JP3418081B2 - Expanded resin particles - Google Patents
Expanded resin particlesInfo
- Publication number
- JP3418081B2 JP3418081B2 JP01792797A JP1792797A JP3418081B2 JP 3418081 B2 JP3418081 B2 JP 3418081B2 JP 01792797 A JP01792797 A JP 01792797A JP 1792797 A JP1792797 A JP 1792797A JP 3418081 B2 JP3418081 B2 JP 3418081B2
- Authority
- JP
- Japan
- Prior art keywords
- melting point
- resin particles
- expanded
- thermoplastic resin
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、発泡樹脂粒子に関
し、詳しくは、優れた融着性を有し、そのため、型内成
形体を得るための成形温度を低くすることが出来、しか
も、得られた成形体の機械的物性および熱的特性が良好
である発泡樹脂粒子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to expanded resin particles, and more particularly, it has excellent fusion-bonding properties, and therefore the molding temperature for obtaining an in-mold molded article can be lowered, The present invention relates to expanded resin particles having excellent mechanical properties and thermal properties.
【０００２】[0002]
【従来の技術】発泡樹脂粒子は、任意の形状を採り得る
と共に独立気泡構造に基づく低い熱伝導率を有し、その
ため、断熱材、緩衝材、芯材などの成形原料として広く
使用されている。そして、上記の発泡樹脂粒子を構成す
る熱可塑性樹脂としては、通常、ポリエチレン、ポリプ
ロピレン、ポリスチレン等が使用される。2. Description of the Related Art Expanded resin particles can have any shape and have a low thermal conductivity based on a closed cell structure. Therefore, they are widely used as a molding raw material for heat insulating materials, cushioning materials, core materials and the like. . As the thermoplastic resin forming the expanded resin particles, polyethylene, polypropylene, polystyrene or the like is usually used.
【０００３】しかしながら、発泡樹脂粒子がポリプロピ
レン系樹脂に代表される高融点樹脂の場合は、融点が１
３５℃以上と高いため、型内成形の際、発泡樹脂粒子同
士の融着に必要な圧力として、２ｋｇ／ｃｍ2Ｇを超え
る高圧の蒸気が必要である。そのため、成形にかかるコ
ストが高くなり、しかも、成形サイクルが長くなるとい
う欠点がある。また、上記の高融点樹脂より成る発泡樹
脂粒子の場合は、広く普及している発泡ポリスチレン用
の型内発泡成形機では成形できないため、高圧蒸気の制
御システムを備えた型締め圧力の高い成型機が必要とな
る。However, when the expanded resin particles are high melting point resin represented by polypropylene resin, the melting point is 1
Since the temperature is as high as 35 ° C. or higher, high pressure steam exceeding 2 kg / cm 2 G is required as the pressure required for fusion of the foamed resin particles during in-mold molding. Therefore, there are disadvantages that the cost for molding becomes high and the molding cycle becomes long. Further, in the case of expanded resin particles composed of the above-mentioned high melting point resin, it cannot be molded by the in-mold expansion molding machine for expanded polystyrene that is widely used, so a molding machine equipped with a high-pressure steam control system and having a high clamping pressure. Is required.
【０００４】一方、ポリエチレン系樹脂の場合は、融点
が１２５℃以下と低いため、発泡樹脂粒子同士の融着の
ための蒸気圧は２ｋｇ／ｃｍ2Ｇ未満の低圧であればよ
く、発泡ポリスチレン用の成型機でも殆ど仕様を変える
ことなく成形できるという利点を有している。しかしな
がら、ポリエチレン系樹脂の発泡成形体は、その低融点
のために耐熱性が低く、特に、高発泡の発泡成形体は、
エネルギー吸収性能が小さい。したがって、ポリエチレ
ン系樹脂の発泡成形体は、他の熱可塑性樹脂の発泡成形
体と比較し、低発泡においてのみ使用可能である。On the other hand, in the case of polyethylene resin, since the melting point is as low as 125 ° C. or lower, the vapor pressure for fusing the expanded resin particles to each other may be a low pressure of less than 2 kg / cm 2 G. This molding machine has the advantage that molding can be performed without changing the specifications. However, the foamed molded product of polyethylene resin has low heat resistance because of its low melting point, and in particular, the foamed molded product of high foaming is
Energy absorption performance is small. Therefore, the foamed molded product of polyethylene resin can be used only in low foaming, as compared with the foamed molded products of other thermoplastic resins.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記実情に
鑑みなされたものであり、その目的は、型締め圧の低い
汎用成型機で成形しても高融点の熱可塑性樹脂発泡粒子
を使用した従来の成形体と略同等の物性を有し且つ耐熱
温度も高い成形体を与えることが出来る発泡樹脂粒子を
提供することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to use expanded thermoplastic resin particles having a high melting point even when molded by a general-purpose molding machine having a low mold clamping pressure. It is an object of the present invention to provide a foamed resin particle which has substantially the same physical properties as those of the conventional molded product described above and which can provide a molded product having a high heat resistant temperature.
【０００６】[0006]
【課題を解決するための手段】すなわち、本発明の要旨
は、結晶性の熱可塑性樹脂から成る発泡状態の芯層と、
前記熱可塑性樹脂より融点が低いか、または、実質的に
融点を示さないエチレン系重合体から成り、且つ、実質
的に非発泡状態である被覆層とから構成されていること
を特徴とする発泡樹脂粒子に存する。That is, the gist of the present invention is to provide a foamed core layer made of a crystalline thermoplastic resin,
Foaming characterized by comprising a coating layer having a melting point lower than that of the thermoplastic resin or having substantially no melting point, and a coating layer which is substantially in a non-foaming state. Exists in resin particles.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明の発泡樹脂粒子は、芯層と被覆層とから構成され
る複合構造を有する。芯層は、結晶性の熱可塑性樹脂に
て構成される。斯かる熱可塑性樹脂の具体例としては、
ポリプロピレン系樹脂、ポリブテン系樹脂、ポリメチル
ペンテン系樹脂、ポリエステル系樹脂、ポリアミド系樹
脂、フッ素系樹脂、結晶性のスチレン系樹脂などが挙げ
られるが、プロピレン単独重合体、プロピレンとプロピ
レン以外のα−オレフィンとのランダム共重合体やブロ
ック共重合体が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The expanded resin particles of the present invention have a composite structure composed of a core layer and a coating layer. The core layer is made of a crystalline thermoplastic resin. Specific examples of such a thermoplastic resin include:
Polypropylene resin, polybutene resin, polymethylpentene resin, polyester resin, polyamide resin, fluorine resin, crystalline styrene resin and the like, propylene homopolymer, propylene and α-other than propylene Random copolymers and block copolymers with olefins are preferred.
【０００８】被覆層は、前記熱可塑性樹脂より融点が低
いか、または、実質的に融点を示さないエチレン系重合
体から構成される。斯かる低融点のエチレン系重合体と
しは、高圧法低密度ポリエチレン、直鎖状低密度ポリエ
チレン、直鎖状超低密度ポリエチレンの他、酢酸ビニ
ル、不飽和カルボン酸エステル、不飽和カルボン酸、ビ
ニルアルコール等とエチレンの共重合体が挙げられる。The coating layer is composed of an ethylene polymer having a melting point lower than that of the thermoplastic resin or having substantially no melting point. Such low-melting point ethylene polymers include high-pressure process low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, vinyl acetate, unsaturated carboxylic acid ester, unsaturated carboxylic acid, and vinyl. Examples thereof include copolymers of alcohol and ethylene.
【０００９】また、上記の実質的に融点を示さないエチ
レン系重合体としては、例えば、エチレン・プロピレン
ゴム、エチレン・プロピレン・ジエンゴム、エチレン・
アクリルゴム、塩素化ポリエチレンゴム、クロロスルホ
ン化ポリエチレンゴム等のゴム・エラストマーが挙げら
れる。これらのエチレン系重合体は、単独使用の他、２
種以上の組成物として使用することが出来る。Further, examples of the above-mentioned ethylene polymer having substantially no melting point include, for example, ethylene / propylene rubber, ethylene / propylene / diene rubber, and ethylene / propylene rubber.
Examples thereof include rubber elastomers such as acrylic rubber, chlorinated polyethylene rubber, and chlorosulfonated polyethylene rubber. These ethylene-based polymers are used alone and in addition to 2
It can be used as one or more compositions.
【００１０】上記のエチレン系重合体の中では、高圧法
低密度ポリエチレン、直鎖状低密度ポリエチレン、直鎖
状超低密度ポリエチレンが好ましい。中でもメタロセン
触媒を使用して重合された直鎖状低密度ポリエチレン、
直鎖状超低密度ポリエチレンが最も好ましい。また、本
発明においては、被覆層として、エチレン系重合体と芯
層と同一の結晶性の熱可塑性樹脂から成るエチレン系重
合体組成物も好適に使用することが出来る。斯かるエチ
レン系重合体組成物によれば、芯層と被覆層の接着性が
向上するという利点がある。Among the above-mentioned ethylene polymers, high-pressure low-density polyethylene, linear low-density polyethylene, and linear ultra-low-density polyethylene are preferable. Among them, linear low-density polyethylene polymerized using a metallocene catalyst,
Most preferred is linear ultra low density polyethylene. Further, in the present invention, an ethylene polymer composition comprising an ethylene polymer and the same crystalline thermoplastic resin as the core layer can be preferably used as the coating layer. According to such an ethylene polymer composition, there is an advantage that the adhesiveness between the core layer and the coating layer is improved.
【００１１】上記の熱可塑性樹脂の使用割合は、エチレ
ン系重合体１００重量部に対し、１〜１００重量部の範
囲から選択される。熱可塑性樹脂の使用割合が１００重
量部を超える場合には、被覆層の海島形態が変化し、熱
可塑性樹脂が連続した海の相を構成することとなり、型
内成形の蒸気圧力が余り低下しない。熱可塑性樹脂の好
ましい割合は、１〜５０重量部の範囲である。The proportion of the thermoplastic resin used is selected from the range of 1 to 100 parts by weight with respect to 100 parts by weight of the ethylene polymer. If the proportion of the thermoplastic resin used exceeds 100 parts by weight, the sea-island morphology of the coating layer will change, and the thermoplastic resin will form a continuous sea phase, and the steam pressure for in-mold molding will not drop so much. . The preferable ratio of the thermoplastic resin is in the range of 1 to 50 parts by weight.
【００１２】本発明においては、芯層を構成する熱可塑
性樹脂に対し、１５℃以上低い融点のエチレン系重合体
を選択して使用するのが好ましい。エチレン系重合体と
熱可塑性樹脂の上記の融点差は、好ましくは２０℃〜６
０℃、更に好ましくは２０℃〜４０℃の範囲である。上
記の融点差が１５℃未満の場合、芯層の熱可塑性樹脂を
発泡させる条件下においては、エチレン系重合体から成
る被覆層が発泡する虞がある。In the present invention, it is preferable to select and use an ethylene polymer having a melting point lower than 15 ° C. with respect to the thermoplastic resin constituting the core layer. The melting point difference between the ethylene polymer and the thermoplastic resin is preferably 20 ° C to 6 ° C.
The temperature is 0 ° C, more preferably 20 ° C to 40 ° C. If the melting point difference is less than 15 ° C., the coating layer made of the ethylene polymer may foam under the condition of foaming the thermoplastic resin of the core layer.
【００１３】更に、前記のエチレン系重合体の融点は、
１２５℃以下、好ましくは１００〜１２５℃の範囲から
選ばれる。融点が１２５℃を超えるエチレン系重合体を
使用する場合は、発泡樹脂粒子を成形する際の必要蒸気
圧力が高くなる傾向にある。Further, the melting point of the ethylene polymer is
It is selected from the range of 125 ° C or lower, preferably 100 to 125 ° C. When an ethylene polymer having a melting point of more than 125 ° C. is used, the vapor pressure required for molding the expanded resin particles tends to be high.
【００１４】本発明の発泡樹脂粒子において、被覆層の
厚さは、１〜１５０μｍ、好ましくは１０〜１００μｍ
の範囲である。被覆層の厚さが１μｍ未満の場合には、
成形の際、蒸気圧力を十分に低下させる効果が少ない。
一方、被覆層の厚さが１５０μｍを超える場合には、成
形の際、蒸気圧力は下げることが出来るものの、被覆層
の実質的に非発泡性部分の割合が大きく、成形体の機械
的強度が発泡倍率の割には低くなる傾向にある。In the expanded resin particles of the present invention, the coating layer has a thickness of 1 to 150 μm, preferably 10 to 100 μm.
Is the range. When the thickness of the coating layer is less than 1 μm,
At the time of molding, the effect of sufficiently reducing the steam pressure is small.
On the other hand, when the thickness of the coating layer exceeds 150 μm, the vapor pressure can be lowered during molding, but the proportion of the non-foaming portion of the coating layer is substantially large and the mechanical strength of the molded body is high. It tends to be low for the expansion ratio.
【００１５】本発明の発泡樹脂粒子は、基本的には、結
晶性の熱可塑性樹脂から成る芯層と、前記熱可塑性樹脂
より融点が低いか、または、実質的に融点を示さないエ
チレン系重合体から成る被覆層にて構成される複合体粒
子に揮発性発泡剤を含浸させた後、加熱発泡して得られ
る。The expanded resin particles of the present invention basically comprise a core layer made of a crystalline thermoplastic resin and an ethylene-based polymer having a melting point lower than that of the thermoplastic resin or substantially no melting point. It is obtained by impregnating the volatile foaming agent into the composite particles composed of the coating layer made of coalesced and then foaming by heating.
【００１６】上記の揮発性発泡剤としては、プロパン、
ブタン、ペンタン、ヘプタン、シクロペンタン、シクロ
ヘキサン等の低級脂肪族炭化水素類、ジクロロジフロロ
メタン、トリクロロモノフロロメタン等のハロゲン化炭
化水素、窒素、空気、炭酸ガス等の無機ガス等が挙げら
れ、これらは、単独または２種類以上組合わせて使用さ
れる。The above volatile blowing agent is propane,
Butane, pentane, heptane, cyclopentane, lower aliphatic hydrocarbons such as cyclohexane, dichlorodifluoromethane, halogenated hydrocarbons such as trichloromonofluoromethane, nitrogen, air, inorganic gases such as carbon dioxide, and the like, These are used alone or in combination of two or more.
【００１７】本発明の発泡樹脂粒子の原料となる複合体
粒子の具体的製造方法としては、次の各方法が使用され
る。例えば、特公昭４１−１６１２５号公報、同４３−
２３８５８号公報、同４４−２９５２２号公報、特開昭
６０−１８５８１６号公報などに記載の鞘芯型の複合ダ
イが使用される。この場合、２基の押出し機が使用さ
れ、一方の押出し機で芯層を構成する熱可塑性樹脂を溶
融混練し、他方の押出し機で被覆層を構成するエチレン
系重合体組成物を溶融混練した後、ダイで熱可塑性樹脂
を芯層とし、エチレン系重合体組成物を被覆層として鞘
芯型の複合体を吐出させる。Each of the following methods is used as a specific method for producing composite particles as a raw material for the expanded resin particles of the present invention. For example, Japanese Examined Patent Publication No. 41-16125 and No. 43-
The sheath-core type composite dies described in JP-A-23858, JP-A-44-29522 and JP-A-60-185816 are used. In this case, two extruders were used, one extruder melt-kneading the thermoplastic resin forming the core layer, and the other extruder melt-kneading the ethylene polymer composition forming the coating layer. After that, a sheath-core type composite is discharged by using a die with a thermoplastic resin as a core layer and an ethylene-based polymer composition as a coating layer with a die.
【００１８】次いで、この様にして得られた複合体をカ
ットして０．１〜１０ｍｇの複合体粒子とする。複合体
粒子の重量が０．１ｍｇ未満の場合は、成形加工の蒸気
圧を効果的に低下させる被覆層比率が高くなるため、得
られる発泡成形体の機械的強度が低下する。一方、複合
体粒子の重量が１０ｍｇを超える場合は、成形時の金型
への充填性が悪化し易い。Next, the composite thus obtained is cut into 0.1 to 10 mg of composite particles. If the weight of the composite particles is less than 0.1 mg, the ratio of the coating layer that effectively lowers the vapor pressure of the molding process becomes high, and the mechanical strength of the obtained foamed molded product decreases. On the other hand, when the weight of the composite particles exceeds 10 mg, the moldability during molding tends to deteriorate.
【００１９】上記の鞘芯型の複合体粒子に揮発性発泡剤
を含浸した後、加熱発泡する方法としては、具体的に
は、例えば、特公昭４９−２１８３号公報、同５６−１
３４４号公報、西ドイツ特開第１２８５７２２号公報、
同第２１０７６８３号公報などに記載の方法を使用し得
る。As a method of heat-foaming after impregnating the above-mentioned sheath-core type composite particles with a volatile foaming agent, specifically, for example, JP-B-49-2183 and JP-A-56-1.
344, West German Patent No. 1285722,
The method described in Japanese Patent No. 2107683 can be used.
【００２０】この場合、密閉容器内に揮発性発泡剤と共
に鞘芯型の複合体粒子を入れ、芯層の結晶性樹脂の軟化
温度以上に加熱する共に、複合体粒子に揮発性発泡剤を
含浸させる。その後、密閉容器内の内容物を密閉容器よ
り低圧の雰囲気に放出した後、乾燥処理することによ
り、本発明の発泡樹脂粒子が得られる。In this case, the sheath-core type composite particles are put in a closed container together with the volatile foaming agent and heated to a temperature not lower than the softening temperature of the crystalline resin of the core layer, and the composite particles are impregnated with the volatile foaming agent. Let Then, the foamed resin particles of the present invention are obtained by releasing the contents in the closed container from the closed container to a low-pressure atmosphere and then drying the contents.
【００２１】複合体粒子の発泡時の加熱温度は、通常、
芯層の熱可塑性樹脂の軟化温度以上とされるが、被覆層
のエチレン系重合体の融点（組成物の場合は主成分の融
点）より高い温度にするのが好ましい。また、本発明で
は、密閉容器中で複合体粒子同士が相互に融着しない様
にするため、攪拌装置が付備される。The heating temperature for foaming the composite particles is usually
The temperature is not lower than the softening temperature of the thermoplastic resin of the core layer, but is preferably higher than the melting point of the ethylene polymer of the coating layer (the melting point of the main component in the case of a composition). Further, in the present invention, a stirring device is provided in order to prevent the composite particles from being fused to each other in the closed container.
【００２２】加熱発泡時には、複合体粒子の分散媒とし
て、水、アルコール類などを使用することが好ましい。
さらに、複合体粒子が分散媒に均一に分散する様に、酸
化アルミニウム、第三リン酸カルシウム、ピロリン酸マ
グネシウム、酸化亜鉛などの難水溶性の無機物質、ポリ
ビニルピロリドン、ポリビニルアルコール、メチルセル
ロース等の水溶性保護コロイド、ドデシルベンゼンスル
ホン酸ナトリウム、α−オレフィンスルホン酸ナトリウ
ム等の陰イオン性界面活性剤を単独または２種類以上混
合して使用するのが好ましい。At the time of foaming by heating, it is preferable to use water, alcohols or the like as a dispersion medium for the composite particles.
Furthermore, so that the composite particles are uniformly dispersed in the dispersion medium, a poorly water-soluble inorganic substance such as aluminum oxide, tricalcium phosphate, magnesium pyrophosphate, and zinc oxide, water-soluble protection such as polyvinylpyrrolidone, polyvinyl alcohol, and methylcellulose. It is preferable to use anionic surfactants such as colloid, sodium dodecylbenzene sulfonate and sodium α-olefin sulfonate, either alone or in combination of two or more.
【００２３】低圧の雰囲気に複合体粒子を放出する際、
当該放出を容易にするため、前記と同様な無機ガス又は
揮発性発泡剤を外部より密閉容器に導入して密閉容器内
の圧力を一定に保持することが好ましい。When releasing the composite particles into a low pressure atmosphere,
In order to facilitate the release, it is preferable to introduce the same inorganic gas or volatile foaming agent as described above from the outside into the closed container to keep the pressure in the closed container constant.
【００２４】本発明の発泡樹脂粒子は、様々な条件の金
型を使用して成形される。例えば、大気圧または減圧下
の凹凸一対の金型より成るキャビティー内へ発泡樹脂粒
子を充填した後に金型キャビティー体積を５〜７０％減
少する様に圧縮し、次いで、スチーム等の熱媒をキャビ
ティー内に導入して発泡樹脂粒子を加熱融着させる圧縮
成型法（例えば特公昭４６−３８３５９号公報）が挙げ
られる。The expanded resin particles of the present invention are molded using molds under various conditions. For example, foamed resin particles are filled into a cavity formed by a pair of concave and convex molds under atmospheric pressure or reduced pressure, and then compressed so that the mold cavity volume is reduced by 5 to 70%, and then a heat medium such as steam is used. Is introduced into the cavity and the foamed resin particles are heated and fused (for example, Japanese Patent Publication No. 46-38359).
【００２５】また、揮発性発泡剤または無機ガスの１種
または２種以上で予め発泡樹脂粒子を処理して発泡樹脂
粒子の二次発泡力を高め、次いで、その二次発泡力を保
持しつつ大気圧または減圧下の金型キャビティーに充填
した後、キャビティー内に熱媒を導入して加熱融着させ
る加圧熟成法（例えば特公昭５１−２２９５１号公報）
が挙げられる。Further, the expanded resin particles are previously treated with one or more kinds of a volatile foaming agent or an inorganic gas to enhance the secondary expansion power of the expanded resin particles, and then the secondary expansion power is maintained. A pressure aging method in which a mold cavity is filled under atmospheric pressure or reduced pressure, and then a heating medium is introduced into the cavity for heat fusion (for example, Japanese Patent Publication No. 51-22951).
Is mentioned.
【００２６】圧縮ガスにより大気圧以上に加圧した金型
キャビティーに当該圧力以上に加圧した発泡樹脂粒子を
充填した後、キャビティー内に熱媒を導入して加熱融着
させる圧縮充填法（例えば特公平４−４６２１７号公
報）が挙げられる。A compression-filling method in which a mold cavity pressurized to a pressure higher than atmospheric pressure with a compressed gas is filled with expanded resin particles pressurized to a pressure higher than the pressure, and then a heating medium is introduced into the cavity for heat fusion. (For example, Japanese Patent Publication No. 4-46217).
【００２７】特殊な条件にて得られる二次発泡力の高い
発泡樹脂粒子を使用して大気圧または減圧下の凹凸一対
の金型より成るキャビティー内へ発泡樹脂粒子を充填
し、次いで、キャビティー内にスチーム等の熱媒を導入
して加熱融着させる常圧充填法（例えば特公平６−４９
７９５号公報）が挙げられる。本発明で使用される成形
方法は、以上の何れの方法でもよく、また、上記の方法
の組合わせによっても成形できる（例えば特公平６−２
２９１９号公報参照）。Using expanded resin particles having a high secondary expansion power obtained under special conditions, the expanded resin particles are filled into a cavity formed by a pair of concave and convex molds under atmospheric pressure or reduced pressure, and then the cavities Atmospheric pressure filling method in which a heat medium such as steam is introduced into the tee and heated and fused (for example, Japanese Patent Publication No. 6-49
No. 795). The molding method used in the present invention may be any of the above methods, or may be a combination of the above methods (for example, Japanese Patent Publication No. 6-2.
(See Japanese Patent No. 2919).
【００２８】本発明の発泡樹脂粒子は、その粒子のカッ
ト断面の状態から、芯層の熱可塑性樹脂が独立気泡構造
の発泡状態を呈し、一方、被覆層のエチレン系重合体が
実質的に非発泡のフィルム状態となっている。In the expanded resin particles of the present invention, the thermoplastic resin of the core layer exhibits a closed cell structure in an expanded state from the state of the cut cross section of the particles, while the ethylene polymer of the coating layer is substantially non-existent. It is in a foamed film state.
【００２９】本発明においては、上記の何れの成形法に
おいても低い蒸気圧で発泡樹脂粒子同士が充分に融着し
た成形体を得ることが出来る。また、この様にして得ら
れた成形体は、優れた機械的強度と共に、耐熱性も高
く、断熱材、構造部材、芯材として有用である。In the present invention, a molded body in which the expanded resin particles are sufficiently fused to each other can be obtained with a low vapor pressure by any of the above molding methods. Further, the molded product thus obtained has high mechanical strength and high heat resistance, and is useful as a heat insulating material, a structural member and a core material.
【００３０】[0030]
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明はその要旨を超えない限り、以下の実施例に
よって限定されたものではない。なお、以下の各例にお
いて、各物性は次の様にして求めた。The present invention is described in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, in each of the following examples, each physical property was determined as follows.
【００３１】＜融点＞示差走査熱量計（ＤＳＣ）により
測定する。先ず、３〜５ｍｇの樹脂をその結晶が融解す
る温度まで昇温後、１０℃／分の速度で室温まで冷却す
る。次いで、１０℃／分の速度で加熱昇温し、得られる
吸熱曲線のピーク温度をもって融点とする。<Melting point> Measured by a differential scanning calorimeter (DSC). First, 3 to 5 mg of resin is heated to a temperature at which the crystals melt, and then cooled to room temperature at a rate of 10 ° C./min. Then, the temperature is increased by heating at a rate of 10 ° C./min, and the peak temperature of the endothermic curve obtained is taken as the melting point.
【００３２】＜融着試験＞長さ２００ｍｍ、巾３０ｍ
ｍ、厚さ１２．５ｍｍの試験片を作製し、試験片を直径
５０ｍｍの円筒の円周に沿って９０度まで曲げて、次の
基準で判定した。<Fusion test> Length 200 mm, width 30 m
A test piece having a thickness of 12.5 mm and a thickness of 12.5 mm was prepared, and the test piece was bent to 90 degrees along the circumference of a cylinder having a diameter of 50 mm and judged according to the following criteria.
【００３３】[0033]
【表１】 ○：試験片総数の８０％以上が割れない。 ×：試験片総数の２０％を超えるものが割れる。[Table 1] ◯: 80% or more of the total number of test pieces did not crack. X: More than 20% of the total number of test pieces break.
【００３４】＜耐熱試験＞ＪＩＳ Ｋ ６７６７に準じ
て１１０℃における耐熱寸法変化率を次の基準で測定し
た。<Heat Resistance Test> According to JIS K 6767, the heat resistant dimensional change rate at 110 ° C. was measured according to the following criteria.
【００３５】[0035]
【表２】 ○：寸法収縮率が３％未満である。 △：寸法収縮率が３〜６％である。 ×：寸法収縮率が６％を超える。[Table 2] ◯: The dimensional shrinkage ratio is less than 3%. Δ: The dimensional shrinkage ratio is 3 to 6%. X: The dimensional shrinkage exceeds 6%.
【００３６】実施例１
内径４０ｍｍの単軸押出し機を使用してエチレン含量
１．５％のエチレン・プロピレンランダム共重合体（融
点１５３℃）を混練し、内径２５ｍｍの単軸押出し機を
使用して密度０．９２０の直鎖状低密度ポリエチレン
（融点１２３℃）を混練した。次いで、直径１．５ｍｍ
のダイオリフィースを有するダイから、エチレン・プロ
ピレンランダム共重合体を芯層とし、直鎖状低密度ポリ
エチレンを被覆層としてストランドを押し出した。Example 1 An ethylene / propylene random copolymer having an ethylene content of 1.5% (melting point 153 ° C.) was kneaded using a single-screw extruder having an inner diameter of 40 mm, and a single-screw extruder having an inner diameter of 25 mm was used. And linear low-density polyethylene (melting point: 123 ° C.) having a density of 0.920 was kneaded. Then 1.5 mm in diameter
From the die having the die orifice, the strand was extruded with the ethylene / propylene random copolymer as the core layer and the linear low-density polyethylene as the coating layer.
【００３７】さらに、このストランドを水槽を通して冷
却した後、１．２ｍｇに切断した。この複合体粒子の断
面を位相差顕微鏡により観察したところ、厚さ３０μｍ
の直鎖状低密度ポリエチレンがエチレン・プロピレンラ
ンダム共重合体を被覆していた。Further, this strand was cooled through a water bath and then cut into 1.2 mg. When the cross section of the composite particles was observed by a phase contrast microscope, the thickness was 30 μm.
The linear low-density polyethylene of the above was coated with an ethylene / propylene random copolymer.
【００３８】次に、密閉容器内に上記の複合体粒子１０
０部、水２５０部、粒径０．３〜０．５μｍの第三リン
酸カルシウム１．０部およびドデシルベンゼンスルホン
酸ナトリウム０．００７部を仕込み、次いで、攪拌下に
てブタン２０部を密閉容器内へ供給した。内容物を充填
率６２％で充填した後、一時間かけて１４５℃まで昇温
して同温度で３０分間保持した。Next, the above composite particles 10 are placed in a closed container.
0 parts, 250 parts of water, 1.0 part of tribasic calcium phosphate having a particle size of 0.3 to 0.5 μm and 0.007 part of sodium dodecylbenzenesulfonate are charged, and then 20 parts of butane are stirred under a closed container. Supplied to. After the contents were filled at a filling rate of 62%, the temperature was raised to 145 ° C. over 1 hour and kept at the same temperature for 30 minutes.
【００３９】その後、密閉容器の底部にある放出孔の弁
を開くと共に外部より密閉容器内の気相部へ窒素ガスを
導入し、容器内の圧力を保持しつつ内容物を大気圧下へ
放出して発泡樹脂粒子を得た。こうして得られた発泡樹
脂粒子は、平均嵩密度１７ｋｇ／ｍ3、平均気泡径１２
０μｍであり、発泡樹脂粒子同士のブロッキングもなか
った。After that, the valve of the discharge hole at the bottom of the closed container is opened, and nitrogen gas is introduced from the outside into the gas phase part of the closed container to release the contents under atmospheric pressure while maintaining the pressure inside the container. Thus, expanded resin particles were obtained. The expanded resin particles thus obtained had an average bulk density of 17 kg / m 3 and an average cell diameter of 12
It was 0 μm, and there was no blocking between the expanded resin particles.
【００４０】この発泡樹脂粒子の断面を位相差顕微鏡に
て観察したところ、芯層のエチレン・ブロピレンランダ
ム共重合体は、独立気泡の発泡状態にあり、一方、直鎖
状低密度ポリエチレンは、実質的に非発泡のフィルム状
態でエチレン・プロピレンランダム共重合体の発泡体を
被覆していた。Observation of the cross section of the foamed resin particles with a phase contrast microscope revealed that the ethylene-propylene copolymer of the core layer was in the foamed state of closed cells, while the linear low-density polyethylene was The ethylene / propylene random copolymer foam was covered in a substantially non-foamed film state.
【００４１】この発泡樹脂粒子を４０℃の乾燥室にて完
全に乾燥し、２．０ｋｇ／ｃｍ2Ｇの圧縮空気にて加圧
し、発泡樹脂粒子を収縮させた後、１．５ｋｇ／ｃｍ2
Ｇの圧縮空気にて加圧した雰囲気下にあるスチーム孔を
有する凹凸一対のアルミニウム製金型のキャビティー内
に充填し、さらに、１．０ｋｇ／ｃｍ2Ｇのスチームを
導入して発泡樹脂粒子同士を加熱融着させた。The foamed resin particles were completely dried in a drying chamber at 40 ° C., compressed with 2.0 kg / cm 2 G of compressed air to shrink the foamed resin particles, and then 1.5 kg / cm 2.
Expanded resin particles by filling the inside of the cavity of a pair of concave and convex aluminum molds having steam holes under the atmosphere pressurized with G compressed air, and further introducing 1.0 kg / cm 2 G steam. The two were heat fused.
【００４２】次いで、水冷２０秒後に３５秒間放冷し、
金型面圧が０．３ｋｇ／ｃｍ2Ｇになったところで金型
を開いて成型体を取り出した。金型より取り出された成
型体は、密度３０ｋｇ／ｃｍ3、縦２００ｍｍ、横３０
０ｍｍ、厚さ２５ｍｍであり、金型に対する寸法収縮率
は１．９％であった。Then, after cooling with water for 20 seconds, it is left to cool for 35 seconds,
When the surface pressure of the mold reached 0.3 kg / cm 2 G, the mold was opened and the molded product was taken out. The molded body taken out from the mold has a density of 30 kg / cm 3 , a length of 200 mm, and a width of 30.
The thickness was 0 mm and the thickness was 25 mm, and the dimensional shrinkage ratio to the mold was 1.9%.
【００４３】上記の成型体から、長さ２００ｍｍ、巾３
０ｍｍ、厚さ１２．５ｍｍの試験片２０片を作製し、直
径５０ｍｍの円筒の円周に巻き、９０°の角度まで曲げ
たところ、試験片の８０％以上が割れなかった。また、
同一成形条件で成形した別の成型体から、縦５０ｍｍ、
横５０ｍｍ、厚さ２５ｍｍの試験片を作製し、ＪＩＳＫ
６７６７に準じて、圧縮試験を実施したところ、５０
％圧縮の応力が２．９ｋｇ／ｃｍ2であった。更に、Ｊ
ＩＳ Ｋ ６７６７に準じて１１０℃で耐熱試験を実施
したところ、寸法収縮率が３％未満であった。これらの
結果を表３に示す。From the above molded body, length 200 mm, width 3
Twenty test pieces of 0 mm and a thickness of 12.5 mm were produced, wound around the circumference of a cylinder having a diameter of 50 mm and bent to an angle of 90 °, and 80% or more of the test pieces did not crack. Also,
From another molded body molded under the same molding conditions, length 50mm,
A test piece with a width of 50 mm and a thickness of 25 mm is produced and JISK
According to 6767, a compression test was carried out and found to be 50
The% compressive stress was 2.9 kg / cm 2 . Furthermore, J
When a heat resistance test was performed at 110 ° C. according to IS K 6767, the dimensional shrinkage was less than 3%. The results are shown in Table 3.
【００４４】実施例２〜９及び比較例１〜９
実施例１において、発泡樹脂粒子として表３〜８に記載
の粒子を使用し、表３〜８に示す条件下にて発泡および
成形を実施した以外は、実施例１と同様に実施した。結
果を表３〜７に示す。本発明の発泡樹脂粒子および成形
体は、優れた融着性、高い機械的強度および耐熱性を示
すことが分かった。Examples 2 to 9 and Comparative Examples 1 to 9 In Example 1, the particles shown in Tables 3 to 8 were used as the expanded resin particles, and foaming and molding were carried out under the conditions shown in Tables 3 to 8. The same procedure as in Example 1 was carried out except that the above was carried out. The results are shown in Tables 3-7. It has been found that the expanded resin particles and the molded product of the present invention exhibit excellent fusion bondability, high mechanical strength and heat resistance.
【００４５】[0045]
【表３】 [Table 3]
【００４６】[0046]
【表４】 [Table 4]
【００４７】[0047]
【表５】 [Table 5]
【００４８】[0048]
【表６】 [Table 6]
【００４９】[0049]
【表７】 [Table 7]
【００５０】[0050]
【表８】 [Table 8]
【００５１】[0051]
【発明の効果】以上説明した本発明の発泡樹脂粒子は、
型内成形における加熱蒸気圧が低圧でも優れた融着性を
示すと共に、得られる成形体は、機械的強度が高く且つ
耐熱性も高い優れた物性を有する。The expanded resin particles of the present invention described above are
In addition to exhibiting excellent fusion-bonding properties even when the heating steam pressure in in-mold molding is low, the resulting molded product has excellent mechanical properties and high heat resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大桑 輝也 三重県四日市市川尻町1000番地 三菱化 学ビーエーエスエフ株式会社内 (56)参考文献 特開 昭60−181139（ＪＰ，Ａ) 特開 昭58−145739（ＪＰ，Ａ) 特開 昭60−235850（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 9/16 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Teruya Oguwa 1000 Kawajiri-cho, Yokkaichi-shi, Mie Mitsubishi Kagaku BSF Co., Ltd. (56) References JP-A-60-181139 (JP, A) JP-A-58 -145739 (JP, A) JP 60-235850 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08J 9/16
Claims (7)
の芯層と、前記熱可塑性樹脂より融点が低いか、また
は、実質的に融点を示さないエチレン系重合体から成
り、且つ、実質的に非発泡状態である被覆層とから構成
されていることを特徴とする発泡樹脂粒子。1. A foamed core layer made of a crystalline thermoplastic resin, and an ethylene-based polymer having a melting point lower than or substantially no melting point of the thermoplastic resin, A foamed resin particle comprising a non-foamed coating layer.
に対して芯層と同一の結晶性の熱可塑性樹脂を１〜１０
０重量部ブレンドした組成物である請求項１に記載の発
泡樹脂粒子。2. The coating layer contains 1 to 10 parts of the same crystalline thermoplastic resin as the core layer based on 100 parts by weight of the ethylene polymer.
The expanded resin particles according to claim 1, which is a composition obtained by blending 0 part by weight.
融点のエチレン系重合体を使用する請求項１又は２に記
載の発泡樹脂粒子。3. The expanded resin particles according to claim 1, wherein an ethylene polymer having a melting point lower than the melting point of the thermoplastic resin by 15 ° C. or more is used.
である請求項１〜３の何れかに記載の発泡樹脂粒子。4. The expanded resin particles according to claim 1, wherein the ethylene polymer has a melting point of 125 ° C. or lower.
求項１〜４の何れかに記載の発泡樹脂粒子。5. The expanded resin particle according to claim 1, wherein the coating layer has a thickness of 1 to 150 μm.
求項１〜５の何れかに記載の発泡樹脂粒子。6. The expanded resin particles according to claim 1, wherein the weight of one particle is 0.1 to 10 mg.
前記熱可塑性樹脂より融点が低いか、または、実質的に
融点を示さないエチレン系重合体から成る被覆層にて構
成される複合体粒子に揮発性発泡剤を含浸させた後、加
熱発泡して得られる請求項１〜６の何れかに記載の発泡
樹脂粒子。7. A core layer made of a crystalline thermoplastic resin,
A volatile foaming agent is impregnated into the composite particles having a melting point lower than that of the thermoplastic resin or a coating layer made of an ethylene-based polymer having substantially no melting point, and then heat-foamed. The expanded resin particles according to claim 1, which are obtained.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01792797A JP3418081B2 (en) | 1996-07-10 | 1997-01-16 | Expanded resin particles |
| TW086119979A TW424103B (en) | 1996-07-10 | 1997-12-30 | Expanded resin beads |
| US09/003,342 US6027806A (en) | 1997-01-16 | 1998-01-06 | Expanded resin beads |
| CN98103793A CN1122071C (en) | 1997-01-16 | 1998-01-06 | Expanded resin beads |
| ES98300088T ES2190041T3 (en) | 1997-01-16 | 1998-01-07 | EXPANDED RESIN BALLS. |
| EP98300088A EP0928806B1 (en) | 1997-01-16 | 1998-01-07 | Expanded resin beads |
| DE69812571T DE69812571T2 (en) | 1997-01-16 | 1998-01-07 | Expanded resin beads |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19975996 | 1996-07-10 | ||
| JP8-199759 | 1996-07-10 | ||
| JP01792797A JP3418081B2 (en) | 1996-07-10 | 1997-01-16 | Expanded resin particles |
| US09/003,342 US6027806A (en) | 1997-01-16 | 1998-01-06 | Expanded resin beads |
| EP98300088A EP0928806B1 (en) | 1997-01-16 | 1998-01-07 | Expanded resin beads |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1077359A JPH1077359A (en) | 1998-03-24 |
| JP3418081B2 true JP3418081B2 (en) | 2003-06-16 |
Family
ID=27443706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01792797A Expired - Lifetime JP3418081B2 (en) | 1996-07-10 | 1997-01-16 | Expanded resin particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3418081B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4336440B2 (en) | 2000-04-21 | 2009-09-30 | 株式会社ジェイエスピー | Polyolefin resin composite molded body |
| JP4272016B2 (en) * | 2002-09-02 | 2009-06-03 | 株式会社ジェイエスピー | Polypropylene resin expanded particles and in-mold molded body using the same |
| TW200533701A (en) | 2004-01-28 | 2005-10-16 | Jsp Corp | Thick foam molding and process for production thereof |
| JP2005240025A (en) * | 2004-01-28 | 2005-09-08 | Jsp Corp | Thick-walled foam molded product and method for manufacturing the same |
| WO2009047998A1 (en) | 2007-10-11 | 2009-04-16 | Kaneka Corporation | Pre-expanded polypropylene resin particle, and method for production thereof |
| US20090169895A1 (en) | 2007-12-27 | 2009-07-02 | Jsp Corporation | Foamed polyolefin resin beads |
| SG176841A1 (en) | 2009-06-26 | 2012-01-30 | Jsp Corp | Expanded polypropylene resin beads and expanded bead molding |
| JP5356157B2 (en) * | 2009-08-28 | 2013-12-04 | 積水化成品工業株式会社 | Vehicle seat core |
| JP6096564B2 (en) * | 2013-03-29 | 2017-03-15 | 積水化成品工業株式会社 | Method for producing foam molded body and foam molded body |
| JP6211913B2 (en) | 2013-12-11 | 2017-10-11 | 株式会社ジェイエスピー | Polyolefin resin expanded particles |
| US10385178B2 (en) | 2014-01-17 | 2019-08-20 | Jsp Corporation | Propylene-based resin foam particle and foam particle molded body |
| US10336880B2 (en) | 2015-01-09 | 2019-07-02 | Jsp Corporation | Propylene resin foam particles and foam particle molded article |
| JP6060220B1 (en) | 2015-07-15 | 2017-01-11 | 株式会社ジェイエスピー | Propylene-based resin expanded particles and expanded molded articles |
| CN111234292B (en) * | 2020-03-13 | 2022-06-14 | 广州骆驼家居家纺科技有限公司 | Foaming particles, preparation method and application thereof |
-
1997
- 1997-01-16 JP JP01792797A patent/JP3418081B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1077359A (en) | 1998-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1707592B1 (en) | Method of producing expanded polypropylene beads | |
| JP3418081B2 (en) | Expanded resin particles | |
| WO2020049802A1 (en) | Polyamide resin foamed particles and method for producing same | |
| JP3441165B2 (en) | Flame retardant polyolefin resin foam particles | |
| JPH0739501B2 (en) | Non-crosslinked linear low density polyethylene pre-expanded particles | |
| JPH0386736A (en) | Production of foamed polyolefin resin particle | |
| JPS6215239A (en) | Uncrosslinked straight chain low-density polyethylene preexpanded partifle and molding thereof | |
| JP2805286B2 (en) | Polyolefin-based resin foam molded article having communicating voids and method for producing the same | |
| EP0928806B1 (en) | Expanded resin beads | |
| JP2003039565A (en) | Foamed particle molded object | |
| JP4157206B2 (en) | Polypropylene resin foamed particles and molded polypropylene resin foam particles | |
| JP3692760B2 (en) | Method for producing foamed molded product in polypropylene resin mold | |
| JP3858517B2 (en) | Polypropylene resin pre-expanded particles, and method for producing the pre-expanded particles and in-mold foam molding | |
| WO2018084245A1 (en) | Foam particles and foam particle molded body | |
| JP3950557B2 (en) | Polypropylene-based resin pre-expanded particles and method for producing in-mold expanded molded articles therefrom | |
| JP2000000894A (en) | Production of thermoplastic resin foam molding | |
| JP2777429B2 (en) | Pre-expanded polypropylene resin particles and method for producing the same | |
| JP2001162640A (en) | Method for manufacturing thermoplastic resin foamed molding | |
| JP4940688B2 (en) | Method for producing polypropylene resin pre-expanded particles | |
| JP2000129028A (en) | Polypropylene resin foamed particle and molded product thereof | |
| JP3504055B2 (en) | Flame-retardant polyolefin resin foam particles and in-mold foam molded article using the same | |
| JP5399126B2 (en) | Method for producing polyolefin resin expanded particles and polyolefin resin expanded particles | |
| US20040151879A1 (en) | Polypropylene resin molding composite for automobile | |
| JP2790791B2 (en) | Method for producing foamed molded article in polypropylene resin mold | |
| JPH08113667A (en) | Molded linear low-density polyethylene resin foam and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20030324 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090411 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090411 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100411 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110411 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110411 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120411 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130411 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130411 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140411 Year of fee payment: 11 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |