JPH06256530A - Production of fine polymer granule - Google Patents
Production of fine polymer granuleInfo
- Publication number
- JPH06256530A JPH06256530A JP4137093A JP4137093A JPH06256530A JP H06256530 A JPH06256530 A JP H06256530A JP 4137093 A JP4137093 A JP 4137093A JP 4137093 A JP4137093 A JP 4137093A JP H06256530 A JPH06256530 A JP H06256530A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- solvent
- fine particles
- solubility
- polymer fine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は色材、例えば静電写真用
液体現像剤用あるいは充填材用のポリマー微粒子の製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing fine particles of a color material, for example, a liquid developer for electrostatic photography or a filler.
【０００２】[0002]
【従来の技術】従来のポリマー微粒子の製造方法として
は主に粉砕法と重合法がある。2. Description of the Related Art Conventional methods for producing fine polymer particles include a pulverization method and a polymerization method.
【０００３】[0003]
【発明が解決しようとする課題】粉砕法では樹脂を機械
的に粉砕するため粒径分布が幅広くなり、所望の粒径の
微粒子の収率が低くまた粒子の形状がそろわない。数μ
ｍ以下の粒子を得ようとすると大きな粉砕エネルギが必
要であり、さらに収率が低くなる。従って粉砕法で数μ
ｍ以下のポリマー微粒子を収率よく製造することは困難
であり、特に１μｍ以下のポリマー微粒子を製造するこ
とは事実上不可能である。In the crushing method, since the resin is mechanically crushed, the particle size distribution is widened, the yield of fine particles having a desired particle size is low, and the particle shapes are not uniform. Several μ
If particles of m or less are to be obtained, a large grinding energy is required, and the yield will be further reduced. Therefore, a few μ
It is difficult to produce polymer fine particles of m or less in high yield, and it is practically impossible to produce polymer fine particles of 1 μm or less.
【０００４】重合法によって均一な粒径のポリマー粒子
を生成した例はあるが、重合条件の制御が難かしい。ま
た、水系で重合した微粒子をインキや塗料等のビヒクル
中あるいは静電写真用液体現像剤の場合のように非水系
溶媒中に一次粒子で均一・安定に分散させることは難か
しい。さらに水系及び非水系での重合のどちらの場合
も、重合時に用いる分散剤、界面活性剤、重合開始剤、
未反応モノマー等が粒子表面に付着することは避けられ
ず、重合法で製造した微粒子を各種機能材として用いる
場合、それらの粒子表面の不純物を除去し精製すること
が必須であるが、微粒子になるほど精製は困難になる。Although there is an example in which polymer particles having a uniform particle size are produced by the polymerization method, it is difficult to control the polymerization conditions. Further, it is difficult to uniformly and stably disperse fine particles polymerized in an aqueous system as primary particles in a vehicle such as ink or paint or in a non-aqueous solvent as in the case of a liquid developer for electrostatic photography. Furthermore, in both cases of aqueous and non-aqueous polymerization, a dispersant used during polymerization, a surfactant, a polymerization initiator,
It is unavoidable that unreacted monomers etc. adhere to the particle surface, and when using fine particles produced by the polymerization method as various functional materials, it is essential to remove impurities on the surface of these particles and purify them. Indeed, purification becomes difficult.
【０００５】カルボキシル基又はエステル基を有するオ
レフィン系樹脂を該樹脂に対する溶解性において温度依
存性が高い溶媒中に加熱溶解した後、冷却して樹脂を微
粒子状に凝固させる方法が開示されているが（特公平４
−１３７０７号公報）、溶媒の溶解度パラメータ（以
下、ＳＰ値という）についての解析はなく、さらに析出
粒子径の制御方法について何も記されていない。A method has been disclosed in which an olefinic resin having a carboxyl group or an ester group is heated and dissolved in a solvent having a high temperature dependency in solubility with respect to the resin, and then cooled to solidify the resin into fine particles. (Patent Fairness 4
No. 13707), there is no analysis on the solubility parameter of the solvent (hereinafter, referred to as SP value), and nothing is described about the method of controlling the precipitated particle size.
【０００６】本発明は上記技術水準に鑑み、極めて微粒
で、かつ粒度分布も均一なポリマー微粒子の製造方法を
提供しようとするものである。In view of the above-mentioned state of the art, the present invention is to provide a method for producing polymer fine particles which are extremely fine and have a uniform particle size distribution.
