JP3222905B2 - Method for producing aromatic polycarbonate powder - Google Patents
Method for producing aromatic polycarbonate powderInfo
- Publication number
- JP3222905B2 JP3222905B2 JP33342891A JP33342891A JP3222905B2 JP 3222905 B2 JP3222905 B2 JP 3222905B2 JP 33342891 A JP33342891 A JP 33342891A JP 33342891 A JP33342891 A JP 33342891A JP 3222905 B2 JP3222905 B2 JP 3222905B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polycarbonate
- powder
- present
- weight
- pulverization
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は、芳香族ポリカーボネー
トの簡便な機械的粉砕方法に関するものであり、芳香族
ポリカーボネート成形品のリサイクルのための粉砕や、
粉体成形等の粉体用途に用いられる芳香族ポリカーボネ
ート粉末を簡便に得る機械的粉砕方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for mechanically pulverizing an aromatic polycarbonate, and more particularly to a method for pulverizing an aromatic polycarbonate molded article for recycling.
The present invention relates to a mechanical pulverization method for easily obtaining an aromatic polycarbonate powder used for powder applications such as powder molding.
【０００２】[0002]
【従来の技術】近年、芳香族ポリカーボネートは、耐熱
性、耐衝撃性、透明性などに優れたエンジニアリングプ
ラスチックとして、多くの分野において幅広く用いられ
ている。そのなかで、回転成形、焼結成形、流動浸漬、
粉体塗料等の芳香族ポリカーボネートの粉末を用いた粉
体成形分野が注目されている。一方、近年のプラスチッ
クリサイクル化の潮流の中で、芳香族ポリカーボネート
成形品も粉砕リサイクルが多く行われるようになっき
た。その際、リサイクルの用途は、芳香族ポリカーボネ
ート成形品を破砕し、バージン樹脂と混合して再成形し
たり、又は、粉末まで粉砕し、アロイ用途や着色用途、
粉体成形用途に用いたりしている。2. Description of the Related Art In recent years, aromatic polycarbonates have been widely used in many fields as engineering plastics having excellent heat resistance, impact resistance and transparency. Among them, rotational molding, sinter molding, fluid immersion,
The field of powder molding using an aromatic polycarbonate powder such as a powder coating has attracted attention. On the other hand, in the tide of plastic recycling in recent years, pulverizing and recycling of aromatic polycarbonate molded articles have been increasingly performed. At that time, the recycling application is to crush the aromatic polycarbonate molded product, mix it with a virgin resin and re-mold it, or pulverize it into powder, use it for alloys and coloring,
It is used for powder molding applications.
【０００３】従来、芳香族ポリカーボネートの粉体を得
る方法としては、芳香族ポリカーボネート製造中の精製
工程で重合溶液から直接得る方法と、芳香族ポリカーボ
ネートペレットからの化学的粉砕や機械的粉砕により得
る方法が知られている。重合溶液から直接得る方法は、
簡便であるが、設備が大型であるため、着色粉末の製造
に難がある。また、リサイクルの場合は利用できない。[0003] Conventionally, there are two methods for obtaining aromatic polycarbonate powder: a method of directly obtaining the powder from a polymerization solution in a purification step during the production of an aromatic polycarbonate, and a method of chemically or mechanically pulverizing aromatic polycarbonate pellets. It has been known. The method of obtaining directly from the polymerization solution is
Although simple, it is difficult to produce colored powder due to the large size of the equipment. It cannot be used for recycling.
【０００４】化学的粉砕法は、芳香族ポリカーボネート
を塩化メチレンのような良溶媒に溶解した後、メタノー
ルのような貧溶媒中に噴霧して粉末化する方法や、濃縮
や冷却により析出粉末化する方法が知られている。しか
しながら、これらの方法では、溶解操作に時間がかか
る、大量の溶媒がいる、着色粉末が得られない、コスト
が高い等の問題点がある。Chemical pulverization involves dissolving an aromatic polycarbonate in a good solvent such as methylene chloride and then spraying it into a poor solvent such as methanol to form a powder, or concentrating or cooling to form a precipitated powder. Methods are known. However, these methods have problems in that the dissolution operation takes time, a large amount of solvent is used, a colored powder cannot be obtained, and the cost is high.
