JPH0512371B2 - - Google Patents
Info
- Publication number
- JPH0512371B2 JPH0512371B2 JP17877586A JP17877586A JPH0512371B2 JP H0512371 B2 JPH0512371 B2 JP H0512371B2 JP 17877586 A JP17877586 A JP 17877586A JP 17877586 A JP17877586 A JP 17877586A JP H0512371 B2 JPH0512371 B2 JP H0512371B2
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- amount
- solvent
- powder
- methylene chloride
- 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
Links
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- 239000004431 polycarbonate resin Substances 0.000 claims description 45
- 229920005668 polycarbonate resin Polymers 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 24
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000013557 residual solvent Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 239000007921 spray Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- -1 and furthermore Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリカーボネート樹脂粉状体の製造
法に係わり、公知の溶液法によつて得られるポリ
カーボネート樹脂粉粒状体から塩化メチレンその
他の溶媒の残存量が少なく、かつ、微粉が少な
く、高い嵩密度を有するポリカーボネート樹脂粉
状体の製造法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a method for producing polycarbonate resin powder, in which methylene chloride and other solvents are extracted from polycarbonate resin powder and granules obtained by a known solution method. The present invention relates to a method for producing a polycarbonate resin powder having a small residual amount, a small amount of fine powder, and a high bulk density.
ビスフエノール類とホスゲンとの反応により得
られるポリカーボネート樹脂の一般的な製法は、
塩化メチレンとアルカリ水系との界面重縮合反応
による方法である。そのため、重縮合反応並びに
精製終了後、樹脂は塩化メチレン溶液として取り
出される。そして溶液のままでは輸送等の取り扱
いにも不都合であり、更には、安定剤、染顔料、
充填剤等各種の添加剤を混合する操作の便利さの
ため、通常、この溶液からポリカーボネート樹脂
を粉状体として単離する。この粉体に安定剤、染
顔料、充填剤等各種の添加量を混合し、最終的に
は溶融押出しによるペレツト状体とし、このペレ
ツトが射出成形その他の用に供せられる。
The general manufacturing method for polycarbonate resin obtained by the reaction of bisphenols and phosgene is as follows:
This method is based on an interfacial polycondensation reaction between methylene chloride and an alkaline aqueous system. Therefore, after the polycondensation reaction and purification are completed, the resin is taken out as a methylene chloride solution. In addition, it is inconvenient to transport and handle as a solution, and furthermore, stabilizers, dyes and pigments, etc.
For the convenience of mixing various additives such as fillers, the polycarbonate resin is usually isolated from this solution as a powder. This powder is mixed with various amounts of stabilizers, dyes and pigments, fillers, etc., and finally formed into pellets by melt extrusion, and these pellets are used for injection molding and other purposes.
ポリカーボネート樹脂の塩化メチレン溶液から
樹脂を単離する方法としては、既に多くの方法が
提案されているが、例えば、特公昭46−37424号
公報に開示されている塩化メチレン溶液自体を濃
縮し、最終的に塩化メチレンを数千〜数百ppm含
有する粉状体とする方法と、例えば、特公昭53−
137297号公報に開示される塩化メチレン溶液にポ
リカーボネート樹脂の非溶媒を添加し、これを濃
縮し、最終的に非溶媒を数千ppm含有する粉状体
とする方法とによつて代表される。 Many methods have already been proposed for isolating a polycarbonate resin from a methylene chloride solution. For example, there is a method of preparing a powder containing several thousand to several hundred ppm of methylene chloride.
A typical example is the method disclosed in Japanese Patent No. 137297, in which a non-solvent of polycarbonate resin is added to a methylene chloride solution, this is concentrated, and the resulting powder is finally made into a powder containing several thousand ppm of the non-solvent.
