JPH04110340A - Flame-retarding resin composition - Google Patents
Flame-retarding resin compositionInfo
- Publication number
- JPH04110340A JPH04110340A JP22997390A JP22997390A JPH04110340A JP H04110340 A JPH04110340 A JP H04110340A JP 22997390 A JP22997390 A JP 22997390A JP 22997390 A JP22997390 A JP 22997390A JP H04110340 A JPH04110340 A JP H04110340A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- parts
- weight
- resin composition
- pts
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 18
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005977 Ethylene Substances 0.000 claims abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 4
- 239000003063 flame retardant Substances 0.000 claims description 14
- 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 13
- 229920000800 acrylic rubber Polymers 0.000 claims description 11
- 229920000058 polyacrylate Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 abstract description 9
- 229910052736 halogen Inorganic materials 0.000 abstract description 7
- 150000002367 halogens Chemical class 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 2
- 229920001971 elastomer Polymers 0.000 abstract 2
- 239000000806 elastomer Substances 0.000 abstract 2
- -1 Vamac HG Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 230000005855 radiation Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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、燃焼時でも有毒なハロゲン系ガスを発生しな
い難燃性電線・ケーブルを製造するための被覆用の難燃
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 flame-retardant resin composition for coating for manufacturing flame-retardant electric wires and cables that do not generate toxic halogen gas even when burned. .
［従来の技術］
従来より、電線・ケーブルの難燃化が望まれており、ハ
ロゲン含有樹脂やハロゲン系難燃剤を配合した樹脂組成
物か電線等の被覆用飼料として用いられてきた。[Prior Art] It has been desired to make electric wires and cables flame retardant, and resin compositions containing halogen-containing resins and halogen-based flame retardants have been used as feed for coating electric wires, etc.
しかしながら、これらは加熱・燃焼時に、機器への腐食
性や人体への有害性を有するノ＼ロゲン系ガスを発生す
るため、ハロゲンを含有しないエチレン・アクリルエラ
スト▽マーに水酸化マグネシウムや水酸化アルミニウム
等の無機系難燃剤を添加した樹脂組成物か開発された（
特開昭６２−１８６４１１号）。However, when heated and burned, these generate halogen-based gases that are corrosive to equipment and harmful to the human body. A resin composition containing inorganic flame retardants such as
(Japanese Patent Application Laid-open No. 186411/1982).
［発明が解決しようとする課題］
しかし、エチレン・アクリルエラストマーに水酸化マグ
ネシウムを配合すると、練り加工中にスコーチか起こり
、実用的ではない。また、水酸化アルミニウムをエチレ
ン・アクリルエラストマーに単独で添加する場合には、
実用的な難燃性を付与するためにはかなり大量に配合し
なければならず、でき上かった難燃性樹脂組成物の機械
的特性や耐油性等か著しく低下する。[Problems to be Solved by the Invention] However, when magnesium hydroxide is blended with ethylene-acrylic elastomer, scorch occurs during kneading, which is not practical. In addition, when aluminum hydroxide is added alone to ethylene/acrylic elastomer,
In order to impart practical flame retardancy, a fairly large amount must be blended, and the mechanical properties, oil resistance, etc. of the resulting flame retardant resin composition will be significantly reduced.
本発明の課題は、上記のような従来の難燃性樹脂組成物
の欠点を解消し得て、優れた難燃性のみならず、機械特
性、耐熱性、ノンハロゲン性、耐油性、耐放射線性等を
バランスよく有する電線・ケーブル被覆用の難燃性樹脂
組成物を提供する処にある。The object of the present invention is to overcome the drawbacks of conventional flame-retardant resin compositions as described above, and to provide not only excellent flame retardancy but also mechanical properties, heat resistance, non-halogen properties, oil resistance, and radiation resistance. The purpose of the present invention is to provide a flame-retardant resin composition for covering electric wires and cables, which has a good balance of the following.
［課題を解決するための手段及び作用］本発明の難燃性
樹脂組成物は、エチレン、メチルアクリレート及び重合
性有機カルボン酸よりなるアクリル系エラストマー１０
０重量部、水酸化アルミニウム２５〜１４０重量部、赤
リン３〜３０重量部、並びにファーネス系カーボンブラ
ック８〜４０重量部からなる。[Means and effects for solving the problems] The flame-retardant resin composition of the present invention comprises an acrylic elastomer 10 made of ethylene, methyl acrylate, and a polymerizable organic carboxylic acid.