【０００５】一方、機械的粉砕法は、せん断や衝撃を加
える形式の粉砕機で、冷媒を用いて芳香族ポリカーボネ
ートを冷却しながら粉砕する方法で、ボールミル、ジェ
ットマイザー、ピンミル、アトリションミル、ターボミ
ル、ビクトリーミル等の各種粉砕機を用いて行われてい
る。しかしながら、この方法では、芳香族ポリカーボネ
ートが溶融するため、それを防ぐために、冷媒として多
量のドライアイスや液体窒素が用いられ高コストであ
る、特殊な粉砕機を用いる必要がある、処理能力が小さ
い、処理動力が大きい等の問題点があった。[0005] On the other hand, the mechanical pulverization method is a pulverizer of a type in which a shear or impact is applied, in which an aromatic polycarbonate is pulverized while cooling using a refrigerant. And a crusher such as a Victory mill. However, in this method, since the aromatic polycarbonate is melted, a large amount of dry ice or liquid nitrogen is used as a refrigerant and a high cost is required. And the processing power is large.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、前述のよう
な従来の芳香族ポリカーボネートの粉砕が有している問
題点を克服し、芳香族ポリカーボネート成形品のリサイ
クルのための粉砕や、粉体成形等の粉体用途に用いられ
る芳香族ポリカーボネート粉末を、特殊な粉砕機や高価
な冷媒を用いることなく簡便に得る機械的粉砕方法を提
供するものである。SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned problems of the conventional pulverization of an aromatic polycarbonate, and provides pulverization for recycling an aromatic polycarbonate molded article and powder. An object of the present invention is to provide a mechanical pulverization method for easily obtaining an aromatic polycarbonate powder used for powder applications such as molding without using a special pulverizer or an expensive refrigerant.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、芳香族ポ
リカーボネート粉末を簡便に得る機械的粉砕方法を鋭意
研究した結果、粉砕助剤の存在下に機械的に粉砕を行う
とドライアイスや液体窒素等の冷媒を用いることなく、
微細な粉末が得られることを見い出し、この知見に基づ
き本発明を完成するに至った。The present inventors have intensively studied a mechanical pulverization method for easily obtaining an aromatic polycarbonate powder. As a result, when mechanical pulverization is performed in the presence of a pulverization aid, dry ice or dry ice is obtained. Without using a refrigerant such as liquid nitrogen,
The inventors have found that a fine powder can be obtained, and have completed the present invention based on this finding.
【０００８】すなわち、本発明は、数平均分子量１００
０以上の芳香族ポリカーボネートの成形品またはその破
砕品を機械的粉砕するに当たり、エステル類およびケト
ン類から選ばれる少なくとも１種の有機溶媒を、上記芳
香族ポリカーボネート１００重量部に対して、０．５〜
１００重量部、機械的粉砕前もしくは機械的粉砕時に添
加し、冷却機構を有する混練機を用いて水冷却しなが
ら、上記成形品またはその破砕品を機械的粉砕すること
を特徴とする芳香族ポリカーボネート粉末の製造方法を
提供するものである。That is, the present invention provides a number average molecular weight of 100
In mechanically pulverizing a molded article of 0 or more aromatic polycarbonate or a crushed article thereof, at least one organic solvent selected from esters and ketones is added in an amount of 0.5 to 100 parts by weight of the aromatic polycarbonate. ~
100 parts by weight, added before or during mechanical pulverization, and water-cooled using a kneader with a cooling mechanism
Another object of the present invention is to provide a method for producing an aromatic polycarbonate powder, which comprises mechanically pulverizing the above-mentioned molded product or its crushed product .
【０００９】本発明で用いる芳香族ポリカーボネート
は、特に限定されないが、例えば、化１の繰り返し単位
で表されるものが挙げられる。The aromatic polycarbonate used in the present invention is not particularly restricted but includes, for example, those represented by the repeating unit of the formula (1).
【００１０】[0010]
【化１】 Embedded image
【００１１】[0011]
【化２】 Embedded image
【００１２】また、化３の繰り返し単位で表わされるポ
リカーボネートを共重合することにより得られたもので
もよい。Further, it may be obtained by copolymerizing a polycarbonate represented by the repeating unit of the formula (3).
【００１３】[0013]
【化３】 Embedded image
【００１４】さらには、このようなアリーレン基（Ａ
ｒ、Ａｒ1 、Ａｒ2 ）において１つ以上の水素原子が、
反応に悪影響を及ぼさない他の置換基、例えば、ハロゲ
ン原子、低級アルキル基、低級アルコキシ基、フェニル
基、フェノキシ基、ビニル基、シアノ基、エステル基、
アミド基、ニトロ基などによって置換されたものであっ
てもよい。Further, such an arylene group (A
r, Ar 1 , Ar 2 ) has one or more hydrogen atoms
Other substituents that do not adversely affect the reaction, for example, a halogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group,
It may be substituted by an amide group, a nitro group or the like.
【００１５】これらの中で、２，２−ビス（４′−ヒド
ロキシフェニル）プロパンであるビスフェノールＡ及び
置換ビスフェノールＡ類をジオキシ成分としたポリカー
ボネートが好ましい。また、コモノマーとして３官能以
上のモノマーを、少量用いて共重合することにより分岐
構造を導入したものでもよい。該芳香族ポリカーボネー
トは、例えば、特開平１−１５８０３３号公報等に記載
の方法を用いて重合することが出来る。Of these, polycarbonates containing bisphenol A, which is 2,2-bis (4'-hydroxyphenyl) propane, and substituted bisphenols A as a dioxy component are preferred. Further, a copolymer having a branched structure may be introduced by copolymerizing a small amount of a trifunctional or higher functional monomer as a comonomer. The aromatic polycarbonate can be polymerized using a method described in, for example, JP-A-1-158033.
