JPH0144250B2 - - Google Patents
Info
- Publication number
- JPH0144250B2 JPH0144250B2 JP60089772A JP8977285A JPH0144250B2 JP H0144250 B2 JPH0144250 B2 JP H0144250B2 JP 60089772 A JP60089772 A JP 60089772A JP 8977285 A JP8977285 A JP 8977285A JP H0144250 B2 JPH0144250 B2 JP H0144250B2
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- weight
- flame
- magnesium hydroxide
- polypropylene
- 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
- 239000003063 flame retardant Substances 0.000 claims description 34
- 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 32
- 239000000203 mixture Substances 0.000 claims description 30
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 21
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 21
- 239000000347 magnesium hydroxide Substances 0.000 claims description 21
- 239000004743 Polypropylene Substances 0.000 claims description 18
- -1 polypropylene Polymers 0.000 claims description 18
- 229920001155 polypropylene Polymers 0.000 claims description 18
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 description 15
- 238000005469 granulation Methods 0.000 description 14
- 230000003179 granulation Effects 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 2
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229940007424 antimony trisulfide Drugs 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は難燃性ポリプロピレン組成物に関す
る。さらに詳しくはポリプロピレンに水酸化マグ
ネシウム、有機ハロゲン系難燃剤を配合してなる
造粒性に優れ、かつ高度の難燃性を有するポリプ
ロピレン組成物に関する。
ポリオレフインに水酸化マグネシウムを配合し
てなる難燃性ポリオレフイン組成物に関しては、
従来よりよく知られており、例えば特公昭54−
25541号公報、特公昭54−21227号公報、特開昭54
−83952号公報に開示されている。
しかしながら、ポリオレフインに水酸化マグネ
シウムを配合して難燃化する場合には、60重量％
以上と多量の水酸化マグネシウムを添加する必要
があり、嵩高な水酸化マグネシウム粉末を60重量
％以上ポリオレフインに添加すると該混合物を押
出機を用いて溶融混練押出して造粒する際の造粒
性が悪化し、場合によつては造粒が不可能となる
などの欠点がある。また得られた組成物を用い
て、射出成形法、押出成形法などの成形法で成形
加工する場合、溶融物の流動性が悪いため、得ら
れた成形品の表面にシルバーストリークの発生な
どがみられ、外観不良を起こすといつた問題や得
られた成形品の機械的強度、特に衝撃強度が著る
しく低下するといつた欠点を有している。
本発明者は、水酸化マグネシウムを含有してな
る難燃性ポリオレフイン組成物の上述の問題点を
解決するべく鋭意研究した。その結果、ポリプロ
ピレンに特定量の水酸化マグネシウムおよび有機
ハログン系難燃剤を配合することにより、造粒性
に優れ、かつ高度の難燃化を達成できる組成物が
得られることを見い出し、この知見にもとづいて
本発明を完成した。
以上の記述から明らかなように、本発明の目的
は造粒性に優れ、かつ高度の難燃性を有するポリ
オレフイン組成物を提供することである。
本発明は以下の構成を有する。
次の(A)、(B)、(C)の合計量を100重量％として、
(A)ポリプロピレン50〜80重量％に(B)水酸化マグネ
