JP4651856B2 - Flame retardant elastomer composition - Google Patents
Flame retardant elastomer composition Download PDFInfo
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- JP4651856B2 JP4651856B2 JP2001152322A JP2001152322A JP4651856B2 JP 4651856 B2 JP4651856 B2 JP 4651856B2 JP 2001152322 A JP2001152322 A JP 2001152322A JP 2001152322 A JP2001152322 A JP 2001152322A JP 4651856 B2 JP4651856 B2 JP 4651856B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、家電部品、屋内配線等に使用される非ハロゲン系難燃性エラストマーに関するものである。
【０００２】
【発明の背景】
従来、熱可塑性エラストマーに難燃性を付与した難燃性エラストマーが提供されているが、該難燃性エラストマーは熱可塑性エラストマーに難燃剤を添加することで製造されている。
該難燃剤としてはハロゲン系の難燃剤が使用されており、該難燃剤が添加された難燃性エラストマーは優れた難燃性を有する反面、該難燃性エラストマーの成形加工時あるいは該難燃性エラストマーの燃焼時において、毒性および腐食性を有するハロゲン系ガスが発生することが問題とされていた。
【０００３】
【従来の技術】
したがってハロゲン系の難燃剤に代わる難燃剤として、水酸化アルミニウム、水酸化マグネシウム等の金属水酸化物が使用されている。
【０００４】
【発明が解決しようとする課題】
しかし、上記金属水酸化物を難燃性エラストマーの難燃剤として使用する場合、該難燃性エラストマーに充分な難燃性を付与するためには、上記ハロゲン系の難燃剤と比べ多量の金属水酸化物を使用する必要があり、そのため該難燃性エラストマーより得られる成形物の機械的特性を著しく低下させ、かつ組成物および成形物の比重を増加させる原因となっている。
【０００５】
【課題を解決するための手段】
本発明は上記課題を解決するために、スチレン−エチレン−ブチレン−スチレンブロック共重合体（ＳＥＢＳ）に難燃剤として膨張性黒鉛および赤燐が分散されている難燃性エラストマー組成物であって、該難燃性エラストマー組成物にはポリフェニレンエーテル（ＰＰＥ）が添加されている難燃性エラストマー組成物を提供するものである。
該難燃性エラストマー組成物には、ポリプロピレン（ＰＰ）および／または軟化剤が添加されることが望ましく、該軟化剤はパラフィン系オイルであることが望ましい。
【０００６】
該膨張性黒鉛は、ＳＥＢＳ１００重量部に対して１０重量部以上〜１００重量部以下添加され、該赤燐は、ＳＥＢＳ１００重量部に対して５重量部以上〜５０重量部以下添加され、および該ポリフェニレンエーテルは、ＳＥＢＳ１００重量部に対して１０重量部以上〜１００重量部以下添加されることが望ましい。
【０００７】
本発明を以下、詳細に説明する。
【０００８】
【発明の実施の形態】
〔熱可塑性エラストマー〕
本発明で使用する熱可塑性エラストマーは、スチレン−エチレン−ブチレン−スチレンブロック共重合体（ＳＥＢＳ）である。
【０００９】
〔難燃剤〕
本発明の難燃性エラストマー組成物において使用される難燃剤は、膨張性黒鉛および赤燐である。
該膨張性黒鉛とは加熱することにより体積が膨張する黒鉛のことである。
【００１０】