【００１６】本発明で用いられる芳香族ポリカーボネー
トの数平均分子量（Ｍｎ）は、１０００以上が必要であ
る。これより分子量が低い場合は、芳香族ポリカーボネ
ートとしての特性が出ず、好ましくない。通常は、１０
００〜１０００００の数平均分子量の芳香族ポリカーボ
ネートが用いられ、特に、２０００〜５００００の範囲
の芳香族ポリカーボネートがよく用いられる。The aromatic polycarbonate used in the present invention must have a number average molecular weight (Mn) of 1,000 or more. When the molecular weight is lower than this, characteristics as an aromatic polycarbonate are not obtained, which is not preferable. Usually 10
Aromatic polycarbonates having a number average molecular weight of 00 to 100,000 are used, and in particular, aromatic polycarbonates having a number average molecular weight of 2000 to 50,000 are often used.
【００１７】本発明に用いられる芳香族ポリカーボネー
トの形態、及び大きさは、特に限定されないが、通常用
いられる形態としては、各種成形品、板状、糸状、塊
状、ペレット状、フィルム状のものが使用され、その大
きさは１ｍｍ〜数１００ｍｍの範囲にある。大きな形態
のものは破砕して用いることもできる。好ましくは３〜
６ｍｍ程度のペレット（粒状物）が用いられる。また、
本発明に用いられる芳香族ポリカーボネートには、耐熱
安定剤、耐候剤、滑剤、紫外線吸収剤等の添加剤や、染
料、顔料等の着色剤等を含有していてもよい。The form and size of the aromatic polycarbonate used in the present invention are not particularly limited. Examples of the form generally used include various molded articles, plates, threads, blocks, pellets, and films. And its size is in the range of 1 mm to several 100 mm. The large form can be crushed and used. Preferably 3 to
Pellets (granules) of about 6 mm are used. Also,
The aromatic polycarbonate used in the present invention may contain additives such as heat stabilizers, weathering agents, lubricants, and ultraviolet absorbers, and coloring agents such as dyes and pigments.
【００１８】本発明で用いられる粉砕助剤は、芳香族ポ
リカーボネートの粉砕時に、粉砕動力の低減や発熱の低
減を伴うものであればよく、水、有機溶媒、滑剤等が使
用できる。特に好ましくは、溶解度パラメーター値（Ｓ
Ｐ値）が８から１３の範囲にある有機溶媒が用いられ
る。本発明における溶解度パラメーター値（ＳＰ値）と
は、下式により示されるものである。The grinding aid used in the present invention only needs to reduce the grinding power and reduce heat generation during the grinding of the aromatic polycarbonate, and water, an organic solvent, a lubricant and the like can be used. Particularly preferably, the solubility parameter value (S
An organic solvent having a P value in the range of 8 to 13 is used. The solubility parameter value (SP value) in the present invention is represented by the following formula.
【００１９】 （ＳＰ）2 ＝ΔＥ／Ｖ＝（ΔＨ−ＲＴ）／Ｖ＝ｄ（ΔＨ−ＲＴ）／Ｍ ここで、ΔＥ：蒸発エネルギー ｃａｌ／ｍｏｌ ｄ：密 度 ｇ／ｃｃ Ｖ：モル容積 ｃｃ／ｍｏｌ Ｍ：グラム分子量 ｇ／ｍｏｌ ΔＨ：蒸発潜熱 ｃａｌ／ｍｏｌ Ｔ：絶対温度 ゜Ｋ Ｒ：ガス定数 １．９８７ｃａｌ／ｍｏｌ ゜Ｋ 各種有機溶媒の溶解度パラメーター（ＳＰ値）は高分子
データハンドブック（高分子学会編、１巻、５９５〜５
９８頁）に記載されている。この中でも、酢酸メチル、
酢酸エチルなどのエステル類；アセトン、メチルエチル
ケトン、メチルイソブチルケトンなどのケトン類；ベン
ゼン、トルエン、キシレンなどの芳香族炭化水素類；テ
トラヒドロフラン、ジオキサンなどのエーテル類などが
好ましく用いられ、特にアセトンが好ましく用いられ
る。これらの溶媒は、一種で用いても、二種以上混合し
て用いても良い。(SP) 2 = ΔE / V = (ΔH-RT) / V = d (ΔH-RT) / M where ΔE: evaporation energy cal / mol d: density g / cc V: molar volume cc / Mol M: gram molecular weight g / mol ΔH: latent heat of vaporization cal / mol T: absolute temperature ΔK R: gas constant 1.987 cal / mol ΔK The solubility parameter (SP value) of various organic solvents is described in Polymer Data Handbook (High Edited by Molecular Society, Volume 1, 595-5
98). Among them, methyl acetate,
Esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as tetrahydrofuran and dioxane are preferably used, and acetone is particularly preferably used. Can be These solvents may be used alone or as a mixture of two or more.
