JP2006131720A - Flame retardant resin composition for mixing with silane-crosslinkable polyolefin and molding thereof - Google Patents
Flame retardant resin composition for mixing with silane-crosslinkable polyolefin and molding thereof Download PDFInfo
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Abstract
Description
本発明は、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物及びその成形体に関し、特に電線被覆用のシラン架橋性ポリオレフィンとの混合用難燃性架橋樹脂組成物、及び該シラン架橋性ポリオレフィンとの混合用難燃性架橋樹脂組成物を成形した電線被覆用材料に関する。 TECHNICAL FIELD The present invention relates to a flame retardant resin composition for mixing with a silane crosslinkable polyolefin and a molded body thereof, and more particularly to a flame retardant crosslinked resin composition for mixing with a silane crosslinkable polyolefin for coating an electric wire, and the silane crosslinkable The present invention relates to a wire coating material obtained by molding a flame retardant crosslinked resin composition for mixing with polyolefin.
近年、火災時の安全の観点から、発煙性が低く、ハロゲン化水素等の有害ガスの発生の少ないハロゲンフリー難燃性樹脂組成物で被覆した電線の検討が行われている。
ハロゲンフリー難燃性樹脂組成物としては、主としてポリオレフィン系の樹脂をベースポリマーとし、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和物を多量に配合したものが使用されている。
In recent years, electric wires coated with a halogen-free flame-retardant resin composition that has low smoke generation and generates little harmful gas such as hydrogen halide have been studied from the viewpoint of safety in the event of a fire.
As the halogen-free flame retardant resin composition, a composition in which a polyolefin resin is mainly used as a base polymer and a metal hydrate such as aluminum hydroxide or magnesium hydroxide is blended in a large amount as a flame retardant is used.
しかしながら、ベースポリマーとして使用されるポリエチレンや、エチレンとα−オレフィンとの共重合体、エチレン-酢酸ビニル共重合体（ＥＶＡ）、エチレン-アクリル酸エチル共重合体（ＥＥＡ）等のポリオレフィンは、程度の差こそあるものの、常温領域では結晶部を有している結晶性のポリマーであり、比較的剛性が高い。そこで、剛性を低くするには結晶性を低下させる必要があるが、強度保持に寄与している結晶部を減少させてしまうと、材料強度が低下してしまう。また、結晶性の低下は、融点の低下も伴う。このような結晶性のポリマーの場合、融点以上の温度下では加熱変形性が著しく増大し、高い耐熱性を有するのは非常に困難である。このような結晶性の低下による強度及び耐熱性の低下を補う方法としては、一般的に、これらのポリマー間の架橋が行われている。 However, polyolefins such as polyethylene used as a base polymer, copolymers of ethylene and α-olefin, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA) However, in the normal temperature region, it is a crystalline polymer having a crystal part and has relatively high rigidity. Therefore, it is necessary to lower the crystallinity in order to reduce the rigidity. However, if the crystal part contributing to the strength retention is reduced, the material strength is lowered. In addition, a decrease in crystallinity is accompanied by a decrease in melting point. In the case of such a crystalline polymer, the heat deformability is remarkably increased at a temperature equal to or higher than the melting point, and it is very difficult to have high heat resistance. As a method for compensating for such a decrease in strength and heat resistance due to a decrease in crystallinity, crosslinking between these polymers is generally performed.
このような架橋には、電子線架橋、架橋剤架橋、シラン架橋などの方法が用いられるが、中でもシラン架橋は、大規模な製造設備が不要であり、操作が簡便である利点がある。このシラン架橋の方法としては、ポリオレフィン系ポリマー、シラノール触媒および金属水和物を溶融混練して得られる難燃性樹脂組成物と、シラン架橋性ポリオレフィンとを押出成形時に混練して得られる成形品を、水分と接触させ架橋させる方法が提案されている（例えば、特許文献１および２参照）。しかしながら、比較的剛性の高いポリオレフィン樹脂をベースポリマーとしており、柔軟性を与えることが出来る成分に欠けるため、得られる成形品の柔軟性が不充分である。 For such cross-linking, methods such as electron beam cross-linking, cross-linking agent cross-linking, and silane cross-linking are used. Among them, silane cross-linking does not require a large-scale production facility and has an advantage of easy operation. As a method of silane crosslinking, a molded product obtained by kneading a flame-retardant resin composition obtained by melt-kneading a polyolefin polymer, a silanol catalyst and a metal hydrate and a silane-crosslinkable polyolefin during extrusion molding. Has been proposed in which water is brought into contact with moisture and crosslinked (see, for example, Patent Documents 1 and 2). However, since a polyolefin resin having a relatively high rigidity is used as a base polymer and a component capable of imparting flexibility is lacking, the obtained molded product has insufficient flexibility.
一方、電線被覆用材料には、安全性の面から、厳しい難燃性規格、例えば、ＵＬ１５８１（電線、ケーブルおよびフレキシブルコードのための関連規格（Ｒｅｆｅｒｅｎｃｅ Ｓｔａｎｄａｒｄ ｆｏｒ Ｅｌｅｃｔｒｉｃａｌ Ｗｉｒｅｓ，Ｃａｂｌｅｓ，ａｎｄ Ｆｌｅｘｉｂｌｅ Ｃｏｒｄｓ））などに規定されている垂直燃焼試験（Ｖｅｒｔｉｃａｌ Ｆｌａｍｅ Ｔｅｓｔ）、ＶＷ−１規格や水平難燃規格、ＪＩＳ Ｃ３００５に規定される６０度傾斜難燃特性等が定められている。近年は、これらの難燃性規格の中でもより厳しい規格に対応することが要求されるようになってきている。
また、電線被覆用材料には、安全性の面から、難燃性規格以外にも厳しい諸物性の規格が定められている。これらの諸要求特性を満たすためには、難燃剤である金属水和物の配合割合を非常に多くし、高強度、高硬度の熱可塑性樹脂を使用する必要があり、必然的に非常に硬い電線被覆用材料になってきてしまい、このような材料では、柔軟性、耐熱性等において満足するものとはなっていないのが現状である。特に自動車のエンジンルーム内等にて使用される電線の被覆用材料は、高耐熱性及び耐油性も必要であり、かつ組み付け時の作業性を損なわない柔軟性も必要であり、柔軟性、高耐熱性及び耐油性を有する材料が望まれていた。
On the other hand, for wire coating materials, from the viewpoint of safety, strict flame retardant standards, for example, UL1581 (Reference Standard for Electrical Wires, Cables, and Flexible Cords)) Vertical flame test (Vertical Flame Test) defined in the above, VW-1 standard, horizontal flame retardant standard, 60-degree inclined flame retardant characteristic defined in JIS C3005, etc. are defined. In recent years, it has been required to meet stricter standards among these flame retardant standards.
In addition, from the viewpoint of safety, strict standards for various physical properties other than the flame retardant standard are set for the wire coating material. In order to satisfy these required characteristics, it is necessary to increase the blending ratio of the metal hydrate, which is a flame retardant, and to use a high-strength, high-hardness thermoplastic resin, which is inevitably very hard It is becoming a wire coating material, and such a material is not satisfactory in flexibility, heat resistance, and the like at present. In particular, the coating material for electric wires used in the engine room of automobiles must have high heat resistance and oil resistance, and also has flexibility that does not impair workability during assembly. A material having heat resistance and oil resistance has been desired.
本発明は、上記問題点に鑑み、難燃性が良好で、さらに柔軟性及び耐熱性を高い次元で両立させた、特に電線被覆用材料に用いる、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物、及び該シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物から成形された成形品を提供することを目的とする。 In view of the above-mentioned problems, the present invention has good flame retardancy, and further has both flexibility and heat resistance at a high level. Particularly, the flame retardancy for mixing with a silane crosslinkable polyolefin used for a wire coating material. It aims at providing the molded article shape | molded from the flame retardant resin composition for mixing with a resin composition and this silane crosslinkable polyolefin.
すなわち、本発明の第１の態様によれば、
（Ａ）熱可塑性樹脂、ゴム、および熱可塑性エラストマーからなる群から選ばれる少なくとも１つの重合体１００質量部、
（ｅ）有機過酸化物０.０１〜０.６質量部、
（ｆ）シラノール縮合触媒０．０５〜０．５質量部、および
（ｇ）金属水和物１００〜３００質量部
を含む、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物が提供される。
That is, according to the first aspect of the present invention,
(A) 100 parts by mass of at least one polymer selected from the group consisting of thermoplastic resins, rubbers, and thermoplastic elastomers,
(E) 0.01 to 0.6 parts by mass of an organic peroxide,
There is provided a flame retardant resin composition for mixing with a silane crosslinkable polyolefin, comprising (f) 0.05 to 0.5 parts by mass of a silanol condensation catalyst, and (g) 100 to 300 parts by mass of a metal hydrate. .
また、本発明の第２の態様によれば、第１の態様において、前記成分（Ａ）が、
（ａ）結晶性エチレン系重合体１０〜８０質量％、および
（ｄ）酸変性ポリオレフィン２〜２０質量％
を含むことを特徴とする、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物が提供される。
According to the second aspect of the present invention, in the first aspect, the component (A) is:
(A) 10-80% by mass of crystalline ethylene polymer, and (d) 2-20% by mass of acid-modified polyolefin.
A flame retardant resin composition for mixing with a silane crosslinkable polyolefin is provided.
また、本発明の第３の態様によれば、第１または第２の態様において、前記成分（Ａ）が、
（ａ）結晶性エチレン系重合体１０〜８０質量％、
（ｂ）結晶性プロピレン系重合体０〜２５質量％、
（ｃ）芳香族ビニル化合物をその構成成分の主体とした少なくとも２個の重合体ブロック（ｃ’）と共役ジエン化合物をその構成成分の主体とした少なくとも１個の重合体ブロック（ｃ”）とからなるブロック共重合体（ｃ−０）及び／またはこれを水素添加して得られる水添ブロック共重合体（ｃ−１）と、非芳香族系ゴム用軟化剤（ｃ−２）とからなるエラストマー組成物０〜６５質量％、および
（ｄ）酸変性ポリオレフィン２〜２０質量％
を含むことを特徴とする、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物が提供される。
According to the third aspect of the present invention, in the first or second aspect, the component (A) is:
(A) 10 to 80% by mass of a crystalline ethylene polymer,
(B) 0 to 25% by mass of a crystalline propylene polymer,
(C) at least two polymer blocks (c ′) mainly composed of an aromatic vinyl compound and at least one polymer block (c ″) mainly composed of a conjugated diene compound. A block copolymer (c-0) and / or a hydrogenated block copolymer (c-1) obtained by hydrogenating the block copolymer and a non-aromatic rubber softener (c-2) 0 to 65% by mass of an elastomer composition, and (d) 2 to 20% by mass of an acid-modified polyolefin
A flame retardant resin composition for mixing with a silane crosslinkable polyolefin is provided.
また、本発明の第４の態様によれば、第１〜第３のいずれかの態様において、更に、押出成形用であることを特徴とする、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物が提供される。 According to the fourth aspect of the present invention, in any one of the first to third aspects, the flame-retardant resin for mixing with a silane-crosslinkable polyolefin, which is further for extrusion molding A composition is provided.
また、本発明の第５の態様によれば、第１〜第４のいずれかの態様において、前記成分（Ａ）１００質量部に対し、（ｈ）架橋助剤０．０１〜１．５質量部をさらに含有することを特徴とする、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物が提供される。 According to the fifth aspect of the present invention, in any one of the first to fourth aspects, (h) 0.01 to 1.5 parts by mass of a crosslinking aid with respect to 100 parts by mass of the component (A). A flame retardant resin composition for mixing with a silane crosslinkable polyolefin, characterized by further containing a part.
また、本発明の第５の態様によれば、第１〜第５のいずれかの態様において、前記成分（Ａ）１００質量部に対し、（ｉ）銅害防止剤０．０１〜４質量部をさらに含むことを特徴とする、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物が提供される。 Moreover, according to the 5th aspect of this invention, in any one of the 1st-5th aspect, (i) copper damage inhibitor 0.01-4 mass parts with respect to 100 mass parts of said components (A). A flame retardant resin composition for mixing with a silane crosslinkable polyolefin is further provided.
また、本発明の第６の態様によれば、第１〜第６のいずれかの態様において得られた、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物と、シラン架橋性ポリオレフィン（Ｂ）とを、前者：後者として５：５〜９：１の重量比で押出成形してなることを特徴とする成形体が提供される。 Moreover, according to the 6th aspect of this invention, the flame-retardant resin composition for mixing with the silane crosslinkable polyolefin obtained in any one of the 1st-6th aspects, and silane crosslinkable polyolefin (B) ) In the weight ratio of 5: 5 to 9: 1 as the former: the latter is provided.
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物は、難燃性が良好で、さらに柔軟性および耐熱性を高い次元で両立させた難燃性樹脂組成物であるので、これらの特性を生かし、これらの特性を要求される様々な用途に好適に使用出来、特に電線被覆用材料として最適に用いることが出来る。 Since the flame-retardant resin composition for mixing with the silane-crosslinkable polyolefin of the present invention is a flame-retardant resin composition having good flame retardancy and further having both flexibility and heat resistance at a high level, Taking advantage of these characteristics, it can be suitably used for various applications that require these characteristics, and in particular, can be optimally used as a wire coating material.