【０００７】[0007]
【課題を解決するための手段】本発明は （１）非水系溶媒中にカルボキシル基又はエステル基を
有するオレフィン系樹脂を溶解し、次いで樹脂の溶媒に
対する溶解度を下げて樹脂の微粒子を析出させる方法に
おいて、上記非水系溶媒の溶解度パラメータが 樹脂
の溶解度パラメータに近く、かつ 樹脂の軟化点より
低い温度で樹脂が析出する値となるように溶媒組成を配
合した後、樹脂の溶媒に対する溶解度を下げて樹脂粒子
を析出させることを特徴とするポリマー微粒子の製造方
法。 （２）樹脂の溶解度パラメータと非水系溶媒の溶解度パ
ラメータの差を制御することにより０．１〜５０μｍの
範囲の任意の粒径のポリマー微粒子を製造することを特
徴とする上記（１）記載のポリマー微粒子の製造方法。 （３）樹脂を溶解した状態の非水系溶媒中の樹脂に対す
る良溶媒成分を除くことにより上記溶媒の樹脂に対する
溶解度を下げてポリマー微粒子を析出させることを特徴
とする上記（１）または（２）記載のポリマー微粒子の
製造方法。 （４）樹脂を溶解した状態の非水系溶媒中に、樹脂に対
する貧溶媒を加えることにより上記溶媒の樹脂に対する
溶解度を下げてポリマー微粒子を析出させることを特徴
とする上記（１）または（２）記載のポリマー微粒子の
製造方法。 （５）樹脂を溶解した状態の非水系溶媒を冷却すること
により、上記溶媒の樹脂に対する溶解度を下げてポリマ
ー微粒子を析出させることを特徴とする上記（１）また
は（２）記載のポリマー微粒子の製造方法。 （６）顔料又は染料により着色した樹脂を用いることに
より、あるいは樹脂の析出前に顔料又は染料を添加する
ことにより着色ポリマー微粒子を製造することを特徴と
する上記（１）〜（５）いずれかに記載のポリマー微粒
子の製造方法。 （７）樹脂の析出前に界面活性剤、分散剤その他の常用
添加剤を添加した後、樹脂を析出させることを特徴とす
る上記（１）〜（５）いずれかに記載のポリマー微粒子
の製造方法。 である。The present invention provides (1) a method of dissolving an olefinic resin having a carboxyl group or an ester group in a non-aqueous solvent, and then lowering the solubility of the resin in the solvent to precipitate fine particles of the resin. In the above, the solvent composition was blended so that the solubility parameter of the non-aqueous solvent was close to the solubility parameter of the resin and the resin was deposited at a temperature lower than the softening point of the resin, and then the solubility of the resin in the solvent was lowered. A method for producing fine polymer particles, which comprises depositing resin particles. (2) The polymer fine particles having an arbitrary particle size in the range of 0.1 to 50 μm are produced by controlling the difference between the solubility parameter of the resin and the solubility parameter of the non-aqueous solvent. Method for producing fine polymer particles. (3) The above-mentioned (1) or (2), wherein the good solvent component for the resin in the non-aqueous solvent in which the resin is dissolved is removed to reduce the solubility of the solvent in the resin to precipitate the fine polymer particles. A method for producing the fine polymer particles described above. (4) The above-mentioned (1) or (2), wherein the poor solvent for the resin is added to the non-aqueous solvent in the state where the resin is dissolved to reduce the solubility of the solvent in the resin to precipitate the polymer fine particles. A method for producing the fine polymer particles described above. (5) The polymer fine particles according to the above (1) or (2), wherein the solubility of the solvent in the resin is lowered to precipitate the polymer fine particles by cooling the non-aqueous solvent in which the resin is dissolved. Production method. (6) Any of the above-mentioned (1) to (5), wherein the colored polymer fine particles are produced by using a resin colored with a pigment or a dye, or by adding the pigment or the dye before the precipitation of the resin. The method for producing fine polymer particles according to [4]. (7) Preparation of polymer fine particles according to any one of the above (1) to (5), characterized in that the resin is precipitated after the addition of a surfactant, a dispersant and other commonly used additives before the precipitation of the resin. Method. Is.
【０００８】本発明において使用される樹脂はカルボキ
シル基又はエステル基を有するオレフィン系樹脂であ
り、例えばエチレン・酢酸ビニル共重合体、エチレン・
酢酸ビニル共重合体の部分ケン化物、エチレン・（メ
タ）アクリル酸共重合体、エチレン・（メタ）アクリル
酸エステル共重合体、（メタ）アクリル酸エステル樹
脂、スチレン・（メタ）アクリル酸共重合体、スチレン
・（メタ）アクリル酸エステル共重合体等がある。これ
らの中から１種もしくは必要に応じて２種以上を混ぜて
使用することができる。The resin used in the present invention is an olefinic resin having a carboxyl group or an ester group, such as ethylene / vinyl acetate copolymer and ethylene / vinyl acetate.
Partially saponified vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / (meth) acrylic acid ester copolymer, (meth) acrylic acid ester resin, styrene / (meth) acrylic acid copolymer Examples include coalesced products and styrene / (meth) acrylic acid ester copolymers. Among these, one kind may be used, or two or more kinds may be mixed and used as necessary.
【０００９】また、上記樹脂を顔料および／又は染料等
の着色材で着色しても差支えなく、具体的にはあらかじ
め樹脂に加熱混練等の手段により着色材を添加しておく
が、本発明の製造工程中の樹脂析出前に着色材を添加す
る等の手段を採用すればよい。There is no problem even if the above-mentioned resin is colored with a coloring material such as a pigment and / or a dye. Specifically, the coloring material is added to the resin in advance by means such as heat kneading. Means such as adding a colorant before the resin deposition during the manufacturing process may be adopted.
【００１０】本発明で用いる非水溶媒は単独溶媒又は混
合溶媒のどちらでもよい。用いる溶媒の例としては直鎖
脂肪族炭化水素、分岐鎖脂肪族炭化水素、ハロゲン化脂
肪族炭化水素、芳香族炭化水素、全炭素原子数１２以下
の直鎖又は分岐鎖脂肪族アルコール等の中から選ばれた
１種又は必要に応じて２種以上の混合溶媒等があげられ
る。The non-aqueous solvent used in the present invention may be either a single solvent or a mixed solvent. Examples of the solvent to be used include straight-chain aliphatic hydrocarbons, branched-chain aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, and straight-chain or branched-chain aliphatic alcohols having 12 or less carbon atoms in total. Examples thereof include one kind selected from the above or a mixed solvent of two or more kinds as necessary.
【００１１】[0011]
【作用】本発明において、カルボキシル基又はエステル
基を有するオレフィン系樹脂を用いて０．１〜５０μｍ
の任意の粒径の微粒子を生成するためには、樹脂のＳＰ
値と溶媒のＳＰ値の差を制御した状態で溶媒の樹脂に対
する溶解度を下げて樹脂を微粒子状に析出させるとよ
い。以下に詳細に説明する。In the present invention, an olefinic resin having a carboxyl group or an ester group is used to form 0.1 to 50 μm.
In order to generate fine particles of any particle size,
It is advisable to reduce the solubility of the solvent in the resin and precipitate the resin in the form of fine particles while controlling the difference between the value and the SP value of the solvent. The details will be described below.