前者の方法によつて塩化メチレン溶液自体から
得た粉状体には、乾燥後においても、前述の通
り、数千〜数百ppmの塩化メチレンが残存するた
め、これを溶融押出しした場合には、塩化メチレ
ンの熱分解により樹脂が著しく着色する。一方、
非溶媒を用いる後者の方法では、非溶媒の種類に
より、その影響が異なるが、例えば、アルコール
類を用いた場合には、残存アルコールによる熱時
のアルコリシスによつて樹脂の分解が起こり、好
ましくない。そのため、一般には脂肪族炭化水素
類もしくは芳香族炭化水素類等の不活性溶媒が多
く用いられている。しかし、これらの溶媒は、溶
融押出時にも樹脂から完全には離脱せず、最終成
形品にまで残存し、実使用下での応用亀裂の発生
による著しい強度低下の原因となる。 Even after drying, the powder obtained from the methylene chloride solution itself by the former method contains several thousand to several hundred ppm of methylene chloride, so when it is melt-extruded, , the resin is significantly colored due to thermal decomposition of methylene chloride. on the other hand,
The latter method using a non-solvent has different effects depending on the type of non-solvent, but for example, when alcohols are used, the residual alcohol causes decomposition of the resin due to alcoholysis during heating, which is undesirable. . Therefore, inert solvents such as aliphatic hydrocarbons or aromatic hydrocarbons are generally used. However, these solvents do not completely separate from the resin during melt extrusion and remain in the final molded product, causing a significant decrease in strength due to the occurrence of application cracks during actual use.
以上のように、ポリカーボネート樹脂粉状体中
の残存溶媒は極力少なくすることが、耐熱性なら
びに耐久性に優れたポリカーボネート樹脂成形品
を製造するための必要条件である。 As described above, minimizing the amount of residual solvent in the polycarbonate resin powder is a necessary condition for producing polycarbonate resin molded products with excellent heat resistance and durability.
さて、少量の有機溶媒を包含する粉状体より有
機溶媒を除去するために、その粉状体をさらに微
粉化し、乾燥する試みは、当業者が当然に想起す
るところであるが、微粉とするために要する装
置、動力を考えた場合、この方法は必ずしも経済
的に有利な方法ではない。また、かかる微粉体
は、乾燥、種々の添加剤その他との混合などの作
業において、粉塵の飛散による環境悪化等の取り
扱い上の問題、およびスクリユー押出機によるペ
レツト化の際にスクリユーへの食い込み不良によ
るサージングを生じたりして生産量が低下すると
いう問題の原因となる。なお、嵩密度の高いポリ
カーボネート樹脂粉状体とすることは、粉末計
量、輸送及び貯蔵等の粉状体取り扱い上、極めて
重要なことである。 Now, in order to remove the organic solvent from a powder containing a small amount of organic solvent, an attempt is made to further pulverize the powder and dry it, as those skilled in the art will naturally recall. Considering the equipment and power required, this method is not necessarily economically advantageous. In addition, such fine powder may cause handling problems such as environmental deterioration due to scattering of dust during operations such as drying and mixing with various additives, etc., and poor penetration into the screw when pelletizing with a screw extruder. This may cause problems such as surging caused by this, resulting in a decrease in production. Note that it is extremely important to obtain a polycarbonate resin powder having a high bulk density in terms of powder handling such as powder measurement, transportation, and storage.
本発明者らは、上記粉状体の微粉化による不都
合を避け、乾燥後に粒度分布の整つた嵩密度の高
いポリカーボネート樹脂粉状体を得る方法につい
て鋭意検討した結果、極めて簡単に、しかも、20
〜40メツシユが粒度分布の主体となり、微粉体を
含まず、嵩密度が0.5〜0.7ｇ／cm3であるポリカー
ボネート樹脂粉状体を得ることに成功し、本発明
を完成させた。
The present inventors have conducted intensive studies on a method for obtaining polycarbonate resin powder with a uniform particle size distribution and high bulk density after drying, avoiding the inconvenience caused by pulverization of the powder.
The present invention was completed by successfully obtaining a polycarbonate resin powder having a bulk density of 0.5 to 0.7 g/cm 3 , with a particle size distribution consisting mainly of ~40 mesh and no fine powder.
すなわち、本発明は、その全量の90％以上が16
メツシユの篩を通過せず、乾燥後の残存塩化メチ
レンの量が100ppm以下であり、かつ、その他の
残存溶媒の量が500ppm以下であるポリカーボネ
ート樹脂粉粒状体を乾式圧縮成形し、次いで、得
られた成形物を破砕することからなる残存溶媒量
が少なく、かつ、嵩密度が高いポリカーボネート
樹脂粉状体の製造法である。 That is, in the present invention, 90% or more of the total amount is 16
A polycarbonate resin powder that does not pass through a mesh sieve and has a residual methylene chloride content of 100 ppm or less and a remaining solvent content of 500 ppm or less after drying is dry compression molded. This is a method for producing a polycarbonate resin powder with a small amount of residual solvent and a high bulk density, which involves crushing a molded product.
以下、本発明の構成について説明する。 The configuration of the present invention will be explained below.
まず、本発明のその全量の90％以上が16メツシ
ユの篩を通過せず、乾燥後の残存塩化メチレンの
量が100ppm以下であり、かつ、その他の残存溶
媒の量が500ppm以下であるポリカーボネート樹
脂粉粒状体とは、界面重合法により得られたポリ
カーボネート樹脂の塩化メチレン溶液にポリカー
ボネート樹脂の非溶媒、例えば、ｎ−ヘプタン、
ｎ−ヘキサン、シクロヘキサン、ベンゼン、クロ
ルベンゼン、トルエンなどを沈澱物が生成しない
程度の量だけ添加混合し、この混合液を約45〜
100℃に保持した温熱水中に滴下もしくは噴霧し
て、塩化メチレンおよび添加非溶媒を蒸発せしめ
ポリカーボネート樹脂固体状物を得、その後、そ
の全量の90％以上が16メツシユの篩を通過しない
粒度になるように湿式粉砕もしくは乾燥粉砕して
なるものである。 First, the polycarbonate resin of the present invention, of which 90% or more of its total amount does not pass through a 16-mesh sieve, the amount of residual methylene chloride after drying is 100 ppm or less, and the amount of other residual solvents is 500 ppm or less The powder or granule is obtained by adding a non-solvent of the polycarbonate resin, such as n-heptane, to a methylene chloride solution of the polycarbonate resin obtained by an interfacial polymerization method.
Add and mix n-hexane, cyclohexane, benzene, chlorobenzene, toluene, etc. in an amount that does not form a precipitate, and mix this mixture for about 45 to 50 minutes.
Dropped or sprayed into hot water maintained at 100℃ to evaporate methylene chloride and added non-solvent to obtain a polycarbonate resin solid, after which 90% or more of the total amount has a particle size that does not pass through a 16-mesh sieve. It is made by wet pulverization or dry pulverization.
ここに、ポリカーボネート樹脂の塩化メチレン
溶液に添加する非溶媒の添加量が、少なすぎると
緻密な粉粒状体となり乾燥が困難となり、多すぎ
ると溶媒蒸発時に微粉化してしまいその後の取り
扱いが、例えば、水との分離の際、濾布の目を通
過するとか、目づまりするとか、濾過分離機では
微粉が水側に排出されるなどの不都合があり、極
めて困難となる。本発明において固形化は、ポリ
カーボネート樹脂の溶媒と非溶媒との混合液か
ら、この混合溶媒を同時に留出することによつて
行われる。ポリカーボネート樹脂の溶媒のみの溶
液の場合、溶媒が留去されていつてもポリカーボ
ネート樹脂と溶媒とは完全相溶性であるために、
単にポリカーボネート樹脂の濃度が上昇し、結果
として固形化されることになると考えられる。 Here, if the amount of non-solvent added to the methylene chloride solution of polycarbonate resin is too small, it will become a dense granular material that will be difficult to dry, and if it is too large, it will become fine powder when the solvent evaporates, making subsequent handling difficult, for example. Separation from water is extremely difficult due to inconveniences such as passing through the openings of the filter cloth, clogging, and fine particles being discharged to the water side in a filtration separator. In the present invention, solidification is carried out by simultaneously distilling a mixed solvent of a polycarbonate resin solvent and a non-solvent. In the case of a polycarbonate resin solution containing only a solvent, the polycarbonate resin and solvent are completely compatible even after the solvent is distilled off.
It is thought that the concentration of the polycarbonate resin simply increases, resulting in solidification.
ところが、本発明の混合溶媒の場合、ポリカー
ボネート樹脂と混合溶媒とは完全相溶性ではない
ので、ポリカーボネート樹脂に対して混合溶媒が
減少してくると通常考えられないような高濃度の
状態で沈澱の生成が起こることとなり、結果とし
て沈澱を生成しながら混合溶媒を留去することに
なると推定される。 However, in the case of the mixed solvent of the present invention, since the polycarbonate resin and the mixed solvent are not completely miscible, the precipitate cannot be formed at a high concentration that would not normally be thought of as the mixed solvent decreases with respect to the polycarbonate resin. It is presumed that the mixed solvent will be distilled off while forming a precipitate.
