JP3246004B2 - Halogen-free flame retardant composition and tube - Google Patents
Halogen-free flame retardant composition and tubeInfo
- Publication number
- JP3246004B2 JP3246004B2 JP30316092A JP30316092A JP3246004B2 JP 3246004 B2 JP3246004 B2 JP 3246004B2 JP 30316092 A JP30316092 A JP 30316092A JP 30316092 A JP30316092 A JP 30316092A JP 3246004 B2 JP3246004 B2 JP 3246004B2
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- JP
- Japan
- Prior art keywords
- weight
- tube
- eva
- polyester
- halogen
- 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.)
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- Organic Insulating Materials (AREA)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、電線（ケーブル）等の
末端部の絶縁被覆或いは電子部品の保護などに用いられ
る、チューブ、特に熱収縮チューブの構成材の改良に関
するものである。特に、本発明は、ハロゲン系難燃剤等
を含まなくとも非常に優れた難燃性と共に機械的特性に
も優れているＥＶＡを主成分とする、ノンハロゲン難燃
性組成物、特に成形品、例えばチューブ、熱収縮チュー
ブの構成材の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tube, particularly a heat-shrinkable tube, which is used for insulating a terminal portion of an electric wire (cable) or protecting an electronic component. In particular, the present invention is a non-halogen flame-retardant composition, particularly a molded article, which contains EVA as a main component and has excellent mechanical properties as well as excellent flame retardancy without containing a halogen-based flame retardant or the like. The present invention relates to improvement of components of tubes and heat-shrinkable tubes.
【０００２】[0002]
【従来の技術】従来、ポリマーの難燃化は、ハロゲン
（塩素、臭素など）を分子中に含んだ化合物を難燃剤と
してベース樹脂に配合することにより容易にできる。し
かし、近年、該ハロゲン化合物の燃焼時に発生する有毒
なガスが問題となってきている。このために、ポリマー
の難燃化をノン（非）ハロゲン化で行う方法として、金
属水和物等をポリマーに配合する手法が採用されてい
る。これは、ポリエチレン、エチレン共重合体などのポ
リオレフィンに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が配合されたものである。2. Description of the Related Art Conventionally, flame retardancy of a polymer can be easily achieved by blending a compound containing halogen (chlorine, bromine, etc.) in a molecule as a flame retardant in a base resin. However, in recent years, toxic gas generated during the combustion of the halogen compound has become a problem. For this reason, as a method of performing flame retardation of a polymer by non- (non-) halogenation, a method of blending a metal hydrate or the like with the polymer has been adopted. This is obtained by blending a metal hydrate such as aluminum hydroxide or magnesium hydroxide with a polyolefin such as polyethylene or ethylene copolymer.
【０００３】[0003]
【発明が解決しようとする課題】ポリオレフィンの中で
もＥＶＡの限界酸素指数は大きい。これは燃焼時の脱酢
酸によるものである。しかし、ＥＶＡの限界酸素指数が
大きくても、ＵＬ９４垂直燃焼試験やチューブのＵＬ２
２４のＶＷ−１燃焼試験のように、下部から垂直方向に
燃焼させた場合に、樹脂の垂れ落ち及び殻作りに乏しく
燃え易い問題がある。また、ポリエステルなどに金属水
和物を配合した系の場合、機械的特性や難燃性などにお
いて充分でない。Among the polyolefins, EVA has a large limit oxygen index. This is due to the removal of acetic acid during combustion. However, even if the limiting oxygen index of EVA is large, UL94 vertical combustion test and UL2
As in the VW-1 combustion test of No. 24, when the resin is burned vertically from the lower part, there is a problem that resin dripping and shell formation are poor and easily burned. Also, if the system compounded with metal hydrates such as poly ester, not sufficient in such mechanical properties and flame retardancy.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記種々の
課題について検討した結果、ＥＶＡ、ポリエステル単独
では金属水和物を配合しても難燃性に劣るが、（Ａ）Ｅ
ＶＡと（Ｂ）式(1) の繰り返し単位を持つポリエステル
との配合物にした場合に、金属水和物を配合しても予期
せずして難燃性が向上することを見出し、本発明を完成
するに至った。The present inventors SUMMARY OF THE INVENTION As a result of investigation of the above various problems, EVA, be blended with the metal hydrate in the port Riesuteru alone inferior in flame retardancy, (A) E
It has been found that when a blend of VA and (B) a polyester having a repeating unit of the formula (1) is used, the flame retardancy is unexpectedly improved even when a metal hydrate is blended. Was completed.
【０００７】すなわち、本発明は： （Ａ）酢酸ビニル含有量２０重量％以上を有するエ
チレン−酢酸ビニル系共重合体（以下ＥＶＡと略称す
る）と、（Ｂ）下記式(1) で示される主鎖にエステル結
合を有する２種の繰り返し単位からなるビカット軟化点
（ＡＳＴＭ−１５２５）１５０℃以下のポリエステルか
ら少なくとも構成され、かつ（Ａ）／（Ｂ）の重量比が
１〜１０であり、金属水和物がベース樹脂１００重量部
当たり１５０〜２５０重量部含まれるノンハロゲン難燃
性組成物を提供する。また、That is, the present invention provides: (A) D having a vinyl acetate content of 20% by weight or more
Tylene-vinyl acetate copolymer (hereinafter abbreviated as EVA)
)(B)The following formula(1)Ester bond to the main chain represented by
From two types of repeating unitsToVicat softening point
(ASTM-1525) Polyester below 150 ° C
At least composed of(A) / (B)Weight ratio of
1 to 10 and the metal hydrate is 100 parts by weight of the base resin
Halogen-free flame retardant contained at 150 to 250 parts by weight
An ionic composition is provided. Also,
【化２】 （ただし、ｎは６〜４０である） 前記 に記載の組
成物よりなるチューブを提供する。また、 前記 記
載のチューブが架橋されてなる熱収縮チューブである、
熱収縮チューブを提供する。Embedded image(However, n is 6 to 40) Said The set described in
A tube made of the composition is provided. Also, Said Record
Is a heat-shrinkable tube in which the above-mentioned tube is cross-linked,
A heat shrink tube is provided.
【０００８】以下、本発明を詳細に説明する。本発明に
おいて、（Ａ）のＥＶＡとは、酢酸ビニル含有量２０重
量％以上を有するエチレン−酢酸ビニル系共重合体であ
る。すなわち、本発明に用いるＥＶＡは、酢酸ビニル含
有量２０重量％以上、好ましくは２０〜７０重量％、よ
り好ましくは２５〜４０重量％を有し、少なくともエチ
レンモノマーと酢酸ビニルモノマーとを基本構成単位と
する共重合体である。従って、該ＥＶＡには、エチレン
モノマーと酢酸ビニルモノマー以外に、ＥＶＡの性格を
損なわない限り、他のエチレン性不飽和モノマー、例え
ばプロピレン、ブテン、ペンテン、ヘキセン、（メタ）
クリル酸、（メタ）クリル酸メチル、（メタ）クリル酸
エチルなど少量を共重合させたものも含むものである。
該ＥＶＡ中の酢酸ビニル含有量が２０重量％未満と少な
い場合には、ポリエチレンと似た難燃性を示すため難燃
レベルが低い。燃焼時に脱酢酸の効果を高めるために
は、ＥＶＡ中の酢酸ビニル含有量２０重量％以上である
ことが望ましい。Hereinafter, the present invention will be described in detail. In the present invention, the EVA of (A) is an ethylene-vinyl acetate copolymer having a vinyl acetate content of 20% by weight or more. That is, the EVA used in the present invention has a vinyl acetate content of 20% by weight or more, preferably 20 to 70% by weight, more preferably 25 to 40% by weight, and comprises at least an ethylene monomer and a vinyl acetate monomer as a basic structural unit. Is a copolymer represented by the formula: Accordingly, the EVA includes, besides the ethylene monomer and the vinyl acetate monomer, other ethylenically unsaturated monomers such as propylene, butene, pentene, hexene, (meta), as long as the properties of EVA are not impaired.
It also includes those obtained by copolymerizing a small amount such as crylic acid, methyl (meth) acrylate, and ethyl (meth) acrylate.
When the vinyl acetate content in the EVA is as low as less than 20% by weight, the flame retardancy is similar to that of polyethylene, so that the flame retardancy level is low. In order to enhance the effect of deacetic acid during combustion, the content of vinyl acetate in EVA is desirably 20% by weight or more.
【０００９】本発明において、上記ＥＶＡに配合する樹
脂としては、ＥＶＡとの相溶性、難燃性の観点からエス
テル結合を有する樹脂、即ち（Ｂ）のポリエステル（又
はＥＡ：参考）を用いることが必要である。In the present invention, the resin to be mixed with the EVA is a resin having an ester bond from the viewpoint of compatibility with EVA and flame retardancy, that is, a polyester ( B) (or
It is necessary to use EA: Reference) .
【００１０】本発明における（Ｂ）のポリエステルと
は、下記式(1) で示される主鎖にエステル結合を有する
２種の繰り返し単位からなり、ビカット軟化点（ＡＳＴ
Ｍ−１５２５）１５０℃以下のポリエステルである。The polyester (B ) in the present invention comprises two kinds of repeating units having an ester bond in the main chain represented by the following formula (1) , and has a Vicat softening point (AST).
M-1525) It is a polyester of 150 ° C or lower.
【化３】 （ただし、ｎは６〜４０である）Embedded image (However, n is 6 to 40)
【００１１】本発明に用いる（Ｂ）のポリエステルは、
下記のＥＡの場合と同様の構成で同様の効果が有ること
が分かった。従って、組成物中のＥＶＡと（Ｂ）のポリ
エステルとの配合割合は、上記のＥＡの場合と同様に、
難燃性、燃焼時の垂れ落ちを考慮すると、ＥＶＡ／
（Ｂ）のポリエステルの重量比は１〜１０、好ましくは
１〜６が良い。特に、（Ｂ）のポリエステルが、上記
(1) で示される構造を持ち、且つ（Ａ）のＥＶＡとの相
溶性、加工性の観点からＥＶＡ中の酢酸ビニル含有量が
２０重量％以上であり、ポリエステルのビカット軟化点
（ＡＳＴＭ Ｄ−１５２５）が１５０℃以下、好ましく
は６０〜１２０℃であることが望ましい。The polyester (B) used in the present invention comprises:
It was found that the same effect as in the case of EA described below was obtained. Therefore, the mixing ratio of EVA and the polyester of (B) in the composition is the same as in the case of EA described above.
Considering flame retardancy and dripping during combustion, EVA /
The weight ratio of the polyester of (B) is 1 to 10, preferably 1 to 6. In particular, the polyester of (B) is
It has the structure shown by (1), and the vinyl acetate content in EVA is 20% by weight or more from the viewpoint of compatibility with EVA and workability of (A), and the Vicat softening point (ASTM D- 1525) is 150 ° C. or less, preferably 60 to 120 ° C.
【００１２】本発明に用いる（Ｂ）のポリエステルは、
特に、（Ｂ）のポリエステルが上記(1) で示される構造
を持ち、且つ（Ａ）のＥＶＡとの相溶性、加工性の観点
からＥＶＡ中の酢酸ビニル含有量が２０重量％以上であ
り、ポリエステルのビカット軟化点（ＡＳＴＭ Ｄ−１
５２５）が１５０℃以下、好ましくは６０〜１２０℃で
あることが望ましい。（Ｂ） のポリエステルは、一般的には、上記(1) で示さ
れる構造を持ち、その中主鎖にエステル結合を有する繰
り返し単位ａと主鎖にエステル結合とエーテル結合とを
有する繰り返し単位ｂからなる（ａｂ）n 型のマルチブ
ロック共重合体の構造を呈する。The polyester (B) used in the present invention is:
In particular, the polyester of (B) has the structure shown in the above (1) , and the vinyl acetate content in EVA is 20% by weight or more from the viewpoint of compatibility with EVA of (A) and processability; Vicat softening point of polyester (ASTM D-1
525) is preferably 150 ° C. or lower, more preferably 60 to 120 ° C. The polyester (B) generally has a structure represented by the above (1) , in which a repeating unit a having an ester bond in the main chain and a repeating unit b having an ester bond and an ether bond in the main chain. (Ab) having the structure of an n- type multi-block copolymer.
【００１３】該（Ｂ）のポリエステルを製造するには、
一般に、上記繰り返し単位ａと繰り返し単位ｂとを所望
の割合でマルチブロック共重合化できればよく、ポリエ
ステルの製造に用いられる公知の原料モノマーを、常法
に従って（エステル交換法、エステル化法、重縮合法な
ど）重縮合触媒の存在下で処理することにより得ること
ができる。To produce the polyester (B) ,
Generally, it is sufficient that the repeating unit a and the repeating unit b can be multiblock-copolymerized at a desired ratio, and a known raw material monomer used for the production of a polyester can be prepared by a conventional method (ester exchange method, esterification method, It can be obtained by treating in the presence of a polycondensation catalyst.
【００１４】なお、参考としての上記ＥＡとは、含有量
２０重量％以上の式(2) で示されるエステル結合を持つ
モノマーとエチレンモノマーとを含む共重合体である。 The above EA as a reference is a copolymer containing a monomer having an ester bond represented by the formula (2) having a content of 20% by weight or more and an ethylene monomer.
【化４】 （ただし、Ｒ1 はＨ又はＣＨ3 であり、Ｒ2 はＣＨ3 又
はＣ2 Ｈ5 である。）ＥＡを構成する上記(2) で示され
るエステル結合を持つモノマーとしては、例えばアクリ
ル酸、メタクリル酸、アクリル酸メチル、メタクリル酸
メチルなどを挙げることができる。Embedded image (However, R 1 is H or CH 3 , and R 2 is CH 3 or C 2 H 5. ) Examples of the monomer having an ester bond represented by the above (2) constituting EA include acrylic acid, Examples thereof include methacrylic acid, methyl acrylate, and methyl methacrylate.
【００１５】該ＥＡ中の上記(1) で示されるエステル結
合を持つモノマーの含有量が２０重量％未満と少ない場
合には、ＥＶＡとの相溶性を欠き、該組成物からの成形
品の機械的特性が劣るばかりか、難燃性も不十分とな
る。エステル結合を持つモノマーの含有量２０重量％以
上が望ましい。また、ＥＡ単独に金属水和物を配合した
場合に、該組成物からの成形品の抗張力が低下し、機械
的強度が不足する。組成物中のＥＶＡとＥＡとの配合割
合は、難燃性、燃焼時の垂れ落ちを考慮すると、ＥＶＡ
／ＥＡの重量比が１〜１０、好ましくは１〜６が良い。When the content of the monomer having an ester bond represented by the above (1) in the EA is as small as less than 20% by weight, the EA lacks compatibility with EVA, and the mechanical properties of a molded article from the composition are reduced. Not only are the mechanical properties inferior, but also the flame retardancy is insufficient. The content of the monomer having an ester bond is desirably 20% by weight or more. Further, when a metal hydrate is blended with EA alone, the tensile strength of a molded article made from the composition is reduced, and the mechanical strength is insufficient. The mixing ratio of EVA and EA in the composition is determined in consideration of flame retardancy and dripping during combustion.
The weight ratio of / EA is 1 to 10, preferably 1 to 6.
【００１６】本発明に用いる金属水和物としては、例え
ばアルミニウム水和物、マグネシウム水和物など２価金
属の含水金属化合物（含む金属水酸化物）が利用でき
る。該金属水和物の配合量としては、ベース樹脂１００
重量部当たり１５０〜２５０重量部、好ましくは１７０
〜２３０重量部が望ましい。該金属水和物の配合量が１
５０重量部未満では、ＵＬ９４のＶ−０垂直燃焼試験や
ＵＬ２２４のＶＷ−１燃焼試験において、難燃性が充分
に得られないし、また、２５０重量部を越えると該組成
物からの成形品の機械的強度、伸びが低下する。As the metal hydrate used in the present invention, a hydrated metal compound (including metal hydroxide) of a divalent metal such as aluminum hydrate and magnesium hydrate can be used. The blending amount of the metal hydrate is 100 base resin.
150 to 250 parts by weight, preferably 170 parts by weight
２３０230 parts by weight is desirable. The compounding amount of the metal hydrate is 1
If the amount is less than 50 parts by weight, sufficient flame retardancy cannot be obtained in a UL-0 V-0 vertical combustion test or UL224 VW-1 combustion test. Mechanical strength and elongation decrease.
【００１７】本発明のノンハロゲン難燃性組成物は、ベ
ース樹脂として上記（Ａ）のＥＶＡと（Ｂ）のポリエス
テル（又はＥＡ：参考）とを本質的構成とするが、この
組成物の性能を損なわない限り、他の熱可塑性樹脂を少
量配合しても構わない。本発明のノンハロゲン難燃性組
成物には、上記金属水和物の他に任意の添加剤、例えば
タルク、シリカ、炭酸カルシウム、炭酸マグネシウム、
ほう酸塩などの充填剤；三酸化アンチモンなどの難燃助
剤；リン系化合物、窒素含有化合物、シリコン含有化合
物などや；多官能性モノマーや；アミン系やヒンダード
フェノール系安定剤などの酸化防止剤；ベンゾフェノン
系化合物、ベンゾトリアゾール系化合物やヒンダードア
ミン系化合物などの光安定剤；加工助剤、顔料などを配
合することができる。The non-halogen flame-retardant composition of the present invention essentially comprises the above-mentioned (A) EVA and (B) polyester (or EA: reference ) as a base resin. A small amount of other thermoplastic resin may be blended as long as it is not damaged. The non-halogen flame-retardant composition of the present invention includes, in addition to the metal hydrate, any additive such as talc, silica, calcium carbonate, magnesium carbonate,
Fillers such as borate; flame retardant aids such as antimony trioxide; phosphorus compounds, nitrogen-containing compounds, silicon-containing compounds, etc .; polyfunctional monomers; antioxidants, such as amine-based and hindered phenol-based stabilizers Agents; light stabilizers such as benzophenone-based compounds, benzotriazole-based compounds and hindered amine-based compounds; processing aids, pigments, and the like.
【００１８】これらの添加剤ならびに本発明に係る金属
水和物とは、ベース樹脂に混練等の手段により配合させ
てペレットなどの成形粉に加工して後、各種成形手段に
よりノンハロゲン難燃性成形品にする。具体的には、本
発明のノンハロゲン難燃性組成物は、公知成形手段、例
えば押出被覆、押出成形、射出成形、プレス成形などの
手段により各種成形品、例えばチューブ、熱収縮チュー
ブなどにする。These additives and the metal hydrate according to the present invention are mixed with the base resin by means of kneading or the like, processed into molding powder such as pellets, and then subjected to non-halogen flame-retardant molding by various molding means. Product. Specifically, the non-halogen flame-retardant composition of the present invention is formed into various molded articles, for example, tubes, heat-shrinkable tubes, and the like by known molding means, for example, extrusion coating, extrusion molding, injection molding, press molding and the like.
【００１９】本発明において、得られたノンハロゲン難
燃性成形品は、耐熱性、機械的強度などを向上させるた
めに、或いは熱収縮チューブとするために、その後公知
の電離性放射線（電子線など）の照射により架橋して架
橋成形品にする。この場合に、架橋促進剤としてトリメ
チロールプロパントリメリテート、トリアリルシアヌレ
ート、トリアリルイソシアヌレート等の多官能性モノマ
ーを好適には予かじめ添加するとよい。また、上記架橋
には、電離性放射線照射の他に、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
ンゼンなどの有機過酸化物の配合後の熱架橋も可能であ
る。In the present invention, the obtained non-halogen flame-retardant molded article is then treated with a known ionizing radiation (such as an electron beam) in order to improve heat resistance, mechanical strength, etc., or to form a heat-shrinkable tube. Cross-linking is performed by irradiation in step (1) to form a cross-linked molded article. In this case, a polyfunctional monomer such as trimethylolpropane trimellitate, triallyl cyanurate or triallyl isocyanurate is preferably added in advance as a crosslinking accelerator. In addition to the irradiation with ionizing radiation, thermal crosslinking after the addition of an organic peroxide such as dicumyl peroxide or 3-bis (t-butylperoxyisopropyl) benzene can be used for the crosslinking.
【００２０】また、本発明の成形品の場合、特に以下の
ような成形手段などにより各種成形物にすることができ
る。即ち、本発明のノンハロゲン難燃性組成物を押出成
形によりチューブとすることができる。また、該チュー
ブを例えば電離性放射線を照射することにより架橋後、
加熱条件下で成形品の内部に圧縮空気を送り込む等の方
法により拡径して冷却固定する方法で、熱収縮チューブ
とすることもできる。In the case of the molded article of the present invention, various molded articles can be formed by the following molding means. That is, the non-halogen flame-retardant composition of the present invention can be formed into a tube by extrusion molding. Further, after crosslinking the tube by irradiating, for example, ionizing radiation,
A heat-shrinkable tube can also be formed by a method of expanding the diameter by, for example, sending compressed air into the inside of the molded product under heating conditions and cooling and fixing.
【００２１】ここで、熱収縮チューブとは、架橋結合に
より予め形状を記憶させたチューブ形状物を、該チュー
ブ形状物の融点以上に加熱し、チューブ形状物を拡大し
急冷することにより得られるものである。このようにし
て作製した熱収縮チューブを融点以上に加熱することに
より、予め記憶させたチューブ形状物に復元するもので
ある。また、銅などの導体からなる単芯或いは複数本の
絶縁電線の多芯撚り絶縁電線の外周に、本発明のノンハ
ロゲン難燃性組成物を押出被覆などの成形手段により被
覆し、更に電離性放射線を照射し架橋して、絶縁ケーブ
ルとすることもできる。Here, the heat-shrinkable tube is obtained by heating a tube-shaped article, whose shape has been previously memorized by cross-linking, to a temperature equal to or higher than the melting point of the tube-shaped article, and expanding and rapidly cooling the tube-shaped article. It is. By heating the heat-shrinkable tube thus manufactured to a temperature equal to or higher than the melting point, the heat-shrinkable tube is restored to a tube shape stored in advance. Further, the non-halogen flame-retardant composition of the present invention is coated on the outer periphery of a single-core or multi-core stranded insulated wire made of a conductor such as copper by a molding means such as extrusion coating, and further ionized radiation is applied. To form an insulated cable.
【００２２】[0022]
【実施例】本発明を下記の実施例により説明するが、こ
れらは本発明の範囲を制限するものではない。 （実施例１、比較例１〜４及び参考実施例１、２、参考
比較例１〜７） 実施例、比較例及び参考実施例、参考比較例において、
シート作製後、１０Ｍｒｄの照射量で電子線照射にて架
橋した。これらのシートについて、抗張力、伸び、難燃
性を評価して下記表１に示した。The present invention is illustrated by the following examples, which do not limit the scope of the invention. (Example 1, Comparative Examples 1-4 and Reference Examples 1, 2, Reference
Comparative Examples 1 to 7 ) In Examples, Comparative Examples, Reference Examples, and Reference Comparative Examples ,
After the preparation of the sheet, it was cross-linked by electron beam irradiation at an irradiation amount of 10 Mrd. These sheets were evaluated for tensile strength, elongation and flame retardancy, and are shown in Table 1 below.
【００２３】[0023]
【表１】 （注）実は実施例の略称である。[Table 1] (Note) Actually, it is an abbreviation of the embodiment .
【００２４】 ＥＶＡ１：酢酸ビニル含有量２５重量％、ＭＩ＝１．５ ＥＶＡ２：酢酸ビニル含有量１５重量％（本発明の範囲外）、ＭＩ＝３ ＥＡ１：Ｒ1 ＝Ｈ、Ｒ2 ＝Ｃ2 Ｈ5 のモノマー含有量２５重量％、ＭＩ＝４ ＥＡ２：Ｒ1 ＝Ｈ、Ｒ2 ＝ＣＨ3 のモノマー含有量５０重量％、ＭＩ＝６．７ ポリエステル１：ＭＩ＝１４ｇ／１０分、ビカット軟化点６８℃ 但し、ＭＩは１９０℃、２．１６ｋｇｆ下でＡＳＴＭ
Ｄ−１２３８により測定した。EVA1: 25% by weight of vinyl acetate, MI = 1.5 EVA2: 15% by weight of vinyl acetate ( outside the scope of the present invention ), MI = 3 EA1: R 1 = H, R 2 = C 2 monomer content 25% by weight of H 5, MI = 4 EA2: R 1 = H, R 2 = CH monomer content 50% by weight of 3, MI = 6.7 polyester 1: MI = 14g / 10 min, Vicat softening 68 ° C where MI is ASTM at 190 ° C under 2.16 kgf
It was measured according to D-1238.
【００２５】上記表１の結果から、ＥＶＡ、ポリエステ
ル１（又はＥＡ１、２：参考）単独では、抗張力、伸
び、難燃性の何れかが少なくとも劣るが、ＥＶＡとポリ
エステル１（又はＥＡ１、２：参考）とを配合すること
により、これらの物性を満たすことが予期せず認められ
た。更に、下記実施例２、比較例５、６では、チューブ
を押出機で作製し、相溶性、難燃性などを調べた。From the results in Table 1 above , EVA and polyester
EA1 (or EA1, 2: ref. ) Alone is at least inferior in tensile strength, elongation, or flame retardancy, but EVA and poly
It was unexpectedly recognized that these properties were satisfied by blending with Ester 1 (or EA1, 2: Reference ). Further, in Example 2 and Comparative Examples 5 and 6 described below , tubes were manufactured with an extruder, and compatibility, flame retardancy, and the like were examined.
【００２６】（実施例２） ＥＶＡ１を１８５重量部に上記ポリエステル１を１５重
量部、水酸化アルミニウムを１６０重量部配合し、２軸
押出機で混練り後、内径３ｍｍ、外径４．５ｍｍのチュ
ーブを押出機で押出した。外観、伸びの良好なチューブ
が得られた。このチューブを電子線照射（１０ＭＲＤ）
により架橋させた後、１５０℃下で内圧をかけ、急冷し
て熱収縮チューブを得た。１３０℃で熱収縮させた後、
ＵＬ２２４ ＶＷ−１燃焼試験を実施した。試験数５点
全てが合格した。Example 2 EVA1 was mixed with 185 parts by weight of EVA1, 15 parts by weight of the polyester 1 and 160 parts by weight of aluminum hydroxide, and kneaded with a twin-screw extruder to form an inner diameter of 3 mm and an outer diameter of 4.5 mm. The tube was extruded with an extruder. A tube with good appearance and elongation was obtained. This tube is irradiated with electron beam (10 MRD)
After that, the internal pressure was applied at 150 ° C., followed by rapid cooling to obtain a heat-shrinkable tube. After heat shrinking at 130 ° C,
A UL224 VW-1 combustion test was performed. All five tests passed.
【００２７】（比較例５） ＥＶＡ１を８０重量部にビカット軟化点１７０℃（本発
明の範囲外）、ＭＩ＝９のポリエステルを２０重量部、
水酸化アルミニウムを１６０重量部配合し、２軸押出機
で混練り後、内径３ｍｍ、外径４ｍｍのチューブを押出
機で押出した。チューブの外観は凹凸が激しく、かつ伸
びも少なく相溶性に劣っていた。 （比較例６） ＥＶＡ２（ＶＡ含量が本発明の範囲外）を８０重量部に
ポリエステル１を２０重量部、水酸化アルミニウムを１
６０重量部配合し、２軸押出機で混練り後、内径３ｍ
ｍ、外径４ｍｍのチューブを押出機で押出した。ＥＶＡ
２との相溶性が悪くチューブが得られなかった。[0027] (Comparative Example 5) EVA1 Vicat softening point 170 ° C. to 80 parts by weight (the onset
Akira outside the range), 20 parts by weight of polyester of MI = 9,
After 160 parts by weight of aluminum hydroxide was mixed and kneaded with a twin-screw extruder, a tube having an inner diameter of 3 mm and an outer diameter of 4 mm was extruded with an extruder. The appearance of the tube was severely uneven, had little elongation, and was poor in compatibility. (Comparative Example 6 ) 80 parts by weight of EVA2 ( VA content is out of the range of the present invention ), 20 parts by weight of polyester 1, and 1 part by weight of aluminum hydroxide
After mixing 60 parts by weight and kneading with a twin screw extruder, inner diameter 3 m
m, a tube having an outer diameter of 4 mm was extruded with an extruder. EVA
Tube 2 was not obtained due to poor compatibility with 2.
【００２８】[0028]
【発明の効果】本発明においては、特定のポリエステル
を配合したので、ＥＶＡに金属水和物を配合したノンハ
ロゲン難燃性組成物の機械的強度を低下させずに、垂直
燃焼試験における難燃性を高めたノンハロゲン難燃性組
成物を提供すると共に、燃焼時に有毒のハロゲンガスの
発生がなく、ノンハロゲンが要求されるケーブルの絶縁
保護用チューブなどの利用に適している。According to the present invention, since a specific polyester is blended, the flame-retardant composition in a vertical burning test can be obtained without lowering the mechanical strength of a non-halogen flame-retardant composition comprising EVA and a metal hydrate. The present invention provides a non-halogen flame-retardant composition having an improved non-halogen content and is suitable for use in insulation protection tubes and the like of cables that require no non-halogen without generating toxic halogen gas during combustion.
Claims (3)
を有するエチレン−酢酸ビニル系共重合体（以下ＥＶＡ
と略称する）と、（Ｂ）下記式(1) で示される主鎖にエ
ステル結合を有する２種の繰り返し単位からなるビカッ
ト軟化点（ＡＳＴＭ−１５２５）１５０℃以下のポリエ
ステルから少なくとも構成され、且つ（Ａ）／（Ｂ）の
重量比が１〜１０であり、金属水和物がベース樹脂１０
０重量部当たり１５０〜２５０重量部含まれることを特
徴とするノンハロゲン難燃性組成物。 【化１】 （ただし、ｎは６〜４０である）1. An ethylene-vinyl acetate copolymer (A) having a vinyl acetate content of 20% by weight or more (hereinafter referred to as EVA).
Abbreviated as), (B) the following formula (1) ing from 2 kinds of repeating units having an ester bond in its main chain represented by Bika'<br/> preparative softening point (ASTM-1525) 0.99 ° C. or less of the polyester and And the weight ratio of (A) / (B) is 1 to 10, and the metal hydrate is a base resin 10
A non-halogen flame-retardant composition characterized by being contained in an amount of 150 to 250 parts by weight per 0 parts by weight. Embedded image (However, n is 6 to 40)
特徴とするチューブ。2. A tube comprising the composition according to claim 1 .
る熱収縮チューブであることを特徴とする熱収縮チュー
ブ。3. A heat-shrinkable tube which is a heat-shrinkable tube obtained by crosslinking the tube according to claim 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30316092A JP3246004B2 (en) | 1992-10-16 | 1992-10-16 | Halogen-free flame retardant composition and tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30316092A JP3246004B2 (en) | 1992-10-16 | 1992-10-16 | Halogen-free flame retardant composition and tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06128428A JPH06128428A (en) | 1994-05-10 |
| JP3246004B2 true JP3246004B2 (en) | 2002-01-15 |
Family
ID=17917607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30316092A Expired - Fee Related JP3246004B2 (en) | 1992-10-16 | 1992-10-16 | Halogen-free flame retardant composition and tube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3246004B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4700779B2 (en) * | 2000-02-02 | 2011-06-15 | 三井・デュポンポリケミカル株式会社 | Flame retardant resin composition |
| US6667358B1 (en) * | 1999-05-17 | 2003-12-23 | Dupont-Mitsui Polychemicals Co. | Flame retardant resin composition |
| JP4749524B2 (en) * | 1999-10-15 | 2011-08-17 | 三井・デュポンポリケミカル株式会社 | Flame retardant resin composition |
| JP4584690B2 (en) * | 2004-11-29 | 2010-11-24 | リケンテクノス株式会社 | Flame retardant resin composition |
| JP2007262418A (en) * | 2007-05-21 | 2007-10-11 | Furukawa Electric Co Ltd:The | Resin composition for transmission line coating, and transmission line |
| JP2007321155A (en) * | 2007-07-23 | 2007-12-13 | Riken Technos Corp | Flame-retardant resin composition and insulated wire |
| JP2009120680A (en) * | 2007-11-13 | 2009-06-04 | Shin Etsu Chem Co Ltd | Flame-retardant resin composition |
| KR102432742B1 (en) * | 2021-06-08 | 2022-08-18 | 주식회사 세하테크 | Composition for flame-retardant tube with excellent tensile strength, manufacturing method thereof, and flame-retardant tube |
-
1992
- 1992-10-16 JP JP30316092A patent/JP3246004B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06128428A (en) | 1994-05-10 |
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