本発明の難燃性エラストマー組成物において、該膨張性黒鉛はＳＥＢＳ１００重量部に対して、１０重量部以上〜１００重量部以下の範囲の添加量で添加され、また該赤燐はＳＥＢＳ１００重量部に対して、５重量部以上〜５０重量部以下の範囲の添加量で添加される。
【００１１】
〔難燃補助剤〕
本発明において、上記難燃剤と併用することで難燃性エラストマー組成物に難燃性を付与する難燃補助剤として使用されるのは、ポリフェニレンエーテル（ＰＰＥ）である。
該ＰＰＥはそれ自身が自己消火性を有し、かつ、良好な物性を有するポリマーであるため、エラストマーの物性を低下させることなく難燃性を付与することができる。
【００１２】
本発明の難燃性エラストマー組成物において、該ＰＰＥはＳＥＢＳ１００重量部に対して１０重量部以上〜１００重量部以下の範囲の添加量で添加される。
【００１３】
〔硬度調節剤〕
本発明の難燃性エラストマー組成物では、硬度を調節するためにポリプロピレン（ＰＰ）および／または軟化剤が添加される。
【００１４】
硬度調節剤として添加されるＰＰは、難燃性エラストマー組成物に硬さを付与するために添加される。
該ＰＰはＳＥＢＳ１００重量部に対して、１重量部以上〜５０重量部以下の範囲の添加量で添加される。
【００１５】
上記ＰＰ以外にＳＥＢＳと相溶性の良い合成樹脂、合成ゴムあるいは熱可塑性エラストマーを添加してもよく、該合成樹脂、合成ゴムあるいは熱可塑性エラストマーとしては、ポリエチレン、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、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、ポリ酢酸ビニル、フッ素樹脂、熱可塑性アクリル樹脂、熱可塑性ポリエステル、熱可塑性ポリアミド、熱可塑性ウレタン樹脂、エチレン−酢酸ビニル共重合体等の合成樹脂、アクリルゴム、ブチルゴム、ケイ素ゴム、ウレタンゴム、フッ化物系ゴム、多硫化物系ゴム、グラフトゴム、ブタジエンゴム、イソプレンゴム、クロロプレンゴム、ポリイソブチレンゴム、ポリブテンゴム、イソブテン−イソプレンゴム、アクリレート−ブタジエンゴム、スチレン−ブタジエンゴム、アクリロニトリル−ブタジエンゴム、ピリジン−ブタジエンゴム、スチレン−イソプレンゴム（ＳＩＲ）、アクリロニトリル−クロロプレンゴム（ＮＣＲ）、スチレン−クロロプレンゴム（ＳＣＲ）、アクリロニトリル−ブタジエン−スチレン共重合体、エチレン−プロピレン共重合体、エチレン−プロピレンターポリマー、スチレン−エチレン共重合体、ポリ（α−メチルスチレン）−ポリブタジエン−ポリ（α−メチルスチレン）共重合体（α−ＭｅＳ−Ｂ−α−ＭｅＳ）、ポリ（α−メチルスチレン）−ポリイソプレン−ポリ（α−メチルスチレン）、ブタジエン−スチレン共重合体（ＢＳ）、エチレン−プロピレン−エチリデン共重合体、エチレン−ブテン−１共重合体、エチレン−プロピレン−エチルデンノルボルネン共重合体、エチレン−プロピレン−ジシクロペンタジエン共重合体、エチレン−プロピレン−１，４ヘキサジエン共重合体、エチレン−ブテン−１−エチリデンノルボルネン共重合体、エチレン−ブテン−１−ジシクロペンタジエン共重合体、エチレン−ブテン−１−１，４ヘキサジエン共重合体等の合成ゴム、スチレン−ブタジエン−スチレンブロック共重合体（ＳＢＳ）、スチレン−イソプレン−スチレンブロック共重合体（ＳＩＳ）等のスチレン系熱可塑性エラストマー等の熱可塑性エラストマー等が例示され、これらの一種または二種以上をＳＥＢＳと併用しても良い。
【００１６】
本発明において使用される軟化剤はパラフィン系オイルである。
該軟化剤はＳＥＢＳ１００重量部に対して、２０重量部以上〜５００重量部以下の範囲の添加量で添加される。
