JPH0559935B2 - - Google Patents
Info
- Publication number
- JPH0559935B2 JPH0559935B2 JP24647784A JP24647784A JPH0559935B2 JP H0559935 B2 JPH0559935 B2 JP H0559935B2 JP 24647784 A JP24647784 A JP 24647784A JP 24647784 A JP24647784 A JP 24647784A JP H0559935 B2 JPH0559935 B2 JP H0559935B2
- Authority
- JP
- Japan
- Prior art keywords
- red phosphorus
- ammonium salt
- orthophosphoric acid
- composition
- polyolefin
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 229920000098 polyolefin Polymers 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 235000011007 phosphoric acid Nutrition 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 11
- 239000003063 flame retardant Substances 0.000 claims description 8
- 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 7
- 239000010419 fine particle Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
（産業上の利用分野）
本発明は難燃性が付与されたポリオレフイン組
成物に関する。
（従来の技術）
ポリオレフインに難燃性を付与するために、ハ
ロゲンを含む化合物を添加することが通常行われ
ている。
しかしながら、該ハロゲン含有化合物により難
燃性付与の目的は達成出来たとしても、該化合物
は熱によりハロゲン化水素を脱離しやすいため、
金型、押出機スクリユー等成形加工に使用する装
置類を腐蝕するといつた欠点が常にあり、さら
に、加工温度を高めると樹脂の分解を起こす危険
があるので、加工温度領域が限られ、より高い加
工温度条件を採用して、生産性よく、ポリオレフ
イン成形品の製造を行うことは困難であつた。
上記の様な問題点を解決する試みとして、例え
ば特開昭51−105996号公報に示される如く、ポリ
オレフイン等の樹脂に、耐熱性等を向上させる目
的で、赤リン微粒子を配合することが提案されて
おり、又、特公昭51−27461号公報には、ポリオ
レフインへの耐焔性付与のために赤リン及びメラ
ミン（又はポリアクリルニトリル）を用いること
が記載されている。しかしながら、上記の如き赤
リン等を添加しても、ポリオレフインに十分な難
燃性を付与することは困難であり、例えばUL−
94規規格による燃焼試験法のＶ−２に合格するこ
とは困難である。
（発明が解決しようとする問題点）
本発明は上記の如き状況にかんがみ、ハロゲン
含有化合物を用いることなくすぐれた難燃性が付
与されたポリオレフイン組成物を提供することを
目的とする。
（問題点を解決するための手段）
本発明の難燃性ポリオレフイン組成物はは、ポ
リオレフインに、赤リン微粒子と正リンのアンモ
ニウム塩が添加されてなるもので、そのことによ
り上記目的が達成される。
本発明に用いられるポリオレフインは、ポリエ
チレン、ポリプロピレン、エチレンプロピレン共
重合体など、エチレン、プロピレン等のオレフイ
ンモノマーを構成成分とする重合体や共重合体で
ある。
又、赤リン微粒子としては、そのまゝであると
空気中の水分によつて変質し、取扱い上危険でも
あるので、例えば特開昭51−105996号や同52−
125489号公報に示される如く、その表面を熱硬化
性樹脂で被覆するのが一般的であり、本発明にお
いてはその様な表面処理された赤リン微粒子が好
適に用いられる。又、本発明に用いられる正リン
酸のアンモニウム塩にはポリリン酸アンモニウム
や第１リン酸アンモニウムが含まれる。
そしてこれらの使用量としては、組成物中に、
上記赤リンと正リン酸のアンモニウム塩が合計量
10〜30重量％含有される様に配合するのが好まし
く、又、赤リン対正リン酸のアンモニウム塩の使
用比率については、99：１〜１：99の範囲で用い
るのが好ましい。
本発明の組成物は、ポリオレフイン、赤リン微
粒子及び正リン酸のアンモニウム塩を加え合せて
混合若しくは混練することにより得ることが出
来、その組成物は、押出機、射出成型機等適宜な
成形機により所望の形状に成形することが出来
る。そして、本発明組成物は耐熱性が良好にして
ハロゲンを含んでもいないので、上記混練や成形
時の加熱状況下において、変色その他の熱劣化を
受けることがないのは勿論のこと、従来のハロゲ
ン元素含有の難燃剤を用いた場合の様に、脱離し
たハロゲン化水素によつて、金型、スクリユー等
が腐蝕されると言つた不都合を生じることもない
のである。
一般にンの難燃剤としての作用機構としては、
燃焼時の加熱によつて生成したリン酸がメタリン
酸、ポリメタリン酸となつて、燃焼するプラスチ
ツクスの固相又は溶融相面に不揮発性のリン酸ポ
リマー被膜を形成し、それによつて難燃効果を奏
するものと知られているが、本発明においてさら
に添加される正リン酸のアンモニウム塩は、上記
ポリメタリン酸等の生成を助長し、さらにそれ自
体も加熱によつてアンモニアを放出して脱水炭化
触媒として作用するものと考えられ、これらの作
用が相俟つて本発明組成物のすぐれた難燃化効果
が得られるものと推測される。
本発明組成物は、上記以外に、着色剤、充填
剤、その他の適宜な添加剤が添加されて差し支え
ない。
（実施例）
ポリプロピレン（商品名 三菱ノーブレンMA
−８、三菱油化社製）100重量部に対し、第１表
に示される量の防湿表面処理された赤リン（商品
名 ノーバレツド＃120、燐化学工業社製）及び
ポリリン酸アンモニウム又は第１リン酸アンモニ
ウムを加え合せ、加熱ロールで混練し、プレスで
厚さ１mm、巾12.7，mmのシートに成形し、これを
試験片とした。
(Industrial Application Field) The present invention relates to a polyolefin composition imparted with flame retardancy. (Prior Art) In order to impart flame retardancy to polyolefin, it is common practice to add a compound containing a halogen. However, even if the purpose of imparting flame retardance is achieved by using the halogen-containing compound, the compound easily desorbs hydrogen halide due to heat.
There is always the disadvantage that it corrodes the equipment used in the molding process, such as molds and extruder screws.Furthermore, if the processing temperature is increased, there is a risk of decomposition of the resin, so the processing temperature range is limited and higher It has been difficult to manufacture polyolefin molded products with good productivity by employing processing temperature conditions. In an attempt to solve the above-mentioned problems, for example, as shown in JP-A-51-105996, it has been proposed to blend red phosphorus fine particles into resins such as polyolefin for the purpose of improving heat resistance, etc. Furthermore, Japanese Patent Publication No. 51-27461 describes the use of red phosphorus and melamine (or polyacrylonitrile) to impart flame resistance to polyolefins. However, even if red phosphorus is added as described above, it is difficult to impart sufficient flame retardancy to polyolefins. For example, UL-
It is difficult to pass V-2 of the combustion test method according to the 94th standard. (Problems to be Solved by the Invention) In view of the above-mentioned circumstances, an object of the present invention is to provide a polyolefin composition imparted with excellent flame retardancy without using a halogen-containing compound. (Means for Solving the Problems) The flame-retardant polyolefin composition of the present invention is made by adding red phosphorus fine particles and orthophosphorus ammonium salt to a polyolefin, thereby achieving the above object. Ru. The polyolefin used in the present invention is a polymer or copolymer having an olefin monomer such as ethylene or propylene as a constituent, such as polyethylene, polypropylene, or ethylene-propylene copolymer. In addition, if red phosphorus fine particles are left as they are, they will deteriorate due to moisture in the air and are dangerous to handle.
As shown in Japanese Patent No. 125489, it is common to coat the surface with a thermosetting resin, and such surface-treated red phosphorus fine particles are preferably used in the present invention. Further, ammonium salts of orthophosphoric acid used in the present invention include ammonium polyphosphate and monoammonium phosphate. The amounts used in the composition include:
Total amount of the above red phosphorus and ammonium salt of orthophosphoric acid
It is preferable to blend the red phosphorus to the ammonium salt of orthophosphoric acid in an amount of 10 to 30% by weight, and the ratio of red phosphorus to ammonium salt of orthophosphoric acid to be used is preferably in the range of 99:1 to 1:99. The composition of the present invention can be obtained by adding and mixing or kneading polyolefin, red phosphorus fine particles, and ammonium salt of orthophosphoric acid, and the composition can be processed using a suitable molding machine such as an extruder or an injection molding machine. It can be molded into a desired shape. Furthermore, since the composition of the present invention has good heat resistance and does not contain halogen, it does not suffer from discoloration or other thermal deterioration under the heating conditions during kneading and molding, and it does not contain conventional halogens. Unlike when flame retardants containing elements are used, there is no problem such as corrosion of molds, screws, etc. due to the released hydrogen halide. In general, the mechanism of action of N as a flame retardant is as follows:
Phosphoric acid generated by heating during combustion becomes metaphosphoric acid and polymetaphosphoric acid, forming a non-volatile phosphoric acid polymer film on the solid phase or molten phase surface of the burning plastic, thereby improving the flame retardant effect. However, the ammonium salt of orthophosphoric acid that is further added in the present invention promotes the production of the above-mentioned polymetaphosphoric acid, and also releases ammonia upon heating, resulting in dehydration and carbonization. It is thought that it acts as a catalyst, and it is presumed that these actions work together to provide the excellent flame retardant effect of the composition of the present invention. In addition to the above, colorants, fillers, and other appropriate additives may be added to the composition of the present invention. (Example) Polypropylene (Product name: Mitsubishi Noblen MA
-8, manufactured by Mitsubishi Yuka Co., Ltd.), the amounts of moisture-proof surface-treated red phosphorus (trade name: Novarez #120, manufactured by Rin Kagaku Kogyo Co., Ltd.) and ammonium polyphosphate or Ammonium phosphate was added, kneaded with heated rolls, and pressed into a sheet with a thickness of 1 mm and a width of 12.7 mm, which was used as a test piece.
【表】
用意した試験片についてUL−94規格に従つて
燃焼試験を行つた所、第１表に示される判定結果
が得られた。
なお、試験における接炎は１試料料につき２回
（各10秒間）行ない、同一試験における試料数は
５とした。
比較例
第２表の実験番号５−８に示される配合組成の
ものについて、実施例と同様にして燃焼試験を行
つた所、同表に示される結果を得た。なお、ポリ
プロピレン、表面処理赤リン及びポリリン酸アン
モニウムは実施例で用いたのと同じものを用い
た。[Table] When the prepared test pieces were subjected to a combustion test in accordance with the UL-94 standard, the judgment results shown in Table 1 were obtained. In addition, the flame contact in the test was performed twice (for 10 seconds each) for each sample, and the number of samples in the same test was 5. Comparative Example A combustion test was conducted in the same manner as in the example for the composition shown in Experiment No. 5-8 in Table 2, and the results shown in the table were obtained. Note that the polypropylene, surface-treated red phosphorus, and ammonium polyphosphate were the same as those used in Examples.
【表】
（発明の効果）
本発明はポリオレフインに赤リン微粒子と正リ
ン酸のアンモニウム塩が添加されることによつ
て、ハロゲン含有化合物を用いることなく、すぐ
れた難燃効果を発揮出来、例えばUL−94によよ
る燃焼試験に合格するものであるので、難燃性が
要求される建材部品や電気部品その他の用途に用
いられて好適なるものである。[Table] (Effects of the invention) By adding red phosphorus fine particles and ammonium salt of orthophosphoric acid to polyolefin, the present invention can exhibit an excellent flame retardant effect without using a halogen-containing compound. Since it passes the combustion test according to UL-94, it is suitable for use in building parts, electrical parts, and other applications that require flame retardancy.
Claims (1)
のアンモニウム塩が添加されてなる難燃性ポリオ
レフイン組成物。 ２ 組成物中における赤リンと正リン酸のアンモ
ニウム塩の合計量が10〜30重量％であり、赤リン
対正リン酸のアンモニウム塩の比率が99：１〜
１：99である第１項記載の難燃性ポリオレフイン
組成物。[Claims] 1. A flame-retardant polyolefin composition comprising a polyolefin to which red phosphorus fine particles and an ammonium salt of orthophosphoric acid are added. 2 The total amount of red phosphorus and ammonium salt of orthophosphoric acid in the composition is 10 to 30% by weight, and the ratio of red phosphorus to ammonium salt of orthophosphoric acid is 99:1 to 99:1.
1. The flame retardant polyolefin composition according to claim 1, wherein the ratio is 1:99.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24647784A JPS61223045A (en) | 1984-11-21 | 1984-11-21 | Flame-retardant polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24647784A JPS61223045A (en) | 1984-11-21 | 1984-11-21 | Flame-retardant polyolefin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61223045A JPS61223045A (en) | 1986-10-03 |
| JPH0559935B2 true JPH0559935B2 (en) | 1993-09-01 |
Family
ID=17148979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24647784A Granted JPS61223045A (en) | 1984-11-21 | 1984-11-21 | Flame-retardant polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61223045A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2588331B2 (en) * | 1991-10-03 | 1997-03-05 | 積水化学工業株式会社 | Flame retardant resin composition |
| JP3340946B2 (en) | 1997-07-18 | 2002-11-05 | キョーワ株式会社 | Flame retardant for mesh sheet and flameproof mesh sheet using the same |
| JP3245555B2 (en) | 1997-10-09 | 2002-01-15 | キョーワ株式会社 | Flame retardant for mesh sheet and flameproof mesh sheet using the same |
| JP3249940B2 (en) | 1997-12-05 | 2002-01-28 | キョーワ株式会社 | Flame retardant for mesh sheet and flameproof mesh sheet using the same |
| NL1010837C2 (en) * | 1997-12-18 | 1999-07-13 | Kyowa Kk | Flame retardant for netting and non-flammable netting material containing it. |
| JP3781250B2 (en) | 1998-06-11 | 2006-05-31 | キョーワ株式会社 | Flame retardant for mesh sheet and flameproof mesh sheet using the same |
| US20080110663A1 (en) * | 2004-08-23 | 2008-05-15 | Jinder Jow | Communications Cable-Flame Retardant Separator |
-
1984
- 1984-11-21 JP JP24647784A patent/JPS61223045A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61223045A (en) | 1986-10-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |