acrylate monomers such as acrylate, glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate and butanediol mono (meth) acrylate; unsaturated carboxylic acids such as (meth) acrylic acid and maleic acid Monomers; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl ester monomers such as vinyl acetate and vinyl butyrate; N-alkyl-substituted (meth) acrylamides such as N-methyl (meth) acrylamide and N-ethyl (meth) acrylamide; Examples thereof include nitrile monomers such as (meth) acrylonitrile. These non-crosslinkable monomers can be used alone or in combination of two or more.
【０００９】本発明における前記架橋性単量体と非架橋
性単量体の混合割合は、架橋性単量体が50重量％以上、
特に70重量％以上が好ましい。前記混合割合よりも架橋
性単量体が少ない場合には充分な圧縮弾性率が得られな
いため好ましくない。The mixing ratio of the crosslinkable monomer and the non-crosslinkable monomer in the present invention is such that the crosslinkable monomer is 50% by weight or more,
In particular, 70% by weight or more is preferable. When the amount of the crosslinkable monomer is smaller than the mixing ratio, a sufficient compression elastic modulus cannot be obtained, which is not preferable.
【００１０】本発明において用いられる有機過酸化物系
ラジカル重合開始剤としては、例えば、過酸化ベンゾイ
ル、過酸化ラウロイル等が挙げられ、特に過酸化ベンゾ
イルを好適に用いることができる。これらの有機過酸化
物系ラジカル重合開始剤は単独又は２種以上混合して用
いることができる。従来、これらのラジカル重合開始剤
の添加量は通常、一般的に単量体に対し0.1 〜３重量％
であったが、本発明においては３〜10重量％、より好ま
しくは４〜７重量％添加することにより達成される。有
機過酸化物系ラジカル重合開始剤の添加量が前記添加量
の範囲より少ない場合にも、多い場合にも、適当な強度
の架橋重合体微粒子が得られない。またアゾ系の開始剤
では使用量を多くしてもさほど弾性率の向上は見られな
い。The organic peroxide-based radical polymerization initiator used in the present invention includes, for example, benzoyl peroxide, lauroyl peroxide and the like. In particular, benzoyl peroxide can be suitably used. These organic peroxide-based radical polymerization initiators can be used alone or in combination of two or more. Conventionally, these radical polymerization initiators are usually added in an amount of generally 0.1 to 3% by weight based on the monomer.
However, in the present invention, it is achieved by adding 3 to 10% by weight, more preferably 4 to 7% by weight. When the amount of the organic peroxide-based radical polymerization initiator is smaller or larger than the above range, crosslinked polymer fine particles having appropriate strength cannot be obtained. In the case of an azo-based initiator, even if the amount used is increased, no significant improvement in the elastic modulus is observed.
【００１１】架橋重合体微粒子の強度を圧縮弾性率で表
したとき、従来の架橋ポリスチレン系では高々360 kg／
mm2 であったが、。本発明によれば 370〜 550kg／mm2
の高弾性率の架橋重合体微粒子が得られる。When the strength of the crosslinked polymer fine particles is represented by the compressive modulus, the conventional crosslinked polystyrene system has a strength of at most 360 kg / kg.
It was the mm 2,. According to the present invention, 370 to 550 kg / mm 2
Thus, a crosslinked polymer fine particle having a high elastic modulus is obtained.
【００１２】本発明でいう圧縮弾性率とは、下記方法に
より測定した値である。The compression modulus in the present invention is a value measured by the following method.
【００１３】＜圧縮弾性率の測定方法＞島津粉体圧縮試
験機（（株）島津製作所製 PCT−200)により、試料台上
に散布した試料粒子１個について、粒子の中心方向へ荷
重をかけ、荷重−圧縮変位を測定し、10％変位時の荷重
を求めた。これを次式に代入し、10％圧縮弾性率を算出
した。この操作を異なる３個の粒子について行い、その
平均値を粒子の10％圧縮弾性率とした。なお、測定は室
温で行った。<Measurement Method of Compressive Elastic Modulus> A load is applied to one sample particle scattered on a sample table in the direction of the center of the particle by a Shimadzu powder compression tester (PCT-200 manufactured by Shimadzu Corporation). , Load-compression displacement was measured, and the load at 10% displacement was determined. This was substituted into the following equation to calculate a 10% compression modulus. This operation was performed for three different particles, and the average value was defined as the 10% compression modulus of the particles. The measurement was performed at room temperature.