【００２０】芳香族ポリカーボネートに対する粉砕助剤
の使用量は、芳香族ポリカーボネート１００重量部に対
して、０．５〜１５０重量部であり、好ましくは５〜１
２０重量部、特に好ましくは、２０〜１００重量部であ
る。粉砕助剤の量が、０．５重量部より少ないと、粉砕
助剤としての効果が十分でなく、１５０重量部より多い
と、助剤としての効果は大きいが、粉砕後の助剤の除去
操作が繁雑になり、好ましくない。The amount of the grinding aid to be used with respect to the aromatic polycarbonate is 0.5 to 150 parts by weight, preferably 5 to 1 part by weight, per 100 parts by weight of the aromatic polycarbonate.
20 parts by weight, particularly preferably 20 to 100 parts by weight. If the amount of the grinding aid is less than 0.5 part by weight, the effect as the grinding aid is not sufficient, and if it is more than 150 parts by weight, the effect as the aid is large, but the removal of the aid after grinding is not sufficient. Operation becomes complicated, which is not preferable.
【００２１】粉砕後の粉末からの粉砕助剤の除去方法と
して、粉砕助剤が水や有機溶媒の場合には、一般に乾燥
操作が用いられる。また、粉砕助剤が滑剤の場合には、
水又は有機溶媒による洗浄除去や比重差を利用した分別
除去等が用いられるが、用途によっては、除去しないで
用いることも可能である。本発明において、粉砕助剤効
果の発生機構は、明らかになっていないが、粉砕助剤が
芳香族ポリカーボネートの限界応力を低下させ、小さな
せん断力や衝撃力で芳香族ポリカーボネートが破砕され
るためと考えられる。そのため、粉砕動力の低減や粉砕
処理量の増加が可能となり、さらに、ポリカーボネート
の溶融が防止できる。As a method for removing the grinding aid from the powder after grinding, when the grinding aid is water or an organic solvent, a drying operation is generally used. Also, when the grinding aid is a lubricant,
Washing and removing with water or an organic solvent, fractional removal using a difference in specific gravity, and the like are used, but depending on the use, it is also possible to use without removing. In the present invention, the mechanism of the generation of the grinding aid effect is not clear, but the grinding aid lowers the critical stress of the aromatic polycarbonate, and the aromatic polycarbonate is crushed by a small shear force or impact force. Conceivable. Therefore, it is possible to reduce the pulverizing power and increase the pulverization processing amount, and further, it is possible to prevent the polycarbonate from melting.
【００２２】本発明において、芳香族ポリカーボネート
の機械的粉砕するのに用いる粉砕機は、公知の粉砕機
（粉体工学便覧、日刊工業新聞社 ５０３〜５０５頁に
記載）や、一般に混練機と呼ばれる機器（粉体工学便
覧、日刊工業新聞社 ６４４〜６４８頁に記載）が使用
できる。本発明においては、特に後者の混練機が使用で
きることが特徴であり、混練機の使用が好ましく、中で
もジャケットやスクリューを水等で冷却できるものが好
ましい。In the present invention, the pulverizer used for mechanically pulverizing the aromatic polycarbonate is known as a known pulverizer (described in Powder Engineering Handbook, pages 503 to 505 of Nikkan Kogyo Shimbun) or a kneader. Equipment (described in Powder Engineering Handbook, pages 644-648, Nikkan Kogyo Shimbun) can be used. The present invention is characterized in that the latter kneading machine can be used, and the use of a kneading machine is preferred. Among them, a kneading machine capable of cooling a jacket or a screw with water or the like is preferred.
【００２３】また、１軸、２軸及び多軸押出機やスクリ
ューフィーダーも、上記混練機と同様の機能を有してい
るので、本発明の粉砕機として使用できる。これらの中
で、パドルミキサー、ニーダー、バンバリーミキサー、
コンティニアスニーダー等に代表されるブレード型やロ
ール型の混練機が好ましく用いられ、特に２軸混練機が
好ましい。なかでも、特に、セルフクリーニング性の高
い２軸同方向回転型混練機が好ましい。Also, single-screw, twin-screw and multi-screw extruders and screw feeders have the same function as the above-mentioned kneader, and can be used as the crusher of the present invention. Among these, paddle mixer, kneader, banbury mixer,
A blade-type or roll-type kneader typified by a continuous kneader is preferably used, and a biaxial kneader is particularly preferable. Among them, a two-axis co-rotating kneader having high self-cleaning property is particularly preferable.
【００２４】本発明において機械的粉砕は粉砕助剤の存
在下で行わなければならない。粉砕助剤は、機械的粉砕
の時に添加してもよいし、粉砕助剤を添加した後に機械
的粉砕を行ってもよい。通常は、機械的粉砕の時に添加
するほうが、操作が簡単で好ましい。また、本発明にお
いて、粉砕温度は、特に限定されないが、液体窒素温度
から芳香族ポリカーボネートの融点以下もしくは、粉砕
助剤の沸点以下の温度範囲で行うことができる。特に、
０℃から芳香族ポリカーボネートの融点以下もしくは、
粉砕助剤の沸点以下の温度範囲で行うことが、特殊な冷
媒を用いる必要がなく簡便で好ましい。In the present invention, mechanical grinding must be performed in the presence of a grinding aid. The grinding aid may be added at the time of mechanical grinding, or mechanical grinding may be performed after adding the grinding aid. Usually, it is preferable to add at the time of mechanical pulverization because the operation is simple. In the present invention, the pulverization temperature is not particularly limited, but the pulverization can be performed in a temperature range from liquid nitrogen temperature to the melting point of the aromatic polycarbonate or lower, or the boiling point of the pulverization aid or lower. In particular,
0 ° C. to below the melting point of the aromatic polycarbonate or
It is preferable to carry out the reaction in a temperature range equal to or lower than the boiling point of the pulverization aid, because it is not necessary to use a special refrigerant and is simple and convenient.
