JPH0515735B2 - - Google Patents
Info
- Publication number
- JPH0515735B2 JPH0515735B2 JP63264140A JP26414088A JPH0515735B2 JP H0515735 B2 JPH0515735 B2 JP H0515735B2 JP 63264140 A JP63264140 A JP 63264140A JP 26414088 A JP26414088 A JP 26414088A JP H0515735 B2 JPH0515735 B2 JP H0515735B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- flame
- amount
- mixture
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000003063 flame retardant Substances 0.000 claims description 32
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 26
- 239000004604 Blowing Agent Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 239000006260 foam Substances 0.000 claims description 17
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 15
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 13
- 229920001890 Novodur Polymers 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 5
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000005187 foaming Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical class C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- PWXTUWQHMIFLKL-UHFFFAOYSA-N 1,3-dibromo-5-[2-(3,5-dibromo-4-prop-2-enoxyphenyl)propan-2-yl]-2-prop-2-enoxybenzene Chemical compound C=1C(Br)=C(OCC=C)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(OCC=C)C(Br)=C1 PWXTUWQHMIFLKL-UHFFFAOYSA-N 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- RZLLIOPGUFOWOD-UHFFFAOYSA-N 1,3,5-tribromo-2-prop-2-enoxybenzene Chemical compound BrC1=CC(Br)=C(OCC=C)C(Br)=C1 RZLLIOPGUFOWOD-UHFFFAOYSA-N 0.000 description 1
- JQZFYIGAYWLRCC-UHFFFAOYSA-N 1-chloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)(F)Cl JQZFYIGAYWLRCC-UHFFFAOYSA-N 0.000 description 1
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 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
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 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
（産業上の利用分野）
この発明は、難燃性スチレン系樹脂板状発泡体
の製造方法に関するものである。
（従来の技術及び解決しようとする課題）
一般に、難燃性樹脂は合成樹脂に難燃化剤を混
合して作られる。難燃化剤は、種々のものが知ら
れている。難燃化剤には、無機化合物と有機化合
物とがあり、無機化合物としては、酸化アンチモ
ン、燐酸塩等が用いられ、有機化合物としては専
ら種々のハロゲン化合物が用いられた。
スチレン系樹脂を難燃性のものとし、これを非
発泡のものとして用いる場合には格別の困難がな
い。それは、非発泡のものとする場合には、スチ
レン系樹脂に上記の難燃化剤を単に混合すれば足
りるからである。ところが、難燃性スチレン系樹
脂を発泡体にしようとするときは、非発泡の場合
のように簡単に片付かない。難燃化剤の樹脂の発
泡性を阻害することが起るからである。そのた
め、難燃化剤を特別に選択して使用したり、使用
方法を格別に考慮したりすることが必要となるか
らである。とりわけ、有機性の難燃化剤は分解し
やすいので、これに安定剤を配合する必要が生
じ、従つて安定剤が又発泡剤の働きに影響すると
いう新たな問題を生ずるからである。
今までは、スチレン系樹脂の発泡剤として脂肪
族炭化水素、例えばプロパン、ブタンが多く用い
られた。脂肪族炭化水素は一般に反応性に乏しい
から、これを用いている限りでは、発泡剤と難燃
化剤並びに安定剤との関係がさほど大きな問題に
はならない。しかし、脂肪族炭化水素は燃えやす
く、従つて、これを用いると火災の危険性があ
り、又気泡そのものの調整も困難となるから、脂
肪族炭化水素を用いる方法が優れているとは云え
ない。そこで発泡剤としては、ハロゲン化された
脂肪族炭化水素が用いられるようになつた。
しかし、安全に良好な発泡体を得るために用い
られるハロゲン化脂肪族炭化水素のうち、ペルク
ロロフロオロカーボン類（例えばジクロロジフル
オロメタン、トリクロロモノフルオロメタン）は
成層圏にあり有害な紫外線−Ｂ（波長範囲290〜
320nｍ）を吸収して地表への到達を防ぐと共に
大気温度の維持を行なつているオゾン層を破壊す
ることが知られ、その使用が規制される。
本発明者は、ペルフルオロカーボン類に替わる
発泡剤として、テトラフルオロエタン（以下、
134aという）を用い、又特公昭60−29743号公報
に記載されている難燃化剤であるヘキサブロモシ
