JPS6343208A - Flame resisting electrically insulating composition - Google Patents
Flame resisting electrically insulating compositionInfo
- Publication number
- JPS6343208A JPS6343208A JP61187057A JP18705786A JPS6343208A JP S6343208 A JPS6343208 A JP S6343208A JP 61187057 A JP61187057 A JP 61187057A JP 18705786 A JP18705786 A JP 18705786A JP S6343208 A JPS6343208 A JP S6343208A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- weight
- parts
- electrically insulating
- insulating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 16
- 239000012796 inorganic flame retardant Substances 0.000 claims description 11
- 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 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 238000010292 electrical insulation Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- BYDOXMDGHAWVGN-UHFFFAOYSA-N 1-(5-methoxy-2,2,8,8-tetramethylpyrano[3,2-g]chromen-10-yl)ethanone Chemical compound O1C(C)(C)C=CC2=C1C(C(C)=O)=C1OC(C)(C)C=CC1=C2OC BYDOXMDGHAWVGN-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 polyethylene, ethylene vinyl acetate Polymers 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000000474 Poliomyelitis Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、燃焼時に有毒なハロゲン系ガスを発生しない
難燃性電気絶縁組成物、特に、電線・ケーブルの絶縁材
料やシース材料への適用に好適な難燃性電気絶縁組成物
に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is a flame-retardant electrical insulation composition that does not generate toxic halogen gas when burned, and is particularly applicable to insulation materials and sheath materials for electric wires and cables. The present invention relates to a flame-retardant electrical insulation composition suitable for.
［従来の技術］
電線・ケーブルの絶縁材料やシース材料としては電気絶
縁性に優れたポリオレフィンが多く用いられてきている
。最近の趨勢として原子力発電所用電線・ケーブル、車
両用電線・ケーブル、船舶用電線・ケーブルに垂直トレ
イ燃焼試験レベルの高度の難燃性が要望されるようにな
ってきた。[Prior Art] Polyolefins, which have excellent electrical insulation properties, have been widely used as insulating materials and sheath materials for electric wires and cables. A recent trend is that electric wires and cables for nuclear power plants, electric wires and cables for vehicles, and electric wires and cables for ships are required to have a high degree of flame retardancy at the level of the vertical tray combustion test.
ポリオレフィンを難燃化する方法としてはハロゲン含有
化合物等を混和する方法が一般に採用されてきている。As a method of making polyolefin flame retardant, a method of incorporating a halogen-containing compound or the like has generally been adopted.
しかし、これらは燃焼時多量の煙を発生し、機器への腐
食性、人体への有害性等が聞届になっている。特に、最
近は安全面からこの様なハロゲン系ガスを発生しないこ
とが要望されるようになってきている。However, these produce a large amount of smoke when burned, and it has been reported that they are corrosive to equipment and harmful to the human body. In particular, recently there has been a demand for not generating such halogen-based gases from the standpoint of safety.
この様な情勢を踏まえ、発煙性、を毒性の非常に少ない
無機系難燃剤が注目されるようになってきた。In light of this situation, inorganic flame retardants with very low smoke-emitting and toxic properties are attracting attention.
［発明が解決しようとする問題点］
しかし、無機系難燃剤は難燃効果が小さいため、単にポ
リマに混和しただけでは燃焼時に溶融滴下するというド
リップ現象がみられ、高度の難燃性を付与することは難
しい。なお、高度の難燃性を付与するためには無機系難
燃剤を多量加えることも有効であるが、得られる絶縁体
やシースの引張特性の低下を招いたり、押出加工性が低
下するという問題がある。[Problems to be solved by the invention] However, inorganic flame retardants have a small flame retardant effect, so if they are simply mixed into a polymer, a drip phenomenon in which they melt and drip during combustion is observed, resulting in a high degree of flame retardancy. It's difficult to do. Although it is effective to add a large amount of inorganic flame retardant to impart a high degree of flame retardancy, it causes problems such as deterioration of the tensile properties of the resulting insulator and sheath and deterioration of extrusion processability. There is.
本発明は上記に基いてなされたものであり、垂直トレイ
燃焼試験レベルに合格する高度の難燃性を付与できると
共に有毒なハロゲン系ガスを発生しない難燃性電気絶縁
組成物の提供を目的とするものである。The present invention has been made based on the above, and aims to provide a flame-retardant electrical insulating composition that can impart a high degree of flame retardancy that passes the vertical tray combustion test level and does not generate toxic halogen gases. It is something to do.
［問題点を解決するための手段］
本発明の難燃性電気絶縁組成物は、ポリオ、レフイン１
００重量部に対して無機系難燃剤を５０〜５００重量部
および硫酸カルシウムウィスカを１〜５０重量部含有す
ることを特徴とするものである。[Means for Solving the Problems] The flame-retardant electrical insulation composition of the present invention contains polio, Refine 1
It is characterized by containing 50 to 500 parts by weight of an inorganic flame retardant and 1 to 50 parts by weight of calcium sulfate whiskers per 00 parts by weight.
本発明において、ポリオレフィンとしては、エチレンプ
ロピレンコポリマ、エチレンプロピレンジェンターポリ
マ、ポリエチレン、エチレン酢酸ビニルコポリマ、エチ
レンエチルアクリレートコポリマ、エチレンブテンコポ
リマ、エチレンブテンジエ゛ンターポリマといったもの
があげられ、これらは単独使用または２種以上の併用が
可能である。In the present invention, examples of the polyolefin include ethylene propylene copolymer, ethylene propylene terpolymer, polyethylene, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene butene copolymer, and ethylene butene dieterpolymer, which may be used alone or in combination. It is possible to use more than one species in combination.
無機系難燃剤としては、水酸化アルミニウム、水酸化マ
グネシウム、塩基性炭酸マグネシウム、水酸化カルシウ
ム、ハイドロタルサイト類等があげられる。無機系難燃
剤の含有量は、ポリオレフィン１００重量部に対して５
０〜５００重量部の範囲とする必要があり、５０重量部
未満では目的とする難燃性を付与てきず、５００重量部
を越えると加工性が著しく低下して押出成形が困難にな
る。Examples of inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, and hydrotalcites. The content of inorganic flame retardant is 5 parts by weight per 100 parts by weight of polyolefin.
The amount must be in the range of 0 to 500 parts by weight; if it is less than 50 parts by weight, the desired flame retardancy cannot be imparted, and if it exceeds 500 parts by weight, the processability is markedly reduced and extrusion molding becomes difficult.
本発明においては、無機系難燃剤に加えて硫酸カルシウ
ムウィスカを併用することにより燃焼時のドリップを防
止でき、難燃性を大幅に向上できることが見出された。In the present invention, it has been found that by using calcium sulfate whiskers in addition to an inorganic flame retardant, drips during combustion can be prevented and flame retardancy can be significantly improved.
硫酸カルシウムウィスカとしては、Ｆｒａｎｋｌｉｎ
Ｆｉｂｅｒの商品名で米国Ｇｙｐｓｕｍ社から市販さ
れているものがあげられる。硫酸カルシウムウィスカは
、ポリオレフィン１００重量部に対して１〜５０重量部
の範囲で配合する必要があり、１重量部未満では燃焼時
のドリップを防止できず、５０重量部を越えると混和物
の粘度が増加して押出加工性を損なう。As a calcium sulfate whisker, Franklin
One example is one commercially available from Gypsum Inc. in the United States under the trade name Fiber. Calcium sulfate whiskers must be blended in a range of 1 to 50 parts by weight per 100 parts by weight of the polyolefin; less than 1 part by weight will not prevent dripping during combustion, and more than 50 parts by weight will reduce the viscosity of the mixture. increases, impairing extrusion processability.
本発明においては、上記成分に加えて架橋剤、酸化防止
剤、滑剤、軟化剤、分散剤等を適宜添加してもよい。架
橋剤としては、ジクミルパーオキサイド、３−ビス（ｔ
−ブチルパーオキシイソプロピル）ベンゼンに代表され
る有機過酸化物が適切であり、これに架橋助剤として、
硫黄、エチレンジメタアクリレート、ジアリルフタレー
ト、ｐ−キノンジオキシム等を併用してもよい。また、
電子線等の電離性放射線による架橋の場合は、架橋助剤
としてトリメチロールプロパントリメリテート、トリア
リルイソシアヌレート等の反応性のモノマを添加するの
が一般的である。酸化防止剤としては、フェニル−α−
ナフチルアミン Ｎ。In the present invention, in addition to the above components, crosslinking agents, antioxidants, lubricants, softeners, dispersants, etc. may be added as appropriate. As a crosslinking agent, dicumyl peroxide, 3-bis(t
-butylperoxyisopropyl)benzene is suitable, and as a crosslinking agent,
Sulfur, ethylene dimethacrylate, diallyl phthalate, p-quinone dioxime, etc. may be used in combination. Also,
In the case of crosslinking using ionizing radiation such as an electron beam, a reactive monomer such as trimethylolpropane trimellitate or triallyl isocyanurate is generally added as a crosslinking aid. As an antioxidant, phenyl-α-
Naphthylamine N.
Ｎ′−ジ−β−ナフチル−ｐ−フ二二レンジアミン等の
アミン系酸化防止剤、２，６−ジーｔ−ブチル−４−メ
チルフェノール、ヒンダードフェノール等のフェノール
系酸化防止剤があげられる。Examples include amine antioxidants such as N'-di-β-naphthyl-p-phenyl diamine, and phenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol and hindered phenol. It will be done.
