JPH05255531A - Production of molded polymer foam - Google Patents

Production of molded polymer foam

Info

Publication number
JPH05255531A
JPH05255531A JP4055569A JP5556992A JPH05255531A JP H05255531 A JPH05255531 A JP H05255531A JP 4055569 A JP4055569 A JP 4055569A JP 5556992 A JP5556992 A JP 5556992A JP H05255531 A JPH05255531 A JP H05255531A
Authority
JP
Japan
Prior art keywords
particles
polymer
inorganic gas
foaming
temperature
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
Application number
JP4055569A
Other languages
Japanese (ja)
Other versions
JPH07116314B2 (en
Inventor
Toshiki Ikeda
敏喜 池田
Shinpei Nakayama
新平 中山
Yasuhiro Ueda
靖博 上田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Kasei Co Ltd
Original Assignee
Sekisui Plastics Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sekisui Plastics Co Ltd filed Critical Sekisui Plastics Co Ltd
Priority to JP4055569A priority Critical patent/JPH07116314B2/en
Publication of JPH05255531A publication Critical patent/JPH05255531A/en
Publication of JPH07116314B2 publication Critical patent/JPH07116314B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Molding Of Porous Articles (AREA)

Abstract

PURPOSE:To efficiently and stably obtain a highly expanded homogeneous molded foam by using an inorganic gas to obtain highly expanded uniform prefoamed particles and foaming and molding the particles. CONSTITUTION:Polymer particles are impregnated with an inorganic gas at a mild temp. and an elevated pressure. The particles are heated by contact with steam to foam them, thereby giving primarily prefoamed particles (a). The particles (a) are impregnated with an inorganic gas at an elevated pressure and then thermally foamed to obtain secondarily prefoamed particles (b). After being made to have an internal pressure by impregnation with an inorganic gas, the particles (b) are packed in a mold and thermally foamed to obtain a molded polymer foam.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は発泡重合体成形品の製造
方法に関する。さらは詳しくは、予備発泡粒子を水蒸気
を通す孔を有する発泡成形型内に充填し、水蒸気加熱し
て相互に融着させて緩衝材、包装材、断熱材等に有用な
発泡成形品を製造する方法に関するものである。
FIELD OF THE INVENTION The present invention relates to a method for producing a foamed polymer molded article. More specifically, the pre-expanded particles are filled in a foaming mold having pores through which water vapor passes, and heated with steam to fuse them to produce a foamed molded product useful as a cushioning material, packaging material, heat insulating material, etc. It is about how to do.

【0002】[0002]

【従来の技術と発明が解決しようとする課題】従来より
ポリスチレンを主体に熱可塑性樹脂発泡体粒子を型内成
形して発泡成形品を得る方法は広く行われている。この
発泡粒子を得るのに、スチレン系樹脂の場合、まずブタ
ン、ペンタン等の揮発性有機発泡剤を、分散剤を有する
水系分散媒体で樹脂の軟化点以上の温度で当該発泡剤の
蒸気圧下で樹脂粒子に含浸し、冷却して取り出し脱水乾
燥、薬剤等で表面処理し、熟成して発泡性樹脂粒子を製
造している。次いでこの発泡性樹脂粒子を水蒸気の大気
圧もしくは0.2kg/cm2Gまでの加圧下で発泡して通常
予備発泡粒子と呼ばれる発泡樹脂粒子が得られる。この
ようにして得られた予備発泡粒子は所定の成形型内に導
入され、水蒸気下で加熱発泡して各種発泡成形品を提供
するために用いられる。
2. Description of the Related Art Conventionally, a method for obtaining a foam-molded article by molding in-mold thermoplastic resin foam particles mainly of polystyrene has been widely used. To obtain the expanded beads, in the case of a styrene-based resin, first, a volatile organic foaming agent such as butane or pentane is added to an aqueous dispersion medium having a dispersant under a vapor pressure of the foaming agent at a temperature equal to or higher than the softening point of the resin. The resin particles are impregnated, cooled, taken out, dehydrated and dried, surface-treated with a chemical or the like, and aged to produce expandable resin particles. Next, the expandable resin particles are expanded under atmospheric pressure of steam or under a pressure of up to 0.2 kg / cm 2 G to obtain expanded resin particles usually called pre-expanded particles. The pre-expanded particles thus obtained are introduced into a predetermined molding die and used to provide various foam-molded articles by heat-foaming under steam.

【0003】一方ポリエチレン、ポリプロピレン等のポ
リオレフィン系樹脂の場合、ブタン、ジクロロフロロメ
タン等の揮発性有機発泡剤を水分散系で樹脂の軟化点以
上の温度で含浸させた後、当該発泡剤の蒸気圧を保持し
ながら容器水面下の一端を開放し、内圧より低圧の雰囲
気に放出することによって予備発泡粒子を得ている。こ
のように従来の予備発泡粒子の一般的な製造方法におい
ては、発泡剤としては専ら揮発性有機発泡剤が採用され
ており、且つその含浸も主として水分散系に於いて行わ
れていた。
On the other hand, in the case of a polyolefin resin such as polyethylene or polypropylene, a volatile organic foaming agent such as butane or dichlorofluoromethane is impregnated in a water dispersion system at a temperature higher than the softening point of the resin, and then the vapor of the foaming agent is impregnated. The pre-expanded particles are obtained by opening one end under the water surface of the container while maintaining the pressure and discharging into the atmosphere at a pressure lower than the internal pressure. As described above, in the conventional general method for producing pre-expanded particles, the volatile organic foaming agent is exclusively used as the foaming agent, and the impregnation thereof is mainly performed in the water dispersion system.

【0004】しかしながら上記の揮発性有機発泡剤は樹
脂基材に対して親和性もあり、保持性に優れ、発泡剤と
して効能がよい反面、含浸時及び予備発泡時に良溶媒と
して作用して樹脂粒子相互の合着を発生させ易くする等
の難点を有している。またあるものは毒性や可燃性の危
険性を有している。あるものは高価であり、しかも殆ど
の場合大気に放出することになるのでオゾン層の破壊、
光化学スモッグ等の大気汚染の問題を生じるものであっ
た。
However, the above-mentioned volatile organic foaming agent has an affinity for the resin base material and is excellent in retention and is effective as a foaming agent, but on the other hand, it acts as a good solvent at the time of impregnation and pre-foaming, and thus resin particles. It has a problem that it is easy to cause mutual adhesion. Others have the risk of toxicity and flammability. Some are expensive, and most of the time they are released to the atmosphere, which destroys the ozone layer,
This caused the problem of air pollution such as photochemical smog.