クロドデカンと２，2′−ビス−（４−アリロキシ
−３，５−ジブロモフエニル）プロパンとの混合
物を用いて押出を行なつたところ難燃性の優れた
発泡体を得ることに成功した。しかし、従来の方
法により得られる発泡体に較べ気泡が粗く、板状
発泡体として期待される断熱性を有するものでは
なかつた。
そこで、本発明者は、上記の点を改良するため
に、発泡剤としてF134aと他のハロゲン化脂肪族
炭化水素との混合物を用い、且つ難燃化剤として
ハロゲン元素含有の多員環状化合物やフエニルア
リルエーテル誘導体を用い、更に、安定剤及び気
泡調整剤としてトリフエニルフオスフアイトを用
い、これらをスチレン系樹脂に含有させて発泡さ
せたところ、難燃性が優れ、且つ気泡サイズを小
さく、断熱性に優れた難燃性スチレン系樹脂板状
発泡体を得ることを見出し、本発明を完成するに
至つたもので、本発明の目的は、オゾン破壊を起
こす危険性が少ないF134aと他のハロゲン化脂肪
族炭化水素との混合物を発泡剤として用いて難燃
性スチレン系樹脂発泡体を製造する方法を提供す
るにある。
（課題を解決するための手段）
本発明の要旨は、発泡剤として、スチレン系樹
脂１Kgに対して0.2ないし1.6モルのテトラフルオ
ロエタンと0.2ないし2.0モルのハロゲン化脂肪族
炭化水素の混合物をスチレン系樹脂に対して５な
いし20重量％用い、難燃化剤としてヘキサブロモ
シクロドデカン及び２，2′−ビス−（４−アリロ
キシ−３，５−ジブロモフエニル）−プロパン及
び／又は２，４，６−トリブロモフエニルアリル
エーテルの混合物をスチレン系樹脂に対して0.5
ないし10重量％用い、安定剤としてトリフエニル
フオスフアイトを難燃化剤に対して1.0〜30重量
％用いることを特徴とする難燃性スチレン系樹脂
板状発泡体の製造方法である。
すなわち、本発明においては、F134aとハロゲ
ン化脂肪族炭化水素との混合物を発泡剤とし、ハ
ロゲン元素含有の多員環状アルカン及びフエニル
アリルエーテル誘導体の混合物を難燃化剤として
発泡体を得ようとする場合に、トリフエニルフオ
スフアイトを添加することによつて難燃性が優
れ、且つ気泡サイズを小さくすることによつて断
熱性の優れた発泡体が得られるという知見に基づ
いてなされたものである。
本発明について、更に詳細に説明する。
本発明方法で用いることのできるスチレン系樹
脂は、スチレン系単独重合体に限らず、共重合体
を含んいる。スチレン系単量体は、スチレンの
他、メチルスチレン、エチルスチレンとのスチレ
ン誘導体を含んでいる。又、共重合体はスチレン
系単量体を50重量％以上含み、その余が他の単量
体からなるものを含んでいる。他の単量体として
は、メチルメタクリレート、アクリロニトリル、
無水マレイン酸等を挙げることができる。そのほ
か、スチレン系樹脂は、それら単独重合体又は共
重合体に、他の樹脂を混合して得られたブレンド
物をも含んでいる。他の樹脂としては、ポリエチ
レン、合成ゴム等を挙げることができる。ブレン
ド物は、その中でスチレンが50重量％以上を占め
ている。
発泡剤としては前述のように、テトラフルオロ
エタン（F134a）と他のハロゲン化脂肪族炭化水
素との混合物を用いる。F134aの添加量はスチレ
ン系樹脂１Kgに対して0.2ないし1.6モルが必要で
ある。F134aの添加量が0.2モル以下では、断熱性
が劣り、又1.6モル以上では、成型不良となる。
混合する他のハロゲン化脂肪族炭化水素として
は、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、モノクロロジフルオロメタン
（F22）、ジクロロモノフルオロメタン（F21）、モ
ノクロロジフルオロエタン（F142b）、ジフルオ
ロエタン（F152a）、ジクロロトリフルオロエタ
ン（F123）、モノクロロテトラフルオロエタン
（F124）及びオゾン破壊能が大きいと云われては
いるが、スチレン系樹脂発泡体の発泡剤としての
特性が良いため、規制範囲内での使用にかぎりジ
クロロオロメタン（F12）の中から選ばれた少な
くとも１種又は２種以上の混合物を用いる。その
混合物の添加量はスチレン系樹脂１Kgに対して、
0.2ないし2.0モルが必要である。この混合物の添
加量が0.2モル以下では、期待される成型性が得
られず、又2.0モル以上では断熱性が劣る。そし
て、用いられる発泡剤の総量はスチレン系樹脂に
対して５ないし20重量％である。その理由は、５
重量％以下では高倍率に発泡させることができ
ず、逆に20重量％以上になると、発泡剤が樹脂か
ら突沸し、均一な発泡が困難となり、成型性が悪
くなるためである。
これら混合発泡剤は、別々に樹脂に加えても良
く、また樹脂に加える前に予め混合してもよい。
またその添加は、押出成型機の中で加えても良
く、あるいは押出成型機に入れる以前に樹脂に加
えておいてもよい。
本発明では、難燃化剤としてヘキサブロモシク
ロドデカン又は２，2′−ビス−（４−アリロキシ
−３，５−ジブロモフエニル）−プロパン及び／
又は２，４，６−トリブロモフエニルアリルエー
テルとの混合物を用いる。これら難燃化剤の添加
量は、スチレン系樹脂に対して0.5ないし10重量
％とする。その理由は、0.5重量％以下では、難
燃化剤の効果が充分発揮されないからであり、逆
に10重量％以上にすると、増加分だけの効果が現
われないだけでなく、押出安定性と発泡性が悪く
なるからである。
本発明では、安定剤としてトリフエニルフオス
フアイトを用いる。トリフエニルフオスフアイト
は安定化効果と共に気泡微細化効果をも有する。
トリフエニルフオスフアイトの添加量は、難燃剤
に対して1.0ないし30重量％用いる。その理由は、
1.0重量％以下では難燃化剤、発泡剤に対する安
定化効果及び気泡微細化効果は見られず、30重量
％以上ではコストの上昇に見合つた効果は得られ
ず、逆に押出安定性を著しく低下させるためであ
る。
発泡剤、難燃化剤、安定剤をスチレン系樹脂に
加える順序は特に限定されていない。しかし、望
ましいのは、難燃化剤、安定剤をスチレン系樹脂
にドライブレンドしておき、この混合物を押出機
に入れ、押出機中で発泡剤を圧入する方法であ
る。
又、この発明方法では上記化合物のほかに、従
来からの気泡調整剤であるタルクや顔料染料のよ
うな着色剤ノニオン系界面活性剤のような界面活
性剤を加えることができる。
以下に、実施例と比較例とを述べて、この発明
方法を具体的に説明する。実施例及び比較例にお
いて、単に部というのは、重量部を表す。
実施例１〜８及び比較例１〜４
ポリスチレン（新日鉄化学〓エスチレンＧ−
10）100部に対して、気泡調整剤として微粉末タ
ルク0.7部、難燃化剤及び安定剤を表の割合で混
合したものを、口径40mmと口径50mmのものを連結
した押出機へ約15Kg／ｈの割合で供給した。
発泡剤としては、テトラフルオロエタン
（F134a）と他のハロゲン化脂肪族炭化水素とを
表の割合で混合したものを口径40mmの押出機の先
端付近から樹脂中に圧入混合した。口金として
は、先端に厚さ0.6mm、幅60mm、長さ５mmの矩形
の樹脂排出口を備えたものを使用し、口金の先端
には入口寸法が実質的に樹脂排出口寸法に等し
く、出口寸法が厚さ12mm、幅120mmであり、入口
付近から出口に向かつて緩やかに拡大された長さ
50mmの樹脂通路を備えた樹脂通路壁に弗素樹脂を
被膜した成形具を使用した。
口径40mmの押出機に供給された樹脂は、220℃
に加熱し、溶融混練され、続く口径50mmの押出機
で樹脂温度を110℃〜130℃に調整し、口金に供給
した。口金から排出された樹脂は大きく発泡し、
厚さ15〜23mm、幅150〜200mmに整えられ押出安定
性、成形性も良好であつた。
(Industrial Application Field) The present invention relates to a method for manufacturing a flame-retardant styrene resin plate-like foam. (Prior art and problems to be solved) Generally, flame-retardant resins are made by mixing a flame retardant with a synthetic resin. Various flame retardants are known. Flame retardants include inorganic compounds and organic compounds. Antimony oxide, phosphate, etc. have been used as the inorganic compounds, and various halogen compounds have been used as the organic compounds. If the styrene resin is flame retardant and used as a non-foaming material, there will be no particular difficulty. This is because, in the case of non-foaming, it is sufficient to simply mix the above-mentioned flame retardant with the styrene resin. However, when trying to make a foam from flame-retardant styrene resin, it is not as easy to clean up as when making a non-foamed material. This is because the foamability of the flame retardant resin may be inhibited. This is because it is necessary to specially select and use a flame retardant and to give special consideration to the method of use. In particular, since organic flame retardants are easily decomposed, it becomes necessary to incorporate a stabilizer into them, which creates a new problem in that the stabilizer also affects the function of the blowing agent. Until now, aliphatic hydrocarbons such as propane and butane have often been used as blowing agents for styrenic resins. Since aliphatic hydrocarbons generally have poor reactivity, as long as they are used, the relationship between the blowing agent, flame retardant, and stabilizer does not pose much of a problem. However, aliphatic hydrocarbons are easily flammable, so there is a risk of fire when using them, and it is also difficult to control the bubbles themselves, so it cannot be said that the method using aliphatic hydrocarbons is superior. . Therefore, halogenated aliphatic hydrocarbons have come to be used as blowing agents. However, among the halogenated aliphatic hydrocarbons used to safely obtain good foams, perchlorofluorocarbons (e.g. dichlorodifluoromethane, trichloromonofluoromethane) are in the stratosphere and harmful ultraviolet-B ( Wavelength range 290~
320nm), preventing it from reaching the earth's surface and destroying the ozone layer, which maintains atmospheric temperature, and its use is regulated. The present inventor has discovered that tetrafluoroethane (hereinafter referred to as