【００１２】（１）溶媒のＳＰ値が樹脂のＳＰ値′
に近く、かつ樹脂の軟化点Ｔｓより低い温度で樹脂が析
出するように溶媒成分を決める。この時の溶媒のＳＰ値
と樹脂のＳＰ値′の差ΔＳＰによって析出粒径が決
定される。ΔＳＰが小さいほど粒径は小さくなる。図１
に示すように、“溶媒のＳＰ値対析出粒径”の曲線は、
樹脂のＳＰ値′を中心に見た場合、必ずしも左右対称
となるとは限らないが、溶媒のＳＰ値を樹脂のＳＰ値
′より高く設定するか、低く設定するかは後の操作
上、粒径制御をしやすい側に設定すればよい。図１、後
記の図２では溶媒のＳＰ値を樹脂のＳＰ値′より低
い側に設定した例である。溶媒のＳＰ値を樹脂のＳＰ
値′と全く同じ値に設定してもよいことはもちろんで
ある。(1) The SP value of the solvent is the SP value of the resin '
The solvent component is determined so that the resin is deposited at a temperature close to the temperature Ts and lower than the softening point Ts of the resin. At this time, the precipitation particle size is determined by the difference ΔSP between the SP value of the solvent and the SP value 'of the resin. The smaller the ΔSP, the smaller the particle size. Figure 1
As shown in, the curve of “SP value of solvent vs. precipitation particle size” is
The SP value of the resin is not necessarily symmetrical when viewed from the center, but whether the SP value of the solvent is set higher or lower than the SP value of the resin depends on the particle size depending on the subsequent operation. It may be set on the side where control is easy. FIG. 1 and FIG. 2 described later are examples in which the SP value of the solvent is set lower than the SP value 'of the resin. SP value of solvent is SP of resin
Of course, it may be set to the same value as the value '.
【００１３】（２）ＳＰ値に設定した溶媒に樹脂を溶
解する。この時、溶解させる樹脂量は樹脂の軟化点Ｔｓ
以下の任意の温度Ｔ1 における溶解度Ｓ1 よりわずかに
少ない程度とするとよい（図２の（ａ）参照）。(2) Dissolve the resin in the solvent set to the SP value. At this time, the amount of resin to be dissolved depends on the softening point Ts of the resin.
The solubility may be slightly lower than the solubility S 1 at any temperature T 1 below (see (a) of FIG. 2).
【００１４】（３）溶媒のＳＰ値を→→と変える
ことで樹脂の溶解度を下げてポリマー微粒子を析出させ
る例を図１，２に示す。溶媒のＳＰ値の状態で析出開
始し、溶媒のＳＰ値→でポリマー微粒子を析出させ
ると図１から判るように、粒径０．２〜１．０μｍの間
の粒度分布をもつポリマー微粒子が析出する。粒径頻度
がピークとなる粒径および粒度分布状態は溶媒の温度Ｔ
1 、溶媒のＳＰ値の変化速度、溶媒の攪拌速度等によっ
て制御すればよい。溶媒の最初のＳＰ値を樹脂のＳＰ値
より高い側に設定した場合は、溶媒のＳＰ値をさらに高
い側へ変化させることで溶媒の樹脂に対する溶解度を下
げて樹脂を析出させてもよい。(3) FIGS. 1 and 2 show an example in which the solubility of the resin is lowered and the polymer fine particles are deposited by changing the SP value of the solvent to →→. As shown in FIG. 1, when the precipitation starts in the state of the SP value of the solvent and the polymer particles are precipitated with the SP value of the solvent →, the polymer particles having a particle size distribution between 0.2 and 1.0 μm are precipitated as shown in FIG. To do. The particle size and the particle size distribution state where the particle size frequency peaks are the temperature T of the solvent.
1. It may be controlled by the changing speed of the SP value of the solvent, the stirring speed of the solvent, and the like. When the initial SP value of the solvent is set higher than the SP value of the resin, the solubility of the solvent in the resin may be lowered to precipitate the resin by changing the SP value of the solvent to the higher side.
【００１５】（４）溶媒の樹脂に対する溶解度を下げる
方法としては前記（３）項のように溶媒のＳＰ値を変化
させることが好ましく、その手段として良溶媒除去ある
いは貧溶媒添加などがあるが、溶媒の温度Ｔ1 をさらに
下げることで溶解度を下げる方法を用いてもよい。(4) As a method of decreasing the solubility of the solvent in the resin, it is preferable to change the SP value of the solvent as described in the above item (3), and as a means therefor, there are removal of a good solvent and addition of a poor solvent. A method of lowering the solubility by further lowering the temperature T 1 of the solvent may be used.
【００１６】[0016]
（実施例１）攪拌機、温度計、還流冷却器、真空脱気装
置を備えた容器に、分岐鎖脂肪族炭化水素 アイソパー
Ｇ（エッソ石油社製）：７２部、芳香族炭化水素 トル
エン（片山化学社製）：４８部、脂肪族アルコール エ
タノール（片山化学社製）：３０部を投入しＳＰ値９．
１８の非水系溶媒とした。この中にエチレン・酢酸ビニ
ル共重合体の部分ケン化物 デュミランＣ−２２８０
（武田薬品社製 ＳＰ値８．９３）：２部を加え、７５
℃で攪拌しデュミランを完全に溶解した後、デュミラン
Ｃ−２２８０の軟化点７８℃より低い４０℃に溶媒の温
度を保ちながら（この時、デュミランは溶解した状態）
容器中を真空脱気し、トルエン、エタノールを溶媒中か
ら除去することによってポリマー微粒子を析出させた。
このようにして得られたポリマー微粒子は体積基準の５
０％粒径が１．０μｍであった。(Example 1) In a container equipped with a stirrer, a thermometer, a reflux condenser, and a vacuum degassing device, a branched chain aliphatic hydrocarbon Isopar G (manufactured by Esso Oil Co., Ltd.): 72 parts, aromatic hydrocarbon toluene (Katayama Chemical) (Manufactured by Katayama Chemical Co., Ltd.): 48 parts, ethanol of aliphatic alcohol (manufactured by Katayama Chemical Co., Ltd.): 30 parts, and SP value of 9.
Eighteen non-aqueous solvents were used. Partially saponified product of ethylene / vinyl acetate copolymer Dumilan C-2280
(Takeda Yakuhin SP value 8.93): 2 parts added, 75
After stirring to completely dissolve dumilan, the temperature of the solvent was maintained at 40 ° C, which is lower than the softening point of 78 ° C of dumilan C-2280 (at this time, dumilan was in a dissolved state).
