JP3308633B2 - Foamable flame-retardant resin composition - Google Patents

Foamable flame-retardant resin composition

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Publication number
JP3308633B2
JP3308633B2 JP06173993A JP6173993A JP3308633B2 JP 3308633 B2 JP3308633 B2 JP 3308633B2 JP 06173993 A JP06173993 A JP 06173993A JP 6173993 A JP6173993 A JP 6173993A JP 3308633 B2 JP3308633 B2 JP 3308633B2
Authority
JP
Japan
Prior art keywords
flame
weight
resin composition
retardant resin
parts
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 - Fee Related
Application number
JP06173993A
Other languages
Japanese (ja)
Other versions
JPH06271700A (en
Inventor
正樹 戸野
眞男 小笠
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.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co 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 Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to JP06173993A priority Critical patent/JP3308633B2/en
Publication of JPH06271700A publication Critical patent/JPH06271700A/en
Application granted granted Critical
Publication of JP3308633B2 publication Critical patent/JP3308633B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Description

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

【0001】[0001]

【産業上の利用分野】本発明は、発泡性難燃樹脂組成物
に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamable flame-retardant resin composition.

【0002】[0002]

【従来の技術】ポリオレフィン系樹脂発泡体は、本来燃
え易い発泡体であるが、近年、使用用途の拡大に伴い難
燃材料としての性能が要求され、各種の方法で難燃化処
理が施されてきた。上記難燃化処理の方法としては、ポ
リオレフィン系樹脂にハロゲン化合物を添加して発泡さ
せる方法が一般的であった。この方法により得られるポ
リオレフィン系樹脂発泡体は、難燃性及び成形性に優
れ、該ポリオレフィン系樹脂発泡体を用いて得られる成
形品の強度の低下は少なかったが、燃焼時あるいは成形
時ハロゲン系ガスが発生し、機器を腐食したり、人体に
害を及ぼしたりするという欠点があった。
2. Description of the Related Art Polyolefin resin foams are inherently flammable foams, but in recent years, their performance has been required as a flame-retardant material in accordance with the expansion of applications, and flame-retardant treatment has been performed by various methods. Have been. As a method of the flame retarding treatment, a method of adding a halogen compound to a polyolefin-based resin and foaming the same was generally used. The polyolefin-based resin foam obtained by this method is excellent in flame retardancy and moldability, and the strength of a molded article obtained by using the polyolefin-based resin foam is small. There is a drawback that gas is generated and corrodes the equipment and harms the human body.

【0003】上記欠点を解決するために、特開昭49−
5171号公報及び特開平3−269029号公報にお
いては、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等の無機系難燃剤が添加されて、
燃焼時ハロゲン系ガスを発生することのない難燃性樹脂
発泡体が提案されたが、本来燃え易いポリオレフィン系
樹脂発泡体に充分な難燃性を付与するためには多量の無
機系難燃剤を添加する必要があり、そのために得られる
難燃性樹脂発泡体の発泡性が低下するという欠点があっ
た。
In order to solve the above-mentioned drawbacks, Japanese Patent Laid-Open Publication No.
No. 5,171, and JP-A-3-269029, an inorganic flame retardant such as aluminum hydroxide, magnesium hydroxide, or basic magnesium carbonate is added.
Flame-retardant resin foams that do not generate halogen-based gas during combustion have been proposed, but in order to impart sufficient flame retardancy to polyolefin-based resin foams that are inherently flammable, a large amount of inorganic flame retardants must be used. It has to be added, and there is a drawback that the foamability of the resulting flame-retardant resin foam is reduced.

【0004】また、特開平2−187434号公報にお
いては、無機系難燃剤の他に難燃効果を示す赤リンが添
加されて、無機系難燃剤の添加量が低減された難燃性発
泡シートが提案されたが、充分な難燃性を得るには多量
の赤リンを添加する必要があり、そのために、得られる
難燃性発泡シートの発泡性が低下するという欠点があっ
た。
Japanese Patent Application Laid-Open No. 2-187434 discloses a flame-retardant foamed sheet in which red phosphorus exhibiting a flame-retardant effect is added in addition to an inorganic flame retardant, so that the amount of the inorganic flame retardant added is reduced. However, in order to obtain sufficient flame retardancy, it is necessary to add a large amount of red phosphorus, and therefore, there is a disadvantage that the foamability of the obtained flame-retardant foam sheet is reduced.

【0005】[0005]

【発明が解決しようとする課題】本発明は、上記欠点に
鑑み、難燃性及び発泡性に優れた発泡体を得ることので
きる発泡性難燃樹脂組成物を提供することを目的とす
る。
SUMMARY OF THE INVENTION In view of the above-mentioned drawbacks, an object of the present invention is to provide a foamable flame-retardant resin composition capable of obtaining a foam having excellent flame retardancy and foamability.

【0006】[0006]

【課題を解決するための手段】本発明において使用され
るポリオレフィン系樹脂マトリックスは、エチレン−酢
酸ビニル共重合体単独又は50重量%以上のエチレン−
酢酸ビニル共重合体と1種以上の他のポリオレフィン系
樹脂との混合物である。
Polyolefin resin matrix used in the present invention, in order to solve the above-mentioned object, et styrene - vinyl acetate copolymer alone or 50% or more by weight of ethylene -
It is a mixture of a vinyl acetate copolymer and one or more other polyolefin resins.

【0007】上記ポリオレフィン系樹脂マトリックス中
の酢酸ビニルの含有量は、少なくなるとポリオレフィン
系樹脂マトリックスに対する無機系難燃剤の相溶性が低
下し、多くなると本発明の発泡性難燃樹脂組成物から得
られる発泡体の成形性が低下するため、5〜20重量%
に限定される。
When the content of vinyl acetate in the polyolefin resin matrix is reduced, the compatibility of the inorganic flame retardant with the polyolefin resin matrix is reduced. When the content is increased, the vinyl flame retardant resin composition of the present invention is obtained. 5-20% by weight because the moldability of the foam decreases
Is limited to

【0008】なお、上記ポリオレフィン系樹脂マトリッ
クスがエチレン−酢酸ビニル共重合体と1種以上の他の
ポリオレフィン系樹脂との混合物である場合、混合物全
体中の酢酸ビニルの含有量が5〜20重量%であり、好
適に使用されるエチレン−酢酸ビニル共重合体として
は、酢酸ビニルの含有量が10〜25重量%のものが挙
げられる。
When the polyolefin resin matrix is a mixture of an ethylene-vinyl acetate copolymer and one or more other polyolefin resins, the content of vinyl acetate in the whole mixture is 5 to 20% by weight. The ethylene-vinyl acetate copolymer preferably used includes those having a vinyl acetate content of 10 to 25% by weight.

【0009】上記ポリオレフィン系樹脂マトリックスに
おいて、エチレン−酢酸ビニル共重合体とともに用いら
れるポリオレフィン系樹脂としては、例えば、ポリエチ
レン、ポリプロピレン、ポリブテン、エチレン−プロピ
レンコポリマー、エチレン−プロピレン−ジエンターポ
リマー、エチレン−エチルアクリレートコポリマー、エ
チレン−ブテンコポリマー、エチレン−ブテン−ジエン
ターポリマー等が挙げられる。
In the above polyolefin resin matrix, the polyolefin resin used together with the ethylene-vinyl acetate copolymer includes, for example, polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-ethyl An acrylate copolymer, an ethylene-butene copolymer, an ethylene-butene-diene terpolymer and the like can be mentioned.

【0010】本発明において使用される無機系難燃剤と
しては、例えば、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、水
酸化バリウム等が挙げられ、好ましくは、水酸化アルミ
ニウム及び水酸化マグネシウムであり、これらは、単独
で用いられてもよいし併用されてもよい。
The inorganic flame retardant used in the present invention includes, for example, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, barium hydroxide and the like. Magnesium hydroxide, which may be used alone or in combination.

【0011】上記無機系難燃剤の添加量は、少なくなる
と本発明の発泡性難燃樹脂組成物から得られる発泡体の
難燃性が低下し、多くなると本発明の発泡性難燃樹脂組
成物から得られる発泡体の強度が低下するため、ポリオ
レフィン系樹脂マトリックス100重量部に対し、50
〜200重量部に限定される。
When the amount of the inorganic flame retardant is small, the flame retardancy of the foam obtained from the foamable flame-retardant resin composition of the present invention decreases, and when the amount is large, the foamable flame-retardant resin composition of the present invention increases. Since the strength of the foam obtained from is reduced, 50 parts by weight based on 100 parts by weight of the polyolefin resin matrix is used.
It is limited to ~ 200 parts by weight.

