JP2001342304A - Non-halogen flame-retardant resin composition - Google Patents

Non-halogen flame-retardant resin composition

Info

Publication number
JP2001342304A
JP2001342304A JP2000163503A JP2000163503A JP2001342304A JP 2001342304 A JP2001342304 A JP 2001342304A JP 2000163503 A JP2000163503 A JP 2000163503A JP 2000163503 A JP2000163503 A JP 2000163503A JP 2001342304 A JP2001342304 A JP 2001342304A
Authority
JP
Japan
Prior art keywords
resin composition
flame
specific gravity
parts
retardant
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.)
Withdrawn
Application number
JP2000163503A
Other languages
Japanese (ja)
Inventor
Toshiaki Mabuchi
利明 馬淵
Atsushi Suzuki
淳 鈴木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujikura Ltd
Original Assignee
Fujikura Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujikura Ltd filed Critical Fujikura Ltd
Priority to JP2000163503A priority Critical patent/JP2001342304A/en
Publication of JP2001342304A publication Critical patent/JP2001342304A/en
Withdrawn legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which has an flame-retardancy equal to PVC resin composition, is excellent in mechanical characteristics, generates no toxic gas when incineration, and can be separated from a PVC resin composition by specific gravity. SOLUTION: The non-halogen flame-retardant resin composition comprises 100 pts. of a polyolefinic polymer and 20-50 pts. of a metallic hydroxide surface covered with a silicic acid compound by the sol-gel process, has a specific gravity of 1.14 or less and an oxygen index of 24-34, and passes a 60-degree inclined flame-retardant test of JIS C 3005.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】この発明は、ポリ塩化ビニル
(PVC)組成物と同等の難燃性を有し、機械的特性が
良好で、比重がPVC組成物よりも小さくて比重分別が
可能であり、ハロゲンを含まず、焼却処分可能なノンハ
ロゲン難燃性樹脂組成物に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has flame retardancy equivalent to that of a polyvinyl chloride (PVC) composition, has good mechanical properties, has a specific gravity smaller than that of a PVC composition, and is capable of fractionating specific gravity. The present invention relates to a halogen-free flame-retardant resin composition containing no halogen and capable of being incinerated.

【0002】[0002]

【従来の技術】PVC組成物は、電気絶縁性が良く、自
消性であることから、電線被覆材,チューブ,テープ,
包装材,建材等に広く使用されている。ところで、PV
C組成物はハロゲンである塩素を含んでいるため、燃焼
時に塩化水素などの腐食性のガスやダイオキシン等の有
害ガスが発生する。このため、各種のPVC製品が廃棄
物となった場合に、これを焼却処分にできない問題があ
った。そこで現状では埋立処分がなされているがPVC
組成物には鉛系の安定剤が使用されていることから、こ
れが土壌等に溶出する問題もあり、産業廃棄物として処
理が困難になってきている。
2. Description of the Related Art PVC compositions have good electrical insulation properties and are self-extinguishing, so that they can be used for wire coating materials, tubes, tapes, and the like.
Widely used for packaging and building materials. By the way, PV
Since the C composition contains chlorine, which is a halogen, corrosive gases such as hydrogen chloride and harmful gases such as dioxin are generated during combustion. For this reason, when various PVC products became waste, there was a problem that they could not be incinerated. Therefore, at present the landfill is done, but PVC
Since a lead-based stabilizer is used in the composition, there is also a problem that it is eluted into soil or the like, and it has become difficult to treat it as industrial waste.

【0003】これに対して、PVC組成物に代わる樹脂
組成物として、ハロゲンを含まないポリエチレン,ポリ
プロピレンなどを用いれば、燃焼時に有害なガスが発生
しないので焼却処分が可能であるが、これらのハロゲン
を含まない樹脂組成物は、PVCに比べて難燃性が劣る
という欠点がある。そこで、ポリエチレン,ポリプロピ
レンなどからなる樹脂組成物に難燃性を付与するため
に、ノンハロゲン系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酸化物を配合すること
が行われている。
On the other hand, if a halogen-free polyethylene, polypropylene or the like is used as a resin composition instead of the PVC composition, no harmful gas is generated at the time of combustion, so that incineration is possible. The resin composition containing no has a disadvantage that the flame retardancy is inferior to PVC. Therefore, in order to impart flame retardancy to a resin composition made of polyethylene, polypropylene, or the like, aluminum hydroxide, a halogen-free flame retardant,
Mixing of a metal hydroxide such as magnesium hydroxide has been performed.