【００１７】
パラフィン系オイルに代えて、ステアリン酸、ヒマシ油、ヤシ油、パーム油等の脂肪油系オイル等を軟化剤として使用してもよい。
【００１８】
〔その他の成分〕
本発明においては、更に難燃性エラストマー組成物の耐熱性、耐衝撃性、寸法安定性、剛性等を改良するために、例えば炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、硫酸カルシウム、亜硫酸カルシウム、燐酸カルシウム、水酸化カルシウム、水酸化マグネシウム、水酸化アルミニウム、酸化マグネシウム、酸化チタン、酸化鉄、酸化亜鉛、アルミナ、シリカ、ケイ藻土、ドロマイト、石膏、タルク、クレー、アスベスト、マイカ、ガラス繊維、ケイ酸カルシウム、ベントナイト、ホワイトカーボン、カーボンブラック、鉄粉、アルミニウム粉、石粉、高炉スラグ、フライアッシュ、セメント、ジルコニア粉等の充填剤、難燃剤、酸化防止剤、老化防止剤、紫外線吸収剤、帯電防止剤、結晶化促進剤、発泡剤、染料、顔料等の着色剤等が添加されてもよい。
【００１９】
〔難燃性エラストマー組成物〕
本発明の難燃性エラストマー組成物の難燃性は、ＵＬ−９４規格Ｖ−２以上の難燃性を有するものであり、望ましくはＶ−０のものである。
【００２０】
以下、実施例により本発明を説明する。なお本発明は実施例のみに限定されるものではない。
〔実施例〕
ＳＥＢＳ、膨張性黒鉛、赤燐、ＰＰＥ、軟化剤（パラフィン系オイル）、ＰＰを表１に示す配合条件で難燃性エラストマー組成物（実施例１〜実施例３）を調製し、該組成物より成形物を製造した。
該成形物の硬度*1、引張強度*2、および難燃性評価*3の結果を表１に示す。
【００２１】
硬度*1: ＪＩＳ Ｋ６２５３ タイプＡで実施。引張強度*2：ＪＩＳ Ｋ６２５１で実施。難燃性評価*3：ＵＬ−９４規格に準ずる。
【００２２】
〔比較例〕
また比較例として、表１に示すＳＥＢＳ、膨張性黒鉛、赤燐、ＰＰＥ、軟化剤（パラフィン系オイル）、ＰＰの配合条件で組成物（比較例１および比較例２）を調製し、該組成物より成形物を製造した。
該成形物の硬度*1、引張強度*2、および難燃性評価*3の結果を表１に示す。
なお硬度および引張強度の測定、および難燃性評価の方法は上記実施例と同様である。
【００２３】
【表１】
実施例１〜実施例３、比較例１および比較例２の組成物の難燃性評価の結果より、実施例１〜実施例３の組成物は、ＵＬ−９４規格Ｖ−２以上の難燃性を有していることがわかる。
また難燃性エラストマー組成物中のＰＰＥの組成比を大きくすることで、該組成物の難燃性が向上することがわかる（実施例１および実施例３との比較）。
【００２５】
なお難燃剤を添加せずにＰＰＥのみを添加した場合では、比較例１の組成物は難燃性を充分得られていないことがわかり（比較例１）、またＰＰＥを添加せずに難燃剤のみの使用した場合にあっても、上記実施例の組成物が有する難燃性には及ばないことがわかる（比較例２）。
【００２６】
更に上記実施例の組成物の硬度および引張強度の測定結果より、該組成物は家電部品、屋内配線等として使用するのに充分な値を有していることがわかる。
【００２７】
【発明の効果】
膨張性黒鉛および赤燐を難燃剤として使用し、かつ該難燃剤と共に難燃補助剤としてＰＰＥを使用する本発明の難燃性エラストマー組成物は、難燃性に優れ、かつ機械的特性（硬度および引張強度）に優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-halogen flame retardant elastomer used for home appliance parts, indoor wiring, and the like.