【0012】本発明において使用される赤リンの添加量
は、少なくなると本発明の発泡性難燃樹脂組成物から得
られる発泡体の難燃性が低下し、多くなると本発明の発
泡性難燃樹脂組成物から得られる発泡体の強度が低下す
るため、ポリオレフィン系樹脂マトリックス100重量
部に対し、5〜50重量部に限定される。
When the amount of red phosphorus used in the present invention decreases, the flame retardancy of the foam obtained from the foamable flame-retardant resin composition of the present invention decreases. Since the strength of the foam obtained from the resin composition decreases, the amount is limited to 5 to 50 parts by weight based on 100 parts by weight of the polyolefin resin matrix.

【0013】上記赤リンは、そのまま用いられてもよい
が、吸湿性が高く、自然発火の危険性も高いため、粒子
の表面をフェノール樹脂、メラミン樹脂等の樹脂で被膜
された赤リンが用いられてもよい。
Although the above-mentioned red phosphorus may be used as it is, it has a high hygroscopicity and a high risk of spontaneous ignition. Therefore, red phosphorus whose particle surface is coated with a resin such as a phenol resin or a melamine resin is used. You may be.

【0014】本発明において使用されるメラミン化合物
としては、例えば、メラミン、メラミンシアヌレート、
メラミンリン酸塩等が挙げられる。上記メラミン化合物
の添加量は、少なくなると本発明の発泡性難燃樹脂組成
物から得られる発泡体の難燃性が低下し、多くなると本
発明の発泡性難燃樹脂組成物から得られる発泡体の強度
が低下するため、ポリオレフィン系樹脂マトリックス1
00重量部に対し、5〜50重量部に限定される。
The melamine compound used in the present invention includes, for example, melamine, melamine cyanurate,
Melamine phosphate and the like. When the amount of the melamine compound is reduced, the flame retardancy of the foam obtained from the foamable flame-retardant resin composition of the present invention decreases, and when the amount increases, the foam obtained from the foamable flame-retardant resin composition of the present invention increases Of the polyolefin resin matrix 1
It is limited to 5 to 50 parts by weight based on 00 parts by weight.

【0015】本発明において使用される多価アルコール
としては、例えば、ペンタエリスリトール、ジペンタエ
リスリトール、トリペンタエリスリトール、アラビトー
ル、ソルビトール、イノシトール、レゾルシノール等が
挙げられる。
The polyhydric alcohol used in the present invention includes, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, arabitol, sorbitol, inositol, resorcinol and the like.

【0016】上記多価アルコールの添加量は、少なくな
っても多くなっても本発明の発泡性難燃樹脂組成物から
得られる発泡体の難燃性が低下するため、ポリオレフィ
ン系樹脂マトリックス100重量部に対し、1〜15重
量部に限定される。
Regardless of whether the amount of the polyhydric alcohol is small or large, the flame retardancy of the foam obtained from the foamable flame-retardant resin composition of the present invention is reduced. Parts by weight is limited to 1 to 15 parts by weight.

【0017】本発明において使用される発泡剤として
は、例えば、アゾジカルボンアミド、N,N−ジニトロ
ソペンタメチレンテトラミン等の有機系発泡剤、重炭酸
ナトリウム、炭酸アンモニウム等の無機系発泡剤などが
挙げられる。上記発泡剤の添加量は、少なくなると本発
明の発泡性難燃樹脂組成物から得られる発泡体の発泡性
が低下し、多くなると本発明の発泡性難燃樹脂組成物か
ら得られる発泡体の強度が低下するため、15〜30重
量部に限定される。
Examples of the foaming agent used in the present invention include organic foaming agents such as azodicarbonamide and N, N-dinitrosopentamethylenetetramine, and inorganic foaming agents such as sodium bicarbonate and ammonium carbonate. No. When the amount of the foaming agent is reduced, the foamability of the foam obtained from the foamable flame-retardant resin composition of the present invention decreases, and the foaming agent obtained from the foamable flame-retardant resin composition of the present invention increases when the amount increases. Since the strength is reduced, it is limited to 15 to 30 parts by weight.

【0018】本発明の発泡性難燃樹脂組成物の構成は上
述の通りであるが、該発泡性難燃樹脂組成物の物性を損
なわない範囲内で、架橋剤、酸化防止剤、滑剤、軟化
剤、分散剤、加工助剤等が添加されてもよい。
The composition of the foamable flame-retardant resin composition of the present invention is as described above. However, as long as the physical properties of the foamable flame-retardant resin composition are not impaired, a crosslinking agent, an antioxidant, a lubricant, and a softening agent are used. Agents, dispersants, processing aids and the like may be added.