【００２５】本発明で得られる粉末は、芳香族ポリカー
ボネートの分子量、粉砕助剤の種類と量、粉砕機の種
類、粉砕条件等によりコントロールできる。一般に、そ
の粉末を用いる用途に適合するように選択される。本発
明で得られる粉末は、回転成形、焼結成形、流動浸漬、
粉体塗料等の粉体成形分野用途に用いることができる。
また、芳香族ポリカーボネート成形品の粉砕リサイクル
用途、すなわち、アロイ用途や着色用途、粉体成形用途
にも好適に用いられる。また、高品質の芳香族ポリカー
ボネートを提供する新しい製造方法である固相重合法に
適合する芳香族ポリカーボネート粉末として用いること
もできる。特に、粉体成形用途に用いる場合は、できる
だけ球形で、安息角が３５゜以下の粉末が、成形時の粉
末の流動性が良く好ましい。The powder obtained in the present invention can be controlled by the molecular weight of the aromatic polycarbonate, the type and amount of the grinding aid, the type of the pulverizer, the pulverizing conditions and the like. Generally, it is selected to be compatible with the application for which the powder will be used. Powder obtained in the present invention, rotational molding, sinter molding, fluid immersion,
It can be used for powder molding applications such as powder coatings.
Further, it is suitably used for pulverizing and recycling applications of aromatic polycarbonate molded products, that is, alloy applications, coloring applications, and powder molding applications. Further, it can be used as an aromatic polycarbonate powder compatible with a solid-state polymerization method, which is a new production method for providing high-quality aromatic polycarbonate. In particular, when used for powder molding, a powder having a spherical shape as much as possible and an angle of repose of 35 ° or less is preferred because of good flowability of the powder during molding.
【００２６】本発明の粉砕方法で得られる、平均粒径が
１ｍｍ以下で、比表面積が 0.2ｍ2／ｇ以上及び、結晶
化度が５％以上である芳香族ポリカーボネート粉末は、
特に固相重合に好ましく用いられる。平均粒径が１ｍｍ
を超える大きさでは重合速度が遅く好ましくなく、比表
面積が 0.2ｍ2 ／ｇ未満では重合速度が遅く好ましくな
い。結晶化度が５％未満では、重合中に融着が発生する
場合があり好ましくない。本発明において、粒径は粉砕
された一次粒子を指す。従って、粉砕された粉末の一次
粒子が１ｍｍ以下であり、凝集して１ｍｍを超える二次
粒子を形成している場合は、充分な重合速度を有してお
り、本発明の範囲に含まれる。The aromatic polycarbonate powder having an average particle size of 1 mm or less, a specific surface area of 0.2 m 2 / g or more, and a crystallinity of 5% or more, obtained by the pulverization method of the present invention, comprises:
Particularly, it is preferably used for solid phase polymerization. Average particle size is 1mm
When the specific surface area is less than 0.2 m 2 / g, the polymerization rate is unfavorably low. If the crystallinity is less than 5%, fusion may occur during polymerization, which is not preferable. In the present invention, particle size refers to pulverized primary particles. Therefore, when the primary particles of the pulverized powder are 1 mm or less and aggregate to form secondary particles exceeding 1 mm , they have a sufficient polymerization rate and are included in the scope of the present invention.
【００２７】[0027]
【実施例】以下、実施例により本発明をさらに詳細に説
明するが、本発明は、これらの例によってなんら限定さ
れるものではない。また、実施例中で、粒径は、筒井理
化学器械社製ミクロ型電磁振動ふるい器Ｍ−２型を用い
て測定した。平均粒径は、ふるいわけたフラクションの
積分重量５０％の点の粒径で表した。表面積は島津製作
所製アキュアソープ２１００−０２型を使用して、クリ
プトンガスを用いて測定した。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples, the particle size was measured using a micro-type electromagnetic vibration sieve M-2 manufactured by Tsutsui Rikagaku Kikai. The average particle size was expressed as the particle size at the point where the integrated weight of the sieved fraction was 50%. The surface area was measured using Krypton gas using Accure Soap 2100-02 manufactured by Shimadzu Corporation.
【００２８】[0028]
【実施例１】赤色に着色された芳香族ポリカーボネート
（Ｍｎ９１００）成形品（約３×１００×２００ｍｍ形
状）をクラッシャーにて１０ｍｍ角程度に破砕した。こ
のもの１０Ｋｇに、アセトン８．２Ｋｇを混合し、ジャ
ケットが水冷却された同方向回転型ニ軸混練機に２Ｋｇ
／Ｈｒで供給し、回転数約２００ｒｐｍで粉砕した。得
られた粉末を乾燥し、平均粒径２５０μｍ、安息角２９
°の赤色の芳香族ポリカーボネート粉末を得た。Example 1 A red-colored aromatic polycarbonate (Mn9100) molded product (having a shape of about 3 × 100 × 200 mm) was crushed into about 10 mm square by a crusher. 8.2 kg of acetone was mixed with 10 kg of the mixture, and 2 kg was added to a co-rotating twin-screw kneader whose jacket was cooled with water.
/ Hr, and pulverized at a rotation speed of about 200 rpm. The obtained powder was dried and had an average particle size of 250 μm and an angle of repose of 29.
° red aromatic polycarbonate powder was obtained.
【００２９】この粉末を用い、流動浸漬を行ったとこ
ろ、チャンネリングも発生せず良好な粉体流動性を示し
た。また、３５０℃の鉄板を、流動している粉体へ浸漬
後、３００℃のオーブンに５分間入れ、きれいな赤色の
芳香族ポリカーボネート膜の付着した鉄板を得た。When this powder was subjected to fluid immersion, no channeling occurred and good powder fluidity was exhibited. After the iron plate at 350 ° C. was immersed in the flowing powder, it was placed in an oven at 300 ° C. for 5 minutes to obtain a clean iron plate with a red aromatic polycarbonate film attached.
【００３０】[0030]
【比較例１】実施例１において、粉砕助剤のアセトンを
使用しない以外は、同様にして行ったところ、未粉砕の
赤色芳香族ポリカーボネート塊を多量に含み、ほとんど
粉砕されていなかった。COMPARATIVE EXAMPLE 1 The same operation as in Example 1 was carried out except that acetone as a grinding aid was not used. As a result, a large amount of unmilled red aromatic polycarbonate lumps was contained and hardly ground.
【００３１】[0031]
【比較例２】ビスフェノールＡとホスゲンから界面重縮
合でＭｎ４２４０の芳香族ポリカーボネートを製造し、
重合溶液をキャストし１０ｍｍの厚さのシートを得た。
該シート１．８Ｋｇをハンマーで一片が数ｃｍ程度の塊
に破砕し、メチルエチルケトン２．５Ｋｇとともに、１
０リットルヘンシェルミキサーにて、約３５００ｒｐｍ
で３０分間粉砕した。得られた粉末を、乾燥して、メチ
ルエチルケトンを除去し、粉体特性を測定した。得られ
た粉末は、１ｍｍ以上の粒径のものを約２％含む平均粒
径６３０μｍで、比表面積１．９ｍ2 ／ｇであった。Comparative Example 2 An aromatic polycarbonate having Mn4240 was produced from bisphenol A and phosgene by interfacial polycondensation.
The polymerization solution was cast to obtain a sheet having a thickness of 10 mm.
1.8 kg of the sheet is crushed with a hammer into pieces each having a size of about several cm, and together with 2.5 kg of methyl ethyl ketone,
About 3500 rpm with 0 liter Henschel mixer
For 30 minutes. The obtained powder was dried to remove methyl ethyl ketone, and the powder properties were measured. The obtained powder had an average particle diameter of 630 μm containing about 2% of particles having a particle diameter of 1 mm or more, and had a specific surface area of 1.9 m 2 / g.
【００３２】[0032]
【比較例３】比較例２において、粉砕助剤のメチルエチ
ルケトンを使用しない以外は、同様にして行った。その
際、該芳香族ポリカーボネートが溶融し、粉末を得るこ
とは出来なかった。Comparative Example 3 Comparative Example 2 was carried out in the same manner as in Comparative Example 2, except that methyl ethyl ketone as a grinding aid was not used. At that time, the aromatic polycarbonate was melted and powder could not be obtained.
【００３３】[0033]
【比較例４】Ｍｎ＝１２３００の芳香族ポリカーボネー
トの３ｍｍ径×５ｍｍ長の非晶ペレット４０ｇと粉砕助
剤のトルエン２７ｇ加えて、ラボプラストミルを用い
て、室温、６０ｒｐｍで、５分間、粉砕を行った。得ら
れた粉末は、トルエンを真空乾燥除去後、平均粒径が４
５０μｍであり、１ｍｍ以上の粒径のものは無かった。COMPARATIVE EXAMPLE 4 40 g of amorphous pellets of 3 mm diameter × 5 mm length of aromatic polycarbonate having Mn = 12300 and 27 g of toluene as a grinding aid were added, and pulverized for 5 minutes at room temperature and 60 rpm using a Labo Plastomill. went. The resulting powder has an average particle size of 4 after removing toluene by vacuum drying.
It was 50 μm, and none had a particle size of 1 mm or more.
【００３４】[0034]
【比較例５】比較例４において、粉砕助剤のトルエンを
使用しない以外は、同様にして行った。回転をスタート
したら、過負荷のために、シェアピンが切断して、粉砕
できなかった。Comparative Example 5 The same procedure was performed as in Comparative Example 4 , except that the grinding aid toluene was not used. When the spin started, the shear pin was cut off due to overload and could not be crushed.