【００１４】[0014]
【数１】 (Equation 1)
【００１５】 ここで、E ；圧縮弾性率（kg／mm2) F ；圧縮荷重（kg） K ；粒子のポアソン比（定数, 0.38) S ；圧縮変位（mm） R ；粒子の半径（mm） 10％圧縮弾性率の平均値が前記範囲よりも小さい場合
には、ガラスセル押圧時のスペーサの変形が塑性変形と
なるため、セルギャップの再現性等、信頼性の低下を招
き、更には前記下限よりも充分に小さい場合には押圧時
の圧力によりスペーサが破壊される等好ましくない。ま
た、前記範囲よりも大きい場合には前述したように変形
性が乏しく、スペーサの粒径分布がそのままセルギャッ
プムラに反映されるため好ましくない。Here, E: compression elastic modulus (kg / mm 2 ) F: compression load (kg) K: Poisson's ratio of particles (constant, 0.38) S: compression displacement (mm) R: radius of particles (mm) If the average value of the 10% compressive modulus is smaller than the above range, the deformation of the spacer when the glass cell is pressed becomes a plastic deformation, so that the reliability, such as the reproducibility of the cell gap, is reduced. If it is sufficiently smaller than the lower limit, it is not preferable that the spacer is broken by the pressure at the time of pressing. If the diameter is larger than the above range, the deformability is poor as described above, and the particle size distribution of the spacer is directly reflected on the cell gap unevenness, which is not preferable.
【００１６】本発明において、水系重合は常法に従い、
分散安定剤の存在下に撹拌しつつ温度25〜 100℃、より
好ましくは50〜90℃の範囲で行われる。該分散安定剤と
しては、ラウリル硫酸ナトリウム、ラウリルベンゼンス
ルホン酸ナトリウム、ポリオキシエチレンラウリルエー
テル硫酸ナトリウム等の界面活性剤；ゼラチン、澱粉、
ヒドロキシエチルセルロース、カルボキシメチルセルロ
ース、ポリビニルピロリドン、ポリビニルアルキルエー
テル、ポリビニルアルコール等の水溶性高分子；硫酸バ
リウム、硫酸カルシウム、炭酸バリウム、炭酸カルシウ
ム、炭酸マグネシウム、燐酸カルシウム等の難水溶性無
機塩が挙げられる。In the present invention, the aqueous polymerization is carried out according to a conventional method.
The reaction is carried out at a temperature of 25 to 100 ° C, more preferably 50 to 90 ° C, with stirring in the presence of a dispersion stabilizer. Examples of the dispersion stabilizer include surfactants such as sodium lauryl sulfate, sodium lauryl benzene sulfonate, and sodium polyoxyethylene lauryl ether sulfate; gelatin, starch,
Water-soluble polymers such as hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl alkyl ether, and polyvinyl alcohol; and poorly water-soluble inorganic salts such as barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, and calcium phosphate.
【００１７】又、本発明に係る架橋重合体微粒子は、懸
濁重合以外に、シード重合等、通常重合体微粒子の製造
に用いられる方法により得ることもできる。The crosslinked polymer fine particles according to the present invention can also be obtained by a method usually used for producing polymer fine particles, such as seed polymerization, in addition to suspension polymerization.
【００１８】本発明に係る架橋重合体微粒子の平均粒子
径は、目的によって任意に設計し得るが、通常１〜20μ
m 程度が好ましい。また、本発明の架橋重合体微粒子を
スペーサとして用いる場合、粒径分布の広いスペーサを
使用すると、セルギャップムラが発生し易い、その他、
多数個のスペーサのうち、特にセルギャップよりも粒径
の小さいスペーサがパネルの空間内で移動し、電極の周
辺に凝集し易い等の欠点があるため、粒径分布の標準偏
差がその平均粒子径の20％以下であることが好ましく、
より好ましくは10％以下である。The average particle size of the crosslinked polymer fine particles according to the present invention can be arbitrarily designed depending on the purpose.
m is preferred. Further, when using the crosslinked polymer fine particles of the present invention as a spacer, if a spacer having a wide particle size distribution is used, cell gap unevenness is likely to occur.
Among the many spacers, spacers having a smaller particle size than the cell gap move in the space of the panel and have a disadvantage that they are easily aggregated around the electrodes. Preferably not more than 20% of the diameter,
It is more preferably at most 10%.
【００１９】従って、本発明により得られる架橋重合体
微粒子を液晶表示パネル用スペーサとして用いる場合
は、架橋重合体微粒子の粒径分布が広い場合には水簸法
又は風力法等により分級するのが好ましい。Therefore, when the crosslinked polymer fine particles obtained by the present invention are used as a spacer for a liquid crystal display panel, if the particle size distribution of the crosslinked polymer fine particles is wide, it is preferable to classify the particles by elutriation or wind power. preferable.
【００２０】[0020]
【実施例】以下、本発明を実施例によって更に詳細に説
明するが、本発明はこれらの実施例に限定されるもので
はない。なお、実施例中「部」は重量部を示す。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited to these Examples. In the examples, "parts" indicates parts by weight.
【００２１】実施例１ ポリビニルアルコール（日本合成化学工業（株）製GH−
17、ケン化度86.5〜89mol ％）の３％水溶液 800部に、
ｍ−ジビニルベンゼン（純度92％、日精化学工業（株)
製）80部、エチレングリコールジメタクリレート（新中
村化学工業(株)製NK−エステル1G）20部、過酸化ベンゾ
イル５部の混合液を加えて微分散させ、撹拌しながら窒
素気流下80℃で15時間重合を行った。得られた微粒子を
イオン交換水及び溶剤で洗浄後、分級操作を施し、更に
単離乾燥して平均粒子径 7.0μm、標準偏差が0.47μm
である架橋重合体微粒子を得た。Example 1 Polyvinyl alcohol (GH- manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
17, 800 parts of a 3% aqueous solution with a saponification degree of 86.5 to 89 mol%)
m-divinylbenzene (92% purity, Nissei Chemical Co., Ltd.)
80 parts), 20 parts of ethylene glycol dimethacrylate (NK-ester 1G manufactured by Shin-Nakamura Chemical Co., Ltd.) and 5 parts of benzoyl peroxide are added and finely dispersed. Polymerization was performed for 15 hours. After washing the obtained fine particles with ion-exchanged water and a solvent, subjected to a classification operation, further isolated and dried, the average particle diameter is 7.0 μm, the standard deviation is 0.47 μm
Was obtained.
【００２２】得られた架橋重合体微粒子の10％圧縮弾性
率（平均値）を下記の方法により評価したところ、 420
kg／mm2 であり、液晶表示パネル用スペーサとして有用
なものであった。The 10% compression modulus (average value) of the obtained crosslinked polymer fine particles was evaluated by the following method.
kg / mm 2 , which was useful as a spacer for a liquid crystal display panel.
【００２３】実施例２ 実施例１においてｍ−ジビニルベンゼンに代えて市販の
ジビニルベンゼン（純度81％、新日鐡化学（株）製DVB-
810 ）を用いた以外は実施例１と同じ方法により平均粒
子径 6.0μm 、標準偏差が 0.4μm の架橋重合体微粒子
を得た。Example 2 In place of m-divinylbenzene in Example 1, commercially available divinylbenzene (purity 81%, DVB-manufactured by Nippon Steel Chemical Co., Ltd.)
Except that 810) was used, crosslinked polymer fine particles having an average particle diameter of 6.0 μm and a standard deviation of 0.4 μm were obtained in the same manner as in Example 1.
【００２４】この架橋重合体微粒子の10％圧縮弾性率
（平均値）を評価したところ 380kg／mm2 であった。When the 10% compression modulus (average value) of the crosslinked polymer fine particles was evaluated, it was 380 kg / mm 2 .
【００２５】実施例３ 実施例２において過酸化ベンゾイルを７部とした以外は
実施例２と同じ方法により平均粒子径 7.5μm 、標準偏
差が 0.5μm の架橋重合体微粒子を得た。Example 3 Crosslinked polymer fine particles having an average particle diameter of 7.5 μm and a standard deviation of 0.5 μm were obtained in the same manner as in Example 2 except that benzoyl peroxide was used in an amount of 7 parts.
【００２６】この架橋重合体微粒子の10％圧縮弾性率
（平均値）を評価したところ 420kg／mm2 であった。When the 10% compression modulus (average value) of the crosslinked polymer fine particles was evaluated, it was 420 kg / mm 2 .
【００２７】実施例４ 実施例１において、ｍ−ジビニルベンゼンの代わりにジ
ペンタエリスリトールヘキサアクリレート、過酸化ベン
ゾイルの代わりに過酸化ラウロイルを６部用いた以外は
同様な方法により平均粒子径7.75μm 、標準偏差が0.52
μm の架橋重合体微粒子を得た。Example 4 The procedure of Example 1 was repeated, except that dipentaerythritol hexaacrylate was used in place of m-divinylbenzene and lauroyl peroxide was used in place of 6 parts in place of benzoyl peroxide. Standard deviation 0.52
As a result, crosslinked polymer fine particles of μm were obtained.
【００２８】この微粒子の10％圧縮弾性率（平均値）は
520kg／mm2 であった。The 10% compression modulus (average value) of the fine particles is
It was 520 kg / mm 2 .
