JPH0745602B2 - Flame retardant composition - Google Patents
Flame retardant compositionInfo
- Publication number
- JPH0745602B2 JPH0745602B2 JP61163597A JP16359786A JPH0745602B2 JP H0745602 B2 JPH0745602 B2 JP H0745602B2 JP 61163597 A JP61163597 A JP 61163597A JP 16359786 A JP16359786 A JP 16359786A JP H0745602 B2 JPH0745602 B2 JP H0745602B2
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- JP
- Japan
- Prior art keywords
- weight
- parts
- flame
- phosphate
- rubber
- 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
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- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は電線、ケーブル等に用いられる難燃性組成物、
特に分子（化合物を含む）中にハロゲン元素を含有しな
い難燃性組成物に関するものである。TECHNICAL FIELD The present invention relates to a flame-retardant composition used for electric wires, cables and the like,
In particular, it relates to a flame-retardant composition containing no halogen element in its molecule (including compound).
従来の技術 多数のケーブルが布設されている電気設備に於て、万一
火災が発生した場合に電線・ケーブルの絶縁材が燃料と
なつて延焼する危険性がある。2. Description of the Related Art In an electrical installation where many cables are laid, there is a danger that the insulation material of the wires / cables will become a fuel and spread by fire if a fire should occur.
この場合に問題となるのは電線・ケーブルの延焼ととも
に、有害ガスを発生し人畜に被害を及ぼしたり或は家
屋、設備等に腐食の問題を起すことであり、その解決に
ついては種々の提案がなされている。In this case, the problem is that with the spread of the electric wire / cable, harmful gas is generated, which damages humans and animals, or causes a problem of corrosion in houses, facilities, etc. Has been done.
その提案の一例をあげれば特開昭55−69679号ではポリ
クロロプレンに水和アルミナと燐酸塩フリツトを添加し
たものであり、特開昭56−18636号はポリオレフイン類
に無機の含水化合物を添加したものである。One example of the proposal is JP-A-55-69679 in which hydrated alumina and phosphate frit are added to polychloroprene, and JP-A-56-18636 is in which an inorganic hydrous compound is added to polyolefins. It is a thing.
発明が解決しようとする問題点 しかしながら、上記の如き提案に於ても電線・ケーブル
等に塗布して延焼を防止したり有害ガスの発生や多量の
発煙を防止する上からは未だ不充分で、特にテープやシ
ートに成形するについては必ずしも満足すべきものとは
云い難かつた。Problems to be Solved by the Invention However, even in the above proposal, it is still insufficient from the viewpoint of preventing spread of fire by coating electric wires and cables and preventing generation of harmful gas and large amount of smoke, In particular, it has been difficult to say that the tape or sheet is necessarily satisfactory.
問題点を解決するための手段 本発明は上記の如き実情に鑑み、鋭意検討の結果なされ
たもので、その概要は以下のとおりである。Means for Solving the Problems The present invention has been made as a result of intensive studies in view of the above-mentioned actual circumstances, and the outline thereof is as follows.
（１）エチレンプロピレン共重合体と分子中にハロゲン
元素を含まないゴム・プラスチックとの混合物100重量
部と、（Ａ）クレーと、（Ｂ）タルク、アルミナ、硼酸
亜鉛、シリカ、水酸化アルミニウム、水酸化マグネシウ
ム、三酸化アンチモン、炭酸カルシウムの群から選ばれ
たものの一種以上とを、重量比でA/B＝１〜４の割合で
配合した無機充填剤を200〜400重量部と、化合物中にハ
ロゲン元素を含まないリン酸エステル化合物、リン酸塩
フリットあるいは第３リン酸アルミニウムからなる炭化
促進剤５〜35重量部と加硫剤0.1〜10重量部とが配合さ
れていることを特徴とする難燃性組成物。(1) 100 parts by weight of a mixture of ethylene-propylene copolymer and rubber / plastic containing no halogen element in the molecule, (A) clay, (B) talc, alumina, zinc borate, silica, aluminum hydroxide, 200 to 400 parts by weight of an inorganic filler in which at least one selected from the group of magnesium hydroxide, antimony trioxide, and calcium carbonate is mixed at a weight ratio of A / B = 1 to 4 And 5 to 35 parts by weight of a carbonization accelerator composed of a phosphate ester compound containing no halogen element, a phosphate frit, or a tertiary aluminum phosphate and 0.1 to 10 parts by weight of a vulcanizing agent. Flame-retardant composition.
作用 以下これについて詳述する。Action This will be described in detail below.
この発明に於ては配合剤中にすべてハロゲン元素を含有
しないので、人畜に無害で腐食作用もないことが最大の
特徴となる。In this invention, since the compounding agent does not contain any halogen element, the greatest feature is that it is harmless to humans and animals and has no corrosive action.
先づエチレンプロピレン共重合体と分子中にハロゲン元
素を含まないゴム・プラスチツクとの混合物は、組成物
の基準となるもので加工し易さと製品の適当な硬さ等を
保証する。The mixture of the ethylene-propylene copolymer and the rubber / plastic which does not contain a halogen element in the molecule is a standard of the composition and ensures the ease of processing and the appropriate hardness of the product.
ここに用いられるゴム・プラスチツクとしてはブチルゴ
ム、SBR（スチレンブタジエンラバー）、ポリエチレ
ン、ポリプロピレン、エチレン−α−オレフイン共重合
体、エチレン酢酸ビニル共重合体、EEA（エチレン−エ
チルアクリレート）、エチレンアクリリツクエラストマ
ー、EAA（エチレンアクリリツクアシド）等が挙げられ
る。Examples of the rubber / plastic used here are butyl rubber, SBR (styrene butadiene rubber), polyethylene, polypropylene, ethylene-α-olefin copolymer, ethylene vinyl acetate copolymer, EEA (ethylene-ethyl acrylate), ethylene acrylic elastomer. , EAA (ethylene acrylic acid) and the like.
無機充填剤は前記ゴム・プラスチツクの混合物に難燃性
を付与するものであり、クレー、タルク、アルミナ、硼
酸亜鉛、シリカ、水酸化アルミニウム、水酸化マグネシ
ウム、三酸化アンチモン等が使用され、その配合量は20
0〜400重量部が好ましい。200重量部未満では難燃効果
が不充分であり、400重量部を超えると硬くなり過ぎる
等加工性が悪くなり、特にテープやシートに加工する上
で不利となる。The inorganic filler imparts flame retardancy to the rubber / plastic mixture, and clay, talc, alumina, zinc borate, silica, aluminum hydroxide, magnesium hydroxide, antimony trioxide, etc. are used, and their blending is performed. Amount is 20
0 to 400 parts by weight is preferred. If it is less than 200 parts by weight, the flame retardant effect is insufficient, and if it exceeds 400 parts by weight, it becomes too hard and the workability deteriorates, which is particularly disadvantageous in processing into a tape or sheet.
最も好ましい無機充填剤は（Ａ）クレーと（Ｂ）タル
ク、アルミナ、硼酸亜鉛、シリカ、水酸化アルミニウ
ム、三酸化アンチモン、水酸化マグネシウムの群から選
ばれた少なくとも１種以上とを併用することでありその
配合比はA/B＝１〜４（重量比）である。A/Bが１未満で
は炭化した殻の強さが不足し、４を超えると炭化した殻
の層に亀裂が生じるのでいづれも防火目的達成上好まし
くない。The most preferred inorganic filler is a combination of (A) clay and (B) at least one selected from the group consisting of talc, alumina, zinc borate, silica, aluminum hydroxide, antimony trioxide and magnesium hydroxide. The compounding ratio is A / B = 1 to 4 (weight ratio). When A / B is less than 1, the strength of the carbonized shell is insufficient, and when it exceeds 4, cracking occurs in the layer of the carbonized shell, and thus any case is not preferable for achieving the purpose of fire prevention.
次にハロゲン元素を化合物の分子中に含まない、リン酸
エステル化合物、リン酸塩フリツト或いは第３リン酸ア
ルミニウムからなる炭化促進剤を５〜35重量部加え、前
記したプラスチツク、ゴム等が燃焼した際に炭化層即ち
炭化隔壁を構成し、防火目的を達成するものである。Next, 5 to 35 parts by weight of a carbonic acid accelerator composed of a phosphate ester compound, a phosphate frit or a tribasic aluminum phosphate which does not contain a halogen element in the molecule of the compound is added, and the above-mentioned plastic, rubber or the like is burned. At this time, a carbonized layer, that is, a carbonized partition wall is formed to achieve the purpose of fire prevention.
これらのリン系の化合物の代表例はTCP（トリクレジル
ホスフエート）、TOP（トリオクチルホスフエート）、O
DP（オクチルジフエニルホスフエート）等があげられ
る。Typical examples of these phosphorus compounds are TCP (tricresyl phosphate), TOP (trioctyl phosphate), O
DP (octyl diphenyl phosphate) etc. are mentioned.
このような炭化促進剤が５重量部未満だと、炭化膜が脆
弱であり、又、35重量部を越えると却つて難燃性が低下
する。If the amount of such a carbonization promoter is less than 5 parts by weight, the carbonized film is fragile, and if it exceeds 35 parts by weight, the flame retardancy deteriorates.
更に本発明では架硫剤（加硫促進剤を含む）を用いてゴ
ム・プラスチツク類を三次元網目構造にし耐熱性を高め
るものでありその種類はゴム・プラスチツク材料によつ
て適宜選択されるが、ノクセラーTT（大内新興社商品
名、テトラメチルチウラムジサルフアイド）、ノクセラ
ーTRA（大内新工社商品名、ジペンタメチレンチウラム
テトラサルフアイド）、アクセル−TL（川口化学工業社
商品名、テルリウムジエチルジチオカーバメイト）、ノ
クセラーDM（大内新興社商品名、ジベンゾチアジルサル
フアイド）ジクミルパーオキサイド、亜鉛華、ベルノツ
クDGM（大内新興社商品名、P,P′，−ジベンゾイルキノ
ンジオキシム）があげられ、0.1〜10重量部は最も常識
的な配合量である。Further, in the present invention, a vulcanizing agent (including a vulcanization accelerator) is used to make the rubber / plastics have a three-dimensional network structure to enhance heat resistance. The type of rubber / plastics is appropriately selected depending on the rubber / plastic material. , Nocceller TT (Ouchi Shinko Co., Ltd. trade name, tetramethylthiuram disulfide), Noxeller TRA (Ouchi Shinko Co., trade name, dipentamethylene thiuram tetrasulfide), Axel-TL (Kawaguchi Chemical Industry trade name, Tellurium diethyldithiocarbamate), Noxcellar DM (trade name of Ouchi Shinko Co., Ltd., dibenzothiazyl sulfaide) dicumyl peroxide, zinc flower, Vernotsk DGM (trade name of Ouchi Shinko Co., P, P ',-dibenzoylquinone) Dioxime), and 0.1 to 10 parts by weight is the most common amount.
以上の配合の組成物は押出被覆や、モールド、ロール加
工など加工性に富み、容易に加硫される。The composition having the above composition has excellent workability such as extrusion coating, molding, and roll processing, and is easily vulcanized.
又、組成物中には必要に応じ老化防止剤、着色剤、転化
剤、滑剤、紫外線吸収剤等を添加配合し得ることは一般
のゴム・プラスチツク技術と同じである。但しいづれも
分子（化合物）中にハロゲン元素を含まないことが条件
である。In addition, it is the same as the general rubber / plastic technique that an antiaging agent, a colorant, a conversion agent, a lubricant, an ultraviolet absorber and the like may be added and blended into the composition if necessary. However, the condition is that no halogen element is contained in the molecule (compound).
次にの発明は電線・ケーブルの延焼防止等のためにテー
プやシート状に成形加工し、電線・ケーブルの最外層に
巻回したり、蔽つたりするものであり、通常厚さ0.5〜4
mm程度、に加工されテープの場合、電線・ケーブルの最
外層に巻く場合は1/2ラツプで１〜２回重ね巻され、シ
ートでは１回巻して用いられる。The next invention is to form a tape or sheet into a wire or cable to prevent the spread of electric wires / cables, and to wind or cover the outermost layer of the electric wire / cable.
In the case of a tape processed to about mm, when it is wound on the outermost layer of an electric wire / cable, it is used by wrapping it once or twice with a 1/2 lap, and with a sheet, it is wound once.
特にこの発明では分子中にハロゲン元素を含まないゴム
・プラスチツクとしてブチルゴムを選択すると、エチレ
ンプロピレン共重合体とブチルゴムとは化学構造上、C,
Hを主体の化合物で相容性もよく、特にテープやシート
にも成形加工し易く、電線・ケーブルの被巻付け部分に
対し良く接着し、保護効果をあげることができる。Particularly in the present invention, when butyl rubber is selected as a rubber / plastic which does not contain a halogen element in the molecule, ethylene propylene copolymer and butyl rubber have a chemical structure of C,
It is a compound containing H as a main component and has good compatibility, and in particular, it can be easily formed into a tape or sheet, and can be well adhered to the wound part of an electric wire or cable to improve the protective effect.
実施例 実施例１〜４及び比較例１〜２の組成物を作成し、その
伸び特性及び耐火性（絶縁特性；炭化層を形成及び脱落
程度）を調べた。Example The compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were prepared, and their elongation characteristics and fire resistance (insulation characteristics; formation of carbonized layer and degree of falling) were examined.
なお炭化層とその脱落の項の試験は、3mm（厚さ）×200
mm（横長）×200mm（縦長）のシートにブンゼンバーナ
ーの20度の角度の炎を20分間当てて行なつた。これらを
纏めたのが第１表である。The test for the carbonized layer and its drop-off is 3 mm (thickness) x 200
A Bunsen burner with a 20-degree angle of flame was applied to a 20 mm (horizontal) x 200 mm (vertical) sheet for 20 minutes. Table 1 summarizes these.
これによれば本発明の組成物が極めて優れていることが
判る。This shows that the composition of the present invention is extremely excellent.
次に実施例１の組成物を厚さ1mmのテープ状に加工し、
このテープを6.6KV1×150mm2のCVケーブルの最外層に1/
2ラップ２回重ね巻した試料を用意し、第１図に示した
バーナー試験を行なつた。その際の燃焼時間は20分であ
つた。 Next, the composition of Example 1 was processed into a tape having a thickness of 1 mm,
Apply this tape to the outermost layer of a 6.6KV 1 x 150mm 2 CV cable 1 /
A sample obtained by winding two laps twice was prepared and the burner test shown in FIG. 1 was performed. The burning time at that time was 20 minutes.
なお第１図中１は試料、2,2は２本のバーナー、３は内
炎40mm、外炎150mmとした炎で、中心の温度は1020±30
℃としてある。In Fig. 1, 1 is a sample, 2 and 2 are two burners, 3 is a flame with an internal flame of 40 mm and an external flame of 150 mm, and the center temperature is 1020 ± 30.
It is as ° C.
その結果は第２表に示すとおりである。The results are shown in Table 2.
なお比較例は前述の比較例２の組成物を用い、前記と同
様に試験したものである。In the comparative example, the composition of Comparative Example 2 described above was used and tested in the same manner as described above.
発明の効果 本発明によるものは火災に遭遇してもハロゲンガスの発
生がないため、人畜に無害で金属等を腐食せずかつ十分
炭化層を形成しその脱落がないため難燃性となり、電気
特性に優れた難燃性組成物を提供することができ、しか
も成形加工上必要とされる伸びも十分優れているので、
これを例えば電線・ケーブルの最外層に被覆（押出し又
はテープ又はシートの巻付けにより）すれば、難燃性で
防火性能に優れた電線・ケーブルを得ることができる。 Advantageous Effects of the Invention Since the present invention does not generate halogen gas even when encountering a fire, it is harmless to humans and animals, does not corrode metals and the like, forms a sufficient carbonized layer and does not fall off, and becomes flame-retardant. Since it is possible to provide a flame-retardant composition having excellent properties, and since the elongation required for molding is also sufficiently excellent,
By coating the outermost layer of an electric wire / cable (by extrusion or winding a tape or sheet) with this, for example, an electric wire / cable that is flame-retardant and excellent in fire protection can be obtained.
第１図は電線・ケーブルの燃焼試験の方法を示す概略説
明図である。 １…試料、２…バーナー、３…炎FIG. 1 is a schematic explanatory view showing a method of a combustion test for electric wires / cables. 1 ... Sample, 2 ... Burner, 3 ... Flame
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 (Ｃ０８Ｋ 13/02 3:00 3:32 5:521） ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location (C08K 13/02 3:00 3:32 5: 521)
Claims (1)
ロゲン元素を含まないゴム・プラスチックとの混合物10
0重量部と、（Ａ）クレーと、（Ｂ）タルク、アルミ
ナ、硼酸亜鉛、シリカ、水酸化アルミニウム、水酸化マ
グネシウム、三酸化アンチモン、炭酸カルシウムの群か
ら選ばれたものの一種以上とを、重量比でA/B＝１〜４
の割合で配合した無機充填剤200〜400重量部と、化合物
中にハロゲン元素を含まないリン酸エステル化合物、リ
ン酸塩フリットあるいは第３リン酸アルミニウムからな
る炭化促進剤５〜35重量部と加硫剤0.1〜10重量部とが
配合されていることを特徴とする難燃性組成物。1. A mixture 10 of an ethylene-propylene copolymer and a rubber / plastic containing no halogen element in the molecule.
0 parts by weight, (A) clay, and (B) one or more selected from the group consisting of talc, alumina, zinc borate, silica, aluminum hydroxide, magnesium hydroxide, antimony trioxide, and calcium carbonate. A / B = 1-4 in ratio
200 to 400 parts by weight of an inorganic filler compounded in a proportion of 5 to 35 parts by weight of a carbonization promoter composed of a phosphate ester compound containing no halogen element in the compound, a phosphate frit or a tertiary aluminum phosphate. A flame-retardant composition comprising 0.1 to 10 parts by weight of a sulfurizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61163597A JPH0745602B2 (en) | 1986-07-14 | 1986-07-14 | Flame retardant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61163597A JPH0745602B2 (en) | 1986-07-14 | 1986-07-14 | Flame retardant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6320348A JPS6320348A (en) | 1988-01-28 |
| JPH0745602B2 true JPH0745602B2 (en) | 1995-05-17 |
Family
ID=15776945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61163597A Expired - Lifetime JPH0745602B2 (en) | 1986-07-14 | 1986-07-14 | Flame retardant composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745602B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016080511A1 (en) * | 2014-11-21 | 2016-05-26 | 株式会社フジクラ | Flame-retardant resin composition, and cable and optical fiber cable using same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01223141A (en) * | 1988-03-01 | 1989-09-06 | Fujikura Rubber Ltd | Flame retardant rubber composition |
| FR2837614B1 (en) | 2002-03-22 | 2004-06-18 | Nexans | INSULATING COMPOSITION FOR ELECTRIC SECURITY CABLE |
| TWI322176B (en) * | 2002-10-17 | 2010-03-21 | Polymers Australia Pty Ltd | Fire resistant compositions |
| FR2859814A1 (en) * | 2003-09-12 | 2005-03-18 | Nexans | Electrically-insulating and heat-resistant composition, especially for use in security cables for power or telecommunications, contains organic polymer, phyllosilicate and refractory filler |
| EP1733002B1 (en) | 2004-03-31 | 2012-06-06 | Olex Australia Pty Limited | Ceramifying composition for fire protection |
| CN114479193A (en) * | 2021-12-30 | 2022-05-13 | 贵阳学院 | Aluminum phosphate-coated silicon dioxide flame retardant, preparation method thereof, flame-retardant epoxy resin composite material and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5422840B2 (en) * | 1973-03-08 | 1979-08-09 | ||
| JPS572349A (en) * | 1980-06-06 | 1982-01-07 | Mitsui Petrochem Ind Ltd | Rubber composition for vulcanization |
| JPS6212005A (en) * | 1985-07-10 | 1987-01-21 | 日立電線株式会社 | Flame resisting electric insulator compositioin |
| JPH0694522B2 (en) * | 1985-07-29 | 1994-11-24 | 株式会社フジクラ | Flame retardant composition |
| JPS62184042A (en) * | 1986-02-08 | 1987-08-12 | Mitsubishi Cable Ind Ltd | Flame-retardant resin composition |
| JP2534474B2 (en) * | 1986-06-12 | 1996-09-18 | 三菱電線工業株式会社 | Flame retardant composition |
-
1986
- 1986-07-14 JP JP61163597A patent/JPH0745602B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016080511A1 (en) * | 2014-11-21 | 2016-05-26 | 株式会社フジクラ | Flame-retardant resin composition, and cable and optical fiber cable using same |
| US10253262B2 (en) | 2014-11-21 | 2019-04-09 | Fujikura Ltd. | Flame retardant resin composition, and cable and optical fiber cable using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6320348A (en) | 1988-01-28 |
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