JPH0517583A - Granulation of polycarbonate - Google Patents
Granulation of polycarbonateInfo
- Publication number
- JPH0517583A JPH0517583A JP19360791A JP19360791A JPH0517583A JP H0517583 A JPH0517583 A JP H0517583A JP 19360791 A JP19360791 A JP 19360791A JP 19360791 A JP19360791 A JP 19360791A JP H0517583 A JPH0517583 A JP H0517583A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate
- weight
- organic solvent
- methylene chloride
- content
- 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.)
- Granted
Links
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 59
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 59
- 238000005469 granulation Methods 0.000 title abstract description 8
- 230000003179 granulation Effects 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000003960 organic solvent Substances 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000748 compression moulding Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 22
- 238000007906 compression Methods 0.000 abstract description 13
- 230000006835 compression Effects 0.000 abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 111
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 28
- 239000000843 powder Substances 0.000 description 22
- 238000012937 correction Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 12
- 239000008187 granular material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229920005668 polycarbonate resin Polymers 0.000 description 10
- 239000004431 polycarbonate resin Substances 0.000 description 10
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- -1 carbonyl halide Chemical class 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XGIAHMUOCFHQTI-UHFFFAOYSA-N Cl.Cl.Cl.Cl.CC Chemical compound Cl.Cl.Cl.Cl.CC XGIAHMUOCFHQTI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LWRYDHOHXNQTSK-UHFFFAOYSA-N thiophene oxide Chemical compound O=S1C=CC=C1 LWRYDHOHXNQTSK-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリカーボネートの造
粒法、更に詳細には、粉状乃至塊状のポリカーボネート
から保形性、取扱性、流動性に優れ、嵩密度が大きく、
乾燥効率の高いポリカーボネートの粒体を歩留りよく製
造する方法に関する。FIELD OF THE INVENTION The present invention relates to a method for granulating a polycarbonate, more specifically, a powdery or lumpy polycarbonate having excellent shape retention, handleability and fluidity and a large bulk density.
The present invention relates to a method for producing polycarbonate granules having high drying efficiency with good yield.
【０００２】[0002]
【従来の技術】ポリカーボネートは、通常二価フェノー
ルのアルカリ水溶液とホスゲンとを、有機溶媒の存在下
反応させ、得られたポリカーボネートの有機溶媒溶液か
ら有機溶媒を除去して得られるポリカーボネートの粉体
を乾燥することによって製造されている。この乾燥工程
における脱有機溶媒の効率を向上させるために、粉体の
粒子径を小さくしており、その取扱性、流動性、押出性
等に問題がある。2. Description of the Related Art Polycarbonate is usually obtained by reacting an aqueous alkaline solution of a dihydric phenol with phosgene in the presence of an organic solvent, and removing the organic solvent from the resulting organic solvent solution of the polycarbonate to obtain a powder of the polycarbonate. Manufactured by drying. In order to improve the efficiency of the organic solvent removal in this drying step, the particle size of the powder is made small, and there are problems in its handleability, fluidity, extrudability and the like.
【０００３】特に、難燃剤として有用なテトラブロモビ
スフェノールＡを原料とするポリカーボネートは、低分
子量であるため機械的強度が小さく、微粉でしか得るこ
とができず、その取扱性が極めて悪い。また、輸送時及
び乾燥時においては、更に微細化され、機壁に静電付着
し易い。殊に、乾燥に当っては付着した微粉が品質の悪
化をもたらすようになるため１３０℃以下の低温で乾燥
しなければならず、脱溶媒が充分でない等の問題もあ
る。Particularly, a polycarbonate prepared from tetrabromobisphenol A, which is useful as a flame retardant, has a low molecular weight and thus has a low mechanical strength and can be obtained only with fine powder, and its handling property is extremely poor. Further, during transportation and drying, the particles are further miniaturized and are easily electrostatically attached to the machine wall. In particular, when drying, the adhered fine powder deteriorates the quality, so that it has to be dried at a low temperature of 130 ° C. or less, and there is a problem that the desolvation is insufficient.
【０００４】粉体の取扱性を解決するために、粉体を粒
体にする方法が提案されている。例えば特開昭５６−１
５５７１４号公報には、単軸又は多軸のスクリュー式押
出機やインナースクリューを有する射出成形機により、
有機溶媒を多量に含有するポリカーボネートの粉体を、
溶融させずにダイから押出してペレット状に造粒する方
法が提案されている。しかしながら、この方法は負荷電
力及び吐出圧が著しく高くなるので生産性が極めて悪
く、またポリカーボネートの有機溶媒含有量の変動によ
って主モーターの負荷電力が変動し、この変動によって
造粒圧力が変動する。このように有機溶媒含有量の変動
は、得られる粒体の破壊強度のバラツキの原因になる。
従って、この方法では有機溶媒含有量に応じたスクリュ
ーを必要とし、品質管理上、機器設計上有効な方法では
ない。In order to solve the handling property of the powder, a method of making the powder into particles has been proposed. For example, JP-A-56-1
Japanese Patent No. 55714 discloses a single-screw or multi-screw screw type extruder and an injection molding machine having an inner screw.
Polycarbonate powder containing a large amount of organic solvent,
A method of extruding from a die without melting and granulating into pellets has been proposed. However, this method has extremely low productivity because the load power and the discharge pressure are extremely high, and the load power of the main motor fluctuates due to the fluctuation of the organic solvent content of the polycarbonate, and the fluctuation causes the granulation pressure to fluctuate. As described above, the variation in the content of the organic solvent causes variations in the fracture strength of the obtained granules.
Therefore, this method requires a screw according to the content of the organic solvent, and is not an effective method for quality control and equipment design.
