JP2003026815A - Aromatic polycarbonate resin powder and method for producing potation molded article using the same and the molded article - Google Patents
Aromatic polycarbonate resin powder and method for producing potation molded article using the same and the molded articleInfo
- Publication number
- JP2003026815A JP2003026815A JP2001216607A JP2001216607A JP2003026815A JP 2003026815 A JP2003026815 A JP 2003026815A JP 2001216607 A JP2001216607 A JP 2001216607A JP 2001216607 A JP2001216607 A JP 2001216607A JP 2003026815 A JP2003026815 A JP 2003026815A
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- aromatic polycarbonate
- resin powder
- molded article
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、芳香族ポリカーボ
ネート樹脂粉末に関し、さらに詳しくは、良好な色相を
有し、中空内部が平滑で、かつ成形サイクル性に優れ、
回転成形に適した芳香族ポリカーポネート樹脂粉末、お
よび該粉末を用いた回転成形体の製造方法並びに該粉末
を用いて成形されてなる回転成形体に関する。TECHNICAL FIELD The present invention relates to an aromatic polycarbonate resin powder, and more specifically, it has a good hue, has a smooth hollow interior, and is excellent in molding cycle property.
TECHNICAL FIELD The present invention relates to an aromatic polycarbonate resin powder suitable for rotational molding, a method for producing a rotational molded article using the powder, and a rotational molded article molded using the powder.
【０００２】[0002]
【従来の技術】芳香族ポリカーボネート樹脂は、耐熱
性、機械特性、寸法安定性等に優れた樹脂として、電気
電子分野、ＯＡ機器分野、精密・機械分野、医療分野等
に幅広く使用されている。その他、芳香族ポリカーボネ
ート樹脂の特性である透明性を活かした建材、雑貨、ハ
ウジング等に使用されている。従来、樹脂粉末を用いて
成形品を成形する方法として、回転成形方法が大型の中
空状あるいは箱形状の成形品や、これら成形品において
複雑な内部構造を有した成形品を得る場合等によく利用
されている。この回転成形方法は、通常、一軸または直
交する二軸の周りに回転する金型、揺動回転する金型等
の中に、熱可塑性樹脂の粉末を入れて密閉し、加熱下に
回転させながら密閉状態で温調加熱した金型で溶融した
樹脂を遠心力により金型の内部表面に付着させ、次い
で、金型を冷却して金型内表面に形成された成形品を取
り出し所望の成形品を製造する方法である。この方法で
は、原料の樹脂粉末が回転成形金型内に充填され、金型
内部表面から加熱されて、金型内部表面に付着した樹脂
の溶融が開始され、順次内部まで溶融が進行するが、金
型内部表面に付着した樹脂粉末層は粉末の形状等に起因
して空隙部が形成されることがあり、この空隙部が一種
の断熱層となり付着した樹脂層内部まで溶融するために
は長い加熱時間及び／または高温加熱を必要とする。例
えば、回転成形法により成形体を製造しようとする場
合、使用される樹脂粉末によっては長時間、高温に曝さ
れると変色したり、分子量低下を引き起こし機械的強度
の低下を招く場合がある。したがって、回転成形法によ
り比較的低温で、短時間に良好な成形体を製造するため
には、融点または軟化温度が比較的低く、粉末の形状、
粒度が揃った流動性がよい樹脂粉末が使用されることが
望ましい。2. Description of the Related Art Aromatic polycarbonate resins are widely used in electric and electronic fields, OA equipment fields, precision / mechanical fields, medical fields, etc. as resins having excellent heat resistance, mechanical properties and dimensional stability. In addition, it is used for building materials, sundries, housings, etc. that make use of the transparency, which is a characteristic of aromatic polycarbonate resins. Conventionally, as a method of molding a molded product using a resin powder, a rotational molding method is often used for obtaining a large hollow or box-shaped molded product or a molded product having a complicated internal structure in these molded products. It's being used. This rotational molding method is usually performed by placing the thermoplastic resin powder in a mold that rotates around one axis or two axes that intersect at right angles, a mold that rotates in an oscillating manner, and sealing it while rotating it while heating. The resin melted in a mold heated in a sealed state is attached to the inner surface of the mold by centrifugal force, then the mold is cooled and the molded product formed on the inner surface of the mold is taken out to obtain the desired molded product. Is a method of manufacturing. In this method, the resin powder of the raw material is filled in the rotational molding die, heated from the inner surface of the die, the melting of the resin adhering to the inner surface of the die is started, and the melting progresses sequentially to the inside, A void may be formed in the resin powder layer attached to the inner surface of the mold due to the shape of the powder, etc., and this void becomes a kind of heat insulating layer and is long to melt to the inside of the attached resin layer. Requires heating time and / or high temperature heating. For example, when a molded product is produced by the rotational molding method, depending on the resin powder used, it may discolor when exposed to high temperature for a long time, or it may cause a decrease in molecular weight, resulting in a decrease in mechanical strength. Therefore, in order to produce a good compact at a relatively low temperature by the rotational molding method in a short time, the melting point or softening temperature is relatively low, the shape of the powder,
It is desirable to use a resin powder having a uniform particle size and good flowability.
