JP6485139B2 - Propylene-based resin composition for deformation recovery heat resistant structure and deformation recovery heat resistant structure - Google Patents
Propylene-based resin composition for deformation recovery heat resistant structure and deformation recovery heat resistant structure Download PDFInfo
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- JP6485139B2 JP6485139B2 JP2015053551A JP2015053551A JP6485139B2 JP 6485139 B2 JP6485139 B2 JP 6485139B2 JP 2015053551 A JP2015053551 A JP 2015053551A JP 2015053551 A JP2015053551 A JP 2015053551A JP 6485139 B2 JP6485139 B2 JP 6485139B2
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- propylene
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- deformation
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- 238000011084 recovery Methods 0.000 title claims description 35
- 239000004711 α-olefin Substances 0.000 claims description 47
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 8
- 229920001384 propylene homopolymer Polymers 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000000034 method Methods 0.000 description 81
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 41
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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- Lining Or Joining Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、変形回復性耐熱構造体用プロピレン系樹脂組成物および変形回復性耐熱構造体に関し、詳しくは、高温下、好ましくは１２１℃以上の温度条件下でも形状を保持できる耐熱性を有し、尚且つ継続した負荷により継続して変形せしめられた後、負荷を除去した際に変形回復性を有する構造体を構成するプロピレン系樹脂組成物およびそれよりなる変形回復性耐熱構造体に関する。 The present invention relates to a propylene-based resin composition for a deformation-recoverable heat-resistant structure and a deformation-recoverable heat-resistant structure, and in particular, has heat resistance that can maintain a shape even at a high temperature, preferably 121 ° C. or higher. Further, the present invention relates to a propylene-based resin composition that constitutes a structure having deformation recovery properties when the load is removed after being continuously deformed by a continuous load, and a deformation recovery heat resistant structure comprising the same.
従来、変形回復性構造体、例えば、ベッド等の寝具、家庭用や車両・船舶・航空機用座席等のクッション材には、発泡ウレタン、非弾性捲縮繊維詰綿、及び非弾性捲縮繊維を接着した樹脂綿や硬綿などが用いられてきた。 Conventionally, deformation-recoverable structures, for example, bedding such as beds, cushion materials for homes, vehicles, ships, aircraft seats, etc., have been made of urethane foam, non-elastic crimped cotton, and non-elastic crimped fibers. Bonded resin cotton or hard cotton has been used.
近年、熱可塑性樹脂を押出成形によりループ状に押出し、このストランドを熱接着後、冷却固化して得られる三次元網目状構造体を当該クッション材として使用する試みがなされている。当該熱可塑性樹脂として、ポリエステル系エラストマー、ポリウレタン系エラストマー、ポリアミド系エラストマーを用いることが知られている（例えば、特許文献１：特開平７−０６８０６１号公報参照。）。ところが、これらの樹脂は、高価格であり、リサイクルも難しい。
一方、特許文献２（特開２００４−２１８１１６号公報）や特許文献３（特開２００６−２００１１７号公報）には、エチレン−酢酸ビニル共重合体（ＥＶＡ）やエチレン・α−オレフィン共重合体であるポリエチレン系樹脂が開示され、広く用いられているが、これらのポリエチレン系樹脂を用いた三次元網目状構造体は、優れた性能を有するものの、柔軟性能や熱接着性を重視しているため、樹脂の融点が低くなり、高温下（例えば７０℃）での変形回復性が劣るという問題がある。このため、ポリエチレン系樹脂を用いた場合、自動車のクッションや緩衝部品、暖房機能付与のベッド用クッションへの適用には、大きな制限があった。
この問題を解決すべく、例えば、特許文献４（特開２０１３−１８１１１７号公報）では、特定のエチレン系重合体に、特定のエチレン性不飽和シラン化合物をグラフトさせ、得られたグラフト反応物にシラノール縮合触媒を含有させたものを、成形後に、４０℃の温水を霧状に散水する部屋中に１週間保管し、架橋処理する方法により、耐熱性を付与する方法が開示されているが、架橋処理に１週間という長時間を要し、生産性に劣るものであり、尚且つ架橋処理を行っているため、リサイクル性に劣るものであった。
In recent years, an attempt has been made to use a three-dimensional network structure obtained by extruding a thermoplastic resin in a loop shape by extrusion molding, heat-bonding the strands, and cooling and solidifying the strands as the cushioning material. As the thermoplastic resin, it is known to use a polyester-based elastomer, a polyurethane-based elastomer, or a polyamide-based elastomer (see, for example, Patent Document 1: Japanese Patent Laid-Open No. 7-068061). However, these resins are expensive and difficult to recycle.