【０００５】また、特開昭６３−３５６２１号公報に
は、有機溶媒を１００ppm 以下に且つその他の残存溶媒
を５００ppm 以下に乾燥したポリカーボネート粉体を乾
式圧縮して造粒する方法が提案されている。しかしなが
ら、ポリカーボネートは溶融成形時の温度が高いために
高温に耐え、且つポリカーボネートの特性を低下させな
いバインダーは、見出だされていないことから、バイン
ダーを使用しない乾式圧縮造粒法で保形性（破壊強度）
の充分な粒体を得るには、極めて高い圧縮圧力を必要と
する不利があり、更に成形、破砕時に微粉になり、歩留
まりが極めて悪いという欠点もある。Further, Japanese Patent Application Laid-Open No. 63-35621 proposes a method in which a polycarbonate powder obtained by drying an organic solvent to 100 ppm or less and other residual solvents to 500 ppm or less is dry-compressed and granulated. . However, since polycarbonate has a high temperature at the time of melt-molding, it has not been found a binder that withstands high temperatures and does not deteriorate the properties of the polycarbonate. destruction strength)
In order to obtain sufficient granules, there is a disadvantage that an extremely high compression pressure is required, and there is also a drawback that the powder becomes fine powder at the time of molding and crushing and the yield is extremely poor.
【０００６】[0006]
【発明が解決しようとする課題】本発明は保形性、取扱
性、流動性に優れ、嵩密度が大きく、乾燥効率の高いポ
リカーボネートの粒体を、歩留りよく且つ低い圧縮圧力
で製造する圧縮成形造粒法を提供することを目的とす
る。DISCLOSURE OF THE INVENTION The present invention is a compression molding for producing polycarbonate granules having excellent shape retention, handleability, fluidity, large bulk density and high drying efficiency with good yield and low compression pressure. The purpose is to provide a granulation method.
【０００７】本発明者は、上記目的を達成せんとして鋭
意研究した結果、ポリカーボネート粉体を圧縮成形して
造粒するに際し、ポリカーボネート粉体に予め特定量の
有機溶媒を含有させると、有機溶媒がバインダーとして
作用し、成形圧力を低くしても充分な保形強度を有し、
また粒径が大きいにも拘らず乾燥効率が極めて良好で且
つ歩留りよく造粒できることを究明し、本発明を完成し
た。As a result of earnest research aimed at achieving the above object, the present inventor has found that when a polycarbonate powder is made to contain a specific amount of an organic solvent in advance during compression molding and granulation of the polycarbonate powder, the organic solvent is Acts as a binder and has sufficient shape retention strength even when the molding pressure is lowered,
Further, it was clarified that even though the particle size is large, the drying efficiency is extremely good and the granulation can be performed with a good yield, and the present invention was completed.
【０００８】[0008]
【課題を解決するための手段】本発明は、有機溶媒を１
〜５０重量％含有する粉状乃至塊状のポリカーボネート
を圧縮成形し、次いで乾燥することを特徴とするポリカ
ーボネートの造粒法である。According to the present invention, an organic solvent is used.
It is a method for granulating a polycarbonate, characterized in that a powdery or lumpy polycarbonate containing up to 50% by weight is compression molded and then dried.
【０００９】本発明でいうポリカーボネートは二価フェ
ノールとカーボネート前駆体とを反応させて製造され
る。ここで使用する二価フェノールは下記一般式The polycarbonate referred to in the present invention is produced by reacting a dihydric phenol with a carbonate precursor. The dihydric phenol used here has the following general formula
【００１０】[0010]
【化１】
［式中、Ｒは炭素数１〜１５の二価の脂肪族基、脂環族
基、フェニル置換アルキル基、−Ｏ−、−Ｓ−、−ＳＯ
−、−ＳＯ2 −又は−ＣＯ−であり、Ｘはアルキル基又
はハロゲン原子であり、ｍ及びｎは０、１又は２であ
る］で表されるものであり、特に２，２−ビス（４−ヒ
ドロキシフェニル）プロパン［通称ビスフェノールＡ］
が好ましく使用され、その他ビス（４−ヒドロキシフェ
ニル）メタン、１，１−ビス（４−ヒドロキシフェニ
ル）エタン、１，１−ビス（４−ヒドロキシフェニル）
シクロヘキサン、２，２−ビス（４−ヒドロキシ−３−
メチルフェニル）プロパン、ハイドロキノン、ビス（４
−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキ
シジフェニル）エーテル等、更にはビス（３，５−ジブ
ロモ−４−ヒドロキシフェニル）プロパンの如きハロゲ
ン化ビスフェノール類等が例示され、これらは単独で又
は二種以上併用してもよい。カーボネート前駆体として
はカルボニルハライド、カルボニルエステル、ハロホル
メート等があげられ、具体的にはホスゲン、ジフェニル
カーボネート、二価フェノールのジハロホルメート等が
あげられる。また、例えば三官能以上の多官能性芳香族
化合物を二価フェノール及びカーボネート前駆体と反応
させた分岐ポリカーボネートであってもよい。更に二種
以上のポリカーボネートの混合物であってもよい。ま
た、ポリカーボネートの重合度については特に限定する
必要はないが、粘度平均分子量で通常は１２，０００〜
５０，０００、特に１５，０００〜３５，０００のもの
が好ましい。[Chemical 1] [In the formula, R is a divalent aliphatic group having 1 to 15 carbon atoms, an alicyclic group, a phenyl-substituted alkyl group, -O-, -S-, -SO.
-, - SO 2 - or a -CO-, X is an alkyl group or a halogen atom, m and n are those represented by] is 0, 1 or 2, in particular 2,2-bis ( 4-hydroxyphenyl) propane [commonly known as bisphenol A]
Are preferably used, and other bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl)
Cyclohexane, 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, hydroquinone, bis (4
-Hydroxyphenyl) sulfone, bis (4-hydroxydiphenyl) ether and the like, and further halogenated bisphenols such as bis (3,5-dibromo-4-hydroxyphenyl) propane and the like, which may be used alone or in combination. You may use together above. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like. Further, for example, a branched polycarbonate obtained by reacting a trifunctional or higher polyfunctional aromatic compound with a dihydric phenol and a carbonate precursor may be used. Further, it may be a mixture of two or more polycarbonates. The degree of polymerization of the polycarbonate is not particularly limited, but it is usually 12,000 to 1 in terms of viscosity average molecular weight.
Those of 50,000, especially 15,000 to 35,000 are preferable.