【０００３】この回転成形方法に芳香族ポリカーボネー
ト樹脂を用いる場合、製品肉厚にもよるが、通常３００
〜３３０℃の成形温度が必要とされる。この時、該ポリ
カーボネート樹脂は、この熱履歴を受けて分解し、黄色
ないし赤みを帯びた色に変色したり、または分子量の低
下による機械的強度の低下をもたらし、商品価値が低下
するなど商品化において問題となっている。このような
問題を解決する方法としては、例えば、比較的高温で成
形される高密度ポリエチレン樹脂等を用いた回転成形方
法の場合に行われているように、安定剤を使用する方法
があるが、芳香族ポリカーボネート樹脂は、該高密度ポ
リエチレン樹脂に比較して熱安定性において劣り、さら
に構造上の違い等から、ポリエチレン樹脂の場合に比べ
て３００℃を超えるような高温が必要とされるので、こ
の高温領域で有効な安定剤は限られたものになりその選
択幅が少なく、有効な安定剤は限定されたものと成らざ
るを得なく高価なものとなるという問題がある。When an aromatic polycarbonate resin is used in this rotational molding method, it is usually 300 although it depends on the product thickness.
Molding temperatures of ˜330 ° C. are required. At this time, the polycarbonate resin decomposes due to this heat history, discolors to a yellow or reddish color, or causes a decrease in mechanical strength due to a decrease in molecular weight, resulting in a decrease in commercial value, etc. Is a problem in. As a method of solving such a problem, for example, there is a method of using a stabilizer as in the case of a rotational molding method using a high density polyethylene resin or the like which is molded at a relatively high temperature. The aromatic polycarbonate resin is inferior in thermal stability to the high-density polyethylene resin, and due to structural differences and the like, a high temperature exceeding 300 ° C. is required as compared with the polyethylene resin. However, there is a problem that effective stabilizers are limited in this high temperature region and the selection range is small, and effective stabilizers are limited and expensive.
【０００４】ところで、従来一般的な芳香族ポリカーボ
ネート樹脂の製造方法である界面重合法で製造された芳
香族ポリカーボネート樹脂は、重合中に粉末状で得られ
るので、そのまま回転成形に使用できる形状ではある
が、該粉末は結晶性を有するため、回転成形に用いる場
合には、融点以上に加熱して結晶を溶融する必要があ
り、場合により３５０℃以上の加熱が必要となる場合も
ある。このような高温に加熱された場合には分子量低下
や着色をもたらし、商品価値を低下させる。このため、
一旦重合粉末を押出機にて溶融させ、結晶性の一部を非
晶化させることが行なわれているが、この処理を行って
も未非晶化部分のために、完全に溶融させるには、加熱
温度として３００〜３３０℃が必要となり、熱劣化に伴
う着色や分子量低下の問題を十分に解決することは困難
であるのが実状である。By the way, an aromatic polycarbonate resin produced by an interfacial polymerization method, which is a conventional method for producing an aromatic polycarbonate resin, is obtained in powder form during the polymerization, and thus is in a shape that can be directly used for rotational molding. However, since the powder has crystallinity, when it is used for rotational molding, it is necessary to heat the crystal above the melting point to melt the crystal, and in some cases, heating at 350 ° C. or higher may be necessary. When it is heated to such a high temperature, it causes a decrease in molecular weight and coloring, which lowers the commercial value. For this reason,
Once the polymerized powder has been melted in an extruder to amorphize part of the crystallinity, even if this treatment is carried out, it will still be incompletely melted due to the non-amorphized part. However, the heating temperature is required to be 300 to 330 ° C., and in reality, it is difficult to sufficiently solve the problems of coloring and molecular weight reduction due to thermal deterioration.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、色相と中空
内部の平滑性に優れた回転成形体を得るのに適し、成形
サイクル性に優れた芳香族ポリカーボネート樹脂粉末お
よび該樹脂粉末を用いた回転成形体の製造方法を提供す
るものである。DISCLOSURE OF THE INVENTION The present invention uses an aromatic polycarbonate resin powder which is suitable for obtaining a rotomolded product having excellent hue and smoothness in the hollow interior, and which has an excellent molding cycle property, and uses the resin powder. A method for manufacturing a rotomolded article is provided.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記の課題
につき種々検討した結果、特定の製造法による特定の分
子構造を有する芳香族ポリカーボネート樹脂粉末を使用
することで解決されることを見出したものである。すな
わち、本発明は、溶融エステル交換法で製造された芳香
族ポリカーボネート樹脂であって、フェノール性水酸基
を３〜７０モル％含有し、かつ粘度平均分子量が１２，
０００〜２６，０００であることを特徴とする芳香族ポ
リカーボネート樹脂粉末に関するものであり、さらに該
芳香族ポリカーボネート樹脂粉末を用い３００℃未満で
回転成形する成形体の製造方法、ならびに該芳香族ポリ
カーボネート樹脂粉末を用いた回転成形体に関するもの
である。As a result of various studies on the above problems, the present inventor found that the problems can be solved by using an aromatic polycarbonate resin powder having a specific molecular structure by a specific production method. It is a thing. That is, the present invention is an aromatic polycarbonate resin produced by a melt transesterification method, containing 3 to 70 mol% of a phenolic hydroxyl group, and having a viscosity average molecular weight of 12,
2,000 to 26,000, and relates to an aromatic polycarbonate resin powder, and a method for producing a molded article by rotational molding using the aromatic polycarbonate resin powder at less than 300 ° C., and the aromatic polycarbonate resin. The present invention relates to a rotomolded article using powder.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明における芳香族ポリカーボネート樹脂粉末は、芳
香族ジヒドロキシ化合物と炭酸ジエステルとを溶融状態
でエステル交換反応を行わせ重縮合させて得られるペレ
ット状などの粒状樹脂を、機械的または溶剤処理により
粉末状としたものである。本発明の芳香族ポリカーボネ
ート樹脂は、分子構造中に特定量のフェノール性水酸基
を含有することや粘度平均分子量が１２，０００〜２
６，０００のものであることなどによるものと推察され
るものの、詳細には不明であるが、従来の界面重合法で
得られる芳香族ポリカーボネート樹脂を用いた場合とは
異なり、優れた品質の回転成形体が得られることが判明
した。なお、本発明における芳香族ポリカーボネート樹
脂は、芳香族ジヒドロキシ化合物と炭酸ジエステルとを
溶融エステル交換法反応によりプレポリマーを調製し、
これを結晶化させたのち、固相重合を行って重合度を上
げるという製造方法によるものは含まれない。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The aromatic polycarbonate resin powder in the present invention is a granular resin such as pellets obtained by subjecting an aromatic dihydroxy compound and a carbonic acid diester to polycondensation by performing an ester exchange reaction in a molten state, and then powdered by mechanical or solvent treatment. It is what The aromatic polycarbonate resin of the present invention contains a specific amount of phenolic hydroxyl group in the molecular structure and has a viscosity average molecular weight of 12,000 to 2
Although it is presumed that this is due to the fact that it is 6,000, it is not clear in detail, but unlike the case where the aromatic polycarbonate resin obtained by the conventional interfacial polymerization method is used, excellent rotation quality is obtained. It was found that a molded body was obtained. The aromatic polycarbonate resin in the present invention is a prepolymer prepared by a melt transesterification reaction of an aromatic dihydroxy compound and a carbonic acid diester,
This does not include a production method in which crystallization of this is followed by solid phase polymerization to increase the degree of polymerization.
【０００８】本発明における芳香族ポリカーボネート樹
脂は、芳香族ジヒドロキシ化合物と炭酸ジエステルとを
エステル交換反応させて得られる熱可塑性芳香族ポリカ
ーボネート樹脂であり、芳香族ジヒドロキシ化合物は、
芳香族ポリカーボネート樹脂の製造に使用されるものが
使用され、例えば、ビスフェノールＡ、テトラメチルビ
スフェノールＡ、テトラブロモビスフェノールＡなどの
ハロゲン化ビスフェノールＡ、ビス（４−ヒドロキシフ
ェニル）−ｐ−ジイソプロピルベンゼン、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）ペンタン、１，１−ビス（４−ヒドロキシフ
ェニル）シクロヘキサン、ビス（４−ヒドロキシフェニ
ル）スルホン、２，４’−ジヒドロキシジフェニルスル
ホン、ビス（４−ヒドロキシフェニル）スルフィド、
４，４’−ジヒドロキシジフェニルエーテル、ハイドロ
キノン、レゾルシノール、４，４−ジヒドロキシフェニ
ル等が例示されるが、特にビスフェノールＡが好まし
い。The aromatic polycarbonate resin in the present invention is a thermoplastic aromatic polycarbonate resin obtained by transesterifying an aromatic dihydroxy compound and a carbonic acid diester, and the aromatic dihydroxy compound is
What is used for manufacture of an aromatic polycarbonate resin is used, for example, halogenated bisphenol A such as bisphenol A, tetramethylbisphenol A, tetrabromobisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, bis. (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4 -Hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) sulfide,
Examples include 4,4′-dihydroxydiphenyl ether, hydroquinone, resorcinol, 4,4-dihydroxyphenyl and the like, and bisphenol A is particularly preferable.