[0002]
BACKGROUND OF THE INVENTION
Conventionally, a flame retardant elastomer in which flame retardancy is imparted to a thermoplastic elastomer has been provided. The flame retardant elastomer is produced by adding a flame retardant to a thermoplastic elastomer.
As the flame retardant, a halogen-based flame retardant is used, and the flame retardant elastomer to which the flame retardant is added has excellent flame retardancy, but at the time of molding the flame retardant elastomer or the flame retardant. It has been a problem that a halogen-based gas having toxicity and corrosivity is generated during the combustion of the water-soluble elastomer.
[0003]
[Prior art]
Therefore, metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used as flame retardants instead of halogen flame retardants.
[0004]
[Problems to be solved by the invention]
However, when the metal hydroxide is used as a flame retardant for a flame retardant elastomer, in order to give the flame retardant elastomer sufficient flame retardancy, a larger amount of metal water than the halogen flame retardant is used. It is necessary to use an oxide, which causes a significant decrease in the mechanical properties of the molded product obtained from the flame retardant elastomer and an increase in the specific gravity of the composition and the molded product.
[0005]
[Means for Solving the Problems]
In order to solve the above problems, the present invention provides a flame retardant elastomer composition in which expandable graphite and red phosphorus are dispersed as a flame retardant in a styrene-ethylene-butylene-styrene block copolymer (SEBS), A flame retardant elastomer composition in which polyphenylene ether (PPE) is added to the flame retardant elastomer composition is provided.
It is desirable to add polypropylene (PP) and / or a softening agent to the flame retardant elastomer composition, and the softening agent is preferably a paraffinic oil.
[0006]
The expansive graphite is added to 10 to 100 parts by weight with respect to 100 parts by weight of SEBS, the red phosphorus is added to 5 to 50 parts by weight with respect to 100 parts by weight of SEBS, and the polyphenylene. The ether is preferably added in an amount of 10 to 100 parts by weight based on 100 parts by weight of SEBS.
[0007]
The present invention is described in detail below.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
[Thermoplastic elastomer]
The thermoplastic elastomer used in the present invention is a styrene-ethylene-butylene-styrene block copolymer (SEBS).
[0009]
〔Flame retardants〕
The flame retardant used in the flame retardant elastomer composition of the present invention is expandable graphite and red phosphorus.
The expansive graphite is graphite whose volume expands when heated.
[0010]
In the flame retardant elastomer composition of the present invention, the expandable graphite is added in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of SEBS, and the red phosphorus is added to 100 parts by weight of SEBS. On the other hand, it is added at an addition amount in the range of 5 to 50 parts by weight.
[0011]
[Flame Retardant]
In the present invention, polyphenylene ether (PPE) is used as a flame retardant auxiliary agent that imparts flame retardancy to the flame retardant elastomer composition in combination with the above flame retardant.
Since the PPE itself is a polymer having self-extinguishing properties and good physical properties, flame retardancy can be imparted without deteriorating the physical properties of the elastomer.
[0012]
In the flame retardant elastomer composition of the present invention, the PPE is added in an addition amount in the range of 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of SEBS.
[0013]
[Hardness modifier]
In the flame retardant elastomer composition of the present invention, polypropylene (PP) and / or a softening agent is added to adjust the hardness.
[0014]
PP added as a hardness modifier is added to impart hardness to the flame retardant elastomer composition.
The PP is added in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of SEBS.
[0015]
In addition to PP, synthetic resin, synthetic rubber or thermoplastic elastomer having good compatibility with SEBS may be added. Examples of the synthetic resin, synthetic rubber or thermoplastic elastomer include polyethylene, ethylene-propylene copolymer, ethylene- Vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, fluororesin, thermoplastic acrylic resin, thermoplastic polyester, thermoplastic polyamide, thermoplastic urethane resin, ethylene-vinyl acetate copolymer, etc. Synthetic resin, acrylic rubber, butyl rubber, silicon rubber, urethane rubber, fluoride rubber, polysulfide rubber, graft rubber, butadiene rubber, isoprene rubber, chloroprene rubber, polyisobutylene rubber, polybutene rubber, isobutene-isoprene rubber, acrylate − Tadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, pyridine-butadiene rubber, styrene-isoprene rubber (SIR), acrylonitrile-chloroprene rubber (NCR), styrene-chloroprene rubber (SCR), acrylonitrile-butadiene-styrene copolymer, Ethylene-propylene copolymer, ethylene-propylene terpolymer, styrene-ethylene copolymer, poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene) copolymer (α-MeS-B-α-MeS) ), Poly (α-methylstyrene) -polyisoprene-poly (α-methylstyrene), butadiene-styrene copolymer (BS), ethylene-propylene-ethylidene copolymer, ethylene-butene-1 copolymer, ethylene -Propi N-ethyldennorbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,4 hexadiene copolymer, ethylene-butene-1-ethylidene norbornene copolymer, ethylene-butene-1- Synthetic rubber such as dicyclopentadiene copolymer, ethylene-butene-1-1,4 hexadiene copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS) Examples thereof include thermoplastic elastomers such as styrene-based thermoplastic elastomers, and one or more of these may be used in combination with SEBS.
[0016]
The softener used in the present invention is paraffinic oil.
The softener is added in an amount of 20 parts by weight to 500 parts by weight with respect to 100 parts by weight of SEBS.
[0017]
Instead of paraffin oil, stearic acid, castor oil, coconut oil, palm oil, and other fatty oil oils may be used as a softening agent.
[0018]
[Other ingredients]
In the present invention, in order to further improve the heat resistance, impact resistance, dimensional stability, rigidity, etc. of the flame retardant elastomer composition, for example, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, calcium sulfite, calcium phosphate. , Calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium oxide, titanium oxide, iron oxide, zinc oxide, alumina, silica, diatomaceous earth, dolomite, gypsum, talc, clay, asbestos, mica, glass fiber, silicic acid Fillers such as calcium, bentonite, white carbon, carbon black, iron powder, aluminum powder, stone powder, blast furnace slag, fly ash, cement, zirconia powder, flame retardant, antioxidant, anti-aging agent, UV absorber, antistatic Agents, crystallization accelerators, foaming agents, colorants such as dyes, pigments, etc. It may be added.
[0019]
[Flame Retardant Elastomer Composition]
The flame retardancy of the flame retardant elastomer composition of the present invention has flame retardancy of UL-94 standard V-2 or higher, preferably V-0.
[0020]
Hereinafter, the present invention will be described by way of examples. In addition, this invention is not limited only to an Example.
〔Example〕
SEBS, expandable graphite, red phosphorus, PPE, softening agent (paraffinic oil), PP are prepared under the blending conditions shown in Table 1, and flame retardant elastomer compositions (Examples 1 to 3) are prepared. More moldings were produced.
Table 1 shows the results of hardness * 1 , tensile strength * 2 , and flame retardancy evaluation * 3 of the molded product.
[0021]
Hardness * 1 : Implemented according to JIS K6253 Type A. Tensile strength * 2 : Implemented in accordance with JIS K6251. Flame retardant evaluation * 3 : Conforms to UL-94 standard.
[0022]
[Comparative example]
As a comparative example, compositions (Comparative Example 1 and Comparative Example 2) were prepared under the blending conditions of SEBS, expandable graphite, red phosphorus, PPE, softener (paraffinic oil) and PP shown in Table 1, and the composition A molded product was produced from the product.
Table 1 shows the results of hardness * 1 , tensile strength * 2 , and flame retardancy evaluation * 3 of the molded product.
The measurement of hardness and tensile strength and the method of flame retardancy evaluation are the same as in the above examples.
[0023]
[Table 1]
From the results of flame retardant evaluation of the compositions of Examples 1 to 3, Comparative Example 1 and Comparative Example 2, the compositions of Examples 1 to 3 are flame retardant of UL-94 standard V-2 or higher. It turns out that it has sex.