シウム２〜20重量％および(C)有機ハロゲン系難燃
剤５〜40重量％を配合してなる難燃性ポリプロピ
レン組成物。
本発明で用いるポリプロピレンとしては、プロ
ピレンの単独重合体、プロピレンと他の少量のオ
レフイン例えばエチレン、ブテン―１、４―メチ
ルペンテン―１などの１以上との共重合体をあげ
ることができる。また該ポリプロピレンの配合割
合は、ポリプロピレンと後述の水酸化マグネシウ
ムおよび有機ハロゲン系難燃剤の合計量に対し、
50〜80重量％である。
本発明で用いる水酸化マグネシウムとしては、
特に限定はないが粒径0.1〜50μ、好ましくは0.2
〜5μ、BET法比表面積が20m2／ｇ以下のものを
用いると衝撃性が向上し、表面状態が良好な成形
品が得られるので好ましい。
また、該水酸化マグネシウムを、あらかじめス
テアリン酸ナトリウム、ラウリルスルホン酸ナト
リウムなどの化合物で表面処理したものは、該水
酸化マグネシウムの分散性および流動性が向上す
るので好ましく用いられる。該水酸化マグネシウ
ムの配合量は、ポリプロピレン、水酸化マグネシ
ウムおよび有機ハロゲン系難燃剤の合計量に対し
て２〜20重量％である。配合量が２重量％未満の
場合は充分な難燃効果が発揮されず、また配合量
が20重量％を超える場合には、押出機で溶融混練
押出して造粒することが困難となるので好ましく
ない。
本発明で用いる有機ハロゲン系難燃剤として
は、デカブロモジフエニルエーテル、ドデカクロ
ロドデカヒドロジメタノベンゾシクロオクテンを
あげることができ、これらは単独でまたは混合し
て用いることができる。しかしながら、テトラブ
ロモブタンまたはヘキサブロモベンゼンなどの難
燃剤は揮発性が大きいので好ましくない。また本
発明で用いる有機ハロゲン系難燃剤の配合量は、
目的とする難燃性の程度によつて変動するが、通
常、ポリプロピレン、水酸化マグネシウムおよび
有機ハロゲン系難燃剤の合計量に対して５〜40重
量％である。配合量が５重量％未満では、得られ
る難燃効果が不充分であり、40重量％を超えて
も、実用的難燃性はあまり向上しない上、成形品
としたときの該成形品の衝撃強度が低下するので
好ましくない。また、かかる有機ハロゲン系難燃
剤の一部を塩素化パラフインに置換することは、
該組成物を用いて成形した成形品の剛性、熱変形
温度および衝撃強度を低下させ、さらには燃焼時
の溶融滴下性を助長するので好ましくない。さら
に、テトラブロモブタンまたはヘキサブロモベン
ゼンのような揮発性の大きい難燃剤を併用するこ
とは、成形品としたときの該成形品の使用温度が
制限されるので好ましくない。
本発明の組成物にあつては、さらに難燃助剤と
して二酸化アンチモン、三塩化アンチモンまたは
三硫化アンチモンなどのアンチモン化合物を配合
することができる。該難燃助剤の配合量は、難燃
剤に対して10〜70重量％が好ましい。該難燃助剤
は用いる難燃剤と相剰的に作用するので、難燃剤
の配合量を減少することができその結果、成形品
としたときの該成形品の耐衝撃性を間接的に高め
ることができるので、該難燃助剤を併用するのが
好ましい。
また、本発明の組成物にあつては、通常のポリ
プロピレン組成物に添加される各種添加剤例えば
酸化防止剤、紫外線吸収剤、発泡剤、架橋剤、滑
剤、離型剤、造核剤、顔料、染料などを必要に応
じて適宜配合することができる。
本発明の組成物の製造方法は特に限定されない
が、例えば、ポリプロピレン、水酸化マグネシウ
ム、有機ハロゲン系難燃剤および必要に応じて難
燃助剤ならびに上述の添加剤などの所定量をヘン
セルミキサー（商品名）、スーパーミキサーなど
の高速攪拌機付混合器で混合したのち、得られた
混合物を単軸または２軸の押出機に連続的に供給
して溶融混練温度200〜300℃、好ましくは210〜
250℃で溶融混練押出し、押出されたストランド
をカツトして造粒することによつて製造すること
ができる。
本発明の範囲内の組成からなる混合物は溶融混
練押出して造粒する際の造粒性に優れ、安定的に
本発明の組成物が製造でき、かつ得られた本発明
の組成物を用いて、押出成形法、射出成形法、中
空成形法などの成形法により成形された各種成形
品は、高度の難燃性を有し、かつ機械的強度の低
下もなく、難燃性でかつ薄肉の成形品が要望され
る電気絶縁材料、電気製品部品、自動車用部品な
どに好適に使用することができる。
以下、実施例および比較例にもとづいて本発明
を具体的に説明する。なお実施例および比較例で
用いた本発明の評価法は次の方法によつた。
(i) 造粒性
ポリプロピレン、水酸化マグネシウム、有機
ハロゲン系難燃剤およびその他の添加剤をヘン
セルミキサー（商品名）に入れ攪拌混合したの
ち、口径45mmの単軸の押出機を用いて溶融混練
押出するときの単位時間当りの押出量（Kg／
Hr）の大小で評価する。
(ii) 燃焼試験
射出成形法により成形した長さ127mm、巾
12.7mm、厚さ0.8mmの試験片を空気の動いてい
ない部屋内で、上端を固定して垂直につるす。
燃焼用ガスとして37MJ／m3の発熱量の工業用
メタンガスを用いて19mmの長さの青炎を出すよ