［１．各成分について］
［成分（Ａ）］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物において用いられる成分（Ａ）としては、熱可塑性樹脂、ゴム、および熱可塑性エラストマーが挙げられ、エチレン系重合体（エチレン単独重合体、エチレン−α・オレフィン共重合体、エチレン−（メタ）アクリル酸系共重合体、エチレン−（メタ）アクリル酸エステル系共重合体、エチレン−酢酸ビニル系共重合体等）、プロピレン系重合体（プロピレン単独重合体、プロピレン−α・オレフィン（エチレン、ブテン等）ブロック共重合体、プロピレン−α・オレフィン（エチレン、ブテン等）ランダム共重合体、リアクターＴＰＯ等）、スチレン系エラストマー（芳香族ビニル化合物と共役ジエン化合物との共重合体（スチレン・ブタジエン共重合体（ＳＢＲ）、水添スチレン・ブタジエン共重合体（Ｈ−ＳＢＲ）、スチレン−ブタジエン−スチレン共重合体（ＳＢＳ）、スチレン−エチレン・ブテン−スチレン共重合体（ＳＥＢＳ）、スチレン−エチレン・エチレン・プロピレン−スチレン共重合体（ＳＥＥＰＳ）、スチレン−エチレン・プロピレン−スチレン共重合体（ＳＥＰＳ）、部分水添スチレン−ブタジエン−スチレン共重合体（ＳＢＢＳ）、スチレン−イソブチレン−スチレン共重合体（ＳＩＢＳ）等の単体またはオレフィン系重合体等とのアロイ等）、オレフィン系エラストマー（エチレン系ゴム（ＥＰＲ、ＥＢＲ、ＥＰＤＭ等）の単体またはプロピレン系重合体とのアロイ等）、変性ポリオレフィン等が挙げられる。
その中でも、前記成分（Ａ）が、
（ａ）結晶性エチレン系重合体１０〜８０質量％、
（ｂ）結晶性プロピレン系重合体０〜２５質量％、
（ｃ）芳香族ビニル化合物をその構成成分の主体とした少なくとも２個の重合体ブロック（ｃ’）と共役ジエン化合物をその構成成分の主体とした少なくとも１個の重合体ブロック（ｃ”）とからなるブロック共重合体（ｃ−０）及び／またはこれを水素添加して得られる水添ブロック共重合体（ｃ−１）と、非芳香族系ゴム用軟化剤（ｃ−２）とからなるエラストマー組成物０〜６５質量％、および
（ｄ）酸変性ポリオレフィン２〜２０質量％
を含むことがより好ましい。
［（ａ）結晶性エチレン系重合体］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物において用いられる結晶性エチレン系重合体（ａ）成分は、引張強度保持に有用な成分である。結晶性エチレン系重合体（ａ）としては、超低密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン等のエチレン単独重合体；又はエチレンと他のα-オレフィンとの共重合体、エチレン-酢酸ビニル共重合体、エチレン-（メタ）アクリル酸エステル共重合体、エチレン−（メタ）アクリル酸共重合体等の共重合体等が挙げられるが、柔軟性及び引張強度の観点から、メタロセン触媒存在下に合成されたエチレン-α−オレフィン共重合体が好ましい。結晶性エチレン系重合体（ａ）の密度は、柔軟性を考慮すると０．９１５ｇ／ｃｍ３以下が好ましく、更に好ましくは密度０．９０５ｇ／ｃｍ３以下である。また、引張強度を考慮すると０．８７０ｇ／ｃｍ３以上が好ましく、さらに好ましくは０．８８０ｇ／ｃｍ３以上である。
また、更にエチレン-α・オレフィン共重合体の中でも、メルトマスフローレート（ＪＩＳ Ｋ６９２４−２準拠、１９０℃、荷重２．１６kgで測定）が１〜２０ｇ／１０分のものが好ましい。
結晶性エチレン系重合体（ａ）の配合量は、成分（Ａ）中１０〜８０質量％、好ましくは１５〜７５質量％である。１０質量％未満では強度が低下し、８０質量％より多いと押出特性が著しく低下する。
[1. About each component]
[Component (A)]
Examples of the component (A) used in the flame retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention include thermoplastic resins, rubbers, and thermoplastic elastomers. , Ethylene-α / olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-vinyl acetate copolymer, etc.), propylene heavy polymer Polymer (propylene homopolymer, propylene-α / olefin (ethylene, butene, etc.) block copolymer, propylene-α / olefin (ethylene, butene, etc.) random copolymer, reactor TPO, etc.), styrene elastomer (aromatic Copolymer of vinyl compound and conjugated diene compound (styrene / butadiene copolymer (SBR), hydrogenated) Tylene-butadiene copolymer (H-SBR), styrene-butadiene-styrene copolymer (SBS), styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-ethylene / propylene-styrene copolymer (SEPS), partially hydrogenated styrene-butadiene-styrene copolymer (SBBS), styrene-isobutylene-styrene copolymer (SIBS), etc. An alloy with a polymer, etc.), an olefin elastomer (an ethylene rubber (EPR, EBR, EPDM, etc.) or an alloy with a propylene polymer), a modified polyolefin, and the like.
Among them, the component (A) is
(A) 10 to 80% by mass of a crystalline ethylene polymer,
(B) 0 to 25% by mass of a crystalline propylene polymer,
(C) at least two polymer blocks (c ′) mainly composed of an aromatic vinyl compound and at least one polymer block (c ″) mainly composed of a conjugated diene compound. A block copolymer (c-0) and / or a hydrogenated block copolymer (c-1) obtained by hydrogenating the block copolymer and a non-aromatic rubber softener (c-2) 0 to 65% by mass of an elastomer composition, and (d) 2 to 20% by mass of an acid-modified polyolefin
It is more preferable to contain.
[(A) Crystalline ethylene polymer]
The crystalline ethylene polymer (a) component used in the flame-retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention is a component useful for maintaining tensile strength. Examples of the crystalline ethylene polymer (a) include ethylene homopolymers such as ultra-low density polyethylene, low density polyethylene, and linear low density polyethylene; or copolymers of ethylene and other α-olefins, ethylene- Examples include vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, and copolymers such as ethylene- (meth) acrylic acid copolymers. From the viewpoint of flexibility and tensile strength, metallocene catalysts An ethylene-α-olefin copolymer synthesized in the presence is preferred. The density of the crystalline ethylene polymer (a) is preferably from 0.915 g / cm 3 or less in consideration of the flexibility, more preferably not more than density 0.905 g / cm 3. In consideration of tensile strength, it is preferably 0.870 g / cm 3 or more, more preferably 0.880 g / cm 3 or more.
Further, among ethylene-α / olefin copolymers, those having a melt mass flow rate (measured at JIS K6924-2, 190 ° C., load 2.16 kg) of 1 to 20 g / 10 min are preferable.
The compounding quantity of crystalline ethylene polymer (a) is 10-80 mass% in a component (A), Preferably it is 15-75 mass%. If it is less than 10% by mass, the strength is lowered, and if it is more than 80% by mass, the extrusion characteristics are significantly lowered.
［（ｂ）結晶性プロピレン系重合体］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物において必要に応じて用いられる結晶性プロピレン系重合体（ｂ）成分は、過酸化物による架橋時において、本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物の熱可塑性を保持する機能を有する。
（ｂ）結晶性プロピレン系重合体としては、プロピレン単独重合体、プロピレン−α・オレフィン（エチレン、ブテン等）ブロック共重合体、プロピレン−α・オレフィン（エチレン、ブテン等）ランダム共重合体、リアクターＴＰＯ等が挙げられる。
成分（ｂ）の配合量は、成分（Ａ）中０〜２５質量％であり、好ましくは０〜２０質量％である。これが２５質量％より多いと、得られる組成物が硬過ぎ、目的とする柔軟性が得られない。
[(B) Crystalline propylene polymer]
The crystalline propylene polymer (b) component used as necessary in the flame-retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention is the silane of the present invention at the time of crosslinking with a peroxide. It has a function of maintaining the thermoplasticity of the flame retardant resin composition for mixing with the crosslinkable polyolefin.
(B) As a crystalline propylene polymer, a propylene homopolymer, a propylene-α-olefin (ethylene, butene, etc.) block copolymer, a propylene-α-olefin (ethylene, butene, etc.) random copolymer, a reactor TPO etc. are mentioned.
The compounding quantity of a component (b) is 0-25 mass% in a component (A), Preferably it is 0-20 mass%. When this is more than 25% by mass, the resulting composition is too hard and the desired flexibility cannot be obtained.
［（ｃ）エラストマー組成物］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物において必要に応じて用いられるエラストマー組成物（ｃ）成分は、芳香族ビニル化合物を主体とした少なくとも２個の重合体ブロック（ｃ’）と共役ジエン化合物を主体とした少なくとも１個の重合体ブロック（ｃ”）とからなるブロック共重合体（ｃ−０）及び／またはこれを水素添加して得られる水添ブロック共重合体（ｃ−１）と、非芳香族系ゴム用軟化剤（ｃ−２）とからなるエラストマー組成物である。成分（ｃ）において、（ｃ−１）は柔軟性の付与及び非芳香族系ゴム用軟化剤（ｃ−２）の保持を目的とし、（ｃ−２）は柔軟性の付与を目的とした成分である。
成分（ｃ）の配合量は、成分（Ａ）中０〜６５質量％である。これが６５質量％より多いと力学的強度が大きく低下する。
[(C) Elastomer composition]
The elastomer composition (c) component used as necessary in the flame-retardant resin composition for mixing with the silane-crosslinkable polyolefin of the present invention comprises at least two polymer blocks mainly composed of an aromatic vinyl compound ( a block copolymer (c-0) consisting of c ′) and at least one polymer block (c ″) mainly composed of a conjugated diene compound and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer (c-0) It is an elastomer composition comprising a coalescence (c-1) and a non-aromatic rubber softener (c-2), wherein in component (c), (c-1) is imparting flexibility and non-aromatic. (C-2) is a component for the purpose of retaining the softening agent (c-2) for the base rubber.
The compounding quantity of a component (c) is 0-65 mass% in a component (A). When this is more than 65% by mass, the mechanical strength is greatly reduced.
［（ｄ）変性ポリオレフィン］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物において用いられる変性ポリオレフィン（ｄ）成分は、引張強度及び耐摩耗性を向上させる機能を有する。
例えば、プロピレン系重合体（プロピレン単独重合体、プロピレン−α・オレフィン（エチレン、ブテン等）ブロック共重合体、プロピレン−α・オレフィン（エチレン、ブテン等）ランダム共重合体、リアクターＴＰＯ等）、エチレン系重合体（エチレン単独重合体、エチレン−α・オレフィン共重合体、エチレン−（メタ）アクリル酸系共重合体、エチレン−（メタ）アクリル酸エステル系共重合体、エチレン−酢酸ビニル系共重合体等）等を変性し、例えば、エステル基、エポキシ基、カルボキシル基、カルボニル基、水酸基等から選ばれる１種以上の官能基を有している化合物により変性されたものが挙げられる。これらの中でも、カルボキシル基及びカルボニル基を有している化合物により変性されたエチレン系重合体が好ましい。
成分（ｄ）の配合量は、成分（Ａ）中２〜２０質量％であり、好ましくは５〜１２質量％である。これが２０質量％より多いと、得られる組成物が硬過ぎ、熱可塑性も不充分になりやすく、２質量％より少ないと、引張強度及び耐摩耗性が低下する。
[(D) Modified polyolefin]
The modified polyolefin (d) component used in the flame-retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention has a function of improving tensile strength and wear resistance.
For example, propylene polymer (propylene homopolymer, propylene-α / olefin (ethylene, butene, etc.) block copolymer, propylene-α / olefin (ethylene, butene, etc.) random copolymer, reactor TPO, etc.), ethylene Polymer (ethylene homopolymer, ethylene-α / olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene-vinyl acetate copolymer) For example, those modified with a compound having at least one functional group selected from an ester group, an epoxy group, a carboxyl group, a carbonyl group, a hydroxyl group and the like. Among these, an ethylene polymer modified with a compound having a carboxyl group and a carbonyl group is preferable.
The compounding quantity of a component (d) is 2-20 mass% in a component (A), Preferably it is 5-12 mass%. If the amount is more than 20% by mass, the resulting composition is too hard and the thermoplasticity tends to be insufficient, and if it is less than 2% by mass, the tensile strength and the wear resistance are lowered.
［（ｅ）有機過酸化物］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物において用いられる有機過酸化物（ｅ）成分は、ラジカルを発生せしめ、そのラジカルが連鎖的に反応して、成分（ａ）及び（ｃ）を部分架橋せしめ、得られる組成物の引張強度及び耐熱性を向上させる働きをする。
例えば、ジクミルパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３、１，３−ビス（ｔｅｒｔ−ブチルパーオキシイソプロピル）ベンゼン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルパーオキシ）バレレート、ベンゾイルパーオキサイド、ｐ−クロロベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド、ｔｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブチルパーオキシイソプロピルカーボネート、ジアセチルパーオキサイド、ラウロイルパーオキサイド、ｔｅｒｔ‐ブチルクミルパーオキサイドなどを挙げることができる。
これらのうち、臭気性、着色性、スコーチ安定性の点で、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチル−２，５−ジ−（ｔｅｒｔ−ブチルペルオキシ）ヘキシン−３が最も好ましい。
成分（ｅ）の配合量は、成分（Ａ）１００質量部に対して０．０１〜０．６質量部であり、好ましくは０．０５〜０．５質量部である。これが０．６質量部より多いと、架橋が過剰となり熱可塑性を失う。また、０．０１質量部より少ないと架橋を充分達成できず、引張強度に劣る。
[(E) Organic peroxide]
The organic peroxide (e) component used in the flame-retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention generates a radical, and the radical reacts in a chain reaction to form the component (a). And (c) is partially crosslinked, and functions to improve the tensile strength and heat resistance of the resulting composition.
For example, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert- Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4, 4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide Lauroyl peroxide , And the like tert- butyl cumyl peroxide.
Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- in terms of odor, colorability, and scorch stability. (Tert-Butylperoxy) hexyne-3 is most preferred.
The compounding quantity of a component (e) is 0.01-0.6 mass part with respect to 100 mass parts of components (A), Preferably it is 0.05-0.5 mass part. When this is more than 0.6 parts by mass, the crosslinking becomes excessive and the thermoplasticity is lost. Moreover, when less than 0.01 mass part, bridge | crosslinking cannot fully be achieved but it is inferior to tensile strength.