The container was vacuum degassed, and toluene and ethanol were removed from the solvent to precipitate polymer particles.
The polymer fine particles thus obtained have a volume-based value of 5
The 0% particle size was 1.0 μm.
【００１７】（実施例２）実施例１において、アイソパ
ーＧを７２部の代わりに６０部、トルエンを４８部の代
わりに４０部、エタノールを３０部の代わりに５０部と
してＳＰ値９．８９の非水系溶媒とする他は同様にして
ポリマー粒子を析出させた。得られた粒子は体積基準の
５０％粒径が２．４μｍであった。(Example 2) In Example 1, 60 parts instead of 72 parts of Isopar G, 40 parts instead of 48 parts of toluene, and 50 parts instead of 30 parts of ethanol, the SP value was 9.89. Polymer particles were deposited in the same manner except that a non-aqueous solvent was used. The obtained particles had a volume-based 50% particle size of 2.4 μm.
【００１８】（実施例３）実施例１において、容器中を
真空脱気する代わりにエタノール５０部を添加する他は
同様にしてポリマー微粒子を析出させた。得られた粒子
は体積基準の５０％粒径が１．１μｍであった。(Example 3) Polymer particles were deposited in the same manner as in Example 1 except that 50 parts of ethanol was added instead of vacuum degassing the container. The obtained particles had a volume-based 50% particle size of 1.1 μm.
【００１９】（実施例４）実施例１において、容器中を
真空脱気する代わりに、さらに溶媒の温度を下げる他は
同様にしてポリマー微粒子を析出させた。微粒子は３８
℃で析出しはじめ、得られた粒子は体積基準の５０％粒
径が１．０μｍであった。(Example 4) Polymer particles were deposited in the same manner as in Example 1 except that the temperature of the solvent was further lowered instead of vacuum deaeration in the container. 38 fine particles
At 50 ° C., precipitation started, and the obtained particles had a volume-based 50% particle size of 1.0 μm.
【００２０】（実施例５）実施例１において、エチレン
・酢酸ビニル共重合体の部分ケン化物デュミランＣ−２
２８０の代わりに、エチレン・酢酸ビニル共重合体エバ
フレックス２２０（三井・デュポン社製）：２部を加え
る他は同様にしてポリマー微粒子を析出させた。得られ
たポリマー微粒子は体積基準の５０％粒径が１．３μｍ
であった。(Example 5) In Example 1, a partially saponified product of ethylene-vinyl acetate copolymer Dumilan C-2
Instead of 280, polymer fine particles were deposited in the same manner except that 2 parts of ethylene-vinyl acetate copolymer Evaflex 220 (manufactured by Mitsui DuPont) was added. The obtained polymer particles have a volume-based 50% particle size of 1.3 μm.
Met.
【００２１】（実施例６）実施例２において、エチレン
・酢酸ビニル共重合体の部分ケン化物デュミランＣ−２
２８０の代わりに、エチレン・アクリル酸エチル共重合
体ＥＶＡＦＬＥＸ−ＥＥＡ Ａ−７０４（三井・デュポ
ン社製）：２部を加える他は同様にしてポリマー微粒子
を析出させた。得られたポリマー微粒子は体積基準の５
０％粒径が１．５μｍであった。Example 6 In Example 2, partially saponified ethylene-vinyl acetate copolymer Dumilan C-2
Instead of 280, ethylene / ethyl acrylate copolymer EVAFLEX-EEA A-704 (manufactured by Mitsui DuPont): Polymer fine particles were similarly deposited except that 2 parts were added. The polymer particles obtained are 5 by volume.
The 0% particle size was 1.5 μm.
【００２２】（実施例７）実施例１において、エチレン
・酢酸ビニル共重合体の部分ケン化物デュミランＣ−２
２８０の代わりに、エチレン・メタクリル酸共重合体ニ
ュクレル５９９（三井・デュポン社製）：２部を加える
他は同様にしてポリマー微粒子を析出させた。得られた
ポリマー微粒子は体積基準の５０％粒径が１．０μｍで
あった。Example 7 In Example 1, a partially saponified product of ethylene / vinyl acetate copolymer Dumilan C-2
Instead of 280, polymer fine particles were deposited in the same manner except that 2 parts of ethylene / methacrylic acid copolymer Nucrel 599 (manufactured by Mitsui DuPont) was added. The obtained polymer particles had a volume-based 50% particle size of 1.0 μm.
【００２３】（実施例８）実施例１において、デュミラ
ンＣ−２２８０の代わりに、エチレン・酢酸ビニル共重
合体の部分ケン化物デュミランＣ−１５５０（武田薬品
社製・ＳＰ値８．８４）：２部を加える他は同様にし
て、体積基準の５０％粒径が０．４１μｍのポリマー微
粒子を得た。(Example 8) In Example 1, instead of Dumilan C-2280, a partially saponified product of ethylene / vinyl acetate copolymer Dumilan C-1550 (manufactured by Takeda Pharmaceutical Co., SP value 8.84): 2 Polymer particles having a volume-based 50% particle size of 0.41 μm were obtained in the same manner except that parts were added.
