JP2002302567A - Method for continuous production of pre-expanded bead of biodegradable polyester-based resin - Google Patents
Method for continuous production of pre-expanded bead of biodegradable polyester-based resinInfo
- Publication number
- JP2002302567A JP2002302567A JP2001106876A JP2001106876A JP2002302567A JP 2002302567 A JP2002302567 A JP 2002302567A JP 2001106876 A JP2001106876 A JP 2001106876A JP 2001106876 A JP2001106876 A JP 2001106876A JP 2002302567 A JP2002302567 A JP 2002302567A
- Authority
- JP
- Japan
- Prior art keywords
- expanded particles
- expanded
- resin
- particles
- polyester resin
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、生分解性を有す
るポリエステル系樹脂予備発泡粒子の連続製造方法に関
し、ポリエステル系樹脂を架橋することなく連続的に予
備発泡粒子を製造することができるようにしたものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for continuously producing pre-expanded particles of a polyester resin having biodegradability, and to a method of continuously producing the pre-expanded particles without crosslinking the polyester resin. It was done.
【０００２】[0002]
【従来の技術】最近の環境問題の高まりから大量に使用
されているプラスチックの廃棄物による河川、海洋、土
壌の汚染の問題や都市のゴミ増大の問題があり、このよ
うな汚染などを防止するため、水中や土中の微生物によ
って分解される生分解性プラスチックが注目され、種々
の提案がなされている。2. Description of the Related Art In recent years, there has been a problem of pollution of rivers, oceans, soils and an increase of garbage in cities due to a large amount of plastic wastes due to an increase in environmental problems. For this reason, biodegradable plastics that are decomposed by microorganisms in water or soil have attracted attention, and various proposals have been made.
【０００３】一方、プラスチックを用いる成形法の一つ
として、いったん予備発泡粒子を製造し、この予備発泡
粒子を型内に充填し、加熱発泡させて発泡成形体を得る
型内成形があり、この分野においても生分解性を有する
樹脂を用いる予備発泡粒子が開発されつつある。On the other hand, as one of the molding methods using plastic, there is an in-mold molding in which pre-expanded particles are once produced, the pre-expanded particles are filled in a mold, and heated and foamed to obtain a foamed molded article. Also in the field, pre-expanded particles using a biodegradable resin are being developed.
【０００４】このような生分解性を有する樹脂を用いる
予備発泡粒子の製造法としては、例えばＡ：特開２００
０−１７０３７号公報に開示された生分解性を有する発
泡性樹脂組成物があり、生分解性樹脂としてポリ乳酸を
用い、このポリ乳酸に所定量のポリイソシアネート化合
物を押出機中に添加し、反応させてポリ乳酸を架橋させ
た後、ペレット状に押し出し、その後、このペレットを
回転式の反応容器に入れ、ペンタンなどの発泡剤を加
熱、加圧しながら含浸させ、さらに、この発泡剤が含浸
されたペレット（発泡性粒子）を水蒸気などにより加熱
し、発泡された予備発泡粒子を製造するようにしてい
る。As a method for producing pre-expanded particles using such a biodegradable resin, for example, A: JP-A-200
There is a foamable resin composition having biodegradability disclosed in Japanese Patent No. 0-17037, using polylactic acid as a biodegradable resin, adding a predetermined amount of a polyisocyanate compound to the polylactic acid in an extruder, After the reaction, the polylactic acid is crosslinked and extruded into pellets.Then, the pellets are put into a rotary reaction vessel, and a foaming agent such as pentane is impregnated with heat and pressure, and further impregnated with the foaming agent. The formed pellets (expandable particles) are heated by steam or the like to produce expanded pre-expanded particles.
【０００５】また、Ｂ：特許２６０９７９５号（特開平
６−２４８１０６号）公報に開示されたポリエステエル
製発泡性粒子では、生分解性樹脂として脂肪族ポリエス
テルを用い、この脂肪族ポリエステルにジイソシアネー
トを反応させて架橋された脂肪族ポリエステルを得た
後、これを押出機等を用いてペレット化する。そして、
このペレットを水中に懸濁させ、プロパンなどの発泡剤
を添加して加熱、加圧により含浸させ、その後、この発
泡剤が含浸されたペレット（発泡性粒子）を水蒸気など
により加熱して発泡された予備発泡粒子を得るようにし
ている。[0005] B: In the expandable particles made of polyester disclosed in Japanese Patent No. 2609795 (JP-A-6-248106), an aliphatic polyester is used as a biodegradable resin, and a diisocyanate is reacted with the aliphatic polyester. After the crosslinked aliphatic polyester is obtained, it is pelletized using an extruder or the like. And
The pellets are suspended in water, a foaming agent such as propane is added thereto, and the pellets are impregnated with heat and pressure. Then, the pellets (expandable particles) impregnated with the foaming agent are foamed by heating with steam or the like. To obtain pre-expanded particles.
【０００６】さらに、Ｃ：特開平１０−３２４７６６号
公報に開示された生分解性を有しかつ架橋構造を有する
脂肪族ポリエステル系樹脂発泡粒子では、生分解性脂肪
族ポリエステル樹脂を押出機にてストランドに押出し、
ペレット状にカットする。そして、このペレットを水中
に懸濁させた後、この系にジビニルベンゼン、過酸化ベ
ンゾイルを加えて撹拌、昇温して架橋された樹脂粒子を
得る。次に、この樹脂粒子をオートクレーブ容器の水中
に分散させ、発泡剤として炭酸ガスを加えて加熱、加圧
した後、オートクレーブ内の圧力を維持しながらオート
クレーブの一端を開放して内容物を大気中に放出して架
橋樹脂を発泡させて予備発泡粒子を得るようにしてい
る。[0006] Further, in the aliphatic polyester resin expanded particles having a biodegradable and crosslinked structure disclosed in JP-A-10-324766, the biodegradable aliphatic polyester resin is extruded by an extruder. Extrude into strands,
Cut into pellets. After suspending the pellet in water, divinylbenzene and benzoyl peroxide are added to the system, and the mixture is stirred and heated to obtain crosslinked resin particles. Next, the resin particles are dispersed in water in an autoclave container, carbon dioxide gas is added as a foaming agent, and the mixture is heated and pressurized. Then, while maintaining the pressure in the autoclave, one end of the autoclave is opened to release the contents in the air. To foam the crosslinked resin to obtain pre-expanded particles.
【０００７】このような生分解性樹脂を用いた予備発泡
粒子の製造法Ａ，Ｂ，Ｃでは、いずれも生分解性樹脂
を架橋する工程、発泡剤を含浸する工程、含浸した
発泡性粒子を予備発泡させる工程の３つの工程を必要と
するものである。In the methods A, B and C for producing pre-expanded particles using such a biodegradable resin, the steps of cross-linking the biodegradable resin, impregnating with a blowing agent, It requires three steps of a pre-foaming step.