［（ｆ）シラノール縮合触媒］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物において用いられるシラノール縮合触媒（ｆ）成分は、本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物とシラン架橋性ポリオレフィン（Ｂ）とを混合、押出成形して得られる成形品を水分と接触させた際、（Ｂ）をシラン架橋させる反応を触媒する働きを有する。
シラノール縮合触媒（ｆ）は、シリコーンのシラノール間の脱水縮合反応を促進する触媒として使用されるものであり、その例としては、ジブチルスズジラウレート、ジブチルスズジアセテート、ジブチルスズジオレエート、酢酸第一錫、ナフテン酸鉛、ナフテン酸コバルト、カプリル酸亜鉛、２−エチルヘキサン酸鉄、チタン酸エステル、チタン酸テトラブチルエステル、チタン酸テトラノニルエステル、ビス（アセチルアセトニトリル）ジ−イソプロピルチタン−エチルアミン錯体、ヘキシルアミン錯体、ジブチルアミン錯体、ピリジン錯体等が挙げられる。
成分（ｆ）の配合量は、成分（Ａ）１００質量部に対して０．０５〜０．５質量部であり、好ましくは０．１〜０．４質量部である。これが０．５質量部より多いと、本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物と成分（Ｂ）とを混合、押出成形した際、架橋が部分的に過剰となり、スコーチが発生し、押出外観が悪化する。また、０．０５質量部より少ないと、シラン架橋させた際、架橋が不充分であり、目的とする耐熱性が得られない。
[(F) Silanol condensation catalyst]
The silanol condensation catalyst (f) component used in the flame retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention is composed of the flame retardant resin composition for mixing with the silane crosslinkable polyolefin and the silane of the present invention. When a molded product obtained by mixing and extruding the crosslinkable polyolefin (B) is brought into contact with moisture, it functions to catalyze the reaction of crosslinking (B) with silane.
The silanol condensation catalyst (f) is used as a catalyst for promoting a dehydration condensation reaction between silicone silanols, and examples thereof include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioleate, stannous acetate, Lead naphthenate, cobalt naphthenate, zinc caprylate, iron 2-ethylhexanoate, titanate, tetrabutyl titanate, tetranonyl titanate, bis (acetylacetonitrile) di-isopropyltitanium-ethylamine complex, hexylamine A complex, a dibutylamine complex, a pyridine complex, etc. are mentioned.
The compounding quantity of a component (f) is 0.05-0.5 mass part with respect to 100 mass parts of component (A), Preferably it is 0.1-0.4 mass part. When this is more than 0.5 parts by mass, when the flame-retardant resin composition for mixing with the silane crosslinkable polyolefin and the component (B) of the present invention are mixed and extruded, the crosslinking becomes partially excessive, Scorch occurs and the extrusion appearance deteriorates. On the other hand, when the amount is less than 0.05 parts by mass, when silane crosslinking is performed, crosslinking is insufficient and the desired heat resistance cannot be obtained.
［（ｇ）金属水和物］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物において用いられる金属水和物（ｇ）成分は、無機系難燃剤として配合されるものであって、特に限定はしないが、例えば、水酸化マグネシウム、水酸化アルミニウム、水酸化カリウム、水酸化カルシウム、水和珪酸マグネシウム、塩基性炭酸マグネシウム、ハイドロタルサイトなどの水酸化物イオンまたは結晶水を有する化合物を、単独もしくは２種以上を組み合わせて使用することができる。これらの中では、難燃性の面、及び熱分解開始温度と本発明の組成物の製造温度や成形温度との関係から、水酸化マグネシウムが好ましい。
成分（ｇ）の配合量は、成分（Ａ）に対して、１００〜３００質量部であり、好ましくは１１０〜２００質量部である。これが、３００質量部より多いと、得られるシラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物の流動性が著しく低下し、シラン架橋性ポリオレフィン（Ｂ）と混合、成形した際、得られたシラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物および（Ｂ）の分散不足となり、得られる成形品の良好な外観が得られないばかりか、力学的強度も著しく低下する。また、押出負荷も上昇し、押出成形性も悪化する。逆に、１００質量部より少ないと、充分な難燃性が得られない。
[(G) Metal hydrate]
The metal hydrate (g) component used in the flame-retardant resin composition for mixing with the silane-crosslinkable polyolefin of the present invention is blended as an inorganic flame retardant and is not particularly limited. For example, a compound having hydroxide ions or crystal water such as magnesium hydroxide, aluminum hydroxide, potassium hydroxide, calcium hydroxide, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, alone or in combination. Can be used in combination. Among these, magnesium hydroxide is preferable from the viewpoint of flame retardancy and the relationship between the thermal decomposition start temperature and the production temperature and molding temperature of the composition of the present invention.
The compounding quantity of a component (g) is 100-300 mass parts with respect to a component (A), Preferably it is 110-200 mass parts. When this is more than 300 parts by mass, the fluidity of the resulting flame-retardant resin composition for mixing with the silane crosslinkable polyolefin is remarkably lowered, and obtained when mixed and molded with the silane crosslinkable polyolefin (B). Insufficient dispersion of the flame retardant resin composition for mixing with the silane crosslinkable polyolefin and (B) results in not only obtaining a good appearance of the resulting molded product, but also significantly reducing the mechanical strength. Also, the extrusion load increases and the extrusion moldability deteriorates. Conversely, if the amount is less than 100 parts by mass, sufficient flame retardancy cannot be obtained.
［シラン架橋性ポリオレフィン（Ｂ）］
本発明のシラン架橋性ポリオレフィン（Ｂ）成分は、本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物と混合、押出成形時に水分と接触した際、シラン架橋することにより、得られる成形物の耐熱性を向上させる機能を有する。
成分（Ｂ）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-酢酸ビニル系共重合体、エチレン-（メタ）アクリル酸エステル系共重合体、ポリブテン等の、オレフィンの単独又は共重合体等のポリオレフィン系樹脂を、オルガノシランで変性したものを挙げることができる。ポリオレフィンとしては、柔軟性および引張強度の観点から、ポリエチレンが好ましい。密度は柔軟性を考慮すると０．９５０ｇ／ｃｍ３以下が好ましく、更に好ましくは密度０．９３０ｇ／ｃｍ３以下である。また、引張強度を考慮すると０．８９０ｇ／ｃｍ３以上でありさらに好ましくは０．９００ｇ／ｃｍ３以上である。
[Silane-crosslinking polyolefin (B)]
The silane crosslinkable polyolefin (B) component of the present invention is obtained by silane crosslinking when mixed with the flame retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention and in contact with moisture during extrusion molding. It has a function of improving the heat resistance of the molded product.
Component (B) includes polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate ester copolymer, polybutene, etc. Examples thereof include those obtained by modifying polyolefin resins such as coalescence with organosilane. As the polyolefin, polyethylene is preferable from the viewpoints of flexibility and tensile strength. Density is preferably Considering 0.950 g / cm 3 or less flexibility, and still more preferably a density 0.930 g / cm 3 or less. Further, considering the tensile strength, it is 0.890 g / cm 3 or more, more preferably 0.900 g / cm 3 or more.
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物と成分（Ｂ）を混合、押出成形する際の混合比は、前者：後者として５：５〜９：１の質量比であり、好ましくは７：３〜８：２の質量比である。成分（Ｂ）の割合が５割より多いと押出外観が悪化し、充分な難燃性が得られず、１割より少ないと充分な耐熱性が得られない。 The mixing ratio when mixing and extruding the flame retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention and the component (B) is a mass ratio of 5: 5 to 9: 1 as the former: the latter. Yes, preferably a mass ratio of 7: 3 to 8: 2. When the ratio of the component (B) is more than 50%, the extrusion appearance is deteriorated and sufficient flame retardancy cannot be obtained, and when it is less than 10%, sufficient heat resistance cannot be obtained.
［（ｈ）架橋助剤］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物には、必要に応じて架橋助剤（ｈ）成分を配合することができる。架橋助剤（ｈ）は、有機過酸化物（ｅ）の配合に際し用いることができ、これにより、さらに均一かつ効率的な、過酸化物による架橋反応を行うことができる。
成分（ｈ）の配合量は、添加する場合は成分（Ａ）１００質量部に対して０．０１〜１．５質量部が好ましく、より好ましくは０．１〜１質量部である。１．５質量部を超えると、架橋が進みすぎて熱可塑性を失ったり、分散が悪くなったりする。また架橋助剤（ｈ）の自己架橋物による外観不良も起こりやすい。
[(H) Crosslinking aid]
In the flame retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention, a crosslinking assistant (h) component can be blended if necessary. The crosslinking aid (h) can be used in the blending of the organic peroxide (e), whereby a more uniform and efficient crosslinking reaction with the peroxide can be performed.
The amount of component (h) to be added is preferably 0.01 to 1.5 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of component (A). If the amount exceeds 1.5 parts by mass, the crosslinking proceeds so much that the thermoplasticity is lost or the dispersion is deteriorated. Further, poor appearance due to the self-crosslinked product of the crosslinking aid (h) is likely to occur.
［（ｉ）銅害防止剤］
銅害防止剤としては、銅イオンなどの重金属イオンとキレート化合物を形成し、ポリマー中のハイドロパーオキサイドの重金属イオンによる接触分解を防止する化合物、例えば、シュウ酸、サリチル酸などをアミド化した誘導体、ヒドラジン化合物を配合することが出来る。サリチル酸誘導体としては、旭電化工業から、ＣＤＡ−１，ＣＤＡ−６等が市販され、ヒドラジン化合物としては、チバガイギーからＩＲＧＡＮＯＸ ＭＤ１０２４等が市販されている。
成分（ｉ）の配合量は、添加する場合は成分（Ａ）１００質量部に対して０．０１〜４質量部が好ましく、より好ましくは０．０５〜３質量部である。４質量部を超えると、ブルームがおこり好ましくない。
[(I) Copper damage inhibitor]
As a copper damage preventive agent, a compound that forms a chelate compound with a heavy metal ion such as copper ion and prevents catalytic decomposition of the hydroperoxide in the polymer by the heavy metal ion, for example, a derivative obtained by amidating oxalic acid, salicylic acid, etc. A hydrazine compound can be blended. As salicylic acid derivatives, CDA-1, CDA-6 and the like are commercially available from Asahi Denka Kogyo, and IRGANOX MD1024 and the like are commercially available from Ciba Geigy as hydrazine compounds.
The amount of component (i) is preferably 0.01 to 4 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of component (A) when added. If it exceeds 4 parts by mass, bloom occurs, which is not preferable.
［（ｊ）その他の成分］
なお、本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物においては、本発明の目的を損なわない範囲で、熱安定剤、酸化防止剤、光安定剤、紫外線吸収剤、結晶核剤、ブロッキング防止剤、シール性改良剤、ステアリン酸、シリコーンオイル等の離型剤、ポリエチレンワックス等の滑剤、着色剤、顔料、アルミナ等の無機充填剤、発泡剤（有機系、無機系及びマイクロカプセル系）、難燃剤（赤燐、ポリ燐酸アンモニウム、アンチモン及びシリコーン）等を配合することができる。
酸化防止剤としては、例えば、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール、２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，４−ジメチル−６−ｔｅｒｔ−ブチルフェノール、４，４’−ジヒドロキシジフェニル、トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン等のフェノール系酸化防止剤；ホスファイト系酸化防止剤；チオエーテル系酸化防止剤等が挙げられる。これらのうち、フェノール系酸化防止剤及びホスファイト系酸化防止剤が特に好ましい。
[(J) Other ingredients]
In the flame-retardant resin composition for mixing with the silane-crosslinkable polyolefin of the present invention, a heat stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a crystal, and the like as long as the object of the present invention is not impaired. Nucleating agent, anti-blocking agent, sealability improver, mold release agent such as stearic acid and silicone oil, lubricant such as polyethylene wax, colorant, pigment, inorganic filler such as alumina, foaming agent (organic, inorganic and Microcapsules), flame retardants (red phosphorus, ammonium polyphosphate, antimony and silicone) and the like can be blended.
Examples of the antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, and 4,4′-dihydroxy. Examples thereof include phenolic antioxidants such as diphenyl and tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; phosphite antioxidants; thioether antioxidants. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred.
［２．本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物の製造について］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物は、上記（ａ）〜（ｇ）成分、または必要に応じて（ｈ）〜（ｊ）成分を配合し、１５０〜２４０℃の混練温度にて、混練装置にて溶融混練または溶融混合して得ることができる。
本発明で使用する混練装置としては、加圧ニーダー、バンバリーミキサー、単軸押出機、２軸押出機、多軸押出機等を使用することが出来る。加圧ニーダー、バンバリー等のバッチ式混練装置で混練する方法が好ましい。連続的に行う場合には、バッチ式混練装置と押出機とが組み合わされた、例えば、加圧ニーダーと押出機とが組合わされた装置（バッチ供給型連続押出装置）で混練する方法が好ましい。
[2. Production of flame retardant resin composition for mixing with silane crosslinkable polyolefin of the present invention]
The flame-retardant resin composition for mixing with the silane-crosslinkable polyolefin of the present invention contains the above components (a) to (g) or, if necessary, the components (h) to (j), and 150 to 240 It can be obtained by melt-kneading or melt-mixing in a kneading apparatus at a kneading temperature of ° C.
As a kneading apparatus used in the present invention, a pressure kneader, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder, or the like can be used. A method of kneading with a batch kneader such as a pressure kneader or Banbury is preferred. When performing continuously, the method of kneading | mixing with the apparatus (batch supply type | mold continuous extrusion apparatus) with which the batch type kneading apparatus and the extruder were combined, for example, the pressure kneader and the extruder was combined is preferable.
［３．本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物の用途について］
本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物は、難燃性が良好で、柔軟性及び耐熱性を高い次元で両立した難燃性樹脂組成物であるので、用途としては、押出成形で成形される電線被覆、自動車等車輛用内外装材、建築用内外装材、自動車等車輛、電気機器、建築物等のガスケット（パッキング、目地剤、シール材を含む）等の各種成形品、テープ、粘着テープ、ホース、パイプ、シート、チューブ、熱収縮チューブ、フラットケーブル被覆等が挙げられるが、特に自動車のエンジンルーム内等にて使用される、非常に高い耐熱性が必要な電線の被覆用材料にも応用が可能である。
[3. Use of flame retardant resin composition for mixing with silane crosslinkable polyolefin of the present invention]
The flame retardant resin composition for mixing with the silane crosslinkable polyolefin of the present invention is a flame retardant resin composition having good flame retardancy and having both flexibility and heat resistance at a high level. Such as wire coverings formed by extrusion molding, interior and exterior materials for vehicles such as automobiles, interior and exterior materials for buildings, vehicles such as automobiles, electrical equipment, and building gaskets (including packing, joint agents and sealants), etc. Various molded products, tapes, adhesive tapes, hoses, pipes, sheets, tubes, heat-shrinkable tubes, flat cable covers, etc. are mentioned, but extremely high heat resistance, especially used in the engine room of automobiles, is required The present invention can also be applied to a material for covering a simple electric wire.
以下、実施例及び比較例により本発明を更に説明するが、本発明はこれらに限定されるものではない。なお、実施例における評価方法及び使用した材料を、まず以下に示す。 Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. In addition, the evaluation method and the used material in an Example are first shown below.
［１．難燃性樹脂組成物の各種物性の評価方法］
（１）引張強さ、引張伸び及び１００％モジュラス：
ＪＩＳ Ｋ ７１１３に準拠し、２ｍｍ厚の押出成形したテープを８０℃にて２４時間温水処理したものを、２号ダンベル型試験片に打ち抜いて使用した。引張速度は、室温にて２００ｍｍ/分とした。
（２）柔軟性：
幅２０mm、厚み２mmの押し出しテープを長さ２００mmに切断し、端から５０mmを水平に固定し、先端に２０gのおもりをつけた時の押し出しテープのたわみ量によって表した。
（３）押出外観：
該押出テープの表面外観を目視にて確認し、外観が良好なものは○、外観が悪いものは×として評価した。
（４）加熱変形率：
ＪＩＳ Ｃ ３００５に準拠し、２ｍｍ厚の該押出テープを８０℃にて２４時間温水処理したものから、試験片に打ち抜いて使用した。試験温度は１７５℃とし、荷重は１ｋｇとした。
（５）ゲル分率：
ＪＡＳＯ Ｄ ６０８のＡＥＸのゲル分率測定方法に準拠し、試験片は、２ｍｍ厚の該押出テープを８０℃×２４時間温水処理したものから０．１ｇ量り取り使用した。
[1. Evaluation method of various physical properties of flame retardant resin composition]
(1) Tensile strength, tensile elongation and 100% modulus:
In accordance with JIS K 7113, a 2 mm-thick extruded tape treated with warm water at 80 ° C. for 24 hours was punched into a No. 2 dumbbell-shaped test piece and used. The tensile speed was 200 mm / min at room temperature.
(2) Flexibility:
The extruded tape having a width of 20 mm and a thickness of 2 mm was cut into a length of 200 mm, 50 mm from the end was fixed horizontally, and expressed by the amount of deflection of the extruded tape when a 20 g weight was attached to the tip.
(3) Extrusion appearance:
The surface appearance of the extruded tape was visually confirmed, and those having a good appearance were evaluated as ◯, and those having a poor appearance were evaluated as ×.
(4) Heat deformation rate:
According to JIS C 3005, the extruded tape having a thickness of 2 mm was subjected to hot water treatment at 80 ° C. for 24 hours, and then used by punching it into a test piece. The test temperature was 175 ° C. and the load was 1 kg.
(5) Gel fraction:
In accordance with the AEX gel fraction measurement method of JASO D 608, 0.1 g of a test piece was used by weighing 2 mm of the extruded tape after warm water treatment at 80 ° C. for 24 hours.
［２．各種評価試験に使用した材料について］
成分（ａ）については、
（ａ−１）メタロセン系触媒使用直鎖状低密度ポリエチレン：カーネルＫＦ２７１（日本ポリケム社製）、密度０．９１３ｇ／ｃｍ３、ＭＦＲ２．４ｇ／１０分；
（ａ−２）メタロセン系触媒使用直鎖状低密度ポリエチレン：カーネルＫＳ５６０（日本ポリケム社製）、密度０．８９８ｇ／ｃｍ３、ＭＦＲ１６．０ｇ／１０分；
（ａ−３）メタロセン系触媒使用直鎖状低密度ポリエチレン：カーネルＫＳ２４０（日本ポリケム社製）、密度０．８８０ｇ／ｃｍ３、ＭＦＲ２．２ｇ／１０分；
成分（ｂ）については、
（ｂ）結晶性プロピレン系ランダム共重合体：ＦＷ３Ｅ（日本ポリケム社製）、ＭＦＲ７ｇ／１０分、Ｔｍ１４０℃；
成分（ｃ）については、
（ｃ−１）水添ブロック共重合体成分：セプトン４０７７（クラレ株式会社製）、スチレン含有量：３０質量％、数平均分子量：２６０,０００、重量平均分子量：３２０，０００、分子量分布：１．２３、水素添加率：９０％以上；
（ｃ−２）パラフィンオイル：ダイアナプロセスオイルＰＷ−９０（出光興産株式会社製）、動的粘度（４０℃、９５．５４ｃｓｔ）（１００℃、１１．２５ｃｓｔ）、流動点―１５℃；
成分（ｄ）については、
（ｄ）無水マレイン酸変性ポリエチレン：アドマーＸＥ０７０（三井化学社製）ＭＦＲ１ｇ／１０分；
成分（ｅ）については、
（ｅ）有機過酸化物：パーヘキサ２５Ｂ（日本油脂株式会社製）、１分半減期温度１７９℃；
成分（ｆ）については、
（ｆ）シラノール縮合触媒：ＴＮ-１２（堺化学工業株式会社製：ジブチルスズラウレート）；
成分（ｇ）については、
（ｇ）シランカップリング処理水酸化マグネシウム：キスマ５Ｌ（協和化学株式会社製）；
成分（ｈ）については、
（ｈ）架橋助剤：ＮＫエステルＩＮＤ ２−メチル−１，８オクタンジオールジメタクリレート８５％および１，９−ノナンジオールジメタクリレート１５％（新中村化学株式会社製）；
成分（ｉ）については、
（ｉ）銅害防止剤：ＭＡＲＫ ＣＤＡ−１ 、３−（Ｎ−サリチロイル）アミノ−１，２，４−トリアゾール（旭電化株式会社製）；
成分（Ｂ）については、
（Ｂ）シラン架橋性ポリエチレン：リンクロンＸＦ−８００Ｔ（三菱化学株式会社製）、密度９２４ｋｇ／ｍ３、ＭＦＲ０．８ｇ／１０分
を使用した。
[2. About materials used in various evaluation tests]
For component (a)
(A-1) Linear low-density polyethylene using metallocene catalyst: Kernel KF271 (manufactured by Nippon Polychem), density 0.913 g / cm 3 , MFR 2.4 g / 10 min;
(A-2) Linear low-density polyethylene using metallocene catalyst: Kernel KS560 (manufactured by Nippon Polychem), density 0.898 g / cm 3 , MFR 16.0 g / 10 min;
(A-3) Linear low-density polyethylene using metallocene-based catalyst: Kernel KS240 (manufactured by Nippon Polychem), density 0.880 g / cm 3 , MFR 2.2 g / 10 min;
For component (b)
(B) Crystalline propylene random copolymer: FW3E (manufactured by Nippon Polychem), MFR 7 g / 10 min, Tm 140 ° C .;
For component (c):
(C-1) Hydrogenated block copolymer component: Septon 4077 (manufactured by Kuraray Co., Ltd.), styrene content: 30% by mass, number average molecular weight: 260,000, weight average molecular weight: 320,000, molecular weight distribution: 1 .23, hydrogenation rate: 90% or more;
(C-2) Paraffin oil: Diana process oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.), dynamic viscosity (40 ° C., 95.54 cst) (100 ° C., 11.25 cst), pour point—15 ° C .;
For component (d):
(D) Maleic anhydride-modified polyethylene: Admer XE070 (manufactured by Mitsui Chemicals) MFR 1 g / 10 min;
For component (e),
(E) Organic peroxide: Perhexa 25B (manufactured by NOF Corporation), 1 minute half-life temperature of 179 ° C .;
For component (f)
(F) Silanol condensation catalyst: TN-12 (manufactured by Sakai Chemical Industry Co., Ltd .: dibutyltin laurate);
For component (g),
(G) Silane coupling treatment magnesium hydroxide: Kisuma 5L (manufactured by Kyowa Chemical Co., Ltd.);
For ingredient (h)
(H) Crosslinking assistant: NK ester IND 2-methyl-1,8 octanediol dimethacrylate 85% and 1,9-nonanediol dimethacrylate 15% (manufactured by Shin-Nakamura Chemical Co., Ltd.);
For component (i):
(I) Copper damage inhibitor: MARK CDA-1, 3- (N-salicyloyl) amino-1,2,4-triazole (Asahi Denka Co., Ltd.);
For component (B),
(B) Silane crosslinkable polyethylene: Linkron XF-800T (Mitsubishi Chemical Corporation), density 924 kg / m 3 , MFR 0.8 g / 10 min was used.
［実施例１〜６及び比較例１〜７］
以下の表１に示す量の各成分を用い、室温ですべての成分をドライブレンドし、３Ｌ加圧ニーダーを用いて、溶融混練を行い、排出して、実施例１〜６及び比較例１〜７の樹脂組成物を得た。次に、得られた樹脂組成物をロールにてシート化し、それを角ペレタイザーを用いてペレット化した。得られたペレット及びシラン架橋性ポリエチレン（Ｂ）を、表２及び表３に示す比率にて更にドライブレンドし、４０ｍｍ押出機にて２ｍｍ厚のテープ状に押出し、８０℃にて２４時間温水処理した後、前記各種試験を行った。その結果を、以下の表２及び表３にまとめて示す。
[Examples 1-6 and Comparative Examples 1-7]
Using each component in the amounts shown in Table 1 below, all components were dry blended at room temperature, melt kneaded using a 3 L pressure kneader, discharged, and Examples 1 to 6 and Comparative Examples 1 to 7 resin compositions were obtained. Next, the obtained resin composition was formed into a sheet with a roll, and pelletized using a square pelletizer. The obtained pellets and the silane crosslinkable polyethylene (B) were further dry blended at the ratios shown in Tables 2 and 3, extruded into a 2 mm thick tape with a 40 mm extruder, and treated with hot water at 80 ° C. for 24 hours. Then, the various tests were performed. The results are summarized in Table 2 and Table 3 below.
上の表２から明らかなように、本発明の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物である実施例１〜６の樹脂組成物は、いずれも良好な結果を示した。
一方、比較例１は成分（ｅ）有機過酸化物を用いないものであり、引張特性に劣った。
比較例２、３及び４は、成分（ｆ）シラノール縮合触媒を、本発明の範囲外の量にて配合したものである。成分（ｆ）が少ないと加熱変形性に劣り、成分（ｆ）が多いと押出外観が悪化した。
比較例５は、成分（ｇ）金属水和物を、本発明の上限を超えて配合したものであり、押出負荷が高く、押出外観が悪いものであった。
比較例６及び７は、成分（Ｂ）シラン架橋性ポリオレフィンを、本発明の範囲外の量にて配合したものである。成分（Ｂ）が少ないと充分な加熱変形性が得られず、成分（Ｂ）が多いと、得られた樹脂組成物からなる押出成形品の外観が悪化した。
As is clear from Table 2 above, all of the resin compositions of Examples 1 to 6, which are flame retardant resin compositions for mixing with the silane crosslinkable polyolefin of the present invention, showed good results.
On the other hand, Comparative Example 1 did not use the component (e) organic peroxide, and was inferior in tensile properties.
In Comparative Examples 2, 3 and 4, the component (f) silanol condensation catalyst was blended in an amount outside the range of the present invention. When the component (f) is small, the heat deformability is poor, and when the component (f) is large, the extrusion appearance is deteriorated.
In Comparative Example 5, the component (g) metal hydrate was blended in excess of the upper limit of the present invention, and the extrusion load was high and the extrusion appearance was poor.
In Comparative Examples 6 and 7, the component (B) silane crosslinkable polyolefin is blended in an amount outside the range of the present invention. When the amount of the component (B) is small, sufficient heat deformability cannot be obtained, and when the amount of the component (B) is large, the appearance of the extrusion-molded product made of the obtained resin composition is deteriorated.
Claims (7)
（ｅ）有機過酸化物０.０１〜０.６質量部、
（ｆ）シラノール縮合触媒０．０５〜０．５質量部、および
（ｇ）金属水和物１００〜３００質量部
を含む、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物。 (A) 100 parts by mass of at least one polymer selected from the group consisting of thermoplastic resins, rubbers, and thermoplastic elastomers,
(E) 0.01 to 0.6 parts by mass of an organic peroxide,
(F) A flame retardant resin composition for mixing with a silane crosslinkable polyolefin, comprising 0.05 to 0.5 parts by mass of a silanol condensation catalyst, and (g) 100 to 300 parts by mass of a metal hydrate.
（ａ）結晶性エチレン系重合体１０〜８０質量％、および
（ｄ）酸変性ポリオレフィン２〜２０質量％
を含むことを特徴とする、請求項１に記載の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物。 The component (A) is
(A) 10-80% by mass of crystalline ethylene polymer, and (d) 2-20% by mass of acid-modified polyolefin.
The flame-retardant resin composition for mixing with a silane-crosslinkable polyolefin according to claim 1, comprising:
（ａ）結晶性エチレン系重合体１０〜８０質量％、
（ｂ）結晶性プロピレン系重合体０〜２５質量％、
（ｃ）芳香族ビニル化合物を主体とした少なくとも２個の重合体ブロック（ｃ’）と共役ジエン化合物を主体とした少なくとも１個の重合体ブロック（ｃ”）とからなるブロック共重合体（ｃ−０）及び／またはこれを水素添加して得られる水添ブロック共重合体（ｃ−１）と、非芳香族系ゴム用軟化剤（ｃ−２）とからなるエラストマー組成物０〜６５質量％、および
（ｄ）酸変性ポリオレフィン２〜２０質量％
を含むことを特徴とする、請求項１又は２に記載の、シラン架橋性ポリオレフィンとの混合用難燃性樹脂組成物。 The component (A) is
(A) 10 to 80% by mass of a crystalline ethylene polymer,
(B) 0 to 25% by mass of a crystalline propylene polymer,
(C) a block copolymer (c) comprising at least two polymer blocks (c ′) mainly comprising an aromatic vinyl compound and at least one polymer block (c ″) mainly comprising a conjugated diene compound -0) and / or a hydrogenated block copolymer (c-1) obtained by hydrogenation thereof and an elastomer composition 0-65 mass comprising a non-aromatic rubber softener (c-2). And (d) 2-20% by mass of acid-modified polyolefin
The flame-retardant resin composition for mixing with a silane crosslinkable polyolefin according to claim 1 or 2, characterized in that
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| JP2009255271A (en) * | 2007-08-01 | 2009-11-05 | Toray Ind Inc | Polishing pad and its manufacturing method |
| CN101307163B (en) * | 2007-05-17 | 2010-12-08 | 江苏新远程电缆有限公司 | Silanes cross-linked polyethylene insulated cable material and method for making same |
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