【００２４】（実施例９）攪拌機、温度計、還流冷却
器、真空脱気装置を備えた容器に、分岐鎖脂肪族炭化水
素 アイソパーＧ：２１６部、芳香族炭化水素 トルエ
ン：１４４部、脂肪族アルコール エタノール：９０部
を投入しＳＰ値９．１８の非水系溶媒とした。この中に
エチレン・酢酸ビニル共重合体の部分ケン化物 デュミ
ランＣ−１５５０：６部、着色材フタロシアニンブルー
Ｎｏ．１（大日精化社製）：１．２部を加えて７５℃で
攪拌し、デュミランを完全に溶解した後、デュミランＣ
−１５５０の軟化点５０℃より低い４０℃に溶媒の温度
を保ちながら（この時、デュミランは溶解した状態）容
器中を真空脱気し、トルエン、エタノールを溶媒中から
除去することによって着色ポリマー微粒子を析出させ
た。得られたポリマー微粒子は体積基準の５０％粒径が
１．９μｍであった。(Example 9) In a container equipped with a stirrer, a thermometer, a reflux condenser, and a vacuum degasser, a branched chain aliphatic hydrocarbon Isopar G: 216 parts, aromatic hydrocarbon toluene: 144 parts, aliphatic Alcohol ethanol: 90 parts was added to obtain a non-aqueous solvent having an SP value of 9.18. Partially saponified product of ethylene / vinyl acetate copolymer, Dumilan C-1550: 6 parts, coloring material phthalocyanine blue No. 1 (manufactured by Dainichiseika Co., Ltd.): 1.2 parts were added, and the mixture was stirred at 75 ° C. to completely dissolve dumilan, and then dumilan C
While maintaining the temperature of the solvent at 40 ° C., which is lower than the softening point of 50 ° C. of −1550 (at this time, dumilan is in a dissolved state), the container is vacuum-deaerated, and toluene and ethanol are removed from the solvent to obtain colored polymer fine particles. Was deposited. The obtained polymer particles had a volume-based 50% particle size of 1.9 μm.
【００２５】（実施例１０）実施例１において、デュミ
ランＣ−１５５０の代わりにデュミランＣ−２２８０：
６部、フタロシアニンブルーＮｏ．１の代わりにカーミ
ン１４８０（大日精化社製）：１．２部を加える他は同
様にして、体積基準の５０％粒径が３．６μｍの着色
（紅）ポリマー微粒子分散液を得た。このポリマー微粒
子分散液中の混合溶媒をアイソパーＧに置換し、帯電付
与剤等の常用添加剤を加えて静電写真液体現像剤（固形
分３％）とした。この現像剤を市販の湿式電子写真複写
機に入れ、市販のコート紙上にコピーを行ったところ画
像濃度１．６２Ｄ、転写率９９％、地汚れ０．０１Ｄの
解像度にすぐれた像が得られた。なお濃度、地汚れの測
定にはマクベス濃度計を用いた。また転写率は次の式に
よって計算した。 転写率（％）＝（１−転写後の感光面上のトナー濃度／
転写前の感光面上のトナー濃度）×１００Example 10 In Example 1, instead of Dumiran C-1550, Dumiran C-2280:
6 parts, Phthalocyanine Blue No. Carmine 1480 (manufactured by Dainichiseika Co., Ltd.) in place of 1 was added in the same manner as above to obtain a colored (red) polymer fine particle dispersion having a volume-based 50% particle size of 3.6 μm. The mixed solvent in this polymer particle dispersion was replaced with Isopar G, and a conventional additive such as a charge-imparting agent was added to prepare an electrostatic photography liquid developer (solid content: 3%). When this developer was put in a commercially available wet electrophotographic copying machine and copied on a commercially available coated paper, an image having an image density of 1.62D, a transfer rate of 99% and a background stain of 0.01D was obtained. . A Macbeth densitometer was used to measure the density and background stain. The transfer rate was calculated by the following formula. Transfer rate (%) = (1-toner density on photosensitive surface after transfer /
Toner density on the photosensitive surface before transfer) x 100
【００２６】（実施例１１）攪拌機、温度計、還流冷却
器、真空脱気装置を備えた容器に、分岐鎖脂肪族炭化水
素 アイソパーＧ：１９８部、芳香族炭化水素 トルエ
ン：１３２部、脂肪族アルコール エタノール：１２０
部を投入しＳＰ値９．５４の非水系溶媒とした。この中
にデュミランＣ−２２８０：６部、着色材ベンジジンイ
エローＨ７０５５（大日精化社製）：１．２部を加えて
７５℃で攪拌し、デュミランを完全に溶解した後、デュ
ミランＣ−２２８０の軟化点７８℃より低い４０℃に溶
媒の温度を保ちながら容器中を真空脱気し、トルエン、
エタノールを溶媒中から除去することによって着色ポリ
マー微粒子を析出させた。得られたポリマー微粒子は体
積基準の５０％粒径が２．４μｍであった。(Example 11) In a container equipped with a stirrer, a thermometer, a reflux condenser, and a vacuum deaeration device, a branched chain aliphatic hydrocarbon Isopar G: 198 parts, aromatic hydrocarbon toluene: 132 parts, aliphatic Alcohol ethanol: 120
Parts to make a non-aqueous solvent having an SP value of 9.54. Dumilan C-2280: 6 parts, coloring material benzidine yellow H7055 (manufactured by Dainichiseika Chemicals Co., Ltd.): 1.2 parts were added thereto, and the mixture was stirred at 75 ° C. to completely dissolve dumiran, and then dumiran C-2280 was added. Vacuum degas the container while maintaining the temperature of the solvent at 40 ° C, which is lower than the softening point of 78 ° C.
Colored polymer particles were precipitated by removing ethanol from the solvent. The resulting polymer particles had a volume-based 50% particle size of 2.4 μm.
【００２７】（実施例１２）実施例１０において、デュ
ミランＣ−２２８０を加える際に、界面活性剤スバン８
５（ソルビタントリオリエート）：２部を同時に加える
他は同様にして、体積基準の５０％粒径が２．０μｍの
着色（紅）ポリマー微粒子分散液を得た。(Example 12) In Example 10, when Dumilan C-2280 was added, the surfactant Suban 8 was added.
5 (Sorbitan trioriate): A colored (red) polymer fine particle dispersion having a volume-based 50% particle size of 2.0 μm was obtained in the same manner except that 2 parts were simultaneously added.