うに調節した内径9.5mmのブンゼンバーナーの
炎を試験片の下端より10秒間あてる。10秒後に
バーナーを除去し除去後の試験片が炎をあげて
燃えている時間を測定し、これを第１着火燃焼
時間として記録する。試験片が消炎後直ちに該
試験片の下端に同様な方法でバーナーの青炎を
10秒間あて、再度消炎するまでの時間を測定
し、これを第２着火燃焼時間として記録する。
また、ひきつづき炭火状となつて燃えている時
間も測定し、グロー時間として記録する。試験
片の下方305mmのところに綿を置き、試験中に
溶融滴下物によつて綿に着火するかどうかを観
察、記録する。以上の燃焼試験を１試料につき
５本の試験片について行なう。この５回の燃焼
試験の第１着火燃焼時間と第２着火燃焼時間の
うちの最大の時間を最大着火燃焼時間として記
録し、また、この５回の燃焼試験の第１着火燃
焼時間と第２着火燃焼時間の合計時間を合計着
火燃焼時間として記録する。さらにグロー時間
の最大の時間を最大グロー時間として記録す
る。
以上の燃焼試験の結果から、次の基準で難燃性
を区分する。
Ｖ―０：(イ) 最大着火燃焼時間が10秒以下である
こと。
(ロ) 合計着火燃焼時間が50秒以下である
こと。
(ハ) 試験片を固定した先端まで燃え続け
ないこと。
(ニ) 溶融滴下物があつても305mm下に置
かれている綿を燃焼させないこと。
(ホ) 最大グロー時間が30秒以下であるこ
と。
Ｖ―２：(イ) 最大着火燃焼時間が30秒以下である
こと。
(ロ) 合計着火燃焼時間が250秒以下であ
ると。
(ハ) 試験片を固定した先端まで燃え続け
ないこと。
(ニ) 溶融滴下物によつて305mm下の綿が
燃焼してもかまわない。
(ホ) 最大グロー時間が60秒以下であるこ
と。
実施例１〜12、比較例１〜６
実施例１〜12として、
メルトフローレート（温度230℃、2.16Kg荷重
下における10分間の溶融樹脂の吐出量）8.0の粉
末状プロピレン・エチレンブロツク共重合体、平
均粒径0.9μ、BET比表面積９m2／ｇの水酸化マ
グネシウム、有機ハロゲン系難燃剤としてデカブ
ロモジフエニルオキサイドおよび難燃助剤として
三酸化アンチモンを後述の第１表に記載の配合割
合でヘンセルミキサー（商品名）に入れ、これに
ポリプロピレン100重量部に対して0.1重量部の
2.6―ジ―ｔ―ブチル―Ｐ―クレゾール、0.1重量
部のテトラキス〔メチレン3.5―ジ―ｔ―ブチル
―４―ヒドロキシヒドロシンナメート〕メタンお
よび0.2重量部のジミリスチルチオジプロピオネ
ートを安定剤として加えてジヤケツト温度60℃で
５分間攪拌混合した。得られた混合物を口径45mm
の単軸押出機で溶融混練温度230℃で溶融混練押
出してストランドとし、得られたストランドを冷
却固化してカツトしペレツト化する方法で造粒し
た。このときの押出量を測定し造粒性を評価し
た。
また、比較例１〜６として、後述の第１表に記
載の配合割合で実施例１〜15で用いたと同様の粉
末状のプロピレン・エチレンブロツク共重合体、
水酸化マグネシウム、デカブロモジフエニルオキ
サイドおよび三酸化アンチモンをヘンセルミキサ
ー（商品名）に入れ、これに実施例１〜12で用い
たのと同様、同量の安定剤を加えてジヤケツト温
度100℃で10分間攪拌混合した。得られた混合物
を実施例１〜12に準拠して溶融混練押出して造粒
した。
このときの押出量を測定し造粒性を評価した。
また、実施各例および比較各例で得られたペレツ
トを用いて射出成形法により所定の試験片を調製
し、燃焼試験を行なつた。
これらの結果を第１表にまとめて示した。
FIELD OF THE INVENTION This invention relates to flame retardant polypropylene compositions. More specifically, the present invention relates to a polypropylene composition comprising polypropylene mixed with magnesium hydroxide and an organic halogen flame retardant, which has excellent granulation properties and a high degree of flame retardancy. Regarding flame-retardant polyolefin compositions made by blending magnesium hydroxide with polyolefins,
It has been well known for a long time, for example,
Publication No. 25541, Japanese Patent Publication No. 1983-21227, Japanese Patent Publication No. 1983