［実施例コ
第１表に示すような配合にしたがって各種成分を１００
’Ｃに保持された６インチロールに投入してロール混
練を行い、混線後１２０℃に保持された４０ｍ／ｍ押出
機（Ｌ／Ｄ−２５）を用い、外径５．３ｍａ＋の絶縁線
心を３本撚合せた外周に２．０＋ｎｍの厚さで押出被覆
した。なお、実施例１゜４．５および比較例１について
は押出被覆に続いて１３ｋｇ／ｃ−の水蒸気雰囲気中に
３分間保持して架橋した。[Example: 100% of various ingredients were added according to the formulation shown in Table 1.
The insulated wire core with an outer diameter of 5.3 ma The outer periphery of three twisted strands was coated by extrusion to a thickness of 2.0+nm. In addition, in Example 1°4.5 and Comparative Example 1, following extrusion coating, crosslinking was carried out by holding in a steam atmosphere of 13 kg/c- for 3 minutes.
各側で作製した絶縁電線についての評価結果は第１表の
下欄に示した通りである。The evaluation results for the insulated wires produced on each side are shown in the lower column of Table 1.
なお、難燃性評価は次に基いて行った。長さ２ｍのケー
ブルを垂直に８本並べ、下から７万ＢＴＵの炎を２０分
間当て、自己消炎すれば合格であり、自己消炎せず全焼
するものは不合格である。In addition, flame retardancy evaluation was performed based on the following. Eight cables with a length of 2 m are lined up vertically and a 70,000 BTU flame is applied from below for 20 minutes. If the flame self-extinguishes, it passes; if it burns out without self-extinguishing, it fails.
第１表からも明らかな通り、本発明に係わる実施例１〜
６ではいずれも難燃性に合格し、押出加工性に優れてい
る。これに対し無機系難燃剤の含有量が規定値以下の比
較例１では難燃性が不合格であり、規定値以上の比較例
２では押出性が悪く成形不可能であった。また、硫酸カ
ルシウムウィスカの含有量が規定値以下の比較例３では
ドリップが生じて難燃性が不合格であり、規定値を越え
る比較例４では押出ができない。As is clear from Table 1, Examples 1 to 1 according to the present invention
6, all passed the flame retardant test and were excellent in extrusion processability. On the other hand, in Comparative Example 1 in which the content of the inorganic flame retardant was below the specified value, the flame retardance was rejected, and in Comparative Example 2, in which the content of the inorganic flame retardant was above the specified value, the extrudability was poor and molding was impossible. Further, in Comparative Example 3 in which the content of calcium sulfate whiskers was less than the specified value, dripping occurred and the flame retardance was rejected, and in Comparative Example 4 in which the content of calcium sulfate whiskers exceeded the specified value, extrusion could not be performed.
［発明の効果コ
以上説明してきた通り、本発明は難燃剤として無機系難
燃剤と硫酸カルシウムウィスカを併用したものであり、
良好な押出加工性を維持しながら高度の難燃性を付与で
き、しかも燃焼時に有毒なハロゲン系ガスを発生しない
電気絶縁物を得られるようになる。[Effects of the Invention] As explained above, the present invention uses an inorganic flame retardant and calcium sulfate whiskers together as a flame retardant,
It becomes possible to obtain an electrical insulator that can be imparted with a high degree of flame retardancy while maintaining good extrusion processability, and does not generate toxic halogen-based gas when burned.
Claims (1)
剤５０〜５００重量部および硫酸カルシウムウィスカ１
〜５０重量部含有することを特徴とする難燃性電気絶縁
組成物。(1) 50 to 500 parts by weight of inorganic flame retardant and 1 part of calcium sulfate whisker per 100 parts by weight of polyolefin
A flame-retardant electrical insulation composition characterized by containing ~50 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61187057A JPS6343208A (en) | 1986-08-08 | 1986-08-08 | Flame resisting electrically insulating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61187057A JPS6343208A (en) | 1986-08-08 | 1986-08-08 | Flame resisting electrically insulating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6343208A true JPS6343208A (en) | 1988-02-24 |
Family
ID=16199414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61187057A Pending JPS6343208A (en) | 1986-08-08 | 1986-08-08 | Flame resisting electrically insulating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6343208A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0288653A (en) * | 1988-09-27 | 1990-03-28 | Showa Electric Wire & Cable Co Ltd | Flame-retardant vibration-damping material composition |
-
1986
- 1986-08-08 JP JP61187057A patent/JPS6343208A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0288653A (en) * | 1988-09-27 | 1990-03-28 | Showa Electric Wire & Cable Co Ltd | Flame-retardant vibration-damping material composition |
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