【００２８】[0028]
【発明の効果】本発明によれば下記の効果を奏すること
ができる。 粉砕法に比べて粒子径及び粒子形がそろって均一な
粒子となり、又粉砕法では事実上不可能な１μｍ以下の
ポリマー微粒子の生成が再現性よく可能である。 重合法に比べて微粒子の生成条件は制御しやす、又
重合法のように生成したポリマー微粒子表面が分散剤、
重合開始剤等の不純物によって汚染されることがないた
め後処理が容易である。 非水系においてポリマー微粒子を生成させるもので
あるから、生成した微粒子をインキや塗料のビヒクル中
あるいは有機溶媒中に分散させるのが容易である等の効
果を有する。According to the present invention, the following effects can be obtained. Compared with the pulverization method, the particle diameter and particle shape are more uniform and uniform particles are obtained, and it is possible to reproducibly produce polymer fine particles of 1 μm or less, which is virtually impossible by the pulverization method. Compared to the polymerization method, the conditions for producing fine particles are easier to control, and the surface of the polymer particles produced as in the polymerization method is a dispersant,
Post-treatment is easy because it is not contaminated by impurities such as a polymerization initiator. Since the polymer fine particles are generated in a non-aqueous system, it has an effect that it is easy to disperse the generated fine particles in a vehicle of an ink or a paint or an organic solvent.
【図１】本発明における溶媒のＳＰ値と析出粒径の関係
を示す図表。FIG. 1 is a chart showing the relationship between the SP value of a solvent and the precipitated particle size in the present invention.
【図２】本発明における溶媒のＳＰ値と樹脂の溶解度の
関係を示す図表。FIG. 2 is a chart showing the relationship between the SP value of a solvent and the solubility of a resin in the present invention.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年５月７日[Submission date] May 7, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項３[Name of item to be corrected] Claim 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項４[Name of item to be corrected] Claim 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項５[Name of item to be corrected] Claim 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００１[Correction target item name] 0001
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００１】[0001]
【産業上の利用分野】本発明は色材、例えば静電写真用
液体現像剤用、化粧用、添加剤用あるいは充填材用のポ
リマー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 fine particles of a color material, for example, a liquid developer for electrostatic photography , cosmetics, additives or fillers.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００７[Correction target item name] 0007
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００７】[0007]
【課題を解決するための手段】本発明は （１）非水系溶媒中にカルボキシル基又はエステル基を
有するオレフィン系樹脂を溶解し、次いで樹脂の溶媒に
対する溶解度を下げて樹脂の微粒子を析出させる方法に
おいて、上記非水系溶媒の溶解度パラメータが 樹脂
の溶解度パラメータに近く、かつ 樹脂の軟化点より
低い温度で樹脂が析出する値となるように溶媒組成を配
合した後、樹脂の溶媒に対する溶解度を下げて樹脂粒子
を析出させることを特徴とするポリマー微粒子の製造方
法。 （２）樹脂の溶解度パラメータと非水系溶媒の溶解度パ
ラメータの差を制御することにより０．１〜５０μｍの
範囲の任意の粒径のポリマー微粒子を製造することを特
徴とする上記（１）記載のポリマー微粒子の製造方法。 （３）樹脂を溶解した状態の非水系溶媒中の樹脂に対す
る良溶媒成分を除くことにより上記樹脂の溶媒に対する
溶解度を下げてポリマー微粒子を析出させることを特徴
とする上記（１）または（２）記載のポリマー微粒子の
製造方法。 （４）樹脂を溶解した状態の非水系溶媒中に、樹脂に対
する貧溶媒を加えることにより上記樹脂の溶媒に対する
溶解度を下げてポリマー微粒子を析出させることを特徴
とする上記（１）または（２）記載のポリマー微粒子の
製造方法。 （５）樹脂を溶解した状態の非水系溶媒を冷却すること
により、上記樹脂の溶媒に対する溶解度を下げてポリマ
ー微粒子を析出させることを特徴とする上記（１）また
は（２）記載のポリマー微粒子の製造方法。 （６）顔料又は染料により着色した樹脂を用いることに
より、あるいは樹脂の析出前に顔料又は染料を添加する
ことにより着色ポリマー微粒子を製造することを特徴と
する上記（１）〜（５）いずれかに記載のポリマー微粒
子の製造方法。 （７）樹脂の析出前に界面活性剤、分散剤その他の常用
添加剤を添加した後、樹脂を析出させることを特徴とす
る上記（１）〜（５）いずれかに記載のポリマー微粒子
の製造方法。 である。The present invention provides (1) a method of dissolving an olefinic resin having a carboxyl group or an ester group in a non-aqueous solvent, and then lowering the solubility of the resin in the solvent to precipitate fine particles of the resin. In the above, the solvent composition was blended so that the solubility parameter of the non-aqueous solvent was close to the solubility parameter of the resin and the resin was deposited at a temperature lower than the softening point of the resin, and then the solubility of the resin in the solvent was lowered. A method for producing fine polymer particles, which comprises depositing resin particles. (2) The polymer fine particles having an arbitrary particle size in the range of 0.1 to 50 μm are produced by controlling the difference between the solubility parameter of the resin and the solubility parameter of the non-aqueous solvent. Method for producing fine polymer particles. (3) The above-mentioned (1) or (2), characterized in that the good solvent component for the resin in the non-aqueous solvent in which the resin is dissolved is removed to reduce the solubility of the resin in the solvent to precipitate the polymer fine particles. A method for producing the fine polymer particles described above. (4) The above-mentioned (1) or (2), wherein the poor solvent for the resin is added to the non-aqueous solvent in which the resin is dissolved to reduce the solubility of the resin in the solvent to precipitate the fine polymer particles. A method for producing the fine polymer particles described above. (5) The polymer fine particles according to (1) or (2) above, wherein the solubility of the resin in the solvent is lowered to precipitate the polymer fine particles by cooling the non-aqueous solvent in which the resin is dissolved. Production method. (6) Any of the above-mentioned (1) to (5), wherein the colored polymer fine particles are produced by using a resin colored with a pigment or a dye, or by adding the pigment or the dye before the precipitation of the resin. The method for producing fine polymer particles according to [4]. (7) Preparation of polymer fine particles according to any one of the above (1) to (5), characterized in that the resin is precipitated after the addition of a surfactant, a dispersant and other commonly used additives before the precipitation of the resin. Method. Is.
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】また、上記樹脂を顔料および／又は染料等
の着色材で着色しても差支えなく、具体的にはあらかじ
め樹脂に加熱混練等の手段により着色材を添加しておく
か、又は本発明の製造工程中の樹脂析出前に着色材を添
加する等の手段を採用すればよい。There is no problem even if the above-mentioned resin is colored with a coloring material such as a pigment and / or a dye. Specifically, the coloring material is added to the resin in advance by means such as heat kneading.
Alternatively, a means such as adding a colorant before the resin deposition during the manufacturing process of the present invention may be adopted.
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２４[Name of item to be corrected] 0024
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２４】（実施例９）攪拌機、温度計、還流冷却
器、真空脱気装置を備えた容器に、分岐鎖脂肪族炭化水
素 アイソパーＧ：２１６部、芳香族炭化水素 トルエ
ン：１４４部、脂肪族アルコール エタノール：９０部
を投入しＳＰ値９．１８の非水系溶媒とした。この中に
エチレン・酢酸ビニル共重合体の部分ケン化物 デュミ
ランＣ−１５５０：６部、着色材フタロシアニンブルー
Ｎｏ．１（大日精化社製）：１．２部を加えて７５℃で
攪拌し、デュミランを完全に溶解した後、デュミランＣ
−１５５０の軟化点５０℃より低い４０℃に溶媒の温度
を保ちながら（この時、デュミランは溶解した状態）容
器中を真空脱気し、トルエン、エタノールを溶媒中から
除去することによって着色藍ポリマー微粒子を析出させ
た。得られたポリマー微粒子は体積基準の５０％粒径が
１．９μｍであった。(Example 9) In a container equipped with a stirrer, a thermometer, a reflux condenser, and a vacuum degasser, a branched chain aliphatic hydrocarbon Isopar G: 216 parts, aromatic hydrocarbon toluene: 144 parts, aliphatic Alcohol ethanol: 90 parts was added to obtain a non-aqueous solvent having an SP value of 9.18. Partially saponified product of ethylene / vinyl acetate copolymer, Dumilan C-1550: 6 parts, coloring material phthalocyanine blue No. 1 (manufactured by Dainichiseika Co., Ltd.): 1.2 parts were added, and the mixture was stirred at 75 ° C. to completely dissolve dumilan, and then dumilan C
While maintaining the temperature of the solvent to less 40 ° C. than the softening point 50 ° C. of -1550 (at this time, Deyumiran state dissolved) was vacuum degassed in a vessel, colored blue polymer by removing toluene, ethanol from solvent Fine particles were deposited. The obtained polymer particles had a volume-based 50% particle size of 1.9 μm.
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２５[Name of item to be corrected] 0025
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２５】（実施例１０）実施例９において、デュミ
ランＣ−１５５０の代わりにデュミランＣ−２２８０：
６部、フタロシアニンブルーＮｏ１の代わりにカーミン
１４８０（大日精化社製）：１．２部を加える他は同様
にして、体積基準の５０％粒径が３．６μｍの着色
（紅）ポリマー微粒子分散液を得た。このポリマー微粒
子分散液中の混合溶媒をアイソパーＧに置換し、帯電付
与剤等の常用添加剤を加えて静電写真液体現像剤（固形
分３％）とした。この現像剤を市販の湿式電子写真複写
機に入れ、市販のコート紙上にコピーを行ったところ画
像濃度１．６２Ｄ、転写率９９％、地汚れ０．０１Ｄの
解像度にすぐれた像が得られた。なお濃度、地汚れの測
定にはマクベス濃度計を用いた。また転写率は次の式に
よって計算した。 転写率（％）＝｛１−（転写後の感光面上のトナー濃度
／転写前の感光面上のトナー濃度）｝×１００Example 10 In Example 9 , instead of Dumiran C-1550, Dumiran C-2280:
6 parts, Carmine 1480 (manufactured by Dainichiseika Co., Ltd.) in place of phthalocyanine blue No1: 1.2 parts in the same manner except that 1.2% of volume-based 50% particle size 3.6 μm colored (red) polymer fine particle dispersion A liquid was obtained. The mixed solvent in this polymer particle dispersion was replaced with Isopar G, and a conventional additive such as a charge-imparting agent was added to prepare an electrostatic photography liquid developer (solid content: 3%). When this developer was put in a commercially available wet electrophotographic copying machine and copied on a commercially available coated paper, an image having an image density of 1.62D, a transfer rate of 99% and a background stain of 0.01D was obtained. . A Macbeth densitometer was used to measure the density and background stain. The transfer rate was calculated by the following formula. Transfer rate (%) = { 1- ( toner density on photosensitive surface after transfer / toner density on photosensitive surface before transfer) } × 100
【手続補正９】[Procedure Amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２８[Correction target item name] 0028
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２８】[0028]
【発明の効果】本発明によれば下記の効果を奏すること
ができる。 粉砕法に比べて粒子径及び粒子形がそろって均一な
粒子となり、又粉砕法では事実上不可能な１μｍ以下の
ポリマー微粒子の生成が再現性よく可能である。 重合法に比べて微粒子の生成条件は制御しやすく、
又重合法のように生成したポリマー微粒子表面が分散
剤、重合開始剤等の不純物によって汚染されることがな
いため後処理が容易である。 非水系においてポリマー微粒子を生成させるもので
あるから、生成した微粒子をインキや塗料のビヒクル中
あるいは有機溶媒中に分散させるのが容易である等の効
果を有する。According to the present invention, the following effects can be obtained. Compared with the pulverization method, the particle diameter and particle shape are more uniform and uniform particles are obtained, and it is possible to reproducibly produce polymer fine particles of 1 μm or less, which is virtually impossible by the pulverization method. Generating conditions of the fine particles in comparison with the polymerization process rather than ease control,
Further, since the surface of the fine polymer particles produced as in the polymerization method is not contaminated with impurities such as a dispersant and a polymerization initiator, the post-treatment is easy. Since the polymer fine particles are generated in a non-aqueous system, it has an effect that it is easy to disperse the generated fine particles in a vehicle of an ink or a paint or an organic solvent.
Claims (7)
テル基を有するオレフィン系樹脂を溶解し、次いで樹脂
の溶媒に対する溶解度を下げて樹脂の微粒子を析出させ
る方法において、上記非水系溶媒の溶解度パラメータが
樹脂の溶解度パラメータに近く、かつ 樹脂の軟
化点より低い温度で樹脂が析出する値となるように溶媒
組成を配合した後、樹脂の溶媒に対する溶解度を下げて
樹脂粒子を析出させることを特徴とするポリマー微粒子
の製造方法。1. A method of dissolving an olefinic resin having a carboxyl group or an ester group in a non-aqueous solvent and then decreasing the solubility of the resin in the solvent to deposit fine particles of the resin, wherein the solubility parameter of the non-aqueous solvent is Characterized by compounding the solvent composition so that the resin has a value close to the solubility parameter of the resin and at a temperature lower than the softening point of the resin, and then decreasing the solubility of the resin in the solvent to precipitate the resin particles. Method for producing fine polymer particles.
溶解度パラメータの差を制御することにより０．１〜５
０μｍの範囲の任意の粒径のポリマー微粒子を製造する
ことを特徴とする請求項１記載のポリマー微粒子の製造
方法。2. By controlling the difference between the solubility parameter of the resin and the solubility parameter of the non-aqueous solvent, 0.1 to 5 can be obtained.
2. The method for producing polymer fine particles according to claim 1, wherein polymer fine particles having an arbitrary particle size in the range of 0 μm are produced.
脂に対する良溶媒成分を除くことにより上記溶媒の樹脂
に対する溶解度を下げてポリマー微粒子を析出させるこ
とを特徴とする請求項１または２記載のポリマー微粒子
の製造方法。3. The polymer fine particles are precipitated by removing the good solvent component for the resin in the non-aqueous solvent in which the resin is dissolved, thereby decreasing the solubility of the solvent in the resin and precipitating polymer fine particles. The method for producing polymer fine particles of.
樹脂に対する貧溶媒を加えることにより上記溶媒の樹脂
に対する溶解度を下げてポリマー微粒子を析出させるこ
とを特徴とする請求項１または２記載のポリマー微粒子
の製造方法。4. A non-aqueous solvent in which a resin is dissolved,
The method for producing polymer fine particles according to claim 1 or 2, wherein the solubility of the solvent in the resin is lowered to deposit the polymer fine particles by adding a poor solvent for the resin.
することにより、上記溶媒の樹脂に対する溶解度を下げ
てポリマー微粒子を析出させることを特徴とする請求項
１または２記載のポリマー微粒子の製造方法。5. The production of polymer fine particles according to claim 1 or 2, wherein the solubility of the solvent in the resin is lowered to precipitate the polymer fine particles by cooling the non-aqueous solvent in which the resin is dissolved. Method.
ることにより、あるいは樹脂の析出前に顔料又は染料を
添加することにより着色ポリマー微粒子を製造すること
を特徴とする請求項１〜５いずれかに記載のポリマー微
粒子の製造方法。6. The colored polymer fine particles are produced by using a resin colored with a pigment or a dye, or by adding the pigment or the dye before the precipitation of the resin. A method for producing the fine polymer particles described above.
他の常用添加剤を添加した後、樹脂を析出させることを
特徴とする請求項１〜５いずれかに記載のポリマー微粒
子の製造方法。7. The method for producing polymer fine particles according to claim 1, wherein the resin is precipitated after adding a surfactant, a dispersant, and other commonly used additives before the resin is precipitated. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4137093A JP2877284B2 (en) | 1993-03-02 | 1993-03-02 | Polymer fine particle production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4137093A JP2877284B2 (en) | 1993-03-02 | 1993-03-02 | Polymer fine particle production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06256530A true JPH06256530A (en) | 1994-09-13 |
| JP2877284B2 JP2877284B2 (en) | 1999-03-31 |
Family
ID=12606552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4137093A Expired - Fee Related JP2877284B2 (en) | 1993-03-02 | 1993-03-02 | Polymer fine particle production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2877284B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003016383A1 (en) * | 2001-08-21 | 2003-02-27 | Japan Science And Technology Corporation | Method for controlling size of ionic dye molecule aggregate using polymer micro-dome |
| JP2004137497A (en) * | 2002-10-17 | 2004-05-13 | Xerox Corp | Process and device using gellable composition |
| JP2004140359A (en) * | 2002-10-17 | 2004-05-13 | Xerox Corp | Method and device using self-organized polymer |
| JP2007297465A (en) * | 2006-04-28 | 2007-11-15 | Hiroshima Univ | High-performance nucleating agent and method of producing the same |
| KR100878595B1 (en) * | 2008-05-30 | 2009-01-15 | 강원대학교산학협력단 | Powdering method of polyolefin resins by crystallization from solutions using autoclave |
| KR101438019B1 (en) * | 2012-11-29 | 2014-09-04 | 주식회사 투에이취켐 | Polypropylene powder and method for manufacturing the same |
-
1993
- 1993-03-02 JP JP4137093A patent/JP2877284B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003016383A1 (en) * | 2001-08-21 | 2003-02-27 | Japan Science And Technology Corporation | Method for controlling size of ionic dye molecule aggregate using polymer micro-dome |
| JP2004137497A (en) * | 2002-10-17 | 2004-05-13 | Xerox Corp | Process and device using gellable composition |
| JP2004140359A (en) * | 2002-10-17 | 2004-05-13 | Xerox Corp | Method and device using self-organized polymer |
| JP4574975B2 (en) * | 2002-10-17 | 2010-11-04 | ゼロックス コーポレイション | Methods and devices using self-assembled polymers |
| JP2007297465A (en) * | 2006-04-28 | 2007-11-15 | Hiroshima Univ | High-performance nucleating agent and method of producing the same |
| KR100878595B1 (en) * | 2008-05-30 | 2009-01-15 | 강원대학교산학협력단 | Powdering method of polyolefin resins by crystallization from solutions using autoclave |
| KR101438019B1 (en) * | 2012-11-29 | 2014-09-04 | 주식회사 투에이취켐 | Polypropylene powder and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2877284B2 (en) | 1999-03-31 |
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