非溶媒のうちで、アルコール系、エーテル系等
は、上記で説明した如く、加熱時アルコリシス等
による樹脂の分解が起こり易いので不適当であ
り、好ましいものは、前記に例示した脂肪族炭化
水素や芳香族炭化水素類である。 Among non-solvents, alcohol-based, ether-based, etc. are unsuitable as they tend to cause decomposition of the resin due to alcoholysis when heated, as explained above, and preferred ones are aliphatic hydrocarbons and ethers as exemplified above. They are aromatic hydrocarbons.
非溶媒の添加量は、ポリカーボネート樹脂の
SP値と非溶媒のSP値との差、およびポリカーボ
ネート樹脂溶液の濃度により適宜選択されるもの
であり、上記に例示した非溶媒のなかで、例え
ば、ポリカーボネート樹脂溶液の濃度が15〜25重
量％の場合、SP値の差が約2.3であるｎ−ヘプタ
ンでは樹脂液の好ましくは、0.15〜0.5容量倍で
あり、SP値の差が約1.55であるシクロヘキサン
では樹脂液の0.3〜0.6容量倍、SP値の差が約0.9
であるトルエンでは樹脂液の0.5〜0.8容量倍の範
囲より適宜選択されるが、非溶媒の使用量および
ポリカーボネート樹脂粉粒状体の安定した生成か
らは、ｎ−ヘプタンが最も好ましい。 The amount of non-solvent added depends on the amount of polycarbonate resin.
It is selected as appropriate depending on the difference between the SP value and the SP value of the nonsolvent and the concentration of the polycarbonate resin solution. Among the nonsolvents listed above, for example, the concentration of the polycarbonate resin solution is 15 to 25% by weight. In the case of n-heptane, where the difference in SP value is about 2.3, it is preferably 0.15 to 0.5 times the volume of the resin liquid, and cyclohexane, whose difference in SP value is about 1.55, is preferably 0.3 to 0.6 times the volume of the resin liquid. The difference in SP value is about 0.9
Toluene is appropriately selected from a range of 0.5 to 0.8 times the volume of the resin liquid, but n-heptane is most preferred in terms of the amount of nonsolvent used and stable production of polycarbonate resin powder.
上記で調整した混合液を45〜100℃の水中に滴
下もしくは噴霧し、溶媒および非溶媒を蒸発線速
度が好ましくは20cm／sec以下となるように蒸発
させてポリカーボネート樹脂粉粒状体とし、その
ままもしくは水を分離した後、粉砕する。蒸発線
速度が、20cm／secより高くなる条件で滴下もし
くは噴霧した場合には、気液界面での泡立ち現象
が激しくなり、蒸発溶媒への樹脂の同伴や気液界
面でブロツク状の樹脂塊が生じたりしがちであり
好ましくない。 The mixed solution prepared above is dropped or sprayed into water at 45 to 100°C, and the solvent and non-solvent are evaporated so that the linear evaporation velocity is preferably 20 cm/sec or less to obtain a polycarbonate resin powder, which can be used as it is or After separating the water, grind. When dripping or spraying is performed under conditions where the linear evaporation velocity is higher than 20 cm/sec, the bubbling phenomenon at the gas-liquid interface becomes more intense, resulting in entrainment of the resin into the evaporated solvent and block-shaped resin lumps at the gas-liquid interface. This is not desirable as it tends to occur.
以上の方法により通常５mm〜10mm程度の粒子径
で、乾燥後の嵩密度が0.25〜0.45程度のポリカー
ボネート樹脂の固体状物が得られる。 By the above method, a solid polycarbonate resin having a particle size of about 5 mm to 10 mm and a bulk density of about 0.25 to 0.45 after drying can be obtained.
