JP4790606B2 - Flame retardant ethylene resin composition and use thereof - Google Patents
Flame retardant ethylene resin composition and use thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
Description
本発明は、熱可塑性樹脂組成物およびその成形体に関し、さらに詳しくは、特に電線の絶縁体、シースの素材として好適な熱可塑性樹脂組成物、高度の難燃性を有する重合体組成物、それらからなる成形体に関わる。The present invention relates to a thermoplastic resin composition and a molded body thereof, and more specifically, a thermoplastic resin composition suitable as a wire insulator and a sheath material, a polymer composition having a high degree of flame retardancy, and the like It relates to a molded body consisting of
従来、電線のシース材および一部絶縁材料は、ポリ塩化ビニル（ＰＶＣ）が多用され、その柔軟性、難燃性、絶縁性が評価されてきた。ＰＶＣには一般に可塑剤が多く含まれるため、加熱などにより可塑剤がなくなると硬化しやすくなること、また、燃焼時に塩素系のガスを発生することから、近年ＰＶＣに代わりうる電線の開発が求められるようになった。Conventionally, polyvinyl chloride (PVC) has been frequently used as a sheath material and a part of an insulating material for electric wires, and its flexibility, flame retardancy, and insulation have been evaluated. Since PVC generally contains a lot of plasticizers, it tends to harden when it disappears due to heating, etc., and generates chlorine-based gas at the time of combustion. It came to be able to.
このような状況のもと、例えばポリエチレン等のエチレン系重合体をベースとした種々の難燃性樹脂組成物が提案されている。Under such circumstances, various flame retardant resin compositions based on ethylene-based polymers such as polyethylene have been proposed.
ＵＳＰ６，２３２，３７７には、エチレン／ビニルエステル共重合体、エチレン／α，β−不飽和カルボン酸共重合体、低密度ポリエチレンから選ばれる特定のエチレン系共重合体等を含み、さらに金属水酸化物、トリアジン化合物および特定の難燃性化合物を含む難燃性樹脂組成物が記載されている。しかしながら、これらのエチレン系重合体は、難燃効果を高めるために金属水酸化物等の無機化合物の添加量を増加した場合、可撓性、柔軟性が低下しやすくなるという問題点がある。（特許文献１）
よって、難燃効果に優れており、しかも可撓性・柔軟性が良好でありかつ、引張物性に優れる樹脂組成物、該組成物からなる成形体、特に電線の絶縁体および／またはシースを提供することが本発明の第１の目的である。USP 6,232,377 includes a specific ethylene copolymer selected from ethylene / vinyl ester copolymer, ethylene / α, β-unsaturated carboxylic acid copolymer, low density polyethylene, etc. A flame retardant resin composition comprising an oxide, a triazine compound and a specific flame retardant compound is described. However, these ethylene-based polymers have a problem that flexibility and flexibility tend to decrease when the amount of an inorganic compound such as a metal hydroxide is increased in order to increase the flame retardancy. (Patent Document 1)
Accordingly, a resin composition having excellent flame retardancy, excellent flexibility and flexibility, and excellent tensile properties, and a molded body made of the composition, particularly an insulator and / or sheath for an electric wire are provided. This is the first object of the present invention.
一方、家庭用電気製品、建築物、室内装飾品、自動車部品、電子機器の内部配線などに多種の熱可塑性重合体、熱硬化性重合体が使用されている。これらの重合体の大部分（特にオレフィン系重合体）は易燃性である。On the other hand, various thermoplastic polymers and thermosetting polymers are used in household electrical products, buildings, interior decorations, automobile parts, internal wiring of electronic devices, and the like. Most of these polymers (especially olefin polymers) are flammable.
防災上の見地から、各種施設、構造物などの不燃化、難燃化の要請が高まり、特に家庭用電気製品等のように火元となる可能性のあるものは高度の難燃性が必要とされている。内部配線材の難燃性の基準は、例えば米国のＵＬ規格（Ｕｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ．）等で定められており、ＶＷ−１試験と呼ばれる垂直燃焼試験で評価される。そこで、高熱や火災に晒された場合でも長時間使用に耐えうる素材が求められており、多くの熱可塑性重合体や熱硬化性重合体などに高い難燃性を付与するために、重合体製造時または成形品製造時などに難燃剤を添加する方法が広く採用されている。From the standpoint of disaster prevention, there is a growing demand for non-flammable and flame-retardant facilities and structures, especially those that can be a source of fire, such as household electrical appliances, that require a high level of flame resistance. It is said that. The standard of flame retardancy of the internal wiring material is determined by, for example, the United States UL standard (Underwriters Laboratories Inc.) and the like, and is evaluated by a vertical combustion test called a VW-1 test. Therefore, there is a demand for materials that can withstand long-term use even when exposed to high heat or fire, and in order to impart high flame retardancy to many thermoplastic polymers and thermosetting polymers, polymers are required. A method of adding a flame retardant at the time of production or production of a molded product is widely adopted.
難燃剤としては、金属水酸化物；ホウ酸塩；有機ハロゲン化物；リン酸塩、赤リン、有機リン化合物等のリン系化合物；有機窒素化合物など多くのものが使われている。これらのうち特に有機ハロゲン化合物、有機リン化合物などが優れた難燃効果を発揮する。Many flame retardants are used such as metal hydroxides; borates; organic halides; phosphorous compounds such as phosphates, red phosphorus and organic phosphorus compounds; and organic nitrogen compounds. Of these, organic halogen compounds, organophosphorus compounds and the like exhibit excellent flame retardant effects.
しかし、これらのハロゲン含有化合物は樹脂成形時に熱分解してハロゲン化水素を発生し、樹脂自身を劣化させ、着色を起こしたり、また火災の際にハロゲン化水素を発生したりするなどの問題がある。However, these halogen-containing compounds are thermally decomposed during resin molding to generate hydrogen halide, which causes problems such as deterioration of the resin itself, coloration, and generation of hydrogen halide in the event of a fire. is there.
従来からハロゲンを含まない難燃剤として、水酸化アルミニウム、水酸化マグネシウムなどの無機系難燃剤が用いられている。しかしこれらの無機化合物のみでは難燃効果が低く、大量に添加しないと十分な効果を発現できず、また大量に添加すると樹脂本来の物性が損なわれる場合があり、その使用範囲には限界があった。Conventionally, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide have been used as flame retardants containing no halogen. However, these inorganic compounds alone have a low flame retardant effect, and if they are not added in a large amount, sufficient effects cannot be expressed. If they are added in a large amount, the original physical properties of the resin may be impaired, and the range of use is limited. It was.
一方、ハロゲンを含まず、比較的良好な難燃効果が得られる難燃剤として、特定の有機リン化合物、特定の有機窒素化合物などがあり、これらもしばしば実用に供されている。On the other hand, there are specific organic phosphorus compounds, specific organic nitrogen compounds, and the like as flame retardants which do not contain halogen and can obtain a relatively good flame retardant effect, and these are often put into practical use.
従来の有機リン酸エステル系難燃剤を代表するものとしてトリフェニルホスフェート（これを以下「ＴＰＰ」という）があるが、この化合物は耐熱性が低くかつ揮発性が高いため、高温で成形する樹脂には適さず、特に成形時金型汚染のため使用範囲が限定される。A representative example of conventional organophosphate flame retardants is triphenyl phosphate (hereinafter referred to as “TPP”). This compound has low heat resistance and high volatility. Is not suitable, and the range of use is particularly limited due to mold contamination during molding.
有機リンを低揮発化し、難燃剤として使用するものとして、特公昭５１−１９８５８号、特開昭５９−２０２２４０号などに記載されている縮合リン酸エステルがある。これらのものはＴＰＰより耐熱性や低揮発性に優れるものの、リン含量当たりでの難燃化効果はＴＰＰを超えるものではなく、大量に添加する必要があり、そのため樹脂の可塑剤としての効果のため熱変形温度を大幅に低下させるなどの問題があった（特許文献２、３）。Condensed phosphoric acid esters described in JP-B 51-19858, JP-A 59-202240 and the like are used as a flame retardant which lowers organic phosphorus. Although these are superior to TPP in heat resistance and low volatility, the flame retardant effect per phosphorus content does not exceed TPP, and it is necessary to add a large amount. For this reason, there has been a problem that the thermal deformation temperature is greatly reduced (Patent Documents 2 and 3).
また、ポリリン酸アンモニウム等のポリリン酸塩、ポリリン酸アミド等の縮合リン酸系の難燃剤を用いる処方も多く提案されている（特開昭５４−２２４５０号公報、特開平９−３１６２５０号公報等）。しかしポリリン酸は、吸水性であり、吸水により電気抵抗が次第に下がるため、電線・ケーブル等の絶縁被覆材には不適であるなど、用途が限られてくる。（特許文献４、５）
また、最近では湖沼など閉鎖水系の富栄養化を抑制するため、リン系難燃剤に代わる処方も求められている。Also, many formulations using polyphosphate flame retardants such as polyphosphates such as ammonium polyphosphate and polyphosphate amides have been proposed (Japanese Patent Laid-Open Nos. 54-22450, 9-316250, etc.) ). However, polyphosphoric acid is water-absorbing, and its electrical resistance gradually decreases due to water absorption, so its use is limited, such as being unsuitable for insulating coating materials such as electric wires and cables. (Patent Documents 4 and 5)
Recently, in order to suppress eutrophication of closed water systems such as lakes, prescriptions to replace phosphorus flame retardants are also required.