【0005】そこで最近上記揮発性有機発泡剤に代え
て、例えば炭酸ガス、窒素、空気等の無機ガスを予備発
泡粒子の工業生産に適用する提案もなされている。例え
ば特公昭62−61227号公報にはポリオレフィン系
樹脂を密閉容器内に水系媒体に分散させ、次いで無機ガ
スを供給し無機ガスの蒸気圧を保持しながら樹脂の軟化
温度以上に加温し、含浸し、水面下の吐出口を開放し低
圧の雰囲気に放出して発泡し予備発泡粒子を製造する方
法が開示されている。また特公昭60−245648号
公報には樹脂粒子を軟化温度以上に加熱する際に分散媒
体としての大量の水も同時に加熱することから、熱エネ
ルギーを要する欠点を克服するべく樹脂粒子融着防止剤
を用いて相互に分離した状態で無機ガス状媒体に於いて
高温高圧域から放出させる製法を開示している。
Therefore, it has recently been proposed to apply an inorganic gas such as carbon dioxide gas, nitrogen or air to the industrial production of pre-expanded particles in place of the volatile organic blowing agent. For example, Japanese Patent Publication No. 62-61227 discloses that a polyolefin resin is dispersed in an aqueous medium in an airtight container, and then an inorganic gas is supplied to the resin while heating the resin to a softening temperature or higher while maintaining the vapor pressure of the inorganic gas to impregnate the resin. However, there is disclosed a method of producing pre-expanded particles by opening a discharge port below the water surface and discharging into a low-pressure atmosphere to foam. Further, in Japanese Patent Publication No. 60-245648, a large amount of water as a dispersion medium is simultaneously heated when the resin particles are heated to a softening temperature or higher. Disclosed is a method of releasing the inorganic gaseous medium from the high temperature and high pressure region in the state of being separated from each other by using.

【0006】しかしながら無機ガスを用いた前記方法に
おいては放出発泡時に樹脂軟化温度以上に加温するので
含浸系全体の温度を均一保持するのに攪拌等が必要とな
り、樹脂粒子相互の合着の恐れがあり、また器壁および
攪拌羽根等にスケールが付着する欠点をもっている。そ
して何れも瞬時に発泡がなされる放出発泡であるので発
泡倍率の制御が困難で得られた予備発泡粒子の均一性、
再現性に劣り、しかも放出初期と後期の容器内圧変動に
対する安定化対策が必要となる等問題があった。
However, in the above method using the inorganic gas, since the resin is heated to a temperature higher than the softening temperature at the time of foaming, agitation or the like is required to keep the temperature of the entire impregnating system uniform, and there is a fear of coalescence of resin particles. However, it also has the drawback that scale adheres to the vessel wall and stirring blades. And since all of them are release foams that are instantly foamed, it is difficult to control the expansion ratio and the uniformity of the pre-expanded particles obtained,
There were problems such as poor reproducibility and the need for stabilization measures against fluctuations in the internal pressure of the container in the early and late stages of release.

【0007】またUSP−4911869号には炭酸ガ
スを含浸し、樹脂のガラス転移点以上の温度で予備発泡
し、その予備発泡粒子を空気、窒素または炭酸ガスで再
含浸して成形を行う方法が開示されている。これら無機
ガスは樹脂基材に対し親和性に乏しく逸散性が大きく、
発泡剤として揮発性有機発泡剤に比べ効能がわるく、特
にポリオレフィン系樹脂に於いてこれらの方法では所望
する発泡倍数が得られない難点があった。
US Pat. No. 4,911,869 is impregnated with carbon dioxide gas, pre-expanded at a temperature equal to or higher than the glass transition point of the resin, and re-impregnated the pre-expanded particles with air, nitrogen or carbon dioxide gas to perform molding. It is disclosed. These inorganic gases have a low affinity for resin base materials and have a large dissipative property,
As a foaming agent, it is less effective than a volatile organic foaming agent, and there is a problem that a desired foaming multiple cannot be obtained by these methods particularly in a polyolefin resin.

【0008】特公平2−50945、特開平2−756
36、特開昭62−18438に提案されているように
発泡剤を含浸し、一段目の発泡を行い、更にこの発泡粒
子に発泡剤を含浸し、二段目の発泡を行い、より高倍な
予備発泡粒子を得る製造方法が開示されている。しかし
ながら、これらの方法は二段目に用いられる発泡剤が空
気等の無機ガスであるにもかかわらず一段目の発泡に用
いられている発泡剤は揮発性有機発泡剤であり、殆どの
場合放出発泡法によるもので上記と同様な問題があっ
た。
Japanese Patent Publication No. 2-50945, Japanese Patent Laid-Open No. 2-756
No. 36, as proposed in JP-A-62-18438, the first step of foaming is impregnated with the foaming agent, and the expanded particles are further impregnated with the foaming agent to perform the second step of foaming. A manufacturing method for obtaining pre-expanded particles is disclosed. However, in these methods, although the blowing agent used in the second step is an inorganic gas such as air, the blowing agent used in the first step is a volatile organic blowing agent, and in most cases, it is released. The foaming method had the same problem as above.

【0009】[0009]

【課題を解決するための手段】本発明はかかる従来の問
題点に鑑みさなれたもので、重合体粒子への無機ガスの
含浸を従来のごとき水分散系でなく気相下でかつ特定の
条件で行い、かつ放出発泡によらずに予備発泡を行い、
得られた予備発泡粒子を発泡成形することにより、重合
体粒子間の合着によるトラブルを招くことなしに、無機
ガスを用いて発泡倍数の均一な高品質な予備発泡粒子が
得られ、しかもこの予備発泡粒子を用いて発泡成形する
ことにより高度に発泡した均一な発泡成形品を効率よく
生産できることを見出し、本発明を完成するに至ったも
のである。
SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and impregnation of polymer particles with an inorganic gas is carried out in a gas phase rather than in a conventional water dispersion system and in a specific manner. Performed under the conditions and pre-foaming without depending on the foaming released,
By foam-molding the obtained pre-expanded particles, it is possible to obtain high-quality pre-expanded particles having a uniform expansion ratio using an inorganic gas without causing troubles due to coalescence between polymer particles. The inventors have found that highly foamed and uniform foam-molded articles can be efficiently produced by foam-molding using pre-expanded particles, and have completed the present invention.

【0010】かくして本発明によればポリオレフィン系
重合体粒子に、その粒子が合着しない緩和な温度下でか
つ加圧下において無機ガスを気相含浸させて、無機ガス
含有量が0.05モル/kg(重合体)以上の一次発泡性
重合体粒子とし、これを無機ガス含有量が0.05モル
/kg(重合体)未満に減少する迄に発泡槽に導入し、上
記重合体粒子の融解ピーク温度(TP )+10℃〜TP
−10℃の温度域で水蒸気導入により加熱発泡させ一次
予備発泡粒子を形成し、次いで該一次予備発泡粒子が合
着しない緩和な温度下でかつ加圧下において一次予備発
泡粒子に無機ガスを気相含浸させて、無機ガス含有量が
0.5モル/kg(重合体)以上の二次発泡性発泡重合体
粒子とし、これを無機ガス含有量が0.5モル/kg(重
合体)未満に減少する迄に発泡槽に導入し、TP +15
℃〜TP −20℃の温度域で水蒸気導入により加熱発泡
させ二次予備発泡粒子を形成した後、更にこの二次予備
発泡粒子に無機ガスを該発泡粒子が合着しない緩和な温
度下でかつ加圧下において気相含浸させて、無機ガス含
有量が0.5モル/kg(重合体)以上になるように二次
予備発泡粒子に内圧付与し、これを無機ガス含有量が
0.5モル/kg(重合体)未満に減少する迄に発泡成形
用型に充填し、TP +15℃〜TP −20℃の温度域で
水蒸気導入により加熱発泡させて発泡成形品を得ること
を特徴とする発泡重合体成形品の製造方法が提供され
る。
Thus, according to the present invention, the polyolefin polymer particles are vapor-impregnated with an inorganic gas in a vapor phase at a moderate temperature at which the particles do not coalesce and under pressure, so that the inorganic gas content is 0.05 mol / min. The primary expandable polymer particles of kg (polymer) or more are introduced into the foaming tank until the inorganic gas content is reduced to less than 0.05 mol / kg (polymer), and the polymer particles are melted. Peak temperature (T P ) + 10 ° C to T P
In the temperature range of −10 ° C., heat expansion is performed by introducing steam to form primary pre-expanded particles, and then an inorganic gas is vapor-phased into the primary pre-expanded particles under a moderate temperature at which the primary pre-expanded particles do not coalesce. Impregnated into secondary expandable foamed polymer particles having an inorganic gas content of 0.5 mol / kg (polymer) or more, and reducing the inorganic gas content to less than 0.5 mol / kg (polymer). It is introduced into the foaming tank until it decreases and T P +15
In the temperature range of ℃ to T P -20 ℃, after heat-foaming by introducing steam to form secondary pre-expanded particles, inorganic gas is further added to the secondary pre-expanded particles at a moderate temperature at which the expanded particles do not coalesce. In addition, the secondary pre-expanded particles are subjected to internal pressure so that the inorganic gas content becomes 0.5 mol / kg (polymer) or more by impregnating in the gas phase under pressure, and the inorganic gas content is 0.5 It is characterized in that it is filled in a foaming mold until it is reduced to less than mol / kg (polymer) and heat-foamed by introducing steam in a temperature range of T P + 15 ° C to T P -20 ° C to obtain a foamed molded product. A method for producing a foamed polymer molded article is provided.

【0011】本発明における重合体粒子の融解ピーク温
度とは、JIS K−7121プラスチックの転移温度
測定方法、示差走査熱量測定(DSC)に準じて測定
(約3〜4mgのサンプルを昇温速度10℃/minで昇
温)して得られるDSC曲線における融解ピークの頂点
温度を言う。この発明におけるポリオレフィン系重合体
粒子の基材樹脂としては、ポリエチレン、ポリプロピレ
ン、エチレンプロピレンランダムコポリマー、エチレン
プロピレンブロックコポリマー、エチレンプロピレンブ
テンコポリマー、ポリエチレン酢ビコポリマー、ポリブ
テン、スチレン改質ポリエチレン架橋重合体、スチレン
改質ポリプロピレン架橋重合体等が用いられる。なお、
これらは、2種以上混合した混合物であってもよい。ま
た、これらのポリオレフィン系樹脂は発泡成形性や発泡
体気泡の均一性等より適度に部分架橋されたものであっ
てよい。
The melting peak temperature of the polymer particles in the present invention is measured according to the method for measuring transition temperature of JIS K-7121 plastic and differential scanning calorimetry (DSC) (a heating rate of about 3 to 4 mg of sample is 10 It is the peak temperature of the melting peak in the DSC curve obtained by heating (° C / min). As the base resin of the polyolefin-based polymer particles in the present invention, polyethylene, polypropylene, ethylene propylene random copolymer, ethylene propylene block copolymer, ethylene propylene butene copolymer, polyethylene vinyl acetate copolymer, polybutene, styrene modified polyethylene cross-linked polymer, styrene A modified polypropylene crosslinked polymer or the like is used. In addition,
These may be a mixture of two or more kinds. Further, these polyolefin-based resins may be appropriately partially cross-linked due to the foaming moldability and the uniformity of foam cells.

【0012】本発明で用いる重合体粒子の粒径は、一般
的には0.2〜3mm程度である。かかる重合体粒子に無
機ガスを含浸するに際し、これらの粒子表面に予め適当
な表面処理剤が被覆されてもよい。これら表面処理剤の
例としては予備発泡時の合着防止、成形時の融着促進、
金型充填性を良くする滑性、帯電防止剤、着色剤等が挙
げられる。これら表面処理剤としてはタルク、炭酸カル
シュウム、シリカ−アルミナのコロイド及びスラリー、
エチレンビスステアロアミド、高級脂肪酸、高級脂肪酸
アルコール、食用油、高級脂肪酸トリグリセライド、パ
ラフィン及びポリエチレンワックス、ジンクステアレー
ト等の金属石鹸変性ポリシロキサン等が挙げられる。
The particle size of the polymer particles used in the present invention is generally about 0.2 to 3 mm. When impregnating such polymer particles with an inorganic gas, the surface of these particles may be coated with an appropriate surface treatment agent in advance. Examples of these surface treatment agents include prevention of coalescence during pre-foaming, promotion of fusion during molding,
Examples include lubricity, an antistatic agent, and a colorant that improve the mold filling property. These surface treatment agents include talc, calcium carbonate, silica-alumina colloids and slurries,
Examples thereof include ethylene bis stearamide, higher fatty acid, higher fatty acid alcohol, edible oil, higher fatty acid triglyceride, paraffin and polyethylene wax, and metal soap-modified polysiloxane such as zinc stearate.

【0013】なお、かかる表面処理は、無機ガス含浸に
先立ち、予め重合体粒子にリボンブレンダー、タンブラ
ー、ナウターミキサー、スパーミキサー、レーディゲミ
キサー等で行うことが望ましい。しかし、無機ガス含浸
容器が回転もしくは攪拌できるものであればガス含浸時
に同時に表面処理を行ってもよい。
The surface treatment is preferably performed on the polymer particles in advance with a ribbon blender, a tumbler, a Nauter mixer, a spur mixer, a Loedige mixer or the like prior to the impregnation with the inorganic gas. However, the surface treatment may be performed at the same time as the gas impregnation as long as the inorganic gas impregnation container can be rotated or stirred.

【0014】本発明において、まず上記重合体粒子は気
相加圧下で無機ガスの含浸処理に付される。本発明にお
ける無機ガスとしては、炭酸ガス、窒素、空気等が用い
られ、これらは単独で或は混合して使用される。含浸処
理は密閉容器内で無機ガスを圧入して行われる。かかる
含浸処理は、重合体粒子が合着しない緩和な温度下で行
なわれる。ここで緩和な温度とは、具体的には重合体粒
子の融解ピーク温度より40℃以上低い温度域とされ
る。好ましい温度或は、使用する樹脂基材によっても変
化し、また無機ガスによっても変化する。
In the present invention, the polymer particles are first impregnated with an inorganic gas under pressure in the vapor phase. As the inorganic gas in the present invention, carbon dioxide gas, nitrogen, air and the like are used, and these may be used alone or in a mixture. The impregnation treatment is performed by press-fitting an inorganic gas in a closed container. Such impregnation treatment is performed at a mild temperature at which the polymer particles do not coalesce. Here, the mild temperature is specifically a temperature range lower than the melting peak temperature of the polymer particles by 40 ° C. or more. It changes depending on the preferable temperature or the resin base material used, and also changes depending on the inorganic gas.

【0015】通常無機ガスの実質的含浸量を多くできる
こと、及び耐圧容器の内圧を低めに設定できること等か
ら、含浸処理温度は、より低温が望ましく、40℃以下
が好ましい。しかし0℃以下の場合、通常冷却のために
工業的にエネルギー消費量が大きくなり、好ましくな
い。ガス含浸速度からは高温が望ましいが、工業的に安
定して高発泡性を得る場合、炭酸ガスは好ましくは5〜
40℃であり、窒素、空気は0〜30℃である。なお重
合体の融解ピーク温度−40℃以上の温度では、含浸時
に重合体粒子が相互に合着する恐れがあり、またガス含
浸後除圧して予備発泡するまでにガス逸散が急激に起こ
り、希望する発泡性が得られない。
Usually, the impregnation temperature is desirably lower, preferably 40 ° C. or lower, because the substantial impregnation amount of the inorganic gas can be increased and the internal pressure of the pressure vessel can be set to be low. However, if the temperature is 0 ° C. or less, energy consumption is industrially increased due to normal cooling, which is not preferable. High temperature is desirable from the gas impregnation rate, but carbon dioxide is preferably 5 to 5 when industrially stable and high foaming property is obtained.
It is 40 degreeC, and nitrogen and air are 0-30 degreeC. When the melting peak temperature of the polymer is −40 ° C. or higher, the polymer particles may adhere to each other during the impregnation, and the gas escapes rapidly before defoaming and prefoaming after gas impregnation. The desired foamability cannot be obtained.

【0016】かかる条件においては、無機ガスの重合体
への溶媒性がなく、緩和な加熱しかなされないことから
重合体粒子相互の合着等の恐れはない。従って重合体粒
子を静置した状態で含浸を行ってもよい。また含浸時、
加圧下の無機ガスを容器上部よりポンプ等により吸引し
て調温室を通した後、容器下部に戻す等循環させてもよ
い。
Under such conditions, there is no possibility of coalescence of polymer particles with each other because the inorganic gas has no solvent property to the polymer and only mild heating is performed. Therefore, the impregnation may be performed while the polymer particles are allowed to stand. Also during impregnation,
The inorganic gas under pressure may be sucked from the upper part of the container with a pump or the like to pass through the greenhouse and then returned to the lower part of the container for circulation.

【0017】重合体粒子に炭酸ガスを含浸させる適当な
圧力は15kg/cm2G以上、好ましくは20kg/cm2G以
上、50kg/cm2G以下、窒素又は空気の場合30kg/cm2
G以上、好ましくは40kg/cm2G以上90kg/cm2G以下
である。含浸圧力が15kg/cm2G未満では、無機ガスを
十分に含浸させることが難しい。一方含浸圧力が90kg
/cm2Gを越えると、無機ガス90kg/cm2G以下の圧力で
十分含浸できるため、耐圧容器に過剰の耐圧性が要求さ
れ、工業生産上好ましくない。
A suitable pressure for impregnating the polymer particles with carbon dioxide is 15 kg / cm 2 G or more, preferably 20 kg / cm 2 G or more, 50 kg / cm 2 G or less, and 30 kg / cm 2 in the case of nitrogen or air.
G or more, preferably 40 kg / cm 2 G or more and 90 kg / cm 2 G or less. If the impregnation pressure is less than 15 kg / cm 2 G, it is difficult to sufficiently impregnate the inorganic gas. On the other hand, the impregnation pressure is 90 kg
When it exceeds / cm 2 G, the inorganic gas can be sufficiently impregnated at a pressure of 90 kg / cm 2 G or less, and therefore the pressure vessel is required to have excessive pressure resistance, which is not preferable in industrial production.

【0018】かかる無機ガスの含浸により、無機ガスを
均一に含浸した重合体粒子が得られる。この含浸時間は
無機ガスの種類、含浸圧力、重合体の種類、重合体粒子
径等によって異なるが少なくとも無機ガスが0.05モ
ル/kg(重合体)以上含浸されるまで行われ、通常1〜
10時間で達成される。特にポリオレフィン系樹脂の場
合、高品質の予備発泡粒子を得るには、無機ガス含有量
を0.05〜1.5モル/kg(重合体)とするのが好ま
しい。
By impregnating the inorganic gas, polymer particles uniformly impregnated with the inorganic gas can be obtained. This impregnation time varies depending on the type of the inorganic gas, the impregnation pressure, the type of the polymer, the polymer particle size, etc., but is carried out until at least 0.05 mol / kg (polymer) of the inorganic gas is impregnated, usually 1 to
Achieved in 10 hours. In particular, in the case of a polyolefin resin, the inorganic gas content is preferably 0.05 to 1.5 mol / kg (polymer) in order to obtain high quality pre-expanded particles.

【0019】なお本発明は無機ガスを使用するものであ
って、その目的からも揮発性有機発泡剤を使用する必要
は特にない。しかしながら本発明の効果が阻害されない
限り、若干の揮発性有機発泡剤を併用することも可能で
あり、プロパン、ブタン、ジクロロフルオロメタン等を
無機ガス1モルに対し、少量例えば0.2モル以下併用
しても同様な効果を得ることができる。
The present invention uses an inorganic gas, and it is not necessary to use a volatile organic foaming agent also for that purpose. However, as long as the effect of the present invention is not impaired, it is also possible to use a small amount of a volatile organic foaming agent in combination, and propane, butane, dichlorofluoromethane, etc. are used in a small amount, for example, 0.2 mol or less per 1 mol of the inorganic gas. Even if it does, the same effect can be obtained.

【0020】このようにして無機ガスが含浸された一次
発泡性重合体粒子は、次いで予備発泡工程に付される。
この際、重要なことは重合体粒子中の無機ガス含有量が
少なくとも0.05モル/kg(重合体)以上の条件で予
備発泡を行うことである。即ち無機ガスを含浸した発泡
性重合体粒子は、含浸加圧容器から大気に取り出すと無
機ガスが除々に逸散する。発泡性重合体粒子のガス含有
量0.05モル/kg(重合体)未満に減少すると均一な
発泡倍数の正常な予備発泡粒子を生産することが困難と
なる。
The primary expandable polymer particles thus impregnated with the inorganic gas are then subjected to a pre-expanding step.
At this time, what is important is that the pre-foaming is performed under the condition that the content of the inorganic gas in the polymer particles is at least 0.05 mol / kg (polymer). That is, in the expandable polymer particles impregnated with the inorganic gas, the inorganic gas gradually dissipates when taken out from the impregnation pressure container to the atmosphere. When the gas content of the expandable polymer particles is reduced to less than 0.05 mol / kg (polymer), it becomes difficult to produce normal pre-expanded particles having a uniform expansion ratio.

【0021】従って工業生産上は含浸処理後、加圧状態
を保ったまま一次発泡性重合体粒子を予備発泡用に計量
し、除圧と殆ど同時に水蒸気で加熱された予備発泡槽に
導入するか、または加圧状態から直接、予備発泡槽に圧
送して加熱発泡することが好ましい。一旦大気に取り出
した後に予備発泡に供する場合には、無機ガス含有量が
0.05モル/kg(重合体)未満に低下する迄に加熱発
泡させる必要がある。これらの対応は状況に応じて適宜
選択されるが何れも本発明の範囲内である。
Therefore, in industrial production, after the impregnation treatment, the primary expandable polymer particles are weighed for pre-expansion while maintaining a pressurized state, and introduced into a pre-expansion tank heated with steam almost simultaneously with depressurization. Alternatively, it is preferable to directly feed the pre-foaming tank under pressure from the pressurized state to heat and foam. When it is used for pre-foaming after being taken out into the air, it is necessary to heat-foam until the inorganic gas content falls below 0.05 mol / kg (polymer). These measures are appropriately selected depending on the situation, but all are within the scope of the present invention.

【0022】予備発泡は発泡槽内で水蒸気を導入し、加
熱することにより行われる。本発明における水蒸気とし
ては、60〜100℃の露点を有する水蒸気、または水
蒸気−空気混合媒体を用いるのが適しており、特に後者
の混合媒体としては70〜100℃の露点を有するもの
が好ましい。なお露点60℃未満のものは高発泡体を得
難く好ましくない。
Pre-foaming is carried out by introducing steam into the foaming tank and heating it. As the steam in the present invention, it is suitable to use steam having a dew point of 60 to 100 ° C. or a steam-air mixed medium, and particularly the latter mixed medium having a dew point of 70 to 100 ° C. is preferable. A dew point of less than 60 ° C. is not preferable because it is difficult to obtain a high foam.

【0023】一段目の予備発泡の加熱は上記加熱水蒸気
によって行われ、重合体粒子の融解ピーク温度(以下T
P という)+10℃〜TP −10℃の温度域になるよう
に制御され、好ましくはTP +5℃〜TP −5℃の温度
域に制御される。この制御温度が、TP −10℃に満た
ない場合は発泡が遅くなり、無機ガスの外部逸散が優位
となって発泡効果が充分得られず、その結果高発泡性が
得られない。また制御温度がTP +10℃より高い場合
は、発泡適正域が極小となり、工業的に正常な予備発泡
粒子が得られない。
The heating of the first-stage pre-foaming is performed by the above heated steam, and the melting peak temperature of the polymer particles (hereinafter referred to as T
P referred) + 10 ℃ ~T P -10 ℃ is controlled to be a temperature range of, preferably controlled to a temperature range of T P + 5 ℃ ~T P -5 ℃. When the control temperature is lower than T P -10 ° C, the foaming becomes slow, the external escape of the inorganic gas becomes dominant and the foaming effect cannot be sufficiently obtained, and as a result, the high foaming property cannot be obtained. Further, when the control temperature is higher than T P + 10 ° C., the proper foaming range becomes extremely small, and industrially normal pre-expanded particles cannot be obtained.

【0024】なお、かかる予備発泡時において発泡槽内
を予め上記加熱制御温度付近に予熱しておくか、または
発泡温度域にある水蒸気下に発泡性重合体粒子を供給す
ることが、良好な発泡性の維持の点で好ましく、通常
0.5〜2.0kg/cm2G程度の加圧下に保っておくのが
適当である。その発泡時間は10〜120秒となり、好
ましくは10〜60秒である。この発泡時に加熱の均一
性と発泡粒子の合着防止のため回転羽根による攪拌をす
ることが好ましい。
In addition, it is preferable to preheat the inside of the foaming tank to near the above heating control temperature during the pre-foaming, or to supply the expandable polymer particles under the steam in the foaming temperature range. It is preferable from the viewpoint of maintaining the sex, and it is suitable to keep it under a pressure of about 0.5 to 2.0 kg / cm 2 G. The foaming time is 10 to 120 seconds, preferably 10 to 60 seconds. At the time of this foaming, it is preferable to stir with a rotary blade to ensure uniform heating and prevention of coalescence of foamed particles.

【0025】更に発泡槽へ水蒸気を供給する初期に、加
圧下の圧力を保持しながら発泡槽の一部を開けて、発泡
性重合体粒子の供給時に共に導入された空気、無機ガス
発泡剤を排出して温度の上昇と熱回りを良くすることも
できる。このようにして得られる一次予備発泡粒子は、
所望する発泡成形品の発泡倍数応じてカサ倍数3〜20
倍に発泡されており、予備発泡粒子間において発泡倍数
のバラツキが他の従来の製造方法にみられない程小さく
均一であり、二段目発泡用原料として適合するものであ
る。即ち工業的生産において二段目含浸発泡で一次予備
発泡粒子の各粒子間の発泡倍数のバラツキはより拡大さ
れる傾向にある。均質な発泡成形品を得るのに、均一な
一次予備発泡粒子を得る本発明の方法における一段目含
浸発泡の特徴がここにある。
Further, at the initial stage of supplying water vapor to the foaming tank, a part of the foaming tank is opened while maintaining the pressure under pressure, and the air and the inorganic gas blowing agent introduced together with the foamable polymer particles are supplied. It can also be discharged to improve the temperature rise and heat flow. The primary pre-expanded particles thus obtained are
Depending on the desired foaming multiple of the foamed article, the bulk multiple of 3 to 20
It is double-expanded, and the variation in the expansion ratio among the pre-expanded particles is so small that it cannot be seen in other conventional production methods, and it is suitable as a second-stage foaming raw material. That is, in industrial production, the dispersion of the expansion ratio among the particles of the primary pre-expanded particles tends to be further expanded by the second-stage impregnation expansion. This is a feature of the first-stage impregnation foaming in the method of the present invention for obtaining uniform primary pre-expanded particles for obtaining a homogeneous expanded molded article.

【0026】次いでより高度に発泡した予備発泡粒子を
得るために、一次予備発泡粒子に二段目の無機ガス含浸
と予備発泡を行い、カサ倍数20倍以上に発泡した二次
予備発泡粒子を得る。一次予備発泡粒子への二段目の無
機ガス含浸は上記重合体粒子の場合とほぼ同様に一次発
泡粒子が合着しない緩和な温度下でかつ加圧下で行う
が、得られる二次発泡性重合体粒子中の無機ガス含有量
が0.5モル/kg(重合体)以上になるように行う。好
ましくは0.5〜4.0モル/kg(重合体)である。含
浸圧力は1kg/cm2G以上、好ましくは10〜50kg/cm2
Gである。含浸圧力が1kg/cm2G未満では、十分に無機
ガスを含浸することができない。一方圧力が50kg/cm2
Gを越えると、一次予備発泡粒子が大気圧に戻した状態
において、元の体積に復元しないほど過剰に収縮するこ
とから好ましくない。
Next, in order to obtain more highly expanded pre-expanded particles, the first pre-expanded particles are impregnated with a second stage inorganic gas and pre-expanded to obtain secondary pre-expanded particles expanded to a bulk multiple of 20 times or more. .. The second-stage inorganic gas impregnation of the primary pre-expanded particles is carried out under a mild temperature and under pressure at which the primary expanded particles do not coalesce in the same manner as in the case of the above-mentioned polymer particles. It is performed so that the content of the inorganic gas in the united particles is 0.5 mol / kg (polymer) or more. It is preferably 0.5 to 4.0 mol / kg (polymer). The impregnation pressure is 1 kg / cm 2 G or more, preferably 10 to 50 kg / cm 2
G. If the impregnation pressure is less than 1 kg / cm 2 G, the inorganic gas cannot be sufficiently impregnated. On the other hand, the pressure is 50 kg / cm 2
When it exceeds G, it is not preferable because the primary pre-expanded particles are excessively shrunk so as not to be restored to the original volume in a state of being returned to the atmospheric pressure.

【0027】この二次発泡性重合体粒子は二段目の予備
発泡に付される。この際重要なことは無機ガス含有量が
少なくとも0.5モル/kg(重合体)以上の条件で、T
P +15℃〜TP −20℃の温度域の水蒸気系で予備発
泡を行うことである。無機ガス含有量が0.5/kg(重
合体)未満になると高倍数の正常な二次予備発泡粒子を
得難くなる。また発泡温度がTP より20℃以上低い場
合には発泡が遅くなり、ガスの外部への逸散が優位にな
り発泡効果が充分得られない。逆にTP より15℃以上
高い温度の場合には発泡適正域が極小となり安定的に正
常な発泡粒が得られない。
The secondary expandable polymer particles are subjected to the second pre-expansion. What is important here is that the T content is at least 0.5 mol / kg (polymer) or more.
Pre-foaming is performed in a steam system in the temperature range of P + 15 ° C to T P -20 ° C. When the inorganic gas content is less than 0.5 / kg (polymer), it becomes difficult to obtain a high multiple normal secondary pre-expanded particles. Further, when the foaming temperature is lower than T P by 20 ° C. or more, foaming becomes slow, and the gas is diffused to the outside, so that the foaming effect cannot be sufficiently obtained. On the contrary, when the temperature is higher than T P by 15 ° C. or more, the proper foaming region becomes extremely small and stable and normal foamed particles cannot be obtained.

【0028】二段目の予備発泡は一段目の予備発泡とほ
ぼ同様に行うが、発泡時間は5〜90秒であり、好まし
くは10〜45秒である。このようにして得られた二次
予備発泡粒子は所望する発泡成形品の発泡倍数に応じて
カサ倍数20倍以上に発泡している。次いで二次予備発
泡粒子に無機ガスを含浸して内圧を付与して型内発泡成
形を行うことにより高度に発泡した成形品が得られる。
二次予備発泡粒子に対する無機ガスによる内圧付与は一
次予備発泡粒子の無機ガス含浸と同様に緩和な温度下、
かつ加圧下で行われ、その含有量が0.5モル/kg(重
合体)以上になるように含浸する。よい成形性を得るに
は、0.5〜4.0モル/kg(重合体)の無機ガス含有
量が好ましい。
The pre-expansion of the second stage is carried out in substantially the same manner as the pre-expansion of the first stage, but the expansion time is 5 to 90 seconds, preferably 10 to 45 seconds. The secondary pre-expanded particles thus obtained are expanded to a bulk ratio of 20 times or more according to the desired expansion ratio of the foam-molded article. Then, the secondary pre-expanded particles are impregnated with an inorganic gas and internal pressure is applied to perform in-mold foam molding to obtain a highly foamed molded product.
The internal pressure applied by the inorganic gas to the secondary pre-expanded particles is at a moderate temperature, similar to the impregnation of the primary pre-expanded particles with the inorganic gas,
Moreover, it is impregnated so that the content thereof is 0.5 mol / kg (polymer) or more. In order to obtain good moldability, an inorganic gas content of 0.5 to 4.0 mol / kg (polymer) is preferable.

【0029】内圧付与した二次予備発泡粒子は無機ガス
含有量が少なくとも0.5モル/kg(重合体)以上の条
件で、TP +15℃〜TP −20℃の温度域にある水蒸
気系で10〜120秒、好ましくは20〜60秒加熱し
て公知手法によるいわゆる型内成形に付されて発泡成形
品を得る。この場合内圧付与した二次予備発泡粒子のガ
ス含有量が0.5モル/kg(重合体)未満になると正常
な発泡成形品は得られず、また成形温度がTP より20
℃以上低い場合には発泡が遅くなり無機ガスの外部逸散
が優位となり、発泡効果が充分得られない。逆にTP
り15℃以上高い温度の場合には重合体の発泡適正域が
極小となり正常な発泡成形品は得られない。
The secondary pre-expanded particles to which the internal pressure is applied have a water vapor system in the temperature range of T P + 15 ° C to T P -20 ° C under the condition that the inorganic gas content is at least 0.5 mol / kg (polymer). It is heated for 10 to 120 seconds, preferably 20 to 60 seconds, and subjected to so-called in-mold molding by a known method to obtain a foam molded article. In this case, if the gas content of the secondary pre-expanded particles applied with the internal pressure is less than 0.5 mol / kg (polymer), a normal foam-molded product cannot be obtained, and the molding temperature is 20 P higher than T P.
When the temperature is lower than 0 ° C, the foaming becomes slow and the external escape of the inorganic gas becomes dominant, so that the foaming effect cannot be sufficiently obtained. On the contrary, when the temperature is higher than T P by 15 ° C. or more, the proper foaming region of the polymer becomes extremely small, and a normal foamed molded product cannot be obtained.

【0030】予備発泡粒の無機ガス含浸加圧時発泡粒は
圧縮され容積は減少している。そのまま圧縮状態で成形
型内に充填してもよいが、除圧して圧縮前の容積にほぼ
回復させてから成形型内に充填してもよい。なお、上記
の説明では、二次予備発泡粒子に内圧を付与して型内発
泡成形するものであるが、更により高度に発泡した成形
品を得るために、二次予備発泡粒子に対して、二段目の
含浸予備発泡と同様に、三段目以降の含浸予備発泡処理
を施した後、得られた予備発泡粒子に無機ガスで内圧を
付与して型内発泡成形することもできる。
Impregnation of pre-expanded granules with an inorganic gas When expanded, the expanded granules are compressed and their volume is reduced. It may be filled in the molding die in the compressed state as it is, but it may be filled in the molding die after depressurizing the volume to almost restore the volume before compression. In the above description, the internal pressure is applied to the secondary pre-expanded particles for in-mold foam molding, but in order to obtain a more highly expanded molded article, for the secondary pre-expanded particles, Similar to the second-stage impregnation pre-expansion, after the third-stage impregnation pre-expansion treatment, the obtained pre-expanded particles can be subjected to internal pressure with an inorganic gas for in-mold expansion molding.

【0031】[0031]

【実施例】以下、本発明を実施例を用いて説明するが、
これにより本発明は限定されるものではない。300m
lのガス含浸容器に、発泡時の合着防止剤炭酸カルシウ
ム0.4gで表面処理された種々ポリオレフィン系重合
体粒子150gを入れて密閉し、無機ガスを圧入して調
温しながら一定時間保持した後、直接加熱水蒸気加圧下
の発泡槽に充填するか、もしくは内圧を取り除き短時間
(約30分以内)の内に発泡槽に投入し、加圧下の水蒸
気系で加熱発泡し、一次予備発泡粒子を得た。
EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited thereby. 300m
In a gas-impregnated container (1), 150 g of various polyolefin-based polymer particles surface-treated with 0.4 g of calcium carbonate, a coalescence-preventing agent for foaming, were placed in a hermetically sealed container, and an inorganic gas was press-fitted to maintain the temperature for a certain time After that, directly fill the foaming tank under heated steam pressure, or remove the internal pressure and put it in the foaming tank within a short time (within about 30 minutes), and heat-foam in the steam system under pressure to perform primary pre-foaming. The particles were obtained.

【0032】1000mlのガス含浸容器に、得られた
一次予備発泡粒子を50g入れて密閉し、無機ガスを圧
入して調温しながら一定時間保持した後、直接加熱水蒸
気加圧下の発泡槽に充填するか、もしくは内圧を取り除
き短時間(約30分以内)の内に発泡槽に投入し、加圧
下の水蒸気系で加熱発泡し、二次予備発泡粒子を得た。
In a 1000 ml gas-impregnated container, 50 g of the obtained primary pre-expanded particles was put and sealed, and an inorganic gas was press-fitted and held for a certain period of time while controlling the temperature, and then directly filled in a foaming tank under steam heating under pressure. Alternatively, the internal pressure was removed, and the mixture was put into a foaming tank within a short time (within about 30 minutes) and heat-foamed by a steam system under pressure to obtain secondary pre-expanded particles.

【0033】3000mlのガス含浸容器に、得られた
二次予備発泡粒子を50g入れて密閉し、無機ガスを圧
入して調温しながら一定時間保持した後、容器内圧を取
り除き短時間(約30分以内)の内に予熱された成形金
型の型筒(30×30×1.5cm)内に充填し、加圧下
の水蒸気で加熱発泡成形し、発泡成形品を得た。以下処
理圧力、処理温度等の条件と得られた予備発泡粒子及び
発泡成形品の特性、性状についての結果を比較例と共に
表1〜4に示す。
In a 3000 ml gas-impregnated container, 50 g of the obtained secondary pre-expanded particles were placed and hermetically sealed, and an inorganic gas was press-fitted to hold the temperature for a certain period of time, and then the internal pressure of the container was removed for a short time (about 30 Within minutes), it was filled in a mold tube (30 × 30 × 1.5 cm) of a preheated molding die, and heat-foam-molded with steam under pressure to obtain a foam-molded article. Tables 1 to 4 show the results of the conditions such as the treatment pressure and the treatment temperature and the properties and properties of the obtained pre-expanded particles and the foam-molded articles together with Comparative Examples.

【0034】[0034]

【表1】 [Table 1]

【0035】[0035]

【表2】 [Table 2]

【0036】[0036]

【表3】 [Table 3]

【0037】[0037]

【表4】 なお、用いた重合体は実施例1、5、比較例1〜12つ
いては住友化学工業社製ノーブレンS−131 エチレ
ン−プロピレンランダム共重合体であり、実施例2は住
友化学工業社製ノーブレンW−501 ポリプロピレン
であり、実施例3は住友化学工業社製ノーブレンFH−
1015 ポリプロピレンであり、実施例4はハイモン
ト社製PRO−FAX−814 特殊ポリプロピレンで
あり、実施例6は三菱油化社製ユカロンHE−60 エ
チレン酢ビコーポリマーである。
[Table 4] The polymers used in Examples 1 and 5 and Comparative Examples 1 to 12 are Noblene S-131 ethylene-propylene random copolymers manufactured by Sumitomo Chemical Co., Ltd., and Example 2 is Nobrene W-produced by Sumitomo Chemical Co., Ltd. 501 polypropylene, Example 3 is Nobrene FH- manufactured by Sumitomo Chemical Co., Ltd.
1015 polypropylene, Example 4 is PRO-FAX-814 special polypropylene manufactured by Highmont, and Example 6 is Yucaron HE-60 ethylene vinegar bicopolymer manufactured by Mitsubishi Petrochemical Co., Ltd.

【0038】なお、実施例1〜6の予備発泡粒子は何れ
も工程中合着等は生じず、得られた発泡成型品は発泡が
均質で融着良好な高品質のものであった。これに対し比
較例1では含浸が高温すぎて合着を生じ、比較例2、
8、11、12ではガス含有量が少なく発泡力不足とな
った。比較例3、5、9、10では発泡成型時の熱不足
で発泡不良となった。比較例4、6、7では発泡時の熱
過剰で収縮を伴う発泡不良となった。
The pre-expanded particles of Examples 1 to 6 did not cause coalescence or the like during the process, and the obtained foamed molded product was of high quality with uniform foaming and good fusion. On the other hand, in Comparative Example 1, the impregnation was too high to cause coalescence,
In Nos. 8, 11, and 12, the gas content was small and the foaming power was insufficient. In Comparative Examples 3, 5, 9, and 10, the heat was insufficient during foam molding, resulting in poor foaming. In Comparative Examples 4, 6, and 7, the foaming failure accompanied by shrinkage due to excessive heat during foaming occurred.

【0039】[0039]

【発明の効果】本発明の発泡重合体成形品の製造方法に
よれば、無機ガスを用いて予備発泡粒子間におけるバラ
ツキの小さな高度に発泡した予備発泡粒子が得られ、こ
の予備発泡粒子を発泡成形することにより、高倍率の均
質な発泡成形品を効率よく安定して製造することができ
る。本発明によれば、従来の無機ガス使用にみられる欠
点が大幅に改善されると共に、ガス含浸時に水分散系を
用いることなく、且つ特に加熱する必要がないため製造
工程上も有利となる。また安全な好ましい作業環境下で
製造でき、環境汚染を引き起こすことなく工業生産する
ことが可能となる。
EFFECTS OF THE INVENTION According to the method for producing a foamed polymer molded article of the present invention, highly expanded pre-expanded particles having a small variation among the pre-expanded particles can be obtained by using an inorganic gas, and the pre-expanded particles are expanded. By molding, it is possible to efficiently and stably manufacture a high-foaming homogeneous foam-molded product. According to the present invention, the drawbacks found in the conventional use of inorganic gas are remarkably improved, and at the same time, there is no need to use a water dispersion system at the time of gas impregnation and there is no need to particularly heat, which is advantageous in the manufacturing process. Further, it can be manufactured in a safe and favorable working environment, and industrial production can be carried out without causing environmental pollution.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C08L 23:00 7107−4J ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C08L 23:00 7107-4J

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 ポリオレフィン系重合体粒子に、その粒
子が合着しない緩和な温度下でかつ加圧下において無機
ガスを気相含浸させて、無機ガス含有量が0.05モル
/kg(重合体)以上の一次発泡性重合体粒子とし、これ
を無機ガス含有量が0.05モル/kg(重合体)未満に
減少する迄に発泡槽に導入し、上記重合体粒子の融解ピ
ーク温度(TP )+10℃〜TP −10℃の温度域で水
蒸気導入により加熱発泡させ一次予備発泡粒子を形成
し、次いで該一次予備発泡粒子が合着しない緩和な温度
下でかつ加圧下において一次予備発泡粒子に無機ガスを
気相含浸させて、無機ガス含有量が0.5モル/kg(重
合体)以上の二次発泡性発泡重合体粒子とし、これを無
機ガス含有量が0.5モル/kg(重合体)未満に減少す
る迄に発泡槽に導入し、TP +15℃〜TP −20℃の
温度域で水蒸気導入により加熱発泡させ二次予備発泡粒
子を形成した後、更にこの二次予備発泡粒子に無機ガス
を該発泡粒子が合着しない緩和な温度下でかつ加圧下に
おいて気相含浸させて、無機ガス含有量が0.5モル/
kg(重合体)以上になるように二次予備発泡粒子に内圧
付与し、これを無機ガス含有量が0.5モル/kg(重合
体)未満に減少する迄に発泡成形用型に充填し、TP
15℃〜TP −20℃の温度域で水蒸気導入により加熱
発泡させて発泡成形品を得ることを特徴とする発泡重合
体成形品の製造方法。
1. A polyolefin-based polymer particle is impregnated with an inorganic gas in a vapor phase at a moderate temperature under which the particles do not coalesce and under pressure to have an inorganic gas content of 0.05 mol / kg (polymer ) The above primary expandable polymer particles are introduced into a foaming tank until the inorganic gas content is reduced to less than 0.05 mol / kg (polymer), and the melting peak temperature (T P ) + 10 ° C. to T P −10 ° C. to form primary pre-expanded particles by heat-expanding by introducing steam, and then primary pre-expanding at a moderate temperature at which the primary pre-expanded particles do not coalesce and under pressure. The particles are impregnated with an inorganic gas in a gas phase to form secondary expandable foamed polymer particles having an inorganic gas content of 0.5 mol / kg (polymer) or more, and the inorganic gas content is 0.5 mol / kg. Introduce into the foaming tank until it decreases to less than kg (polymer), P + 15 ℃ ~T P -20 after the formation of the temperature range in the secondary pre-expanded particles are heated foamed by the water vapor introduction of ° C., further expanded beads of an inorganic gas into the secondary pre-expanded particles do not coalesce mild temperatures The gas phase is impregnated under pressure and under pressure, and the inorganic gas content is 0.5 mol /
An internal pressure is applied to the secondary pre-expanded particles so that the content of the polymer is not less than kg (polymer), and this is filled in a foam molding mold until the inorganic gas content is reduced to less than 0.5 mol / kg (polymer). , T P +
Method for producing a foamed polymer molded article, characterized in that 15 ° C. through T heated foamed by vapor introduced at a P -20 temperature range of ° C. to obtain a foamed molded article.
【請求項2】 ガス含浸時に重合体粒子が合着しない緩
和な温度がその重合体粒子の融解ピーク温度より40℃
以上低い温度域である請求項1の製造方法。
2. The mild temperature at which the polymer particles do not coalesce during gas impregnation is 40 ° C. from the melting peak temperature of the polymer particles.
The manufacturing method according to claim 1, wherein the temperature is in the lower temperature range.
【請求項3】 水蒸気の導入が60〜100℃の露点を
有しかつ重合体粒子の融解ピーク温度(TP )+15℃
〜TP −20℃の温度域の水蒸気または水蒸気−空気混
合媒体を用いて行われる請求項1の製造方法。
3. The introduction of water vapor has a dew point of 60 to 100 ° C. and the melting peak temperature ( TP ) of the polymer particles + 15 ° C.
The production method according to claim 1, which is carried out by using steam or a steam-air mixed medium in a temperature range of to T P -20 ° C.
【請求項4】 二次予備発泡粒子に更に無機ガスを含浸
し、予備発泡させて、三次以降の予備発泡粒子を得、こ
の予備発泡粒子に無機ガスで内圧付与した後、成形型内
で加熱発泡させることを特徴とする請求項1の製造方
法。
4. The secondary pre-expanded particles are further impregnated with an inorganic gas and pre-expanded to obtain pre-expanded particles of the third and subsequent stages, which are given an internal pressure with an inorganic gas and then heated in a molding die. The manufacturing method according to claim 1, wherein foaming is performed.
JP4055569A 1992-03-13 1992-03-13 Method for producing foamed polymer molded article Expired - Fee Related JPH07116314B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4055569A JPH07116314B2 (en) 1992-03-13 1992-03-13 Method for producing foamed polymer molded article

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4055569A JPH07116314B2 (en) 1992-03-13 1992-03-13 Method for producing foamed polymer molded article

Publications (2)

Publication Number Publication Date
JPH05255531A true JPH05255531A (en) 1993-10-05
JPH07116314B2 JPH07116314B2 (en) 1995-12-13

Family

ID=13002353

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4055569A Expired - Fee Related JPH07116314B2 (en) 1992-03-13 1992-03-13 Method for producing foamed polymer molded article

Country Status (1)

Country Link
JP (1) JPH07116314B2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006168192A (en) * 2004-12-16 2006-06-29 Bridgestone Corp Method for adjusting pressure of hollow part of fine hollow particle for safety tire
WO2006100517A1 (en) * 2005-03-24 2006-09-28 Zotefoams Plc Process for introducing a gas into a polymer
JP2009185162A (en) * 2008-02-06 2009-08-20 Kaneka Corp Polyolefin resin pre-foamed particle
CN112157861A (en) * 2020-08-27 2021-01-01 茂泰(福建)鞋材有限公司 Preparation method of secondary mould pressing foaming sole
WO2021106354A1 (en) * 2019-11-29 2021-06-03 株式会社カネカ Device and method for producing expanded particles

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006168192A (en) * 2004-12-16 2006-06-29 Bridgestone Corp Method for adjusting pressure of hollow part of fine hollow particle for safety tire
WO2006100517A1 (en) * 2005-03-24 2006-09-28 Zotefoams Plc Process for introducing a gas into a polymer
GB2439697A (en) * 2005-03-24 2008-01-02 Zotefoams Plc Process for introducing a gas into a polymer
GB2439697B (en) * 2005-03-24 2009-11-04 Zotefoams Plc Process for introducing a gas into a polymer
JP2009185162A (en) * 2008-02-06 2009-08-20 Kaneka Corp Polyolefin resin pre-foamed particle
WO2021106354A1 (en) * 2019-11-29 2021-06-03 株式会社カネカ Device and method for producing expanded particles
CN112157861A (en) * 2020-08-27 2021-01-01 茂泰(福建)鞋材有限公司 Preparation method of secondary mould pressing foaming sole

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