Moreover, it turns out that the flame retardance of this composition improves by enlarging the composition ratio of PPE in a flame retardant elastomer composition (comparison with Example 1 and Example 3).
[0025]
In addition, when only PPE was added without adding a flame retardant, it was found that the composition of Comparative Example 1 did not provide sufficient flame retardancy (Comparative Example 1), and the flame retardant was not added with PPE. It can be seen that the flame retardancy of the compositions of the above-mentioned examples is not reached even when used only (Comparative Example 2).
[0026]
Furthermore, from the measurement results of the hardness and tensile strength of the compositions of the above examples, it can be seen that the compositions have sufficient values for use as home appliance parts, indoor wiring, and the like.
[0027]
【The invention's effect】
The flame-retardant elastomer composition of the present invention, which uses expansive graphite and red phosphorus as a flame retardant, and uses PPE as a flame retardant auxiliary together with the flame retardant, has excellent flame retardancy and mechanical properties (hardness And tensile strength).
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001152322A JP4651856B2 (en) | 2001-05-22 | 2001-05-22 | Flame retardant elastomer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001152322A JP4651856B2 (en) | 2001-05-22 | 2001-05-22 | Flame retardant elastomer composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100436536C (en) * | 2006-06-04 | 2008-11-26 | 浙江三博聚合物有限公司 | Expansion type low-smoke halogen-free thermoplastic flame-retardant rubber and its production method |
| EP2196500B1 (en) | 2008-12-12 | 2013-04-10 | Cheil Industries Inc. | Thermoplastic elastomer composition |
| KR101293785B1 (en) | 2009-12-29 | 2013-08-06 | 제일모직주식회사 | Thermoplastic elastomer composition and molded product usign the same |
| KR101036871B1 (en) | 2010-11-26 | 2011-05-25 | (주) 웹스 | Flame-retardant thermoplastic elastomer composition of halogen free type and method of preparing thereof |
| KR101459120B1 (en) | 2010-12-31 | 2014-11-12 | 제일모직주식회사 | Low hardness and high strength thermoplastic elastomer and diaphragm usign the same |
| KR101482027B1 (en) | 2011-12-15 | 2015-01-21 | 제일모직주식회사 | Low hardness thermoplastic elastomer and diaphragm usign the same |
| CN114773871B (en) * | 2022-03-31 | 2023-08-22 | 上海化工研究院有限公司 | High-stability and high-flame-retardance composite elastomer material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62270657A (en) * | 1986-03-17 | 1987-11-25 | ゼネラル・エレクトリツク・カンパニイ | Polymer mixture consisting of polyphenylene ether, block copolymer, phosphate ester and additive |
| JPH03199256A (en) * | 1989-12-27 | 1991-08-30 | Mitsubishi Cable Ind Ltd | Flame retardant resin composition |
| JPH0873649A (en) * | 1994-09-07 | 1996-03-19 | Sekisui Chem Co Ltd | Flame retardant thermoplastic resin composition |
| JPH10237263A (en) * | 1997-02-25 | 1998-09-08 | Sekisui Chem Co Ltd | Acrylic resin composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62270657A (en) * | 1986-03-17 | 1987-11-25 | ゼネラル・エレクトリツク・カンパニイ | Polymer mixture consisting of polyphenylene ether, block copolymer, phosphate ester and additive |
| JPH03199256A (en) * | 1989-12-27 | 1991-08-30 | Mitsubishi Cable Ind Ltd | Flame retardant resin composition |
| JPH0873649A (en) * | 1994-09-07 | 1996-03-19 | Sekisui Chem Co Ltd | Flame retardant thermoplastic resin composition |
| JPH10237263A (en) * | 1997-02-25 | 1998-09-08 | Sekisui Chem Co Ltd | Acrylic resin composition |
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