【０００８】そこで、生分解性樹脂を用いて製造工程を
簡素化することができる方法Ｄが特開２０００−３１９
４３８号公報に開示されており、３−ヒドロキシブチレ
ートと３−ヒドロキシヘキサノエートからなる脂肪族ポ
リエステル共重合体を基材樹脂とする脂肪族ポリエステ
ル樹脂粒子を、分散剤とともに密閉容器内で水系分散媒
に分散後、発泡剤を密閉容器内に導入し、このポリエス
テル樹脂粒子の軟化温度以上に加熱した後、密閉容器の
一端を開放し、このポリエステル樹脂粒子と水系分散媒
とを密閉容器の圧力よりも低圧の雰囲気下に放出して、
このポリエステル樹脂粒子を発泡させ、示差走査熱量測
定法によるＤＳＣ曲線において２つの融点を示す結晶構
造を有する予備発泡粒子を得るようにしている。Therefore, a method D capable of simplifying the manufacturing process using a biodegradable resin is disclosed in Japanese Patent Application Laid-Open No. 2000-319.
No. 438, which discloses an aliphatic polyester resin particle having an aliphatic polyester copolymer composed of 3-hydroxybutyrate and 3-hydroxyhexanoate as a base resin together with a dispersant in an aqueous container in an airtight container. After dispersing in the dispersion medium, the blowing agent is introduced into the closed container, heated to a temperature equal to or higher than the softening temperature of the polyester resin particles, one end of the closed container is opened, and the polyester resin particles and the aqueous dispersion medium are mixed in the closed container. Release under an atmosphere of lower pressure than pressure,
The polyester resin particles are expanded to obtain pre-expanded particles having a crystal structure exhibiting two melting points in a DSC curve by differential scanning calorimetry.
【０００９】この方法Ｄによれば、上記の生分解性樹
脂を架橋する工程を除いて無架橋で予備発泡粒子を得る
ことができるが、基材樹脂として３−ヒドロキシブチレ
ートと３−ヒドロキシヘキサノエートからなる脂肪族ポ
リエステル共重合体を用いなければならず、ごく一部の
樹脂に限って適用できるものである。According to this method D, pre-expanded particles can be obtained without crosslinking, except for the step of crosslinking the biodegradable resin. However, 3-hydroxybutyrate and 3-hydroxyhexamate are used as base resins. An aliphatic polyester copolymer composed of noate must be used, and can be applied to only a small part of the resin.
【００１０】一方、生分解性は有しないが、型内成形に
用いられる発泡ポリオレフィン系樹脂粒子では、上記Ｃ
の製造法と同様に、押出機によりミニペレット状に加工
されたポリオレフィン樹脂粒子をオートクレーブ容器の
水中に分散させ、発泡剤を添加して高温高圧下に保持し
てペレット中に発泡剤を含浸させた後、その状態を維持
しながらオートクレーブの一端を開放し、一気に放出し
て発泡させ、予備発泡粒子を得る方法（特開昭５２−７
７１７４号公報など）Ｅが良く知られている。On the other hand, although it does not have biodegradability, the expanded polyolefin resin particles used for in-mold molding have the above-mentioned C
In the same manner as in the production method, the polyolefin resin particles processed into mini-pellets by an extruder are dispersed in water of an autoclave container, a blowing agent is added, and the pellets are impregnated with the blowing agent under high temperature and high pressure. After that, while maintaining the state, one end of the autoclave is opened, and the autoclave is released at a stretch to foam and obtain pre-expanded particles (JP-A-52-7).
E is well known.
【００１１】このＥの方法に対して、例えば特開昭６１
−１１３６２７号公報や特開平６−２３４８７８号公報
に開示されている予備発泡粒子の製造法Ｆでは、押出機
中に発泡剤を添加してオレフィン系樹脂を押出し、発泡
ストランドをカットして発泡粒子を得るようにしてい
る。The method of E is described in, for example,
In the method F for producing pre-expanded particles disclosed in JP-A-113627 and JP-A-6-234878, a foaming agent is added to an extruder to extrude an olefin-based resin, and a foamed strand is cut to form a foamed particle. I'm trying to get
【００１２】このＦの方法では、押出機でミニペレット
にする工程、ミニペレットを水中に分散させて発泡剤を
添加する工程、高温高圧下で放出発泡する工程、放出さ
れて得られた予備発泡粒子を乾燥する工程等を無くすこ
とができ、大きく工程を短縮できるが、使用できる樹脂
がオレフィン系樹脂に限られ、しかもオレフィン樹脂に
おいてもある特定のメルトインデックス、溶融強度を持
ち合わせたものでなければならない。In the method F, a step of forming a mini-pellet with an extruder, a step of dispersing the mini-pellet in water and adding a foaming agent, a step of foaming under high temperature and pressure, a step of prefoaming obtained by discharging The process of drying particles can be eliminated, and the process can be greatly shortened.However, usable resins are limited to olefin-based resins, and even if the olefin resin does not have a specific melt index and melt strength. No.
【００１３】[0013]
【発明が解決しようとする課題】以上のように、これま
での生分解性樹脂による予備発泡粒子の製造法では、
Ａ，Ｂ，Ｃの方法では、いずれも生分解性樹脂を架橋す
る工程を必要とし、Ｄの方法では、特別の基材の生分解
性樹脂を用いることで無架橋とすることが出来るもの
の、発泡剤を含浸させた後、得られた発泡性粒子から予
備発泡粒子を得るには、蒸気などにより予備発泡させる
ようにしたり、圧力のかかったオートクレーブの一端よ
り放出して発泡させるようにしなければならない。As described above, in the conventional method for producing pre-expanded particles using a biodegradable resin,
The methods A, B and C all require a step of crosslinking the biodegradable resin, and the method D can be made non-crosslinked by using a special base material of the biodegradable resin. In order to obtain pre-expanded particles from the obtained expandable particles after impregnating the blowing agent, it is necessary to pre-expand them by steam or the like or to release them from one end of a pressured autoclave to expand them. No.
【００１４】ところが、これらの予備発泡工程の多く
は、Ｅの方法のように、オートクレーブ中で行われるバ
ッチ式であることから、加熱と冷却のサイクルを１回ご
とに行わなければならず、エネルギ消費が大きくなると
ともに、連続的に予備発泡粒子を製造することができな
いという問題がある。However, since many of these pre-foaming steps are of the batch type performed in an autoclave as in the method E, heating and cooling cycles must be performed each time, and energy There is a problem that consumption becomes large and pre-expanded particles cannot be produced continuously.
【００１５】また、Ｆの方法（押出発泡粒子法）によれ
ば、押出機中において連続的に発泡剤を含浸させること
ができ、発泡しながら押出される発泡ストランドをカッ
トすることで連続的に予備発泡粒子を得ることができる
が、使用できる樹脂がオレフィン系樹脂に限られ、しか
もオレフィン樹脂においてもある特定のメルトインデッ
クス、溶融強度を持ち合わせたものでなければならない
という問題がある。According to the method F (extruded foamed particle method), the foaming agent can be continuously impregnated in the extruder, and the foamed strand extruded while foaming is continuously cut off. Although pre-expanded particles can be obtained, there is a problem that usable resins are limited to olefin-based resins, and olefin resins must also have a certain specific melt index and melt strength.
【００１６】一方、生分解性の樹脂は、汎用の樹脂群に
比較するとかなり高価なものが多く、生分解性樹脂の予
備発泡粒子を得るための工程の煩雑さ、エネルギ効率の
悪さが一層のコスト増大を招くことから、これらを解消
して生産性の向上を図って製造コストを低減することが
できる予備発泡粒子の製造法の開発が望まれている。On the other hand, many biodegradable resins are considerably expensive as compared with general-purpose resins, and the process of obtaining pre-expanded particles of the biodegradable resin is more complicated, and the energy efficiency is worse. Since the cost is increased, it is desired to develop a method for producing pre-expanded particles capable of solving these problems and improving the productivity to reduce the production cost.
【００１７】この発明は、かかる従来技術の課題と要望
に鑑みてなされたもので、生分解性樹脂の予備発泡粒子
を得るための工程を大幅に簡素化でき、エネルギ効率も
良く、良好な予備発泡粒子を連続的に製造することがで
きる生分解性を有するポリエステル系樹脂予備発泡粒子
の連続製造方法を提供しようとするものである。The present invention has been made in view of the problems and demands of the prior art, and can greatly simplify a process for obtaining pre-expanded particles of a biodegradable resin, has a good energy efficiency, and has a good pre-expansion. It is an object of the present invention to provide a method for continuously producing biodegradable polyester resin pre-expanded particles capable of continuously producing expanded particles.
【００１８】[0018]
【課題を解決するための手段】本発明者は、上記従来技
術が有する課題を解決すべく生分解性を有するポリエス
テル系樹脂予備発泡粒子の製造方法について鋭意研究を
重ねた結果、この発明を完成したもので、生分解性を有
するポリエステル系樹脂を押出機に投入するとともに発
泡剤も加え、発泡させたストランドとして押し出し、こ
れをカットして予備発泡粒子を製造すれば良いことがわ
かった。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a method of producing pre-expanded particles of a polyester resin having biodegradability in order to solve the problems of the prior art, and as a result, completed the present invention. It was found that a biodegradable polyester-based resin was charged into an extruder, a foaming agent was also added, extruded as a foamed strand, and this was cut to produce pre-expanded particles.
【００１９】すなわち、この発明の請求項１記載の生分
解性を有するポリエステル系樹脂予備発泡粒子の連続製
造方法は、生分解性を有するポリエステル系樹脂により
型内成形用の予備発泡粒子を連続して製造するに際し、
生分解性ポリエステル系樹脂と発泡剤とを押出機で混練
し、発泡されたストランドとして押し出し、この発泡ス
トランドをカットして予備発泡粒子を得るようにしたこ
とを特徴とするものである。That is, in the method for continuously producing pre-expanded particles of a biodegradable polyester resin according to claim 1 of the present invention, the pre-expanded particles for in-mold molding are continuously formed of the biodegradable polyester resin. In manufacturing
A biodegradable polyester-based resin and a foaming agent are kneaded by an extruder, extruded as foamed strands, and the foamed strands are cut to obtain pre-expanded particles.
【００２０】この生分解性を有するポリエステル系樹脂
予備発泡粒子の連続製造方法によれば、生分解性を有す
るポリエステル系樹脂により型内成形用の予備発泡粒子
を連続して製造するに際し、生分解性ポリエステル系樹
脂と発泡剤とを押出機で混練し、発泡されたストランド
として押し出し、この発泡ストランドをカットして予備
発泡粒子を得るようにしており、架橋しなくても良く、
予備発泡のための蒸気での加熱や放出発泡などの工程も
必要なく、エネルギ効率も良く、工程を大巾に短縮して
良好な予備発泡粒子を連続的に製造できるようになる。According to the method for continuously producing pre-expanded particles of a biodegradable polyester resin, when the pre-expanded particles for in-mold molding are continuously produced from the biodegradable polyester resin, The polyester resin and the foaming agent are kneaded with an extruder and extruded as a foamed strand, and the foamed strand is cut to obtain pre-expanded particles.
There is no need for a step such as heating with steam for pre-foaming or release foaming, energy efficiency is high, and the process can be greatly shortened to continuously produce good pre-foamed particles.
【００２１】また、この発明の請求項２記載の生分解性
を有するポリエステル系樹脂予備発泡粒子の連続製造方
法は、請求項１記載の構成に加え、前記生分解性ポリエ
ステル系樹脂を、無架橋のポリ乳酸または無架橋のポリ
ブチレンサクシネートで構成したことを特徴とするもの
である。According to a second aspect of the present invention, there is provided a method for continuously producing pre-expanded particles of a biodegradable polyester resin, wherein the biodegradable polyester resin is non-crosslinked. Of polylactic acid or non-crosslinked polybutylene succinate.
【００２２】この生分解性を有するポリエステル系樹脂
予備発泡粒子の連続製造方法によれば、生分解性ポリエ
ステル系樹脂として無架橋のポリ乳酸または無架橋のポ
リブチレンサクシネートを用いるようにしており、これ
ら樹脂により架橋しなくても良く、予備発泡のための蒸
気での加熱や放出発泡などの工程も必要なく、エネルギ
効率も良く、工程を大巾に短縮して良好な予備発泡粒子
を連続的に製造できるようになる。According to this method for continuously producing pre-expanded particles of biodegradable polyester resin, non-crosslinked polylactic acid or non-crosslinked polybutylene succinate is used as the biodegradable polyester resin. It is not necessary to crosslink with these resins, there is no need for steps such as heating with steam for prefoaming or release foaming, energy efficiency is good, the process is greatly shortened and good prefoamed particles are continuously produced. Can be manufactured.
【００２３】[0023]
【発明の実施の形態】以下、この発明の生分解性を有す
るポリエステル系樹脂予備発泡粒子の連続製造方法の一
実施の形態について詳細に説明する。この発明の生分解
性を有するポリエステル系樹脂予備発泡粒子の連続製造
方法は、生分解性を有するポリエステル系樹脂により型
内成形用の予備発泡粒子を連続して製造するに際し、生
分解性ポリエステル系樹脂と発泡剤とを押出機で混練
し、発泡されたストランドとして押し出し、この発泡ス
トランドをカットして予備発泡粒子を得るようにするも
のである。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of a continuous production method of pre-expanded particles of a biodegradable polyester resin according to the present invention will be described in detail. The method for continuously producing pre-expanded particles of a polyester resin having biodegradability according to the present invention includes the steps of continuously producing pre-expanded particles for in-mold molding using a polyester resin having biodegradability. The resin and the foaming agent are kneaded by an extruder, extruded as foamed strands, and the foamed strands are cut to obtain pre-expanded particles.
【００２４】この予備発泡粒子の連続製造方法では、生
分解性を有するポリエステル系樹脂と発泡剤との混合物
を押出機内から圧力開放しながら押出す際に、溶融混合
物中の発泡剤が膨脹することにより予備発泡が行われて
発泡ストランドとして押出され、この発泡ストランドを
カットすることで連続的に予備発泡粒子を得るようにし
ている。In the continuous production method of the pre-expanded particles, the foaming agent in the molten mixture expands when extruding the mixture of the biodegradable polyester resin and the foaming agent while releasing the pressure from the inside of the extruder. , The foam is extruded as a foamed strand, and the foamed strand is cut to continuously obtain pre-expanded particles.
【００２５】このような予備発泡粒子を連続的に製造す
る場合には、溶融混練物温度を高くすると、溶融混合物
の粘度が低下して発泡剤が溶融混合物中に保持されずに
逃散して十分に発泡が行われなかったり、連続気泡の予
備発泡粒子となり、逆に溶融混練温度を低くして粘度を
高くすると、樹脂成分の結晶化が進行し、発泡が不十分
となったり、均一な発泡が起こり難くなる。このため予
備発泡に適した温度範囲は使用樹脂の結晶化温度や分子
量、あるいは発泡剤の量などによって適宜調整する必要
があり、一般に結晶化温度が低く分子量が小さい樹脂を
用いる場合や発泡剤の量が多い場合は押出発泡に適する
温度は低くなる。In the case of continuously producing such pre-expanded particles, when the temperature of the melt-kneaded material is increased, the viscosity of the molten mixture decreases, and the foaming agent escapes without being retained in the molten mixture, and If foaming is not performed or becomes pre-expanded particles of open cells, conversely, if the viscosity is increased by lowering the melt-kneading temperature, crystallization of the resin component progresses and foaming becomes insufficient or uniform foaming occurs Is less likely to occur. For this reason, the temperature range suitable for pre-foaming needs to be appropriately adjusted depending on the crystallization temperature and molecular weight of the resin used, or the amount of the foaming agent. Generally, when using a resin having a low crystallization temperature and a small molecular weight, The higher the amount, the lower the temperature suitable for extrusion foaming.
【００２６】この予備発泡粒子の連続製造方法に用いる
生分解性を有するポリエステル系樹脂としては、特に限
定するものではないが、例えば、ポリ乳酸、ポリブチレ
ンサクシネート、ポリブチレンサクシネート・アジペー
ト、ポリブチレンサクシネート・カーボネート、ポリヒ
ドロキシブチレート、ポリカプロラクトン、又はこれら
の混合物等をあげることができる。The polyester resin having biodegradability used in the continuous production method of the pre-expanded particles is not particularly limited. Examples thereof include polylactic acid, polybutylene succinate, polybutylene succinate adipate, and polybutylene succinate adipate. Examples include butylene succinate carbonate, polyhydroxybutyrate, polycaprolactone, and mixtures thereof.
【００２７】このような生分解性を有するポリエステル
系樹脂には、安定剤として酸化防止剤、中和剤、耐候
剤、紫外線吸収剤、その他の添加剤として帯電防止剤、
滑剤、難燃剤、着色剤、及びタルク、炭酸カルシウム等
の無機充填剤等をこの発明の目的を損なわない範囲で配
合することができる。なお、これらの成分の混合には、
高速撹拌機付き混合機（例えばヘンシェルミキサーやス
ーパーミキサー等）や通常の混合装置（例えばリボンブ
レンダーやタンブラー等）を使用すれば良い。Such a biodegradable polyester resin includes an antioxidant, a neutralizer, a weathering agent, an ultraviolet absorber as a stabilizer, and an antistatic agent as other additives.
Lubricants, flame retardants, colorants, and inorganic fillers such as talc and calcium carbonate can be blended within a range that does not impair the object of the present invention. In addition, in mixing these components,
A mixer with a high-speed stirrer (for example, a Henschel mixer or a super mixer) or a usual mixing device (for example, a ribbon blender or a tumbler) may be used.
【００２８】予備発泡粒子の連続製造に用いる押出機と
しては、単軸押出機や二軸押出機が使用でき、さらに、
押出機１機の１段式及び押出機２機を直列に連結した２
段式（タンデム式）などを使用することができるが、樹
脂の可塑化、樹脂と添加剤との混合、および樹脂の冷却
段階と続いて押出しを効率良く実施して均一な予備発泡
粒子を得るには２段式が特に好ましい。As an extruder used for continuous production of pre-expanded particles, a single-screw extruder or a twin-screw extruder can be used.
A single-stage type extruder and two extruders connected in series
A step type (tandem type) or the like can be used, but the plasticization of the resin, the mixing of the resin and the additive, and the cooling step of the resin, followed by efficient extrusion, to obtain uniform pre-expanded particles. Is particularly preferably a two-stage type.
【００２９】このような押出機による混練温度は、１９
０〜３００℃が一般的であり、好ましくは２００〜２７
０℃、より好ましくは２００〜２５０℃であるが、生分
解性を有するポリエステル系樹脂としてポリ乳酸を用い
る場合には、混練温度は１５０〜２５０℃、好ましくは
１８０〜２３０℃であり、ポリブチレンサクシネートを
用いる場合には、混練温度は１３０〜２３０℃、好まし
くは１５０〜２００℃である。The kneading temperature of such an extruder is 19
0-300 ° C is common, preferably 200-27 ° C.
0 ° C., more preferably 200 to 250 ° C., but when polylactic acid is used as the polyester resin having biodegradability, the kneading temperature is 150 to 250 ° C., preferably 180 to 230 ° C., and polybutylene is used. When succinate is used, the kneading temperature is 130 to 230 ° C, preferably 150 to 200 ° C.
【００３０】次に、押出機より押出された発泡ストラン
ドをカットする方法としては種々の方法があるが、多孔
ダイから押出されて発泡しつつあるストランドを冷却し
ながらカットする、いわゆるホットカット方式が好まし
く、得られる予備発泡粒子の形状が丸みを帯び、得られ
た予備発泡粒子を用いて発泡成形体を成形する場合に型
内への充填をスムーズに行うことができる。Next, there are various methods for cutting the foamed strand extruded from the extruder. There is a so-called hot cut method in which the strand being extruded from the porous die and being foamed is cut while being cooled. Preferably, the shape of the obtained pre-expanded particles is rounded, and when the obtained pre-expanded particles are used to form a foam molded article, the filling into the mold can be performed smoothly.
【００３１】この予備発泡粒子の連続製造方法では、発
泡剤として、無機ガスや揮発性発泡剤などを用いること
ができ、無機ガスとしては二酸化炭素、窒素、水蒸気な
どを用いることができ、揮発性発泡剤としてはプロパ
ン、ｎ−ブタン、ｉ−ブタン、ペンタン、シクロペンタ
ン、ヘプタンなどの脂肪族炭化水素、トリクロルフルオ
ルメタン、ジクロルジフルオルエタン、ジクロルテトラ
フルオルエタン、テトラフルオロエタン、メチルクロラ
イドなどのハロゲン化炭化水素などを用いることがで
き、高発泡倍率の予備発泡粒子が得られ易く、経済性に
も優れている。In this method for continuously producing pre-expanded particles, an inorganic gas or a volatile blowing agent can be used as a blowing agent, and carbon dioxide, nitrogen, water vapor, or the like can be used as an inorganic gas. Examples of the foaming agent include aliphatic hydrocarbons such as propane, n-butane, i-butane, pentane, cyclopentane and heptane, trichlorofluoromethane, dichlorodifluoroethane, dichlorotetrafluoroethane, tetrafluoroethane, and methyl. Halogenated hydrocarbons such as chloride can be used, and pre-expanded particles having a high expansion ratio can be easily obtained, and the economy is excellent.
【００３２】なお、発泡剤は上記のものを単独で用いる
ほか、これらを混合して用いることもできる。The above-mentioned foaming agents may be used alone or in combination.
【００３３】このような発泡剤の添加は、押出機内で生
分解性を有するポリエステル系樹脂と添加剤などの樹脂
成分を溶融した後、押出機の途中に設けたバレル孔より
発泡剤を押出機内に注入することによって行われる。[0033] The addition of the blowing agent is performed by melting a resin component such as a biodegradable polyester resin and additives in the extruder, and then feeding the blowing agent into the extruder through a barrel hole provided in the extruder. This is done by injecting
【００３４】また、予備発泡粒子の発泡セルの大きさを
調整するため、気泡調整剤を添加しても良く、例えばタ
ルク、二酸化珪素、二酸化チタン、炭酸カルシウム、重
炭酸ナトリウムなどの無機粉末や、クエン酸、重炭酸ナ
トリウムとクエン酸の混合物などをあげることができ、
これらを混合して用いることもできる。In order to adjust the size of the expanded cells of the pre-expanded particles, a cell regulator may be added. For example, inorganic powders such as talc, silicon dioxide, titanium dioxide, calcium carbonate, and sodium bicarbonate; Citric acid, a mixture of sodium bicarbonate and citric acid, and the like,
These can be mixed and used.
【００３５】この気泡調整剤の添加量は、所望する予備
発泡粒子の物性により異なるが、一般的には、生分解性
を有するポリエステル系樹脂１００重量部に対し、０．
０１〜３重量部程度である。The amount of the cell regulator varies depending on the desired physical properties of the pre-expanded particles, but is generally 0.1 to 100 parts by weight of the biodegradable polyester resin.
It is about 01 to 3 parts by weight.
【００３６】この予備発泡粒子の連続製造方法で製造す
る予備発泡粒子の発泡倍率は、特に制限はないが、５〜
８０倍が好ましく、５倍より小さいと、発泡体としての
軽量性などの特性を十分得ることが出来ず、８０倍より
大きいと、気泡径が大きくなり過ぎ、機械的強度も低下
してしまう。The expansion ratio of the pre-expanded particles produced by the continuous production method of pre-expanded particles is not particularly limited, but is preferably 5 to 5.
80 times is preferable, and if it is less than 5 times, properties such as light weight as a foam cannot be sufficiently obtained. If it is more than 80 times, the cell diameter becomes too large, and the mechanical strength also decreases.
【００３７】また、予備発泡粒子の気泡径は、５０〜５
００μｍが好ましく、５０μｍより小さいと、緩衝特性
が低下してしまい、５００μｍより大きいと、耐熱性、
機械的強度が不十分となってしまう。The cell diameter of the pre-expanded particles is 50 to 5
When the diameter is smaller than 50 μm, the buffering property is deteriorated. When the diameter is larger than 500 μm, heat resistance,
The mechanical strength becomes insufficient.
【００３８】さらに、予備発泡粒子の独立気泡率は、７
０％以上が好ましく、７０％より小さいと、発泡成形体
を型内成形する場合の二次発泡性、緩衝特性、機械的強
度が不十分となる。Further, the closed cell rate of the pre-expanded particles is 7
0% or more is preferable, and when it is less than 70%, the secondary foaming property, the cushioning property, and the mechanical strength when the foam molded article is molded in a mold become insufficient.
【００３９】なお、予備発泡粒子は、通常の養生後、必
要に応じて内圧付与し、成形金型に充填して加熱発泡成
形が行われる。After the normal curing, the pre-expanded particles are subjected to an internal pressure as needed, filled in a molding die, and subjected to heat expansion molding.
【００４０】以上のように、この発明の生分解性を有す
るポリエステル系樹脂予備発泡粒子の連続製造方法によ
れば、樹脂を押出機へ投入、同時に押出機に発泡剤を加
え、発泡ストランドとして押出し、カットして予備発泡
粒子を得ることができるので、既に説明した生分解性樹
脂を用いる従来の予備発泡粒子の製造法Ａ，Ｂ，Ｃのよ
うな生分解性樹脂を架橋する工程、発泡剤を含浸す
る工程、含浸した発泡性粒子を予備発泡させる工程の
３つの工程を必要とせず、連続する１工程だけで済み、
生分解性樹脂の予備発泡体を得るまでの工程を大幅に短
縮することができる。As described above, according to the continuous production method of the polyester resin pre-expanded particles having biodegradability of the present invention, the resin is charged into an extruder, and simultaneously a foaming agent is added to the extruder, and the extruded resin is extruded as a foamed strand. A process for cross-linking a biodegradable resin, such as a conventional method for producing pre-expanded particles using a biodegradable resin, which can be obtained by cutting the pre-expanded particles, , And the step of pre-expanding the impregnated expandable particles is not required, and only one continuous step is required.
The steps required to obtain a pre-foamed biodegradable resin can be greatly reduced.
【００４１】また、この発明の生分解性を有するポリエ
ステル系樹脂予備発泡粒子の連続製造方法によれば、生
分解性樹脂を架橋しなくても良好な発泡性樹脂粒子を得
ることができる。さらに、この発泡性粒子を予備発泡さ
せて予備発泡粒子とし、これを型内成形により発泡成形
体とした場合にも良好な発泡成形体を得ることができる
とともに、架橋していないので発泡成形体が生分解性に
優れたものとなる。Further, according to the method for continuously producing biodegradable polyester resin pre-expanded particles of the present invention, good expandable resin particles can be obtained without cross-linking the biodegradable resin. Further, when the expandable particles are pre-expanded to obtain pre-expanded particles, which can be formed into an expanded molded product by in-mold molding, a good expanded molded product can be obtained. Are excellent in biodegradability.
【００４２】[0042]
【実施例】次に、この発明の生分解性を有するポリエス
テル系樹脂予備発泡粒子の連続製造方法の実施例につい
て比較例とともに説明するが、この発明は、以下の実施
例に限定するものでない。EXAMPLES Next, examples of the method for continuously producing pre-expanded particles of a polyester resin having biodegradability according to the present invention will be described together with comparative examples, but the present invention is not limited to the following examples.
【００４３】（実施例１）生分解性を有するポリエステ
ル系樹脂としてポリ乳酸１００重量部に気泡調整剤とし
て平均粒径１０μｍのタルクを１．０重量部の割合で加
えた混合物をタンデム式押出機に供給して予備発泡粒子
を製造した。Example 1 A tandem-type extruder was prepared by adding a mixture of 100 parts by weight of polylactic acid as a biodegradable polyester resin and 1.0 part by weight of talc having an average particle diameter of 10 μm as a cell regulator. To produce pre-expanded particles.
【００４４】この予備発泡粒子の製造には、４０ｍｍ
φ、Ｌ／Ｄ比が３２の単軸でバレルの途中に発泡剤注入
用のバレル孔を有する第１段の押出機と５０ｍｍφ、Ｌ
／Ｄ比が２６の単軸の第２段の押出機とを連結して構成
したタンデム式押出機を使用した。For the production of the pre-expanded particles, 40 mm
A single-stage extruder having a barrel hole for injecting a foaming agent in the middle of the barrel with a φ, L / D ratio of 32 and a 50 mm φ, L
A tandem-type extruder constituted by connecting a single-screw second-stage extruder having a / D ratio of 26 was used.
【００４５】上記混合物を第１段の押出機に１５ｋｇ／
ｈｒで供給し、この第１段の押出機のバレルの途中の発
泡剤注入用のバレル孔より発泡剤としてブタンを０．９
ｋｇ／ｈｒで注入して溶融混合した後、第２段の押出機
で発泡粒子の表面に凹凸が発生しない最低の樹脂温度に
なるように温度を調整し、第２段の押出機の先端に取り
付けた孔径：１ｍｍφ、孔数：２４個の多孔ダイより発
泡ストランドを押出して、この多孔ダイに接して回転刃
を有するストランドカッターにて発泡ストランドを切断
し、予備発泡粒子を製造した。The above mixture was placed in a first stage extruder at 15 kg /
hr, and butane as a foaming agent was added in a volume of 0.9 as a blowing agent through a barrel hole for injection of a blowing agent in the middle of the barrel of the first-stage extruder.
After injecting at a rate of kg / hr and melt-mixing, the temperature in the second stage extruder was adjusted so that the surface of the foamed particles did not have irregularities, and the temperature was adjusted to the lowest level. A foamed strand was extruded from a perforated die having an attached hole diameter of 1 mmφ and the number of holes: 24, and the foamed strand was cut by a strand cutter having a rotary blade in contact with the perforated die to produce pre-expanded particles.
【００４６】なお、タンデム式押出機の温度は、第１段
の押出機の１ゾーン：２００℃、２ゾーン：１７０℃、
３ゾーン：１５０℃、４ゾーン：１５０℃、第２段の押
出機の１ゾーン：１３０℃、２ゾーン：１２５℃、３ゾ
ーン〜５ゾーン：１２５℃、第２段の押出機と多孔ダイ
の間に設けたブレーカープレート部での押出樹脂温度は
１２０℃とした。The temperature of the tandem-type extruder was as follows: 1 zone: 200 ° C., 2 zones: 170 ° C.
Three zones: 150 ° C., four zones: 150 ° C., one zone of the second stage extruder: 130 ° C., two zones: 125 ° C., three to five zones: 125 ° C., a second stage extruder and a multi-hole die The extruded resin temperature at the breaker plate portion provided between them was 120 ° C.
【００４７】得られた予備発泡粒子は良好であり、その
かさ比重は０．０１５ｇｒ／ｃｍ3であった。The pre-expanded particles obtained were good and had a bulk specific gravity of 0.015 gr / cm 3 .
【００４８】次に、この予備発泡粒子を用い、型内成形
を行い発泡成形体を製造した。まず、予備発泡粒子を室
温で１日熟成した後、成形用金型に充填し、１０３℃の
水蒸気で２０秒間加熱して型内発泡成形体に加工した。Next, the pre-expanded particles were subjected to in-mold molding to produce an expanded molded article. First, the pre-expanded particles were aged at room temperature for 1 day, filled in a molding die, and heated with steam at 103 ° C. for 20 seconds to be processed into an in-mold foam molded product.
【００４９】得られた発泡成形体は特性の良好なもので
あった。The obtained foam molded article had good properties.
【００５０】（実施例２）生分解性を有するポリエステ
ル系樹脂としてポリブチレンサクシネート１００重量部
に気泡調整剤として平均粒径１０μｍのタルクを１．０
重量部の割合で加えた混合物を用い、実施例１と同一の
タンデム式押出機に供給して予備発泡粒子を製造した。Example 2 100 parts by weight of polybutylene succinate as a polyester resin having biodegradability was added with 1.0 g of talc having an average particle size of 10 μm as a cell regulator.
Using the mixture added in parts by weight, the mixture was supplied to the same tandem extruder as in Example 1 to produce pre-expanded particles.
【００５１】上記混合物を第１段の押出機に１５ｋｇ／
ｈｒで供給し、この第１段の押出機のバレルの途中の発
泡剤注入用のバレル孔より発泡剤としてブタンを１．５
ｋｇ／ｈｒで注入して溶融混合した後、第２段の押出機
で発泡粒子の表面に凹凸が発生しない最低の樹脂温度に
なるように温度を調整し、第２段の押出機の先端に取り
付けた多孔ダイより発泡ストランドを押出して、この多
孔ダイに接するストランドカッターにて発泡ストランド
を切断し、予備発泡粒子を製造した。The above mixture was placed in a first stage extruder at 15 kg /
and butane as a foaming agent through a barrel hole for injection of a foaming agent in the middle of the barrel of the first-stage extruder.
After injecting at a rate of kg / hr and melt-mixing, the temperature in the second stage extruder was adjusted so that the surface of the foamed particles did not have irregularities, and the temperature was adjusted to the lowest level. The foamed strand was extruded from the attached porous die, and the foamed strand was cut by a strand cutter in contact with the porous die to produce pre-expanded particles.
【００５２】なお、タンデム式押出機の温度は、第１段
の押出機の１ゾーン：１８５℃、２ゾーン：１６０℃、
３ゾーン：１４０℃、４ゾーン：１４０℃、第２段の押
出機の１ゾーン：１３０℃、２ゾーン：１２０℃、３ゾ
ーン〜５ゾーン：１２０℃、第２段の押出機と多孔ダイ
の間に設けたブレーカープレート部での押出樹脂温度は
１２０℃とした。The temperature of the tandem type extruder was as follows: 1 zone of the first stage extruder: 185 ° C., 2 zones: 160 ° C.
Three zones: 140 ° C., four zones: 140 ° C., one zone of the second-stage extruder: 130 ° C., two zones: 120 ° C., three to five zones: 120 ° C., a second-stage extruder and a multi-hole die The extruded resin temperature at the breaker plate portion provided between them was 120 ° C.
【００５３】得られた予備発泡粒子は良好であり、その
かさ比重は０．０１３ｇｒ／ｃｍ3であった。The pre-expanded particles obtained were good and had a bulk specific gravity of 0.013 gr / cm 3 .
【００５４】次に、この予備発泡粒子を用い、型内成形
を行い発泡成形体を製造した。まず、予備発泡粒子を
０．３ＭＰａの窒素加圧雰囲気下に１日間保持した後、
成形用金型に充填し、１１０℃の水蒸気で４０秒間加熱
して型内発泡成形体に加工した。得られた発泡成形体は
特性の良好なものであった。Next, in-mold molding was performed using the pre-expanded particles to produce an expanded molded article. First, after keeping the pre-expanded particles under a nitrogen pressurized atmosphere of 0.3 MPa for one day,
The mixture was filled in a molding die and heated with steam at 110 ° C. for 40 seconds to be processed into an in-mold foam molded product. The obtained foam molded article had good properties.
【００５５】（実施例３）実施例１において、発泡剤の
量を０．７５ｋｇ／ｈｒとした以外は同一として予備発
泡粒子を製造した。Example 3 Pre-expanded particles were produced in the same manner as in Example 1, except that the amount of the blowing agent was changed to 0.75 kg / hr.
【００５６】得られた予備発泡粒子は良好であり、その
かさ比重は０．０３２ｇｒ／ｃｍ3であった。The obtained pre-expanded particles were good, and had a bulk specific gravity of 0.032 gr / cm 3 .
【００５７】また、この予備発泡粒子を用い、型内成形
を行って製造した発泡成形体は特性の良好なものであっ
た。The foamed molded article produced by performing in-mold molding using the pre-expanded particles had good properties.
【００５８】（実施例４）実施例２において、発泡剤の
量を０．７５ｋｇ／ｈｒとした以外は同一として予備発
泡粒子を製造した。Example 4 Pre-expanded particles were produced in the same manner as in Example 2 except that the amount of the blowing agent was changed to 0.75 kg / hr.
【００５９】得られた予備発泡粒子は良好であり、その
かさ比重は０．０４９ｇｒ／ｃｍ3であった。The pre-expanded particles obtained were good and had a bulk specific gravity of 0.049 gr / cm 3 .
【００６０】また、この予備発泡粒子を用い、型内成形
を行って製造した発泡成形体は特性の良好なものであっ
た。A foam molded article produced by performing in-mold molding using the pre-expanded particles had good properties.
【００６１】（比較例１）生分解性を有するポリエステ
ル系樹脂としてのポリ乳酸１００重量％にタルク１．０
重量％を加え、２軸押出機でシリンダ温度２８０℃で押
出し、ペレット状粒子を得た後、回転式の反応容器に樹
脂組成物２０００部、発泡剤としてイソペンタン１２０
０部、メタノール５００部を仕込み、密封した後反応容
器の回転数１０回／ｍｉｎ、昇温速度２０℃／ｈｒの割
合で昇温し、７０℃に２時間保持した。その後、室温ま
で冷却し発泡剤含浸樹脂組成物を取り出して風乾した。
次いで得られた発泡剤含浸樹脂組成物を水蒸気で加熱し
て予備発泡したが、収縮して満足な予備発泡粒子を得る
ことが出来ず、発泡成形体を成形することもできなかっ
た。Comparative Example 1 100% by weight of polylactic acid as a polyester resin having biodegradability was added to talc 1.0
Wt.% And extruded at a cylinder temperature of 280 ° C. with a twin-screw extruder to obtain pellet-like particles.
After 0 parts and 500 parts of methanol were charged and sealed, the temperature was raised at a rate of 20 ° C./hr at a rotation speed of the reaction vessel of 10 times / min and maintained at 70 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature, and the blowing agent-impregnated resin composition was taken out and air-dried.
Next, the obtained foaming agent-impregnated resin composition was pre-foamed by heating with steam. However, the pre-foamed particles could not be obtained due to shrinkage, and a foam molded article could not be formed.
【００６２】（比較例２）生分解性を有するポリエステ
ル系樹脂としてのポリブチレンサクシネート２０００ｇ
ｒ、リン酸三カルシウム１０ｇｒ、ドデシルベンゼンス
ルホン酸ナトリウム０．１０ｇｒを純水２０００ｇｒを
入れた内容積５Ｌの撹拌機付きオートクレーブに投入
し、撹拌しながらペンタン２００ｇｒを圧入して１００
℃まで昇温して２時間反応させ、次いで、オートクレー
ブの温度を３０℃まで冷却した後、取り出して発泡性粒
子を得た。Comparative Example 2 2000 g of polybutylene succinate as a polyester resin having biodegradability
r, 10 g of tricalcium phosphate and 0.10 g of sodium dodecylbenzenesulfonate were charged into a 5 L-volume autoclave containing 2000 g of pure water and equipped with a stirrer.
C., and the autoclave was cooled to 30.degree. C. and taken out to obtain expandable particles.
【００６３】得られた発泡性粒子を水蒸気で加熱して予
備発泡したが、収縮して満足な予備発泡粒子を得ること
が出来ず、発泡成形体を成形することもできなかった。The obtained expandable particles were pre-expanded by heating with steam. However, they did not shrink to obtain satisfactory pre-expanded particles and could not be used to form a foamed molded article.
【００６４】（比較例３）生分解性を有するポリエステ
ル系樹脂としてのポリブチレンサクシネート１００重量
部、リン酸三カルシウム２０重量部、ドデシルベンゼン
スルホン酸ナトリウム０．０１重量部を内容積５Ｌのオ
ートクレーブに仕込み、発泡温度まで加熱し、炭酸ガス
をオートクレーブ内圧力が４０ｋｇ／ｃｍ2 Ｇまで注入
し含浸させた。その後、オートクレーブに窒素ガスを導
入しつつオートクレーブの一端を開放して大気圧下に放
出して発泡性樹脂粒子を発泡させて予備発泡粒子を得
た。Comparative Example 3 An autoclave having a content volume of 5 L containing 100 parts by weight of polybutylene succinate as a polyester resin having biodegradability, 20 parts by weight of tricalcium phosphate, and 0.01 part by weight of sodium dodecylbenzenesulfonate was used. The mixture was heated to a foaming temperature, and carbon dioxide gas was injected into the autoclave to a pressure of 40 kg / cm 2 G for impregnation. Thereafter, while introducing nitrogen gas into the autoclave, one end of the autoclave was opened and released under atmospheric pressure to expand the expandable resin particles to obtain pre-expanded particles.
【００６５】得られた予備発泡粒子は、そのかさ比重が
０．０４５ｇｒ／ｃｍ3 であった。次に、この予備発泡
粒子を用い、型内成形により発泡成形体を製造するた
め、予備発泡粒子を６０℃で１日間乾燥熟成した後、成
形用金型に充填し、水蒸気で加熱して発泡成形体を製造
した。The obtained pre-expanded particles had a bulk specific gravity of 0.045 gr / cm 3 . Next, the pre-expanded particles are dried and aged at 60 ° C. for 1 day in order to produce an expanded molded article by in-mold molding using the pre-expanded particles. A molded body was manufactured.
【００６６】得られた発泡成形体は収縮が大きく満足し
たものが得られなかった。The obtained foamed molded article was not satisfactory because of a large shrinkage.
【００６７】次に、この発明の生分解性を有するポリエ
ステル系樹脂予備発泡粒子の連続製造方法では、ポリエ
ステル系樹脂を架橋しなくても良好な予備発泡粒子を連
続的に製造することができるが、架橋しても良いことか
ら、この発明の技術的範囲に含まれる架橋した場合を参
考例として説明する。Next, in the method for continuously producing pre-expanded polyester resin particles having biodegradability of the present invention, good pre-expanded particles can be continuously produced without cross-linking the polyester resin. Since cross-linking may be performed, a case where cross-linking is included in the technical scope of the present invention will be described as a reference example.
【００６８】（参考例１）生分解性を有するポリエステ
ル系樹脂としてポリ乳酸１００重量部にジフェニルメタ
ンジイソシアネートを１重量部と気泡調整剤として平均
粒径１０μｍのタルクを１．０重量部の割合で加えた混
合物を用いた以外、実施例１と同一の工程でタンデム式
押出機に供給して予備発泡粒子を製造した。Reference Example 1 As a biodegradable polyester resin, 100 parts by weight of polylactic acid, 1 part by weight of diphenylmethane diisocyanate, and 1.0 part by weight of talc having an average particle size of 10 μm as a cell regulator were added. Except for using the mixture thus obtained, the mixture was supplied to a tandem extruder in the same process as in Example 1 to produce pre-expanded particles.
【００６９】得られた予備発泡粒子は良好であり、その
かさ比重は０．０２５ｇｒ／ｃｍ3であった。The pre-expanded particles obtained were good and had a bulk specific gravity of 0.025 gr / cm 3 .
【００７０】次に、この予備発泡粒子を用い、実施例１
と同様に、型内成形を行い発泡成形体を製造した。得ら
れた発泡成形体は特性の良好なものであった。Next, using the pre-expanded particles, Example 1 was used.
In the same manner as in the above, in-mold molding was performed to produce a foam molded article. The obtained foam molded article had good properties.
【００７１】（参考例２）生分解性を有するポリエステ
ル系樹脂としてポリブチレンサクシネート１００重量部
にヘキサメチレンジイソシアネートを１．６重量部と気
泡調整剤として平均粒径８μｍのタルクを０．５重量部
の割合で加えた混合物を用いた以外、実施例２と同一の
工程でタンデム式押出機に供給して予備発泡粒子を製造
した。REFERENCE EXAMPLE 2 1.6 parts by weight of hexamethylene diisocyanate per 100 parts by weight of polybutylene succinate as a polyester resin having biodegradability, and 0.5 part by weight of talc having an average particle diameter of 8 μm as a cell regulator. The pre-expanded particles were produced by supplying the mixture to a tandem-type extruder in the same process as in Example 2 except that the mixture added in proportions of parts was used.
【００７２】得られた予備発泡粒子は良好であり、その
かさ比重は０．０１７ｇｒ／ｃｍ3であった。The obtained pre-expanded particles were good, and had a bulk specific gravity of 0.017 gr / cm 3 .
【００７３】次に、この予備発泡粒子を用い、実施例２
と同様に、型内成形を行い発泡成形体を製造した。得ら
れた発泡成形体は特性の良好なものであった。Next, using the pre-expanded particles, Example 2 was used.
In the same manner as in the above, in-mold molding was performed to produce a foam molded article. The obtained foam molded article had good properties.
【００７４】以上説明した各実施例、各比較例、各参考
例をまとめたものが表１である。Table 1 summarizes the above-described embodiments, comparative examples, and reference examples.
【００７５】[0075]
【表１】 [Table 1]
【００７６】[0076]
【発明の効果】以上、一実施の形態とともに具体的に説
明したようにこの発明の請求項１記載の生分解性を有す
るポリエステル系樹脂予備発泡粒子の連続製造方法によ
れば、生分解性を有するポリエステル系樹脂により型内
成形用の予備発泡粒子を連続して製造するに際し、生分
解性ポリエステル系樹脂と発泡剤とを押出機で混練し、
発泡されたストランドとして押し出し、この発泡ストラ
ンドをカットして予備発泡粒子を得るようにしたので、
架橋しなくても良く、予備発泡のための蒸気での加熱や
放出発泡などの工程も必要なく、エネルギ効率も良く、
工程を大巾に短縮して良好な予備発泡粒子を連続的に製
造することができる。According to the method for continuously producing biodegradable polyester resin pre-expanded particles according to claim 1 of the present invention, the biodegradability is reduced as described above in detail with reference to one embodiment. When continuously producing pre-expanded particles for in-mold molding with a polyester resin having, a biodegradable polyester resin and a foaming agent are kneaded with an extruder,
As it extruded as a foamed strand and cut this foamed strand to obtain pre-expanded particles,
There is no need for cross-linking, and there is no need for steps such as heating with steam for preliminary foaming or release foaming, and it has good energy efficiency.
Good pre-expanded particles can be continuously produced by greatly shortening the process.
【００７７】また、この発明の請求項２記載の生分解性
を有するポリエステル系樹脂予備発泡粒子の連続製造方
法によれば、生分解性ポリエステル系樹脂として無架橋
のポリ乳酸または無架橋のポリブチレンサクシネートを
用いるようにしたので、これら樹脂により架橋すること
なく、予備発泡のための蒸気での加熱や放出発泡などの
工程も必要なく、エネルギ効率も良く、工程を大巾に短
縮して良好な予備発泡粒子を連続的に製造することがで
きる。According to the method for continuously producing pre-expanded particles of a polyester resin having biodegradability according to claim 2 of the present invention, non-crosslinked polylactic acid or non-crosslinked polybutylene is used as the biodegradable polyester resin. Since succinate is used, there is no need for cross-linking with these resins, there is no need for a step such as heating with steam for prefoaming or release foaming, and energy efficiency is good. The pre-expanded particles can be continuously produced.
【００７８】さらに、これら各発明で製造された予備発
泡粒子を用いて型内成形を行って製造される発泡成形体
は特性の良好なものとなる。Further, a foam molded article produced by performing in-mold molding using the pre-expanded particles produced in each of the inventions has good properties.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F074 AA66 AA68 BA37 BC12 CA22 CA32 CA38 CA49 CC04Y CC32Y CC47 4F201 AA24 AB02 AC01 AG20 BA02 BC01 BC10 BC13 BC17 BC19 BD05 BL09 4F212 AA24 AB02 AC01 AG20 UA01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F074 AA66 AA68 BA37 BC12 CA22 CA32 CA38 CA49 CC04Y CC32Y CC47 4F201 AA24 AB02 AC01 AG20 BA02 BC01 BC10 BC13 BC17 BC19 BD05 BL09 4F212 AA24 AB02 AC01 AG20 UA01
Claims (2)
より型内成形用の予備発泡粒子を連続して製造するに際
し、生分解性ポリエステル系樹脂と発泡剤とを押出機で
混練し、発泡されたストランドとして押し出し、この発
泡ストランドをカットして予備発泡粒子を得るようにし
たことを特徴とする生分解性を有するポリエステル系樹
脂予備発泡粒子の連続製造方法。When a pre-expanded particle for in-mold molding is continuously produced from a biodegradable polyester resin, the biodegradable polyester resin and a foaming agent are kneaded with an extruder and foamed. A method for continuously producing pre-expanded biodegradable polyester-based resin particles, wherein the pre-expanded particles are extruded as strands, and the expanded strands are cut to obtain pre-expanded particles.
架橋のポリ乳酸または無架橋のポリブチレンサクシネー
トで構成したことを特徴とする請求項１記載の生分解性
を有するポリエステル系樹脂予備発泡粒子の連続製造方
法。2. The pre-expanded biodegradable polyester resin according to claim 1, wherein the biodegradable polyester resin is composed of non-crosslinked polylactic acid or non-crosslinked polybutylene succinate. A method for continuously producing particles.
Priority Applications (1)
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|---|---|---|---|
| JP2001106876A JP2002302567A (en) | 2001-04-05 | 2001-04-05 | Method for continuous production of pre-expanded bead of biodegradable polyester-based resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001106876A JP2002302567A (en) | 2001-04-05 | 2001-04-05 | Method for continuous production of pre-expanded bead of biodegradable polyester-based resin |
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| Publication Number | Publication Date |
|---|---|
| JP2002302567A true JP2002302567A (en) | 2002-10-18 |
Family
ID=18959309
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001106876A Pending JP2002302567A (en) | 2001-04-05 | 2001-04-05 | Method for continuous production of pre-expanded bead of biodegradable polyester-based resin |
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| JP (1) | JP2002302567A (en) |
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| US8962706B2 (en) | 2010-09-10 | 2015-02-24 | Lifoam Industries, Llc | Process for enabling secondary expansion of expandable beads |
| JPWO2013031769A1 (en) * | 2011-08-29 | 2015-03-23 | 積水化成品工業株式会社 | Aromatic polyester resin foamed particles for in-mold foam molding and method for producing the same, in-mold foam molded body, composite structure member, and automotive member |
| KR20180063076A (en) | 2015-09-30 | 2018-06-11 | 세키스이가세이힝코교가부시키가이샤 | Porous resin fine particles and manufacturing method thereof |
| US11548995B2 (en) | 2015-09-30 | 2023-01-10 | Sekisui Plastics Co., Ltd. | Porous resin microparticles and manufacturing method for same |
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