JPH0366760A - Flame-retardant resin composition - Google Patents
Flame-retardant resin compositionInfo
- Publication number
- JPH0366760A JPH0366760A JP20356989A JP20356989A JPH0366760A JP H0366760 A JPH0366760 A JP H0366760A JP 20356989 A JP20356989 A JP 20356989A JP 20356989 A JP20356989 A JP 20356989A JP H0366760 A JPH0366760 A JP H0366760A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- resin composition
- pts
- retardant resin
- powder
- 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.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 15
- 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 title claims abstract description 14
- 239000011342 resin composition Substances 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 229920002545 silicone oil Polymers 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract 1
- 229920000058 polyacrylate Polymers 0.000 abstract 1
- 239000002341 toxic gas Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ノンハロゲン系の難燃性樹脂組成物に係り、
特に存寄ガスの発生がなくｌ！械的強度に優れる難燃性
樹脂組成物に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a non-halogen flame retardant resin composition,
In particular, there is no generation of residual gas! The present invention relates to a flame-retardant resin composition with excellent mechanical strength.
〈従来の技術）
近年、各種シート、フィルム、あるいは電線・ケーブル
の被覆材として用いられている難燃性の樹脂組成物は、
燃焼時の発煙を防ぐためにノンハロゲン系の組成物を用
いて、腐食性のハロゲン化水素ガスの発生を防止してい
る。このような組成物としては、ノンハロゲン系の樹脂
、即ちポリエチレン、エチレン−エチルアクリレートな
どの樹脂に水酸化マグネシウム、水酸化アルミニウムな
どの水和金属化合物を添加したものが一般に用いられて
いる。しかしながら、水和金属化合物は。(Prior Art) In recent years, flame-retardant resin compositions have been used as various sheets, films, or coating materials for electric wires and cables.
In order to prevent smoke during combustion, a non-halogen composition is used to prevent the generation of corrosive hydrogen halide gas. As such a composition, a composition obtained by adding a hydrated metal compound such as magnesium hydroxide or aluminum hydroxide to a non-halogen resin, ie, a resin such as polyethylene or ethylene-ethyl acrylate, is generally used. However, hydrated metal compounds.
充分な難燃性を得るためには多量に配合しなければなら
ず、その結果得られる組成物の機械的特性が著しく低下
してしまうという問題があった。In order to obtain sufficient flame retardancy, a large amount must be added, resulting in a problem in that the mechanical properties of the resulting composition are significantly reduced.
そこで、難燃効果の高い赤リンを単独あるいは水和金属
化合物と併用して配合することが提案されている。Therefore, it has been proposed to incorporate red phosphorus, which has a high flame retardant effect, either alone or in combination with a hydrated metal compound.
しかしながら、赤リンはハロゲン化水素ガスの発生が無
くまた、機械的特性を損なわずに高い難燃性を付与でき
る反面、燃焼時には人体に有害なホスフィンガスを発生
するという新たな問題が生じている。However, while red phosphorus does not generate hydrogen halide gas and can provide high flame retardancy without impairing its mechanical properties, a new problem has arisen: when burned, it generates phosphine gas that is harmful to the human body. .
（発明が解決しようとする課題）
以上の点に鑑みて、本発明は得られる組成物の機械的特
性を良好に保ちながら高い難燃性を有し。(Problems to be Solved by the Invention) In view of the above points, the present invention provides a composition that has high flame retardancy while maintaining good mechanical properties.
しかも燃焼時にハロゲン化水素ガス、ホスフィンガスな
どの有害ガスを発生することの無い難燃性樹脂組成物を
提供することを目的とする。Moreover, it is an object of the present invention to provide a flame-retardant resin composition that does not generate harmful gases such as hydrogen halide gas and phosphine gas when burned.
（課題を解決するための手段）
本発明は即ち、ハロゲン元素をオまない樹脂１００重量
部に、（イ）粒径４３０μｍ以下のアンチモン粉末３−
５０重ＩＩ部、（ロ）粒径８５ ｔｔ ｍ以ドの亜鉛粉
末３〜５０重量部、（ハ）１０〜２００万センチストー
クスのポリオルガノシロキサン１〜１０重量部からなる
群から選ばれた少なくとも２種を配合してなることを特
徴とする難燃性樹脂組成物に関する。(Means for Solving the Problems) In other words, the present invention is characterized in that (a) antimony powder with a particle size of 430 μm or less is added to 100 parts by weight of a resin that does not contain halogen elements;
(b) 3 to 50 parts by weight of zinc powder with a particle size of 85 ttm or less; (c) 1 to 10 parts by weight of polyorganosiloxane with a particle size of 10 to 2 million centistokes. The present invention relates to a flame-retardant resin composition characterized by blending two types.
本発明は、上記くイ〉、（ロ）、および〈ハ）からなる
群の中から少なくとも２種を併用して配合することによ
り、非常に高い難燃性を有し、かつ得られる組成物の機
械的特性を良好に保つことができ２しかも燃焼時にハロ
ゲン化水素ガス、ホスフィンガスなどの有害ガスを発生
しない。The present invention provides a composition that has extremely high flame retardancy and is obtained by blending together at least two types from the group consisting of (a), (b), and (c) above. The mechanical properties of the fuel can be maintained well, and no harmful gases such as hydrogen halide gas or phosphine gas are generated during combustion.
本発明におけるハロゲン元素を含まないｖＡ脂としては
、ボリエ千しン５ポリプロピレンを初めとするポリオレ
フィン、エチレン−エチルアクリレートコポリマー（Ｅ
ＥＡ）、エチレン−酢酸ヒニル共重合体（ＥＥＡ）など
を＋１独あるいは混合したもの、およびその架橋物等を
使用することができる。In the present invention, the vA fat that does not contain a halogen element includes polyolefins such as Borie Senshin 5 polypropylene, ethylene-ethyl acrylate copolymer (E
EA), ethylene-hinyl acetate copolymer (EEA), etc. alone or a mixture thereof, and crosslinked products thereof can be used.
本発明における（イ）アンチモン粉末は、粒径４３０μ
ｍ以下の金属アンチモン粉末を用い、また本発明におけ
る（口）亜鉛粉末は、粒径８５７４ｍ以下の金属亜鉛粉
末を用いる。さらにこれらの粉末の表面を融点２００〜
３００℃の範囲内にある高分子化合物にて表ｌ１ｉｉ処
理したものを用いても良い、アンチモン粉末または亜鉛
粉末の粒径がに記の数幀を越えると、樹脂に対する分散
が悪くなり、また得られる組成物の８！械的強度が低下
する。(a) Antimony powder in the present invention has a particle size of 430 μm.
Metallic antimony powder having a particle size of 8574m or less is used, and as zinc powder in the present invention, a metal zinc powder having a particle size of 8574m or less is used. Furthermore, the surface of these powders has a melting point of 200~
It is possible to use antimony powder or zinc powder treated with a polymer compound in the range of 300°C in Table 11ii. If the particle size of the antimony powder or zinc powder exceeds the several squares shown below, the dispersion in the resin will be poor and the yield will be poor. 8 compositions that can be used! Mechanical strength decreases.
また１表面処理に用いる融点２００℃以−Ｅの高分子化
合物としては、アクリル系樹脂、ポリカーボネート系樹
脂等がある。これらのＶＩ４脂で亜鉛粉末を表面処理す
ることにより、亜鉛粉末は混線時に樹脂との相溶性が向
上して均一に分散され、また着色が可能となる０表面処
理に用いる高分子化合物は融点が２００〜３００℃の範
囲内のものが組成物の燃焼時に優れた難燃効果を発揮す
る０表面処理の方法は、使用する高分子化合物をその融
点付近の温度で上記粉末に吹き付けた後１００℃程度で
乾燥させれば良い、（イ）アンチモン粉末または（口〉
亜鉛粉末の配合割合はハロゲン元素を含まない樹脂１０
０重最部に対してそれぞれ３〜５０重量部であり、これ
より少ないと難燃性が不十分となり、これより多いと得
られる組成物の機械的特性が低下する傾向にある。Further, examples of the polymer compound having a melting point of -E of 200° C. or higher used for surface treatment include acrylic resins, polycarbonate resins, and the like. By surface-treating the zinc powder with these VI4 resins, the zinc powder improves its compatibility with the resin and is dispersed uniformly when cross-wired, and the melting point of the polymer compound used for surface treatment that enables coloring is increased. The method of surface treatment, in which a temperature within the range of 200 to 300°C exhibits an excellent flame retardant effect when the composition is combusted, is to spray the polymer compound to be used on the powder at a temperature near its melting point, and then heat the powder at 100°C. (a) Antimony powder or (mouth)
The blending ratio of zinc powder is 10% of the resin that does not contain halogen elements.
The amount is 3 to 50 parts by weight, respectively, based on the zero weight part. If the amount is less than this, the flame retardance will be insufficient, and if it is more than this, the mechanical properties of the resulting composition will tend to deteriorate.
本発明における（ハ）１０〜２００万センチストークス
のポリオルガノシロキサンは、メチル基、フェニル基等
を測鎖に持つシリコーンオイルまたはシリコーンゴムを
使用することができる。またその配合割合はハロゲン元
素を含まない樹脂１００重量部に対にて１〜１０重盪部
であり、これより少ないと難燃性の向上が少なく、また
これより多いと滑性が増大しコンパウンディングや押し
出し加工性が著しく低下する。As the (c) polyorganosiloxane of 100,000 to 2,000,000 centistokes in the present invention, silicone oil or silicone rubber having a methyl group, phenyl group, etc. in the chain can be used. The blending ratio is 1 to 10 parts by weight per 100 parts by weight of resin that does not contain halogen elements; if it is less than this, there will be little improvement in flame retardancy, and if it is more than this, the lubricity will increase and the compound will ding and extrusion processability will be significantly reduced.
また、本発明においては他の難燃剤として水酸化アルミ
ニウム、水酸化マグネシウムなどの金属水和物、あるい
はカーボンを併用して配合することができる。この場合
、水酸化アルミニウムおよび水酸化マグネシウムの平均
粒径は樹脂との分散性を良くするために１μｍ程度が好
ましい、また配合割合は、ハロゲン元素を含まない樹脂
１００重厘部に対してカーボンを４重ｉ部以下、また水
酸１ヒアルミニウム、水酸化マグネシウムは単独あるい
は両者を混合して７０〜９００〜９０重量部く２この範
囲外では得られる組成物の機械的特性の低下が生じ、難
燃性の向上に寄与しない。Further, in the present invention, other flame retardants such as metal hydrates such as aluminum hydroxide and magnesium hydroxide, or carbon may be used in combination. In this case, the average particle size of aluminum hydroxide and magnesium hydroxide is preferably about 1 μm in order to improve dispersibility with the resin, and the blending ratio is that carbon is added to 100 parts by weight of resin that does not contain halogen elements. 4 parts by weight or less, and hyaluminum hydroxide and magnesium hydroxide, alone or in combination, 70 to 900 to 90 parts by weight.2 Outside this range, the mechanical properties of the resulting composition will deteriorate; Does not contribute to improving flame retardancy.
（実施例） 本発明の実施例について説明する。(Example) Examples of the present invention will be described.
実施例１〜１１
表に示す割合で各成分を配合し、充分混練して難燃性樹
脂組成物を製造した。これを用いて次の試験をした。Ｒ
械的特性は、１００％モジュラス、引っ張り強さ（Ｔｓ
）、伸び（Ｅｌ）を測定した。Examples 1 to 11 Each component was blended in the proportions shown in the table and thoroughly kneaded to produce a flame-retardant resin composition. The following test was conducted using this. R
Mechanical properties include 100% modulus, tensile strength (Ts
) and elongation (El) were measured.
また１、 ＯＯ℃×１２０時間加熱後および７０℃Ｘ４
時間油中に浸漬した後の引っ張り強さ残率（ＴＳ残率）
、伸び強さ残率（Ｅｌ残率）を測定した。Also 1. After heating at OO℃ x 120 hours and at 70℃ x 4
Tensile strength residual rate (TS residual rate) after being immersed in oil for an hour
, the elongation strength retention (El retention) was measured.
難燃性は、酸素指数の測定およびＵＬ−９４Ｍｉ格試験
全試験た。結果を表に示す。Flame retardancy was determined by oxygen index measurement and all UL-94Mi rating tests. The results are shown in the table.
比較１３’ｌｌ〜４
表に示す割合で各成分を配合し、その他は実施例１と同
様にして製造および試験をした。結果を表に示す。Comparison 13'll~4 Each component was blended in the proportions shown in the table, and the manufacturing and testing were carried out in the same manner as in Example 1 except for the following. The results are shown in the table.
〈以下余白〉
表に示されるように、本発明の難燃性樹脂組成物は、水
和金民化合物と赤リンを併用した場合と同等の難燃性１
機械的特性を有しながら、かつ有害ガスを発生すること
がない、また、上記（イ〉、（ロ）、および〈ハ〉から
なる群の中から少なくとも２種を併用して配合している
ので、これらを単独で配合した場合に比して難燃性が大
幅に向りしている。(Left below) As shown in the table, the flame retardant resin composition of the present invention has a flame retardance of 1 equivalent to that of the combination of the hydrated gold compound and red phosphorus.
It has mechanical properties and does not generate harmful gases, and is formulated in combination with at least two types from the group consisting of (a), (b), and (c) above. Therefore, flame retardancy is significantly improved compared to when these are blended alone.
（発明の効果）
以上本発明の難燃性樹脂組成物は、機械的特性を良好に
保ちながら、難燃性を大幅に向」−１７、また燃焼特に
ハロゲン化水素ガス、ホスフィンガスなどの有害ガスを
発生しないので極めて安全であり幅広い用途に提供でき
るものである。(Effects of the Invention) As described above, the flame-retardant resin composition of the present invention has significantly improved flame retardancy while maintaining good mechanical properties. Since it does not generate gas, it is extremely safe and can be used in a wide range of applications.
Claims (1)
イ）粒径４３０μｍ以下のアンチモン粉末３〜５０重量
部、（ロ）粒径８５μｍ以下の亜鉛粉末３〜５０重量部
、（ハ）１０〜２００万センチストークスのポリオルガ
ノシロキサン１〜１０重量部からなる群から選ばれた少
なくとも２種を配合してなることを特徴とする難燃性樹
脂組成物。(1) To 100 parts by weight of resin that does not contain halogen elements, (
a) 3 to 50 parts by weight of antimony powder with a particle size of 430 μm or less, (b) 3 to 50 parts by weight of zinc powder with a particle size of 85 μm or less, and (c) 1 to 10 parts by weight of polyorganosiloxane with a particle size of 10 to 2 million centistokes. A flame-retardant resin composition comprising at least two selected from the group consisting of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20356989A JPH0366760A (en) | 1989-08-04 | 1989-08-04 | Flame-retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20356989A JPH0366760A (en) | 1989-08-04 | 1989-08-04 | Flame-retardant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0366760A true JPH0366760A (en) | 1991-03-22 |
Family
ID=16476299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20356989A Pending JPH0366760A (en) | 1989-08-04 | 1989-08-04 | Flame-retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0366760A (en) |
-
1989
- 1989-08-04 JP JP20356989A patent/JPH0366760A/en active Pending
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