【0019】本発明の発泡性難燃樹脂組成物は、ポリオ
レフィン系樹脂マトリックス、無機系難燃剤、赤リン、
メラミン化合物、多価アルコール及び発泡剤を、例え
ば、単軸押出機、二軸押出機、バンバリーミキサー、ニ
ーダーミキサー、ロール等に供給して溶融混練すること
により得られる。
The foamable flame-retardant resin composition of the present invention comprises a polyolefin resin matrix, an inorganic flame retardant, red phosphorus,
It is obtained by supplying a melamine compound, a polyhydric alcohol and a foaming agent to, for example, a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, a roll, or the like and melt-kneading them.

【0020】上記発泡性難燃樹脂組成物を用いて発泡体
を製造する方法としては、例えば、発泡性難燃樹脂組成
物をシート状に成形し、得られた発泡性難燃樹脂シート
に電離性放射線を照射し架橋させて発泡性難燃樹脂架橋
シートを得、得られた発泡性難燃樹脂架橋シートを発泡
炉に供給して加熱発泡させる方法が挙げられる。
As a method for producing a foam using the foamable flame-retardant resin composition, for example, the foamable flame-retardant resin composition is formed into a sheet, and the resulting foamable flame-retardant resin sheet is ionized. Irradiating with radiating radiation to form a crosslinkable foamable flame-retardant resin sheet, and then supplying the obtained crosslinkable foamable flame-retardant resin sheet to a foaming furnace for foaming by heating.

【0021】上記電離性放射線としては、例えば、電子
線、γ線、X線、中性子線等が挙げられ、好ましくは電
子線である。上記電離性放射線の照射量は、少なくなる
と本発明の発泡性難燃樹脂組成物から得られる発泡体の
強度が低下し、多くなると本発明の発泡性難燃樹脂組成
物から得られる発泡体の発泡性が低下するため、1〜1
0Mradが好ましい。
The ionizing radiation includes, for example, an electron beam, a γ-ray, an X-ray, a neutron beam and the like, preferably an electron beam. The irradiation amount of the ionizing radiation is reduced, the strength of the foam obtained from the foamable flame-retardant resin composition of the present invention is reduced, and when the irradiation amount is increased, the foam obtained from the foamable flame-retardant resin composition of the present invention is increased. Since the foaming property is reduced, 1-1
0 Mrad is preferred.

【0022】[0022]

【実施例】次に、本発明の実施例を説明する。なお、
「部」とあるのは、「重量部」を意味する。 実施例1〜3、比較例1〜4 表1に示した所定量(部)の、酢酸ビニル含有量19重
量%、密度0.94g/cm3 、メルトインデックス
2.5g/10分のエチレン−酢酸ビニル共重合体(三
井ポリケミカル社製、商品名:エバフレックスEV46
0);密度0.92g/cm3 、メルトインデックス
3.4g/10分の低密度ポリエチレン(三菱油化社
製、商品名:ユカロンYK−40);水酸化アルミニウ
ム(日本軽金属社製、商品名:B703S);水酸化マ
グネシウム(協和化学工業社製、商品名:キスマ5
A);赤リン(燐化学工業社製、商品名:ノーバレッド
120);メラミン(日産化学工業社製);メラミンシ
アヌレート(日産化学工業社製、商品名:MC61
0);ペンタエリスリトール(和光純薬工業社製);デ
カブロモジフェニルエーテル(旭硝子社製、商品名:A
FR−1021);三酸化アンチモン(三国製練社製)
及びアゾジカルボンアミドをラボプラストミルに供給
し、温度140℃、60rpmで5分間溶融混練して発
泡性難燃樹脂組成物を得、得られた発泡性難燃樹脂組成
物を温度140℃で熱圧プレスして、厚さ2.5mmの
発泡性難燃樹脂シートを得た。
Next, embodiments of the present invention will be described. In addition,
“Parts” means “parts by weight”. Examples 1 to 3 and Comparative Examples 1 to 4 Ethylene of a predetermined amount (part) shown in Table 1 having a vinyl acetate content of 19% by weight, a density of 0.94 g / cm 3 , and a melt index of 2.5 g / 10 min. Vinyl acetate copolymer (manufactured by Mitsui Polychemicals, trade name: Evaflex EV46)
0); low-density polyethylene (manufactured by Mitsubishi Yuka Co., trade name: Yucalon YK-40) having a density of 0.92 g / cm 3 and a melt index of 3.4 g / 10 min; aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd.) : B703S); magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., trade name: Kisuma 5)
A); red phosphorus (manufactured by Rin Kagaku Kogyo Co., Ltd., trade name: Nova Red 120); melamine (manufactured by Nissan Kagaku Kogyo Co., Ltd.);
0); pentaerythritol (manufactured by Wako Pure Chemical Industries); decabromodiphenyl ether (manufactured by Asahi Glass Co., Ltd., trade name: A)
FR-1021); antimony trioxide (manufactured by Sangoku Seisakusho)
And azodicarbonamide were supplied to Labo Plastomill and melt-kneaded at a temperature of 140 ° C. and 60 rpm for 5 minutes to obtain a foamable flame-retardant resin composition, and the obtained foamable flame-retardant resin composition was heated at a temperature of 140 ° C. Pressing was performed to obtain a foamable flame-retardant resin sheet having a thickness of 2.5 mm.