134a), and hexabromocyclododecane and 2,2'-bis-(4-allyloxy-3,5-dibromophenyl), which are flame retardants described in Japanese Patent Publication No. 60-29743. When extrusion was carried out using a mixture with propane, a foam with excellent flame retardancy was successfully obtained. However, compared to foams obtained by conventional methods, the cells were coarser and did not have the heat insulation properties expected of a plate-shaped foam. Therefore, in order to improve the above points, the present inventor used a mixture of F134a and other halogenated aliphatic hydrocarbons as a blowing agent, and a multimembered cyclic compound containing a halogen element or a flame retardant. When a phenyl allyl ether derivative was used and triphenyl phosphorite was used as a stabilizer and a bubble regulator, these were added to a styrene resin and foamed, resulting in excellent flame retardancy and small bubble size. It was discovered that a flame-retardant styrene-based resin sheet foam with excellent heat insulation properties could be obtained, and the present invention was completed. The object of the present invention is to provide a method for producing a flame-retardant styrenic resin foam using a mixture with a halogenated aliphatic hydrocarbon as a blowing agent. (Means for Solving the Problem) The gist of the present invention is to use a mixture of 0.2 to 1.6 mol of tetrafluoroethane and 0.2 to 2.0 mol of halogenated aliphatic hydrocarbon per 1 kg of styrenic resin as a blowing agent. Hexabromocyclododecane and 2,2'-bis-(4-allyloxy-3,5-dibromophenyl)-propane and/or 2,4 are used as flame retardants in an amount of 5 to 20% by weight based on the system resin. , 6-tribromophenyl allyl ether to styrenic resin at 0.5
This is a method for producing a flame-retardant styrenic resin plate-like foam, characterized in that triphenyl phosphite is used as a stabilizer in an amount of 1.0 to 30% by weight based on the flame retardant. That is, in the present invention, a foam is obtained using a mixture of F134a and a halogenated aliphatic hydrocarbon as a blowing agent, and a mixture of a halogen element-containing multi-membered cyclic alkane and a phenyl allyl ether derivative as a flame retardant. This was based on the knowledge that adding triphenyl phosphite can provide a foam with excellent flame retardancy, and by reducing the cell size, a foam with excellent heat insulation properties can be obtained. It is. The present invention will be explained in more detail. The styrenic resin that can be used in the method of the present invention is not limited to styrenic homopolymers, but also includes copolymers. Styrenic monomers include styrene derivatives such as methylstyrene and ethylstyrene in addition to styrene. Further, the copolymer contains 50% by weight or more of a styrene monomer, with the remainder consisting of other monomers. Other monomers include methyl methacrylate, acrylonitrile,
