WO1993001236A1 - Thermoplastic elastomer composition - Google Patents

Thermoplastic elastomer composition Download PDF

Info

Publication number
WO1993001236A1
WO1993001236A1 PCT/JP1991/000938 JP9100938W WO9301236A1 WO 1993001236 A1 WO1993001236 A1 WO 1993001236A1 JP 9100938 W JP9100938 W JP 9100938W WO 9301236 A1 WO9301236 A1 WO 9301236A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoplastic elastomer
ethylene
copolymer
elastomer composition
olefin
Prior art date
Application number
PCT/JP1991/000938
Other languages
French (fr)
Japanese (ja)
Inventor
Masaji Yamamori
Mitsuaki Maeda
Original Assignee
Monsanto Japan Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Japan Limited filed Critical Monsanto Japan Limited
Publication of WO1993001236A1 publication Critical patent/WO1993001236A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L23/10—Homopolymers or copolymers of propene

Definitions

  • the present invention relates to a thermoplastic elastomer composition, and more particularly, to a thermoplastic elastomer composition having high tear strength while maintaining low hardness (flexibility).
  • ⁇ ⁇ ⁇ ⁇ elastomer an olefin-based thermoplastic elastomer (hereinafter referred to as ⁇ ⁇ ⁇ ⁇ elastomer) composed of ⁇ -monoolefin copolymer rubber (typically EPDM) and crystalline polyolefin resin (typically PP) has been used.
  • EPDM ⁇ -monoolefin copolymer rubber
  • PP crystalline polyolefin resin
  • the present invention relates to an orifice-based thermoplastic elastomer ( a ) composed of an ⁇ -monoolefin copolymer rubber and a crystalline polyolefin resin, ( a ) 30 to 90% by weight;
  • thermoplastic elastomer composition comprising a C- or more ethylene- ⁇ -refined copolymer (b) in an amount of 7% to 10% by weight.
  • thermoplastic elastomer composition of the present invention comprises a TPO elastomer and a density of 0.870 to 0.91 ⁇ g ⁇ , and a vicatification temperature of 50 ° C or more.
  • the two components of the ethylene- ⁇ -refined copolymer are essential components.
  • the ⁇ -monoolefin copolymer rubber that constitutes the ⁇ 0 elastomer is essentially a non-polymer composed of a copolymer of at least one polyene (usually a gen) and two or more ⁇ -monoolefins.
  • a crystalline rubbery copolymer, P-DM is preferred.
  • the fin resin is a crystalline polymer obtained by polymerizing an olefin such as ethylene, propylene, butene-11, pentene-11, etc., alone or in combination of two or more thereof by an ordinary method.
  • a copolymer typically, such as polyethylene, a copolymer containing ethylene as a main component, polypropylene, a copolymer containing propylene as a main component, and polybutene.
  • a copolymer containing propylene as a main component is preferable.
  • the proportions of the ⁇ -monoolefin copolymer rubber and the crystalline polyolefin resin are usually 40 to 80% by weight of the ⁇ -monoolefin copolymer rubber and 60 to 20% by weight of the crystalline polyolefin resin. %. Both components are kneaded at a temperature higher than the melting point and become an elastomer.
  • the kneading treatment is performed by using a peroxide, a fuanol resin, sulfur, or the like. It is carried out in the presence of a vulcanizing agent.
  • the elastomer may contain other components as long as the rubber properties and the like are not impaired. Specifically, for example, an oil, a filler, a carbon black, a stabilizer and the like are mixed.
  • the one-year-old olefin to be copolymerized with ethylene generally has 3 to 6 carbon atoms. Specifically, propylene, butene-1, 1,4-methylpentene-11, hexene-11, etc.
  • the ⁇ -olefin content in the copolymer is not particularly limited, but is preferably from 5 to 4 mol%.
  • the ethylene one-year-old olefin copolymer used in the present invention has a density of 0.870 to 0.910 g ZCTI, preferably 0.895 to 0.910 g ZCTi. There must be. Dense Echiren the density exceeds 0. 9 1 0 g Zc / n 3 - a
  • the Orefui down copolymer upon the composition by blending the TP 0 Heras Tomah foremost, the flexibility of the composition lost Also, there is no effect of improving the tear strength of the composition.
  • an ethylene- ⁇ -olefin copolymer having a density lower than 0.870 g is not preferred because the tensile strength of the composition is reduced and the tackiness is too large.
  • the density of a general ethylene-based polymer is, for example, low density polyethylene (LDPE): 0.910 to
  • the ethylene- ⁇ -olefin copolymer used in the present invention is an extremely low-density ethylene-based polymer, unlike such a general polyethylene or a copolymer thereof, and generally comprises VLDPE. (Very Low Dens i ty
  • the ethylene- ⁇ -olefin copolymer used in the present invention must have a density in the specific range described above and have a vicat softening temperature (JISK7206) of 50 C or more.
  • Bikatsu preparative softening temperature in the present invention is used as the crystalline index, Bika' preparative softening temperature 5 0 e C than the polymer is a crystalline polymer. Therefore, the ethylene-one-year-old olefin copolymer used in the present invention is not an amorphous polymer.
  • the upper limit of the vicat softening temperature is not particularly limited.
  • Ethylene mono- ⁇ -olefin copolymers having such specific ranges of densities and bicut softening temperatures are commercially available from various companies under various brands. Co., Ltd.'s Nackflex® D One one
  • the blending ratio of the ethylene- ⁇ -age olefin copolymer is an important requirement, and TP0 elastomer and ethylene-free olefin copolymer have a total amount of TP 0
  • the proportion of the elastomer is 30 to 90% by weight 96, preferably 40 to 75% by weight, and the proportion of the ethylene- ⁇ -olefin copolymer is 70 to 10% by weight, preferably. Or between 6 ° and 25% by weight. If the proportion of the ethylene- ⁇ -olefin copolymer is less than the above range, the effect of improving the tear strength is not sufficient, and if it is more than the above range, the flexibility is lost and the elastomer is lost. Rubber elasticity, which is a characteristic of, is eliminated.
  • additives such as a plasticizer, a filler, a pigment, and a stabilizer can be blended within a range not to impair the purpose.
  • other rubbers or thermoplastic resins may be blended according to the purpose.
  • thermoplastic elastomer composition of the present invention can be obtained by uniformly kneading the elastomer, the ethylene- ⁇ -olefin copolymer, and other optional components in a molten state.
  • the kneading method is not particularly limited, and an ordinary kneading machine such as an extruder or a barrel can be used.
  • the kneading temperature is 18 ⁇ ⁇ 23 ⁇ .
  • the range of C is preferred.
  • the tear strength of TP0 elastomers varies significantly depending on their hardness.
  • the TP0 elastomer having the same hardness ethylene- ⁇ -olefin of component (b)
  • the physical properties of ⁇ ⁇ 0 elastomers of various hardnesses were measured and shown as a control.
  • test piece was prepared by pressing TP elastomer (Sant Plane®) into a flat plate having a thickness of 2 ⁇ (forming temperature: 180 ° C).
  • TPO Elastomer Santoprene®
  • Ethylene Eleven-Year-Olefin Copolymer Nakflex®
  • the kneaded material was taken out and formed into a plate having a thickness of 2 mni by a press (forming temperature: 180 ° C.) to prepare a test piece. Physical properties were measured for the above test pieces, and the results are shown in Table 1. I did not.
  • Specimens were prepared in the same manner as in the examples, except that polyethylene ( ⁇ ) was used instead of the ethylene- ⁇ -olefin copolymer.
  • thermoplastic elastomer composition of the present invention comprising a specific amount of an ethylene-olefin copolymer having specific physical properties, in contrast to the TP0 elastomer, The tear strength is improved without significantly impairing the flexibility.
  • LDPE, LLDPE, and HDPE are blended, the hardness increases, and therefore, only a small amount can be blended to maintain flexibility, and the blending also improves the tear strength. It is not allowed.
  • thermoplastic elastomer composition of the present invention has low hardness, that is, flexibility, and also has high tear strength. Therefore, the thermoplastic elastomer composition is advantageously used particularly in application fields where low hardness is required. can do.

Abstract

A thermoplastic elastomer composition comprising: a) 30 to 90 wt.% of an olefinic thermoplastic elastomer comprising an α-monoolefin copolymer rubber and a crystalline polyolefin resin and b) 70 to 10 wt.% of an ethylene-α-olefin copolymer with a density of 0.870 to 0.910 g/cm3 and a Vicat softening point of 50 °C or above.

Description

明 細 熱可塑性エラス トマ一組成物 技 術 分 野  Membrane Thermoplastic elastomer composition Technical field
本発明は熱可塑性エラス トマ一組成物に関するもので あり、 詳しく は、 低い硬度 （柔軟性） を維持した上で高 い引裂強度を有する熱可塑性エラス トマー組成物に関す る ものである。  The present invention relates to a thermoplastic elastomer composition, and more particularly, to a thermoplastic elastomer composition having high tear strength while maintaining low hardness (flexibility).
背 景 技 術  Background technology
従来、 α—モノォレフィ ン共重合体ゴム （代表的には E P D M ) と結晶性ポリオレフイ ン樹脂 （代表的には P P ) から成るォレフィ ン系熱可塑性エラス トマ一 （以下、 Γ Τ Ρ Οエラス トマ一」 と略記する） は、 比較的安価で あり、 バランスのとれた優.れた性能.を発揮する めに.、 広く使用されている。  Conventionally, an olefin-based thermoplastic elastomer (hereinafter referred to as Γ Τ Ρ 一 elastomer) composed of α-monoolefin copolymer rubber (typically EPDM) and crystalline polyolefin resin (typically PP) has been used. ) Is relatively inexpensive and widely used to provide well-balanced and excellent performance.
近年、 T P 0エラス トマ一の応用範囲が拡大されるに つれ、 要求性能も厳しく なつてきている。 特に、 低い硬 度が要求される用途に於いては、 材料が引き裂かれて破 断することが多く 、 引裂強度の改善が望まれている。  In recent years, as the application range of the TP0 elastomer has been expanded, the required performance has also become strict. In particular, in applications where low hardness is required, the material often tears and breaks, and improvement in tear strength is desired.
しかしながら、 従来の T P 0エラス トマ一では、 引裂 強度が十分ではないために、 低い硬度が要求される用途 には使用できず、 その物性改善が切望されている。  However, conventional TP0 elastomers cannot be used for applications requiring low hardness because of insufficient tear strength, and there is an urgent need to improve their physical properties.
発 明 の 開 示 一 一 本発明者等は上記実情に鑑み、 低い硬度を維持した上 で高い引裂強度を有する T P Oエラス トマ一を提供すベ く鋭意検討を重ねた結果、 特定量のある種のポリマーの 配合が効杲的であるとの知見を得、 それに基づいて本発 明を完成した。 Disclosure of the invention In view of the above circumstances, the present inventors have conducted intensive studies to provide a TPO elastomer having a high tear strength while maintaining a low hardness. We obtained a finding that it was effective, and based on that, completed the present invention.
即ち、 本発明は、 α—モノォレフィ ン共重合体ゴムと 結晶性ポリオレフィ ン樹脂から成るォレフィ ン系熱可塑 性エラス トマ一 （ a ) 3 0〜 9 0重量％と、 密度 That is, the present invention relates to an orifice-based thermoplastic elastomer ( a ) composed of an α-monoolefin copolymer rubber and a crystalline polyolefin resin, ( a ) 30 to 90% by weight;
0, 87 0〜 0. 9 1 0 g Z 、 ビカ ッ ト軟化温度 5 〇 。C以上のエチレン一 α—才レフィ ン共重合体 （ b ) 7 〇 〜 1 0重量％とを含んで成る熱可塑性エラス トマ一組成 物を提供するものである。  0, 870 0-0.910 g Z, Vicat softening temperature 5〇. It is intended to provide a thermoplastic elastomer composition comprising a C- or more ethylene-α-refined copolymer (b) in an amount of 7% to 10% by weight.
発明を実施するための最良の形態 本発明の熱可塑性エラス トマ一組成物は、 T P Oエラ ス トマーと密度 0. 87 0〜 0. 9 1 ◦ g Ζο、 ビカ ツ 卜软化温度 5 0 °C以上のェチレン一 α—才レフィ ン共重 合体の 2成分を必須成分とする。  BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic elastomer composition of the present invention comprises a TPO elastomer and a density of 0.870 to 0.91 ◦g Ζο, and a vicatification temperature of 50 ° C or more. The two components of the ethylene-α-refined copolymer are essential components.
先ず、 Τ Ρ 0エラス トマ一について説明する。  First, the Ρ に つ い て 0 elastomer will be described.
Τ Ρ 0エラス 卜マーを構成する α—モノォレフィ ン共 重合体ゴムは、 少く とも 1種のポリェン （通常はジェン） と 2種以上の α—モノォレフィ ンとの共重合体から成る 本質的に非晶性のゴム状共重合体であり、 P—D-Mが好 適でめる。  The α-monoolefin copolymer rubber that constitutes the 非 0 elastomer is essentially a non-polymer composed of a copolymer of at least one polyene (usually a gen) and two or more α-monoolefins. A crystalline rubbery copolymer, P-DM is preferred.
また、 Τ Ρ 0エラス トマ一を構成する結晶性ポリオレ フィ ン樹脂は、 エチレン、 プロ ピレン、 ブテン一 1、 ぺ ンテン一 1等のォレフィ ンを単独で、 又はこれらの 2種 以上を組合わせて、 常法で重合して得られる結晶性の重 合体又は共重合体であり、 代表的には、 ポ リエチレン、 エチレンを主成分とする共重合体、 ポ リ プロ ピレン、 プ ロビレンを主成分とする共重合体、 ポリブテン等が挙げ られるが、 ポリプロ ピレン又はプロピレンを主成分とす る共重合体が好適である。 In addition, the crystalline polyol that constitutes the Τ Ρ 0 elastomer is The fin resin is a crystalline polymer obtained by polymerizing an olefin such as ethylene, propylene, butene-11, pentene-11, etc., alone or in combination of two or more thereof by an ordinary method. Or a copolymer, typically, such as polyethylene, a copolymer containing ethylene as a main component, polypropylene, a copolymer containing propylene as a main component, and polybutene. Alternatively, a copolymer containing propylene as a main component is preferable.
α—モノォレフィ ン共重合体ゴムと結晶性ポリオレフ ィ ン樹脂の割合は、 通常、 α—モノォレフィ ン共重合体 ゴムが 4 0〜 8 0重量％、 結晶性ポリオレフィ ン樹脂が 6 0〜 2 0重量％でぁる。 両成分は、 融点以上で混練処 理され、 Τ Ρ Οエラス トマ一となる。  The proportions of the α-monoolefin copolymer rubber and the crystalline polyolefin resin are usually 40 to 80% by weight of the α-monoolefin copolymer rubber and 60 to 20% by weight of the crystalline polyolefin resin. %. Both components are kneaded at a temperature higher than the melting point and become an elastomer.
エラス トマ一と して有用な性質を付与するために、 α 一モノォレフィ ン共重合体ゴムを加硫するのが好ま しく、 この場合、 前記混練処理は、 過酸化物、 フユノール樹脂、 硫黄などの加硫剤の存在下に実施される。  In order to impart useful properties as an elastomer, it is preferable to vulcanize the α-monoolefin copolymer rubber. In this case, the kneading treatment is performed by using a peroxide, a fuanol resin, sulfur, or the like. It is carried out in the presence of a vulcanizing agent.
なお、 Τ Ρ Οエラス トマ一は、 そのゴム特性等を損わ ない限り他の成分を含んでいてもよい。 具体的には、 例 えばオイル、 充填剤、 カーボンブラ ック、 安定剤等が配 合される。  The elastomer may contain other components as long as the rubber properties and the like are not impaired. Specifically, for example, an oil, a filler, a carbon black, a stabilizer and the like are mixed.
Τ Ρ Οエラス トマ一は、 各社より種々の銘柄が市販さ れており、 例えば、 本出願人のサン 卜プレーン ®等が挙 げられる。 一 一 次に、 エチレン— α—ォレフィ ン共重合体について説 明する。 Various brands of Elastomer are commercially available from various companies, for example, the present applicant's Sunplane®. Next, the ethylene-α-olefin copolymer will be described.
ェチレンと共重合させる 一才レフィ ンは、 通常、 炭 素数 3〜 6のものであり、 具体的には、 プロ ピレン、 ブ テン一 1、 4ーメチルペンテン一 1、 へキセン一 1等で エチレン一 一ォレフィ ン共重合体中の α—ォ レフィ ン含有量は、 特に制限されるものではないが、 5〜4 ◦ モル％であることが好ま しい。  The one-year-old olefin to be copolymerized with ethylene generally has 3 to 6 carbon atoms. Specifically, propylene, butene-1, 1,4-methylpentene-11, hexene-11, etc. The α-olefin content in the copolymer is not particularly limited, but is preferably from 5 to 4 mol%.
本発明で使用するエチレン一 一才レフィ ン共重合体 は、 密度が 0. 8 7 0〜 0. 9 1 0 g ZCTI、 好ま しく は 0. 895〜 0. 9 1 0 g Z CTiのものでなければならな い。 密度が 0. 9 1 0 g Zc/n3を超える高密度のェチレン — な ーォレフイ ン共重合体では、 T P 0エラス トマ一に 配合して組成物と した際に、 組成物の柔軟性が失われ、 また、 組成物の引裂強度の改善効果もない。 そして、 逆 に、 0. 87 0 g より低密度のエチレン一 α—ォレ フィ ン共重合体では、 組成物の引張強度が低下し、 また、 粘着性が大きく なり過ぎ、 好ま しく ない。 The ethylene one-year-old olefin copolymer used in the present invention has a density of 0.870 to 0.910 g ZCTI, preferably 0.895 to 0.910 g ZCTi. There must be. Dense Echiren the density exceeds 0. 9 1 0 g Zc / n 3 - a The Orefui down copolymer, upon the composition by blending the TP 0 Heras Tomah foremost, the flexibility of the composition lost Also, there is no effect of improving the tear strength of the composition. Conversely, an ethylene-α-olefin copolymer having a density lower than 0.870 g is not preferred because the tensile strength of the composition is reduced and the tackiness is too large.
なお、 一般的なエチレン系ポリマーの密度は、 例えば、 低密度ポリエチレン （L D P E ) ： 0. 9 1 0〜  The density of a general ethylene-based polymer is, for example, low density polyethylene (LDPE): 0.910 to
0. 9 2 5 g- /cm, 線伏低密度ポリエチレン （ L L D P E ) ： 0. 9 1 8〜 0. 94 0 g: Zc/zi、 高密度ポリェチ レン （H D P E) : 0. 94 1〜◦ . 9 6 5 g ΖαιΙであ り、 本発明で使用するエチレン— α —ォレフィ ン共重合 体は、 このような一般的なポリ エチレン又はその共重合 体とは異なり、 極めて低密度のエチレン系重合体であつ て、 一般に、 V L D P E ( Very Low Dens i ty 0.925 g- / cm, low density low density polyethylene (LLDPE): 0.918 to 0.94 g: Zc / zi, high density polyethylene (HDPE): 0.941 to ◦. 9 6 5 g ΖαιΙ In contrast, the ethylene-α-olefin copolymer used in the present invention is an extremely low-density ethylene-based polymer, unlike such a general polyethylene or a copolymer thereof, and generally comprises VLDPE. (Very Low Dens i ty
Pol yethy l ene) と称せられるものである。  Pol yethy lene).
本発明で使用するエチレン一 α—才レフィ ン共重合体 は、 前記特定範囲の密度を有すると共にビカツ ト軟化温 度 （ J I S K 7 2 0 6 ) が 5 0 C以上のものでなけれ ばならない。  The ethylene-α-olefin copolymer used in the present invention must have a density in the specific range described above and have a vicat softening temperature (JISK7206) of 50 C or more.
上記範囲より低軟化温度のェチレン— α—才レフィ ン 共重合体では、 T P 0エラス トマ一に配合して組成物と した際に、 組成物の引張強度が低下し、 また、 耐熱性も 著しく低下し、 その結果、 熱可塑性エラス トマ一組成物 と しての有用な性質が失われる。  In the case of the ethylene-α-branched olefin copolymer having a softening temperature lower than the above range, when the composition is blended with the TP0 elastomer, the tensile strength of the composition is lowered and the heat resistance is also remarkably high. And loses its useful properties as a thermoplastic elastomer composition.
お、 本発明においてビカツ ト軟化温度は、 結晶性の 指標と して用いられており、 ビカッ ト軟化温度 5 0 eC以 上のポリマーは結晶性ポリマーである。 従って、 本発明 で使用するエチレン一 一才レフィ ン共重合体は、 非結 晶ポリマーではない。 また、 ビカッ ト軟化温度の上限は 特に制限されるものではない。 Contact, Bikatsu preparative softening temperature in the present invention is used as the crystalline index, Bika' preparative softening temperature 5 0 e C than the polymer is a crystalline polymer. Therefore, the ethylene-one-year-old olefin copolymer used in the present invention is not an amorphous polymer. The upper limit of the vicat softening temperature is not particularly limited.
このような特定範囲の密度およびビカツ ト軟化温度を 有するエチレン一 α —ォレフィ ン共重合体は、 各社より 種々の銘柄で市販されており、 本発明においては、 例え ば、 日本ュニ力一 （株） 製のナッ クフ レ ッ クス ®の " D 一 一 Ethylene mono-α-olefin copolymers having such specific ranges of densities and bicut softening temperatures are commercially available from various companies under various brands. Co., Ltd.'s Nackflex® D One one
F D A— 1 1 3 7 " (密度 0. 9 0 6 g Z m、 ビカ ッ ト 軟化温度 84 V) や "D E F D - 1 2 1 0 " (密度FDA—1 1 3 7 ”(density 0.909 g g m, vicat softening temperature 84 V) or“ D E F D-1 2 1 0 ”(density
0. 8 9 0 g /cm, ビカッ ト軟化温度 58で） が好適に 使用される。 0.890 g / cm, at a vicat softening temperature of 58).
本発明においては、 前記エチレン— α—才レフィ ン共 重合体の配合割合は重要な要件であり、 T P 0エラス ト マーとエチレン一 なーォレフィ ン共重合体の両成分の合 計に対し、 T P 0エラス トマ一の割合を 3 0〜 9 0重量 96, 好ま しく は 4 0〜 7 5重量％と し、 エチレン一 α _ ォレフィ ン共重合体の割合を 7 0〜 1 0重量％、 好ま し く は 6 ◦〜 2 5重量％にする必要がある。 エチレン一 α —ォレフィ ン共重合体の配合割合が上記範囲より少ない 場合は引裂強度の改善効果が十分ではなく、 逆に、 上記 範囲より多い場合は柔軟性が失われてエラス トマ一と し ての特徴であるゴム弾性がなく なる。  In the present invention, the blending ratio of the ethylene-α-age olefin copolymer is an important requirement, and TP0 elastomer and ethylene-free olefin copolymer have a total amount of TP 0 The proportion of the elastomer is 30 to 90% by weight 96, preferably 40 to 75% by weight, and the proportion of the ethylene-α-olefin copolymer is 70 to 10% by weight, preferably. Or between 6 ° and 25% by weight. If the proportion of the ethylene-α-olefin copolymer is less than the above range, the effect of improving the tear strength is not sufficient, and if it is more than the above range, the flexibility is lost and the elastomer is lost. Rubber elasticity, which is a characteristic of, is eliminated.
本発明においては、 その目的を損わない範囲で他の任 意成分、 例えば、 可塑剤、 充填剤、 顔料、 安定剤等の添 加剤を配合することができる。 また、 目的に応じて他の ゴムや熱可塑性樹脂を配合してもよい。  In the present invention, other optional components, for example, additives such as a plasticizer, a filler, a pigment, and a stabilizer can be blended within a range not to impair the purpose. Further, other rubbers or thermoplastic resins may be blended according to the purpose.
本発明の熱可塑性エラス トマ一組成物は、 Τ Ρ Οエラ ス トマー、 エチレン一 α—ォレフィ ン共重合体、 及び他 の任意成分を溶融状態で均一に混練することによ 得ら れる。 混練法は特に限定するものではなく、 押出機、 ンバリー等の通常の混鍊機が使用できる。 混練温度は、 18◦〜 23◦。Cの範囲が好適である。 The thermoplastic elastomer composition of the present invention can be obtained by uniformly kneading the elastomer, the ethylene-α-olefin copolymer, and other optional components in a molten state. The kneading method is not particularly limited, and an ordinary kneading machine such as an extruder or a barrel can be used. The kneading temperature is 18◦ ～ 23◦. The range of C is preferred.
以下、 本発明を実施例により更に詳细に説明するが、 本発明は、 その要旨を越えない限り、 以下の実施例に限 定されるものではない。 使用材料  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless departing from the gist of the present invention. Materials used
(1 ) ォレフィ ン系熱可塑性エラス トマ一  (1) Off-line thermoplastic elastomer
日本モンサン ト （株） 製 サン トプレーン ®  Santoprene ® manufactured by Nippon Monsanto Co., Ltd.
ショァ一 A硬度  Shore A hardness
1 0 1 64 64  1 0 1 64 64
1 0 1 73 73  1 0 1 73 73
1 0 1 S 0 80  1 0 1 S 0 80
1 0 1 87 87  1 0 1 87 87
(2) エチレン一 α—ォレフィ ン共重合体  (2) Ethylene-α-olefin copolymer
日本ュニカー （株） 製 ナッ クフ レッ クス ® 密度 g Z o ビカ ツ 卜 軟化温度 (。C) Nakflex® manufactured by Nippon Tunicer Co., Ltd. Density g Z o Viccut Softening temperature (.C)
D F DA- 1 1 37 0. 906 84 D E F D - 1 2 1 0 0. 890 5 S D F DA- 1 1 37 0.906 84 D E F D-1 2 1 0 0.890 5 S
( 3 ) ポ リエチレン 三 菱 化 成 （株） 製 ダイヤポリマー ® 密度 ( g- X c/?I) F l 〇 〇 ( L D P E ) 0. 922 (3) Diamond Polymer ®, manufactured by Polyethylene Mitsubishi Chemical Co., Ltd. Density (g-X c /? I) Fl 〇 〇 (LDPE) 0.922
U E 320 (L L D P E) 0. 924  U E 320 (L L D P E) 0.924
B R 300 (HD P E) 0. 947 物性試験法 BR 300 (HD PE) 0.947 Physical property test method
J I S K 6 3 0 1に準拠 （但し、 引裂強度は J I S K 6 3 0 1 B型によった）  Compliant with JISK6301 (However, tear strength is based on JISK6301B type)
対照例 1〜 _  Controls 1 to _
T P 0エラス トマ一の引裂強度は、 その硬度に応じて 大幅に異なる。 そこで、 本発明の T P 0エラス 卜マ一組 成物の物性、 特に引裂強度を評価するにあたり、 同一硬 度の T P 0エラス 卜マー （成分 （ b ) のエチ レ ン— α — ォ レフ ァ ン共重合体を含まない） と比較すべく 、 各種硬 度の Τ Ρ 0エラス トマ一の物性測定を行い、 対照例と し て示すことと した。  The tear strength of TP0 elastomers varies significantly depending on their hardness. Thus, in evaluating the physical properties, particularly the tear strength, of the TP0 elastomer composition of the present invention, the TP0 elastomer having the same hardness (ethylene-α-olefin of component (b)) was used. (Without copolymer), physical properties of Τ 硬 0 elastomers of various hardnesses were measured and shown as a control.
T P〇エラス トマ一 （サン ト プレー ン ®) をプ レスに て 2πιπι厚さの平板に成形し （成形温度 1 8 0 °C) 、 試験 片を作成した。  A test piece was prepared by pressing TP elastomer (Sant Plane®) into a flat plate having a thickness of 2πιπι (forming temperature: 180 ° C).
上記試験片について物性測定を行い、 その結果を表 1 に示した。  The physical properties of the above test pieces were measured, and the results are shown in Table 1.
実施例 1〜 7 Examples 1 to 7
T P Oエラス 卜マ一 （サン ト プレー ン ®) とエチ レ ン 一 一才 レフ イ ン共重合体 （ナ ッ ク フ レ ッ ク ス ®) の 2 成分を表一 1に示す割合でプラスチコーダに仕込み、 1 8〇。C、 1 0 ◦ rpm の条件下に 4分間混練した。  The two components of TPO Elastomer (Santoprene®) and Ethylene Eleven-Year-Olefin Copolymer (Nakflex®) were added to plastic coder at the ratios shown in Table 11. Preparation, 18〇. C, and kneaded for 4 minutes at 10 ° rpm.
次いで、 混練物を取出し、 プレスにて 2 mni厚さの平板 に成形し （成形温度 1 8 0 °C) 、 試験片を作成した。 上記試験片について物性測定を行い、 その結果を表 1 に不 した。 Next, the kneaded material was taken out and formed into a plate having a thickness of 2 mni by a press (forming temperature: 180 ° C.) to prepare a test piece. Physical properties were measured for the above test pieces, and the results are shown in Table 1. I did not.
比較例 1〜 6 Comparative Examples 1 to 6
実施例において、 エチレン一 α —ォレフィ ン共重合体 に代え、 ポ リ エチレン （Ρ Ε) を使用 した他は、 同様に して試験片を作成した。  Specimens were prepared in the same manner as in the examples, except that polyethylene (Ε) was used instead of the ethylene-α-olefin copolymer.
上記試験片について物性測定を行い、 その結果を表 - 1に示した。 Physical properties were measured for the above test pieces, and the results are shown in Table-1.
¾ ― ¾ ―
1：!] NO. 对 例 例  1 :!] NO. 对 Example Example
1 2 3 4 1 2 3 4 5 サン卜プレーン ®101— 64 100 ― 一 ― 70 50 ― 80 60  1 2 3 4 1 2 3 4 5 SUNPLANE ® 101-64 100-1-70 50-80 60
101 - 73 ― 100 ― 一 ― 60 ― ― 成  101-73-100-I-60--
101- 80 ― ― 100 ― 一 ― ― ― ― 101- 80 ― ― 100 ― One ― ― ― ―
101- 87 ― ― ― 100 ― ― ― ― ― v 101- 87 ― ― ― 100 ― ― ― ― ― v
分 ナックフレックス Min Nack Flex
DEFD-1210 ― ― ― ― 30 50 40 ― ―DEFD-1210 ― ― ― ― 30 50 40 ― ―
DFDA- 1137 ― ― 一 ― ― ― ― 20 4〇 DFDA-1137 ― ― one ― ― ― ― 20 4〇
'ンョァー A硬度 64 73 80 87 68 73 79 73 81 物 'No-A A hardness 64 73 80 87 68 73 79 73 81
引脹 (kg/cn 66 85 100 120 70 79 110 72 109 性 仲 び （％) 400 420 450 460 550 700 720 510 700 引裂' 波 Ckg/cin) 1 ？ 9 35 43 30 39 51 34 48 Expansion (kg / cn 66 85 100 120 70 79 110 72 109 Sexual relationship (%) 400 420 450 460 550 700 720 510 700 Tearing 'wave Ckg / cin) 1? 9 35 43 30 39 51 34 48
1 (つづき） 例 No. 実 施 例 比 較 例 1 (continued) Example No. Example Example Comparative example
6 7 1 2 3 4 5 • 6 サントプレーン 丄 01— 64 80 60 80 60 80 成 6 7 1 2 3 4 5 • 6 Santoplane 丄 01— 64 80 60 80 60 80
〇 i  〇 i
1 U 1— 3 8 U r c"  1 U 1— 3 8 U r c "
D D 80 分 DFDA- 1137 20 35  D D 80 minutes DFDA- 1137 20 35
P E LD LD LD LLD LLD HD  P E LD LD LD LLD LLD HD
20 40 20 20 40 20 ショァ— A硬度 79 87 79 89 86 78 85 85 物  20 40 20 20 40 20 Shore A hardness 79 87 79 89 86 78 85 85
引張強度 (kg/crf) 101 127 62 81 79 72 107 99 性 仲 び （％) 710 750 430 550 540 490 550 540 引裂 ¾i¾ (kg/cm) 46 60 29 42 35 34 42 40 Tensile strength (kg / crf) 101 127 62 81 79 72 107 99 Sex relationship (%) 710 750 430 550 540 490 550 540 Tear ¾i¾ (kg / cm) 46 60 29 42 35 34 42 40
一 — 表一 1から明らかなように、 T P 0エラス トマ一に対 し、 特定物性のエチレン一 —ォレフィ ン共重合体を特 定量配合して成る本発明の熱可塑性エラス トマ一組成物 は、 柔軟性を余り損わずに引裂強度が改善される。 これ に対し、 L D P E、 L L D P E、 HD P Eを配合した場 合には、 硬度が大き く なり、 従って、 柔软性を維持する ためには少量しか配合できず、 また、 配合によっても引 裂強度の改善は認められない。 As is clear from Table 1, Table 1 shows that the thermoplastic elastomer composition of the present invention comprising a specific amount of an ethylene-olefin copolymer having specific physical properties, in contrast to the TP0 elastomer, The tear strength is improved without significantly impairing the flexibility. In contrast, when LDPE, LLDPE, and HDPE are blended, the hardness increases, and therefore, only a small amount can be blended to maintain flexibility, and the blending also improves the tear strength. It is not allowed.
産業上の利用可能性 Industrial applicability
本発明の熱可塑性エラス トマ一組成物は、 低い硬度、 即ち柔軟性を有すると同時に、 高い引裂強度をも有する ものであり、 このため、 特に低硬度の要求される応用分 野において有利に使用することができる。  The thermoplastic elastomer composition of the present invention has low hardness, that is, flexibility, and also has high tear strength. Therefore, the thermoplastic elastomer composition is advantageously used particularly in application fields where low hardness is required. can do.

Claims

請 求 の 範 囲 The scope of the claims
1 . な一モノォレフィ ン共重合体ゴムと結晶性ポリ ォレフィ ン樹脂から成るォレフィ ン系熱可塑性エラス ト マー （ a ) 3 0〜9 0重量％と、 密度 0 . 8 7 0〜〇 . 9 1 0 g / cm , ビカッ ト軟化温度 5 0 。C以上のエチレン — —ォレフィ ン共重合体 （ b ) 7 0 〜 ： L 0重量％とを 含んで成る熱可塑性エラス トマ一組成物。 1. Monoolefin copolymer rubber and crystalline thermoplastic resin (a) 30 to 90% by weight of a thermoplastic elastomer, and a density of 0.870 to 0.99. 0 g / cm, vicat softening temperature 50. A thermoplastic elastomer composition comprising: ethylene or higher C-olefin copolymer (b) 70-: 0% by weight of L.
2 . ォレフィ ン系熱可塑性エラス トマ一 （ a ) 4 0 〜 7 5重量％と、 エチレン一 α—ォレフィ ン共重合体 2. Orolefin-based thermoplastic elastomer (a) 40-75% by weight, ethylene-α-olefin copolymer
( b ) 6 0〜 2 5重量％とを含んで成る、 請求項 1に記 載の熱可塑性エラス トマ一組成物。 The thermoplastic elastomer composition of claim 1, comprising (b) 60 to 25% by weight.
3 . α—乇ノォレフイ ン共重合体ゴムが E P D で ある請求項 1に記載の熱可塑性エラス トマ一組成物。  3. The thermoplastic elastomer composition according to claim 1, wherein the α- 乇 olefin copolymer rubber is EPD.
4 . 結晶性ポリオレフィ ン樹脂が、 ポリエチレン、 エチレンを主成分とする共重合体、 ポ リ プロ ピレン、 プ ロピレンを主成分とする共重合体、 及びポリ ブテンから なる群から選ばれたものである、 請求項 1に記載の熱可 塑性エラス トマ一組成物。  4. The crystalline polyolefin resin is selected from the group consisting of polyethylene, a copolymer containing ethylene as a main component, polypropylene, a copolymer containing propylene as a main component, and polybutene. The thermoplastic elastomer composition according to claim 1.
5 . 結晶性ポリオレフイ ン樹脂がポリプロピレン又 はプロ ピレンを主成分とする共重合体である、 請求項 4 に記載の熱可塑性エラス トマー組成物。  5. The thermoplastic elastomer composition according to claim 4, wherein the crystalline polyolefin resin is a copolymer containing polypropylene or propylene as a main component.
6 . ォレフィ ン系熱可塑性エラス トマ一 （ a ) が、 α—モノォレフィ ン共重合体ゴム 4 0〜8 0重量％と、 結晶性ポリオレフィ ン樹脂 60〜 20重量％とから成る、 請求項 1に記載の熱可塑性エラス トマ一組成物。 6. The olefin-based thermoplastic elastomer (a) contains 40 to 80% by weight of α-monoolefin copolymer rubber, The thermoplastic elastomer composition according to claim 1, comprising 60 to 20% by weight of a crystalline polyolefin resin.
7. エチレン一 一才 レフイ ン共重合体 （ b ) 力く、 エチレンと、 プロ ピレン、 ブテン一 1、 4ーメチルペン テン— 1及びへキセン一 1からなる群から選ばれた 1種 の α—ォレフィ ンとの共重合体である、 請求項 1に記載 の熱可塑性エラス トマ一組成物。  7. Ethylene-one-year olefin copolymer (b) One type of α-olefin selected from the group consisting of strong ethylene, propylene, butene-11, 4-methylpentene-1 and hexene-11 2. The thermoplastic elastomer composition according to claim 1, which is a copolymer with an elastomer.
8. エチレン一 な 一ォレフィ ン共重合体 （b) 中の 一才レフィ ン含有量が 5〜4 0モル％である、 請求項 1に記載の熱可塑性エラス トマ一組成物。  8. The thermoplastic elastomer composition according to claim 1, wherein the one-year olefin content in the ethylene-like monoolefin copolymer (b) is 5 to 40 mol%.
9. 可塑剤、 充填剤、 顔料、 安定剤等の添加剤を更 に含む、 請求項 1に記載の熱可塑性エラス トマ一組成物。  9. The thermoplastic elastomer composition according to claim 1, further comprising additives such as a plasticizer, a filler, a pigment, and a stabilizer.
PCT/JP1991/000938 1990-02-13 1991-07-12 Thermoplastic elastomer composition WO1993001236A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3199790A JPH03234744A (en) 1990-02-13 1990-02-13 Thermoplastic elastomer composition

Publications (1)

Publication Number Publication Date
WO1993001236A1 true WO1993001236A1 (en) 1993-01-21

Family

ID=12346553

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1991/000938 WO1993001236A1 (en) 1990-02-13 1991-07-12 Thermoplastic elastomer composition

Country Status (2)

Country Link
JP (1) JPH03234744A (en)
WO (1) WO1993001236A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0887378A1 (en) * 1996-03-15 1998-12-30 Sumitomo Chemical Company Limited Thermoplastic elastomer composition and powder and molded article thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69822193T2 (en) 1997-11-20 2005-01-20 Advanced Elastomer Systems, L.P., Akron MODIFICATION OF THERMOPLASTIC VULCANISTS WITH A THERMOPLASTIC STATISTIC COPOLYMER OF ETHYLENE
CN103797067B (en) 2011-09-15 2016-06-01 旭化成株式会社 The manufacture method of cross-linked composition, cross-linked composition and formed body

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58101135A (en) * 1981-12-10 1983-06-16 Idemitsu Petrochem Co Ltd Polypropylene composition
JPS59219350A (en) * 1983-05-27 1984-12-10 Showa Denko Kk Ethylene copolymer composition for laminate
JPS6198756A (en) * 1984-10-20 1986-05-17 Mitsui Petrochem Ind Ltd Polypropylene composition having improved low-temperature impact resistance
JPS6295334A (en) * 1985-10-21 1987-05-01 Mitsubishi Petrochem Co Ltd Ethylene copolymer resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58101135A (en) * 1981-12-10 1983-06-16 Idemitsu Petrochem Co Ltd Polypropylene composition
JPS59219350A (en) * 1983-05-27 1984-12-10 Showa Denko Kk Ethylene copolymer composition for laminate
JPS6198756A (en) * 1984-10-20 1986-05-17 Mitsui Petrochem Ind Ltd Polypropylene composition having improved low-temperature impact resistance
JPS6295334A (en) * 1985-10-21 1987-05-01 Mitsubishi Petrochem Co Ltd Ethylene copolymer resin composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0887378A1 (en) * 1996-03-15 1998-12-30 Sumitomo Chemical Company Limited Thermoplastic elastomer composition and powder and molded article thereof
EP0887378A4 (en) * 1996-03-15 1999-07-14 Sumitomo Chemical Co Thermoplastic elastomer composition and powder and molded article thereof
US6331360B1 (en) 1996-03-15 2001-12-18 Sumitomo Chemical Company, Limited Thermoplastic elastomer composition and powder and molded article thereof

Also Published As

Publication number Publication date
JPH03234744A (en) 1991-10-18

Similar Documents

Publication Publication Date Title
CA1261505A (en) Thermoplastic elastomer composition
US4087485A (en) Polypropylene blends having high impact strength and improved optical properties
US4088714A (en) Cross-linked melt-flowable thermoplastic elastomer blend comprising EPR or EPDM, polyethylene and polypropylene
JP2610426B2 (en) Thermoplastic elastomer composition
EP0229156B1 (en) Thermoplastic elastomer composition
CA2117859C (en) Compositions of propylene polymer materials and olefin polymer materials with reduced gloss
US6399710B1 (en) Modification of thermolastic vulcanizates with a thermoplastic random copolymer of ethylene
ES2212205T3 (en) ELASTOMERO TERNARIO THERMARY COMPOSITE OF A TECHNICAL THERMOPLASTIC, A POLYMER OF ETHYLENE AND / OR FUNCTIONALIZED DIENO, AND A P-METHYLENE BROMED ISOBUTILENE COPOLYMER.
JPH09208761A (en) Polyolefin-based resin composition
WO1993001236A1 (en) Thermoplastic elastomer composition
JP3396153B2 (en) Thermoforming resin composition and sheet
JP3503339B2 (en) Thermoplastic elastomer composition
KR100550313B1 (en) Polypropylene Resin Composition Having Good Low Heat Sealing Property, Good Transparency and Good Tear Strength
WO2002072690A1 (en) Thermoplastic olefin elastomer composition
JP3910313B2 (en) Resin composition for skin member and laminate thereof
JP3535640B2 (en) Thermoplastic elastomer composition
JPH0753789A (en) Thermoplastic polyolefinic elastomer
JPS61247747A (en) Thepoplastic elastomeric composition
JP2019206695A (en) Resin composition and method for producing the same
JPH0760907A (en) Thermoplastic elastomer laminate
JPH0770380A (en) Thermoplastic olefin elastomer
JP3451112B2 (en) 3-methyl-1-butene polymer composition
JP2002020563A (en) Ionomer composition and its use
JP3451113B2 (en) 3-methyl-1-butene polymer composition
JPS5880335A (en) Resin composition

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU NL SE

NENP Non-entry into the national phase

Ref country code: CA