【００３５】[0035]
【実施例２】ジフェニルカーボネートと、ビスフェノー
ルＡから、特開平２−１８０９２５号公報と同様の方法
で、Ｍｎ＝４０１０の芳香族ポリカーボネートを得た。
この芳香族ポリカーボネートを溶融状態２３０℃でダイ
スより押し出し、アンダーウオーターカット造粒を行い
約３ｍｍ径のほぼ球形の非晶ペレットを得た。該ペレッ
トと粉砕助剤としてのアセトンを、各々１．５Ｋｇ／Ｈ
ｒ、０．８Ｋｇ／Ｈｒの量比で、ジャケットが水冷却さ
れた同方向回転型２軸混練機に投入し連続的に機械的粉
砕を行った。この際、混練機の回転数は約２００ｒｐ
ｍ、モーター負荷は、約１．６アンペアであった。Example 2 An aromatic polycarbonate having Mn = 4010 was obtained from diphenyl carbonate and bisphenol A in the same manner as in JP-A-2-180925.
This aromatic polycarbonate was extruded from a die at 230 ° C. in a molten state, and underwater cut granulation was performed to obtain a substantially spherical amorphous pellet having a diameter of about 3 mm. The pellets and acetone as a grinding aid were each mixed with 1.5 kg / H
At a rate of 0.8 kg / Hr, the jacket was charged into a water-cooled, co-rotating, twin-screw kneader to continuously perform mechanical pulverization. At this time, the rotation speed of the kneading machine was about 200 rpm.
m, motor load was about 1.6 amps.
【００３６】この粉末の一部を用い、真空乾燥でアセト
ンを除去し得られた芳香族ポリカーボネート粉末の粉体
特性を測定した。その結果、１ｍｍ以上の粒径のものは
全く見られず、平均粒径が３００μｍ、比表面積が２．
５ｍ2 ／ｇ、結晶化度が２６％の粉末であった。この結
晶性芳香族ポリカーボネート粉体を、ターンブルドライ
ヤーに入れ、１０Ｎｌ／Ｈｒの窒素ガスを流しながら回
転させて、２〜３ｍｍＨｇに減圧し、徐々に昇温して、
２２０℃で固相重合を１２時間行ったところ、得られた
重合体のＭｎは１１９００であった。Using a part of this powder, the powder properties of the aromatic polycarbonate powder obtained by removing acetone by vacuum drying were measured. As a result, no particles having a particle diameter of 1 mm or more were observed at all, and the average particle diameter was 300 μm and the specific surface area was 2.
The powder had a particle size of 5 m 2 / g and a crystallinity of 26%. This crystalline aromatic polycarbonate powder was put in a turntable dryer and rotated while flowing a nitrogen gas of 10 Nl / Hr, the pressure was reduced to 2-3 mmHg, and the temperature was gradually increased.
When solid phase polymerization was performed at 220 ° C. for 12 hours, Mn of the obtained polymer was 11,900.
【００３７】[0037]
【比較例６】実施例２で用いた非晶ペレットを粉砕助剤
のアセトンを用いない以外は実施例２と同様にして機械
的粉砕を行った。その際、モーター負荷は定格の３．２
アンペア以上となり、過負荷で緊急停止したため、芳香
族ポリカーボネートの粉末を得ることはできなかった。
その後、同方向回転型二軸混練機のバレルを解放し内部
の状態を見たところ、芳香族ポリカーボネートが完全に
溶融し、パドルに巻き付いているのが確認された。Comparative Example 6 The amorphous pellets used in Example 2 were mechanically pulverized in the same manner as in Example 2 except that acetone as a grinding aid was not used. At that time, the motor load was rated 3.2
Since the amperage was not less than an ampere and the operation was stopped due to an overload, an aromatic polycarbonate powder could not be obtained.
Thereafter, when the barrel of the co-rotating twin-screw kneader was released and the internal state was observed, it was confirmed that the aromatic polycarbonate was completely melted and wound around the paddle.