Examples include maleic anhydride. In addition, styrenic resins also include blends obtained by mixing these homopolymers or copolymers with other resins. Examples of other resins include polyethylene and synthetic rubber. In the blend, styrene accounts for 50% or more by weight. As described above, a mixture of tetrafluoroethane (F134a) and other halogenated aliphatic hydrocarbons is used as the blowing agent. The amount of F134a added is required to be 0.2 to 1.6 mol per 1 kg of styrene resin. If the amount of F134a added is less than 0.2 mol, the heat insulation properties will be poor, and if it is more than 1.6 mol, molding will be defective.
Other halogenated aliphatic hydrocarbons to mix include methyl chloride, ethyl chloride, methylene chloride, monochlorodifluoromethane (F22), dichloromonofluoromethane (F21), monochlorodifluoroethane (F142b), difluoroethane (F152a), and dichlorotrifluoromethane (F21). Although fluoroethane (F123) and monochlorotetrafluoroethane (F124) are said to have a high ozone depletion ability, they can only be used within the regulated range because styrene resin foam has good properties as a blowing agent. At least one type or a mixture of two or more types selected from dichloroolomethane (F12) is used. The amount of the mixture added is per 1 kg of styrene resin.
0.2 to 2.0 mol is required. If the amount of this mixture added is less than 0.2 mol, the expected moldability cannot be obtained, and if it is more than 2.0 mol, the heat insulation properties will be poor. The total amount of blowing agent used is 5 to 20% by weight based on the styrene resin. The reason is 5.
This is because if the amount is less than 20% by weight, foaming cannot be achieved at a high magnification, whereas if the amount is more than 20% by weight, the foaming agent will bump from the resin, making uniform foaming difficult and poor moldability. These mixed blowing agents may be added to the resin separately, or may be mixed in advance before being added to the resin.
Further, the additive may be added in the extrusion molding machine, or may be added to the resin before being put into the extrusion molding machine. In the present invention, hexabromocyclododecane or 2,2'-bis-(4-allyloxy-3,5-dibromophenyl)-propane and/or
Alternatively, a mixture with 2,4,6-tribromophenyl allyl ether is used. The amount of these flame retardants added is 0.5 to 10% by weight based on the styrene resin. The reason for this is that if the flame retardant is less than 0.5% by weight, the effect of the flame retardant will not be fully demonstrated.On the other hand, if it is more than 10% by weight, not only will the effect of the increased amount not appear, but the extrusion stability and foaming This is because the sex becomes worse. In the present invention, triphenyl phosphorite is used as a stabilizer. Triphenyl phosphite has not only a stabilizing effect but also a bubble-refining effect.