この固体状物はそのままでは乾燥速度が不充分
であるので、水懸濁液のままもしくは濾過後、粉
砕し乾燥する。粉砕は、上記の如く、その全量の
90％以上が16メツシユの篩を通過しない粒度にな
るよう行い、ついで、この粉粒状体を通常、温度
120〜150℃で1.0〜10.0時間乾燥し、乾燥後の残
存塩化メチレンの量が100ppm以下であり、かつ、
その他の残存溶媒の量が500ppm以下であるポリ
カーボネート樹脂粉粒状体とする。ここに、粉体
の粒子径が小さい程、乾燥は容易となり、かつ、
乾燥温度も高い程乾燥時間が短くてよいと考えら
れるが、粉体の高温による固結や乾燥時の劣化な
どの点から、粒度、嵩密度および乾燥温度が上記
のごとくに選択されるものである。 Since the drying rate of this solid substance is insufficient as it is, it is pulverized and dried either as an aqueous suspension or after filtration. As mentioned above, pulverization
This is done so that 90% or more of the particles do not pass through a 16-mesh sieve, and then this powder is usually heated at a temperature
Dry at 120 to 150°C for 1.0 to 10.0 hours, and the amount of residual methylene chloride after drying is 100 ppm or less, and
The amount of other residual solvent is 500 ppm or less in polycarbonate resin powder. Here, the smaller the particle size of the powder, the easier it is to dry, and
It is thought that the higher the drying temperature, the shorter the drying time, but the particle size, bulk density, and drying temperature are selected as described above, from the viewpoint of caking of the powder due to high temperatures and deterioration during drying. be.
以上の方法で調製したポリカーボネート樹脂粉
粒状体は、そのままでは嵩密度が低く、貯蔵、運
搬の際、さらには溶融ペレツト化時の生産能力が
低下するなどの不都合があるので、乾式圧縮成形
し粉砕することにより、嵩密度のより高い粉状体
とする。 The polycarbonate resin powder prepared by the above method has a low bulk density as it is, and there are disadvantages such as a decrease in production capacity during storage, transportation, and even when turning it into melt pellets, so it is dry compression molded and pulverized. By doing so, a powder having a higher bulk density is obtained.
圧縮成形は、室温〜170℃程度の範囲で、圧力
５Kg／cm2以上で適宜選択することにより、粉砕可
能な高嵩密度の板状体とすることによる。例え
ば、室温で圧縮圧力1200Kg／cm2と170℃で５Kg／
cm2の条件で得た板状体を、粉状体の粒度分布の主
成分が20〜40メツシユとなるように粉砕したもの
の嵩密度は、前者で0.58ｇ／c.c.、後者で0.6ｇ／
c.c.であつた。 Compression molding is performed by appropriately selecting a pressure of 5 Kg/cm 2 or more at a temperature in the range from room temperature to about 170° C. to form a plate-shaped body with a high bulk density that can be crushed. For example, compression pressure is 1200Kg/ cm2 at room temperature and 5Kg/cm2 at 170℃.
The bulk density of the plate-like material obtained under the conditions of cm 2 is 0.58 g/cc for the former and 0.6 g/cc for the latter when the main component of the particle size distribution of the powder is 20-40 meshes.
It was cc.
圧縮成形温度が170℃を越えると、僅かの加圧
により得られる板状体は高強度のものとなり粉砕
が困難となる。また、圧縮成形後の粉砕粉状体の
粒度は、粉砕機の機種、条件その他により任意に
選択することが可能であるが、押出ペレツト化時
などに種々の添加物を均一に混合するため、ある
いは粉塵の発生による障害を無くすることなどの
ため、20〜40メツシユとなるように粉砕するのが
好ましい。 If the compression molding temperature exceeds 170°C, the plate-shaped body obtained by slight pressure will have high strength and will be difficult to crush. In addition, the particle size of the pulverized powder after compression molding can be arbitrarily selected depending on the type of pulverizer, conditions, etc., but in order to uniformly mix various additives during extrusion pelletization, etc. Alternatively, in order to eliminate problems caused by dust generation, it is preferable to crush the material into 20 to 40 mesh pieces.
以上の方法により得た本発明のポリカーボネー
ト樹脂粉状体は、通常、押出ペレツト化し、成形
に用いる。 The polycarbonate resin powder of the present invention obtained by the above method is usually extruded into pellets and used for molding.
以下、本発明を実施例により説明する。 The present invention will be explained below with reference to Examples.