【０００９】炭酸ジエステルとしては、例えば、ジフェ
ニルカーボネート、ジメチルカーボネートが例示され
る。炭酸ジエステルとビスフェノールＡのような芳香族
ジヒドロキシ化合物とのエステル交換反応により芳香族
ポリカーボネート樹脂を効率的に製造するには、通常、
触媒の存在下に定法により製造される。このような触媒
としては、従来公知の触媒が使用され、例えば、アルカ
リ金属またはアルカリ土類金属、またはこれらの酸化
物、水酸化物、炭酸塩、アミド化合物、アルコラート、
フェノラート、あるいは例えば、ＺｎＯ、ＰｂＯ、Ｓｂ
２Ｏ３などの塩基性化合物、有機チタン化合物、可溶性
マンガン化合物、Ｃａ、Ｍｇ、Ｚｎ、Ｍｎ、Ｃｄ、Ｃｏ
等の酢酸塩とアンチモン化合物との混合物、ハイドロサ
ルファイトと２，６−ジターシャリーブチル−ｐ−クレ
ゾールとの混合物、塩基性触媒と燐酸ジアリールエステ
ル又はその塩との混合物、第４級アンモニウム塩、第４
級ホスホニウム塩などが例示される。Examples of carbonic acid diesters include diphenyl carbonate and dimethyl carbonate. To efficiently produce an aromatic polycarbonate resin by a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound such as bisphenol A,
It is produced by a conventional method in the presence of a catalyst. As such a catalyst, a conventionally known catalyst is used, and examples thereof include alkali metals or alkaline earth metals, or oxides, hydroxides, carbonates, amide compounds, alcoholates thereof,
Phenolate or, for example, ZnO, PbO, Sb
2 O 3 and other basic compounds, organic titanium compounds, soluble manganese compounds, Ca, Mg, Zn, Mn, Cd, Co
And the like, a mixture of an acetate salt and an antimony compound, a mixture of hydrosulfite and 2,6-ditertiarybutyl-p-cresol, a mixture of a basic catalyst and a phosphoric acid diaryl ester or a salt thereof, a quaternary ammonium salt, Fourth
Examples thereof include phosphonium salts.
【００１０】本発明における回転成形に適した芳香族ポ
リカーボネート樹脂の特徴は、溶融エステル交換法で製
造されたものであって、分子中にフェノール性水酸基を
３〜７０モル％含有し、かつ粘度平均分子量が１２，０
００〜２６，０００を有するものであることである。本
発明においては、分子中のフェノール性水酸基含有量が
３〜７０モル％であることが重要であり、好ましくは１
０〜６０モル％であることが望ましい。分子中のフェノ
ール性水酸基含有量が３モル％よりも少ない場合は、回
転成形において、金型に付着した樹脂内部まで均一に溶
融するように加熱した場合、例えばナチュラル透明品の
製品を製造したとき、黄色に着色し、または成形品内面
が粗になる等良好な成形品が得られない。またフェノー
ル性水酸基含有量が７０モル％より多い場合は、金型と
の密着強度が高くなり、離型性が劣るという問題があ
る。The characteristic feature of the aromatic polycarbonate resin suitable for rotational molding in the present invention is that it is produced by the melt transesterification method and contains 3 to 70 mol% of phenolic hydroxyl group in the molecule and has an average viscosity. Molecular weight is 12,0
It is a thing which has 00-26,000. In the present invention, it is important that the content of the phenolic hydroxyl group in the molecule is 3 to 70 mol%, preferably 1
It is preferably 0 to 60 mol%. When the content of phenolic hydroxyl groups in the molecule is less than 3 mol%, in rotational molding, when heating is performed so that the inside of the resin attached to the mold is evenly melted, for example, when a natural transparent product is manufactured. However, a good molded product cannot be obtained because it is colored yellow or the inner surface of the molded product becomes rough. Further, when the content of the phenolic hydroxyl group is more than 70 mol%, there is a problem that the adhesion strength with the mold becomes high and the releasability becomes poor.
【００１１】また、本発明の芳香族ポリカーボネート樹
脂は粘度平均分子量が１２，０００〜２６，０００の範
囲にあることも重要な要件であり、好ましくは１６，０
００〜２２，０００である。粘度平均分子量が１２，０
００よりも低い樹脂であるときは、良好な粉末が得られ
難く、また得られる成形品の機械的強度が低く好ましく
ない。一方粘度平均分子量が２６，０００を超えるよう
な高分子量の樹脂は、回転成形において高い加熱温度を
必要とし、これに伴う分解により着色や変色、分子量が
低下し機械的強度の低下を招く等好ましくない。It is also an important requirement that the aromatic polycarbonate resin of the present invention has a viscosity average molecular weight in the range of 12,000 to 26,000, preferably 16.0.
It is 00-22,000. Viscosity average molecular weight is 12,0
When the resin is lower than 00, it is difficult to obtain a good powder, and the resulting molded product has low mechanical strength, which is not preferable. On the other hand, a high molecular weight resin having a viscosity average molecular weight of more than 26,000 requires a high heating temperature in rotational molding, which causes decomposition and discoloration, and a decrease in molecular weight to cause a decrease in mechanical strength. Absent.
【００１２】本発明における芳香族ポリカーボネート樹
脂のフェノール性水酸基濃度は、四塩化チタン／酢酸法
（Ｍａｋｒｏｍｏｌ． Ｃｈｅｍ．，８８，２１５（１
９６５）に記載の方法）により、比色定量を行ってフェ
ノール性水酸基量を求め、次いで、ゲルパーミエーショ
ンクロマトグラフィー（東ソー（株）製、商品名：ＨＬ
Ｃ−８０２０）（溶離液にはテトラヒドロフラン使用）
によりポリカーボネート換算で数平均分子量（Ｍｎ）を
算出し、フェノール性水酸基濃度（モル％）を算出す
る。The phenolic hydroxyl group concentration of the aromatic polycarbonate resin in the present invention is determined by the titanium tetrachloride / acetic acid method (Makromol. Chem., 88, 215 (1
965)) to determine the amount of phenolic hydroxyl group by colorimetric determination, and then gel permeation chromatography (manufactured by Tosoh Corp., trade name: HL).
C-8020) (tetrahydrofuran is used as an eluent)
Then, the number average molecular weight (Mn) is calculated in terms of polycarbonate, and the phenolic hydroxyl group concentration (mol%) is calculated.
【００１３】本発明における芳香族ポリカーボネート樹
脂の粘度平均分子量は、ウベローデ粘度計を用いてメチ
レンクロライド溶媒中、２０℃で極限粘度［η］を測定
し、下記式から求めた。The viscosity average molecular weight of the aromatic polycarbonate resin in the present invention was determined from the following formula by measuring the intrinsic viscosity [η] at 20 ° C. in a methylene chloride solvent using an Ubbelohde viscometer.
【００１４】[0014]
【数１】 ［η］＝１．２３×１０−４×（Ｍｖ）０．８３ [Η] = 1.23 × 10 −4 × (Mv) 0.83
【００１５】なお、本発明において、フェノール性末端
基は、反応に由来するのものの他に、重縮合反応後ある
いは重縮合反応工程中において末端基の修飾や末端封止
により付加されたものも包含される。フェノール性末端
基を修飾する方法としては、例えば、脂肪族カルボキシ
化合物、オキザゾリン化合物、エポキシ化合物など公知
の技術が適用されるが、これらに限定されるものではな
い。In the present invention, the phenolic end group includes not only those derived from the reaction but also those added by modification or end capping of the end group after the polycondensation reaction or during the polycondensation reaction step. To be done. As a method for modifying the phenolic terminal group, for example, known techniques such as an aliphatic carboxy compound, an oxazoline compound, and an epoxy compound are applied, but the method is not limited thereto.
【００１６】本発明においては、芳香族ポリカーボネー
ト樹脂には、所望に応じて、安定剤、離型剤、帯電防止
剤、染料、顔料、滑剤、紫外線防止剤等、芳香族ポリカ
ーボネート樹脂に配合される従来公知の添加剤や、無機
あるいは有機の繊維物質からなる補強材、充填材などを
配合することができる。本発明において上記各種添加剤
を使用した樹脂組成物を調製するに際しては、従来公知
の方法を採用することができ、例えば、押出機、バンバ
リーミキサー、ロールなどにより混練する方法が適宜採
用される。また、添加剤の種類によっては、重縮合工程
の終わりに添加することができる。In the present invention, the aromatic polycarbonate resin may be blended with the aromatic polycarbonate resin, if desired, such as a stabilizer, a release agent, an antistatic agent, a dye, a pigment, a lubricant, an anti-UV agent and the like. A conventionally known additive, a reinforcing material made of an inorganic or organic fibrous substance, a filler, and the like can be blended. In preparing a resin composition using the above various additives in the present invention, a conventionally known method can be adopted, for example, a method of kneading with an extruder, a Banbury mixer, a roll or the like is appropriately adopted. Also, depending on the type of additive, it can be added at the end of the polycondensation step.
【００１７】本発明における芳香族ポリカーボネート樹
脂粉末は、溶融エステル交換法により得られた粒状樹脂
又は該樹脂に上記方法により各種の添加剤を添加して得
られた粒状樹脂組成物を粉砕して粉末とすることにより
得られる。粉砕方法としては、機械的粉砕、機械的冷凍
粉砕、溶剤処理などの方法が適用できるが、特にターボ
ミルまたは低温ターボミルによる粉砕が好ましい。粉末
は、回転成形に適した流動性を示す形状、大きさで粒径
が１５００μｍ〜１００μｍ、好ましくは５００μｍ〜
１５０μｍを有するものであり、ＪＩＳ標準ふるいで１
０〜１５０メッシュパスの範囲の粒度を有することが好
ましく、さらに３０〜１００メッシュパスの範囲の粒度
を有することがより好ましい。The aromatic polycarbonate resin powder in the present invention is a powder obtained by pulverizing a granular resin obtained by the melt transesterification method or a granular resin composition obtained by adding various additives to the resin by the above method. It is obtained by As a pulverization method, methods such as mechanical pulverization, mechanical freezing pulverization, and solvent treatment can be applied, but pulverization by a turbo mill or a low temperature turbo mill is particularly preferable. The powder has a shape and a size suitable for rotational molding and a particle size of 1500 μm to 100 μm, preferably 500 μm to
It has a size of 150 μm, and has a JIS standard sieve of 1
It is preferable to have a particle size in the range of 0 to 150 mesh pass, and more preferable to have a particle size in the range of 30 to 100 mesh pass.
【００１８】本発明の回転成形体を製造する方法は、従
来公知の方法で実施することができる。具体的には、例
えば次ぎのような方法である。一軸または直交する二軸
の周りに回転する金型、揺動回転する金型等の中に、本
発明の芳香族ポリカーボネート樹脂粉末を入れ、該粉末
を入れる前か後に金型を加熱して、密閉状態で回転し金
型の内部表面に樹脂を付着、融着させ、次いで、金型を
冷却して金型内表面に形成された成形品を取り出すこと
により回転成形体を得ることができる。金型から取り出
し後、回転成形における成形残留歪は少ないが、形状に
よっては離型時に残留歪を発生することがあるので必要
に応じてアニーリング処理が行なわれる。The method for producing the rotationally molded product of the present invention can be carried out by a conventionally known method. Specifically, for example, the following method is used. A mold that rotates around one axis or two axes that intersect at right angles, in a mold that oscillates, etc., put the aromatic polycarbonate resin powder of the present invention, and heat the mold before or after putting the powder, A rotation molded article can be obtained by rotating in a sealed state to adhere and fuse resin to the inner surface of the mold, and then cooling the mold and taking out the molded product formed on the inner surface of the mold. After removal from the mold, the molding residual strain in rotational molding is small, but depending on the shape, residual strain may occur at the time of mold release, so an annealing treatment is performed as necessary.
【００１９】本発明において回転成形時の成形温度は、
成形品の肉厚、大きさ、形状、使用される樹脂の分子
量、あるいは樹脂組成などにより異なるが、本発明の芳
香族ポリカーボネート樹脂においては、成形温度は３０
０℃未満、通常２７０℃〜２９０℃で成形が可能であ
り、それによりポリカーボネート樹脂の熱劣化が抑えら
れ、着色や分子量低下に伴う強度低下も認められず、ま
た成形品内部の平滑性も良好で、成形サイクルも良好な
ものである。本発明においては、成形時に、成形用原料
樹脂粉末等に随伴する空気が存在すると、ポリカーボネ
ート樹脂の劣化を促進するので、該樹脂粉末を金型内に
入れた後、該金型内の空気を窒素ガスなどの不活性ガス
で置換してから成形する方法を採用することができ、好
ましい方法である。In the present invention, the molding temperature during rotational molding is
The molding temperature of the aromatic polycarbonate resin of the present invention varies depending on the thickness, size, shape of the molded product, the molecular weight of the resin used, the resin composition, etc.
Molding is possible at less than 0 ° C, usually at 270 ° C to 290 ° C, whereby thermal deterioration of the polycarbonate resin is suppressed, no decrease in strength due to coloring or decrease in molecular weight is observed, and smoothness inside the molded product is also good. The molding cycle is also good. In the present invention, the presence of air accompanying the molding raw material resin powder during molding accelerates the deterioration of the polycarbonate resin, so after the resin powder is put into the mold, the air in the mold is removed. A method of substituting with an inert gas such as nitrogen gas and then molding can be adopted, which is a preferable method.
【００２０】[0020]
【実施例】以下に実施例、比較例を挙げ、本発明を具体
的に説明するが、本発明はこれらにより何ら限定される
ものではない。EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００２１】実施例１
ビスフェノールＡとジフェニルカーボネートとのエステ
ル交換反応によって得られた芳香族ポリカーボネート樹
脂（粘度平均分子量２２０００、フェノール性水酸基濃
度１０ｍｏｌ％）のペレットをターボミルで粉砕し、粒
径が１５０μｍ〜５００μｍの粉末を得た。これを１１
０℃で２４時間減圧乾燥したのち、この粉末６００ｇを
内容積５リットルで、外側に加熱オイル循環配管を配
し、予め２４０℃に予熱した円柱形金型に入れ、密閉し
たのち、窒素置換を行い、その後該オイル循環配管に約
２８５℃に加熱したオイルを循環させた。この金型を公
転１０ｒｐｍ、自転２０ｒｐｍで２軸回転をさせなが
ら、同温度で１５分間保持した後、オイル循環を１００
℃の循環系に切り替えて９分間保持した。その後型を開
放し、室温環境に移して自然冷却して成形品を得た。こ
の成形品の色相および外観は表１の通りであった。Example 1 Pellets of an aromatic polycarbonate resin (viscosity average molecular weight 22000, phenolic hydroxyl group concentration 10 mol%) obtained by transesterification reaction of bisphenol A and diphenyl carbonate were pulverized with a turbo mill to have a particle size of 150 μm- A powder of 500 μm was obtained. This 11
After drying under reduced pressure at 0 ° C. for 24 hours, 600 g of this powder having an internal volume of 5 liters is arranged on the outside with a heating oil circulation pipe, placed in a cylindrical mold preheated to 240 ° C. in advance and sealed, and then replaced with nitrogen. After that, the oil heated to about 285 ° C. was circulated through the oil circulation pipe. The mold was held at the same temperature for 15 minutes while being rotated biaxially at a revolution of 10 rpm and a rotation of 20 rpm, and then oil circulation was performed at 100 rpm.
The system was switched to a circulating system at 0 ° C and kept for 9 minutes. After that, the mold was opened, transferred to a room temperature environment, and naturally cooled to obtain a molded product. The hue and appearance of this molded product are shown in Table 1.
【００２２】実施例２
芳香族ポリカーボネート樹脂として、粘度平均分子量２
２０００、フェノール性水酸基濃度が５モル％である溶
融エステル交換法ポリカーボネート樹脂を使用した以外
は実施例１と同様に実施して回転成形品を得た。この結
果は表１に示す通りであった。Example 2 As an aromatic polycarbonate resin, a viscosity average molecular weight of 2 was used.
2000. A rotomolded product was obtained in the same manner as in Example 1 except that a melt transesterification polycarbonate resin having a phenolic hydroxyl group concentration of 5 mol% was used. The results are shown in Table 1.
【００２３】実施例３
芳香族ポリカーボネート樹脂として、粘度平均分子量２
２０００、フェノール性水酸基濃度が６０モル％である
溶融エステル交換法ポリカーボネート樹脂を使用した以
外は実施例１と同様に実施して回転成形品を得た。この
結果は表１に示す通りであった。Example 3 As an aromatic polycarbonate resin, a viscosity average molecular weight of 2 was used.
2000. A rotomolded product was obtained in the same manner as in Example 1 except that a melt transesterification polycarbonate resin having a phenolic hydroxyl group concentration of 60 mol% was used. The results are shown in Table 1.
【００２４】比較例１
界面重合法により得られた芳香族ポリカーボネート樹脂
（粘度平均分子量２２０００、フェノール性水酸基濃度
３モル％）を使用し、実施例１と同様にして成形品を得
た。この結果は表１の通りであった。Comparative Example 1 A molded article was obtained in the same manner as in Example 1 except that an aromatic polycarbonate resin obtained by the interfacial polymerization method (viscosity average molecular weight 22000, phenolic hydroxyl group concentration 3 mol%) was used. The results are shown in Table 1.
【００２５】比較例２
比較例１に使用したと同様の芳香族ポリカーボネート樹
脂を使用し、成形温度を３２０度にした以外は比較例１
と同様に行って成形品を得た。この結果は表１の通りで
あった。Comparative Example 2 Comparative Example 1 except that the same aromatic polycarbonate resin as that used in Comparative Example 1 was used and the molding temperature was 320 ° C.
A molded article was obtained in the same manner as above. The results are shown in Table 1.
【００２６】比較例３
芳香族ポリカーボネート樹脂として、粘度平均分子量２
２０００、フェノール性水酸基濃度が８０モル％である
溶融エステル交換法ポリカーボネート樹脂を使用した以
外は実施例１と同様に実施した。この結果は表１に示す
通りであった。なお、離型性については、金型への密着
が強く、離型する際に変形させないと型から取り出すこ
とができなかった。Comparative Example 3 An aromatic polycarbonate resin having a viscosity average molecular weight of 2
2000, the same procedure as in Example 1 was carried out except that a melt transesterification polycarbonate resin having a phenolic hydroxyl group concentration of 80 mol% was used. The results are shown in Table 1. Regarding the mold releasability, the mold was strongly adhered to the mold and could not be taken out from the mold unless it was deformed during the mold release.
【００２７】[0027]
【表１】 [Table 1]
【００２８】 色相（ＹＩ）：日本電色工業（株）製、「ＳＰＥＣＴＲＯ ＣＯＬＯＲ ＭＥＴＥＲ ＳＥ−２０００」により測定。 外観 ：得られた回転成形体の状態を目視観察した。 離型性 ：型から離型する際に、変形や破壊がおきたものを「×」とし、 離型が問題なくできたものについては「○」とした。[0028] Hue (YI): "SPECTRO COLOR" manufactured by Nippon Denshoku Industries Co., Ltd. Measured by METER SE-2000 ". Appearance: The state of the obtained rotomolded product was visually observed. Releasability: When the mold is released from the mold, the one that is deformed or destroyed is defined as "x", Those that could be released without problems were marked with "○".
【００２９】[0029]
【発明の効果】本発明の芳香族ポリカーボネート樹脂粉
末は、色相と中空内部が平滑で成形性に優れた回転成形
体を得ることができる。また、本発明の芳香族ポリカー
ボネート樹脂粉末を用いることにより、３００℃未満の
成形温度で回転成形を行うことが可能であり、成形サイ
クルにも優れている。本発明による芳香族ポリカーボネ
ート樹脂を使用した回転成形体は、特に透明性や風情の
ある外観を有する大型照明グローブ、大型照明器具のハ
ウジング、水タンク等の他に、機械的強度を活用したア
ミューズメント用品、家具などに適している。INDUSTRIAL APPLICABILITY The aromatic polycarbonate resin powder of the present invention makes it possible to obtain a rotationally molded product having a smooth hue and hollow interior and excellent moldability. Further, by using the aromatic polycarbonate resin powder of the present invention, it is possible to perform rotational molding at a molding temperature of less than 300 ° C., which is also excellent in molding cycle. The rotational molded body using the aromatic polycarbonate resin according to the present invention is amusement products utilizing mechanical strength in addition to large lighting gloves, housings for large lighting fixtures, water tanks, etc., which have a particularly transparent and elegant appearance. Suitable for furniture.
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Claims (3)
リカーボネート樹脂であって、フェノール性水酸基を３
〜７０モル％含有し、かつ粘度平均分子量が１２，００
０〜２６，０００であることを特徴とする芳香族ポリカ
ーボネート樹脂粉末。1. An aromatic polycarbonate resin produced by a melt transesterification method, comprising a phenolic hydroxyl group of 3
˜70 mol% and viscosity average molecular weight of 12,000
Aromatic polycarbonate resin powder, characterized in that it is from 0 to 26,000.
脂粉末を用い成形温度３００℃未満で回転成形すること
を特徴とする回転成形体の製造方法。2. A method for producing a rotomolded article, which comprises rotationally molding the aromatic polycarbonate resin powder according to claim 1 at a molding temperature of less than 300.degree.
脂粉末を用いた回転成形体。3. A rotationally molded product using the aromatic polycarbonate resin powder according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001216607A JP2003026815A (en) | 2001-07-17 | 2001-07-17 | Aromatic polycarbonate resin powder and method for producing potation molded article using the same and the molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001216607A JP2003026815A (en) | 2001-07-17 | 2001-07-17 | Aromatic polycarbonate resin powder and method for producing potation molded article using the same and the molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003026815A true JP2003026815A (en) | 2003-01-29 |
Family
ID=19051066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001216607A Pending JP2003026815A (en) | 2001-07-17 | 2001-07-17 | Aromatic polycarbonate resin powder and method for producing potation molded article using the same and the molded article |
Country Status (1)
| Country | Link |
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| JP (1) | JP2003026815A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007024425A3 (en) * | 2005-08-24 | 2007-04-12 | Gen Electric | Method of producing polycarbonate articles by rotation molding and rotation molded articles made by the method |
| JP2010274571A (en) * | 2009-05-29 | 2010-12-09 | Mitsubishi Engineering Plastics Corp | Rotational molding method and rotational molded article of polycarbonate resin |
| JP2010275462A (en) * | 2009-05-29 | 2010-12-09 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition for rotational molding and pellet |
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|---|---|---|---|---|
| JPH01158033A (en) * | 1987-09-28 | 1989-06-21 | Asahi Chem Ind Co Ltd | Production of aromatic polycarbonate and crystalline aromatic polycarbonate |
| JPH02180925A (en) * | 1988-12-27 | 1990-07-13 | Asahi Chem Ind Co Ltd | Production of aromatic polycarbonate |
| JPH0543678A (en) * | 1990-12-27 | 1993-02-23 | Asahi Chem Ind Co Ltd | Grinding of aromatic polycarbonate and aromatic polycarbonate powder obtained thereby |
| JPH0880575A (en) * | 1994-09-13 | 1996-03-26 | Rotsuso:Kk | Signboard apparatus |
| JPH0987378A (en) * | 1995-09-27 | 1997-03-31 | Teijin Ltd | Production of polycarbonate |
| JPH11106634A (en) * | 1997-09-30 | 1999-04-20 | Ge Plastics Japan Ltd | Aromatic polycarbonate resin composition |
| JP2000226506A (en) * | 1999-02-04 | 2000-08-15 | Teijin Ltd | Polycarbonate resin composition excellent in stability, and molded product of the composition |
| JP2002020496A (en) * | 2000-07-07 | 2002-01-23 | Teijin Chem Ltd | Polycarbonate resin granule, and rotational molding product composed thereof |
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2001
- 2001-07-17 JP JP2001216607A patent/JP2003026815A/en active Pending
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|---|---|---|---|---|
| JPH01158033A (en) * | 1987-09-28 | 1989-06-21 | Asahi Chem Ind Co Ltd | Production of aromatic polycarbonate and crystalline aromatic polycarbonate |
| JPH02180925A (en) * | 1988-12-27 | 1990-07-13 | Asahi Chem Ind Co Ltd | Production of aromatic polycarbonate |
| JPH0543678A (en) * | 1990-12-27 | 1993-02-23 | Asahi Chem Ind Co Ltd | Grinding of aromatic polycarbonate and aromatic polycarbonate powder obtained thereby |
| JPH0880575A (en) * | 1994-09-13 | 1996-03-26 | Rotsuso:Kk | Signboard apparatus |
| JPH0987378A (en) * | 1995-09-27 | 1997-03-31 | Teijin Ltd | Production of polycarbonate |
| JPH11106634A (en) * | 1997-09-30 | 1999-04-20 | Ge Plastics Japan Ltd | Aromatic polycarbonate resin composition |
| JP2000226506A (en) * | 1999-02-04 | 2000-08-15 | Teijin Ltd | Polycarbonate resin composition excellent in stability, and molded product of the composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007024425A3 (en) * | 2005-08-24 | 2007-04-12 | Gen Electric | Method of producing polycarbonate articles by rotation molding and rotation molded articles made by the method |
| 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 |
| JP2010274571A (en) * | 2009-05-29 | 2010-12-09 | Mitsubishi Engineering Plastics Corp | Rotational molding method and rotational molded article of polycarbonate resin |
| JP2010275462A (en) * | 2009-05-29 | 2010-12-09 | Mitsubishi Engineering Plastics Corp | Polycarbonate resin composition for rotational molding and pellet |
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