【0004】しかしながら、PVCと同等程度の難燃性
を得るには、金属水酸化物を多量に例えば、ベースポリ
マー100部(重量部、以下同様)に対して120部程
度配合せねばならず、これでは樹脂組成物の比重がPV
Cと同程度となってしまい、水を用いたプラスチックの
比重分別によって、PVC製品との分別回収ができない
問題がある。また、樹脂組成物の機械的特性も低下する
不都合がある。
However, in order to obtain flame retardancy equivalent to that of PVC, a large amount of metal hydroxide, for example, about 120 parts with respect to 100 parts (parts by weight, hereinafter the same) of the base polymer must be blended. In this case, the specific gravity of the resin composition is PV
C, and there is a problem that the specific gravity separation of plastic using water cannot be separated and recovered from PVC products. In addition, there is a disadvantage that the mechanical properties of the resin composition are reduced.

【0005】[0005]

【発明が解決しようとする課題】よって、本発明におけ
る課題は、PVC樹脂組成物と同等の難燃性を有し、焼
却時に有害ガスを発生せず、PVC樹脂組成物との比重
分別が可能であり、機械的特性も良好な、樹脂組成物を
得ることにある。
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to have the same flame retardancy as a PVC resin composition, generate no harmful gas upon incineration, and separate the specific gravity from the PVC resin composition. Another object of the present invention is to obtain a resin composition having good mechanical properties.

【0006】[0006]

【課題を解決するための手段】かかる課題は、ポリオレ
フィン系ポリマー100部に、ゾルゲル法によってケイ
酸化合物を表面被覆した20〜50部、難燃助剤2〜1
0部を配合し、その組成物の比重が1.14以下、酸素
指数が24〜34で、JISC3005に定められる6
0度傾斜燃料試験に合格するノンハロゲン難燃性樹脂物
によって解決される。
The object of the present invention is to provide a polyolefin polymer having 100 parts by weight coated with a silicate compound by a sol-gel method on a surface of 20 to 50 parts, a flame retardant auxiliary of 2 to 1 part.
0 parts, the specific gravity of the composition is 1.14 or less, the oxygen index is 24-34, and the composition is defined by JISC3005.
The problem is solved by a non-halogen flame-retardant resin material that passes the 0-degree tilt fuel test.

【0007】[0007]

【発明の実施の形態】以下、本発明を詳しく説明する。
本発明のノンハロゲン難燃性樹脂組成物のベースポリマ
ーとなるポリオレフィン系ポリマーとしては、ポリエチ
レン,ポリプロピレン,エチレン−プロピレン共重合
体,エチレン−酢酸ビニル共重合体,エチレン−エチル
アクリレート共重合体,エチレン−ブテン1共重合体な
どの1種もしくは2種以上のブレンドポリマーが用いら
れる。これらのなかでも、エチレン−酢酸ビニル共重合
体,エチレン−エチルアクリレート共重合体が好まし
い。
DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Examples of the polyolefin-based polymer serving as the base polymer of the non-halogen flame-retardant resin composition of the present invention include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene- One or two or more blend polymers such as butene 1 copolymer are used. Of these, ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer are preferred.

【0008】本発明で用いられるノンハロゲン系難燃剤
としては、ゾルゲル法によってケイ酸化合物を表面被覆
した金属水酸化物が用いられる。このものは、水酸化マ
グネシウム,水酸化アルミニウム,水酸化カルシウムな
どの金属水酸化物の粉末の表面を酸化ケイ素,ケイ酸ナ
トリウム,ケイ酸などのケイ酸化合物の薄膜でコーティ
ングしたもので、金属水酸化物表面が厚み0.1〜5μ
mのケイ酸化合物で被覆されたものである。この表面被
覆処理された金属水酸化物は、樹脂組成物に対する難燃
性向上効果が、通常の金属水酸化物に比べて高いもので
あり、少量の配合で高い難燃性を得ることができる。こ
の表面被覆処理された金属水酸化物の配合量は、ポリオ
レフィン系ポリマー100部当り20〜50部、好まし
くは25〜40部とされ、20部未満では難燃性が不足
し、50部を越えると機械的特性が低下する。
[0008] As the non-halogen flame retardant used in the present invention, a metal hydroxide coated with a silicate compound by a sol-gel method is used. This is a metal hydroxide powder such as magnesium hydroxide, aluminum hydroxide and calcium hydroxide coated on the surface with a thin film of a silicate compound such as silicon oxide, sodium silicate and silicic acid. Oxide surface thickness 0.1-5μ
m coated with a silicate compound. The metal hydroxide subjected to the surface coating has a higher flame retardancy improving effect on the resin composition than the ordinary metal hydroxide, and a high flame retardancy can be obtained with a small amount of compounding. . The amount of the metal hydroxide subjected to the surface coating treatment is 20 to 50 parts, preferably 25 to 40 parts per 100 parts of the polyolefin-based polymer. If less than 20 parts, the flame retardancy is insufficient, and more than 50 parts. And the mechanical properties decrease.