【００３８】[0038]
【００３９】[0039]
【００４０】[0040]
【発明の効果】本発明の粉砕方法は、芳香族ポリカーボ
ネートの溶融を防ぎ、粉砕を容易にするとともに、良好
な特性の粉末を与えることができる。また、本発明の粉
砕方法によって得られた芳香族ポリカーボネート粉末
は、各種リサイクル用途や、回転成形、焼結成形、流動
浸漬、粉体塗料等の粉体成形及び、高品質の芳香族ポリ
カーボネートを提供する固相重合にも好適に使用でき、
エンジニアリングプラスチックの分野において非常に有
用である。According to the pulverization method of the present invention, the melting of the aromatic polycarbonate is prevented, the pulverization is facilitated, and a powder having good characteristics can be obtained. In addition, the aromatic polycarbonate powder obtained by the pulverization method of the present invention provides various kinds of recycling applications, powder molding such as rotational molding, sinter molding, fluid immersion, powder coating, and high-quality aromatic polycarbonate. Suitable for solid phase polymerization,
Very useful in the field of engineering plastics.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 国際公開90／7536（ＷＯ，Ａ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 64/00 - 64/42 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References International Publication 90/7536 (WO, A1) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 64/00-64/42
Claims (1)
カーボネートの成形品またはその破砕品を機械的粉砕す
るに当たり、エステル類及びケトン類から選ばれる少な
くとも１種の有機溶媒を、上記芳香族ポリカーボネート
１００重量部に対して、０．５〜１００重量部、機械的
粉砕前もしくは機械的粉砕時に添加し、冷却機構を有す
る混練機を用いて水冷却しながら、上記成形品またはそ
の破砕品を機械的粉砕することを特徴とする芳香族ポリ
カーボネート粉末の製造方法。When a molded article of an aromatic polycarbonate having a number average molecular weight of 1,000 or more or a crushed article thereof is mechanically pulverized, at least one organic solvent selected from esters and ketones is mixed with 100 parts by weight of the aromatic polycarbonate. Parts by weight, 0.5 to 100 parts by weight, added before or during mechanical pulverization, has a cooling mechanism
While cooling with water using a kneader,
A method for producing an aromatic polycarbonate powder, comprising mechanically pulverizing a crushed product of the above .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33342891A JP3222905B2 (en) | 1990-12-27 | 1991-12-17 | Method for producing aromatic polycarbonate powder |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-407912 | 1990-12-27 | ||
| JP40791290 | 1990-12-27 | ||
| JP33342891A JP3222905B2 (en) | 1990-12-27 | 1991-12-17 | Method for producing aromatic polycarbonate powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0543678A JPH0543678A (en) | 1993-02-23 |
| JP3222905B2 true JP3222905B2 (en) | 2001-10-29 |
Family
ID=26574506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33342891A Expired - Fee Related JP3222905B2 (en) | 1990-12-27 | 1991-12-17 | Method for producing aromatic polycarbonate powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3222905B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD484311S1 (en) | 2001-01-12 | 2003-12-30 | Water Pik, Inc. | Disposable toothbrush |
| US8943634B2 (en) | 2011-05-02 | 2015-02-03 | Water Pik, Inc. | Mechanically-driven, sonic toothbrush system |
| US9468511B2 (en) | 2013-03-15 | 2016-10-18 | Water Pik, Inc. | Electronic toothbrush with vibration dampening |
| US9987109B2 (en) | 2013-03-15 | 2018-06-05 | Water Pik, Inc. | Mechanically-driven, sonic toothbrush and water flosser |
| USD844997S1 (en) | 2016-12-15 | 2019-04-09 | Water Pik, Inc. | Toothbrush handle |
| USD845636S1 (en) | 2016-12-15 | 2019-04-16 | Water Pik, Inc. | Toothbrush handle |
| US10449023B2 (en) | 2015-07-08 | 2019-10-22 | Water Pik, Inc. | Oral cleansing device with energy conservation |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0673958B1 (en) * | 1993-09-21 | 1999-04-14 | Teijin Chemicals, Ltd. | Aromatic polycarbonate resin particulate and process for producing the same |
| US5760160A (en) * | 1993-09-21 | 1998-06-02 | Teijin Chemicals Ltd. | Aromatic polycarbonate resin granule |
| JP2003026815A (en) * | 2001-07-17 | 2003-01-29 | Mitsubishi Engineering Plastics Corp | Aromatic polycarbonate resin powder and method for producing potation molded article using the same and the molded article |
| US7309755B2 (en) | 2005-08-24 | 2007-12-18 | General Electric Company | Method of producing polycarbonate articles by rotation molding and rotation molded articles made by the method |
-
1991
- 1991-12-17 JP JP33342891A patent/JP3222905B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD484311S1 (en) | 2001-01-12 | 2003-12-30 | Water Pik, Inc. | Disposable toothbrush |
| US8943634B2 (en) | 2011-05-02 | 2015-02-03 | Water Pik, Inc. | Mechanically-driven, sonic toothbrush system |
| US9144477B2 (en) | 2011-05-02 | 2015-09-29 | Water Pik, Inc. | Mechanically-driven, sonic toothbrush system |
| US9468511B2 (en) | 2013-03-15 | 2016-10-18 | Water Pik, Inc. | Electronic toothbrush with vibration dampening |
| US9987109B2 (en) | 2013-03-15 | 2018-06-05 | Water Pik, Inc. | Mechanically-driven, sonic toothbrush and water flosser |
| US11744690B2 (en) | 2013-03-15 | 2023-09-05 | Water Pik, Inc. | Toothbrush tip |
| US10449023B2 (en) | 2015-07-08 | 2019-10-22 | Water Pik, Inc. | Oral cleansing device with energy conservation |
| USD844997S1 (en) | 2016-12-15 | 2019-04-09 | Water Pik, Inc. | Toothbrush handle |
| USD845636S1 (en) | 2016-12-15 | 2019-04-16 | Water Pik, Inc. | Toothbrush handle |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0543678A (en) | 1993-02-23 |
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