【0023】得られた発泡性難燃樹脂シートに、電離性
放射線を3Mrad照射し架橋させて発泡性難燃樹脂架橋シ
ートを得、得られた発泡性難燃樹脂架橋シートをオーブ
ン中に入れ、温度230℃で加熱発泡させて発泡体を得
た。
The obtained foamable flame-retardant resin sheet is irradiated with 3 Mrad of ionizing radiation and crosslinked to obtain a foamable flame-retardant resin crosslinked sheet, and the obtained foamable flame-retardant resin crosslinked sheet is placed in an oven. Foaming was performed by heating and foaming at a temperature of 230 ° C.

【0024】[0024]

【表1】 [Table 1]

【0025】上記実施例1〜3及び比較例1〜4で得ら
れた発泡体について、JIS K7201に準拠し、酸
素指数を測定して難燃性を評価した。また、発泡倍率及
び発泡体の厚さを測定して発泡性を評価し、得られた結
果を表2に示した。
The flame retardancy of the foams obtained in Examples 1 to 3 and Comparative Examples 1 to 4 was evaluated by measuring the oxygen index in accordance with JIS K7201. In addition, the expansion ratio and the thickness of the foam were measured to evaluate the expandability, and the obtained results are shown in Table 2.

【0026】[0026]

【表2】 [Table 2]

【0027】[0027]

【発明の効果】本発明の発泡性難燃樹脂組成物の構成は
上述の通りであるから、難燃性及び発泡性に優れた発泡
体が得られる。
As described above, the composition of the foamable flame-retardant resin composition of the present invention is excellent in flame retardancy and foamability.

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 エチレン−酢酸ビニル共重合体単独又は
50重量%以上のエチレン−酢酸ビニル共重合体と1種
以上の他のポリオレフィン系樹脂との混合物よりなり、
かつ、酢酸ビニルの含有量が5〜20重量%のポリオレ
フィン系樹脂マトリックス100重量部、無機系難燃剤
50〜200重量部、赤リン5〜50重量部、メラミン
化合物5〜50重量部、多価アルコール1〜15重量部
及び発泡剤15〜30重量部からなることを特徴とする
発泡性難燃樹脂組成物。
An ethylene-vinyl acetate copolymer alone or
50% by weight or more of ethylene-vinyl acetate copolymer and one kind
Consisting of a mixture with the above other polyolefin resin,
And the content is 100 parts by weight 5 to 20 wt% of the polyolefin resin matrix of vinyl acetic acid, 50-200 parts by weight inorganic flame retardants, red phosphorus 5 to 50 parts by weight, the melamine compound 5-50 parts by weight, multi A foamable flame-retardant resin composition comprising 1 to 15 parts by weight of a polyhydric alcohol and 15 to 30 parts by weight of a foaming agent.
JP06173993A 1993-03-22 1993-03-22 Foamable flame-retardant resin composition Expired - Fee Related JP3308633B2 (en)

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JP3308633B2 true JP3308633B2 (en) 2002-07-29

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JP3485353B2 (en) * 1994-06-10 2004-01-13 新日鐵化学株式会社 Styrene-based flame-retardant resin composition
JP4774199B2 (en) * 2004-03-19 2011-09-14 三和化工株式会社 Method for producing flame retardant conductive cross-linked polyolefin foam
CN103804775B (en) 2014-03-06 2016-03-30 福州大学 A kind of halogen-free anti-flaming polyolefin composite foam material and preparation method thereof
US11066533B2 (en) * 2014-10-01 2021-07-20 Dupont Polymers. Inc. Low smoke halogen free flame retardant thermoplastic elastomer compositions

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