【００１１】本発明で使用する粉状乃至塊状のポリカー
ボネートは、任意の方法で製造されたものであってもよ
いが、二価フェノールのアルカリ水溶液とホスゲンと
を、有機溶媒の存在下反応させ、得られたポリカーボネ
ートの有機溶媒溶液から有機溶媒を除去して得られる所
定量の有機溶媒を含有するポリカーボネート粉体が好ま
しく使用される。勿論、乾燥状態の粉状乃至塊状のポリ
カーボネートを有機溶媒に浸漬して所定量の有機溶媒を
含有させてもよい。The powdery or lumpy polycarbonate used in the present invention may be produced by any method, but an alkaline aqueous solution of a dihydric phenol and phosgene are reacted in the presence of an organic solvent, A polycarbonate powder containing a predetermined amount of the organic solvent obtained by removing the organic solvent from the obtained organic solvent solution of the polycarbonate is preferably used. Of course, a powdery or lumpy polycarbonate in a dry state may be immersed in an organic solvent to contain a predetermined amount of the organic solvent.
【００１２】粉状乃至塊状のポリカーボネートに含有さ
せる有機溶媒としては、例えば四塩化エタン、三塩化エ
タン、二塩化エタン、塩化メチレン、二塩化エチレン、
クロロホルム、チオフェノン、ジオキサン、テトロヒド
ロフラン等の単独又は混合物があげられる他に、圧縮成
形に供するポリカーボネートを２０重量％以上溶解する
ものであればよい。かかる有機溶媒の含有量は１〜５０
重量％である。有機溶媒含有量が１重量％未満では、圧
縮成形する際のバインダーとしての効果が充分でなく、
保形性を保持するためには高い圧縮力を必要とし、本発
明の目的を達成し得ない。また、有機溶媒含有量が５０
重量％より多くなると、貯槽及び供給機内で大きな塊を
成形してトラブルの原因となったり、乾燥能力の大きな
機器を必要とするようになるので適当でない。Examples of the organic solvent contained in the powdery or lumpy polycarbonate include ethane tetrachloride, ethane trichloride, ethane dichloride, methylene chloride, ethylene dichloride,
Other than chloroform, thiophenone, dioxane, and tetrohydrofuran, which may be used alone or as a mixture, they may be those which dissolve 20% by weight or more of the polycarbonate used for compression molding. The content of the organic solvent is 1 to 50.
% By weight. If the organic solvent content is less than 1% by weight, the effect as a binder during compression molding is not sufficient,
A high compressive force is required to maintain shape retention, and the object of the present invention cannot be achieved. In addition, the organic solvent content is 50
If it exceeds 5% by weight, large lumps may be formed in the storage tank and the feeder to cause troubles, or equipment with a large drying capacity is required, which is not suitable.
【００１３】更に、粉状乃至塊状のポリカーボネートに
有機溶媒と共に特定量の非又は貧溶媒を含有させると、
非又は貧溶媒がポリカーボネートに浸透し、乾燥時の脱
有機溶媒効率を著しく改善することができ、こうするこ
とは好ましいことである。Furthermore, when a powdery or lumpy polycarbonate contains a specific amount of a non- or poor solvent together with an organic solvent,
Non- or poor solvents can penetrate the polycarbonate and significantly improve the efficiency of organic solvent removal during drying, which is preferred.
【００１４】非又は貧溶媒としては、例えばｎ−ヘプタ
ン、ｎ−ヘキサン等の炭化水素類、シクロヘキサン、シ
クロヘキサノン等の脂環族類、トルエン、ベンゼン、キ
シレン等の芳香族類、アセトン等のケトン類等があげら
れ、これらは単独又は二種以上混合して使用できる。非
又は貧溶媒は０．１〜２５重量％使用するのが好まし
い。非又は貧溶媒の使用量が０．１重量％未満では、乾
燥時の脱有機溶媒の改善効果が少く、２５重量％より多
くなると、脱有機溶媒の改善効果が飽和するばかりか、
有機溶媒のバインダー作用の低下、非又は貧溶媒の回収
量の増大、成形時における非又は貧溶媒のポリカーボネ
ートからの離脱の悪化による噛込み不良等の欠点が生じ
るようになる。Examples of the non- or poor solvent include hydrocarbons such as n-heptane and n-hexane, alicyclic compounds such as cyclohexane and cyclohexanone, aromatics such as toluene, benzene and xylene, and ketones such as acetone. Etc., and these may be used alone or in combination of two or more. The non- or poor solvent is preferably used in an amount of 0.1 to 25% by weight. When the amount of the non- or poor solvent used is less than 0.1% by weight, the improvement effect of the organic solvent during drying is small, and when the amount is more than 25% by weight, the improvement effect of the organic solvent is saturated.
Defects such as a decrease in the binder action of the organic solvent, an increase in the recovery amount of the non- or poor solvent, and a poor biting due to the deterioration of the separation of the non- or poor solvent from the polycarbonate during molding will occur.
【００１５】非又は貧溶媒は、ポリカーボネートの有機
溶媒溶液に添加しても、有機溶媒を含有する粉状乃至塊
状のポリカーボネートに添加してもよいが、特にこれら
の方法に限定されるものではなく、ポリカーボネート中
に浸透する方法であればどんな方法でもよい。The non- or poor solvent may be added to the solution of the polycarbonate in the organic solvent or may be added to the powdery or lumpy polycarbonate containing the organic solvent, but is not particularly limited to these methods. Any method can be used as long as it penetrates into the polycarbonate.
【００１６】本発明で行う圧縮成形には、例えばブリケ
ッティングマシン、コンパクティングマシン、ギャー式
押出造粒機、リングダイス式造粒機、タブレットマシン
等が使用される。また、成形時の温度はポリマーの融点
以下であればよい。また、圧縮成形においては、直接粒
状にせずに、例えば圧縮成形によってシート状になした
後粉砕機により粉砕してもよい。For the compression molding performed in the present invention, for example, a briquetting machine, a compacting machine, a gear type extrusion granulator, a ring die type granulator, a tablet machine and the like are used. Further, the temperature at the time of molding may be equal to or lower than the melting point of the polymer. Further, in the compression molding, it is also possible to use, for example, a sheet-like material by compression molding and then pulverize with a pulverizer instead of directly granulating.
【００１７】造粒後行う乾燥には任意の乾燥機が使用さ
れ、例えば流動乾燥機、パドル式乾燥機、熱風循環乾燥
機等があげられる。乾燥温度は１１５℃以上からポリカ
ーボネートの二次転移温度以下が好ましい。Any dryer can be used for drying after granulation, and examples thereof include a fluidized dryer, a paddle type dryer, a hot air circulating dryer and the like. The drying temperature is preferably 115 ° C. or higher and lower than the second-order transition temperature of polycarbonate.
