JP4503720B2 - Method for producing foamed article with skin - Google Patents
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- JP4503720B2 JP4503720B2 JP01716399A JP1716399A JP4503720B2 JP 4503720 B2 JP4503720 B2 JP 4503720B2 JP 01716399 A JP01716399 A JP 01716399A JP 1716399 A JP1716399 A JP 1716399A JP 4503720 B2 JP4503720 B2 JP 4503720B2
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Description
【０００１】
【発明の属する技術分野】
本発明は表皮付き発泡成形体の製造方法に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
ブロー成形等によって得られる中空成形体の内部に熱可塑性樹脂発泡粒子を充填し、スチーム等によって加熱して発泡粒子相互を融着させて得られる表皮付き発泡成形体は、箱型容器、建築パネル、緩衝材、自動車内装材等の各種の分野において広く利用されている。この種の表皮付き発泡成形体を製造する場合、中空成形体がスチーム透過性に乏しいと、加熱用スチームが中空成形体内に充填された発泡粒子間に充分に浸透し難い。
【０００３】
このような問題を解決し得る方法として、中空成形体内に充填した発泡粒子層内にスチーム供給用ピンを差し込み、発泡粒子層の内部にまでスチームが浸透するようにし、発泡粒子相互が融着する前にスチーム供給用ピンを抜き取る方法が提案されている（特公昭６２−１９２９３号公報、実公昭６２−９０７３号公報等）。しかしながら、発泡粒子として、一般に略球状発泡粒子が用いられているため、中空成形体内に充填された発泡粒子の深層部までスチームが浸透し難いことから、中空成形体内に充填した発泡粒子相互の融着性や、発泡粒子と中空成形体との融着性がある場合、融着性に劣る表皮付き発泡成形体しか得られないという問題があった。特に、複雑な構造のものや、厚さが厚い表皮付き発泡成形体を得ようとした場合には、上記した融着不良は著しくなるという問題があった。
【０００４】
本発明は上記従来の問題を解決するためになされたもので、発泡体片相互の融着性が優れた表皮付き発泡成形体を製造することのできる方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
即ち本発明の表皮付き発泡成形体の製造方法は、熱可塑性樹脂発泡体片を、熱可塑性樹脂からなり、内面側が該発泡体片と融着性を有する素材である中空ブロー成形体の内部に充填した後に、中空ブロー成形体の内部に差し込んだ孔が設けられたピンより加熱媒体を供給して、発泡体片相互間を融着させ、かつ発泡体片と中空ブロー成形体内面とを融着させることによる、発泡体片成形体と中空ブロー成形体とが融着している表皮付き発泡成形体の製造方法であって、該発泡体片が筒状の発泡粒子で、該発泡体片の最密充填時の空間率が４５〜７０％であることを特徴とする。
【０００６】
本発明において、中空ブロー成形体（以下、単に「中空成形体」ということがある。）の内部に、孔が設けられた少なくとも２本のピンを差し込み、少なくとも１本のピンより加熱媒体を供給すると共に、他方の少なくとも１本のピンより加熱媒体を吸引して、該発泡体片を加熱することが好ましい。
また前記ピンによる加熱媒体の供給、吸引を所定時間毎に交替して行うこともできる。
【０００７】
【発明の実施の形態】
本発明において用いる熱可塑性樹脂発泡体片の基材樹脂としては、ポリ塩化ビニル等の塩化ビニル系樹脂、ポリスチレン等のポリスチレン系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂等のポリオレフィン系樹脂、ポリメチルメタクリレート等のアクリル系樹脂、ポリカーボネート樹脂等が挙げられる。上記ポリエチレン系樹脂やポリプロピレン系樹脂としては、例えば低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、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、エチレン−プロピレンブロック共重合体、エチレン−プロピレンランダム共重合体、エチレン−ブテンブロック共重合体、エチレン−ブテンランダム共重合体、エチレン−酢酸ビニル共重合体、エチレン−メチルメタクリレート共重合体、エチレン−メタクリル酸共重合体の分子間を金属イオンで架橋したアイオノマー系樹脂、プロピレン単独重合体、プロピレン−エチレンランダム共重合体、プロピレン−ブテンランダム共重合体、プロピレン−エチレンブロック共重合体、プロピレン−ブテンブロック共重合体、ポリブテン、ポリペンテン、プロピレン−エチレン−ブテン三元共重合体、プロピレン−アクリル酸共重合体、プロピレン−無水マレイン酸共重合体等が挙げられる。また、これらの他に、エチレン、プロピレン、ブテン、ペンテン等のオレフィン系モノマーと、これらオレフィン系モノマーと共重合し得るスチレン等のモノマーとの共重合体も使用することができる。
【０００８】
上記熱可塑性樹脂のなかでも、緩衝性、圧縮歪回復性が良好な、ポリオレフィン系樹脂が好ましく、なかでも低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、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等のポリエチレン系樹脂や、ポリプロピレン、ポリブテン、プロピレン−エチレン共重合体、プロピレン−ブテン共重合体、プロピレン−エチレン−ブテン三元共重合体が好ましく、特にプロピレン−エチレンランダム共重合体、プロピレン−ブテンランダム共重合体、プロピレン−エチレン−ブテン三元共重合体、直鎖状低密度ポリエチレンが好ましい。
【０００９】
上記ポリオレフィン系樹脂は、過酸化物や放射線により架橋したものを用いても、無架橋のまま用いても良いが、生産工程が簡易で、リサイクルの可能な無架橋のものが好ましい。
【００１０】
本発明において、中空成形体の内部に充填される熱可塑性樹脂発泡体片としては、最密充填時の空間率が４５〜７０％、好ましくは５０〜７０％の形状を有するものが良い。空間率が４５％未満であると、加熱媒体の透過性が悪く発泡体片相互間の融着が悪い表皮付き発泡成形体しか得られないため好ましくない。上記のような形状を有するものを、１種又は２種以上混合して用いることができる。上記最密充填時の空間率とは、熱可塑性樹脂発泡体片の一定量をメスシリンダー等の目盛り付き容器に充填し、容器を上下に振動させて熱可塑性樹脂発泡体片を圧縮することなく、発泡体片の嵩が最小となるようにした時の、容器の目盛りから求められる一定量の発泡体片の体積を見掛けの体積：Ａ（ｃｍ３ ） とし、次に見掛けの体積を測定した後の発泡体片を、アルコールを入れた目盛り付き容器のアルコール中に沈めてアルコールのみの時の容積からの増加分から、一定量の発泡体片の真の体積：Ｂ（ｃｍ３ ） を求め、見掛け体積：Ａと真の体積：Ｂとから下記式より求められるものである。
【００１１】
【数１】
空間率（％）＝｛（Ａ−Ｂ）／Ａ｝×１００
【００１２】
本発明方法において発泡体片を融着させる加熱媒体としては、スチーム、熱風等が挙げられるが、工業的に有利なスチームが好ましい。
【００１３】
また本発明において成形に用いる熱可塑性樹脂発泡体片としては、上記熱可塑性樹脂を基材樹脂とする、筒状の発泡粒子や、後述する表面に突起を有する発泡粒子が好ましい。
【００１５】
筒状の発泡粒子としては、外部に連通する中空穴を有する形状であるとともに（以下、中空穴が外部に連通する方向を「穴方向」と呼ぶ。）、（ａ）穴方向に垂直な断面（以下、この断面を「垂直断面」と呼ぶ。）における外周形状及び中空穴形状が共に円形であるもの、（ｂ）垂直断面における外周形状及び中空穴形状が共に多角形であるもの、（ｃ）垂直断面における外周形状、中空穴形状のいずれか一方が円形で、他方が多角形であるもの、（ｄ）上記（ａ）〜（ｃ）の如き断面形状を有するものを、その外周において互いに複数結合せしめたもの、（ｅ）穴方向に垂直な、どの断面においても突起が設けられた上記（ａ）〜（ｄ）の如き断面形状を有するもの、（ｆ）ある垂直断面においては上記（ａ）〜（ｄ）の如き断面形状を有しており、別の垂直断面においては突起が設けられた上記（ａ）〜（ｄ）の如き断面形状を有するもの等を例示することができる。
【００１６】
図１の（ア）〜（ソ）に示す発泡粒子のうち、上記（ａ）に対応するものとしては、（ア）の発泡粒子が、（ｂ）に対応するものとしては（イ）〜（エ）の発泡粒子が、（ｃ）に対応するものとしては（オ）、（カ）の発泡粒子が、（ｄ）に対応するものとしては（キ）、（ク）の発泡粒子が、（ｅ）に対応するものとしては（ケ）〜（ス）の発泡粒子が、（ｆ）に対応するものとしては（セ）、（ソ）の発泡粒子が挙げられる。尚、図１において、１は発泡粒子、Ｐは中空穴、ｅは突起を示す。
【００１７】
図１に示した発泡粒子は、本発明において用い得る筒状の発泡粒子の一例に過ぎず、この他にも垂直断面における外周形状や中空穴形状が楕円状、正多角形以外の多角形状となるもの、穴方向に沿って発泡粒子の一部がくびれているもの、穴方向に沿って発泡粒子が捩れているもの、垂直断面においてその中心から中空穴がずれているもの等、筒状の発泡粒子であればいかなる形状のものも使用可能である。尚、本発明において、垂直断面形状がＣ字型等になるように筒状発泡粒子の一部が切り裂かれた形状のものも筒状の発泡粒子に含めるものとする。
【００１８】
上記筒状の発泡粒子は、垂直断面における最大外径：Ｄと、穴方向に沿った最大長さ：Ｌとの比、Ｌ／Ｄが０．２〜５．０、特に０．５〜２．０であることが好ましい。筒状の発泡粒子のＬ／Ｄが０．２〜５．０の範囲にある場合には、発泡粒子の中空成形体内部への充填性が良好になるとともに、発泡粒子相互の融着性が良好となるため好ましい。上記最大外径：Ｄは、図１の（ア）、（キ）、（ケ）、（セ）に示す如く垂直断面における外周と接する２本の平行する接線間の距離の最大値であり、ノギスにより測定することができる。また、Ｌについても図１（ア）、（ケ）に示す如き最大長さであり、ノギスにより測定することができる。
【００１９】
図１に示す（ア）〜（ク）の発泡粒子のように突起ｅを有さないものは、発泡粒子を中空成形体内部に充填する際の充填機内等における発泡粒子の詰まりが生じ難く、中空成形体内部に均一な充填をし易いため好ましい。更に、（ア）、（キ）、（ク）の発泡粒子のように垂直断面における外周形状及び中空穴形状がともに円形であるものは、発泡粒子の製造が比較的容易であるため好ましい。
【００２１】
上記したように本発明においては、図１に示した如き各種の筒状の発泡粒子を用いることができるが、特に熱可塑性発泡粒子の基材樹脂がオレフィン系樹脂である場合、熱可塑性樹脂中空成形体内部で発泡粒子同士を融着させることが難しい。このため、加熱媒体を深層部まで浸透させ、確実に融着させることのできる、図１の（ア）、（オ）に示した如き筒状の発泡粒子、特に円筒状の発泡粒子が好ましい。尚、図１の（ア）、（オ）に示した如き円筒形状の発泡粒子は、垂直断面の外周形状が真円形でなくとも、略円形を有していれば良い。
【００２２】
特に上記筒状の発泡粒子は、平均粒子重量が１〜５０ｍｇのものが好ましいが、より好ましくは平均粒子重量が１〜１０ｍｇのものである。平均粒子重量が１ｍｇに満たない発泡粒子は製造そのものが困難であり、５０ｍｇを超えると成形時の中空成形体への充填性が悪くなり易い。また平均粒子重量によっても異なるが、例えば平均粒子重量が１〜１０ｍｇの筒状の発泡粒子の場合、任意の垂直断面における中空穴の最小径をｄMIN 、同じ垂直断面における外周の最小径をＤMIN とした時、ｄMIN が０．５ｍｍ以上で、且つｄMIN ／ＤMIN の値が０．３０〜０．９０であることが好ましく、より好ましくはｄMIN が１．０ｍｍ以上で、且つｄMIN ／ＤMIN の値が０．４０〜０．８５である。尚、ｄMIN の上限は２０ｍｍ、特に１０ｍｍ以下であることが好ましい。
【００２３】
ｄMIN とＤMIN との間に上記関係が成り立つ円筒形状の発泡粒子を用いて成形すると、収縮率が小さく、粒子相互の融着性がより良好な表皮付き発泡成形体を得ることができる。またｄMIN ／ＤMIN の値が０．９０を超える発泡粒子は、製造そのものが難しいという問題があるとともに、寸法安定性に欠ける表皮付き発泡成形体となり易い。
【００２４】
尚、図１の（キ）、（ク）、（ソ）等のように複数の中空穴が存在する場合には、その全ての中空穴について、また（ケ）〜（ソ）等のように外周に突起が設けられている場合には突起を除いた形状について、上記の関係が満たされていることが好ましい。
【００２５】
本発明方法では発泡体片として、上記した発泡粒子を用いるため、中空成形体が加熱媒体の透過性を有していなくても、中空成形体内に充填された発泡体片の深層部まで、加熱媒体が発泡体片間を透過して到達し、この結果、中空成形体の内側付近に位置して充填された発泡体片が充分に加熱され、中空成形体内側付近の発泡体片相互間が確実に融着され、中空成形体の内面側が発泡体片と融着性を有する素材である場合、発泡体片と中空成形体との間が確実に融着される。
【００２６】
上記発泡粒子は、例えば密閉容器内で熱可塑性樹脂粒子と発泡剤とを分散媒に分散させ、攪拌しながら加熱して樹脂粒子中に発泡剤を含浸させ、次いで発泡温度にて樹脂粒子と分散媒とを容器内より低圧下（通常は、大気圧下）に放出し、樹脂粒子を発泡させる等の方法によって得ることができる。
【００２７】
発泡粒子製造に用いる熱可塑性樹脂粒子は、基材樹脂を押出機内で溶融混練した後、ダイスからストランド状に押出して冷却した後、適宜長さに切断する等の方法で得ることができるが、押出機内で基材樹脂を溶融混練する際に、必要に応じてタルク、炭酸カルシウム、硼砂、水酸化アルミニウム、ホウ酸亜鉛等の無機物を添加して樹脂と溶融混練し、樹脂粒子中にこれらの無機物を含有せしめても良い。また用途や目的に応じ、黒色、灰色、茶色、黄色、赤色、桃色、緑色、青色等の着色顔料や染料を添加して着色することもできる。樹脂粒子中に上記無機物や着色顔料、染料等を添加する場合、これらの分散性を考慮して、通常はマスターバッチ法を採用する。無機物や着色顔料、染料の添加量は、通常、樹脂粒子１００重量部当たり、０．００１〜５重量部である。樹脂粒子中に無機物を含有させると、発泡粒子の発泡倍率を向上でき、また気泡径を二次発泡性、寸法安定性において好適な５０〜３５０μｍに調整することができる。
【００２８】
溶融した樹脂をダイスから押出す際に、得ようとする発泡粒子の断面形状と略相似形状の樹脂押出口を有するダイス（例えば筒状発泡粒子を得る場合は筒状発泡粒子の垂直断面形状と略相似形状の樹脂押出口を有するダイス）を用いることにより、目的形状の発泡粒子と相似形状の樹脂粒子を得ることができ、このような樹脂粒子を用いて上記したように発泡を行えば、目的形状の発泡粒子を得ることができる。
【００２９】
発泡粒子製造に用いる上記分散媒としては、樹脂粒子を溶解させないものであれば良く、例えば水、エチレングリコール、グリセリン、メタノール、エタノール等が挙げられるが、通常は水が使用される。また発泡剤としては、通常、プロパン、ブタン、ヘキサン、シクロブタン、シクロヘキサン、トリクロロフロロメタン、ジクロロフロロメタン、クロロフロロメタン、トリフロロメタン、1,1,1,2-テトラフロロエタン、1-クロロ-1,1- ジフロロエタン、1,1-ジフロロエタン、1-クロロ-1,2,2,2- テトラフロロエタン等の揮発性発泡剤や、窒素、二酸化炭素、アルゴン、空気等の無機ガス系発泡剤が用いられる。また揮発性発泡剤と無機ガス系発泡剤との混合発泡剤を使用することもできる。これらのうち、オゾン層破壊の虞れがなく、安価な無機ガス系発泡剤が好ましく、特に窒素、二酸化炭素、空気が好ましい。窒素、空気以外の上記発泡剤の使用量は、通常、樹脂粒子１００重量部当たり、２〜５０重量部であり、また窒素、空気の場合、その使用量は密閉容器内へ圧入する圧力範囲が５〜６０ｋｇｆ／ｃｍ2 Ｇとなるように添加することが好ましい。発泡剤の使用量は、得ようとする発泡粒子の発泡倍率等に応じて適宜調整する。
【００３０】
上記樹脂粒子と発泡剤とを分散媒に分散させて加熱するに際し、樹脂粒子相互の融着を防止するため、融着防止剤を分散媒に添加することができる。融着防止剤としては分散媒に溶解せず、加熱によって溶融しないものであれば無機系、有機系を問わず使用可能であるが、一般には無機系のものが好ましい。無機系の融着防止剤としては、カオリン、タルク、マイカ、酸化アルミニウム、酸化チタン、水酸化アルミニウム等の粉体が好適である。融着防止剤は、平均粒径０．００１〜１００μｍ、特に０．０１〜３０μｍのものが好ましい。融着防止剤は樹脂粒子１００重量部に対し、通常、０．０１〜１０重量部を添加することが好ましい。また分散助剤として、ドデシルベンゼンスルホン酸ナトリウム、オレイン酸ナトリウム等のアニオン系界面活性剤を併用することができる。分散助剤は樹脂粒子１００重量部当たり、通常、０．００１〜５重量部を分散媒に添加することが好ましい。
【００３１】
尚、発泡粒子は発泡前の樹脂粒子よりも全体の寸法が大きくなっているが、通常、発泡粒子のｄMIN ／ＤMIN 及びＬ／Ｄの値と、これに対応する未発泡の樹脂粒子のｄMIN ´／ＤMIN ´及びＬ´／Ｄ´の値とは殆ど変わらず、未発泡の樹脂粒子のｄMIN ´／ＤMIN ´、Ｌ´／Ｄ´の値が前記条件を満たしていれば、発泡粒子のｄMIN ／ＤMIN 、Ｌ／Ｄの値も前記条件を概ね満たしている。
【００３３】
本発明において熱可塑性樹脂からなる中空成形体の基材樹脂は、上記した熱可塑性樹脂発泡体片の基材樹脂と同様なものが挙げられる。
【００３４】
本発明において中空成形体としては、ブロー成形等の方法で、所望の形状に成形したものを用いることができる。例えばブロー成形で中空成形体を得るには、熱可塑性樹脂のパリソンを金型上方より降下させ、金型でパリソンを挟み、パリソン内にエアーブローピンより空気を吹き込んでパリソンを膨らませるとともに、金型に設けた吸引穴より吸引してパリソンを金型内面に密着させることで中空成形体を形成する。また予め成形したものではなくとも良く、中空成形体と表皮付き発泡成形体とを同一の金型で製造しても良く、例えば熱可塑性樹脂の中空成形体を成形した後、発泡体片を中空成形体に充填して表皮付き発泡成形体としても良い。中空成形体は未発泡、発泡の単層構造のものに限らず、未発泡層や発泡層等を有する多層構造のものであっても良い。また、中空成形体の内面側は、発泡体片と融着性を有する素材を用いるので、高強度、高剛性の表皮付き発泡体成形体を要求する場合は、融着性を有する素材で構成されていることにより、発泡体片成形体と中空成形体との融着性に優れた表皮付き発泡成形体が得られる。中空成形体の肉厚は１〜５ｍｍのものが好ましい。中空成形体の肉厚が１ｍｍ未満であると中空成形体の形状保持が悪くなる虞れがあり、５ｍｍを超えると表皮付き発泡成形体の重量が重くなることから好ましくない。中空成形体の形状としては、例えば貫通した筒状、底のある筒状、中空板状、箱型容器状等の形状のものを用いることができる。
【００３５】
熱可塑性樹脂発泡粒子と熱可塑性樹脂からなる中空成形体との融着性を有する素材は、熱可塑性樹脂発泡粒子の基材樹脂の違いによって異なる。熱可塑性樹脂発泡粒子の基材樹脂が、例えばポリプロピレン系樹脂である場合、熱可塑性樹脂からなる中空成形体の基材樹脂もポリプロピレン系樹脂やポリプロピレン系熱可塑性エラストマーであること、発泡粒子の基材樹脂がポリエチレン系樹脂である場合には、熱可塑性樹脂からなる中空成形体の基材樹脂もポリエチレン系樹脂であることが好ましいが、発泡粒子と融着性を有するものであればこれらに限定されない。
【００３６】
上記した熱可塑性樹脂発泡粒子と融着性を有する中空成形体の素材としては、使用する熱可塑性樹脂発泡粒子の基材樹脂の融点以下の融点を有するものを選択すると、発泡粒子と中空成形体との融着性が更に良好となり好ましい。
【００３７】
中空成形体が多層構造の場合、表面側（熱可塑性樹脂発泡体片と接しない側）を構成する素材としては、上記した熱可塑性樹脂発泡体片との融着性を有する素材の他に、熱可塑性樹脂発泡体片と融着性を有さないポリ塩化ビニル等や、ポリエステル系樹脂等の素材も用いることができる。
【００３８】
高強度、高剛性の表皮付き発泡成形体を得ようとする際は、中空成形体の素材（多層構造の場合には、少なくとも内面側の素材）と、発泡体片の基材樹脂とは、上記したように相互に熱融着性を有するような素材を選択することが好ましい。特に本発明の表皮付き発泡成形体を、例えば自動車内装材やバンパー等の車両用として用いる場合、耐熱性、剛性、エネルギー吸収性、リサイクル性等を考慮すると、中空成形体の素材、発泡体片の基材樹脂ともに、ポリプロピレン系樹脂を選択することが好ましい。また本発明の表皮付き発泡成形体を寝具、家具等に使用する場合、クッション性等を考慮すると、発泡体片の基材樹脂としてポリエチレン系樹脂、特に直鎖状低密度ポリエチレンが好ましく、中空成形体の素材（或いは中空成形体の内面側の素材）も、これと熱融着性を有するポリエチレン系樹脂を選択することが好ましい。
【００３９】
また本発明の製造方法で得られる表皮付き発泡成形体（以下、単に「本発明の表皮付き発泡成形体」とも言う。）において、連通した空隙を有する発泡体片成形体を得るために、中空成形体内に充填される発泡体片としては、前述した通り最密充填時の空間率が４５〜７０％となる筒状の発泡粒子であることを必要とするが、特に円筒状の発泡粒子が好ましい。前記発泡体片を用いたため発泡体片相互の融着性に優れ、中空成形体の内層側が発泡体片と融着生を有するので、発泡体片成形体と中空成形体との融着性に優れた表皮付き発泡成形体となる。本発明の表皮付き発泡成形体において連通した空隙を有する発泡体片成形体の空隙率は５％以上であることが好ましい。さらに５〜７５％の空隙率が好ましく、特に１０〜４５％の空隙率が好ましい。空隙率が５％未満の発泡体片成形体であると、通気性のある断熱パネル、吸音、防音のパネル等、更に濾過材、透水材、保水材等として利用できないため好ましくない。上記発泡体片成形体の空隙率（％）は、発泡体片成形体サンプルの外形寸法（２５ｍｍ×２５ｍｍ×１００ｍｍ）より求めた体積をａ（ｃｍ３ ）、該サンプルをアルコールを入れた目盛り付き容器のアルコール中に沈めた時の、目盛りの上昇分から求められるサンプルの真の体積をｂ（ｃｍ３ ）としたとき、下記式より求められる値である。
【００４０】
【数２】
空隙率（％）＝｛１−（ｂ／ａ）｝×１００
【００４１】
本発明の表皮付き発泡体を得る方法としては、例えば、ブロー成形機により中空成形体を得て、金型に中空成形体を装着し、発泡体片を金型に装着した中空成形体内部に充填して成形し、表皮付き成形体を得る方法、中空成形体を成形する機能をも有する金型で中空成形体の成形と表皮付き発泡体の成形とを行う方法、中空成形体自体に剛性が有る場合には、金型を使用しないで中空成形体内部に発泡体片を充填して表皮付き発泡体を得る方法が挙げられる。
【００４２】
上記表皮付き発泡成形体を得る金型は、例えば凹型と凸型とからなる合せ金型で、表皮付き発泡成形体を金型面の冷却により間接冷却するための空間を有し、発泡体片を中空成形体内に充填するフィーダー、加熱媒体を供給、エアー又は加熱媒体を吸引させるスリット状又は円形状の孔を多数配置したピンを有している。特に中空成形体を成形する機能をも有する場合には、パリソンを膨らませるためのエアーブローピンを金型下方より挿入するための穴が金型に設けられている。
【００４３】
また本発明において中空成形体自体で剛性が有る場合、発泡体片が最密充填時の空間率４５〜７０％の形状であることから、スチームが発泡体片の相互に透過しやすいため、スチーム圧力が低くできる。よって、中空成形体の強度があれば上記のような表皮付き発泡成形体製造用金型がなくとも可能である。
【００４４】
図２は本発明の表皮付き発泡成形体２の一例を示し、３は中空成形体、４は発泡体片１の相互を融着させて形成される発泡体片成形体である。図３は本発明の表皮付き発泡成形体を製造装置の一例を略図的に示すもので、図中、５は金型、６は中空成形体の内部に発泡体片を充填するフィーダーである。この充填方法としては、圧縮充填方法、加圧充填方法等の公知の充填法を採用することができる。また７、８は加熱用スチームを供給したり、供給されたスチームを吸引したり、スチームのドレンを吸引するためのピンで、該ピン７、８は、エアシリンダー９、１０にガイドされて摺動し、金型５内に装着された中空成形体３内に充填された発泡体片１の層内への差し込みや、引き抜きが可能に構成されている。上記のピンは発泡体片よりも小さい孔、スリット状又は円形状の孔が多数あいており、中空成形体の大きさにより一本または、複数本挿入させ成形することができる。
【００４５】
本発明において表皮付き発泡成形体を得る方法の一例として、金型５内に中空成形体３を装着した後、フィーダー６より発泡体片１を中空成形体３内に充填し、次いで中空成形体３内に充填された発泡体片１の層内に差し込まれたピン７、８の一方より、加熱用スチームを供給することにより発泡体片１を加熱する方法を用いることができるが、この際に他方のピンよりスチームを吸引することによりスチームの流れが円滑になり、供給したスチームを発泡体片１間に満遍なく浸透させることができる。またピンを所定時間毎に交替して加熱、吸引を行うことにより、更に円滑にスチームを供給することができる。加熱用スチーム供給後、ピン７、８の一方又は両方から吸引することにより、発泡体片１間に溜まっている熱やドレンを効率よく排出することができる。このようにして加熱、冷却した後、ピン７、８を抜き取り、得られた成形体を金型５から取り出して養生する。養生は、６０℃、大気圧下で２４時間程度行うことが好ましい。
【００４６】
本発明の表皮付き発泡成形体の製造方法により得られる、発泡体片成形体の表面を熱可塑性樹脂からなる中空成形体にて被覆してなる表皮付き発泡成形体としては、例えば熱可塑性発泡体片成形体の全面を被覆した表皮付き発泡成形体が挙げられる。このような表皮付き発泡成形体の用途としては、例えばパレット、台車等の流通分野、断熱パネル、防音パネル等の建築分野、濾過材、透水材等の土木分野、各種浮力用部材、自動車内装用、バンパー材、家具、寝具等が挙げられる。
【００４７】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明する。
【００４８】
実施例１
エチレン−プロピレンブロック共重合体（ＭＩ＝０．６ｇ／１０分（２３０℃、荷重２．１６ｋｇｆ）、融点１６１℃、エチレン含量７．０重量％）の層と、内層がプロピレン−エチレンランダム共重合体（ＭＩ＝８ｇ／１０分、融点１３２℃、エチレン含量５．８重量％）の層からなる２層構成のパリソン（プロピレン−エチレンランダム共重合体の層が内面側）を共押出法によって押出機より押出し、このパリソンを中空成形体製造用金型（縦４００ｍｍ×横２５０ｍｍ×深さ１００ｍｍ）の上方から金型に供給し、パリソン内に空気を吹き込みながら金型を型締めし、冷却して中空成形体（肉厚２．６ｍｍ）を得た。次にこの中空成形体を、発泡粒子供給用フィーダーを備えた表皮付き発泡成形体製造用の金型（縦３９６ｍｍ×横２４８ｍｍ×深さ１００ｍｍ）内に装着して型締めした後、プロピレン−エチレンランダム共重合体（エチレン含量２．４重量％、融点１４６℃）を基材樹脂とする、図１の（ア）に示す形状の円筒形状の発泡粒子（平均粒子重量２ｍｇ、嵩発泡倍率２０倍、ｄMIN ＝１．６ｍｍ、ＤMIN ＝２．５ｍｍ、ｄMIN ／ＤMIN ＝０．６４、Ｌ＝３．５ｍｍ、Ｌ／Ｄ＝１．０、粒子内圧２．０ｋｇ／ｃｍ2 （絶対圧））を中空成形体内に充填した。
【００４９】
中空成形体内に発泡粒子を充填する際、中空成形体内に差し込まれた両方のピンより中の空気を吸引しながら充填した後、充填された発泡粒子の層内に差し込んだ片方のピンから、吸引しながらもう一方のピンよりスチームを５秒間供給し、次いでスチームを供給していたピンと吸引していたピンを交換し、吸引しながらスチームを５秒間供給し、発泡粒子の層内に残存する空気を排気した後、１５０℃のスチームを両方のピンから発泡粒子の層内に供給して発泡粒子を加熱成形した。次いで、発泡粒子の層（この時点では発泡粒子は相互に融着している。）内に差し込んだピンにより吸引冷却した後、型を開いて表皮付き発泡成形体を取り出した。この成形体を６０℃、大気圧下で２４時間養生し、室温下で保持した。成形に用いた発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００５０】
【表１】
【表２】
【表３】
※４ 折り曲げ破断試験：発泡体片（発泡粒子）の融着性を評価し、具体的には図５に示すように表皮付き発泡成形体の内部（Ａ）と表皮付近（Ｂ）とから切り出したサンプル（サイズ：２５ｍｍ×２５ｍｍ×１００ｍｍ）を折り曲げて破断させ、各々の破断面を観察し、
○・・・発泡体片（発泡粒子）の大部分に材料破壊が起こっている。
△・・・発泡体片（発泡粒子）の材料破壊と発泡粒子相互間の界面剥離が混在している。
×・・・発泡体片（発泡粒子）相互間の大部分が界面剥離している。
として評価した。
【００５５】
※５ 表皮材と発泡体片（発泡粒子）の融着性は、表皮付き発泡成形体を幅１５ｍｍに切り出したサンプルにおける表皮材の９０°剥離試験を行い、剥離面の発泡体片（発泡粒子）の状態を観察し、
○・・・発泡体片（発泡粒子）の大部分に材料破壊が起こっている。
×・・・発泡体片（発泡粒子）の大部分が界面剥離している。
として評価した。
【００５６】
実施例２
嵩発泡倍率１０倍の、図１の（ア）に示す円筒形状の発泡粒子を使用した他は、実施例１と同様の条件で表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００５７】
実施例３
中空成形体製造用金型及び表皮付き発泡成形体製造用金型の深さを１５０ｍｍとした他は、実施例１と同様の条件で表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００５８】
実施例４
中空成形体の肉厚を１．５ｍｍとした他は、実施例３と同様の条件で表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００５９】
実施例５
中空成形体を成形する機能をも有する表皮付き発泡成形体の製造用金型（深さ１５０ｍｍ）にパリソンを供給して中空成形体を成形した後、金型に挟まれた状態にある中空成形体内に発泡粒子を充填して成形した他は、実施例４と同様の条件にして表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００６０】
実施例６
中空成形体として、内層側が直鎖状低密度ポリエチレン（ＭＩ＝１．３ｇ／１０分（１９０℃、荷重２．１６ｋｇｆ）、融点１２４℃）の層、外層側が高密度ポリエチレン（ＭＩ＝０．８ｇ／１０分、融点１３４℃）の層からなる２層構成のものを用い、直鎖状低密度ポリエチレン（ＭＩ＝１．３ｇ／１０分、融点１２４℃）を基材樹脂とする、図１の（ア）に示す形状の円筒形状の発泡粒子（平均粒子重量２ｍｇ、嵩発泡倍率２０倍、ｄMIN ＝１．３ｍｍ、ＤMIN ＝２．８ｍｍ、ｄMIN ／ＤMIN ＝０．４６、Ｌ＝３．２ｍｍ、Ｌ／Ｄ＝１．０、内圧１．０ｋｇ／ｃｍ2 （絶対圧））のものを用いた他は、実施例１と同様の条件で表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００６１】
実施例７
中空成形体製造用金型及び表皮付き発泡成形体製造用金型の深さを１５０ｍｍとした他は、実施例６と同様の条件で表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００６４】
実施例８
中空成形体として直鎖状低密度ポリエチレン（ＭＩ＝１．３ｇ／１０分、融点１２４℃）の単層構造のものを用いた他は実施例６と同様の条件で表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００６６】
比較例１
発泡粒子形状が略球状である点を除いて実施例１と同様の条件で成形した。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００６７】
比較例２
中空成形体の肉厚を１．５ｍｍとした点を除き、比較例１と同様の条件で成形した。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００６８】
比較例３
中空成形体製造用金型及び表皮付き発泡成形体製造用金型の深さを１５０ｍｍとした他は、比較例１と同様の条件で表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００６９】
比較例４
発泡粒子の形状として略球状発泡粒子を用いた他は、実施例７と同様の条件で表皮付き発泡成形体を得た。使用した発泡粒子の諸物性を表１に、成形条件を表２に、得られた表皮付き発泡成形体の諸物性を表３に示す。
【００７０】
【発明の効果】
以上説明したように本発明方法は、筒状の熱可塑性樹脂発泡体片を熱可塑性樹脂からなり、内面側が該発泡体片と融着性を有する素材である中空成形体の内部に充填し、該発泡体片を加熱媒体により加熱して発泡体片相互間を融着させる表皮付き発泡成形体の製造方法において、該発泡体片として最密充填時の空間率４５〜７０％の形状のものを用いるため、中空成形体が加熱媒体の透過性に乏しいものであっても、中空成形体の内部に充填された発泡体片の間に加熱媒体が充分に透過し、この結果、中空成形体の内部に充填された発泡体片が良好に融着されるとともに、中空成形体の厚さが厚くなった場合や、形状が複雑になった場合でも、発泡体片相互の融着性に優れた表皮付き発泡成形体を得ることができる。また、中空成形体の内層側が発泡体片と融着性を有するので、発泡体片成形体と中空成形体との融着性に優れた表皮付き発泡成形体を得ることができる。更に本発明方法では、発泡体片の成形時に発泡体片成形体と中空成形体とを一体にすることができるため、表皮付き発泡成形体の製造効率に優れる。また熱可塑性樹脂からなる中空成形体の内部に充填する熱可塑性樹脂発泡体片が筒状発泡粒子であるので、発泡体片（発泡粒子）の基材樹脂がオレフィン系樹脂の場合であっても、加熱媒体を深層部まで浸透させることができ発泡粒子を確実に融着させることができる。よって融着性に優れた表皮付き発泡成形体が得られる。
【００７１】
また本発明の表皮付き発泡成形体の製造方法により得られる、表皮付き発泡成形体は、連通した空隙を有する熱可塑性樹脂発泡体片成形体の表面を熱可塑性樹脂からなる中空成形体にて被覆してなる表皮付き発泡成形体は、実施例に示したように折り曲げ破断試験において大部分が界面剥離してしまうことがなく、良好に発泡体片同士が融着しているものであるため、強度、通気性、吸音性等に優れ、建築分野では通気性のある断熱パネル、吸音、防音のパネル等、更に土木分野では濾過材、透水材、保水材等として好適に利用することができる効果を有する。
【図面の簡単な説明】
【図１】本発明において用いる発泡体片の形状の一例を示す略図である。
【図２】本発明の製造方法により得られる表皮付き発泡成形体の一例を示す縦断面図である。
【図３】本発明の製造方法により得られる表皮付き発泡成形体の製造過程の一例を示す断面略図である。 [0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a foamed article with a skin.InRelated.
[0002]
[Prior art and problems to be solved by the invention]
The foamed molded body with a skin obtained by filling the hollow molded body obtained by blow molding or the like with thermoplastic resin foamed particles and heating them with steam or the like to fuse the foamed particles together is a box-type container or building panel. It is widely used in various fields such as cushioning materials and automobile interior materials. When manufacturing this type of foamed molded article with a skin, if the hollow molded article has poor steam permeability, it is difficult for the steam for heating to sufficiently penetrate between the foamed particles filled in the hollow molded article.
[0003]
As a method for solving such a problem, a steam supply pin is inserted into the foamed particle layer filled in the hollow molded body so that the steam penetrates into the foamed particle layer, and the foamed particles are fused to each other. A method for extracting a steam supply pin has been proposed (Japanese Patent Publication No. 62-19293, Japanese Utility Model Publication No. 62-9073, etc.). However, since generally spherical foam particles are generally used as the foam particles, it is difficult for steam to penetrate into the deep layer of the foam particles filled in the hollow molded body. In the case where there is adhesiveness or fusion between the foamed particles and the hollow molded article, there is a problem that only a foamed molded article with a skin having poor adhesion can be obtained. In particular, in the case of trying to obtain a foam structure with a complicated structure or a thick skin, there has been a problem that the above-mentioned poor fusion becomes remarkable.
[0004]
The present invention has been made to solve the above-described conventional problems, and is a method capable of producing a foamed molded article with a skin having excellent fusion property between foam pieces.TheThe purpose is to provide.
[0005]
[Means for Solving the Problems]
That is, in the method for producing a foamed molded article with a skin according to the present invention, a thermoplastic resin foam piece is formed of a thermoplastic resin, and the inner surface side is placed inside a hollow blow molded article that is a material having a fusion property with the foam piece. After filling, inside the hollow blow molded bodyFrom a pin with a hole insertedBy supplying a heating medium, the foam pieces are fused to each other, and the foam pieces and the hollow blow molded article are fused to each other by fusing the foam pieces and the inner surface of the hollow blow molded article. A method for producing a foamed molded article with a skin, wherein the foam pieces are cylindrical foam particles, and the space ratio at the time of closest packing of the foam pieces is 45.~ 70%It is characterized by being.
[0006]
In the present invention, a hollow blow molded article(Hereafter, it may be simply referred to as “hollow molded body”.)At least two pins provided with holes are inserted into the inside, and the heating medium is supplied from the at least one pin, and the heating medium is sucked from the other at least one pin. It is preferable to heat.
Moreover, the supply and suction of the heating medium by the pins can be performed alternately every predetermined time.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
As the base resin of the thermoplastic resin foam piece used in the present invention, polyvinyl chloride resin such as polyvinyl chloride, polystyrene resin such as polystyrene, polyolefin resin such as polyethylene resin and polypropylene resin, polymethyl methacrylate, etc. And acrylic resins such as polycarbonate resins and the like. Examples of the polyethylene resins and polypropylene resins include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, ethylene-propylene block copolymer, and ethylene-propylene. Random copolymer, ethylene-butene block copolymer, ethylene-butene random copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer intermolecular metal ions Ionomer-based resin, propylene homopolymer, propylene-ethylene random copolymer, propylene-butene random copolymer, propylene-ethylene block copolymer, propylene-butene block copolymer, polybutene, polypentene, polypropylene Pyrene - ethylene - butene terpolymer, a propylene - acrylic acid copolymer, propylene - co-maleic anhydride polymers, and the like. In addition to these, copolymers of olefin monomers such as ethylene, propylene, butene and pentene and monomers such as styrene which can be copolymerized with these olefin monomers can also be used.
[0008]
Among the above thermoplastic resins, polyolefin resins having good buffering properties and compressive strain recovery properties are preferable, and among them, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear Polyethylene resins such as low-density polyethylene, polypropylene, polybutene, propylene-ethylene copolymer, propylene-butene copolymer, propylene-ethylene-butene terpolymer are preferred, particularly propylene-ethylene random copolymer, Propylene-butene random copolymer, propylene-ethylene-butene terpolymer, and linear low density polyethylene are preferred.
[0009]
The polyolefin-based resin may be one that has been crosslinked by peroxide or radiation, or may be used without crosslinking, but a non-crosslinked one that has a simple production process and can be recycled is preferable.
[0010]
In the present invention, the thermoplastic resin foam piece filled in the hollow molded body has a space ratio of 45 at the closest packing.~ 70%, Preferably 50~What has a shape of 70% is good. If the space ratio is less than 45%, it is not preferable because only the foamed molded article with a skin having poor permeability of the heating medium and poor fusion between the foam pieces can be obtained. What has the above shapes can be used 1 type or in mixture of 2 or more types. The space ratio at the time of close-packing means filling a certain amount of thermoplastic resin foam pieces into a graduated container such as a graduated cylinder, and vibrating the container up and down without compressing the thermoplastic resin foam pieces. When the volume of the foam piece is minimized, the volume of the foam piece of a certain amount obtained from the scale of the container is apparent volume: A (cm3 Then, the foam piece after measuring the apparent volume is submerged in alcohol in a calibrated container containing alcohol, and the amount of the foam piece of a certain amount of Volume: B (cm3 ) And the apparent volume: A and the true volume: B are obtained from the following formula.
[0011]
[Expression 1]
Space ratio (%) = {(A−B) / A} × 100
[0012]
Examples of the heating medium for fusing the foam pieces in the method of the present invention include steam and hot air. Industrially advantageous steam is preferable.
[0013]
In addition, as the thermoplastic resin foam piece used for molding in the present invention, cylindrical foam particles having the thermoplastic resin as a base resin,, Described laterFoamed particles having protrusions on the surface are preferred.
[0015]
The cylindrical expanded particle has a shape having a hollow hole communicating with the outside (hereinafter, a direction in which the hollow hole communicates with the outside is referred to as “hole direction”), and (a) a cross section perpendicular to the hole direction. (Hereinafter, this cross section is referred to as “vertical cross section.”) The outer peripheral shape and the hollow hole shape are both circular, and (b) the outer peripheral shape and the hollow hole shape are both polygonal in the vertical cross section. ) Any one of the outer peripheral shape and the hollow hole shape in the vertical cross section is circular and the other is a polygon, and (d) those having the cross sectional shapes as in the above (a) to (c) (E) one having a cross-sectional shape as shown in the above (a) to (d) provided with a protrusion in any cross section perpendicular to the hole direction, and (f) the above ( Has a cross-sectional shape such as a) to (d) And which, in another vertical cross-section can be exemplified such as those having such cross-sectional shape of the protrusion is provided (a) ~ (d).
[0016]
Among the foamed particles shown in (a) to (so) of FIG. 1, the foamed particles of (a) correspond to the above (a), and (b) to (b) correspond to (b). As for the foamed particles of (d) corresponding to (c), the foamed particles of (f) and (f) are corresponding to (d), and (f) and (g) are expanded particles of ( Examples of the particles corresponding to e) include the expanded particles of (K) to (S), and those corresponding to (f) include the expanded particles of (C) and (SO). In FIG. 1,
[0017]
The expanded particles shown in FIG. 1 are merely examples of cylindrical expanded particles that can be used in the present invention. In addition to this, the outer peripheral shape and the hollow hole shape in the vertical cross section are elliptical, and polygonal shapes other than regular polygons. Such as a part of the foam particles constricted along the hole direction, a part of the foam particles twisted along the hole direction, a case where the hollow hole is displaced from the center in the vertical section, etc. Any shape of foamed particles can be used. In the present invention, the cylindrical foamed particles include those in which a part of the cylindrical foamed particles is cut so that the vertical cross-sectional shape becomes a C-shape or the like.
[0018]
The cylindrical expanded particles have a ratio of the maximum outer diameter D in the vertical section: D and the maximum length along the hole direction L: L / D is 0.2 to 5.0, particularly 0.5 to 2. 0.0 is preferred. When the L / D of the cylindrical foamed particles is in the range of 0.2 to 5.0, the filling property of the foamed particles into the hollow molded body becomes good and the fusion property between the foamed particles is good. Since it becomes favorable, it is preferable. The maximum outer diameter: D is the maximum value of the distance between two parallel tangents in contact with the outer periphery in the vertical section as shown in (a), (ki), (ke), (c) of FIG. It can be measured with calipers. L is also the maximum length as shown in FIGS. 1A and 1K and can be measured with calipers.
[0019]
Those having no protrusions e like the foamed particles (a) to (ku) shown in FIG. 1 are less likely to cause clogging of the foamed particles in the filling machine when filling the foamed particles inside the hollow molded body, This is preferable because uniform filling of the hollow molded body is easy. Further, it is preferable that the outer peripheral shape and the hollow hole shape in the vertical cross section are circular as in the foamed particles (a), (ki), and (ku) because the foamed particles can be produced relatively easily.
[0021]
As described above, in the present invention, various cylindrical expanded particles as shown in FIG.TheAlthough it can be used, particularly when the base resin of the thermoplastic foam particles is an olefin resin, it is difficult to fuse the foam particles inside the hollow thermoplastic resin molded body. For this reason, cylindrical foamed particles, particularly cylindrical foamed particles, as shown in FIGS. 1A and 1E, in which the heating medium can penetrate to the deep layer and can be reliably fused, are preferable. In addition, cylindrical expanded particles as shown in FIGS.IsEven if the outer peripheral shape of the vertical section is not a perfect circle, it is sufficient if it has a substantially circular shape.
[0022]
In particular, the cylindrical expanded particles preferably have an average particle weight of 1 to 50 mg, more preferably an average particle weight of 1 to 10 mg. Foamed particles having an average particle weight of less than 1 mg are difficult to produce, and when it exceeds 50 mg, the filling property of the hollow molded body at the time of molding tends to deteriorate. Also, depending on the average particle weight, for example, in the case of cylindrical expanded particles having an average particle weight of 1 to 10 mg, the minimum diameter of the hollow hole in an arbitrary vertical cross section is defined as d.MIN , D is the minimum diameter of the outer circumference in the same vertical sectionMIN DMIN Is 0.5 mm or more and dMIN / DMIN Is preferably 0.30 to 0.90, more preferably dMIN Is 1.0 mm or more and dMIN / DMIN Is 0.40 to 0.85. DMIN Is preferably 20 mm, particularly preferably 10 mm or less.
[0023]
dMIN And DMIN When the cylindrical foamed particles satisfying the above relationship are formed, a foamed molded body with a skin having a small shrinkage ratio and better fusion property between the particles can be obtained. DMIN / DMIN Expanded particles having a value of more than 0.90 have a problem that the production itself is difficult, and a foamed molded product with a skin that lacks dimensional stability tends to be obtained.
[0024]
In addition, when there are a plurality of hollow holes as shown in (ki), (ku), (so), etc. in FIG. 1, all of the hollow holes are also as shown in (ke) to (so). In the case where protrusions are provided on the outer periphery, it is preferable that the above relationship is satisfied for the shape excluding the protrusions.
[0025]
In the method of the present invention, since the above-mentioned foamed particles are used as the foam piece, heating is performed up to the deep layer portion of the foam piece filled in the hollow molded body even if the hollow molded body does not have the permeability of the heating medium. The medium penetrates between the foam pieces and arrives. As a result, the filled foam pieces located near the inside of the hollow molded body are sufficiently heated, and the foam pieces near the inside of the hollow molded body are separated from each other. When it is reliably fused and the inner surface side of the hollow molded body is a material having fusibility with the foam piece, the foam piece and the hollow molded body are reliably fused.
[0026]
The foamed particles are, for example, dispersed in a closed container with thermoplastic resin particles and a foaming agent dispersed in a dispersion medium, heated with stirring to impregnate the foaming agent in the resin particles, and then dispersed with the resin particles at the foaming temperature. It can be obtained by a method such as releasing the medium from the inside of the container under a low pressure (usually under atmospheric pressure) and foaming the resin particles.
[0027]
The thermoplastic resin particles used in the production of the foamed particles can be obtained by a method such as melt-kneading the base resin in an extruder, extruding into a strand shape from a die and cooling, and then cutting to a suitable length. When melt-kneading the base resin in the extruder, if necessary, inorganic substances such as talc, calcium carbonate, borax, aluminum hydroxide, zinc borate are added and melt-kneaded with the resin. An inorganic substance may be contained. Depending on the purpose and purpose, black, gray, brown, yellow, red, pink, green, blue, or other colored pigments or dyes may be added for coloring. When adding the inorganic substance, the color pigment, the dye, or the like to the resin particles, the master batch method is usually employed in consideration of these dispersibility. The addition amount of the inorganic substance, the color pigment, and the dye is usually 0.001 to 5 parts by weight per 100 parts by weight of the resin particles. When an inorganic substance is contained in the resin particles, the expansion ratio of the expanded particles can be improved, and the cell diameter can be adjusted to 50 to 350 μm, which is suitable in terms of secondary foamability and dimensional stability.
[0028]
When extruding the molten resin from the die, a die having a resin extrusion port having a shape substantially similar to the cross-sectional shape of the foamed particles to be obtained (for example, when obtaining the cylindrical foamed particles, the vertical cross-sectional shape of the cylindrical foamed particles and By using a die having a resin extrusion port having a substantially similar shape), it is possible to obtain a resin particle having a similar shape to the foam particle having a target shape, and performing foaming as described above using such a resin particle, Foamed particles having a target shape can be obtained.
[0029]
Any dispersion medium that does not dissolve the resin particles may be used as the dispersion medium used for producing the foamed particles. Examples thereof include water, ethylene glycol, glycerin, methanol, ethanol, and the like, but usually water is used. As the blowing agent, propane, butane, hexane, cyclobutane, cyclohexane, trichlorofluoromethane, dichlorofluoromethane, chlorofluoromethane, trifluoromethane, 1,1,1,2-tetrafluoroethane, 1-chloro- Volatile blowing agents such as 1,1-difluoroethane, 1,1-difluoroethane, 1-chloro-1,2,2,2-tetrafluoroethane, and inorganic gas-based blowing agents such as nitrogen, carbon dioxide, argon, and air Is used. A mixed foaming agent of a volatile foaming agent and an inorganic gas-based foaming agent can also be used. Among these, there is no fear of ozone layer destruction, and an inexpensive inorganic gas-based foaming agent is preferable, and nitrogen, carbon dioxide, and air are particularly preferable. The amount of the blowing agent other than nitrogen and air is usually 2 to 50 parts by weight per 100 parts by weight of the resin particles. In the case of nitrogen and air, the amount used is within the pressure range for press-fitting into a sealed container. 5-60kgf / cm2 It is preferable to add so as to be G. The amount of the foaming agent used is appropriately adjusted according to the expansion ratio of the foamed particles to be obtained.
[0030]
When the resin particles and the foaming agent are dispersed in a dispersion medium and heated, an anti-fusing agent can be added to the dispersion medium in order to prevent fusion between the resin particles. As the anti-fusing agent, any inorganic or organic one can be used as long as it does not dissolve in the dispersion medium and does not melt by heating. In general, an inorganic one is preferable. As the inorganic anti-fusing agent, powders such as kaolin, talc, mica, aluminum oxide, titanium oxide, and aluminum hydroxide are suitable. The anti-fusing agent preferably has an average particle size of 0.001 to 100 μm, particularly 0.01 to 30 μm. In general, it is preferable to add 0.01 to 10 parts by weight of the anti-fusing agent to 100 parts by weight of the resin particles. In addition, an anionic surfactant such as sodium dodecylbenzenesulfonate and sodium oleate can be used in combination as a dispersion aid. Usually, it is preferable to add 0.001 to 5 parts by weight of the dispersion aid to the dispersion medium per 100 parts by weight of the resin particles.
[0031]
The expanded particle has a larger overall dimension than the resin particle before expansion, but usually d of the expanded particle.MIN / DMIN And the value of L / D and d of the unexpanded resin particles corresponding to the valuesMIN '/ DMIN The values of 'and L' / D 'are almost the same, and d of the unfoamed resin particlesMIN '/ DMIN If the values of ', L' / D 'satisfy the above conditions, d of the expanded particlesMIN / DMIN , L / D values also generally satisfy the above conditions.
[0033]
In the present invention, the base resin of the hollow molded body made of the thermoplastic resin may be the same as the base resin of the thermoplastic resin foam piece described above.
[0034]
In the present invention, the hollow molded body isTheWhat was shape | molded by methods, such as a low molding, can be used. For example, in order to obtain a hollow molded body by blow molding, the parison of the thermoplastic resin is lowered from above the mold, the parison is sandwiched by the mold, air is blown into the parison from the air blow pin, and the parison is expanded. A hollow molded body is formed by sucking from a suction hole provided in the mold and bringing the parison into close contact with the inner surface of the mold. Moreover, it may not be pre-molded, and the hollow molded body and the foamed molded body with a skin may be manufactured with the same mold. For example, after molding a hollow molded body of a thermoplastic resin, the foam piece is hollow. It is good also as a foaming molding body with a skin by filling a molding. The hollow molded body is not limited to a non-foamed and foamed single-layer structure, and may have a multilayer structure having an unfoamed layer, a foamed layer, and the like. In addition, the inner surface of the hollow molded body is made of a material having a fusion property with the foam piece.BecauseWhen requesting a foam molded body with a skin with high strength and high rigidity, it must be made of a material that has fusibility.By, A foam-molded article with a skin having excellent fusion properties between the foam-molded article and the hollow-molded article is obtained.Ru. The thickness of the hollow molded body is preferably 1 to 5 mm. If the thickness of the hollow molded body is less than 1 mm, the shape retention of the hollow molded body may be deteriorated, and if it exceeds 5 mm, the weight of the foamed molded body with a skin increases, which is not preferable. As the shape of the hollow molded body, for example, a cylindrical shape having a penetration, a cylindrical shape with a bottom, a hollow plate shape, a box-shaped container shape, or the like can be used.
[0035]
The material having the fusibility between the thermoplastic resin expanded particles and the hollow molded body made of the thermoplastic resin varies depending on the difference in the base resin of the thermoplastic resin expanded particles. When the base resin of the thermoplastic resin foam particles is, for example, a polypropylene resin, the base resin of the hollow molded body made of the thermoplastic resin is also a polypropylene resin or a polypropylene thermoplastic elastomer, and the base material of the foam particles When the resin is a polyethylene-based resin, the base resin of the hollow molded body made of a thermoplastic resin is preferably also a polyethylene-based resin, but is not limited thereto as long as it has fusibility with expanded particles. .
[0036]
As the material of the above-mentioned thermoplastic resin foamed particles and a hollow molded article having a fusion property, if a material having a melting point lower than the melting point of the base resin of the thermoplastic resin foamed particles to be used is selected, the foamed particles and the hollow molded article This is preferable because the fusing property is further improved.
[0037]
In the case where the hollow molded body has a multilayer structure, as a material constituting the surface side (side not in contact with the thermoplastic resin foam piece), in addition to the material having the fusion property with the above-described thermoplastic resin foam piece, It is also possible to use materials such as polyvinyl chloride that does not have fusibility with the thermoplastic resin foam piece, and polyester resins.
[0038]
When trying to obtain a foam molded body with a skin having a high strength and high rigidity, the material of the hollow molded body (in the case of a multilayer structure, at least the material on the inner surface side) and the base resin of the foam piece are: As described above, it is preferable to select materials having mutual heat-fusibility. In particular, when the foamed molded body with a skin of the present invention is used for vehicles such as automobile interior materials and bumpers, considering the heat resistance, rigidity, energy absorption, recyclability, etc., the material of the hollow molded body, the foam piece It is preferable to select a polypropylene resin for the base resin. In addition, when the foamed article with a skin of the present invention is used for bedding, furniture, etc., in consideration of cushioning properties and the like, a polyethylene resin, particularly a linear low density polyethylene is preferable as the base resin of the foam piece, and hollow molding As the body material (or the material on the inner surface side of the hollow molded body), it is preferable to select a polyethylene-based resin having heat-fusibility with it.
[0039]
The present inventionObtained by manufacturing methodFoam molding with skin(Hereinafter, it is also simply referred to as the “foamed molded article with skin of the present invention”.)In order to obtain a foam piece molded body having a continuous void, the foam piece filled in the hollow molded body has a space ratio of 45 at the close-packing as described above.Cylindrical foam particles of ~ 70%In particular, cylindrical foam particles are preferable. Since the foam piece is used, it is excellent in the fusion property between the foam pieces, and the inner layer side of the hollow molded article has a fusion piece with the foam piece.Because, Foam-molded body with skin excellent in fusion property between foam piece molded body and hollow molded bodyBecome. It is preferable that the porosity of the foam piece molded body having voids communicating with each other in the foam molded body with a skin of the present invention is 5% or more. Furthermore, a porosity of 5 to 75% is preferable, and a porosity of 10 to 45% is particularly preferable. A foam piece molded article having a porosity of less than 5% is not preferable because it cannot be used as a breathable heat insulating panel, a sound absorbing panel, a sound insulating panel, a filter medium, a water permeable material, a water retaining material, or the like. The porosity (%) of the foam piece molded body is the volume obtained from the outer dimensions (25 mm × 25 mm × 100 mm) of the foam piece molded body sample as a (cm3 ), When the sample is submerged in alcohol in a graduated container containing alcohol, the true volume of the sample determined from the increment of the scale is b (cm3 ) Is a value obtained from the following formula.
[0040]
[Expression 2]
Porosity (%) = {1- (b / a)} × 100
[0041]
As a method of obtaining the foam with a skin of the present invention, for example, a hollow molded body is obtained by a blow molding machine, the hollow molded body is mounted on a mold, and the foam piece is mounted inside the mold. A method of filling and molding to obtain a molded body with a skin, a method of molding a hollow molded body and a foam with a skin with a mold that also has the function of molding a hollow molded body, and rigidity to the hollow molded body itself When there is, there can be mentioned a method of obtaining a foam with a skin by filling the hollow molded body with a foam piece without using a mold.
[0042]
The mold for obtaining the above-mentioned foam-molded body with a skin is a laminated mold composed of, for example, a concave mold and a convex mold, and has a space for indirectly cooling the foam-molded body with a skin by cooling the mold surface. And a pin in which a large number of slit-shaped or circular holes for supplying a heating medium and sucking air or a heating medium are arranged. In particular, when it also has a function of molding a hollow molded body, a hole for inserting an air blow pin for inflating the parison from below the mold is provided in the mold.
[0043]
Further, in the present invention, when the hollow molded body itself has rigidity, the porosity of the foam piece at the closest packing is 45.~ 70%Since the steam is easy to permeate the foam pieces, the steam pressure can be lowered. Therefore, if the strength of the hollow molded body is sufficient, it is possible even without a mold for producing a foamed molded body with a skin as described above.
[0044]
FIG.Shows an example of the foamed molded
[0045]
In the present invention, as an example of a method for obtaining a foam-molded body with a skin, after mounting the hollow molded
[0046]
Of the present inventionObtained by the method for producing a foamed molded article with a skin,Surface of foam pieceTheAs the foam-molded body with a skin coated with a hollow molded body made of a thermoplastic resin, for example, a foam-molded body with a skin covering the entire surface of a thermoplastic foam piece molded bodyButCan be mentioned.like thisApplications of foamed molded products with skin include, for example, distribution fields such as pallets and carts, construction fields such as heat insulation panels and sound insulation panels, civil engineering fields such as filter media and water permeable materials, various buoyancy members, automobile interiors, and bumper materials , Furniture, bedding and the like.
[0047]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0048]
Example 1
A layer of an ethylene-propylene block copolymer (MI = 0.6 g / 10 min (230 ° C., load 2.16 kgf), melting point 161 ° C., ethylene content 7.0% by weight) and an inner layer of propylene-ethylene random copolymer A two-layer parison (a propylene-ethylene random copolymer layer is the inner surface side) composed of a layer of coalescence (MI = 8 g / 10 min, melting point 132 ° C., ethylene content 5.8 wt%) is extruded by a coextrusion method. Extruded from the machine, this parison is supplied to the mold from above the mold for manufacturing a hollow molded body (length 400 mm x width 250 mm x depth 100 mm), and the mold is clamped and cooled while air is blown into the parison. Thus, a hollow molded body (wall thickness 2.6 mm) was obtained. Next, this hollow molded body was mounted in a mold for manufacturing a foam molded body with a skin equipped with a feeder for supplying foamed particles (length 396 mm × width 248 mm × depth 100 mm), and then clamped, and then propylene-ethylene Cylindrical foamed particles (
[0049]
When filling the hollow molded body with foamed particles, the air inside the hollow molded body is filled while sucking air from both pins, and then sucked from one of the pins inserted into the filled foam particle layer. While supplying steam from the other pin for 5 seconds, the pin that was supplying steam was replaced with the pin that was being sucked, and steam was supplied while sucking, and air remaining in the layer of foam particles After evacuating, steam at 150 ° C. was supplied from both pins into the layer of foamed particles to heat-mold the foamed particles. Next, after sucking and cooling with a pin inserted into a layer of foamed particles (the foamed particles were fused to each other at this point), the mold was opened and the foamed molded product with a skin was taken out. This molded body was cured at 60 ° C. under atmospheric pressure for 24 hours and held at room temperature. Various physical properties of the foamed particles used for molding are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded product with skin are shown in Table 3.
[0050]
[Table 1]
[Table 2]
[Table 3]
* 4 Bending fracture test: Evaluates the fusing property of foam pieces (foamed particles). Specifically, as shown in Fig. 5, cut out from the inside (A) and the vicinity of the skin (B) of the foamed product with skin. The sample (size: 25 mm × 25 mm × 100 mm) was bent and broken, and each fractured surface was observed,
○: Material destruction occurs in most of the foam pieces (foamed particles).
Δ: Material destruction of foam pieces (foamed particles) and interfacial peeling between the foamed particles are mixed.
X: Most of the foam pieces (foamed particles) are separated from each other.
As evaluated.
[0055]
* 5 The fusing property between the skin material and the foam piece (foamed particles) was determined by conducting a 90 ° peel test on the skin material of a sample obtained by cutting a foamed molded body with a skin into a width of 15 mm, )
○: Material destruction occurs in most of the foam pieces (foamed particles).
X: Most of the foam pieces (foamed particles) are peeled off at the interface.
As evaluated.
[0056]
Example 2
A foamed molded article with a skin was obtained under the same conditions as in Example 1 except that the cylindrical foamed particles shown in FIG. Various physical properties of the used expanded particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded article with skin are shown in Table 3.
[0057]
Example 3
A foam-molded article with a skin was obtained under the same conditions as in Example 1 except that the depth of the mold for producing a hollow molded article and the mold for producing a foam-molded article with a skin was 150 mm. Various physical properties of the used expanded particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded article with skin are shown in Table 3.
[0058]
Example 4
A foamed molded article with a skin was obtained under the same conditions as in Example 3 except that the thickness of the hollow molded article was 1.5 mm. Various physical properties of the used expanded particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded article with skin are shown in Table 3.
[0059]
Example 5
Hollow molding that is sandwiched between molds after the parison is supplied to a mold (150 mm depth) for producing a foamed molded article with a skin that also has the function of molding a hollow molded article. A foamed molded article with a skin was obtained under the same conditions as in Example 4 except that the body was filled with foamed particles and molded. Various physical properties of the used expanded particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded article with skin are shown in Table 3.
[0060]
Example 6
As a hollow molded body, the inner layer side is a linear low density polyethylene (MI = 1.3 g / 10 min (190 ° C., load 2.16 kgf), melting point 124 ° C.), the outer layer side is a high density polyethylene (MI = 0.8 g). FIG. 1 uses a two-layer structure composed of layers of / 10 minutes, melting point 134 ° C., and uses linear low-density polyethylene (MI = 1.3 g / 10 minutes, melting point 124 ° C.) as a base resin. (A) Cylindrical expanded particles (
[0061]
Example 7
A foam-molded article with a skin was obtained under the same conditions as in Example 6 except that the depth of the mold for producing the hollow molded article and the mold for producing the foam-molded article with skin was 150 mm. Various physical properties of the used expanded particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded article with skin are shown in Table 3.
[0064]
Example8
A foamed molded article with a skin is obtained under the same conditions as in Example 6 except that a single-layer structure of linear low density polyethylene (MI = 1.3 g / 10 min, melting point 124 ° C.) is used as the hollow molded article. It was. Various physical properties of the used expanded particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded article with skin are shown in Table 3.
[0066]
Comparative Example 1
Molding was performed under the same conditions as in Example 1 except that the foamed particles were substantially spherical. Various physical properties of the used foamed particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded product with skin are shown in Table 3.
[0067]
Comparative Example 2
The hollow molded body was molded under the same conditions as in Comparative Example 1 except that the thickness of the hollow molded body was 1.5 mm. Various physical properties of the used expanded particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded article with skin are shown in Table 3.
[0068]
Comparative Example 3
A foamed article with a skin was obtained under the same conditions as in Comparative Example 1 except that the depth of the mold for producing the hollow molded article and the mold for producing the foamed article with skin was 150 mm. Various physical properties of the used expanded particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded article with skin are shown in Table 3.
[0069]
Comparative Example 4
A foamed molded article with a skin was obtained under the same conditions as in Example 7 except that substantially spherical foamed particles were used as the shape of the foamed particles. Various physical properties of the used foamed particles are shown in Table 1, molding conditions are shown in Table 2, and various physical properties of the obtained foamed molded product with skin are shown in Table 3.
[0070]
【The invention's effect】
As described above, the method of the present inventionTubularThe thermoplastic resin foam piece is made of thermoplastic resin,The inner surface is a material having a fusion property with the foam piece.In a method for producing a foamed molded product with a skin, in which the foamed piece is filled with the inside and the foamed piece is heated with a heating medium to fuse the foamed pieces together, the space at the time of closest packing as the foamed piece Rate 45~ 70%Therefore, even if the hollow molded body is poor in the permeability of the heating medium, the heating medium sufficiently permeates between the foam pieces filled in the hollow molded body. The foam pieces filled in the hollow molded body are fused well, and even if the thickness of the hollow molded body is increased or the shape is complicated, the foam pieces are melted together. It is possible to obtain a foamed article with a skin having excellent adhesion. Moreover, the inner layer side of the hollow molded body has a fusion property with the foam piece.BecauseThus, a foamed molded product with a skin excellent in the fusing property between the foam piece molded product and the hollow molded product can be obtained. Furthermore, in the method of the present invention, since the foam piece molded body and the hollow molded body can be integrated when the foam piece is molded, the production efficiency of the foam molded body with a skin is excellent. In addition, the thermoplastic resin foam piece filled in the hollow molded body made of thermoplastic resin is a cylindrical foam particle.BecauseEven when the base resin of the foam piece (foamed particles) is an olefin resin, the heating medium can be penetrated to the deep layer portion, and the foamed particles can be reliably fused. Therefore, a foamed molded article with a skin having excellent fusing property is obtained.
[0071]
The present inventionObtained by the method for producing a foamed molded article with a skin,The foamed molded body with a skin is the surface of a thermoplastic resin foam piece molded body having continuous voids.TheFoam-molded body with skin formed by coating with a hollow molded body made of thermoplastic resinIsAs shown in the examples, most of the interface does not peel off in the bending fracture test, and the foam pieces are well fused with each other, so that the strength, breathability, sound absorption, etc. In the construction field, it has an effect that it can be suitably used as a heat insulating panel, a sound absorbing panel, a soundproof panel and the like in the construction field, and further as a filtering material, a water permeable material, a water retaining material, etc. in the civil engineering field.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an example of the shape of a foam piece used in the present invention.
[Figure 2]It is a longitudinal cross-sectional view which shows an example of the foaming molding with a skin obtained by the manufacturing method of this invention.
[Fig. 3]It is a cross-sectional schematic diagram which shows an example of the manufacture process of the foaming molding with a skin obtained by the manufacturing method of this invention.
Claims (3)
該発泡体片が筒状の発泡粒子で、該発泡体片の最密充填時の空間率が４５〜７０％であることを特徴とする表皮付き発泡成形体の製造方法。 Holes inserted into the hollow blow molded article after the thermoplastic resin foam piece is made of a thermoplastic resin and the inner surface side is filled into the hollow blow molded article, which is a material having fusion properties with the foam piece . Foam piece molded body and hollow blow molding by supplying a heating medium from a pin provided with an adhesive, fusing the foam pieces together, and fusing the foam pieces and the inner surface of the hollow blow molded body A method for producing a foamed molded article with an outer skin fused to a body,
The method for producing a foam-molded article with a skin, wherein the foam piece is a cylindrical foam particle, and the space ratio when the foam piece is closely packed is 45 to 70% .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP01716399A JP4503720B2 (en) | 1999-01-26 | 1999-01-26 | Method for producing foamed article with skin |
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| Application Number | Priority Date | Filing Date | Title |
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| JP01716399A JP4503720B2 (en) | 1999-01-26 | 1999-01-26 | Method for producing foamed article with skin |
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| JP2000210967A JP2000210967A (en) | 2000-08-02 |
| JP4503720B2 true JP4503720B2 (en) | 2010-07-14 |
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| JP01716399A Expired - Fee Related JP4503720B2 (en) | 1999-01-26 | 1999-01-26 | Method for producing foamed article with skin |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003039512A (en) * | 2001-08-01 | 2003-02-13 | Sumitomo Chem Co Ltd | Thermoplastic resin foamed molded object |
| JP2006077484A (en) * | 2004-09-10 | 2006-03-23 | Kaneka Corp | Thermal insulation panel and its manufacturing method |
| JP4837356B2 (en) * | 2005-02-01 | 2011-12-14 | 株式会社カネカ | Thermoplastic resin in-mold foam molding and production method |
| JP2008036822A (en) * | 2006-08-01 | 2008-02-21 | Kaneka Corp | Mold for in-mold foam molding of synthetic resin formed particles and molding method |
| JP6514576B2 (en) | 2014-07-18 | 2019-05-15 | 株式会社ジェイエスピー | Method for producing surface material coated foamed particle molded body |
| KR101911790B1 (en) * | 2017-01-18 | 2018-10-26 | 코스파 주식회사 | Laminate for sound insulation |
| EP3581613B1 (en) | 2017-02-13 | 2021-07-21 | Asahi Kasei Kabushiki Kaisha | Resin foamed particles, resin foam molded body, and laminated body |
| JP6982972B2 (en) * | 2017-03-31 | 2021-12-17 | 旭化成株式会社 | Laminate |
| KR102323648B1 (en) | 2018-04-09 | 2021-11-09 | 아사히 가세이 가부시키가이샤 | Foam molded article, and method for producing the same |
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