JPH0344100B2 - - Google Patents
Info
- Publication number
- JPH0344100B2 JPH0344100B2 JP4239583A JP4239583A JPH0344100B2 JP H0344100 B2 JPH0344100 B2 JP H0344100B2 JP 4239583 A JP4239583 A JP 4239583A JP 4239583 A JP4239583 A JP 4239583A JP H0344100 B2 JPH0344100 B2 JP H0344100B2
- Authority
- JP
- Japan
- Prior art keywords
- foam
- foaming
- polyolefin
- weight
- composition
- 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
- 239000000203 mixture Substances 0.000 claims description 32
- 238000005187 foaming Methods 0.000 claims description 27
- 229920000098 polyolefin Polymers 0.000 claims description 21
- 239000004604 Blowing Agent Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000001408 amides Chemical class 0.000 claims description 11
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 150000008282 halocarbons Chemical group 0.000 claims description 6
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 claims description 5
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000006260 foam Substances 0.000 description 37
- 238000000034 method Methods 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 15
- 239000000654 additive Substances 0.000 description 13
- -1 polyethylene Polymers 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 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
- 239000002667 nucleating agent Substances 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006866 deterioration Effects 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
- 238000010097 foam moulding Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- ARZGWBJFLJBOTR-UHFFFAOYSA-N tetradecanamide Chemical compound CCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCC(N)=O ARZGWBJFLJBOTR-UHFFFAOYSA-N 0.000 description 2
- ZXUJWPHOPHHZLR-UHFFFAOYSA-N 1,1,1-trichloro-2-fluoroethane Chemical compound FCC(Cl)(Cl)Cl ZXUJWPHOPHHZLR-UHFFFAOYSA-N 0.000 description 1
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 description 1
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- RVMIUSRRVBURBU-UHFFFAOYSA-N 2-(2-hydroxyethyl)tetradecanamide Chemical compound OCCC(C(=O)N)CCCCCCCCCCCC RVMIUSRRVBURBU-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- MMBILEWCGWTAOV-UHFFFAOYSA-N N-(2-Hydroxypropyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCC(C)O MMBILEWCGWTAOV-UHFFFAOYSA-N 0.000 description 1
- LMVSBYPDMNAXPF-UHFFFAOYSA-N N-(decanoyl)ethanolamine Chemical compound CCCCCCCCCC(=O)NCCO LMVSBYPDMNAXPF-UHFFFAOYSA-N 0.000 description 1
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 1
- OTGQIQQTPXJQRG-UHFFFAOYSA-N N-(octadecanoyl)ethanolamine Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCO OTGQIQQTPXJQRG-UHFFFAOYSA-N 0.000 description 1
- GSILMNFJLONLCJ-UHFFFAOYSA-N N-(octanoyl)ethanolamine Chemical compound CCCCCCCC(=O)NCCO GSILMNFJLONLCJ-UHFFFAOYSA-N 0.000 description 1
- JHIXEZNTXMFXEK-UHFFFAOYSA-N N-(tetradecanoyl)ethanolamine Chemical compound CCCCCCCCCCCCCC(=O)NCCO JHIXEZNTXMFXEK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 1
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 1
- 229940081141 hexadecanamide Drugs 0.000 description 1
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WBGPNPZUWVTYAA-UHFFFAOYSA-N methane;dihydrochloride Chemical compound C.Cl.Cl WBGPNPZUWVTYAA-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- YQSBEIIQKPQGCO-UHFFFAOYSA-N n-(2-hydroxypropyl)decanamide Chemical compound CCCCCCCCCC(=O)NCC(C)O YQSBEIIQKPQGCO-UHFFFAOYSA-N 0.000 description 1
- VQNMGLLFMPXVFN-UHFFFAOYSA-N n-(2-hydroxypropyl)hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCC(C)O VQNMGLLFMPXVFN-UHFFFAOYSA-N 0.000 description 1
- WEJHDPCZRFVRCX-UHFFFAOYSA-N n-(2-hydroxypropyl)hexanamide Chemical compound CCCCCC(=O)NCC(C)O WEJHDPCZRFVRCX-UHFFFAOYSA-N 0.000 description 1
- QCTVGFNUKWXQNN-UHFFFAOYSA-N n-(2-hydroxypropyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCC(C)O QCTVGFNUKWXQNN-UHFFFAOYSA-N 0.000 description 1
- HYALHALGUKZZPY-UHFFFAOYSA-N n-(2-hydroxypropyl)octanamide Chemical compound CCCCCCCC(=O)NCC(C)O HYALHALGUKZZPY-UHFFFAOYSA-N 0.000 description 1
- WGBIOGHOLKYEAM-UHFFFAOYSA-N n-(2-hydroxypropyl)tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCC(C)O WGBIOGHOLKYEAM-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- XWIHRGFIPXWGEF-UHFFFAOYSA-N propafenone hydrochloride Chemical compound Cl.CCCNCC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 XWIHRGFIPXWGEF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003756 stirring Methods 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は発泡性ポリオレフイン組成物に関し、
さらに詳しくは、ポリオレフインと揮発性有機発
泡剤に特定のアミド及び特定の水酸基を有する化
合物から成る発泡改良剤を配合した新規な発泡性
ポリオレフイン組成物に関するものである。
これまで、無架橋ポリオレフインに、揮発性有
機発泡剤を加えて押出発泡させることによりポリ
オレフイン発泡成形体を得ることは知られてお
り、このようにして得られた発泡成形体は、断熱
材、緩衝材、包装材などとして広く用いられてい
る。
しかしながら、一般にポリオレフインは、加熱
溶融時の粘弾性が小さく発泡剤のガス圧を十分に
保持し得ないため、形成されるセルがある程度大
きくなると崩壊する、冷却し結晶化する際に発熱
を伴うため、セルの冷却固化が円滑に行われな
い、ガスに対する透過性が大きいため、発泡剤が
気化する際、揮散しやすく十分な発泡が行われな
いなどの欠点を有し、均質なセル構造をもち、外
観の良好な高発泡体を得ることが困難である。
例えば、これまでに提案されている方法（特公
昭35−4341号公報）は、高発泡が可能な発泡条件
が非常に狭い範囲に制限されている上に、この発
泡条件を長時間にわたつて制御することが困難で
あり、また、特殊な設備を必要とするため、工業
的に実施する方法として必ずしも満足しうるもの
とはいえない。
このような問題点を解決するために、ポリオレ
フインを約５倍以上の発泡倍率の高発泡成形体と
するには、ポリオレフインをあらかじめ過酸化物
又は放射線などで処理して架橋化し、これを発泡
成形する方法が提案されているが、これには架橋
化のための特別な工程を必要とすることになり、
製品がコスト高になるのを免れない。
他方、高密度ポリエチレンのような結晶化度の
高いポリエチレンは、低密度ポリエチレンに比べ
て融点付近での粘弾性的特性の変化が大きいため
押出成形温度の範囲が著しく制限され、特に厚み
のある発泡体を目的とした連続押出成形の適正な
条件、管理を維持することが、いつそう困難にな
る。また、高密度ポリエチレンは、低密度ポリエ
チレンに比べて結晶化度が高いため前記した結晶
化の際の発熱量が大きく、冷却時のセルの固化が
より妨害される結果、セルの破壊や変形を生じ押
出成形性の低下や製品の品質劣化を生じる。そし
て、一般に、発泡体の厚みが厚くなるほど結晶化
の際の発熱の蓄積が多くなり、いつそうセルの冷
却固化が順調に行われなくなるため、この傾向は
大きくなる。さらに、高密度ポリエチレンは、低
密度ポリエチレンが長鎖分岐を有していて溶融粘
弾性が高いのに対し、長鎖分岐を有さず溶融粘弾
性が低いため発泡剤とともにダイスから押出し、
発泡成形する際に、ダイス内での気泡の発生を抑
制するだけの耐圧性を示すことができず、ダイス
内ですでに形成されたセルが押出発泡の過程で熱
及びせん断力を受けて破壊され、発泡体の品質劣
化をもたらす。そして、これはダイス開口部の断
面積が大きくなるほど、すなわち発泡体の厚みを
厚くするほど増大する傾向にある。この点を解決
するには、押出量を増大して樹脂圧力を大きくす
ればよいが、ダイス内での気泡生成による悪影響
を完全に除くには著しく大量の押出量を必要とす
るため、大押出容量の能力を有する極めて特殊な
装置を用いなければならないし、また押出量を極
端に増加させるとメルトフラクチヤーなどの流れ
の乱れを生じ、押出成形性が低下することになる
ので実用的でない。
このように、これまで知られているポリエチレ
ンを原料として、品質の優れた高発泡成形体を製
造するための方法は、いずれも工業的に実施可能
な方法として、必ずしも満足しうるものとはいえ
ず、特に断面積の大きな肉厚発泡体を得ることは
困難であつた。
本発明者らは、このような事情に鑑み、無架橋
のポリエチレン特に高密度ポリエチレンを原料と
して、外観が良好であつて独立したセル構造を有
し、かつ断面積の大きな高発泡成形体を得るため
に鋭意研究を重ねた結果、発泡改良剤として特定
のアミドと特定の水酸基を有する化合物の組合せ
を用いることにより、その目的を達成しうること
を見出し、この知見に基づいて本発明を完成する
に至つた。
すなわち、本発明は、(イ)ポリオレフインと、(ロ)
揮発性有機発泡剤と、(ハ)一般式
（式中のR1は炭素数１〜23の炭化水素基、R2は
炭素数１〜５のアルキレン基、ｘは１〜10の整
数、ｙは０又は１〜２の整数である）
で示されるアミドの少なくとも一種及び一般式
（式中のｌ及びｎは０又は１以上の整数、ｍは１
以上の整数である）
で示される化合物の少なくとも１種を組み合わせ
た発泡改良剤とから成る発泡性ポリオレフイン組
成物を提供するものである。
本発明組成物においては、発泡改良剤として、
前記(ハ)成分発泡改良剤として一般式（）で示さ
れるアミド類と一般式（）で示される化合物と
の組合せを用いることが必要であつて、この組合
せを用いることにより、肉厚発泡体の成形により
適した発泡性組成物を得ることができる。
前記の一般式（）及び（）で示される化合
物は、いずれも既知の化合物であるか、あるいは
既知の方法によつて容易に製造しうるものであ
る。この一般式（）で示されるアミドの例とし
ては、ヘキサンアミド、オクタンアミド、デカン
アミド、ドデカンアミド、テトラデカンアミド、
オクタデカンアミドＮ−２−ヒドロキシエチル−
ヘキサンアミド、Ｎ−２−ヒドロキシエチル−オ
クタンアミド、Ｎ−２−ヒドロキシエチル−デカ
ンアミド、Ｎ−２−ヒドロキシエチル−ドデカン
アミド、Ｎ−２−ヒドロキシエチル−テトラデカ
ンアミド、Ｎ−２−ヒドロキシエチル−ヘキサデ
カンアミド、Ｎ−２−ヒドロキシエチル−オクタ
デカンアミド、Ｎ，Ｎ−ジ−２−ヒドロキシエチ
ル−ヘキサンアミド、Ｎ，Ｎ−ジ−２−ヒドロキ
シエチル−オクタンアミド、Ｎ，Ｎ−ジ−２−ヒ
ドロキシエチル−デカンアミド、Ｎ，Ｎ−ジ−２
−ヒドロキシエチル−ドデカンアミド、Ｎ，Ｎ−
２−ヒドロキシエチル−テトラデカンアミド、
Ｎ，Ｎ−ジ−２−ヒドロキシエチル−ヘキサデカ
ンアミド、Ｎ，Ｎ−ジ−２−ヒドロキシエチル−
オクタデカンアミド、Ｎ−モノ−２−ヒドロキシ
プロピル−ヘキサンアミド、Ｎ−モノ−２−ヒド
ロキシプロピル−オクタンアミド、Ｎ−モノ−２
−ヒドロキシプロピル−デカンアミド、Ｎ−モノ
−２−ヒドロキシプロピル−ドデカンアミド、Ｎ
−モノ−２−ヒドロキシプロピル−テトラデカン
アミド、Ｎ−モノ−２−ヒドロキシプロピル−ヘ
キサデカンアミド、Ｎ−モノ−２−ヒドロキシプ
ロピル−オクタデカンアミド、Ｎ，Ｎ−ジ−２−
ヒドロキシプロピル−ヘキサンアミド、Ｎ，Ｎ−
ジ−２−ヒドロキシプロピル−オクタンアミド、
Ｎ，Ｎ−ジ−２−ヒドロキシプロピル−デカンア
ミド、Ｎ，Ｎ−ジ−２−ヒドロキシプロピル−ド
デカンアミド、Ｎ，Ｎ−２−ヒドロキシプロピル
−テトラデカンアミド、Ｎ，Ｎ−ジ−２−ヒドロ
キシプロピル−ヘキサデカンアミド、Ｎ，Ｎ−ジ
−２−ヒドロキシプロピル−オクタデカンアミ
ド、ポリオキシエチレンヘキサンアミド、ポリオ
キシエチレンオクタンアミド、ポリオキシエチレ
ンデカンアミド、ポリオキシエチレンドデカンア
ミド、ポリオキシエチレンテトラデカンアミド、
ポリオキシエチレンヘキサデカンアミド、ポリオ
キシエチレンオクタデカンアミドなどを挙げるこ
とができる。これらの中で特に好ましいものは、
ドデカンアミド、テトラデカンアミド、ヘキサデ
カンアミド、オクタデカンアミド、Ｎ−モノ−
（及びＮ，Ｎ−ジ）２−ヒドロキシエチルドデカ
ンアミド、Ｎ−モノ−（及びＮ，Ｎ−ジ−）２−
ヒドロキシエチルテトラデカンアミド、Ｎ−モノ
−（及びＮ，Ｎ−ジ−）２−ヒドロキシエチルヘ
キサデカンアミド、Ｎ−モノ−（及びＮ，Ｎ−ジ
−）２−ヒドロキシエチルオクタデカンアミドな
どである。これらのアミドは単独で用いてもよい
し、２種以上組み合せて用いてもよい。
また、一般式（）で示される化合物の例とし
ては、ポリプロピレングリコール及び例えばポリ
プロピレングリコールの両端に酸化エチレンを付
加重合させて得られるポリオキシエチレン−ポリ
オキシプロピレンブロツクポリマーなどを挙げる
ことができるが、好ましいものは、ポリオキシエ
チレン−ポリオキシプロピレンブロツクポリマー
であり、特に好ましいものは、一般式（）にお
いて、ｌ及びｎが１〜90、ｍが10〜40の範囲にあ
るポリオキシエチレン−ポリオキシプロピレンブ
ロツクポリマーである。これらの化合物は単独で
用いてもよいし、あるいは２種以上組み合わせて
用いてもよい。
前記一般式（）で示されるアミド及び一般式
（）で示される化合物の配合量としては、(イ)成
分のポリオレフイン100重量部当り、両者合わせ
て0.05〜15重量部、好ましくは0.1〜10重量部の
範囲内で選ばれる。この量が0.05重量部未満では
発泡体の断面積増大効果が十分でなく、また15重
量部を超えると量が増大してもその割に効果が増
大せず経済的でない。
この一般式（）で示されるアミドと一般式
（）で示される化合物の配合比は80：20ないし
１：99の範囲であることが好ましく、特に７：３
ないし１：９の範囲が好適である。
本発明の組成物に用いられる(イ)成分のポリオレ
フインとしては、例えばポリエチレン、ポリプロ
ピレン、ポリブテン−１、１，２−ポリブタジエ
ン、１，３−ポリブタジエン、エチレン−プロピ
レン共重合体、エチレン又はプロピレンと他のα
−オレフイン類との共重合体、あるいはエチレン
−酢酸ビニル共重合体、エチレン−エチルアクリ
レート共重合体、エチレン−塩化ビニル共重合
体、エチレン系アイオノマー（エチレン−アクリ
ル酸共重合体の亜鉛又はナトリウム塩のようなエ
チレンと不飽和カルボン酸の共重合体の金属塩）
などのエチレンを主成分とする共重合体などが挙
げられるが、これらの中で密度0.930ｇ／cm3以上
の高密度ポリエチレンが好ましい。
本発明の組成物においては、これらのポリオレ
フインを単独で用いてもよいし、また２種以上混
合して用いてもよく、さらにこれらのポリオレフ
インを主成分として他の樹脂類を適宜配合して用
いることもできる。
本発明の組成物に用いる(ロ)成分の揮発性有機発
泡剤としては、例えば炭化水素、ハロゲン化炭化
水素があり、この炭化水素の具体例としてはプロ
パン、ブタン、ペンタン、ペンテン、ヘキサンな
どが、またハロゲン化炭化水素の具体例としては
塩化メチル、二塩化メタン、トリクロロモノフル
オロエタン、ジクロロジフルオロメタン、モノク
ロロトリフルオロメタン、ジクロロモノフルオロ
メタン、モノクロロジフルオロメタン、トリクロ
ロトリフルオロエタン、ジクロロテトラフルオロ
エタン、モノクロロペンタフルオロエタンなどが
挙げられる。これらの中で好ましいものは、少な
くともジクロロテトラフルオロエタンを含むハロ
ゲン化炭化水素であり、特にジクロロジフルオロ
エタン30重量％以上を含むハロゲン化炭化水素が
好適である。
本発明の組成物における前記揮発性有機発泡剤
の混合割合は、ポリオレフイン100重量部当り５
〜150重量部の範囲が望ましく、さらに好ましく
は10〜100重量部の範囲であつて、５重量部未満
では高発泡体を得ることが困難であり、また150
重量部を超えると発泡体の断面積の増大効果が小
さくなる。
本発明の組成物として特に好適なものは、温度
190℃、荷重21.6Kgで測定したメルトインデツク
ス（HMI）が35ｇ／10分以下でかつ密度が0.930
ｇ／cm3以上の高密度ポリエチレンに対し、揮発性
有機発泡剤としてジクロロテトラフルオロエタン
と、他のハロゲン化炭化水素例えばトリクロロモ
ノフルオロメタン、ジクロロモノフルオロメタ
ン、ジクロロジフルオロメタン、トリクロロトリ
フルオロエタン、塩化メチル、二塩化メタンの中
から選ばれた少なくとも１種との組合せと、前記
一般式（）のアミド及び一般式（）の化合物
とを配合したものである。
本発明組成物には、必要に応じて、通常使用さ
れる気泡核形成剤を含ませることができる。この
気泡核形成剤としては、例えばタルク、酸化ケイ
素のような無機質微粉末や、ステアリン酸亜鉛、
ステアリン酸カルシウムのような有機質微粉末や
クエン酸、炭酸水素ナトリウムのような加熱によ
りガスを発生しうる微粉末などが用いられる。そ
の他、紫外線吸収剤、酸化防止剤、帯電防止剤、
着色剤なども所望に応じて含ませることができ
る。
本発明組成物を調製するには、前記(イ)〜(ニ)成分
及び必要に応じて配合される添加成分の所定量
を、均一な混合物の調製の際に慣用されている任
意の方法によつて混合する。特に好適なのは、マ
スターバツヂ法やドライブレンド法である。各成
分の添加順序には特に制限はないが、通常は、あ
らかじめ揮発性有機発泡剤以外の成分を混合した
のち、押出発泡工程でこの発泡剤を混入する方法
がとられる。
本発明の組成物から発泡体を製造する方法とし
ては、例えば組成物を高温高圧下で調製し、次い
でこれを低温低圧域に開放して発泡体を形成させ
る方法が通常用いられる。この際の成形方法とし
ては、例えば押出発泡法、プレス発泡法、射出発
泡法、型内発泡法などを適用しうるが、有利なの
は押出発泡法である。
このようにして、各種形状の押出発泡体成形
体、例えばシート、ボード、棒、チユーブ、パイ
プ、ネツトなどを製造することができる。
また、本発明の組成物は特に肉厚のボードを製
造する際に好適である。
本発明の組成物から得られた発泡体は、その発
泡倍率が５〜150倍の高発泡体であつて、優れた
断熱性と緩衝性を有しており、例えば断熱材、緩
衝材、包装材などとして有用である。
次に実施例によつて本発明をさらに詳細に説明
する。
なお、実施例及び比較例中の発泡体の評価は次
の評価方法及び基準に従つて行つた。
(1) 発泡倍率
発泡体密度をJIS−K6767に基づいて発泡後
15日を経た発泡体の重量と体積より算出し、発
泡倍率を次の式に従つて求めた。
発泡倍率＝発泡前の樹脂密度／発泡体の密度
(2) 断面積係数
断面積の大きい肉厚成形品の成形に対する適
性を評価する尺度であつて、次式に従つて断面
積係数を求めた。
断面積係数
＝発泡体断面積／（ダイ開口部断面積）×（発泡倍
率）2/3
この値が大きいほど、例えば円形ダイならば押
出方向よりも直径方向に、短形ダイならば押出方
向よりも厚み方向に大きく発泡し、少量の押出量
で発泡体断面積の大きい発泡体が得られ、厚物の
成形に適していることになる。
また、各実施例及び比較例で用いた添加剤を第
１表と第２表に示す。
The present invention relates to a foamable polyolefin composition,
More specifically, the present invention relates to a novel foamable polyolefin composition in which a foaming improver consisting of a compound having a specific amide and a specific hydroxyl group is blended with a polyolefin and a volatile organic blowing agent. Until now, it has been known to obtain a polyolefin foam molded product by adding a volatile organic foaming agent to non-crosslinked polyolefin and foaming it by extrusion. It is widely used as materials, packaging materials, etc. However, in general, polyolefins have low viscoelasticity when heated and melted and cannot sufficiently maintain the gas pressure of the blowing agent, so they collapse when the formed cells grow to a certain extent, and generate heat when cooled and crystallized. , the cells do not cool and solidify smoothly, and because the foaming agent is highly permeable to gas, it easily evaporates when the foaming agent evaporates, preventing sufficient foaming. , it is difficult to obtain a highly foamed product with good appearance. For example, in the method proposed so far (Japanese Patent Publication No. 35-4341), the foaming conditions that allow for high foaming are limited to a very narrow range, and the foaming conditions are not maintained for a long time. Since it is difficult to control and requires special equipment, it cannot necessarily be said to be a satisfactory method for industrial implementation. To solve these problems, in order to make polyolefin into a highly foamed molded product with an expansion ratio of about 5 times or more, polyolefin is first treated with peroxide or radiation to crosslink it, and then this is foam-molded. However, this method requires a special process for crosslinking.
It is inevitable that products will cost more. On the other hand, polyethylene with a high degree of crystallinity, such as high-density polyethylene, has a large change in viscoelastic properties near its melting point compared to low-density polyethylene, so the extrusion temperature range is significantly restricted. Maintaining proper conditions and controls for continuous extrusion molding for body purposes becomes increasingly difficult. In addition, because high-density polyethylene has a higher degree of crystallinity than low-density polyethylene, it generates a large amount of heat during the crystallization described above, and as a result, the solidification of cells during cooling is further hindered, resulting in cell destruction and deformation. This results in decreased extrusion moldability and product quality deterioration. In general, the thicker the foam, the more heat is accumulated during crystallization, and the cells no longer cool and solidify smoothly, so this tendency becomes more pronounced. Furthermore, while low-density polyethylene has long chain branches and high melt viscoelasticity, high-density polyethylene does not have long chain branches and has low melt viscoelasticity, so it is extruded from a die together with a blowing agent.
During foam molding, the die did not have sufficient pressure resistance to suppress the generation of bubbles, and the cells already formed in the die were destroyed by heat and shear force during the extrusion foaming process. This results in deterioration of the quality of the foam. This tends to increase as the cross-sectional area of the die opening increases, that is, as the thickness of the foam increases. To solve this problem, it is possible to increase the resin pressure by increasing the extrusion rate. Extremely special equipment with a large capacity must be used, and if the extrusion rate is excessively increased, flow disturbances such as melt fractures will occur, resulting in a decrease in extrusion moldability, which is impractical. In this way, all of the methods known so far for producing high-quality, highly foamed molded products using polyethylene as a raw material are not necessarily satisfactory as industrially viable methods. However, it has been difficult to obtain a thick foam with a particularly large cross-sectional area. In view of these circumstances, the present inventors used non-crosslinked polyethylene, particularly high-density polyethylene, as a raw material to obtain a highly foamed molded product with a good appearance, an independent cell structure, and a large cross-sectional area. As a result of intensive research, it was discovered that the purpose could be achieved by using a combination of a specific amide and a compound having a specific hydroxyl group as a foaming improver, and based on this knowledge, the present invention was completed. It came to this. That is, the present invention comprises (a) polyolefin and (b)
Volatile organic blowing agent and (c) general formula (In the formula, R 1 is a hydrocarbon group having 1 to 23 carbon atoms, R 2 is an alkylene group having 1 to 5 carbon atoms, x is an integer of 1 to 10, and y is an integer of 0 or 1 to 2.) At least one amide shown and general formula (l and n in the formula are 0 or an integer of 1 or more, m is 1
The present invention provides a foamable polyolefin composition comprising a foaming improver which is a combination of at least one compound represented by the above integer. In the composition of the present invention, as a foaming improver,
It is necessary to use a combination of an amide represented by the general formula () and a compound represented by the general formula () as the component (c) foaming improver, and by using this combination, thick-walled foams can be improved. A foamable composition suitable for molding can be obtained. The compounds represented by the above general formulas () and () are all known compounds or can be easily produced by known methods. Examples of amides represented by this general formula () include hexane amide, octane amide, decane amide, dodecan amide, tetradecan amide,
Octadecanamide N-2-hydroxyethyl-
Hexanamide, N-2-hydroxyethyl-octanamide, N-2-hydroxyethyl-decanamide, N-2-hydroxyethyl-dodecanamide, N-2-hydroxyethyl-tetradecanamide, N-2-hydroxyethyl-hexadecane Amide, N-2-hydroxyethyl-octadecanamide, N,N-di-2-hydroxyethyl-hexanamide, N,N-di-2-hydroxyethyl-octanamide, N,N-di-2-hydroxyethyl -Decanamide, N,N-di-2
-Hydroxyethyl-dodecanamide, N,N-
2-hydroxyethyl-tetradecanamide,
N,N-di-2-hydroxyethyl-hexadecanamide, N,N-di-2-hydroxyethyl-
Octadecanamide, N-mono-2-hydroxypropyl-hexanamide, N-mono-2-hydroxypropyl-octanamide, N-mono-2
-hydroxypropyl-decanamide, N-mono-2-hydroxypropyl-dodecanamide, N
-Mono-2-hydroxypropyl-tetradecanamide, N-mono-2-hydroxypropyl-hexadecaneamide, N-mono-2-hydroxypropyl-octadecanamide, N,N-di-2-
Hydroxypropyl-hexanamide, N,N-
di-2-hydroxypropyl-octanamide,
N,N-di-2-hydroxypropyl-decanamide, N,N-di-2-hydroxypropyl-dodecanamide, N,N-2-hydroxypropyl-tetradecanamide, N,N-di-2-hydroxypropyl- Hexadecaneamide, N,N-di-2-hydroxypropyl-octadecanamide, polyoxyethylenehexaneamide, polyoxyethyleneoctanamide, polyoxyethylenedecanamide, polyoxyethylene dodecanamide, polyoxyethylene tetradecaneamide,
Examples include polyoxyethylene hexadecaneamide and polyoxyethylene octadecaneamide. Among these, particularly preferred are:
Dodecanamide, Tetradecanamide, Hexadecaneamide, Octadecanamide, N-Mono-
(and N,N-di)2-hydroxyethyldodecanamide, N-mono-(and N,N-di-)2-
These include hydroxyethyltetradecanamide, N-mono-(and N,N-di-)2-hydroxyethylhexadecaneamide, N-mono-(and N,N-di-)2-hydroxyethyloctadecaneamide, and the like. These amides may be used alone or in combination of two or more. Further, examples of compounds represented by the general formula () include polypropylene glycol and polyoxyethylene-polyoxypropylene block polymers obtained by addition polymerizing ethylene oxide to both ends of polypropylene glycol. Preferred are polyoxyethylene-polyoxypropylene block polymers, and particularly preferred are polyoxyethylene-polyoxy in the general formula () in which l and n are in the range of 1 to 90 and m is in the range of 10 to 40. It is a propylene block polymer. These compounds may be used alone or in combination of two or more. The amount of the amide represented by the above general formula () and the compound represented by the general formula () is 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the polyolefin of component (A). selected within the department. If this amount is less than 0.05 parts by weight, the effect of increasing the cross-sectional area of the foam will not be sufficient, and if it exceeds 15 parts by weight, the effect will not be commensurately increased even if the amount is increased, making it uneconomical. The blending ratio of the amide represented by the general formula () to the compound represented by the general formula () is preferably in the range of 80:20 to 1:99, particularly 7:3.
A range of 1:9 to 1:9 is preferred. Examples of the polyolefin of component (a) used in the composition of the present invention include polyethylene, polypropylene, polybutene-1, 1,2-polybutadiene, 1,3-polybutadiene, ethylene-propylene copolymer, ethylene or propylene, and others. α of
- Copolymers with olefins, or ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-vinyl chloride copolymers, ethylene ionomers (zinc or sodium salts of ethylene-acrylic acid copolymers) metal salts of copolymers of ethylene and unsaturated carboxylic acids, such as
Among these, high-density polyethylene with a density of 0.930 g/cm 3 or more is preferred. In the composition of the present invention, these polyolefins may be used alone or in a mixture of two or more, and further, these polyolefins may be used as a main component and other resins may be appropriately blended. You can also do that. Volatile organic blowing agents as component (b) used in the composition of the present invention include, for example, hydrocarbons and halogenated hydrocarbons, and specific examples of these hydrocarbons include propane, butane, pentane, pentene, hexane, etc. , Specific examples of halogenated hydrocarbons include methyl chloride, dichloride methane, trichloromonofluoroethane, dichlorodifluoromethane, monochlorotrifluoromethane, dichloromonofluoromethane, monochlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, Examples include monochloropentafluoroethane. Among these, preferred are halogenated hydrocarbons containing at least dichlorotetrafluoroethane, and particularly preferred are halogenated hydrocarbons containing 30% by weight or more of dichlorodifluoroethane. The mixing ratio of the volatile organic blowing agent in the composition of the present invention is 5 parts by weight per 100 parts by weight of polyolefin.
The range of 150 parts by weight is desirable, and more preferably the range of 10 to 100 parts by weight; if it is less than 5 parts by weight, it is difficult to obtain a highly foamed product;
If the amount exceeds parts by weight, the effect of increasing the cross-sectional area of the foam will be reduced. Particularly suitable compositions of the present invention include temperature
The melt index (HMI) measured at 190℃ and a load of 21.6Kg is 35g/10 minutes or less and the density is 0.930.
g/cm 3 or more, dichlorotetrafluoroethane as a volatile organic blowing agent and other halogenated hydrocarbons such as trichloromonofluoromethane, dichloromonofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, It is a combination of at least one selected from methyl chloride and methane dichloride, and the amide of the general formula () and the compound of the general formula (). The composition of the present invention may contain a commonly used cell nucleating agent, if necessary. Examples of the bubble nucleating agent include inorganic fine powder such as talc and silicon oxide, zinc stearate,
Fine organic powders such as calcium stearate and fine powders that can generate gas when heated such as citric acid and sodium hydrogen carbonate are used. In addition, ultraviolet absorbers, antioxidants, antistatic agents,
Coloring agents and the like can also be included as desired. To prepare the composition of the present invention, predetermined amounts of the components (a) to (d) and optionally added components are added by any method commonly used for preparing a homogeneous mixture. Stir to mix. Particularly suitable are the master batch method and the dry blend method. Although there is no particular restriction on the order of addition of each component, a method is usually used in which components other than the volatile organic blowing agent are mixed in advance and then this blowing agent is mixed in during the extrusion foaming process. As a method for producing a foam from the composition of the present invention, for example, a method is usually used in which the composition is prepared under high temperature and high pressure, and then exposed to a low temperature and low pressure region to form a foam. As the molding method at this time, for example, an extrusion foaming method, a press foaming method, an injection foaming method, an in-mold foaming method, etc. can be applied, but the extrusion foaming method is advantageous. In this way, extruded foam molded bodies of various shapes, such as sheets, boards, rods, tubes, pipes, nets, etc., can be manufactured. Furthermore, the composition of the present invention is particularly suitable for producing thick boards. The foam obtained from the composition of the present invention is a high foam with an expansion ratio of 5 to 150 times, and has excellent heat insulation and cushioning properties. It is useful as a material. Next, the present invention will be explained in more detail with reference to Examples. The foams in Examples and Comparative Examples were evaluated according to the following evaluation method and criteria. (1) Foaming ratio Foam density after foaming based on JIS-K6767
It was calculated from the weight and volume of the foam after 15 days, and the expansion ratio was determined according to the following formula. Expansion ratio = Resin density before foaming / Density of foam (2) Cross-sectional area coefficient A measure to evaluate the suitability for molding thick molded products with large cross-sectional areas, and the cross-sectional area coefficient was calculated according to the following formula. . Cross-sectional area coefficient = Foam cross-sectional area / (die opening cross-sectional area) x (foaming ratio) 2/3 The larger this value, the more diametrically than the extrusion direction for a circular die, and the extrusion direction for a rectangular die. This means that the foam expands more in the thickness direction than the foam, and a foam with a large cross-sectional area can be obtained with a small amount of extrusion, making it suitable for molding thick objects. Additionally, Tables 1 and 2 show the additives used in each Example and Comparative Example.
【表】【table】
【表】
実施例 １
高密度ポリエチレン（密度0.960ｇ／cm3、
HMI26ｇ／10分、旭化成工業(株)製サンテツク
B870）100重量部に対し、第３表に示した添加剤
所定量と、気泡核形成剤としてタルク0.1重量部
を添加し、ヘンシエルミキサーでドライブレンド
したのち混練押出機で十分均一に混練して発泡成
形用基材を調整した。
シリンダーに発泡剤注入口を有する第一押出機
（口径30mmφ、Ｌ／Ｄ＝30）とシリンダーに冷却
用オイルジヤケツトを備えた第二押出機（口径40
mmφ、Ｌ／Ｄ＝30）を直列に連結した構造をもつ
押出発泡用装置を用い、最高220℃に加熱した第
一押出機に、４Kg／時の供給速度で前記基材を供
給し、これが溶融混練されている帯域に所定の発
泡剤を注入し、発泡用組成物を調整した。この発
泡剤としては、ジクロロテトラフルオロエタンと
トリクロロトリフルオロエタンを等モル比で混合
したものを用い、高密度ポリエチレン100重量部
に対し50重量部の割合で高圧ポンプで連続的に供
給した。このようにして得た組成物を連結管を通
じて第二押出機に供給し、ここで徐々に発泡最適
温度まで冷却し、この組成物を第二押出機先端に
取り付けた口径３mmφのロツド用ダイスより押出
し、発泡体を得た。
得られた発泡体の評価結果を第３表に示した。[Table] Example 1 High-density polyethylene (density 0.960 g/cm 3 ,
HMI26g/10min, Santec manufactured by Asahi Kasei Industries, Ltd.
To 100 parts by weight of B870), the prescribed amounts of additives shown in Table 3 and 0.1 part by weight of talc as a bubble nucleating agent were added, dry-blended in a Henschel mixer, and sufficiently uniformly kneaded in a kneading extruder. A base material for foam molding was prepared. The first extruder (caliber 30 mmφ, L/D = 30) has a blowing agent inlet in the cylinder, and the second extruder (caliber 40 mm) has a cooling oil jacket in the cylinder.
mmφ, L/D=30) connected in series, the base material was fed to the first extruder heated to a maximum of 220°C at a feeding rate of 4 kg/hour. A prescribed foaming agent was injected into the melt-kneaded zone to prepare a foaming composition. The blowing agent used was a mixture of dichlorotetrafluoroethane and trichlorotrifluoroethane in an equimolar ratio, and was continuously supplied using a high-pressure pump at a ratio of 50 parts by weight to 100 parts by weight of high-density polyethylene. The composition obtained in this way is supplied to the second extruder through a connecting pipe, where it is gradually cooled to the optimum foaming temperature, and the composition is passed through a rod die with a diameter of 3 mmφ attached to the tip of the second extruder. A foam was obtained by extrusion. The evaluation results of the obtained foams are shown in Table 3.
【表】
この表から判るように、実験番号１〜５の組成
物から得られた発泡体は、いずれも高い断面積係
数を示すことにより、これらの組成物は断面積の
大きな厚物の成形に適したものであり、かつ発泡
体はすべて高倍率に発泡しており、外観、独立気
泡性ともに良好で、十分な商品価値を有するもの
であつた。
比較例 １
添加剤が本発明の範囲外であるか、又は添加剤
をまつたく用いない以外は、実施例１と同様にし
て発泡体を製造した。
得られた発泡体の評価結果を第４表に示した。[Table] As can be seen from this table, the foams obtained from the compositions of Experiment Nos. 1 to 5 all showed high cross-sectional area coefficients, making it possible for these compositions to mold thick objects with large cross-sectional areas. The foams were all foamed to a high magnification, had good appearance and closed cell properties, and had sufficient commercial value. Comparative Example 1 A foam was produced in the same manner as in Example 1, except that the additive was outside the scope of the present invention or no additive was used at all. The evaluation results of the obtained foams are shown in Table 4.
【表】
この表から判るように、本発明の範囲外の添加
剤を用いた場合、実験番号６〜８では、発泡体は
高倍率に発泡しているものの、独立気泡性に劣
り、断面積係数の小さいものであつた。また実験
番号９〜11では、発泡体は高倍率に発泡してい
て、外観及び独立気泡性ともに優れているもの
の、実施例１に比べて断面積係数が小さく、肉厚
成形性の劣つたものであつた。
一方、添加剤をまつたく用いない実験番号12で
は、前記実験番号６〜８と同様な結果が得られ
た。
実施例 ２
実施例１における添加剤の種類及び量を、第５
表に示すものに代える以外は、実施例１と同様に
して発泡体を製造した。
得られた発泡体の評価結果を第５表に示す。[Table] As can be seen from this table, when additives outside the scope of the present invention were used, in Experiments Nos. 6 to 8, the foams were foamed to a high ratio, but the closed cell properties were poor, and the cross-sectional area The coefficient was small. In addition, in Experiment Nos. 9 to 11, the foams were foamed at a high magnification and had excellent appearance and closed cell properties, but compared to Example 1, the cross-sectional area coefficient was smaller and the thickness moldability was inferior. It was hot. On the other hand, in Experiment No. 12 in which no additives were used, the same results as in Experiments No. 6 to 8 were obtained. Example 2 The types and amounts of additives in Example 1 were changed to
A foam was produced in the same manner as in Example 1 except that the materials were replaced with those shown in the table. Table 5 shows the evaluation results of the obtained foams.
【表】
この表から判るように、実験番号13〜16におい
ては、いずれの評価項目も優れており、肉厚成形
品の成形に適した組成物であつたが、添加剤の合
計量が0.04重量部である実験番号17では、高倍率
に発泡しているものの、肉厚成形性に劣つたもの
であり、また添加剤の合計量が20重量部である実
験番号18では、添加量の割には肉厚成形性に大き
な効果が得られなかつた。
実施例 ３
添加剤としてアマイドＴ及びプロノン201を用
い、使用量をそれぞれ、0.75重量部及び0.25重量
部、0.25重量部及び0.75重量部とした以外は実施
例１と同様にして発泡体を製造した。
この際の発泡改良剤の配合比を変化させた場合
の断面積係数の変化をグラフとして図に示した。
この図から分るように、アマイドＴとプロノン
201の配合比が80：20〜１：99の場合に、組合せ
による断面積係数増大の効果が認められた。
実施例 ４
ポリオレフイン及び発泡剤が第６表実験番号19
〜21に示したものであり、添加剤としてアマイド
T0.5重量部及びプロノン201を0.5重量部用いた以
外は実施例１と同様にして発泡体を製造した。
得られた発泡体の評価結果を第６表実験番号19
〜21に示した。
この表から判るように、実験番号19〜21におい
ては、いずれの評価項目も優れており、肉厚成形
品の成形に適した組成物であつた。
比較例 ２
ポリオレフイン及び発泡剤が第６表実験番号22
〜24に示したものであり、かつ添加剤を用いない
以外は、実施例１と同様にして発泡体を製造し
た。
得られた発泡体の評価結果を第６表実験番号22
〜24に示した。
この表から分るように、実験番号22〜24におい
ては、実験番号19〜21に比べて、いずれも断面積
係数が小さく肉厚成形性に劣つたものであつた。[Table] As can be seen from this table, in experiment numbers 13 to 16, all evaluation items were excellent and the composition was suitable for molding thick-walled products, but the total amount of additives was 0.04 Experiment No. 17, in which the total amount of additives was 20 parts by weight, was foamed at a high expansion ratio, but had poor wall thickness formability, and Experiment No. 18, in which the total amount of additives was 20 parts by weight, was foamed at a high expansion ratio. However, no significant effect on wall thickness formability was obtained. Example 3 A foam was produced in the same manner as in Example 1, except that Amide T and Pronone 201 were used as additives, and the amounts used were 0.75 parts by weight, 0.25 parts by weight, 0.25 parts by weight, and 0.75 parts by weight, respectively. . The graph shows the changes in the cross-sectional area coefficient when the blending ratio of the foaming improver was changed. As you can see from this figure, amide T and pronon
When the blending ratio of 201 was 80:20 to 1:99, the effect of increasing the cross-sectional area coefficient due to the combination was observed. Example 4 Polyolefin and blowing agent were tested in Table 6, Experiment No. 19.
~21, with amide as an additive
A foam was produced in the same manner as in Example 1, except that 0.5 parts by weight of T and 0.5 parts by weight of Pronone 201 were used. The evaluation results of the obtained foam are shown in Table 6, Experiment No. 19.
~21. As can be seen from this table, in Experiment Nos. 19 to 21, all evaluation items were excellent and the compositions were suitable for molding thick molded products. Comparative Example 2 Polyolefin and blowing agent were Table 6 Experiment No. 22
A foam was produced in the same manner as in Example 1, except that the foam was as shown in Example 1 to 24 and no additives were used. The evaluation results of the obtained foam are shown in Table 6, Experiment No. 22.
~24. As can be seen from this table, in Experiment Nos. 22 to 24, the cross-sectional area coefficients were smaller than in Experiment Nos. 19 to 21, and the thickness formability was inferior.
【表】【table】
図は、本発明における発泡改良剤の組成と断面
積係数との関係を表わすグラフである。
The figure is a graph showing the relationship between the composition of the foaming improver and the cross-sectional area coefficient in the present invention.
Claims (1)
と、(ハ)一般式 （式中のR1は炭素数１〜23の炭化水素基、R2は
炭素数１〜５のアルキレン基、ｘは１〜10の整
数、ｙは０又は１〜２の整数である） で示されるアミドの少なくとも一種及び一般式 （式中のｌ及びｎは０又は１以上の整数、ｍは１
以上の整数である） で示される化合物の少なくとも１種を組み合わせ
た発泡改良剤とから成る発泡性ポリオレフイン組
成物。 ２ 一般式（）におけるｌ、ｍ及びｎが、それ
ぞれ１以上の整数である特許請求の範囲第１項記
載の組成物。 ３ 発泡改良剤の配合量が、ポリオレフイン100
重量部当り両者合わせて0.05〜15重量部である特
許請求の範囲第１項又は第２項記載の組成物。 ４ ポリオレフインが高密度ポリエチレンである
特許請求の範囲第１項、第２項又は第３項記載の
組成物。 ５ 揮発性有機発泡剤がジクロロテトラフルオロ
エタンを含むハロゲン化炭化水素である特許請求
の範囲第１項、第２項、第３項又は第４項記載の
組成物。[Claims] 1 (a) polyolefin, (b) volatile organic blowing agent, and (c) general formula (In the formula, R 1 is a hydrocarbon group having 1 to 23 carbon atoms, R 2 is an alkylene group having 1 to 5 carbon atoms, x is an integer of 1 to 10, and y is an integer of 0 or 1 to 2) At least one amide shown and general formula (l and n in the formula are 0 or an integer of 1 or more, m is 1
A foamable polyolefin composition comprising a foaming improver in combination with at least one compound represented by the following integer: 2. The composition according to claim 1, wherein l, m and n in the general formula () are each an integer of 1 or more. 3 The amount of foaming improver is 100% polyolefin.
The composition according to claim 1 or 2, wherein the total amount of both is 0.05 to 15 parts by weight. 4. The composition according to claim 1, 2 or 3, wherein the polyolefin is high density polyethylene. 5. The composition according to claim 1, 2, 3 or 4, wherein the volatile organic blowing agent is a halogenated hydrocarbon including dichlorotetrafluoroethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4239583A JPS59168040A (en) | 1983-03-16 | 1983-03-16 | Expandable polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4239583A JPS59168040A (en) | 1983-03-16 | 1983-03-16 | Expandable polyolefin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59168040A JPS59168040A (en) | 1984-09-21 |
| JPH0344100B2 true JPH0344100B2 (en) | 1991-07-04 |
Family
ID=12634871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4239583A Granted JPS59168040A (en) | 1983-03-16 | 1983-03-16 | Expandable polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59168040A (en) |
-
1983
- 1983-03-16 JP JP4239583A patent/JPS59168040A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59168040A (en) | 1984-09-21 |
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