The amount of triphenyl phosphite added is 1.0 to 30% by weight based on the flame retardant. The reason is,
If it is less than 1.0% by weight, no stabilizing effect on flame retardant or blowing agent or bubble refining effect will be observed, and if it is more than 30% by weight, no effect commensurate with the increase in cost will be obtained, and on the contrary, extrusion stability will be significantly reduced. This is to reduce the The order in which the blowing agent, flame retardant, and stabilizer are added to the styrenic resin is not particularly limited. However, what is desirable is a method in which a flame retardant and a stabilizer are dry blended with a styrenic resin, this mixture is placed in an extruder, and a blowing agent is press-fitted into the extruder. In addition to the above-mentioned compounds, in the method of the present invention, a surfactant such as talc, which is a conventional foam regulator, a colorant such as a pigment dye, or a nonionic surfactant, can be added. The method of the present invention will be specifically explained below with reference to Examples and Comparative Examples. In Examples and Comparative Examples, "parts" simply refers to parts by weight. Examples 1 to 8 and Comparative Examples 1 to 4 Polystyrene (Nippon Steel Chemical Co., Ltd. Estyrene G-
10) For 100 parts, mix 0.7 parts of finely powdered talc as a bubble regulator, a flame retardant, and a stabilizer in the proportions shown in the table, and transfer approximately 15 kg to an extruder connected to a 40 mm diameter and a 50 mm diameter extruder. /h. As a blowing agent, a mixture of tetrafluoroethane (F134a) and other halogenated aliphatic hydrocarbons in the proportions shown in the table was press-mixed into the resin from near the tip of an extruder with a diameter of 40 mm. The nozzle used was one with a rectangular resin outlet with a thickness of 0.6 mm, a width of 60 mm, and a length of 5 mm at the tip. The dimensions are 12 mm thick and 120 mm wide, and the length gradually increases from near the entrance to the exit.
A molding tool with a 50 mm resin passage and a resin passage wall coated with fluororesin was used. The resin supplied to the extruder with a diameter of 40 mm is heated to 220℃.
The resin temperature was adjusted to 110° C. to 130° C. using an extruder with a diameter of 50 mm, and the resin was supplied to a die. The resin discharged from the nozzle foams greatly,
It had a thickness of 15 to 23 mm and a width of 150 to 200 mm, and had good extrusion stability and moldability.
【表】
（発明の効果）
既に詳述したように、本発明方法によれば、発
泡剤としてF134aと他のハロゲン化脂肪族炭化水
素を用いるから、発泡剤が脂肪族炭化水素である
場合に較べて、発泡剤が火災を起こす危険性が少
なくなり、又ペルクロロフルオロカーボン類であ
る場合に較べてオゾン破壊を起こす危険性が少な
くなる。又、難燃化剤として８員以上からなる多
員環状アルカンのハロゲン置換物又は、ハロゲン
置換フエニルアリルエーテル誘導体を用いるか
ら、これが固状有機物であつて、スチレン系樹脂
に均一によく溶解するので、難燃性の大きいスチ
レン系樹脂を得ることが出来る。
さらに、安定剤として用いるトリフエニルフオ
スフアイトが安定化効果と共に、気泡調整剤とし
ての効果を有するために難燃化剤の分解を防ぎ、
難燃性の向上をはかることができ、さらに、断熱
性の向上をも導き、従つて良好な難熱性スチレン
系樹脂板状発泡体を得ることが出来る。[Table] (Effects of the invention) As already detailed, according to the method of the present invention, F134a and other halogenated aliphatic hydrocarbons are used as blowing agents. By comparison, the blowing agent poses less risk of fire and also has less risk of ozone depletion than perchlorofluorocarbons. In addition, since a halogen-substituted multi-membered cyclic alkane consisting of 8 or more members or a halogen-substituted phenyl allyl ether derivative is used as a flame retardant, this is a solid organic substance that dissolves uniformly and well in the styrene resin. Therefore, a styrenic resin with high flame retardancy can be obtained. Furthermore, triphenyl phosphite used as a stabilizer has a stabilizing effect as well as an effect as a bubble regulator, which prevents the decomposition of the flame retardant.
It is possible to improve the flame retardancy and also lead to an improvement in the heat insulation property, and therefore it is possible to obtain a good heat-retardant styrene resin plate-like foam.
Claims (1)
0.2ないし1.6モルのテトラフルオロエタンと0.2な
いし2.0モルのハロゲン化脂肪族炭化水素の混合
物をスチレン系樹脂に対して５ないし20重量％用
い、難燃化剤としてヘキサブロモシクロドデカン
及び２，2′−ビス−（４−アリロキシ−３，５−
ジブロモフエニル）−プロパン及び／又は２，４，
６−トリブロモフエニルアリルエーテルの混合物
をスチレン系樹脂に対して0.5ないし10重量％用
い、安定剤としてトリフエニルフオスフアイトを
難燃化剤に対して1.0〜30重量％用いることを特
徴とする難燃性スチレン系樹脂板状発泡体の製造
方法。1 As a blowing agent, per 1 kg of styrene resin.
A mixture of 0.2 to 1.6 moles of tetrafluoroethane and 0.2 to 2.0 moles of halogenated aliphatic hydrocarbon is used in an amount of 5 to 20% by weight based on the styrenic resin, and hexabromocyclododecane and 2,2' are used as flame retardants. -bis-(4-allyloxy-3,5-
dibromophenyl)-propane and/or 2,4,
A mixture of 6-tribromophenyl allyl ether is used in an amount of 0.5 to 10% by weight based on the styrene resin, and triphenyl phosphorite is used as a stabilizer in an amount of 1.0 to 30% by weight based on the flame retardant. A method for producing a flame-retardant styrene resin plate-like foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26414088A JPH02113037A (en) | 1988-10-21 | 1988-10-21 | Production of flame-retardant styrene resin board foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26414088A JPH02113037A (en) | 1988-10-21 | 1988-10-21 | Production of flame-retardant styrene resin board foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02113037A JPH02113037A (en) | 1990-04-25 |
| JPH0515735B2 true JPH0515735B2 (en) | 1993-03-02 |
Family
ID=17399016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26414088A Granted JPH02113037A (en) | 1988-10-21 | 1988-10-21 | Production of flame-retardant styrene resin board foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02113037A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0418603A3 (en) * | 1989-08-28 | 1991-07-17 | Daikin Industries, Limited | Blowing compositions |
| JP2537426B2 (en) * | 1990-06-26 | 1996-09-25 | 鐘淵化学工業株式会社 | Method for producing styrene resin foam excellent in long-term heat insulation |
| BE1005222A3 (en) * | 1991-01-18 | 1993-06-01 | Solvay | Compositions comprising 1,1,1,2-tetrafluoroethane and uses thereof. |
| EP0557533A1 (en) * | 1991-09-12 | 1993-09-01 | Daikin Industries, Ltd. | Blowing agent composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6029743A (en) * | 1983-07-09 | 1985-02-15 | Fuji Photo Film Co Ltd | Packaging material for photosensitive material and its molded body |
| JPS612097A (en) * | 1984-04-10 | 1986-01-08 | トランスニュークリア株式会社 | Rack for transport and storage vessel |
| JPH0198638A (en) * | 1987-10-12 | 1989-04-17 | Du Pont Mitsui Fluorochem Co Ltd | Blowing agent composition for expanding thermoplastic resin |
-
1988
- 1988-10-21 JP JP26414088A patent/JPH02113037A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6029743A (en) * | 1983-07-09 | 1985-02-15 | Fuji Photo Film Co Ltd | Packaging material for photosensitive material and its molded body |
| JPS612097A (en) * | 1984-04-10 | 1986-01-08 | トランスニュークリア株式会社 | Rack for transport and storage vessel |
| JPH0198638A (en) * | 1987-10-12 | 1989-04-17 | Du Pont Mitsui Fluorochem Co Ltd | Blowing agent composition for expanding thermoplastic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02113037A (en) | 1990-04-25 |
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