-Disclosed in Publication No. 83952. However, when blending magnesium hydroxide into polyolefin to make it flame retardant, 60% by weight
As mentioned above, it is necessary to add a large amount of magnesium hydroxide, and if more than 60% by weight of bulky magnesium hydroxide powder is added to polyolefin, the granulation properties will be reduced when the mixture is melt-kneaded and extruded using an extruder. There are drawbacks such as deterioration and in some cases, granulation becomes impossible. Furthermore, when the obtained composition is molded using a molding method such as injection molding or extrusion, the fluidity of the melt is poor, so silver streaks may occur on the surface of the obtained molded product. However, it has problems such as poor appearance and a significant decrease in mechanical strength, particularly impact strength, of the molded product obtained. The present inventor conducted extensive research to solve the above-mentioned problems of flame-retardant polyolefin compositions containing magnesium hydroxide. As a result, they discovered that by blending specific amounts of magnesium hydroxide and organic halogen flame retardants with polypropylene, a composition with excellent granulation properties and a high degree of flame retardancy could be obtained. Based on this, the present invention was completed. As is clear from the above description, an object of the present invention is to provide a polyolefin composition that has excellent granulation properties and a high degree of flame retardancy. The present invention has the following configuration. The total amount of the following (A), (B), and (C) is 100% by weight,
A flame-retardant polypropylene composition comprising (A) 50-80% by weight of polypropylene, (B) 2-20% by weight of magnesium hydroxide, and (C) 5-40% by weight of an organic halogen flame retardant. The polypropylene used in the present invention may be a homopolymer of propylene or a copolymer of propylene with a small amount of one or more other olefins such as ethylene, 1-butene, 1-4-methylpentene, and the like. In addition, the blending ratio of the polypropylene is based on the total amount of polypropylene, magnesium hydroxide, and organic halogen flame retardant described below.
It is 50-80% by weight. Magnesium hydroxide used in the present invention includes:
There is no particular limitation, but the particle size is 0.1 to 50μ, preferably 0.2
It is preferable to use a material with a BET specific surface area of 20 m 2 /g or less, since impact resistance is improved and a molded product with a good surface condition can be obtained. Moreover, magnesium hydroxide whose surface has been previously treated with a compound such as sodium stearate or sodium lauryl sulfonate is preferably used because the dispersibility and fluidity of the magnesium hydroxide are improved. The amount of magnesium hydroxide blended is 2 to 20% by weight based on the total amount of polypropylene, magnesium hydroxide, and organic halogen flame retardant. If the blending amount is less than 2% by weight, a sufficient flame retardant effect will not be exhibited, and if the blending amount exceeds 20% by weight, it will be difficult to melt, knead, extrude and granulate using an extruder, so it is preferable. do not have. Examples of the organic halogen flame retardant used in the present invention include decabromodiphenyl ether and dodecachlorododecahydrodimethanobenzocyclooctene, which can be used alone or in combination. However, flame retardants such as tetrabromobutane or hexabromobenzene are undesirable because of their high volatility. The amount of the organic halogen flame retardant used in the present invention is as follows:
Although it varies depending on the desired degree of flame retardancy, it is usually 5 to 40% by weight based on the total amount of polypropylene, magnesium hydroxide, and organic halogen flame retardant. If the amount is less than 5% by weight, the obtained flame retardant effect will be insufficient, and even if it exceeds 40% by weight, the practical flame retardance will not improve much and the impact of the molded product will be reduced. This is not preferable because the strength decreases. In addition, replacing a part of the organic halogen flame retardant with chlorinated paraffin
This is undesirable because it lowers the rigidity, heat distortion temperature and impact strength of molded articles formed using the composition, and further promotes melt dripping during combustion. Further, it is not preferable to use a highly volatile flame retardant such as tetrabromobutane or hexabromobenzene in combination, since this limits the operating temperature of the molded product. The composition of the present invention may further contain an antimony compound such as antimony dioxide, antimony trichloride, or antimony trisulfide as a flame retardant aid. The blending amount of the flame retardant aid is preferably 10 to 70% by weight based on the flame retardant. Since the flame retardant aid acts additively with the flame retardant used, the amount of flame retardant added can be reduced, and as a result, the impact resistance of the molded product is indirectly increased. Therefore, it is preferable to use the flame retardant aid in combination. In addition, in the composition of the present invention, various additives added to ordinary polypropylene compositions, such as antioxidants, ultraviolet absorbers, foaming agents, crosslinking agents, lubricants, mold release agents, nucleating agents, pigments, etc. , dyes, etc. can be appropriately blended as necessary. The method for producing the composition of the present invention is not particularly limited, but for example, predetermined amounts of polypropylene, magnesium hydroxide, an organic halogen flame retardant, and if necessary a flame retardant aid and the above-mentioned additives are mixed in a Hensel mixer. After mixing in a mixer equipped with a high-speed stirrer such as Super Mixer (trade name), the resulting mixture is continuously fed to a single-screw or twin-screw extruder to melt and knead at a temperature of 200 to 300°C, preferably 210 to 300°C.
It can be produced by melt-kneading and extruding at 250°C, cutting the extruded strands, and granulating them. A mixture having a composition within the range of the present invention has excellent granulation properties when granulated by melt-kneading and extrusion, and the composition of the present invention can be stably produced, and the obtained composition of the present invention can be used. Various molded products made by molding methods such as extrusion molding, injection molding, and blow molding have a high degree of flame retardancy and no decrease in mechanical strength. It can be suitably used for electrical insulating materials, electrical product parts, automobile parts, etc. that require molded products. The present invention will be specifically described below based on Examples and Comparative Examples. The evaluation method of the present invention used in Examples and Comparative Examples was as follows. (i) Granulation After polypropylene, magnesium hydroxide, organic halogen flame retardant, and other additives are stirred and mixed in a Hensel mixer (trade name), they are melt-kneaded using a single-screw extruder with a diameter of 45 mm. Amount of extrusion per unit time during extrusion (Kg/
Evaluate based on the size of Hr). (ii) Combustion test Length 127mm, width molded by injection molding method
A specimen measuring 12.7 mm and 0.8 mm thick is hung vertically with its upper end fixed in a room with no air movement.
Using industrial methane gas with a calorific value of 37 MJ/m 3 as the combustion gas, the flame of a Bunsen burner with an inner diameter of 9.5 mm adjusted to emit a blue flame with a length of 19 mm is applied from the lower end of the test piece for 10 seconds. After 10 seconds, remove the burner, measure the time it takes for the removed test piece to emit a flame, and record this as the first ignition combustion time. Immediately after the test piece goes out, apply the blue flame of the burner to the lower end of the test piece in the same way.
Apply the flame for 10 seconds, measure the time until the flame goes out again, and record this as the second ignition combustion time.
In addition, the time it continues to burn like charcoal is also measured and recorded as the glow time. Place the cotton 305 mm below the test piece and observe and record whether the cotton is ignited by the molten drops during the test. The above combustion test is performed on five test pieces per sample. The maximum time of the first ignition combustion time and the second ignition combustion time of these five combustion tests was recorded as the maximum ignition combustion time. Record the total ignition and burn time as the total ignition and burn time. Furthermore, the maximum glow time is recorded as the maximum glow time. Based on the results of the above combustion tests, flame retardancy is classified according to the following criteria. V-0: (a) The maximum ignition combustion time is 10 seconds or less. (b) The total ignition combustion time shall be 50 seconds or less. (c) Do not continue burning to the tip where the test piece is fixed. (d) Do not burn the cotton placed 305mm below even if there is molten drippings. (e) The maximum glow time shall be 30 seconds or less. V-2: (a) The maximum ignition combustion time shall be 30 seconds or less. (b) The total ignition combustion time is 250 seconds or less. (c) Do not continue burning to the tip where the test piece is fixed. (d) It does not matter if the cotton below 305mm is burned by the molten drippings. (e) The maximum glow time shall be 60 seconds or less. Examples 1 to 12, Comparative Examples 1 to 6 As Examples 1 to 12, powdered propylene/ethylene block copolymer with a melt flow rate (amount of molten resin discharged in 10 minutes at a temperature of 230°C and a load of 2.16 kg) of 8.0 was used. Magnesium hydroxide with an average particle size of 0.9 μm and a BET specific surface area of 9 m 2 /g, decabromodiphenyl oxide as an organic halogen flame retardant, and antimony trioxide as a flame retardant aid are blended as shown in Table 1 below. Add 0.1 part by weight to 100 parts by weight of polypropylene to a Hensel mixer (trade name) in proportions.
2.6-di-t-butyl-P-cresol, 0.1 part by weight of tetrakis[methylene 3.5-di-t-butyl-4-hydroxyhydrocinnamate]methane and 0.2 part by weight of dimyristylthiodipropionate as stabilizers. In addition, the mixture was stirred and mixed for 5 minutes at a jacket temperature of 60°C. The resulting mixture was made into a caliber of 45 mm.
The mixture was melt-kneaded and extruded into strands using a single-screw extruder at a melt-kneading temperature of 230°C, and the resulting strands were cooled, solidified, cut, and granulated into pellets. The extrusion amount at this time was measured and the granulation property was evaluated. In addition, as Comparative Examples 1 to 6, powdered propylene/ethylene block copolymers similar to those used in Examples 1 to 15 at the blending ratios listed in Table 1 below,
Magnesium hydroxide, decabromodiphenyl oxide, and antimony trioxide were placed in a Hensel mixer (trade name), and the same amount of stabilizer was added thereto as used in Examples 1 to 12, and the jacket temperature was raised to 100°C. The mixture was stirred and mixed for 10 minutes. The resulting mixture was melt-kneaded and extruded to granulate according to Examples 1 to 12. The extrusion amount at this time was measured and the granulation property was evaluated.
In addition, prescribed test pieces were prepared by injection molding using the pellets obtained in each of the Examples and Comparative Examples, and a combustion test was conducted. These results are summarized in Table 1.
【表】
第１表の記載から明らかなように、本発明の範
囲に入る配合割合からなる組成物は造粒性が極め
てよくかつ高度の難燃性を有することが判明し
た。
また、水酸化マグネシウムの量が本発明の範囲
を超えて配合された比較各例はいずれも造粒性が
わるく、比較的造粒性の良い比較例１〜２は難燃
性が悪化して高度の難燃性を必要とする用途には
使用できない。比較例３，６は難燃性は優れてい
るが造粒性が極めてわるく、かつ機械的強度も低
下して実用に適さないことが判明した。
以上記述したように、本発明の組成物は製造時
の造粒性に優れ、かつ得られた組成物を用いて成
形品としたときに該成形品が高度の難燃性を有
し、機械的強度にも優れ、電気絶縁材料、電気製
品部品、自動車用部品などに好適に使用すること
ができることが判明した。[Table] As is clear from the description in Table 1, it was found that the composition comprising the blending ratio within the range of the present invention had extremely good granulation properties and a high degree of flame retardancy. In addition, the comparative examples in which the amount of magnesium hydroxide was blended beyond the range of the present invention all had poor granulation properties, and the comparative examples 1 and 2, which had relatively good granulation properties, had deteriorated flame retardancy. Cannot be used in applications that require a high degree of flame retardancy. It was found that Comparative Examples 3 and 6 had excellent flame retardancy, but extremely poor granulation properties and decreased mechanical strength, making them unsuitable for practical use. As described above, the composition of the present invention has excellent granulation properties during production, and when the obtained composition is used to form a molded product, the molded product has a high degree of flame retardancy and It has been found that it has excellent mechanical strength and can be suitably used for electrical insulating materials, electrical product parts, automobile parts, etc.
Claims (1)
(A)ポリプロピレン50〜80重量％に(B)水酸化マグネ
シウム２〜20重量％および(C)有機ハロゲン系難燃
剤５〜40重量％を配合してなる難燃性ポリプロピ
レン組成物。 ２ 有機ハロゲン系難燃剤として、デカブロモジ
フエニルエーテルおよびドデカクロロドデカヒド
ロジメタノベンゾシクロオクテンから選ばれた１
以上ののものを用いる特許請求の範囲第１項に記
載の難燃性ポリプロピレン組成物。[Claims] 1. The total amount of the following (A), (B), and (C) is 100% by weight,
A flame-retardant polypropylene composition comprising (A) 50-80% by weight of polypropylene, (B) 2-20% by weight of magnesium hydroxide, and (C) 5-40% by weight of an organic halogen flame retardant. 2 As an organic halogen flame retardant, 1 selected from decabromodiphenyl ether and dodecachlorododecahydrodimethanobenzocyclooctene
The flame-retardant polypropylene composition according to claim 1, which uses the above composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8977285A JPS61247746A (en) | 1985-04-25 | 1985-04-25 | Flame-retardant polypropylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8977285A JPS61247746A (en) | 1985-04-25 | 1985-04-25 | Flame-retardant polypropylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61247746A JPS61247746A (en) | 1986-11-05 |
| JPH0144250B2 true JPH0144250B2 (en) | 1989-09-26 |
Family
ID=13979970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8977285A Granted JPS61247746A (en) | 1985-04-25 | 1985-04-25 | Flame-retardant polypropylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61247746A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE921328A1 (en) * | 1992-04-23 | 1993-11-03 | Defped Ltd | Particulate magnesium hydroxide |
| KR100407724B1 (en) * | 1999-12-30 | 2003-12-31 | 삼성아토피나주식회사 | Flame retardant polypropylene resin composition |
| CN100384948C (en) * | 2006-06-09 | 2008-04-30 | 沈阳化工学院 | Composite modifier surface modified brucite powder preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56139546A (en) * | 1980-04-01 | 1981-10-31 | Tokuyama Soda Co Ltd | Flame-retardant polyolefin composition |
-
1985
- 1985-04-25 JP JP8977285A patent/JPS61247746A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56139546A (en) * | 1980-04-01 | 1981-10-31 | Tokuyama Soda Co Ltd | Flame-retardant polyolefin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61247746A (en) | 1986-11-05 |
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