【００１８】[0018]
【実施例】以下に実施例をあげて本発明を更に説明す
る。なお、塩化メチレン、ｎ−ヘプタン及びアセトンの
定量はガスクロマトグラフィー［（株）日立製作所製２
６３型］によりカラム充填剤にDioctyl Sebacateを用い
て８５℃でヘットスペース法で測定した。EXAMPLES The present invention will be further described with reference to the following examples. The amounts of methylene chloride, n-heptane and acetone were determined by gas chromatography [Hitachi Ltd. 2
63 type] was measured by a headspace method at 85 ° C. using Dioctyl Sebacate as a column packing material.
【００１９】[0019]
【実施例１】ビスフェノールＡとホスゲンを原料として
溶液法により得られた粘度平均分子量２３，５００の精
製ポリカーボネートの塩化メチレン溶液（濃度１５重量
％）２００kgを容量１００リットルのニーダーに投入
し、同時に攪拌下水蒸気の供給を開始して塩化メチレン
を蒸発させてポリカーボネート樹脂のゲル化した塊状物
を得たところで水蒸気の供給を停止すると同時に攪拌を
停止し、ニーダーの底から凝縮水を抜取った。得られた
塊状物の塩化メチレン含有量は２５重量％であった。更
にニーダーにて攪拌混合して粗砕物を得た。得られた粗
砕物をコンパクティングマシンにより常温で圧縮圧力２
００kg／cm2 で圧縮して厚さ２mmの板状体に成形し、ハ
ンマークラッシャーにより粉砕し、防爆型熱風乾燥機に
より１４０℃で６時間乾燥して塩化メチレン含有量４０
０ppm 、粒度分布は８〜３０メッシュ８８重量％、３０
メッシュ未満９重量％と微粉が少ない。Example 1 200 kg of a methylene chloride solution (concentration 15% by weight) of purified polycarbonate having a viscosity average molecular weight of 23,500 obtained by a solution method using bisphenol A and phosgene as raw materials was put into a kneader having a volume of 100 liters and stirred at the same time. When the supply of lower steam was started to evaporate methylene chloride to obtain a gelled lump of the polycarbonate resin, the supply of steam was stopped and stirring was stopped at the same time, and condensed water was extracted from the bottom of the kneader. The methylene chloride content of the obtained lump was 25% by weight. Further, the mixture was stirred and mixed with a kneader to obtain a coarsely crushed product. The obtained coarsely crushed material is compressed with a compacting machine at room temperature to a compression pressure 2
Compressed at 00 kg / cm 2 to form a plate with a thickness of 2 mm, crushed with a hammer crusher, and dried with an explosion-proof hot air dryer at 140 ° C for 6 hours to give a methylene chloride content of 40.
0ppm, particle size distribution 8 to 30 mesh 88% by weight, 30
Less than 9% by weight of mesh and less fine powder.
【００２０】[0020]
【実施例２】ビスフェノールＡとホスゲンを主原料とし
て溶液法により得られた粘度平均分子量２３，５００の
精製ポリカーボネート樹脂の塩化メチレン溶液（濃度１
５重量％）２００kgを容量１００リットルのニーダーに
投入し、同時に攪拌下水蒸気の供給を開始して塩化メチ
レンを蒸発させてポリカーボネート樹脂のゲル化した塊
状物を得たところで水蒸気の供給を停止すると同時に攪
拌を停止し、ニーダーの底から凝縮水を抜き取った。得
られた塊状物の塩化メチレン含有量は２５重量％であっ
た。次いでニーダーにｎ−ヘプタンを４．５kg投入し、
攪拌混合して粗砕物を得た。得られた粗砕物をコンパク
ティングマシンにより常温で圧縮圧力２００kg／cm2 で
圧縮して厚さ２mmの板状体とし、ハンマークラッシャー
により粉砕し、防爆型熱風乾燥機により１４０℃で６時
間乾燥して塩化メチレン含有量３５ppm 、ｎ−ヘプタン
含有量１２０ppm 、粒度分布は８〜３０メッシュ８７重
量％、３０メッシュ未満１０重量％と微粉が少なく、塩
化メチレン含有量の少ないポリカーボネート樹脂の粒体
を得た。Example 2 A methylene chloride solution (concentration: 1) of a purified polycarbonate resin having a viscosity average molecular weight of 23,500 obtained by a solution method using bisphenol A and phosgene as main raw materials.
(5% by weight) 200 kg was put into a kneader having a capacity of 100 liters, and at the same time, the supply of water vapor was started with stirring to evaporate methylene chloride to obtain a gelled lump of the polycarbonate resin. At the same time, the supply of water vapor was stopped. The stirring was stopped and the condensed water was drained from the bottom of the kneader. The methylene chloride content of the obtained lump was 25% by weight. Next, add 4.5 kg of n-heptane to the kneader,
The mixture was stirred and mixed to obtain a coarsely crushed product. The obtained coarsely crushed material was compressed at a room temperature with a compacting machine at a compression pressure of 200 kg / cm 2 to form a plate having a thickness of 2 mm, crushed with a hammer crusher, and dried at 140 ° C. for 6 hours with an explosion-proof hot air dryer. The content of methylene chloride was 35 ppm, the content of n-heptane was 120 ppm, and the particle size distribution was 8 to 30 mesh, 87% by weight, less than 30 mesh, 10% by weight. .