0 parts by weight, 25 to 140 parts by weight of aluminum hydroxide, 3 to 30 parts by weight of red phosphorus, and 8 to 40 parts by weight of furnace carbon black.
本発明におけるアクリル系エラストマーは、エチレン、
メチルアクリレート及び重合性有機カルボン酸よりなり
、下記一般式で示される。The acrylic elastomer in the present invention includes ethylene,
It consists of methyl acrylate and polymerizable organic carboxylic acid and is represented by the following general formula.
このようなアクリル系エラストマーとしては、デュポン
社製のベイマックＢ−：１．２４ 、ヘイマックＨＧ、
ベイマックＧ１ベイマックＮ−１２３等（いずれも商品
名）か例示される。Examples of such acrylic elastomers include Baymac B-:1.24, Haymac HG, manufactured by DuPont.
Baymac G1, Baymac N-123, etc. (all product names) are exemplified.
水酸化アルミニウムとしては、特に限定はな、いか、粒
子径が０．５〜１．Ｃ１μｍでステアリン酸などで表面
処理をしたものが好ましい。このようなものとしては、
例えば、昭和電工社製のハイジライｌ−Ｈ−４２Ｓ 、
ハイシライトＨ４３Ｓかある。Aluminum hydroxide is not particularly limited, and has a particle size of 0.5 to 1. It is preferable to use C1 μm and surface-treated with stearic acid or the like. As such,
For example, Hijirai l-H-42S manufactured by Showa Denko Co., Ltd.
I have Hishilight H43S.
赤リンについても特に限定はないか、平均粒子径が１５
μｍ以下で、表面をフェノール樹脂などでコーティング
してマイクロカプセル化したものが好ましい。このよう
なものとしては、例えば、燐化学工業社製のノーバレッ
ト１２０ＵＦ、ノーバレット１２０ＵＦＡかある。Is there any particular limitation for red phosphorus? The average particle size is 15
It is preferable to use microcapsules whose surface is coated with a phenol resin or the like and whose diameter is less than μm. Examples of such products include Noballet 120UF and Noballet 120UFA manufactured by Rin Kagaku Kogyo Co., Ltd.
本発明で用いるファーネス系カーボンブラックとしては
、ＳＲＦ、ＨＡＦ、ｌ５ＡＦ等が好ましい。As the furnace carbon black used in the present invention, SRF, HAF, 15AF, etc. are preferable.
本発明の難燃性樹脂組成物における各成分の配合割合は
次の通りである。The blending ratio of each component in the flame-retardant resin composition of the present invention is as follows.
水酸化アルミニウムは、アクリル系エラスＩ・マー１０
０重量部に対して２５〜１４０重量部配合する。２５重
量部未満だと、充分な難燃性をイ附与することができな
い。１４０重量部を超えると、機械特性、耐油性、耐放
射線性等が低下して実用的でない。水酸化アルミニウム
の好ましい配合量は、アクリル系エラストマー１００重
量部に対して３０〜１２０重量部である。Aluminum hydroxide is acrylic elas I/Mar 10
25 to 140 parts by weight are added to 0 parts by weight. If it is less than 25 parts by weight, sufficient flame retardancy cannot be imparted. If it exceeds 140 parts by weight, mechanical properties, oil resistance, radiation resistance, etc. deteriorate, making it impractical. The preferred amount of aluminum hydroxide is 30 to 120 parts by weight per 100 parts by weight of the acrylic elastomer.
赤リンは、アクリル系エラストマー１００重量部に対し
て３〜３０重量部配合する。３重量部未満だと、難燃性
か向上しない。３０重量部を超えると、難燃性や機械特
性か低下する。赤リンの好ましい配合量は、アクリル系
エラストマー１００重量部に対して５〜２０重量部であ
る。Red phosphorus is added in an amount of 3 to 30 parts by weight per 100 parts by weight of the acrylic elastomer. If it is less than 3 parts by weight, flame retardancy will not improve. If it exceeds 30 parts by weight, flame retardancy and mechanical properties will deteriorate. The preferred amount of red phosphorus is 5 to 20 parts by weight per 100 parts by weight of the acrylic elastomer.
ファーネス系カーボンブラックは、アクリル系エラスト
マー１００重量部に対して８〜４０重量部配合する。８
重量部未満だと、機械特性か向上しないたけてなく、難
燃性も向」ニしない。The furnace carbon black is blended in an amount of 8 to 40 parts by weight based on 100 parts by weight of the acrylic elastomer. 8
If it is less than 1 part by weight, the mechanical properties will not be improved and the flame retardance will not be improved either.
４０重量部を超えると、機械特性や難燃性が低下する。If it exceeds 40 parts by weight, mechanical properties and flame retardancy will deteriorate.
ファーネス系カーボンブラックの好ましい配合量は、ア
クリル系エラストマー１００重量部に対して１０〜３０
重量部である。The preferred blending amount of furnace carbon black is 10 to 30 parts by weight per 100 parts by weight of the acrylic elastomer.
Parts by weight.
以上のように、本発明の難燃性樹脂組成物には、水酸化
アルミニウム、赤リン及びファーネス系カーボンブラッ
クが特定の割合で配合されているので、三者の相乗作用
により、比較的少量の水酸化アルミニウムで優れた難燃
性や耐熱性を付与することかできる。また、このように
水酸化アルミニウム（無機系難燃剤）の配合量を減らす
ことかできるので、アクリル系エラストマーの有する機
械特性、耐油性、耐放射線性を損うことなく、バランス
のとれた実用的な難燃性樹脂組成物となる。As described above, the flame-retardant resin composition of the present invention contains aluminum hydroxide, red phosphorus, and furnace carbon black in specific proportions, so the synergistic effect of the three causes a relatively small amount of Aluminum hydroxide can provide excellent flame retardancy and heat resistance. In addition, since the amount of aluminum hydroxide (inorganic flame retardant) can be reduced in this way, the mechanical properties, oil resistance, and radiation resistance of acrylic elastomers are not compromised, and a well-balanced practical product can be achieved. It becomes a flame-retardant resin composition.
従って、原子力発電所施設等に使われる電線等の被覆材
料として特に有用である。Therefore, it is particularly useful as a coating material for electric wires used in nuclear power plant facilities and the like.
なお、本発明の難燃性樹脂組成物には、上記した必須の
成分のほかに、公知の架橋剤、架橋促進剤、老化防止剤
等を適宜配合することができる。In addition to the above-mentioned essential components, the flame-retardant resin composition of the present invention may appropriately contain known crosslinking agents, crosslinking accelerators, anti-aging agents, and the like.
［実施例］
以下、実施例及び比較例により本発明の詳細な説明する
。[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples.
実施例１〜５及び比較例１〜７
第１表に示す割合（重量部）で各成分を配合し、これを
水冷ロールを用いて混練した後に、１７０°Ｃで２５分
間プレスしてシートを成形した。このシー トから第１
表に示す各特性を４Ｉｌｌ定するに適した試験片を作成
した。Examples 1 to 5 and Comparative Examples 1 to 7 Each component was blended in the proportions (parts by weight) shown in Table 1, kneaded using a water-cooled roll, and then pressed at 170°C for 25 minutes to form a sheet. Molded. 1st from this sheet
Test pieces suitable for determining each of the characteristics shown in the table were prepared.
各試験片を用いてＡＩＩ］定した結果を第１表に併記し
た。The results of the AII test using each test piece are also listed in Table 1.
（以下余白）
第１表から明らかなように、実施例１〜５の樹脂組成物
は、優れた難燃性のみならず、機械特性、耐油性、耐放
射線性等をバランスよく有していた。(Left below) As is clear from Table 1, the resin compositions of Examples 1 to 5 not only had excellent flame retardancy, but also had well-balanced mechanical properties, oil resistance, radiation resistance, etc. .
これに対し、比較例１の組成物は、ファーネス系カーボ
ンブラックか少ないため、抗張力か劣っていた。比較例
２の組成物は、ファーネス系カーボンブラックが多すぎ
るため、引張特性か低下していた。比較例３の組成物は
、水酸化アルミニウムか少ないため、難燃性に劣ってい
た。比較例４の組成物は、赤リンが少ないため、難燃性
が向」ニジていなかった。比較例５の組成物は、赤リン
が多すぎるため、難燃性と抗張力が低下していた。比較
例６の組成物は、水酸化アルミニウムの代わりに水酸化
マグネシウムを用いたので、混練時にスコーチが生じ、
試験片の作成かできなかった。比較例７の組成物は、フ
ァーネス系カーボンブラックと赤リンとを配合せずに水
酸化アルミニウムを大量に配合したので、耐放射線性、
耐油性、加熱後の抗張力か劣っていた。On the other hand, the composition of Comparative Example 1 had poor tensile strength because it contained less furnace carbon black. The composition of Comparative Example 2 contained too much furnace carbon black, so its tensile properties were degraded. The composition of Comparative Example 3 had poor flame retardancy because it contained less aluminum hydroxide. Since the composition of Comparative Example 4 contained less red phosphorus, the flame retardance did not deteriorate. The composition of Comparative Example 5 contained too much red phosphorus, so its flame retardancy and tensile strength were reduced. The composition of Comparative Example 6 used magnesium hydroxide instead of aluminum hydroxide, so scorch occurred during kneading.
I was unable to create a test piece. The composition of Comparative Example 7 did not contain furnace carbon black and red phosphorus, but contained a large amount of aluminum hydroxide, so it had good radiation resistance and
Oil resistance and tensile strength after heating were poor.
［発明の効果］
以上のように、本発明の樹脂組成物は、優れた＠ト性は
もちろん、機械特性、耐熱性、ノンハロゲン性、耐油性
、耐放射線性等をバランスよく有するので、電線・ケー
ブル被覆用の難燃性樹脂組成物として広い範囲で極めて
実用的である。[Effects of the Invention] As described above, the resin composition of the present invention has not only excellent @ properties but also mechanical properties, heat resistance, non-halogen properties, oil resistance, radiation resistance, etc. in a well-balanced manner. It is extremely practical in a wide range of applications as a flame-retardant resin composition for cable coating.
特許出願人 タック電線株式会社
代 理 人 弁理士 蔦 １） 璋 子
ほか１名Patent applicant: TAC Electric Cable Co., Ltd. Agent: Patent attorney: Tsuta 1) Shoko and 1 other person
Claims (1)
ボン酸よりなるアクリル系エラストマー１００重量部、
水酸化アルミニウム２５〜１４０重量部、赤リン３〜３
０重量部、並びにファーネス系カーボンブラック８〜４
０重量部からなる電線・ケーブル被覆用の難燃性樹脂組
成物。1. 100 parts by weight of an acrylic elastomer made of ethylene, methyl acrylate and polymerizable organic carboxylic acid;
25-140 parts by weight of aluminum hydroxide, 3-3 parts by weight of red phosphorus
0 parts by weight, and furnace carbon black 8-4
A flame-retardant resin composition for covering electric wires and cables consisting of 0 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22997390A JPH04110340A (en) | 1990-08-30 | 1990-08-30 | Flame-retarding resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22997390A JPH04110340A (en) | 1990-08-30 | 1990-08-30 | Flame-retarding resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04110340A true JPH04110340A (en) | 1992-04-10 |
Family
ID=16900610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22997390A Pending JPH04110340A (en) | 1990-08-30 | 1990-08-30 | Flame-retarding resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04110340A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543447A (en) * | 1994-09-28 | 1996-08-06 | Southwest Research Institute | Stabilization of red amorphous phosphorus by ordered polymeric structures for the manufacture of non-emissive fire retardant plastics |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59140242A (en) * | 1983-01-31 | 1984-08-11 | Shin Etsu Chem Co Ltd | Flame-retardant rubber composition |
| JPS61213234A (en) * | 1985-03-20 | 1986-09-22 | Dainichi Nippon Cables Ltd | Flame-retardant resin composition |
| JPS63165447A (en) * | 1986-12-26 | 1988-07-08 | Mitsubishi Cable Ind Ltd | Electrically semiconductive and flame-retardant composition |
| JPS6460642A (en) * | 1987-08-28 | 1989-03-07 | Showa Electric Wire & Cable Co | Flame-retarding composition |
-
1990
- 1990-08-30 JP JP22997390A patent/JPH04110340A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59140242A (en) * | 1983-01-31 | 1984-08-11 | Shin Etsu Chem Co Ltd | Flame-retardant rubber composition |
| JPS61213234A (en) * | 1985-03-20 | 1986-09-22 | Dainichi Nippon Cables Ltd | Flame-retardant resin composition |
| JPS63165447A (en) * | 1986-12-26 | 1988-07-08 | Mitsubishi Cable Ind Ltd | Electrically semiconductive and flame-retardant composition |
| JPS6460642A (en) * | 1987-08-28 | 1989-03-07 | Showa Electric Wire & Cable Co | Flame-retarding composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543447A (en) * | 1994-09-28 | 1996-08-06 | Southwest Research Institute | Stabilization of red amorphous phosphorus by ordered polymeric structures for the manufacture of non-emissive fire retardant plastics |
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