JPH0417977B2 - - Google Patents
Info
- Publication number
- JPH0417977B2 JPH0417977B2 JP14968183A JP14968183A JPH0417977B2 JP H0417977 B2 JPH0417977 B2 JP H0417977B2 JP 14968183 A JP14968183 A JP 14968183A JP 14968183 A JP14968183 A JP 14968183A JP H0417977 B2 JPH0417977 B2 JP H0417977B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- expanded particles
- particles
- crosslinking
- block copolymer
- 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
Links
- 229920005989 resin Polymers 0.000 claims description 53
- 239000011347 resin Substances 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 47
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000008096 xylene Substances 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 8
- 238000005187 foaming Methods 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920006039 crystalline polyamide Polymers 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 description 25
- 239000000806 elastomer Substances 0.000 description 21
- 238000004132 cross linking Methods 0.000 description 16
- 239000002612 dispersion medium Substances 0.000 description 10
- 229920002647 polyamide Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000004604 Blowing Agent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000004927 fusion Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000010097 foam moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 2
- 229940099364 dichlorofluoromethane Drugs 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- QSFTWOJPCWPORR-UHFFFAOYSA-N 2-(2-tert-butylperoxypropan-2-ylperoxy)-2-methylpropane Chemical compound CC(C)(C)OOC(C)(C)OOC(C)(C)C QSFTWOJPCWPORR-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- WFLLVHFOYBVDOG-UHFFFAOYSA-N bis(tert-butylperoxy)-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](OOC(C)(C)C)(OOC(C)(C)C)C1=CC=CC=C1 WFLLVHFOYBVDOG-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- -1 cyclic aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、高度のゴム弾性を示す発泡成形体を
製造するための成形材料としてすぐれた性質を有
する、熱可塑性エラストマー樹脂の発泡粒子に関
するものである。
高度のゴム弾性を示す発泡成形体としては従来
ポリウレタンフオームが代表的なものであるが、
これは気泡が連続気砲であるため、圧縮特性にお
いて劣り、また高価であるという欠点があつた。
近年、熱可塑性エラストマー樹脂の品質改良が
進んだ結果、多くの点でポリウレタン樹脂よりも
すぐれているものが安価に利用できるようになつ
ているから、これをポリスチレン、ポリオレフイ
ン等の熱可塑性樹脂について広く実施されている
発泡成形法、すなわちこれらの樹脂の粒子を予備
的に発泡させて発泡粒子としたのち成形用型内で
加熱することにより発泡粒子を再発泡させるとと
もに粒子同士を融着させて成形する方法によつて
発泡成形することができれば、高物性の弾性発泡
成形体が高能率で得られる筈である。しかしなが
ら、期待に反して、熱可塑性エラストマー樹脂は
ポリスチレンやポリオレフインと同様に溶融状態
で発泡させて成形しようとすると、一応発泡する
ものの、その後の収縮が大きく、このため変形
（収縮を含む）が甚しくしかも気泡が粗大になる
など、とうてい満足な成形体は得られない。
本発明者らは、上述のように困難な熱可塑性エ
ラストマー樹脂の発泡成形を原料樹脂の面から改
良を加えることにより可能にすることに想到し、
種々検討を重ねた結果、ポリアミド系エラストマ
ー樹脂を架橋処理して得られるエラストマーが、
従来の熱可塑性エラストマー樹脂にはみられない
すぐれた発泡成形性を有することを知つた。
本発明は上記知見に基くものであつて、容易に
高品質の弾性発泡成形体を与える発泡粒子、すな
わち発泡粒子を構成する樹脂が結晶性ポリアミド
セグメントおよびポリエーテルセグメントを有す
るブロツク共重合体からなる熱可塑性エラストマ
ー樹脂の架橋処理物であつてメルトインデクスが
40ｇ／10分をこえず熱キシレン不溶解残渣が60％
をこえないものよりなることを特徴とする発泡粒
子を提供するものである（但しメルトインデクス
および熱キシレン不溶解残渣の値は後記測定法に
よる）。
一般に、架橋可能な熱可塑性合成樹脂を架橋処
理すると、処理度に応じてその溶融時の流動性が
低下し、ついには熱可塑性を失うに至る。このよ
うな物性の変化は、特定の用途においては好まし
いものとなることがあるが、一般的には、溶融押
出成形や成形物の後加工（たとえば延伸処理）を
困難にするから、架橋処理が実際に熱可塑性樹脂
を改質する手段として利用されている例は少な
く、ポリオレフインの架橋など、ごく限られた例
があるにすぎない。そして熱可塑性エラストマー
樹脂の分野においては、この樹脂の最大の特長す
なわちエラストマーとしては異例の熱可塑性を減
殺して成形性を悪化させることともにその生命と
するゴム弾性をも低下させることが予想されるた
めか、架橋処理をあえて施すことが検討された例
はほとんど見当らない。特に熱可塑性ポリアミド
エラストマー樹脂については、それが架橋可能か
否かもわかつていなかつたから、本発明で特定さ
れた範囲で架橋処理されたこの樹脂およびその予
備発泡粒子がすぐれた発泡成形性を獲得し、しか
も物理的性質や化学的性質の点でもほとんど劣化
せず、むしろ改良されることは、全く予想外のこ
とであつた。
本発明による発泡粒子は、上述のようにポリア
ミド系エラストマー樹脂を架橋処理したものから
なるが、架橋による樹脂の分子構造の変化は、熱
キシレン不溶解残渣の増加により、間接的に知る
ことができる。すなわち、未架橋のポリアミド系
エラストマーは熱キシレンに完全に溶解するが、
架橋度を大にするにつれて熱キシレン不溶解残渣
は増加し、最大60〜85％程度に達する。本発明に
よる発泡粒子は、熱キシレン不溶解残渣が60％を
こえない程度に架橋処理されそれにより樹脂が好
ましくは0.5ｇ／10分以上、特に好ましは１〜25
ｇ／10分のメルトインデクスを示す溶融時流動性
を保持しているものである。共重合体分子鎖中で
架橋結合が形成されている部位は、まだ完全に解
明されてはいないが、主としてポリエーテルから
なるソフトセグメントと考えられる。
本発明による発泡粒子を構成する架橋エラスト
マーの原料樹脂として好ましいのは、ポリアミド
系エラストマー樹脂の中でもポリラウリンラクタ
ム−ポリテトラハイドロフランブロツク共重合体
である。但しこの重合体のソフトセグメントは、
ポリテトラハイドロフランのほかにアジピン酸、
アゼライン酸、ドデカン二酸等の第三成分に由来
する基を含んでいてもよい。またこの共重合体の
中でも特に好ましいのは、ポリラウリンラクタム
セグメントを30〜80重量％、ポリテトラハイドロ
フランセグメント20〜50重量％、それぞれ含有す
るものである。この樹脂は、上記本発明による発
泡粒子を構成するエラストマー樹脂に要求される
メルトインデクスを維持しながら発泡成形性その
他の性質においてすぐれたエラストマー樹脂を与
える点で、他のポリアミド系エラストマー樹脂よ
りもすぐれている。
ポリアミド系エラストマー樹脂から本発明によ
る発泡粒子用の架橋エラストマー樹脂を製造する
ための架橋法は、ポリオレフイン樹脂等の架橋処
理に採用される化学架橋、電子線架橋、放射線架
橋など、いずれの方法によつてもよいが、最も適
当なのは、化学架橋である。架橋剤としては、ｔ
−ブチルクミルパーオキサイド、ジクミルパーオ
キサイド、２，５−ジメチル−２，５−ジ−ｔ−
ブチルパーオキシ−３−ヘキシン、２，２−ビス
（ｔ−ブチルパーオキシ）プロパン、ビス（ｔ−
ブチルパーオキシ）ジフエニルシランなどが適当
である。処理に際しては、水、エタノール、エチ
レングリコールなどを分散媒として樹脂粒子を懸
濁させ、また適当な架橋助剤を併用するとよい。
架橋による原料樹脂の改質は架橋度にほぼ比例す
る形で進むから、ポリアミド系エラストマー樹脂
改質法として考えるならば架橋処理の程度に下限
はないが、発泡成形が可能なエラストマーを得る
ためには、架橋は熱キシレン不溶解残渣が少なく
とも0.5％に達するまで進めることが望ましい。
上述のようにして得られる架橋ポリアミドエラ
ストマー樹脂から本発明の発泡粒子を製造するの
は容易であつて、この樹脂の粒子を、ポリスチレ
ンやポリオレフインの発泡粒子を製造する場合と
同様に、例えば特公昭56−1344号公報記載の方法
により発泡させればよい。すなわち、上記架橋樹
脂の粒子に揮発性溶剤型発泡剤を吸収させ、更に
分散媒と共に密閉容器中で加圧下に加熱したのち
分散媒と共に容器内よりも低圧の雰囲気に放出し
て発泡させる。用いる発泡剤としては、樹脂粒子
に浸透することのできる低沸点の有機化合物（通
常−50〜110℃程度の沸点を有するもの）が適当
である。その具体例としては、プロパン、ブタ
ン、ペンタン、ヘキサン、ヘプタン等の脂肪族炭
化水素類；シクロブタン、シクロペンタン等の環
式脂肪族炭化水素類；トリクロロフルオロメタ
ン、ジクロロフルオロメタン、ジクロロジフルオ
ロメタン、ジクロロテトラフルオロエタン、メチ
ルクロライド、エチルクロライド、メチレンクロ
ライド等のハロゲン化炭化水素類などがある。発
泡剤を樹脂粒子に吸収させるには、常温で、また
は加熱下に、両者を接触させればよいが、この工
程は、独立に行うほか、樹脂粒子を分散媒と共に
密閉容器中で加熱する工程と同時に行なつてもよ
い。その場合は、未処理の樹脂粒子、発泡剤およ
び分散媒を密閉容器に仕込み、撹拌しながら昇温
する。あるいは密閉容器内で未処理樹脂粒子およ
び分散媒を加熱し、所定の温度に達するまでの任
意の段階で、発泡剤を密閉容器内に注入し混合す
る。分散媒としては水を用いることができる。分
散媒に樹脂粒子を分散させて密閉容器中で加熱す
るに当り、分散媒にはほかに分散剤たとえば酸化
アルミニウム、酸化チタン、塩基性炭酸マグネシ
ウム、塩基性炭酸亜鉛、炭酸カルシウム等の微粉
末を添加して樹脂粒子の融着を防止してもよい。
分散剤の添加量は、樹脂粒子100重量部当り通常
0.01〜10重量部程度にすることが望ましい。加熱
工程における加熱温度は、樹脂の軟化温度以上、
樹脂粒子間の融着が起こらない程度の温度であれ
ばよい。好ましい温度はもちろん原料樹脂の種類
により異なるが、通常110〜150℃である。この温
度が高すぎると粒子同士の融着により次の発泡工
程に移すことが困難になるばかりでなく、気泡の
破壊が起こつて独立気泡率の低い発泡粒子となつ
てしまう。また加熱時間は特に限定されないが、
この加熱中に発泡剤を吸収させる場合は、発泡剤
が粒子中に均一に吸収されるまで処理する必要が
あること、いうまでもない。このあと、密閉容器
の内容物を容器内圧よりも低い圧力の雰囲気に放
出して発泡剤を気化させることにより樹脂粒子を
発泡させる。分散媒として水を用いた場合、上記
のようにして発泡させる雰囲気はふつう常圧の大
気でよい。
本発明による発泡粒子の発泡倍率は、上記の製
造条件を調整することにより、約５〜30倍とし、
また粒径は１〜10mmとすることが望ましい。
本発明による発泡粒子は、型内発泡成形法によ
つて、ポリウレタンフオームなみの高弾性発泡成
形体とすることができる。すなわち、常温常圧下
に養生したのち、望ましくは無機ガス、有機ガス
またはこれらの混合物中、加圧下に養成し、次い
で成形用型内に充填し、水蒸気吹込みにより加熱
して成形する。
本発明による発泡粒子は、上記型内成形におい
てポリスチレンやポリオレフインの発泡粒子とほ
ぼ同程度のすぐれた成形性を示し、成形時の収縮
はほとんどない。また、得られる成形体は、表面
が平滑で、微細かつ均一な気泡を含有し、更に、
架橋ポリアミドエラストマーのすぐれた特性に基
づき、良好なゴム弾性、引張強度、低温特性、耐
摩耗性、耐薬品性、耐水性、耐熱性、接着性、染
料親和性、および適度の親水性を備えているか
ら、ポリウレタンフオームよりも高性能の発泡成
形体として、断熱材、衣料、敷物、寝具、建材、
インテリア、自動車用品、包装材料など、多くの
分野で利用することができる。
以下実施例を示して本発明を説明する。なおこ
の明細書に示したメルトインデクスおよび熱キシ
レン不溶解残渣の測定法は次のとおりである。
メルトインデクス：ASTMD1238のＢ法によ
る。但し、測定温度は250℃とし、荷重は5000ｇ、
オリフイス径は2.1mm、オリフイス高さは８mmと
した。
熱キシレン不溶解残渣：精秤した試料約１ｇを
100c.c.の沸騰キシレンで処理したのち熱時濾過し、
残渣を真空乾燥後精秤し、試料重量に対する百分
率を求める。
実施例および比較例
ポリラウリンラクタムをハードセグメントとし
ポリエーテルエステル（テトラハイドロフランと
ドデカン二酸との共重合物；重合度約1000）をソ
フトセグメントとするポリアミド系エラストマ
ー・ダイアミド−PAE（ダイセル化学工業社製
品；Tm＝152℃）の粒子（平均直径２mm；平均
長さ３mm）100重量部を0.5重量部の微粒子状酸化
アルミニウムと共えに200重量部の水の中に分散
させる。分散液に更に架橋剤・ジクミルパーオキ
サイドを加え、オートクレーブ中で撹拌しながら
150℃まで３℃／分の昇温速度で昇温させ、その
後150℃で180分間、加熱して架橋処理を行う。
架橋剤の添加量を０〜2.0重量部の範囲で種々
変更して上記処理を行ない、５種類の架橋エラス
トマー樹脂を得た。各例樹脂の特性を表１に示
す。
次に樹脂粒子100重量部に対し水300重量部およ
び発泡剤（ジクロロジフルオロメタン）18重量部
を混合したものをオートクレーブに入れ、128℃
に昇温後、窒素ガスで背圧をかけながらオートク
レーブ底部の排出口を開いて内容物を大気中に放
出する方法により、上記処理後の樹脂粒子ならび
に市販のポリエステル系エラストマー樹脂（比較
例３）および熱可塑性ポリウレタン系エラストマ
ー樹脂（比較例４）から発泡粒子を製造した。
次に各発泡粒子は、大気中に48時間放置後、35
℃・2.5Kg／cm2Ｇの空気で48時間加圧養生してか
ら、20mm×300mm×300mmの成形用金型に充填し、
3.5Kg／cm2Ｇの水蒸気を吹込んで再発泡と粒子間
融着を起こさせることにより、板状に成形した。
上記のようにして得られた発泡粒子および発泡
成形体の性状を表２に示す。
The present invention relates to foamed particles of thermoplastic elastomer resin, which have excellent properties as a molding material for producing foamed molded articles exhibiting a high degree of rubber elasticity. Conventionally, polyurethane foam is a typical foam molded product that exhibits a high degree of rubber elasticity.
Since the bubbles are continuous air bubbles, this method has disadvantages in that it has poor compression properties and is expensive. In recent years, as a result of improvements in the quality of thermoplastic elastomer resins, products that are superior to polyurethane resins in many respects are now available at lower prices. The currently used foam molding method is to preliminarily foam these resin particles to form foamed particles, and then heat them in a mold to re-foam the foamed particles and fuse the particles together to form them. If foam molding can be carried out by this method, an elastic foam molded article with high physical properties can be obtained with high efficiency. However, contrary to expectations, when thermoplastic elastomer resins are foamed and molded in a molten state similar to polystyrene and polyolefins, although they do foam, they subsequently shrink significantly, resulting in severe deformation (including shrinkage). Moreover, the bubbles become coarse, and a completely satisfactory molded product cannot be obtained. The present inventors came up with the idea of making the difficult foam molding of thermoplastic elastomer resin possible as described above by improving the raw material resin,
As a result of various studies, we found that an elastomer obtained by crosslinking polyamide elastomer resin,
It was discovered that the resin has excellent foam moldability not found in conventional thermoplastic elastomer resins. The present invention is based on the above-mentioned findings, and the present invention is based on foamed particles that can easily produce high-quality elastic foam molded articles, that is, the resin constituting the foamed particles is composed of a block copolymer having a crystalline polyamide segment and a polyether segment. A cross-linked thermoplastic elastomer resin with a melt index of
Heat xylene insoluble residue is 60% without exceeding 40g/10 minutes
(However, the values of melt index and hot xylene insoluble residue are determined by the measurement method described later). Generally, when a crosslinkable thermoplastic synthetic resin is crosslinked, its fluidity during melting decreases depending on the degree of treatment, and eventually the resin loses its thermoplasticity. Although such changes in physical properties may be desirable in certain applications, they generally make melt extrusion and post-processing of molded products (e.g., stretching) difficult, so crosslinking is not recommended. There are few examples in which it is actually used as a means for modifying thermoplastic resins, and there are only very limited examples, such as crosslinking of polyolefins. In the field of thermoplastic elastomer resins, it is expected that this resin's greatest feature, that is, its thermoplasticity, which is unusual for an elastomer, will be diminished, worsening its moldability, and also reducing its vital rubber elasticity. Perhaps for this reason, there are almost no examples in which the use of crosslinking treatment has been considered. In particular, with regard to thermoplastic polyamide elastomer resin, it was not known whether it could be crosslinked or not, so this resin and its pre-expanded particles that were crosslinked within the range specified in the present invention acquired excellent foam moldability. Furthermore, it was completely unexpected that there was almost no deterioration in terms of physical and chemical properties, but rather improvements. The foamed particles according to the present invention are made of a polyamide elastomer resin that has been crosslinked as described above, but the change in the molecular structure of the resin due to crosslinking can be indirectly known from the increase in hot xylene insoluble residue. . In other words, uncrosslinked polyamide elastomer completely dissolves in hot xylene, but
As the degree of crosslinking increases, the thermal xylene insoluble residue increases, reaching a maximum of about 60 to 85%. The foamed particles according to the invention are crosslinked to such an extent that the hot xylene insoluble residue does not exceed 60%, so that the resin content is preferably 0.5 g/10 min or more, particularly preferably 1 to 25 g/10 min.
It maintains fluidity when melted showing a melt index of g/10 minutes. Although the site where crosslinks are formed in the copolymer molecular chain has not yet been completely elucidated, it is thought to be a soft segment mainly composed of polyether. Among polyamide-based elastomer resins, polylaurinlactam-polytetrahydrofuran block copolymer is preferred as the raw material resin for the crosslinked elastomer constituting the expanded particles of the present invention. However, the soft segment of this polymer is
In addition to polytetrahydrofuran, adipic acid,
It may also contain a group derived from a third component such as azelaic acid or dodecanedioic acid. Particularly preferred among these copolymers are those containing 30 to 80% by weight of polylaurinlactam segments and 20 to 50% by weight of polytetrahydrofuran segments. This resin is superior to other polyamide-based elastomer resins in that it provides an elastomer resin with excellent foam moldability and other properties while maintaining the melt index required for the elastomer resin constituting the expanded particles of the present invention. ing. The crosslinking method for producing the crosslinked elastomer resin for expanded particles according to the present invention from the polyamide elastomer resin may be any of the methods used for crosslinking of polyolefin resins, such as chemical crosslinking, electron beam crosslinking, and radiation crosslinking. However, the most suitable method is chemical crosslinking. As a crosslinking agent, t
-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-t-
Butylperoxy-3-hexyne, 2,2-bis(t-butylperoxy)propane, bis(t-
Butylperoxy)diphenylsilane and the like are suitable. During the treatment, the resin particles may be suspended using water, ethanol, ethylene glycol, or the like as a dispersion medium, and a suitable crosslinking aid may be used in combination.
Modification of the raw material resin by crosslinking proceeds in a manner roughly proportional to the degree of crosslinking, so when considered as a polyamide elastomer resin modification method, there is no lower limit to the degree of crosslinking, but in order to obtain an elastomer that can be foam-molded, It is desirable that the crosslinking proceed until at least 0.5% of the thermally xylene insoluble residue is reached. It is easy to produce the foamed particles of the present invention from the crosslinked polyamide elastomer resin obtained as described above, and the particles of this resin can be used, for example, in the Foaming may be carried out by the method described in Japanese Patent No. 56-1344. That is, the particles of the crosslinked resin absorb a volatile solvent-based foaming agent, are heated under pressure together with a dispersion medium in a closed container, and are then discharged together with the dispersion medium into an atmosphere at a lower pressure than the inside of the container to cause foaming. As the blowing agent to be used, a low boiling point organic compound (usually having a boiling point of about -50 to 110°C) that can permeate into the resin particles is suitable. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, and heptane; cyclic aliphatic hydrocarbons such as cyclobutane and cyclopentane; trichlorofluoromethane, dichlorofluoromethane, dichlorodifluoromethane, and dichlorofluoromethane. Examples include halogenated hydrocarbons such as tetrafluoroethane, methyl chloride, ethyl chloride, and methylene chloride. In order to absorb the blowing agent into the resin particles, the two may be brought into contact at room temperature or under heating, but this step can be carried out independently or by heating the resin particles together with a dispersion medium in a closed container. It may be done at the same time. In that case, untreated resin particles, a blowing agent, and a dispersion medium are placed in a closed container, and the temperature is raised while stirring. Alternatively, untreated resin particles and a dispersion medium are heated in a closed container, and at any stage until a predetermined temperature is reached, a blowing agent is injected into the closed container and mixed. Water can be used as a dispersion medium. When dispersing resin particles in a dispersion medium and heating it in a closed container, the dispersion medium also contains fine powders of dispersants such as aluminum oxide, titanium oxide, basic magnesium carbonate, basic zinc carbonate, calcium carbonate, etc. It may be added to prevent fusion of resin particles.
The amount of dispersant added is usually per 100 parts by weight of resin particles.
It is desirable that the amount is about 0.01 to 10 parts by weight. The heating temperature in the heating process is higher than the softening temperature of the resin,
The temperature may be a temperature that does not cause fusion between resin particles. The preferred temperature naturally varies depending on the type of raw material resin, but is usually 110 to 150°C. If this temperature is too high, not only will it be difficult to proceed to the next foaming step due to fusion of the particles, but also the bubbles will be destroyed, resulting in foamed particles with a low closed cell ratio. Also, the heating time is not particularly limited, but
Needless to say, if the blowing agent is to be absorbed during this heating, it is necessary to carry out the treatment until the blowing agent is uniformly absorbed into the particles. Thereafter, the resin particles are foamed by releasing the contents of the sealed container into an atmosphere having a pressure lower than the internal pressure of the container to vaporize the foaming agent. When water is used as a dispersion medium, the atmosphere in which foaming is carried out as described above may generally be atmospheric pressure. The expansion ratio of the expanded particles according to the present invention is approximately 5 to 30 times by adjusting the above manufacturing conditions,
Further, the particle size is preferably 1 to 10 mm. The foamed particles according to the present invention can be made into a highly elastic foamed molded product comparable to polyurethane foam by an in-mold foaming method. That is, after being cured at room temperature and pressure, it is cured under pressure, preferably in an inorganic gas, an organic gas, or a mixture thereof, and then filled into a mold and heated by steam injection to form the product. The expanded particles according to the present invention exhibit excellent moldability in the above-mentioned in-mold molding, which is almost as good as that of expanded particles of polystyrene or polyolefin, and there is almost no shrinkage during molding. In addition, the obtained molded product has a smooth surface and contains fine and uniform air bubbles, and further,
Based on the excellent properties of crosslinked polyamide elastomers, it has good rubber elasticity, tensile strength, low temperature properties, abrasion resistance, chemical resistance, water resistance, heat resistance, adhesion, dye affinity, and moderate hydrophilicity. Because of this, it can be used as a foam molded product with higher performance than polyurethane foam, such as insulation materials, clothing, rugs, bedding, building materials, etc.
It can be used in many fields such as interior design, automotive supplies, and packaging materials. The present invention will be explained below with reference to Examples. The methods for measuring the melt index and hot xylene insoluble residue shown in this specification are as follows. Melt index: According to method B of ASTMD1238. However, the measurement temperature is 250℃, the load is 5000g,
The orifice diameter was 2.1 mm, and the orifice height was 8 mm. Hot xylene insoluble residue: Approximately 1 g of accurately weighed sample
After treatment with 100c.c. of boiling xylene, it is filtered while hot.
After drying the residue under vacuum, accurately weigh it and determine the percentage relative to the sample weight. Examples and Comparative Examples Polyamide elastomer Diamide-PAE (Daicel Chemical Industries, Ltd. 100 parts by weight of particles (average diameter 2 mm; average length 3 mm) of Tm = 152° C. are dispersed in 200 parts by weight of water together with 0.5 part by weight of finely divided aluminum oxide. Add a cross-linking agent, dicumyl peroxide, to the dispersion and stir in an autoclave.
The temperature is raised to 150°C at a rate of 3°C/min, and then the crosslinking treatment is performed by heating at 150°C for 180 minutes. The above treatment was carried out while varying the amount of the crosslinking agent added in the range of 0 to 2.0 parts by weight to obtain five types of crosslinked elastomer resins. Table 1 shows the properties of each example resin. Next, a mixture of 100 parts by weight of resin particles, 300 parts by weight of water, and 18 parts by weight of a blowing agent (dichlorodifluoromethane) was placed in an autoclave and heated to 128°C.
After raising the temperature to , by applying back pressure with nitrogen gas and opening the outlet at the bottom of the autoclave to release the contents into the atmosphere, the resin particles after the above treatment and commercially available polyester elastomer resin (Comparative Example 3) and a thermoplastic polyurethane-based elastomer resin (Comparative Example 4). Each foamed particle was then left in the atmosphere for 48 hours and then
After curing under pressure in air at 2.5Kg/ cm2G for 48 hours, it was filled into a 20mm x 300mm x 300mm mold.
It was molded into a plate by blowing water vapor at 3.5 kg/cm 2 G to cause re-foaming and interparticle fusion. Table 2 shows the properties of the expanded particles and expanded molded product obtained as described above.
【表】【table】
Claims (1)
子において、該発泡粒子を構成する樹脂が結晶性
ポリアミドセグメントおよびポリエーテルセグメ
ントを有するブロツク共重合体からなる熱可塑性
エラストマー樹脂の架橋処理物であつてメルトイ
ンデクスが40ｇ／10分をこえず熱キシレン不溶解
残渣が60％をこえないものよりなることを特徴と
する発泡粒子。 ２ ブロツク共重合体がポリラウリンラクタムセ
グメントおよびポリテトラハイドロフランセグメ
ントを有するブロツク共重合体である特許請求の
範囲第１項記載の発泡粒子。 ３ ブロツク共重合体がポリラウリンラクタムセ
グメント30〜80重量およびポリテトラハイドロフ
ランセグメント20〜50重量％を含有するものであ
る特許請求の範囲第２項記載の発泡粒子。 ４ 架橋処理物のメルトインデクスが１〜25ｇ／
10分である特許請求の範囲第１項記載の発泡粒
子。 ５ 架橋処理物の熱キシレン不溶解残渣が0.5〜
45％である特許請求の範囲第１項記載の発泡粒
子。[Scope of Claims] 1. Expanded particles for producing thermoplastic synthetic resin foam molded articles, in which the resin constituting the expanded particles is made of a thermoplastic elastomer resin consisting of a block copolymer having a crystalline polyamide segment and a polyether segment. 1. Expanded particles characterized by being crosslinked, having a melt index not exceeding 40 g/10 minutes, and having a thermal xylene insoluble residue not exceeding 60%. 2. The expanded particles according to claim 1, wherein the block copolymer is a block copolymer having a polylaurinlactam segment and a polytetrahydrofuran segment. 3. The expanded particles according to claim 2, wherein the block copolymer contains 30 to 80% by weight of polylaurinlactam segments and 20 to 50% by weight of polytetrahydrofuran segments. 4 The melt index of the crosslinked product is 1 to 25g/
The foamed particles according to claim 1, wherein the foaming time is 10 minutes. 5 The thermal xylene insoluble residue of the crosslinked product is 0.5~
45% expanded particles according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14968183A JPS6042432A (en) | 1983-08-18 | 1983-08-18 | Foamed particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14968183A JPS6042432A (en) | 1983-08-18 | 1983-08-18 | Foamed particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6042432A JPS6042432A (en) | 1985-03-06 |
| JPH0417977B2 true JPH0417977B2 (en) | 1992-03-26 |
Family
ID=15480491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14968183A Granted JPS6042432A (en) | 1983-08-18 | 1983-08-18 | Foamed particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6042432A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016188342A (en) * | 2015-03-30 | 2016-11-04 | 積水化成品工業株式会社 | Amide foamed resin particle and foamed molding |
| JP2017066279A (en) * | 2015-09-30 | 2017-04-06 | 積水化成品工業株式会社 | Surface modified expandable particle, manufacturing method of foam particle and manufacturing method of foam molded body |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1650255A1 (en) * | 2004-10-19 | 2006-04-26 | Arkema | Polyether block amide foam |
| DE102014216992A1 (en) * | 2014-08-26 | 2016-03-03 | Adidas Ag | Expanded polymer pellets |
| US20170283555A1 (en) * | 2014-09-30 | 2017-10-05 | Sekisui Plastics Co., Ltd. | Amide elastomer foam particles, method for producing same, foam molded body and method for producing foam molded body |
| JP6422839B2 (en) * | 2015-09-28 | 2018-11-14 | 積水化成品工業株式会社 | Surface-modified foamable particles, method for producing foamed particles, and method for producing foamed molded articles |
| JP6539612B2 (en) * | 2016-03-30 | 2019-07-03 | 積水化成品工業株式会社 | Polyamide-based resin foam sheet, laminated sheet, foam-molded article, and method for producing polyamide-based resin foam sheet |
| JP7080833B2 (en) * | 2016-06-23 | 2022-06-06 | ビーエーエスエフ ソシエタス・ヨーロピア | A method for producing foamed particles made of a thermoplastic elastomer having a polyamide segment. |
| WO2018142467A1 (en) * | 2017-01-31 | 2018-08-09 | 株式会社アシックス | Sole member and shoe |
| JP6741164B2 (en) | 2017-09-07 | 2020-08-19 | 株式会社村田製作所 | Circuit block assembly |
| CN110294860B (en) * | 2018-03-21 | 2021-08-24 | 加久企业股份有限公司 | Process for producing elastic composite material and product thereof |
-
1983
- 1983-08-18 JP JP14968183A patent/JPS6042432A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016188342A (en) * | 2015-03-30 | 2016-11-04 | 積水化成品工業株式会社 | Amide foamed resin particle and foamed molding |
| JP2017066279A (en) * | 2015-09-30 | 2017-04-06 | 積水化成品工業株式会社 | Surface modified expandable particle, manufacturing method of foam particle and manufacturing method of foam molded body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6042432A (en) | 1985-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0450205B1 (en) | Method for preparing moldable shrunken thermoplastic polymer foam beads | |
| JPS5943492B2 (en) | Manufacturing method of polypropylene resin foam molding | |
| EP0142724B1 (en) | Pre-foamed beads of polyethylene-base resin | |
| EP0296438A2 (en) | Pre-foamed particles of uncrosslinked, linear low-density polyethylene and production method thereof | |
| JPS5943491B2 (en) | Polypropylene resin foam molding | |
| JPH0417977B2 (en) | ||
| JPH0419258B2 (en) | ||
| WO1996025281A1 (en) | Polymeric foam preparation | |
| JP2709395B2 (en) | Non-crosslinked linear low-density polyethylene resin particles for foaming and method for producing non-crosslinked linear low-density polyethylene expanded particles | |
| JP2505543B2 (en) | Method for producing foam containing crystalline propylene resin | |
| JPH06104749B2 (en) | Moldable shrinkable thermoplastic polymer foam beads | |
| JPS6244778B2 (en) | ||
| JP2892210B2 (en) | Lightly crosslinked linear low density polyethylene pre-expanded particles and their preparation | |
| JPH0348936B2 (en) | ||
| JPS5858208B2 (en) | Manufacturing method for crosslinked molded products | |
| JPS6153338A (en) | Foam-molded article having composite structure and its production | |
| JPS5846210B2 (en) | Diaryl phthalate resin foam composition | |
| JPH0464335B2 (en) | ||
| JPS6020943A (en) | Non-crosslinked polyethylene resin expanded particle | |
| JPS6026029A (en) | Thermoplastic elastomer resin | |
| JPH0437095B2 (en) | ||
| JPS6324616B2 (en) | ||
| JPS5865734A (en) | Foamed polypropylene resin particles and preparing same | |
| JPH0350693B2 (en) | ||
| JPH0610275B2 (en) | Expanded polypropylene resin particles and method for producing the same |