メラミン等の有機窒素化合物も比較的高い難燃効果を示している（特開平８−１７６３４３号公報等）。しかし従来は、より高い難燃効果を狙うために、リン系難燃剤と併用することが多かった。（特許文献６）
よって、ハロゲン系難燃剤やリン系難燃剤を含まなくても高度の難燃性を有する重合体組成物、特に電線用被覆材、シースとして好適な難燃性重合体組成物を提供することが、本発明の第２の目的である。
最近、エチレン・α−オレフィン共重合体とグラフト変性エチレン系重合体と金属水酸化物を含む樹脂組成物（ＷＯ０３／１０６５４）、エチレン・α−オレフィン共重合体とグラフト変性エチレン系重合体とエチレンとビニルエステル共重合体と金属水酸化物とを含む樹脂組成物も開示されている（特許文献７，８）。
Accordingly, it is possible to provide a polymer composition having a high degree of flame retardancy without containing a halogen flame retardant or a phosphorus flame retardant, particularly a flame retardant polymer composition suitable as a coating material for a wire or a sheath. This is the second object of the present invention.
Recently, a resin composition containing an ethylene / α-olefin copolymer, a graft-modified ethylene polymer and a metal hydroxide (WO03 / 10654), an ethylene / α-olefin copolymer, a graft-modified ethylene polymer and ethylene Also disclosed is a resin composition containing a vinyl ester copolymer and a metal hydroxide (Patent Documents 7 and 8).
本発明は上記のような課題を解決するため、すなわち可撓性・柔軟性が良好でありかつ難燃効果に優れた樹脂組成物およびそれからなる成形体を得ることにある。In order to solve the above-mentioned problems, the present invention is to obtain a resin composition having excellent flexibility and flexibility and excellent flame retardancy, and a molded product comprising the same.
エチレンと炭素数３〜１０のα−オレフィンとからなるエチレン・α−オレフィン共重合体（Ａ）５１〜９５重量部
エチレンとビニルエステルとの共重合体（Ｂ）５〜４９重量部
（Ａ）（Ｂ）の合計量１００重量部に対してグラフト変性エチレン系重合体（Ｃ）０．１〜５０重量部
金属水酸化物（Ｄ）５０〜２５０重量部
トリアジン系化合物（Ｅ）０．１〜５０重量部
粉末シリコーン（Ｆ）０．１〜４０重量部
を含み、（Ｅ）と（Ｆ）の重量比（（Ｅ）／（Ｆ））が１．２以上であることを特徴とする難燃性エチレン系樹脂組成物。
上記に記載の難燃性エチレン系樹脂組成物を被覆してなる電線・ケーブル。Ethylene / α-olefin copolymer (A) composed of ethylene and α-olefin having 3 to 10 carbon atoms (A) 51 to 95 parts by weight Copolymer of ethylene and vinyl ester (B) 5 to 49 parts by weight (A) Graft-modified ethylene polymer (C) 0.1 to 50 parts by weight Metal hydroxide (D) 50 to 250 parts by weight Triazine compound (E) 0.1 to 100 parts by weight of the total amount of (B) 50 parts by weight powdered silicone (F) 0.1 to 40 parts by weight, (E) and (F) weight ratio ((E) / (F)) is 1.2 or more A flammable ethylene resin composition.
An electric wire / cable formed by coating the flame retardant ethylene-based resin composition described above.
本発明の樹脂組成物は可撓性・柔軟性が良好でありかつ難燃効果に優れる。The resin composition of the present invention has good flexibility and flexibility and is excellent in flame retardancy.
エチレン・α−オレフィン共重合体（Ａ）
本発明で用いられるエチレン・α−オレフィン共重合体（Ａ）は、エチレンと炭素数３〜１０のα−オレフィンとの共重合体である。この炭素数３〜１０のα−オレフィンとしては、具体的に、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−ヘキセン１−オクテン、３−エチル−１−ヘキセン、１−オクテン、１−デセンなどが挙げられ、これらの単独もしくは２種以上のものとエチレンで共重合体は構成される。これらのうち、プロピレン、１−ブテン、１−ヘキセン、１−オクテンのうちの少なくとも１種以上が好ましく使用される。 Ethylene / α-olefin copolymer (A)
The ethylene / α-olefin copolymer (A) used in the present invention is a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. Specific examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl. -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene 1-octene, 3-ethyl-1-hexene, Examples include 1-octene and 1-decene, and the copolymer is composed of ethylene alone or in combination of two or more thereof. Of these, at least one of propylene, 1-butene, 1-hexene and 1-octene is preferably used.
中でも、エチレン・１−ブテン共重合体は同一密度における柔軟性と引張物性のバランスが特に優れているため、より好ましい。Among these, an ethylene / 1-butene copolymer is more preferable because the balance between flexibility and tensile properties at the same density is particularly excellent.
エチレン・αオレフィン共重合体中の各構成単位の含量は、エチレンから誘導される構成単位の含量が通常７５〜９５モル％、好ましくは８０〜９５モル％であり、炭素数３〜１０のα−オレフィンから選ばれる少なくとも１つの化合物から誘導される構成単位の含量が通常５〜２５モル％、好ましくは５〜２０モル％であることが好ましい。The content of each structural unit in the ethylene / α-olefin copolymer is usually 75 to 95 mol%, preferably 80 to 95 mol%, and the content of structural units derived from ethylene is α of 3 to 10 carbon atoms. -It is preferable that the content of the structural unit derived from at least one compound selected from olefins is usually 5 to 25 mol%, preferably 5 to 20 mol%.
さらに本発明で用いられるエチレン・α−オレフィン共重合体（Ａ）は、以下のような性質を有することが好ましい。すなわち、
（ｉ）密度が８５５〜９００ｋｇ／ｍ３、好ましくは、０．８５７〜０．８９０ｋｇ／ｍ３であり、
（ｉｉ）１９０℃、２．１６ｋｇ荷重におけるメルトフローレート（ＭＦＲ２）が０．１〜１００ｇ／１０分、好ましくは、０．１〜２０ｇ／１０分、さらに好ましくは、０．１〜０．９ｇ／１０分の範囲にあり、
（ｉｉｉ）ＧＰＣ法により評価される分子量分布の指数：Ｍｗ／Ｍｎが１．５〜３．５、好ましくは１．５〜３．０、より好ましくは１．８〜２．５の範囲にあり、
（ｉｖ）１３Ｃ−ＮＭＲスペクトルおよび下記式から求められるＢ値が０．９〜１．５、好ましくは０．９〜１．２である；
Ｂ値＝［ＰＯＥ］／（２・［ＰＥ］［ＰＯ］）
（式中、［ＰＥ］は共重合体中のエチレンから誘導される構成単位の含有モル分率であり、［ＰＯ］は共重合体中のα−オレフィンから誘導される構成単位の含有モル分率であり、［ＰＯＥ］は共重合体中の全ダイアド（ｄｙａｄ）連鎖に対するエチレン・α−オレフィン連鎖数の割合である。）。Furthermore, the ethylene / α-olefin copolymer (A) used in the present invention preferably has the following properties. That is,
(I) Density is 855 to 900 kg / m 3 , preferably 0.857 to 0.890 kg / m 3 ;
(Ii) Melt flow rate (MFR 2 ) at 190 ° C. and a load of 2.16 kg is 0.1 to 100 g / 10 minutes, preferably 0.1 to 20 g / 10 minutes, and more preferably 0.1 to 0. In the range of 9 g / 10 min,
(Iii) Index of molecular weight distribution evaluated by GPC method: Mw / Mn is in the range of 1.5 to 3.5, preferably 1.5 to 3.0, more preferably 1.8 to 2.5. ,
(Iv) B value calculated | required from a < 13 > C-NMR spectrum and a following formula is 0.9-1.5, Preferably it is 0.9-1.2;
B value = [POE] / (2 · [PE] [PO])
(Wherein [PE] is the mole fraction of structural units derived from ethylene in the copolymer, and [PO] is the mole fraction of structural units derived from α-olefin in the copolymer. And [POE] is the ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer).
このＢ値は、エチレン・α−オレフィン共重合体中のエチレンと炭素数３〜１０のα−オレフィンとの分布状態を表す指標であり、Ｊ．Ｃ．Ｒａｎｄａｌｌ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１５，３５３（１９８２））、Ｊ．Ｒａｙ（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１０，７７３（１９７７））らの報告に基づいて求めることができる。This B value is an index representing the distribution of ethylene and the α-olefin having 3 to 10 carbon atoms in the ethylene / α-olefin copolymer. C. Randall (Macromolecules, 15, 353 (1982)), J. Am. It can be determined based on the report of Ray (Macromolecules, 10, 773 (1977)).
上記Ｂ値が大きいほど、エチレンまたはα−オレフィン共重合体のブロック的連鎖が短くなり、エチレンおよびα−オレフィンの分布が一様であり、共重合ゴムの組成分布が狭いことを示している。なおＢ値が１．０よりも小さくなるほどエチレン・α−オレフィン共重合体の組成分布は広くなり、取扱性が悪化するなどの悪い点があることがある。As the B value is larger, the block chain of ethylene or α-olefin copolymer becomes shorter, the distribution of ethylene and α-olefin is more uniform, and the composition distribution of the copolymer rubber is narrower. In addition, as the B value becomes smaller than 1.0, the composition distribution of the ethylene / α-olefin copolymer becomes wider, and there are cases where there are bad points such as poor handling.
さらに好ましくは（ｖ）１３Ｃ−ＮＭＲスペクトルにおけるＴααに対するＴαβの強度比（Ｔαβ／Ｔαα）が０．５以下、好ましくは０．４以下、より好ましくは０．３以下である。ここで１３Ｃ−ＮＭＲスペクトルにおけるＴααおよびＴαβは、炭素数３以上のα−オレフィンから誘導される構成単位中のＣＨ２のピーク強度であり、下記に示すように第３級炭素に対する位置が異なる２種類のＣＨ２を意味している。
ＮＭＲ測定装置を用いて測定する。測定は、試料濃度５重量％になるように調整されたヘキサクロロブタジエン／ｄ６−ベンゼン＝２／１（体積比）の混合溶液を用いて、６７．８ＭＨｚ、２５℃、ｄ６−ベンゼン（１２８ｐｐｍ）基準で行う。測定された１３Ｃ−ＮＭＲスペクトルを、リンデマンアダムスの提案（Ａｎａｌｙｓｉｓ Ｃｈｅｍｉｓｔｒｙ，４３，ｐ１２４５（１９７１））、Ｊ．Ｃ．Ｒａｎｄａｌｌ（Ｒｅｖｉｅｗ Ｍａｃｒｏｍｏｌｅｃｕｌａｒ Ｃｈｅｍｉｓｔｒｙ Ｐｈｙｓｉｃｓ，Ｃ２９，２０１（１９８９））に従って解析してＴαβ／Ｔαα強度比を求める。More preferably (v) the intensity ratio of Tαβ to Tαα (Tαβ / Tαα) in the 13 C-NMR spectrum is 0.5 or less, preferably 0.4 or less, more preferably 0.3 or less. Here, Tαα and Tαβ in the 13 C-NMR spectrum are the peak intensities of CH 2 in the structural unit derived from the α-olefin having 3 or more carbon atoms, and the positions relative to the tertiary carbon are different as shown below. Two types of CH 2 are meant.
Measurement is performed using an NMR measuring apparatus. The measurement is performed using a mixed solution of hexachlorobutadiene / d6-benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight, based on 67.8 MHz, 25 ° C., d6-benzene (128 ppm). To do. The measured 13 C-NMR spectrum was analyzed by Lindeman Adams's proposal (Analysis Chemistry, 43, p1245 (1971)), J. Am. C. Analysis is carried out according to Randall (Review Macromolecular Chemistry Physics, C29, 201 (1989)) to determine the Tαβ / Tαα intensity ratio.
本発明のエチレン・α−オレフィン共重合体は上記の特性に加えさらに以下の特性を有するものも好適に用いられる。As the ethylene / α-olefin copolymer of the present invention, those having the following properties in addition to the above properties are also preferably used.
（ｖｉ）１９０℃、１０ｋｇ荷重におけるメルトフローレート（ＭＦＲ１０）と１９０℃、２，１６ｋｇ荷重におけるメルトフローレート（ＭＦＲ２）との比：ＭＦＲ１０／ＭＦＲ２が次の関係を満たす。(Vi) Ratio of melt flow rate (MFR 10 ) at 190 ° C. and 10 kg load to melt flow rate (MFR 2 ) at 190 ° C. and 2,16 kg load: MFR 10 / MFR 2 satisfies the following relationship.
Ｍｗ／Ｍｎ＋４．７≦ＭＦＲ１０／ＭＦＲ２
ここで、ＭＦＲ１０、ＭＦＲ２、Ｍｗ／Ｍｎが上記の関係を満たさない場合は、成形性または材料強度若しくはその両者が低下することがある。Mw / Mn + 4.7 ≦ MFR 10 / MFR 2
Here, when MFR 10 , MFR 2 , and Mw / Mn do not satisfy the above relationship, the formability and / or the material strength may decrease.
［エチレン・α−オレフィン共重合体（Ａ）の製造方法］
このようなエチレン・α−オレフィン共重合体（Ａ）は、Ｖ化合物と有機アルミニウム化合物から構成されるチーグラー系触媒やメタロセン系触媒の存在下にエチレンと少なくとも１種以上の炭素数３〜１０のα−オレフィンとを共重合させることによって製造することができるがメタロセン系触媒が好適に用いられる。[Production Method of Ethylene / α-Olefin Copolymer (A)]
Such an ethylene / α-olefin copolymer (A) is composed of ethylene and at least one or more kinds of 3 to 10 carbon atoms in the presence of a Ziegler catalyst or a metallocene catalyst composed of a V compound and an organoaluminum compound. Although it can be produced by copolymerizing an α-olefin, a metallocene catalyst is preferably used.
このようなメタロセン系触媒は、メタロセン化合物（ａ）と、有機アルミニウムオキシ化合物（ｂ）および／またはメタロセン化合物（ａ）と反応してイオン対を形成する化合物（ｃ）とから形成されていてもよく、さらに（ａ）、（ｂ）および／または（ｃ）とともに有機アルミニウム化合物（ｄ）とから形成されていてもよい。
エチレン・α−オレフィン共重合は、上記触媒の存在下、通常炭化水素溶媒を用いた液相で、バッチ式、半連続式、連続式のいずれの方法でも行うことができる。メタロセン化合物（ａ）と有機アルミニウムオキシ化合物（ｂ）またはイオン化イオン性化合物（ｃ）とからなるメタロセン系触媒が用いられる場合には、重合系内のメタロセン化合物（ａ）の濃度は、通常０．００００５〜０．１ミリモル／リットル（重合容積）、好ましくは０．０００１〜０．０５ミリモル／リットルである。また有機アルミニウムオキシ化合物（ｂ）は、重合系内のメタロセン化合物中の遷移金属に対するアルミニウム原子のモル比（Ａｌ／遷移金属）で、１〜１００００、好ましくは１０〜５０００の量で供給される。イオン化イオン性化合物（ｃ）の場合は、重合系内のメタロセン化合物（ａ）に対するイオン化イオン性化合物（ｃ）のモル比（イオン化イオン性化合物（ｃ）／メタロセン化合物（ａ））で、０．５〜２０、好ましくは１〜１０の量で供給される。また有機アルミニウム化合物を用いる場合には、通常約０〜５ミリモル／リットル（重合容積）、好ましくは約０〜２ミリモル／リットルとなるような量で用いられる。Such a metallocene-based catalyst may be formed from the metallocene compound (a) and the compound (c) that reacts with the organoaluminum oxy compound (b) and / or the metallocene compound (a) to form an ion pair. Further, it may be formed from the organoaluminum compound (d) together with (a), (b) and / or (c).
The ethylene / α-olefin copolymerization can be carried out in a liquid phase using a hydrocarbon solvent in the presence of the above catalyst, and any of batch, semi-continuous and continuous methods. When a metallocene catalyst composed of a metallocene compound (a) and an organoaluminum oxy compound (b) or an ionized ionic compound (c) is used, the concentration of the metallocene compound (a) in the polymerization system is usually from about 0.00. 00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.05 mmol / liter. The organoaluminum oxy compound (b) is supplied in an amount of 1 to 10,000, preferably 10 to 5,000, in terms of the molar ratio of aluminum atom to transition metal in the metallocene compound in the polymerization system (Al / transition metal). In the case of the ionized ionic compound (c), the molar ratio of the ionized ionic compound (c) to the metallocene compound (a) in the polymerization system (ionized ionic compound (c) / metallocene compound (a)) is 0.00. It is supplied in an amount of 5 to 20, preferably 1 to 10. When an organoaluminum compound is used, it is usually used in an amount of about 0 to 5 mmol / liter (polymerization volume), preferably about 0 to 2 mmol / liter.
共重合反応は、通常、反応温度が−２０〜＋１５０℃、好ましくは０〜１２０℃、さらに好ましくは０〜１００℃で、圧力が０を超えて７．８ＭＰａ（８０ｋｇｆ／ｃｍ２、ゲージ圧）以下、好ましくは０を超えて４．９ＭＰａ（５０ｋｇｆ／ｃｍ２、ゲージ圧）以下の条件下に行われる。The copolymerization reaction is usually at a reaction temperature of −20 to + 150 ° C., preferably 0 to 120 ° C., more preferably 0 to 100 ° C., and a pressure exceeding 0 to 7.8 MPa (80 kgf / cm 2 , gauge pressure). Hereinafter, it is preferably carried out under the condition of more than 0 and 4.9 MPa (50 kgf / cm 2 , gauge pressure) or less.
エチレンおよびα−オレフィンは、上記特定組成のエチレン・α−オレフィン共重合体（Ａ）が得られるような量で重合系に供給される。共重合に際しては、水素などの分子量調節剤を用いることもできる。Ethylene and α-olefin are supplied to the polymerization system in such an amount that the ethylene / α-olefin copolymer (A) having the specific composition is obtained. In the copolymerization, a molecular weight regulator such as hydrogen can be used.
エチレンとビニルエステルとの共重合体（Ｂ）
本発明において使用されるエチレンとビニルエステルとの共重合体は、通常、高圧ラジカル重合法で製造される。エチレンと共重合されるビニルエステルモノマーとしては、プロピオン酸ビニル、酢酸ビニル、カプロン酸ビニル、ラウリル酸ビニル、ステアリン酸ビニル、トリフロロ酢酸ビニル等が挙げられるが、この中でも酢酸ビニルが好適に使用される。また、エチレンとビニルエステルとの共重合体は、特性的には、メルトフローレートが０．５〜５０ｇ／１０分、好ましくは０．５〜１０ｇ／１０分で、ビニルモノマーの含有量が５〜４０重量％、好ましくは１０〜３５重量％であることが望ましい。メルトフローレートが０．５ｇ／１０分未満であると、加工性が低下し、一方、５０ｇ／１０分を超えると、得られる樹脂組成物の引張強さ、伸び、硬度、衝撃強度等の機械的特性が低下するので、望ましくない。また、ビニルモノマーの含有量が５重量％未満であると、加工性が低下するとともに充填剤として添加する難燃剤の均一な分散が難しくなり、一方、４０重量％を超えると、得られる樹脂組成物の機械的特性が低下するので、望ましくない。 Copolymer of ethylene and vinyl ester (B)
The copolymer of ethylene and vinyl ester used in the present invention is usually produced by a high pressure radical polymerization method. Examples of the vinyl ester monomer copolymerized with ethylene include vinyl propionate, vinyl acetate, vinyl caproate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. Among these, vinyl acetate is preferably used. . Further, the copolymer of ethylene and vinyl ester has a melt flow rate of 0.5 to 50 g / 10 min, preferably 0.5 to 10 g / 10 min, and a vinyl monomer content of 5 in terms of characteristics. It is desired to be -40% by weight, preferably 10-35% by weight. When the melt flow rate is less than 0.5 g / 10 minutes, the workability is lowered. On the other hand, when the melt flow rate exceeds 50 g / 10 minutes, the resulting resin composition has a tensile strength, elongation, hardness, impact strength, etc. This is undesirable because the mechanical properties are degraded. Further, when the content of the vinyl monomer is less than 5% by weight, the processability is lowered and it is difficult to uniformly disperse the flame retardant added as a filler. On the other hand, when the content exceeds 40% by weight, the resulting resin composition is obtained. This is undesirable because it reduces the mechanical properties of the object.
グラフト変性エチレン系重合体（Ｃ）
本発明でグラフト変性エチレン系重合体の原料として用いられるエチレン系重合体としてはエチレン・α−オレフィン共重合体が好ましい。グラフト変性エチレン系重合体の原料として用いられるエチレン・α−オレフィン共重合体は、エチレンと炭素数３〜１０のα−オレフィンとの共重合体が好ましい。この炭素数３〜１０のα−オレフィンとしては、具体的に、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−ヘキセン、１−オクテン、３−エチル−１−ヘキセン、１−オクテン、１−デセンなどが挙げられる。これらは単独でも２種以上でもよい。これらのうち、プロピレン、１−ブテン、１−ヘキセン、１−オクテンのうちの少なくとも１種以上が特に好ましい。 Graft-modified ethylene polymer (C)
As the ethylene polymer used as a raw material for the graft-modified ethylene polymer in the present invention, an ethylene / α-olefin copolymer is preferable. The ethylene / α-olefin copolymer used as a raw material for the graft-modified ethylene polymer is preferably a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. Specific examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl. -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 1-octene, 3-ethyl-1-hexene , 1-octene, 1-decene and the like. These may be used alone or in combination of two or more. Of these, at least one of propylene, 1-butene, 1-hexene and 1-octene is particularly preferable.
エチレン系共重合体中の各構成単位の含量は、エチレンから誘導される構成単位の含量が通常７５〜９５モル％であり、好ましくは８０〜９５モル％であり、炭素数３〜１０のα−オレフィンから選ばれる少なくとも１つの化合物から誘導される構成単位の含量が通常５〜２５モル％であり、５〜２０モル％であることが好ましい。The content of each structural unit in the ethylene-based copolymer is such that the content of the structural unit derived from ethylene is usually 75 to 95 mol%, preferably 80 to 95 mol%, and α having 3 to 10 carbon atoms. -Content of the structural unit induced | guided | derived from the at least 1 compound chosen from an olefin is 5-25 mol% normally, and it is preferable that it is 5-20 mol%.
グラフト変性に用いられるエチレン・α−オレフィン共重合体は、好ましくは以下のような物性を有している。すなわち、
（ｉ）密度が８５５〜９１０ｋｇ／ｍ３、好ましくは、８５７〜８９０ｋｇ／ｍ３であり、
（ｉｉ）１９０℃、２．１６ｋｇ荷重におけるメルトフローレート（ＭＦＲ２）が０．１〜１００ｇ／１０分、好ましくは、０．１〜２０ｇ／１０分の範囲にあり、
（ｉｉｉ）ＧＰＣ法により評価される分子量分布の指数：Ｍｗ／Ｍｎが１．５〜３．５、好ましくは１．５〜３．０、より好ましくは１．８〜２．５の範囲にあり、さらに好ましくは、
（ｉｖ）１３Ｃ−ＮＭＲスペクトルおよび下記式から求められるＢ値が０．９〜１．５、好ましくは１．０〜１．２である；
Ｂ値＝［ＰＯＥ］／（２・［ＰＥ］［ＰＯ］）
（式中、［ＰＥ］は共重合体中のエチレンから誘導される構成単位の含有モル分率であり、［ＰＯ］は共重合体中のα−オレフィンから誘導される構成単位の含有モル分率であり、［ＰＯＥ］は共重合体中の全ダイアド（ｄｙａｄ）連鎖に対するエチレン・α−オレフィン連鎖数の割合である。）。The ethylene / α-olefin copolymer used for graft modification preferably has the following physical properties. That is,
(I) The density is 855 to 910 kg / m 3 , preferably 857 to 890 kg / m 3 ,
(Ii) The melt flow rate (MFR 2 ) at 190 ° C. and a load of 2.16 kg is 0.1 to 100 g / 10 minutes, preferably 0.1 to 20 g / 10 minutes,
(Iii) Index of molecular weight distribution evaluated by GPC method: Mw / Mn is in the range of 1.5 to 3.5, preferably 1.5 to 3.0, more preferably 1.8 to 2.5. More preferably,
(Iv) B value calculated | required from a < 13 > C-NMR spectrum and a following formula is 0.9-1.5, Preferably it is 1.0-1.2;
B value = [POE] / (2 · [PE] [PO])
(Wherein [PE] is the mole fraction of structural units derived from ethylene in the copolymer, and [PO] is the mole fraction of structural units derived from α-olefin in the copolymer. And [POE] is the ratio of the number of ethylene / α-olefin chains to the total number of dyad chains in the copolymer).
その他、グラフト変性エチレン系重合体の原料として用いられるエチレン・α−オレフィン共重合体は（Ａ）に用いられるエチレン・α−オレフィン共重合体で記載したのものと同じ特徴を有するものが好適に用いられるが、共重合体のコモノマー種、密度、分子量等は（Ａ）と同じでも異なっていてもよい。In addition, the ethylene / α-olefin copolymer used as a raw material for the graft-modified ethylene polymer preferably has the same characteristics as those described for the ethylene / α-olefin copolymer used in (A). Although used, the comonomer type, density, molecular weight, etc. of the copolymer may be the same as or different from (A).
本発明に係るグラフト変性エチレン系重合体は上記エチレン系共重合体中を少なくとも１種の極性基を有するビニル化合物でグラフト変性することで得られる。極性基を有するビニル化合物としては、極性基として酸、酸無水物、エステル、アルコール、エポキシ、エーテル等の酸素含有基を有するビニル化合物、イソシアネート、アミド等の窒素含有基を有するビニル化合物、ビニルシラン等のケイ素含有基を有するビニル化合物等が挙げられる。The graft-modified ethylene polymer according to the present invention can be obtained by graft-modifying the ethylene copolymer with a vinyl compound having at least one polar group. Examples of the vinyl compound having a polar group include vinyl compounds having an oxygen-containing group such as acid, acid anhydride, ester, alcohol, epoxy and ether as polar groups, vinyl compounds having a nitrogen-containing group such as isocyanate and amide, vinyl silane, etc. And vinyl compounds having a silicon-containing group.
この中でも酸素含有基を有するビニル化合物が好ましく、不飽和エポキシ単量体、不飽和カルボン酸およびその誘導体等が好ましい。Among these, vinyl compounds having an oxygen-containing group are preferable, and unsaturated epoxy monomers, unsaturated carboxylic acids and derivatives thereof are preferable.
不飽和エポキシ単量体としては不飽和グリシジルエーテル、不飽和グリシジルエステル（例えばグリシジルメタクリレート）等が挙げられる。Examples of the unsaturated epoxy monomer include unsaturated glycidyl ether and unsaturated glycidyl ester (for example, glycidyl methacrylate).
不飽和カルボン酸の例としてはアクリル酸、マレイン酸、フマール酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸およびナジック酸ＴＭ（エンドシス−ビシクロ［２，２，１］ヘプト−５−エン−２，３−ジカルボン酸）などが挙げられる。Examples of unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid and nadic acid TM (endocis-bicyclo [2,2,1] hept-5 -Ene-2,3-dicarboxylic acid) and the like.
また不飽和カルボン酸の誘導体としては、たとえば上記不飽和カルボン酸の酸ハライド化合物、アミド化合物、イミド化合物、酸無水物、およびエステル化合物などを挙げることができる。具体的には塩化マレニル、マレイミド、無水マレイン酸、無水シトラコン酸、マレイン酸モノメチル、マレイン酸ジメチル、グリシジルマレエートなどが挙げられる。Examples of unsaturated carboxylic acid derivatives include acid halide compounds, amide compounds, imide compounds, acid anhydrides, and ester compounds of the above unsaturated carboxylic acids. Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.
これらの中では、不飽和ジカルボン酸またはその酸無水物が好適であり、特にマレイン酸、ナジック酸ＴＭまたはこれらの酸無水物が好適である。なお、上記未変性のエチレン系共重合体にグラフトされる不飽和カルボン酸またはその誘導体のグラフト位置に特に限定はなく、このグラフト変性エチレン系重合体を構成するエチレン系重合体の任意の炭素原子に不飽和カルボン酸またはその誘導体が結合していればよい。Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid TM or acid anhydrides thereof are particularly preferable. The graft position of the unsaturated carboxylic acid or derivative thereof grafted to the unmodified ethylene copolymer is not particularly limited, and any carbon atom of the ethylene polymer constituting the graft modified ethylene polymer can be used. It is sufficient that an unsaturated carboxylic acid or a derivative thereof is bound to.
上記のようなグラフト変性エチレン系重合体（Ｃ）は、従来公知の種々の方法、例えば次のような方法を用いて調製することができる。
（１）上記未変性エチレン系重合体を押出機等で溶融させて不飽和カルボン酸等を添加してグラフト共重合させる方法。
（２）上記未変性エチレン系重合体を溶媒に溶解させて不飽和カルボン酸等を添加してグラフト共重合させる方法。The graft-modified ethylene polymer (C) as described above can be prepared using various conventionally known methods, for example, the following methods.
(1) A method in which the unmodified ethylene polymer is melted with an extruder or the like, and an unsaturated carboxylic acid or the like is added to carry out graft copolymerization.
(2) A method in which the unmodified ethylene polymer is dissolved in a solvent and an unsaturated carboxylic acid or the like is added to carry out graft copolymerization.
いずれの方法も、上記不飽和カルボン酸等のグラフトモノマーを効率よくグラフト共重合させるためにラジカル開始剤の存在下でグラフト反応を行うのが好ましい。In any method, it is preferable to perform the graft reaction in the presence of a radical initiator in order to efficiently graft copolymerize the above-mentioned unsaturated carboxylic acid or other graft monomer.
上記ラジカル開始剤として有機ペルオキシド、アゾ化合物などが使用される。このようなラジカル開始剤としては、具体的には、ベンゾイルペルオキシド、ジクロルベンゾイルペルオキシド、ジクミルペルオキシドなどの有機ペルオキシド；アゾビスイソブチルニトリル、ジメチルアゾイソブチレート等のアゾ化合物などが挙げられる。これらの中では、ジクミルペルオキシド、ジ−ｔｅｒｔ−ブチルペルオキシド、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキシンー３、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキサン、１，４−ビス（ｔｅｒｔ−ブチルペルオキシイソプロピル）ベンゼンなどのジアルキルペルオキシドが好ましく用いられる。As the radical initiator, an organic peroxide, an azo compound, or the like is used. Specific examples of such radical initiators include organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide, and dicumyl peroxide; azo compounds such as azobisisobutylnitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert- Dialkyl peroxides such as butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.
これらのラジカル開始剤は、未変性エチレン系重合体１００重量部に対して、通常は０．００１〜１重量部、好ましくは０．００３〜０．５重量部、さらに好ましくは０．０５〜０．３重量部の量で用いられる。These radical initiators are usually 0.001-1 part by weight, preferably 0.003-0.5 part by weight, more preferably 0.05-0, based on 100 parts by weight of the unmodified ethylene polymer. Used in an amount of 3 parts by weight.
上記のようなラジカル開始剤を用いたグラフト反応あるいはラジカル開始剤を使用しないで行うグラフト反応における反応温度は、通常６０〜３５０℃、好ましくは１５０〜３００℃の範囲に設定される。The reaction temperature in the graft reaction using the radical initiator as described above or the graft reaction performed without using the radical initiator is usually set in the range of 60 to 350 ° C, preferably 150 to 300 ° C.
金属水酸化物（Ｄ）
本発明で用いられる金属水酸化物としては、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、水酸化マンガン、水酸化亜鉛、ハイドロタルサイト等の単独もしくはこれらの混合物が挙げられ、水酸化マグネシウム単独及び水酸化マグネシウムを含む混合物、あるいは水酸化アルミニウム単独及び水酸化アルミニウムを含む混合物が特に好ましい。 Metal hydroxide (D)
Examples of the metal hydroxide used in the present invention include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, manganese hydroxide, zinc hydroxide, hydrotalcite alone or a mixture thereof. A mixture containing magnesium hydroxide alone and magnesium hydroxide, or a mixture containing aluminum hydroxide alone and aluminum hydroxide is particularly preferred.
トリアジン系化合物（Ｅ）
本発明において使用されるトリアジン環含有化合物（Ｅ）は、一般に難燃剤として知られたものならば何でもよく、例えば、メラミン、アンメリン、メラム、ベンズグアナミン、アセトグアナミン、フタロジグアナミン、メラミンシアヌレート、ピロリン酸メラミン、ブチレンジグアナミン、ノルボルネンジグアナミン、メチレンジメラミン、エチレンジメラミン、トリメチレンジメラミン、テトラメチレンンジメラミン、ヘキサメチレンジメラミン、１，３−ヘキシレンジメラミン等を例示することができる。これらのうち、メラミンシアヌレートが好適に使用される。トリアジン環含有化合物の配合量は、前記したエチレン・α−オレフィン共重合体（Ａ）とエチレンとビニルエステルとの共重合体（Ｂ）の合計量１００重量部に対して０．１〜５０重量部、好ましくは５〜４０重量部である。配合量が１重量部未満であると、この化合物から燃焼不活性ガス（窒素ガス）の発生が有意とならず、他の難燃剤との相乗効果を発揮しない。一方、５０重量部を超えても難燃性の効果はそれほどあがらず、むしろ成形加工性や得られる成形品の機械的特性等に悪影響が生じることがあり、望ましくない。 Triazine compound (E)
The triazine ring-containing compound (E) used in the present invention may be any compound generally known as a flame retardant, such as melamine, ammelin, melam, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, Examples include melamine pyrophosphate, butylene diguanamine, norbornene diguanamine, methylene dimelamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimelamine, and the like. . Of these, melamine cyanurate is preferably used. The compounding quantity of a triazine ring containing compound is 0.1-50 weight with respect to 100 weight part of total amounts of the above-mentioned ethylene-alpha-olefin copolymer (A) and the copolymer (B) of ethylene and vinyl ester. Parts, preferably 5 to 40 parts by weight. When the blending amount is less than 1 part by weight, generation of combustion inert gas (nitrogen gas) from this compound is not significant, and a synergistic effect with other flame retardants is not exhibited. On the other hand, if the amount exceeds 50 parts by weight, the effect of flame retardancy is not so much increased. Rather, the processability and the mechanical properties of the resulting molded product may be adversely affected, which is not desirable.
粉末シリコーン
本発明の粉末シリコーン（シリコーンパウダーとも言う）としては、有機オルガノポリシロキサン粉末、例えばジメチルポリシロキサン粉末等が挙げられる。また本発明の粉末シリコーンとしてはＧＰＣで測定されるその分子量（Ｍｎ）が１０００００〜１０００００００、好ましくは５０００００〜５００００００である。 Powdered silicone The powdered silicone (also referred to as silicone powder) of the present invention includes organic organopolysiloxane powder such as dimethylpolysiloxane powder. The powder silicone of the present invention has a molecular weight (Mn) measured by GPC of 100,000 to 10,000,000, preferably 500,000 to 5,000,000.
その他添加剤
本発明に係る重合体組成物には、上記の他に、必要に応じて、酸化防止剤、紫外線吸収剤、耐候安定剤、耐熱安定剤、帯電防止剤、難燃剤、顔料、染料、滑剤などの添加剤を配合することができる。また本発明に係る重合体組成物には難燃助剤としてホウ酸化合物、好ましくはホウ酸亜鉛を含むとより好ましい。 Other additives In addition to the above, the polymer composition according to the present invention includes, as necessary, an antioxidant, an ultraviolet absorber, a weathering stabilizer, a heat stabilizer, an antistatic agent, and a flame retardant. Additives such as pigments, dyes and lubricants can be blended. Further, it is more preferable that the polymer composition according to the present invention contains a boric acid compound, preferably zinc borate, as a flame retardant aid.
重合体組成物
本発明に係る重合体組成物は
エチレン・α−オレフィン共重合体（Ａ）５１〜９５重量部
エチレンとビニルエステルとの共重合体（Ｂ）５〜４９重量部
（Ａ）（Ｂ）の合計量１００重量部に対して
グラフト変性エチレン系重合体（Ｃ）０．１〜５０重量部
金属水酸化物（Ｄ）５０〜２５０重量部
トリアジン系化合物（Ｅ）０．１〜５０重量部
粉末シリコーン（Ｆ）０．１〜４０重量部
を含み、（Ｅ）と（Ｆ）の重量比（（Ｅ）／（Ｆ））が１．２以上であることを特徴とする。 Polymer composition The polymer composition according to the present invention comprises an ethylene / [alpha] -olefin copolymer (A) of 51 to 95 parts by weight of a copolymer of ethylene and vinyl ester (B) of 5 to 49 parts by weight. (A) Graft-modified ethylene polymer (C) 0.1-50 parts by weight Metal hydroxide (D) 50-250 parts by weight Triazine compound (E) 0 with respect to 100 parts by weight of the total amount of (B) 0.1 to 50 parts by weight Powdered silicone (F) 0.1 to 40 parts by weight, (E) and (F) weight ratio ((E) / (F)) is 1.2 or more And
より好ましくは、エチレン・α−オレフィン共重合体（Ａ）５１〜８５重量部
エチレンとビニルエステルとの共重合体（Ｂ）１５〜４９重量部
（Ａ）（Ｂ）の合計量１００重量部に対して
グラフト変性エチレン系重合体（Ｃ）０．１〜４０重量部
金属水酸化物（Ｄ）５０〜２５０重量部
トリアジン系化合物（Ｅ）１〜４０重量部
粉末シリコーン（Ｆ）０．１〜２６重量部
を含み、（Ｅ）と（Ｆ）の重量比（（Ｅ）／（Ｆ））が１．５以上である。More preferably, ethylene-α-olefin copolymer (A) 51-85 parts by weight Copolymer of ethylene and vinyl ester (B) 15-49 parts by weight (A) (B) Graft-modified ethylene polymer (C) 0.1 to 40 parts by weight Metal hydroxide (D) 50 to 250 parts by weight Triazine compound (E) 1 to 40 parts by weight Powdered silicone (F) 0.1 to Including 26 parts by weight, the weight ratio of (E) to (F) ((E) / (F)) is 1.5 or more.
さらにより好ましくはエチレン・α−オレフィン共重合体（Ａ）５５〜８５重量部
エチレンとビニルエステルとの共重合体（Ｂ）１５〜４５重量部
（Ａ）（Ｂ）の合計量１００重量部に対して
グラフト変性エチレン系重合体（Ｃ）０．１〜３０重量部
金属水酸化物（Ｄ）５０〜２５０重量部
トリアジン系化合物（Ｅ）５〜４０重量部
粉末シリコーン（Ｆ）０．１〜２６重量部
を含み、（Ｅ）と（Ｆ）の重量比（（Ｅ）／（Ｆ））が１．５以上である。
最も好ましくはエチレン・α−オレフィン共重合体（Ａ）５５〜７５重量部
エチレンとビニルエステルとの共重合体（Ｂ）２５〜４５重量部
（Ａ）（Ｂ）の合計量１００重量部に対して
グラフト変性エチレン系重合体（Ｃ）０．１〜３０重量部
金属水酸化物（Ｄ）５０〜２５０重量部
トリアジン系化合物（Ｅ）５〜４０重量部
粉末シリコーン（Ｆ）０．１〜２６重量部
を含み、（Ｅ）と（Ｆ）の重量比（（Ｅ）／（Ｆ））が２．０以上である。Even more preferably, the ethylene / α-olefin copolymer (A) is 55 to 85 parts by weight. The total amount of ethylene and vinyl ester copolymer (B) 15 to 45 parts by weight (A) (B) is 100 parts by weight. Graft-modified ethylene polymer (C) 0.1-30 parts by weight Metal hydroxide (D) 50-250 parts by weight Triazine compound (E) 5-40 parts by weight Powdered silicone (F) 0.1 Including 26 parts by weight, the weight ratio of (E) to (F) ((E) / (F)) is 1.5 or more.
Most preferably, the ethylene / α-olefin copolymer (A) is 55 to 75 parts by weight with respect to 100 parts by weight of the total amount of the copolymer of ethylene and vinyl ester (B) 25 to 45 parts by weight (A) (B). Graft-modified ethylene polymer (C) 0.1-30 parts by weight Metal hydroxide (D) 50-250 parts by weight Triazine compound (E) 5-40 parts by weight Powdered silicone (F) 0.1-26 The weight ratio of (E) to (F) ((E) / (F)) is 2.0 or more, including parts by weight.
また難燃助剤としてホウ酸化合物をエチレン・α−オレフィン共重合体（Ａ）およびエチレンとビニルエステルとの共重合体（Ｂ）の（Ａ）（Ｂ）の合計量１００重量部に対して、０．１〜３０重量部、好ましくは０．１〜２０重量部含むとより好ましい。In addition, boric acid compound as a flame retardant aid is used for 100 parts by weight of the total amount of (A) and (B) of ethylene / α-olefin copolymer (A) and ethylene / vinyl ester copolymer (B). 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight.
本発明に係る重合体組成物は、上記の（Ａ）（Ｂ）（Ｃ）（Ｄ）（Ｅ）および（Ｆ）成分と、必要に応じて配合される添加剤とを、種々の従来公知の方法で溶融混合することにより調製される。The polymer composition according to the present invention comprises the above-described components (A), (B), (C), (D), (E), and (F), and various conventionally known additives that are blended as necessary. It is prepared by melt-mixing by the method of.
例えば、本発明に係る重合体組成物は、上記各成分を同時に、または逐次的に、たとえばヘンシェルミキサー、Ｖ型ブレンダー、タンブラーミキサー、リボンブレンダー等に装入して混合した後、単軸押出機、多軸押出機、ニーダー、バンバリーミキサー等で溶融混練することによって得られる。For example, the polymer composition according to the present invention is prepared by mixing the above-mentioned components simultaneously or sequentially into, for example, a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, etc. It is obtained by melt-kneading with a multi-screw extruder, kneader, Banbury mixer or the like.
これらの内でも、多軸押出機、ニーダー、バンバリーミキサー等の混練性能に優れた装置を使用すると、各成分がより均一に分散された高品質の重合体組成物が得られる。Among these, when a device excellent in kneading performance such as a multi-screw extruder, a kneader, and a Banbury mixer is used, a high-quality polymer composition in which each component is more uniformly dispersed can be obtained.
また、これらの任意の段階で必要に応じて前記添加剤、たとえば酸化防止剤などを添加することもできる。Moreover, the said additive, for example, antioxidant etc., can also be added as needed in these arbitrary steps.
難燃性エチレン系樹脂組成物を含む成形体
本発明に係る成形体は、本発明に係る難燃性エチレン系樹脂組成物を用い、従来公知の溶融成形法、たとえば押出成形、回転成形、カレンダー成形、射出成形、圧縮成形、トランスファー成形、粉末成形、ブロー成形、真空成形などの方法により、種々の形状に成形することができる。 Molded product containing flame retardant ethylene-based resin composition The molded product according to the present invention uses a flame-retardant ethylene-based resin composition according to the present invention, and a conventionally known melt molding method such as extrusion molding, It can be formed into various shapes by methods such as rotational molding, calendar molding, injection molding, compression molding, transfer molding, powder molding, blow molding, and vacuum molding.
本発明に係る難燃性エチレン系樹脂組成物を例えば電線シースや電線の絶縁体などの電線被覆の用途に好適に使用できる。また本発明に係る成形体は、電線シースや電線の絶縁体などの被覆層であり、この電線シースや電線の絶縁体などの被覆層は、従来公知の方法たとえば押出成形などの方法により電線の周囲に形成される。The flame-retardant ethylene-based resin composition according to the present invention can be suitably used for wire coating applications such as a wire sheath or a wire insulator. Further, the molded body according to the present invention is a coating layer such as an electric wire sheath or an electric wire insulator, and the electric wire sheath or electric wire insulation layer such as an electric wire insulator is formed by a conventionally known method such as extrusion molding. Formed around.
以下、本発明を実施例により更に具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
なお、エチレン・α−オレフィン共重合体の物性は以下のようにして評価した。
（１）密度
１９０℃、２．１６ｋｇ荷重におけるＭＦＲ測定後のストランドを、１２０℃で１時間熱処理し、１時間かけて室温まで徐冷したのち、密度勾配管法により測定した。
（２）α−オレフィン含量、Ｔαβ／Ｔαα、Ｂ値
１３Ｃ−ＮＭＲスペクトルによって決定した。
（３）Ｍｗ／Ｍｎ
ＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用い、オルトジクロロベンゼン溶媒で、１４０℃で測定した。
（４）ＭＦＲ１０／ＭＦＲ２
ＡＳＴＭ Ｄ−１２３８に準拠し、１９０℃における１０ｋｇ荷重でのＭＦＲ１０と、２．１６ｋｇ荷重でのＭＦＲ２とを測定し、比を算出した。この比が大きいと、ポリマーの溶融時の流動性が優れていることを示し、すなわち加工性が高い。The physical properties of the ethylene / α-olefin copolymer were evaluated as follows.
(1) The strand after the MFR measurement at a density of 190 ° C. and a load of 2.16 kg was heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured by a density gradient tube method.
(2) α-olefin content, Tαβ / Tαα, B value
Determined by 13 C-NMR spectrum.
(3) Mw / Mn
GPC (gel permeation chromatography) was used and measured at 140 ° C. with an orthodichlorobenzene solvent.
(4) MFR 10 / MFR 2
Based on ASTM D-1238, MFR 10 at a load of 10 kg at 190 ° C. and MFR 2 at a load of 2.16 kg were measured, and the ratio was calculated. When this ratio is large, it indicates that the fluidity at the time of melting of the polymer is excellent, that is, the processability is high.
実施例等で用いたエチレン・α−オレフィン共重合体、エチレンとビニルエステルとの共重合体、グラフト変性エチレン系重合体、金属水酸化物、トリアジン系化合物、粉末シリコーンおよびシリコーンレジンは次のとおりである。The ethylene / α-olefin copolymer, copolymer of ethylene and vinyl ester, graft-modified ethylene polymer, metal hydroxide, triazine compound, powdered silicone and silicone resin used in Examples etc. are as follows: It is.
エチレン・α−オレフィン共重合体（Ａ）：
以下の製造例１で調製したエチレン・１−ブテン共重合体Ａ−１である。Ethylene / α-olefin copolymer (A):
It is the ethylene / 1-butene copolymer A-1 prepared in the following Production Example 1.
［製造例１］
（エチレン・１−ブテン共重合体Ａ−１の調製）
トリフェニルカルベニウム（テトラキスペンタフルオロフェニル）ボレートを１８．４ｍｇとり、トルエンを５ｍｌ加えて溶解させ、濃度が０．００４ｍＭ／ｍｌのトルエン溶液を調製した。［ジメチル（ｔ−ブチルアミド）（テトラメチル−η５−シクロペンタジエニル）シラン］チタンジクロライドを１．８ｍｇとり、トルエンを５ｍｌ加えて溶解させ、濃度が０．００１ｍＭ／ｍｌのトルエン溶液を調製した。重合開始時においてはトリフェニルカルベニウム（テトラキスペンタフルオロフェニル）ボレートのトルエン溶液を０．３８ｍｌ、［ジメチル（ｔ−ブチルアミド）（テトラメチル−η５−シクロペンタジエニル）シラン］チタンジクロライドのトルエン溶液を０．３８ｍｌとり、さらに希釈用のトルエンを４．２４ｍｌ加えて、トリフェニルカルベニウム（テトラキスペンタフルオロフェニル）ボレートがＢ換算で０．００２ｍＭ／Ｌに、［ジメチル（ｔ−ブチルアミド）（テトラメチル−η５−シクロペンタジエニル）シラン］チタンジクロリドがＴｉ換算で０．０００５ｍＭ／Ｌとなるトルエン溶液を５ｍｌ調製した。[Production Example 1]
(Preparation of ethylene / 1-butene copolymer A-1)
18.4 mg of triphenylcarbenium (tetrakispentafluorophenyl) borate was taken and 5 ml of toluene was added and dissolved to prepare a toluene solution having a concentration of 0.004 mM / ml. [Dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] 1.8 mg of titanium dichloride was taken and dissolved by adding 5 ml of toluene to prepare a toluene solution having a concentration of 0.001 mM / ml. At the start of polymerization, 0.38 ml of a toluene solution of triphenylcarbenium (tetrakispentafluorophenyl) borate and a toluene solution of [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium dichloride were added. Take 0.38 ml, add 4.24 ml of toluene for dilution, and triphenylcarbenium (tetrakispentafluorophenyl) borate to 0.002 mM / L in terms of B, [dimethyl (t-butylamide) (tetramethyl- [η5-cyclopentadienyl) silane] titanium dichloride was prepared in an amount of 5 ml of a toluene solution with a Ti conversion of 0.0005 mM / L.
充分窒素置換した容量１．５リットルの攪拌翼付ＳＵＳ製オートクレーブに、２３℃でヘプタン７５０ｍｌを挿入した。このオートクレーブに、攪拌翼を回し、かつ氷冷しながら１−ブテン１０ｇ、水素１００ｍｌを挿入した。次にオートクレーブを１００℃まで加熱し、更に、全圧が６ＫＧとなるようにエチレンで加圧した。オートクレーブの内圧が６ＫＧになった所で、トリイソブチルアルミニウム（ＴＩＢＡ）の１．０ｍＭ／ｍｌヘキサン溶液１．０ｍｌを窒素で圧入した。続いて、上記の如く調製した触媒溶液５ｍｌを、窒素でオートクレーブに圧入し重合を開始した。その後、５分間、オートクレーブを内温１００℃になるように温度調製し、かつ圧力が６ｋｇとなるように直接的にエチレンの供給を行った。重合開始５分後、オートクレーブにポンプでメタノール５ｍｌを挿入し重合を停止し、オートクレーブを大気圧まで脱圧した。反応溶液に３リットルのメタノールを攪拌しながら注いだ。得られた溶媒を含む重合体を１３０℃、１３時間、６００ｔｏｒｒで乾燥して１０ｇのエチレン・ブテン共重合体Ａ−１を得た。得られたエチレン・１−ブテン共重合体の性状を表１に示す。750 ml of heptane was inserted at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 1.5 liters that had been sufficiently purged with nitrogen. In this autoclave, 10 g of 1-butene and 100 ml of hydrogen were inserted while rotating a stirring blade and cooling with ice. Next, the autoclave was heated to 100 ° C. and further pressurized with ethylene so that the total pressure was 6 KG. When the internal pressure of the autoclave reached 6KG, 1.0 ml of a 1.0 mM / ml hexane solution of triisobutylaluminum (TIBA) was injected with nitrogen. Subsequently, 5 ml of the catalyst solution prepared as described above was pressed into the autoclave with nitrogen to initiate polymerization. Thereafter, the temperature of the autoclave was adjusted to an internal temperature of 100 ° C. for 5 minutes, and ethylene was directly supplied so that the pressure became 6 kg. Five minutes after the start of the polymerization, 5 ml of methanol was inserted into the autoclave by a pump to stop the polymerization, and the autoclave was depressurized to the atmospheric pressure. 3 liters of methanol was poured into the reaction solution with stirring. The resulting polymer containing the solvent was dried at 130 ° C. for 13 hours at 600 torr to obtain 10 g of ethylene / butene copolymer A-1. Table 1 shows the properties of the obtained ethylene / 1-butene copolymer.
エチレンとビニルエステルとの共重合体（Ｂ）：
エチレン−酢酸ビニル共重合体商品名ＥＶＡＦＬＥＸ ＥＶ３６０（三井デュポンポリケミカル（株）製）（以下ＥＶＡと略する）。Copolymer of ethylene and vinyl ester (B):
Ethylene-vinyl acetate copolymer trade name EVAFLEX EV360 (manufactured by Mitsui DuPont Polychemical Co., Ltd.) (hereinafter abbreviated as EVA).
グラフト変性エチレン系重合体（Ｃ）：
以下の製造例２で調整した無水マレイン酸グラフト変性エチレン・１−ブテン共重合体である。Graft-modified ethylene polymer (C):
It is a maleic anhydride graft-modified ethylene / 1-butene copolymer prepared in the following Production Example 2.
［製造例２］
（無水マレイン酸グラフト変性エチレン・１−ブテン共重合体の調製）
上記エチレン・１−ブテン共重合体Ａ−１ １０ｋｇと無水マレイン酸５０ｇおよびジーｔｅｒｔ−ブチルペルオキシド３ｇを５０ｇのアセトンに溶解させた溶液とをヘンシェルミキサー中でブレンドした。[Production Example 2]
(Preparation of maleic anhydride graft-modified ethylene / 1-butene copolymer)
10 kg of the above ethylene / 1-butene copolymer A-1 was blended in a Henschel mixer with a solution of 50 g of maleic anhydride and 3 g of di-tert-butyl peroxide in 50 g of acetone.
次いで、上記のようにして得られたブレンド物をスクリュー径４０ｍｍ、Ｌ／Ｄ＝２６の１軸押出機のホッパーより投入し、樹脂温度２６０℃、押出量６ｋｇ／時間でストランド状に押し出して水冷した後、ペレタイズして無水マレイン酸グラフト変性エチレン・１−ブテン共重合体Ｃ−１を得た。Next, the blend obtained as described above was introduced from a hopper of a single screw extruder having a screw diameter of 40 mm and L / D = 26, extruded into a strand at a resin temperature of 260 ° C. and an extrusion rate of 6 kg / hour, and then water-cooled. And then pelletized to obtain maleic anhydride graft-modified ethylene / 1-butene copolymer C-1.
得られたグラフト変性エチレン・１−ブテン共重合体Ｃ−１から未反応の無水マレイン酸をアセトンで抽出後、このグラフト変性エチレン・１−ブテン共重合体中における無水マレイン酸グラフト量を測定した結果、このグラフト量は０．４３重量％であった。Unreacted maleic anhydride was extracted from the graft-modified ethylene / 1-butene copolymer C-1 with acetone, and the amount of maleic anhydride grafted in the graft-modified ethylene / 1-butene copolymer was measured. As a result, the graft amount was 0.43% by weight.
金属水酸化物（Ｄ）：
水酸化マグネシウム商品名キスマ５Ｂ（協和化学（株）製）
トリアジン系化合物（Ｅ）：
メラミンシアヌレート商品名ＭＣ−４４０（日産化学（株）製）
粉末シリコーン（Ｆ）：
ポリオルガノシロキサン商品名ＤＣ４−７０８１（東レ・ダウコーニング（株）製）
ＧＰＣ法により測定した数平均分子量（Ｍｎ）：１００００００
また、絶縁電線サンプルの作製とその評価は次の方法で行った。Metal hydroxide (D):
Magnesium hydroxide trade name Kisuma 5B (manufactured by Kyowa Chemical Co., Ltd.)
Triazine compound (E):
Melamine cyanurate trade name MC-440 (manufactured by Nissan Chemical Co., Ltd.)
Powdered silicone (F):
Polyorganosiloxane product name DC4-7081 (manufactured by Dow Corning Toray)
Number average molecular weight (Mn) measured by GPC method: 1000000
Insulated wire samples were prepared and evaluated by the following method.
（絶縁電線サンプルの作製）
表２に示した組成の重合体組成物を溶融押出機（東洋精機社製、製品名ラボプラストミル）に電線被覆用ダイスを設置したものを用いて、ダイス温度：１９０℃、スクリュー回転：３０ｒｐｍ、押出量：１．６〜１．８ｋｇ／ｈで素線径
０．４５ｍｍの軟銅線の７本撚り導体（外径約１．３５ｍｍ）の周囲を０．８ｍｍ厚の重合体組成物で被覆して仕上がり径３．０ｍｍの絶縁電線サンプルを得た。(Preparation of insulated wire sample)
A polymer composition having the composition shown in Table 2 was prepared by using a melt extruder (manufactured by Toyo Seiki Co., Ltd., product name: Labo Plast Mill) with a wire coating die installed therein. Die temperature: 190 ° C., screw rotation: 30 rpm , Extrusion amount: 1.6 to 1.8 kg / h, coated with a 0.8 mm thick polymer composition around a 7-strand conductor of an annealed copper wire having an element wire diameter of 0.45 mm (outer diameter of about 1.35 mm) Thus, an insulated wire sample having a finished diameter of 3.0 mm was obtained.
（５）破断点強度及び破断点伸び
ＪＩＳ Ｋ６３０１に準拠し、スパン間２０ｍｍ、引張速度２００ｍｍ／分にて引張試験を行い、破断点強度及び破断点伸びを測定した。(5) Strength at break and elongation at break According to JIS K6301, a tensile test was conducted at a span interval of 20 mm and a tensile speed of 200 mm / min to measure the strength at break and the elongation at break.
（６）ねじり剛性
東洋精機（株）製クラッシュバーグ式柔軟度試験機を用い、ＪＩＳ Ｋ６７４５に準拠し、温度２３℃のねじり剛性を測定した。(6) Torsional rigidity The torsional rigidity at a temperature of 23 ° C. was measured according to JIS K6745 using a Crushberg-type flexibility tester manufactured by Toyo Seiki Co., Ltd.
（７）難燃性（燃焼試験）
ＵＬ規格ＶＷ−１に制定される垂直燃焼試験に基づき、上記で作製した絶縁電線サンプルを用いて実施した。(7) Flame resistance (combustion test)
Based on the vertical combustion test established in UL standard VW-1, it carried out using the insulated wire sample produced above.
上記の評価結果を表２に示す。The evaluation results are shown in Table 2.
本発明の樹脂組成物は可撓性・柔軟性が良好でありかつ難燃効果に優れるので例えば電線シースや電線の絶縁体などの電線被覆の用途に好適に使用できる。Since the resin composition of the present invention has good flexibility and flexibility and is excellent in flame retardancy, it can be suitably used for wire coating applications such as wire sheaths and wire insulators.
Claims (3)
エチレンとビニルエステルとの共重合体（Ｂ）５〜４９重量部
（Ａ）（Ｂ）の合計量１００重量部に対して
グラフト変性エチレン系重合体（Ｃ）０．１〜５０重量部
金属水酸化物（Ｄ）５０〜２５０重量部
トリアジン系化合物（Ｅ）２０〜５０重量部
粉末シリコーン（Ｆ）１０〜４０重量部
を含み、（Ｅ）と（Ｆ）の重量比（（Ｅ）／（Ｆ））が１．２以上であることを特徴とする難燃性エチレン系樹脂組成物。Ethylene / α-olefin copolymer (A) 51 to 95 parts by weight Copolymer of ethylene and vinyl ester (B) 5 to 49 parts by weight (A) (B) Graft-modified Ethylene polymer (C) 0.1-50 parts by weight metal hydroxide (D) 50-250 parts by weight triazine compound (E) 20-50 parts by weight powdered silicone (F) 10-40 parts by weight, A flame retardant ethylene-based resin composition, wherein a weight ratio ((E) / (F)) of (E) to (F) is 1.2 or more.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03121149A (en) * | 1989-10-03 | 1991-05-23 | Showa Electric Wire & Cable Co Ltd | Flame-retardant resin composition |
| JPH0931262A (en) * | 1995-07-19 | 1997-02-04 | Nippon Unicar Co Ltd | Flame-retardant ethylene-based resin composition |
| JP2000239459A (en) * | 1999-02-19 | 2000-09-05 | Nippon Unicar Co Ltd | Flame-retardant ethylene resin composition and electrical wire/cable |
| WO2003106554A1 (en) * | 2002-06-14 | 2003-12-24 | 三井化学株式会社 | Thermoplastic resin composition, polymer composition, and molded object obtained from the composition |
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| JPH09296083A (en) * | 1996-05-01 | 1997-11-18 | Nippon Unicar Co Ltd | Flame-retardant electric wire and cable |
| JP2002322325A (en) * | 2001-04-27 | 2002-11-08 | Sumitomo Wiring Syst Ltd | Olefinic elastomer composition |
| JP2003268250A (en) * | 2002-03-20 | 2003-09-25 | Fujikura Ltd | Nonhalogen flame-retardant composition and flame- retardant power source cord |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03121149A (en) * | 1989-10-03 | 1991-05-23 | Showa Electric Wire & Cable Co Ltd | Flame-retardant resin composition |
| JPH0931262A (en) * | 1995-07-19 | 1997-02-04 | Nippon Unicar Co Ltd | Flame-retardant ethylene-based resin composition |
| JP2000239459A (en) * | 1999-02-19 | 2000-09-05 | Nippon Unicar Co Ltd | Flame-retardant ethylene resin composition and electrical wire/cable |
| WO2003106554A1 (en) * | 2002-06-14 | 2003-12-24 | 三井化学株式会社 | Thermoplastic resin composition, polymer composition, and molded object obtained from the composition |
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| TWI293081B (en) | 2008-02-01 |
| CN1934185A (en) | 2007-03-21 |
| WO2005092975A1 (en) | 2005-10-06 |
| CN100567385C (en) | 2009-12-09 |
| TW200619291A (en) | 2006-06-16 |
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