実施例 １
撹拌機、排出口、滴下ノズル、脱気口の付いた
75のジヤケツト付き容器に水を40入れ、撹拌
しながら水温を55℃に昇温した。別に準備した樹
脂濃度25重量％、分子量2.5×104のポリカーボネ
ート樹脂のメチレンクロライド溶液20とｎ−ヘ
プタン５を均一に混合した混合液を、強撹拌下
の上記水に、約１時間で滴下した。滴下中の容器
内の温度は55℃に維持した。滴下終了後、直ちに
容器内温度を95℃以上に昇温し、残余の溶媒を約
30分かかつて蒸発除去した。
Example 1 Equipped with a stirrer, discharge port, dripping nozzle, and deaeration port
40ml of water was placed in a 75ml jacketed container, and the water temperature was raised to 55°C while stirring. A separately prepared mixture of a methylene chloride solution of polycarbonate resin with a resin concentration of 25% by weight and a molecular weight of 2.5×10 4 and 5 parts of n-heptane was added dropwise over about 1 hour to the above water under strong stirring. . The temperature inside the container was maintained at 55°C during the dropping. Immediately after dropping, raise the temperature inside the container to 95℃ or higher to remove the remaining solvent.
Once removed by evaporation for 30 minutes.
ついで、容器内のポリカーボネート樹脂水懸濁
液を取り出し、濾過分離し水切りをした。このよ
うにして得たポリカーボネート樹脂粉粒状体は直
径５mm〜10mm程度の大きさであつた。 Then, the aqueous polycarbonate resin suspension in the container was taken out, filtered and drained. The polycarbonate resin powder thus obtained had a diameter of about 5 mm to 10 mm.
この粉粒状体を粉砕機（ターボ工業(株)製、ター
ボミルＴ−400−４−Ｊ型）を用い、90％以上が
16メツシユの篩を通過しない程度の大きさまで粉
砕し、この粉砕品を140℃で３時間熱風循環乾燥
機で乾燥した。乾燥後の樹脂粉状体品中のメチレ
ンクロライドは10ppm以下、ｎ−ヘプタンは
150ppm、嵩密度は0.32ｇ／c.c.であつた。 This powder and granular material was crushed using a pulverizer (Turbo Mill T-400-4-J type, manufactured by Turbo Kogyo Co., Ltd.) until more than 90% of the material was crushed.
The powder was crushed to a size that did not pass through a 16-mesh sieve, and the crushed product was dried in a hot air circulation dryer at 140°C for 3 hours. Methylene chloride in the resin powder product after drying is 10 ppm or less, and n-heptane is
The content was 150 ppm, and the bulk density was 0.32 g/cc.
この乾燥粉状体を圧縮造粒機（不二パウダル(株)
製、BM−1600SＦ型）を用い、常温で圧縮圧
力2000Kg／cm2で圧縮し、板状品とし、粗粉砕後、
更に、粉砕機を用いて粉砕し、粒度分布が10〜30
メツシユ70％、30メツシユ以下30％で、嵩密度
0.590ｇ／c.c.のポリカーボネート樹脂粉状体を得
た。 This dry powder is processed using a compression granulator (Fuji Powdal Co., Ltd.).
BM-1600SF type) at room temperature with a compression pressure of 2000 kg/cm 2 to form a plate-shaped product, and after coarse grinding,
Furthermore, it is crushed using a crusher to obtain a particle size distribution of 10 to 30.
Bulk density: 70% mesh, 30% below 30 mesh
A polycarbonate resin powder of 0.590 g/cc was obtained.
以上、発明の詳細な説明および実施例から明白
な如く、本発明の方法によれば、容易に粒子径が
揃い、かつ残存溶媒の少ない粉体が得られるもの
であり、熱安定性、その他の優れた高品質のポリ
カーボネート樹脂が得られるものであり、種々の
用途に極めて好適に利用出来るものである。
As is clear from the detailed description of the invention and examples, the method of the present invention can easily produce powders with uniform particle diameters and little residual solvent, and which has excellent thermal stability and other properties. An excellent, high-quality polycarbonate resin can be obtained, and it can be extremely suitably used for various purposes.
Claims (1)
ポリカーボネート樹脂の非溶媒を沈殿が生じない
程度の量を加え、得られた混合液を45〜100℃に
保持した熱水中に滴下あるいは噴霧することによ
り得られる粉状体で、その全量の90％以上が16メ
ツシユの篩を通過せず、乾燥後の残存塩化メチレ
ンの量が100ppm以下であり、かつ、その他の残
存溶媒の量が500ppm以下であるポリカーボネー
ト樹脂粉状体を乾式圧縮成形し、次いで得られた
成形物を破砕することからなる残存溶媒量が少な
く、かつ、嵩密度が高いポリカーボネート樹脂粉
状体の製造法。 ２ ポリカーボネート樹脂の非溶媒がノルマルヘ
プタン（ｎ−ヘプタン）である特許請求の範囲第
１項記載の製造法。 ３ 樹脂量が15〜25重量％の濃度になるように予
め濃縮されたポリカーボネート樹脂の塩化メチレ
ン溶液に容量比で0.15〜0.5となる量のｎ−ヘプ
タンを加え、均一になるまで撹拌混合して得られ
る混合液を用いる特許請求の範囲第１項記載の製
造法。 ４ 室温ないし170℃の温度で成形圧力５Kg／cm2
以上で乾式圧縮成形する特許請求の範囲第１項記
載の製造法。[Claims] 1. Add a non-solvent for polycarbonate resin to a methylene chloride solution of polycarbonate resin in an amount that does not cause precipitation, and drop or spray the resulting mixture into hot water maintained at 45 to 100°C. 90% or more of the total amount does not pass through a 16-mesh sieve, the amount of residual methylene chloride after drying is 100 ppm or less, and the amount of other residual solvents is 500 ppm. A method for producing a polycarbonate resin powder with a small amount of residual solvent and a high bulk density, which comprises dry compression molding the following polycarbonate resin powder and then crushing the obtained molded product. 2. The manufacturing method according to claim 1, wherein the non-solvent for the polycarbonate resin is normal heptane (n-heptane). 3 Add n-heptane in an amount of 0.15 to 0.5 by volume to a methylene chloride solution of polycarbonate resin that has been concentrated in advance so that the resin amount is 15 to 25% by weight, and stir and mix until uniform. The manufacturing method according to claim 1, using the obtained mixed liquid. 4 Molding pressure 5Kg/cm 2 at room temperature to 170℃
The manufacturing method according to claim 1, wherein dry compression molding is performed as described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17877586A JPS6335621A (en) | 1986-07-31 | 1986-07-31 | Production of polycarbonate resin powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17877586A JPS6335621A (en) | 1986-07-31 | 1986-07-31 | Production of polycarbonate resin powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6335621A JPS6335621A (en) | 1988-02-16 |
| JPH0512371B2 true JPH0512371B2 (en) | 1993-02-17 |
Family
ID=16054409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17877586A Granted JPS6335621A (en) | 1986-07-31 | 1986-07-31 | Production of polycarbonate resin powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6335621A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112322015A (en) * | 2020-10-16 | 2021-02-05 | 金发科技股份有限公司 | Polycarbonate/polystyrene alloy and preparation method and application thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4845193A (en) * | 1987-07-21 | 1989-07-04 | Mitsubishi Gas Chemical Co., Inc. | Process for producing polycarbonate resin molding material having low particle content with vented extruder |
| EP0657488A4 (en) * | 1992-08-31 | 1995-12-27 | Mitsubishi Rayon Co | Process for producing powdery thermoplastic copolymer. |
| KR100316986B1 (en) * | 1993-09-21 | 2002-02-28 | 카지와라 마사쯔구 | Aromatic Polycarbonate Resin Powder and Manufacturing Method Thereof |
| US5760160A (en) * | 1993-09-21 | 1998-06-02 | Teijin Chemicals Ltd. | Aromatic polycarbonate resin granule |
| EP3632984B1 (en) * | 2017-05-24 | 2021-03-31 | Mitsubishi Gas Chemical Company, Inc. | Sheet formed from carbon fiber reinforced thermoplastic resin, and production method of said sheet |
| CN117143395A (en) * | 2018-03-30 | 2023-12-01 | 株式会社艾迪科 | Particulate ultraviolet absorber and resin composition |
-
1986
- 1986-07-31 JP JP17877586A patent/JPS6335621A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112322015A (en) * | 2020-10-16 | 2021-02-05 | 金发科技股份有限公司 | Polycarbonate/polystyrene alloy and preparation method and application thereof |
| CN112322015B (en) * | 2020-10-16 | 2022-06-24 | 金发科技股份有限公司 | Polycarbonate/polystyrene alloy and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6335621A (en) | 1988-02-16 |
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