【0009】また、難燃助剤としては、シリコーンパウ
ダー,シリコーンガムなどのシリコーン系難燃剤,モリ
ブデン酸アンモニウムなどのモリブデン化合物,赤リ
ン,カーボンブラック,マレイミド化合物などの1種ま
たは2種以上の混合物が用いられる。この難燃助剤の配
合量は、ポリオレフィン系ポリマー100部に対して2
〜10部とされ、2部未満ではその配合効果が得られ
ず、10部を越えても難燃効果の向上が得られない。こ
の難燃助剤は、樹脂組成物に良好な難燃性を付与し、上
述の表面被覆処理された金属水酸化物の配合量を低減で
き、樹脂組成物の機械的特性の低下および比重の増大を
防止できる。
The flame-retardant auxiliary may be one or a mixture of two or more of silicone-based flame retardants such as silicone powder and silicone gum, molybdenum compounds such as ammonium molybdate, red phosphorus, carbon black, and maleimide compounds. Is used. The amount of the flame retardant aid is 2 parts per 100 parts of the polyolefin polymer.
If the amount is less than 2 parts, the compounding effect cannot be obtained, and if the amount exceeds 10 parts, the flame retardant effect cannot be improved. This flame retardant aid imparts good flame retardancy to the resin composition, can reduce the blending amount of the above-mentioned surface-coated metal hydroxide, lowers the mechanical properties of the resin composition and reduces the specific gravity. An increase can be prevented.

【0010】そして、このような配合組成の樹脂組成物
にあっては、その比重が1.14以下、酸素指数が24
〜34であることが必要である。比重が1.14を越え
ると、PVC組成物の比重に近くなり、比重分別によっ
てPVC組成物と分別できなくなる。酸素指数が24未
満では難燃性が不足し、34を越えるようにするには多
量の金属水酸化物を配合せねばならず、組成物の伸び等
が低下する。さらに、この樹脂組成物を電線,ケーブル
またはその類似品の被覆材料として用いたときに、JI
S C 3005に制定される60度傾斜燃焼試験に合
格する必要がある。
The resin composition having such a composition has a specific gravity of 1.14 or less and an oxygen index of 24 or less.
3434. When the specific gravity exceeds 1.14, the specific gravity approaches the specific gravity of the PVC composition, and it becomes impossible to separate the specific gravity from the PVC composition. If the oxygen index is less than 24, the flame retardancy is insufficient, and if it exceeds 34, a large amount of metal hydroxide must be blended, and the elongation of the composition and the like decrease. Furthermore, when this resin composition is used as a coating material for electric wires, cables or similar products, JI
It is necessary to pass the 60-degree inclined combustion test established in SC 3005.

【0011】このノンハロゲン難燃性樹脂組成物には、
この他に紫外線吸収剤,老化防止剤,銅害防止剤,着色
剤,無機充填剤などの各種配合剤を適量配合することが
できるが、これら配合剤には、ハロゲン,重金属が含ま
れていないものを選択すべきである。また、このノンハ
ロゲン難燃性樹脂組成物にあっては、架橋系としてもよ
い。このためには、ジクミルパーオキサイドなどの有機
過酸化物からなる架橋剤をベースポリマー100部当り
0.5〜2部添加する方法やシランカップリング剤と有
機過酸化物を添加,混練し、シラングラフト化ポリオレ
フィン系ポリマーとしたのち、成形後水分に接触させて
架橋させるシラン架橋や電子線,ガンマー線を照射する
方法がある。
[0011] The non-halogen flame-retardant resin composition includes:
In addition, various compounding agents such as an ultraviolet absorber, an antioxidant, a copper inhibitor, a coloring agent, and an inorganic filler can be compounded in appropriate amounts, but these compounds do not contain halogens and heavy metals. You should choose one. In addition, the non-halogen flame-retardant resin composition may be of a crosslinked type. For this purpose, a method of adding a crosslinking agent composed of an organic peroxide such as dicumyl peroxide in an amount of 0.5 to 2 parts per 100 parts of the base polymer, or adding and kneading a silane coupling agent and an organic peroxide, After forming the silane-grafted polyolefin-based polymer, there is a method of irradiating with silane crosslinking or electron beam or gamma ray which is crosslinked by being brought into contact with moisture after molding.

【0012】このようなノンハロゲン難燃性樹脂組成物
は、押出被覆法によって電線,ケーブルの絶縁体,シー
ス,介在などとされる他,押出成形法,射出成形法など
によってシート,フィルム,パイプ,ダクト,建材など
の種々の製品とすることができる。
Such a non-halogen flame-retardant resin composition is used as an insulator, a sheath, an interposition, and the like of electric wires and cables by extrusion coating, and is also used to form sheets, films, pipes, and the like by extrusion molding, injection molding, and the like. Various products such as ducts and building materials can be used.

【0013】本発明のノンハロゲン難燃性樹脂組成物に
あっては、難燃性がPVC製品と同等程度であり、比重
がPVC製品が比べて小さいので、水による比重分別が
可能である。また、ハロゲンを含有していないので、焼
却しても有害ガスを発生することがない。さらに、難燃
性付与効果の大きなケイ酸化合物を表面被覆した金属水
酸化物を用い、難燃助剤を配合しているので、この金属
水酸化物の配合量を低減でき、これによって比重をより
一層小さくでき、かつ樹脂組成物の機械的特性の低下も
わずかなものになる。また、鉛,カドミウム,クロムな
どの重金属が含まれないので、焼却処分としてもこれら
の重金属で土壌等が汚染されることもない。
In the non-halogen flame-retardant resin composition of the present invention, the flame retardancy is almost equal to that of the PVC product, and the specific gravity is smaller than that of the PVC product, so that the specific gravity can be separated by water. Further, since it does not contain halogen, no harmful gas is generated even when incinerated. Furthermore, since a metal hydroxide coated with a silicate compound having a large flame-retardant effect and a flame-retardant aid is used, the amount of the metal hydroxide can be reduced, thereby increasing the specific gravity. The size can be further reduced, and the mechanical properties of the resin composition are slightly reduced. In addition, since heavy metals such as lead, cadmium, and chromium are not contained, soil and the like are not contaminated by these heavy metals even when incinerated.

【0014】以下、具体例を示す。表1に示す配合組成
物を用意し、押出機で混練,成形して厚み2mmのシー
ト状の試片を作成した。この試片について、比重,引張
強度,伸び,酸素指数,JIS C 3005に定めら
れた60度傾斜燃焼試験による難燃性を測定した。結果
を表1に示す。表1において、EEA樹脂にはエチルア
クリレート含量19重量%,メルトインデックス1.5
のエチレン−エチルアクリレート共重合体を、水酸化マ
グネシウムAには、高級飽和脂肪酸で表面処理した水酸
化マグネシウムを、水酸化マグネシウムBにはゾルゲル
法でケイ酸化合物を被覆した水酸化マグネシウムを、老
化防止剤には、ペンタエリスリチル−テトラキス[3
(3,5−ジ−t−ブチル−4−ヒドロキシフェノー
ル)プロピオネート]を用いた。
A specific example will be described below. The composition shown in Table 1 was prepared, kneaded and molded by an extruder to prepare a 2 mm-thick sheet-like specimen. The specimen was measured for specific gravity, tensile strength, elongation, oxygen index, and flame retardancy by a 60-degree inclined combustion test defined in JIS C 3005. Table 1 shows the results. In Table 1, the EEA resin had an ethyl acrylate content of 19% by weight and a melt index of 1.5.
Of the ethylene-ethyl acrylate copolymer, magnesium hydroxide A, magnesium hydroxide surface-treated with a higher saturated fatty acid, and magnesium hydroxide B, magnesium hydroxide coated with a silicate compound by a sol-gel method. Inhibitors include pentaerythrityl-tetrakis [3
(3,5-di-t-butyl-4-hydroxyphenol) propionate].

【0015】[0015]

【表1】 [Table 1]

【0016】表1の結果から、試験番号1〜4のもの
は、難燃性,機械的特性が優れ、比重も1.14以下と
なることがわかる。
From the results shown in Table 1, it can be seen that the test Nos. 1 to 4 have excellent flame retardancy and mechanical properties, and have a specific gravity of 1.14 or less.

【0017】[0017]

【発明の効果】以上説明したように、本発明のノンハロ
ゲン難燃性樹脂組成物にあっては、PVC組成物と同等
の難燃性を有し、引張強さ,伸びなどの機械的特性も良
好であり、焼却の際に有害ガスを発生することがなく、
焼却残査に鉛,カドミウムなどの重金属が含まれること
もない。さらに、比重分別によりPVC製品との分別が
でき、回収,リサイクルが可能である。
As described above, the non-halogen flame-retardant resin composition of the present invention has the same flame retardancy as the PVC composition, and also has the mechanical properties such as tensile strength and elongation. Good, no harmful gas generated during incineration,
Heavy metals such as lead and cadmium are not contained in the incineration residue. Furthermore, it can be separated from PVC products by specific gravity separation, and can be collected and recycled.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) H01B 3/44 H01B 3/44 G P Fターム(参考) 4J002 BB031 BB051 BB061 BB071 BB121 BB151 DE076 DE086 DE146 FB076 FD136 5G303 AA06 AB20 BA12 CA01 CA09 CB17 5G305 AA02 AA14 AB25 AB35 BA15 BA24 BA26 CA01 CC03 CD13──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) H01B 3/44 H01B 3/44 GPF term (Reference) 4J002 BB031 BB051 BB061 BB071 BB121 BB151 DE076 DE086 DE146 FB076 FD136 5G303 AA06 AB20 BA12 CA01 CA09 CB17 5G305 AA02 AA14 AB25 AB35 BA15 BA24 BA26 CA01 CC03 CD13

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 ポリオレフィン系ポリマー100重量
部に対して、ゾルゲル法によってケイ酸化合物を表面被
覆した金属水酸化物20〜50重量部、難燃助剤2〜1
0重量部を配合してなる組成物であって、その組成物の
比重が1.14以下、酸素指数が24〜34で、電線・
ケーブルまたはその類似品の被覆材料に用いた時にJI
S C 3005に制定される60度傾斜燃焼試験に合
格することを特徴とするノンハロゲン難燃性樹脂組成
物。
1. A metal oxide whose surface is coated with a silicate compound by a sol-gel method in an amount of 20 to 50 parts by weight, a flame-retardant aid 2-1 in 100 parts by weight of a polyolefin-based polymer.
A composition comprising 0 parts by weight, having a specific gravity of 1.14 or less, an oxygen index of 24-34,
JI when used as a coating material for cables or similar products
A non-halogen flame-retardant resin composition, which passes a 60-degree inclined combustion test established in SC 3005.
JP2000163503A 2000-05-31 2000-05-31 Non-halogen flame-retardant resin composition Withdrawn JP2001342304A (en)

Priority Applications (1)

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Publications (1)

Publication Number Publication Date
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Family

ID=18667245

Family Applications (1)

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Country Status (1)

Country Link
JP (1) JP2001342304A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012034198A1 (en) * 2010-09-13 2012-03-22 Braskem S.A. Active and intelligent additive, polymer and article
WO2012077168A1 (en) * 2010-12-10 2012-06-14 株式会社アドマテックス Flame retarder and method for producing same, and flame-retardant resin composition and method for producing same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012034198A1 (en) * 2010-09-13 2012-03-22 Braskem S.A. Active and intelligent additive, polymer and article
WO2012077168A1 (en) * 2010-12-10 2012-06-14 株式会社アドマテックス Flame retarder and method for producing same, and flame-retardant resin composition and method for producing same
CN103328611A (en) * 2010-12-10 2013-09-25 株式会社亚都玛科技 Flame retarder and method for producing same, and flame-retardant resin composition and method for producing same
JP5710643B2 (en) * 2010-12-10 2015-04-30 株式会社アドマテックス Flame retardant and method for producing the same, flame retardant resin composition and method for producing the same

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