【００２１】[0021]
【実施例３】テトラブロモビスフェノールＡとホスゲン
を主原料として溶液法により得られた比粘度０．０４５
の精製テトラブロモビスフェノールＡポリカーボネート
の塩化メチレン溶液（濃度１５重量％）２００kgにｎ−
ヘプタン３kgを混合し、５５℃の温水中に攪拌下滴下し
て塩化メチレンを蒸発させた後、遠心脱水し、得られた
粉体中の塩化メチレンは２５重量％、ｎ−ヘプタンは
５．７重量％であった。この粉体を用いて実施例１と同
様にして圧縮造粒し、防爆型熱風乾燥機により１３０℃
で１０時間乾燥して塩化メチレン含有量３０ppm 、ｎ−
ヘプタン含有量１３０ppm 、粒度分布は８〜３０メッシ
ュ９０重量％、３０メッシュ未満９重量％と粒度が粗
く、塩化メチレン含有量の少ない取扱い易いテトラブロ
モビスフェノールＡポリカーボネートの粒体を得た。Example 3 Tetrabromobisphenol A and phosgene as main raw materials obtained by solution method
N-to 200 kg of purified tetrabromobisphenol A polycarbonate methylene chloride solution (concentration 15% by weight)
Heptane (3 kg) was mixed, and the mixture was added dropwise to warm water at 55 ° C with stirring to evaporate methylene chloride, and then centrifugally dehydrated. Methylene chloride in the obtained powder was 25% by weight and n-heptane was 5.7. % By weight. Using this powder, compression granulation was performed in the same manner as in Example 1, and 130 ° C. was obtained using an explosion-proof hot air dryer.
Methylene chloride content 30ppm, n-
Granules of a tetrabromobisphenol A polycarbonate having a heptane content of 130 ppm, a particle size distribution of 8 to 30 mesh of 90% by weight and a particle size of less than 30 mesh of 9% by weight were coarse, and the methylene chloride content was small and easy to handle were obtained.
【００２２】[0022]
【実施例４】実施例２と同様にして得られた精製テトラ
ブロモビスフェノールＡポリカーボネートの塩化メチレ
ン溶液２００kgを７０℃の温水中に攪拌下滴下して塩化
メチレンを蒸発させた後、遠心脱水し、熱風乾燥機によ
り１３０℃で１０時間乾燥して全量３０メッシュ以下で
塩素含有量５００ppm の粉体を得た。この粉体にアセト
ンを１０重量％添加混合した後、実施例１と同様にして
圧縮造粒し、防爆型熱風乾燥機により１３０℃で６時間
乾燥して塩化メチレン含有量７５ppm 、アセトン含有量
８５ppm 、粒度分布は８〜３０メッシュ７５重量％、３
０メッシュ以下２５重量％と粒度が粗く、塩化メチレン
含有量の少ない取扱い易いテトラブロモビスフェノール
Ａポリカーボネートの粒体を得た。Example 4 200 kg of a purified tetrabromobisphenol A polycarbonate methylene chloride solution obtained in the same manner as in Example 2 was dropped into warm water at 70 ° C. with stirring to evaporate the methylene chloride and then centrifugally dehydrated. It was dried at 130 ° C. for 10 hours with a hot air dryer to obtain a powder having a total amount of 30 mesh or less and a chlorine content of 500 ppm. After 10% by weight of acetone was added to this powder and mixed, the mixture was compression-granulated in the same manner as in Example 1 and dried at 130 ° C. for 6 hours in an explosion-proof hot air drier to give a methylene chloride content of 75 ppm and an acetone content of 85 ppm. , Particle size distribution is 8-30 mesh 75% by weight, 3
Granules of tetrabromobisphenol A polycarbonate having a coarse particle size of 0 mesh or less and 25% by weight and a small content of methylene chloride were obtained.
【００２３】[0023]
【比較例１】ビスフェノールＡとホスゲンを主原料とし
て溶液法により得られた粘度平均分子量２３５００の精
製ポリカーボネート樹脂の塩化メチレン溶液（濃度１５
重量％）２００kgを容量１００リットルのニーダーに投
入し、同時に攪拌下水蒸気の供給を開始して塩化メチレ
ンを蒸発させてポリカーボネート樹脂のゲル化した塊状
物を得たところで水蒸気の供給を停止し、塊状物を粗砕
した後抜き取り、粉砕機により粉砕した。次いで得られ
た粉粒体を９５℃の熱水で２時間蒸留した後、遠心脱水
し、防爆型熱風乾燥機により１４０℃で６時間乾燥して
塩化メチレン含有量３５０ppm 、粒度分布は１６〜３０
メッシュ４２重量％、３０メッシュ以下５８重量％の粉
粒体を得た。この粉粒体を実施例１と同じ圧縮造粒機に
より同条件で造粒したが、強度のある板状物は得られず
実用にならなかった。ハンマークラッシャーによる粉砕
可能な板状物を得るには１０００kg／cm2 以上の高圧力
が必要であった。Comparative Example 1 A methylene chloride solution of purified polycarbonate resin having a viscosity average molecular weight of 23500, obtained by a solution method using bisphenol A and phosgene as main raw materials (concentration: 15
200% by weight) was charged into a kneader having a capacity of 100 liters, and at the same time, the supply of steam was started under stirring to evaporate methylene chloride to obtain a gelled lump of the polycarbonate resin. The material was roughly crushed, then extracted, and crushed by a crusher. Then, the obtained granular material was distilled with hot water of 95 ° C. for 2 hours, centrifugally dehydrated, and dried with an explosion-proof hot air dryer at 140 ° C. for 6 hours to give a methylene chloride content of 350 ppm and a particle size distribution of 16 to 30.
42% by weight of mesh and 58% by weight of 30 mesh or less were obtained. The powder and granules were granulated by the same compression granulator as in Example 1 under the same conditions, but a plate-like material having high strength could not be obtained and was not put into practical use. A high pressure of 1000 kg / cm 2 or more was required to obtain a crushable plate-like material with a hammer crusher.
【００２４】[0024]
【比較例２】テトラブロモビスフェノールＡとホスゲン
を主原料として溶液法により得られた比粘度０．０４５
の精製テトラブロモビスフェノールＡポリカーボネート
の塩化メチレン溶液（濃度１５重量％）２００kgを、７
０℃の温水中に攪拌下滴下して塩化メチレンを蒸発させ
た後、遠心脱水し、防爆型熱風乾燥機により１３０℃で
１０時間乾燥して全量３０メッシュ以下で塩素含有量５
００ppm の粉体を得た。この粉粒体を実施例１と同じ圧
縮造粒機により同条件で造粒したが、強度のある板状物
は得られず実用にならなかった。ハンマークラッシャー
による粉砕可能な板状物を得るには１０００kg／cm2以
上の高圧力が必要であった。COMPARATIVE EXAMPLE 2 Tetrabromobisphenol A and phosgene as main raw materials obtained by solution method
Of purified tetrabromobisphenol A polycarbonate in methylene chloride (concentration 15% by weight) (200 kg)
After the solution was added dropwise to warm water at 0 ° C under stirring to evaporate methylene chloride, it was centrifugally dehydrated and dried at 130 ° C for 10 hours by an explosion-proof hot air dryer to give a chlorine content of 5 or less with a total amount of 30 mesh or less.
A powder of 00 ppm was obtained. The powder and granules were granulated by the same compression granulator as in Example 1 under the same conditions, but a plate-like material having high strength could not be obtained and was not put into practical use. A high pressure of 1000 kg / cm 2 or more was required to obtain a crushable plate-like material with a hammer crusher.
【００２５】[0025]
【発明の効果】本発明は、低い圧力で圧縮成形すること
によって保形性、取扱性、流動性に優れ、嵩密度が大き
く、乾燥効率の高いポリカーボネートの粒体を、歩留り
よく製造することを可能にしたものであり、その奏する
効果は格別なものである。INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce polycarbonate granules having excellent shape retention, handleability, fluidity, large bulk density, and high drying efficiency with good yield by compression molding at low pressure. It's made possible and the effect it produces is exceptional.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年１０月２４日[Submission date] October 24, 1991
【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】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】[0010]
【化１】
［式中、Ｒは炭素数１〜１５の二価の脂肪族基、脂環族
基、フェニル置換脂肪族基、−Ｏ−、−Ｓ−、−ＳＯ
−、−ＳＯ2 −又は−ＣＯ−であり、Ｘはアルキル基又
はハロゲン原子であり、ｍ及びｎは０、１又は２であ
る］で表されるものであり、特に２，２−ビス（４−ヒ
ドロキシフェニル）プロパン［通称ビスフェノールＡ］
が好ましく使用され、その他ビス（４−ヒドロキシフェ
ニル）メタン、１，１−ビス（４−ヒドロキシフェニ
ル）エタン、１，１−ビス（４−ヒドロキシフェニル）
シクロヘキサン、２，２−ビス（４−ヒドロキシ−３−
メチルフェニル）プロパン、ビス（４−ヒドロキシフェ
ニル）スルホン、ビス（４−ヒドロキシフェニル）エー
テル等、更には２，２−ビス（３，５−ジブロモ−４−
ヒドロキシフェニル）プロパンの如きハロゲン化ビスフ
ェノール類等が例示され、これらは単独で又は二種以上
併用してもよい。カーボネート前駆体としてはカルボニ
ルハライド、カーボネート、ハロホルメート等があげら
れ、具体的にはホスゲン、ジフェニルカーボネート、二
価フェノールのジハロホルメート等があげられる。ま
た、例えば三官能以上の多官能性芳香族化合物を二価フ
ェノール及びカーボネート前駆体と反応させた分岐ポリ
カーボネートであってもよい。更に二種以上のポリカー
ボネートの混合物であってもよい。また、ポリカーボネ
ートの重合度については、温度２０℃、濃度０．７g／d
lの塩化メチレン溶液の比粘度で表して、通常は０．２
０〜０．９０、特に０．２８〜０．６５のものが好まし
い。[Chemical 1] [In the formula, R is a divalent aliphatic group having 1 to 15 carbon atoms, an alicyclic group, a phenyl-substituted aliphatic group, -O-, -S-, -SO.
-, - SO 2 - or a -CO-, X is an alkyl group or a halogen atom, m and n are those represented by] is 0, 1 or 2, in particular 2,2-bis ( 4-hydroxyphenyl) propane [commonly known as bisphenol A]
Are preferably used, and other bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl)
Cyclohexane, 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, bi scan (4-hydroxyphenyl) sulfone, bis (4-hydroxy Schiff Eniru) ether, more 2,2-bis (3,5-dibromo-4-
Examples thereof include halogenated bisphenols such as hydroxyphenyl) propane, and these may be used alone or in combination of two or more kinds. Examples of the carbonate precursor include carbonyl halide, carbonate , haloformate and the like, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like. Further, for example, a branched polycarbonate obtained by reacting a trifunctional or higher polyfunctional aromatic compound with a dihydric phenol and a carbonate precursor may be used. Further, it may be a mixture of two or more polycarbonates. Regarding the polymerization degree of polycarbonate , the temperature is 20 ° C. and the concentration is 0.7 g / d.
The specific viscosity of a methylene chloride solution of 1 is usually 0.2
It is preferably 0 to 0.90, particularly 0.28 to 0.65 .
【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】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】粉状乃至塊状のポリカーボネートに含有さ
せる有機溶媒は、W.F.CHRISTOPHER,D.W.FOX著「ポリカ
ーボネート」１９６２年，３２頁の表３−１における分
類の“Good Solvents ”及び“Fair Solvents ”に該当
する溶媒であって、例えば四塩化エタン、１，１，２−
三塩化エタン、１，２−二塩化エタン、塩化メチレン、
１，２−二塩化エチレン、クロロホルム、チオフェン、
ジオキサン、テトラヒドロフラン等の単独又は混合物が
あげられる。かかる有機溶媒の含有量は全溶媒類を含有
したポリカーボネートの重量に基いて１〜５０重量％で
ある。有機溶媒含有量が１重量％未満では、圧縮成形す
る際のバインダーとしての効果が充分でなく、保形性を
保持するためには高い圧縮力を必要とし、本発明の目的
を達成し得ない。また、有機溶媒含有量が５０重量％よ
り多くなると、貯槽及び供給機内で大きな塊を成形して
トラブルの原因となったり、乾燥能力の大きな機器を必
要とするようになるので適当でない。The organic solvent contained in the powdery or lumpy polycarbonate is "Polycarbonate" by WF CHRISTOPHER, DWFOX.
Carbonate, 1962, minutes in Table 3-1 on page 32
Applicable to "Good Solvents" and "Fair Solvents"
A solvent such as ethane tetrachloride, 1,1,2-
Ethane trichloride, 1,2- dichloroethane, methylene chloride,
1,2 ethylene dichloride, chloroform, Chiofu E down,
Dioxane, alone or a mixture of such tetra- hydrofuran and the like. The content of or mow organic solvent contains all solvents
1 to 50% by weight, based on the weight of the polycarbonate prepared. When the content of the organic solvent is less than 1% by weight, the effect as a binder during compression molding is not sufficient, and a high compression force is required to maintain the shape retention property, and the object of the present invention cannot be achieved. . On the other hand, if the content of the organic solvent is more than 50% by weight, a large lump is formed in the storage tank and the feeder to cause a trouble, and a device having a large drying capacity is required, which is not suitable.
【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】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】非又は貧溶媒とは、前記「ポリカーボネー
ト」３２頁の表３−１における分類の“Poor Solvents
”，“Very Poor Solvents”及び“NonSolvents ”に
該当する溶媒であって、例えばn-ヘプタン、n-ヘキサ
ン、シクロヘキサン、トルエン、ベンゼン、キシレン、
アセトン、シクロヘキサノン等があげられ、これらは単
独又は二種以上混合して使用できる。非又は貧溶媒は全
溶媒類を含有したポリカーボネートの重量に基いて０．
１〜２５重量％使用するのが好ましい。非又は貧溶媒の
使用量が０．１重量％未満では、乾燥時の脱有機溶媒の
改善効果が少く、２５重量％より多くなると、脱有機溶
媒の改善効果が飽和するばかりか、有機溶媒のバインダ
ー作用の低下、非又は貧溶媒の回収量の増大、成形時に
おける非又は貧溶媒のポリカーボネートからの離脱の悪
化による噛込み不良等の欠点が生じるようになる。The non- or poor solvent means the above-mentioned "polycarbonate".
“Por Solvents” in Table 3-1 on page 32
”,“ Very Poor Solvents ”and“ NonSolvents ”
Corresponding solvents such as n-heptane, n-hexa
Down, cyclohexane, toluene, benzene, xylene,
Acetone , cyclohexanone, etc. are mentioned, These can be used individually or in mixture of 2 or more types. All non- or poor solvents
Based on the weight of the polycarbonate containing the solvents,
It is preferable to use 1 to 25% by weight. When the amount of the non- or poor solvent used is less than 0.1% by weight, the improvement effect of the organic solvent during drying is small, and when it exceeds 25% by weight, not only the improvement effect of the organic solvent is saturated but also the organic solvent Defects such as a decrease in the binder action, an increase in the recovery amount of the non- or poor solvent, and a deterioration in the detachment of the non- or poor solvent from the polycarbonate during molding will occur.
【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】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１８】[0018]
【実施例】以下に実施例をあげて本発明を更に説明す
る。なお、塩化メチレン、ｎ−ヘプタンの定量はガスク
ロマトグラフィー［（株）日立製作所製２６３型］によ
りカラム充填剤にDioctyl Sebacateを用いて８５℃でヘ
ットスペース法で測定した。EXAMPLES The present invention will be further described with reference to the following examples. Incidentally, methylene chloride, of n- hepta emissions quantification was determined by Het space method at 85 ° C. using a Dioctyl Sebacate the column packing material by gas chromatography [Hitachi, Ltd. Ltd. 263 type.
【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】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１９】[0019]
【実施例１】ビスフェノールＡとホスゲンを原料として
溶液法により得られた比粘度０．４３の精製ポリカーボ
ネートの塩化メチレン溶液（濃度１５重量％）２００kg
を容量１００リットルのニーダーに徐々に投入し、同時
に攪拌下水蒸気の供給を開始して塩化メチレンを蒸発さ
せてポリカーボネート樹脂のゲル化した塊状物を得たと
ころで水蒸気の供給を停止すると同時に攪拌を停止し、
ニーダーの底から凝縮水を抜取った。得られた塊状物の
塩化メチレン含有量は２５重量％であった。更にニーダ
ーにて攪拌混合して粗砕物を得た。得られた粗砕物をコ
ンパクティングマシンにより常温で圧縮圧力２００kg／
cm2 で圧縮して厚さ２mmの板状体に成形し、ハンマーク
ラッシャーにより粉砕し、防爆型熱風乾燥機により１４
０℃で６時間乾燥して塩化メチレン含有量４００ppm の
粒状体を得た。その粒度分布は８〜３０メッシュ８８重
量％、３０メッシュ未満９重量％と微粉が少ない。Example 1 200 kg of a methylene chloride solution (concentration 15% by weight) of purified polycarbonate having a specific viscosity of 0.43 obtained by a solution method using bisphenol A and phosgene as raw materials.
Is gradually charged into a 100 liter capacity kneader, and at the same time, the supply of steam is started under stirring to evaporate methylene chloride to obtain a gelled lump of the polycarbonate resin. Then
The condensed water was drained from the bottom of the kneader. The methylene chloride content of the obtained lump was 25% by weight. Further, the mixture was stirred and mixed with a kneader to obtain a coarsely crushed product. The obtained coarsely crushed material is compressed with a compacting machine at room temperature at a compression pressure of 200 kg /
Compressed at cm 2 to form a plate with a thickness of 2 mm, crushed with a hammer crusher, and crushed with an explosion-proof hot air dryer to 14
0 ℃ in dried 6 hours methylene content of 400ppm chloride
A granular body was obtained. The particle size distribution is 8 to 30 mesh, 88% by weight, and less than 30 mesh, 9% by weight.
【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】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２０】[0020]
【実施例２】ビスフェノールＡとホスゲンを主原料とし
て溶液法により得られた比粘度０．４３の精製ポリカー
ボネート樹脂の塩化メチレン溶液（濃度１５重量％）２
００kgを容量１００リットルのニーダーに徐々に投入
し、同時に攪拌下水蒸気の供給を開始して塩化メチレン
を蒸発させてポリカーボネート樹脂のゲル化した塊状物
を得たところで水蒸気の供給を停止すると同時に攪拌を
停止し、ニーダーの底から凝縮水を抜き取った。得られ
た塊状物の塩化メチレン含有量は２５重量％であった。
次いでニーダーにｎ−ヘプタンを４．５kg投入し、攪拌
混合して粗砕物を得た。得られた粗砕物をコンパクティ
ングマシンにより常温で圧縮圧力２００kg／cm2 で圧縮
して厚さ２mmの板状体とし、ハンマークラッシャーによ
り粉砕し、防爆型熱風乾燥機により１４０℃で６時間乾
燥して塩化メチレン含有量３５ppm、ｎ−ヘプタン含有
量１２０ppm 、粒度分布は８〜３０メッシュ８７重量
％、３０メッシュ未満１０重量％と微粉が少なく、塩化
メチレン含有量の少ないポリカーボネート樹脂の粒体を
得た。Example 2 A methylene chloride solution (concentration: 15% by weight) of a purified polycarbonate resin having a specific viscosity of 0.43 obtained by a solution method using bisphenol A and phosgene as main raw materials 2.
00 kg was gradually charged into a 100 liter capacity kneader, and at the same time, the supply of steam was started under stirring to evaporate methylene chloride to obtain a gelled lump of the polycarbonate resin. It stopped and drained condensed water from the bottom of the kneader. The methylene chloride content of the obtained lump was 25% by weight.
Next, 4.5 kg of n-heptane was added to the kneader and mixed with stirring to obtain a coarsely crushed product. The obtained coarsely crushed material was compressed at a room temperature with a compacting machine at a compression pressure of 200 kg / cm 2 to form a plate having a thickness of 2 mm, crushed with a hammer crusher, and dried at 140 ° C. for 6 hours with an explosion-proof hot air dryer. The content of methylene chloride was 35 ppm, the content of n-heptane was 120 ppm, and the particle size distribution was 8 to 30 mesh, 87% by weight, and less than 30 mesh, 10% by weight. .
【手続補正１０】[Procedure Amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２３[Name of item to be corrected] 0023
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２３】[0023]
【比較例１】ビスフェノールＡとホスゲンを主原料とし
て溶液法により得られた比粘度０．４３の精製ポリカー
ボネート樹脂の塩化メチレン溶液（濃度１５重量％）２
００kgを容量１００リットルのニーダーに徐々に投入
し、同時に攪拌下水蒸気の供給を開始して塩化メチレン
を蒸発させてポリカーボネート樹脂のゲル化した塊状物
を得たところで水蒸気の供給を停止し、塊状物を粗砕し
た後抜き取り、粉砕機により粉砕した。次いで得られた
粉粒体を９５℃の熱水で２時間蒸留した後、遠心脱水
し、防爆型熱風乾燥機により１４０℃で６時間乾燥して
塩化メチレン含有量３５０ppm 、粒度分布は１６〜３０
メッシュ４２重量％、３０メッシュ以下５８重量％の粉
粒体を得た。この粉粒体を実施例１と同じ圧縮造粒機に
より同条件で造粒したが、強度のある板状物は得られず
実用にならなかった。ハンマークラッシャーによる粉砕
可能な板状物を得るには１０００kg／cm2 以上の高圧力
が必要であった。Comparative Example 1 Methylene chloride solution (concentration 15% by weight) of purified polycarbonate resin having a specific viscosity of 0.43 obtained by a solution method using bisphenol A and phosgene as main raw materials 2
00 kg was gradually charged into a kneader having a capacity of 100 liters, and at the same time, the supply of water vapor was started with stirring to evaporate methylene chloride to obtain a gelled lump of the polycarbonate resin. Was roughly crushed, extracted, and then crushed by a crusher. Then, the obtained granular material was distilled with hot water of 95 ° C. for 2 hours, centrifugally dehydrated, and dried with an explosion-proof hot air dryer at 140 ° C. for 6 hours to give a methylene chloride content of 350 ppm and a particle size distribution of 16 to 30.
42% by weight of mesh and 58% by weight of 30 mesh or less were obtained. The powder and granules were granulated by the same compression granulator as in Example 1 under the same conditions, but a plate-like material having high strength could not be obtained and was not put into practical use. A high pressure of 1000 kg / cm 2 or more was required to obtain a crushable plate-like material with a hammer crusher.
Claims (2)
乃至塊状のポリカーボネートを圧縮成形し、次いで乾燥
することを特徴とするポリカーボネートの造粒法。1. A method for granulating a polycarbonate, which comprises compression-molding a powdery or lumpy polycarbonate containing an organic solvent in an amount of 1 to 50% by weight, and then drying.
溶媒を０．１〜２５重量％含有する粉状乃至塊状のポリ
カーボネートを圧縮成形し、次いで乾燥することを特徴
とするポリカーボネートの造粒法。2. A method for producing a polycarbonate, characterized in that a powdery or lumpy polycarbonate containing 1 to 50% by weight of an organic solvent and 0.1 to 25% by weight of a poor or non-solvent is compression-molded and then dried. Grain method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19360791A JP2885970B2 (en) | 1991-07-09 | 1991-07-09 | Granulation of polycarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19360791A JP2885970B2 (en) | 1991-07-09 | 1991-07-09 | Granulation of polycarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0517583A true JPH0517583A (en) | 1993-01-26 |
| JP2885970B2 JP2885970B2 (en) | 1999-04-26 |
Family
ID=16310763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19360791A Expired - Lifetime JP2885970B2 (en) | 1991-07-09 | 1991-07-09 | Granulation of polycarbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2885970B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000327792A (en) * | 1999-05-24 | 2000-11-28 | Hosokawa Micron Corp | Production of thermoplastic resin granule |
| JP2006045472A (en) * | 2004-08-09 | 2006-02-16 | Idemitsu Kosan Co Ltd | Method for producing polycarbonate powder and polycarbonate powder |
-
1991
- 1991-07-09 JP JP19360791A patent/JP2885970B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000327792A (en) * | 1999-05-24 | 2000-11-28 | Hosokawa Micron Corp | Production of thermoplastic resin granule |
| WO2000071610A1 (en) * | 1999-05-24 | 2000-11-30 | Hosokawa Micron Corporation | Method for forming granule of thermoplastic resin |
| US6523763B1 (en) | 1999-05-24 | 2003-02-25 | Hosakawa Micron Corporation | Process for producing thermoplastic resin granules |
| JP2006045472A (en) * | 2004-08-09 | 2006-02-16 | Idemitsu Kosan Co Ltd | Method for producing polycarbonate powder and polycarbonate powder |
| JP4651326B2 (en) * | 2004-08-09 | 2011-03-16 | 出光興産株式会社 | Method for producing polycarbonate powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2885970B2 (en) | 1999-04-26 |
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