【００２９】比較例１ 実施例１において過酸化ベンゾイルを１部とした以外は
実施例１と同じ方法により平均粒子径 6.4μm 、標準偏
差が0.43μm の架橋重合体微粒子を得た。Comparative Example 1 Crosslinked polymer fine particles having an average particle diameter of 6.4 μm and a standard deviation of 0.43 μm were obtained in the same manner as in Example 1 except that benzoyl peroxide was changed to 1 part.
【００３０】この架橋重合体微粒子の10％圧縮弾性率を
評価したところ 280kg／mm2 であり、液晶表示パネル用
スペーサとして使用に耐えないものであった。When the 10% compression modulus of the crosslinked polymer fine particles was evaluated, it was 280 kg / mm 2 , and was not usable as a spacer for a liquid crystal display panel.
【００３１】比較例２ 実施例１において過酸化ベンゾイルを15部とした以外は
実施例１と同じ方法により平均粒子径 6.5μm 、標準偏
差0.43μm の架橋重合体微粒子を得た。Comparative Example 2 Crosslinked polymer fine particles having an average particle diameter of 6.5 μm and a standard deviation of 0.43 μm were obtained in the same manner as in Example 1 except that benzoyl peroxide was used in an amount of 15 parts.
【００３２】この架橋重合体微粒子の10％圧縮弾性率を
評価したところ260 kg／mm2 であり、液晶表示パネル用
スペーサとして使用に耐えないものであった。When the 10% compression modulus of the crosslinked polymer fine particles was evaluated, it was 260 kg / mm 2 , which was unsuitable for use as a spacer for a liquid crystal display panel.
【００３３】比較例３ 実施例３においてモノマーとして、スチレン70部、ジビ
ニルベンゼン30部を用いた以外は実施例３と同じ方法に
より平均粒子径 7.0μm、標準偏差0.47μm の架橋重合
体微粒子を得た。Comparative Example 3 Crosslinked polymer fine particles having an average particle diameter of 7.0 μm and a standard deviation of 0.47 μm were obtained in the same manner as in Example 3 except that 70 parts of styrene and 30 parts of divinylbenzene were used as monomers. Was.
【００３４】この架橋重合体微粒子の10％圧縮弾性率を
評価したところ 200kg／mm2 であり、液晶表示パネル用
スペーサとして使用に耐えないものであった。When the 10% compression modulus of the crosslinked polymer fine particles was evaluated, it was 200 kg / mm 2 , which was unsuitable for use as a spacer for a liquid crystal display panel.
【００３５】[0035]
【発明の効果】以上述べた如く本発明方法は、その操作
が非常に簡単であるにも拘わらず、高弾性率の架橋重合
体微粒子を提供することができ、液晶表示パネル用のス
ペーサ等の製造に有効に利用できる。As described above, the method of the present invention can provide crosslinked polymer fine particles having a high modulus of elasticity despite its very simple operation, and can be used as a spacer for a liquid crystal display panel. It can be used effectively for manufacturing.
Claims (2)
単量体に対し３〜10重量％の有機過酸化物系ラジカル重
合開始剤を用い、水系媒体中で重合させることを特徴と
する架橋重合体微粒子の製造方法。1. A polymerizable monomer containing 50% by weight or more of a crosslinkable monomer is polymerized in an aqueous medium by using an organic peroxide radical polymerization initiator in an amount of 3 to 10% by weight. For producing crosslinked polymer fine particles.
を主成分とするものである請求項１記載の架橋重合体微
粒子の製造方法。2. The method for producing crosslinked polymer fine particles according to claim 1, wherein the crosslinkable monomer is mainly composed of meta-divinylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3011989A JP2635224B2 (en) | 1991-02-01 | 1991-02-01 | Method for producing crosslinked polymer fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3011989A JP2635224B2 (en) | 1991-02-01 | 1991-02-01 | Method for producing crosslinked polymer fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04314704A JPH04314704A (en) | 1992-11-05 |
| JP2635224B2 true JP2635224B2 (en) | 1997-07-30 |
Family
ID=11792999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3011989A Expired - Lifetime JP2635224B2 (en) | 1991-02-01 | 1991-02-01 | Method for producing crosslinked polymer fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2635224B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4009700B2 (en) | 2003-10-20 | 2007-11-21 | 株式会社テクノネットワーク四国 | Method for producing radical polymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0667990B2 (en) * | 1985-07-31 | 1994-08-31 | 東京有機化学工業株式会社 | Crosslinked copolymer and method for producing ion exchange resin using the same as a matrix |
-
1991
- 1991-02-01 JP JP3011989A patent/JP2635224B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04314704A (en) | 1992-11-05 |
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