On the other hand, Patent Document 2 (Japanese Patent Laid-Open No. 2004-218116) and Patent Document 3 (Japanese Patent Laid-Open No. 2006-2001117) describe an ethylene-vinyl acetate copolymer (EVA) and an ethylene / α-olefin copolymer. Certain polyethylene-based resins are disclosed and widely used. However, although three-dimensional network structures using these polyethylene-based resins have excellent performance, they place importance on flexibility and thermal adhesiveness. There is a problem that the melting point of the resin is lowered and the deformation recovery property at a high temperature (for example, 70 ° C.) is inferior. For this reason, when a polyethylene-based resin is used, application to automobile cushions, cushioning parts, and bed cushions with a heating function is greatly limited.
In order to solve this problem, for example, in Patent Document 4 (Japanese Patent Laid-Open No. 2013-181117), a specific ethylenically unsaturated silane compound is grafted to a specific ethylene polymer, and the resulting graft reaction product is grafted. A method of imparting heat resistance by a method of storing a silanol condensation catalyst after molding, storing it in a room for spraying 40 ° C. warm water in a mist for one week, and performing a crosslinking treatment is disclosed. The cross-linking treatment takes a long time of one week, and is inferior in productivity. Further, since the cross-linking treatment is performed, the recyclability is inferior.
更には、近年、病院などでは、クッション自体の洗浄、場合によっては滅菌処理を行うニーズがあり、高温下、好ましくは１２１℃以上の蒸気滅菌処理への耐性が求められている。
ポリエチレン系樹脂組成物を用いたものは、蒸気滅菌処理時に溶融してしまい、形状保持が困難になる。蒸気滅菌処理に耐えられる樹脂としては、ポリプロピレン系樹脂が挙げられるが、ポリプロピレンは、塑性変形を起こすため、変形回復性に乏しい問題がある。
この問題を解決すべく、例えば、特許文献５（特開２００２−０６１０５９号公報）では、ポリプロピレンに、ＳＢＳを５〜３０重量％配合してなる三次元構造体が開示されているが、いかなるポリプロピレンを使用したか明示されていないため、蒸気滅菌に耐えうるものかが、不明であるし、変形回復性を示す圧縮残留歪についても、室温下で保持時間なしの試験結果しか示されておらず、継続した負荷により継続して変形せしめられた後、負荷を除去した際の変形回復性や、高温下での変形回復性について、うかがい知ることができないものであった。
Furthermore, in recent years, hospitals and the like have a need for cleaning the cushion itself and, in some cases, sterilizing treatment, and there is a demand for resistance to steam sterilization treatment at high temperatures, preferably 121 ° C. or higher.
Those using a polyethylene resin composition melt during steam sterilization, making it difficult to maintain the shape. Examples of the resin that can withstand the steam sterilization treatment include a polypropylene-based resin. However, since polypropylene causes plastic deformation, there is a problem of poor deformation recovery.
In order to solve this problem, for example, Patent Document 5 (Japanese Patent Laid-Open No. 2002-061059) discloses a three-dimensional structure in which 5 to 30% by weight of SBS is blended with polypropylene. It is unclear whether it can withstand steam sterilization, and the compressive residual strain that shows deformation recovery is only shown in the test results without holding time at room temperature. However, after being continuously deformed by a continuous load, it is impossible to know the deformation recovery property when the load is removed and the deformation recovery property at high temperatures.
本発明の目的は、上記従来技術の問題点に鑑み、柔軟で、高温下での変形回復性に優れ、尚且つ高温下、好ましくは１２１℃以上の環境下でも、形状が保持できる耐熱性を有する変形回復性耐熱構造体用プロピレン系樹脂組成物および変形回復性耐熱構造体を提供するものである。 In view of the above-mentioned problems of the prior art, the object of the present invention is to provide heat resistance that is flexible and excellent in deformation recovery at high temperature, and that can retain its shape even under high temperature, preferably at 121 ° C. or higher. Provided are a propylene-based resin composition for deformation-recoverable heat-resistant structures and a deformation-recoverable heat-resistant structure.
本発明者は、上記課題を解決すべく鋭意検討を重ねた結果、特定のプロピレン系重合体成分（Ａ）と特定のプロピレン−α−オレフィン共重合体（Ｂ）を特定の比率で配合してなるプロピレン系樹脂組成物（Ｘ）を必須成分とした変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）を用いることにより、得られた構造体が、例えば、７０℃といった高温下でも、優れた変形回復性を示し、尚且つ１２１℃以上の高温下でも形状を保持できるという従来にない特性を発現することを見出し、本発明を完成させた。
本発明は、以下の変形回復性耐熱構造体用プロピレン系樹脂組成物およびそれよりなる変形回復性耐熱構造体を提供する。
As a result of intensive studies to solve the above problems, the present inventor formulated a specific propylene polymer component (A) and a specific propylene-α-olefin copolymer (B) at a specific ratio. By using the propylene-based resin composition (Y) for deformation-recoverable heat-resistant structures having the propylene-based resin composition (X) as an essential component, the obtained structure can be obtained at a high temperature of, for example, 70 ° C. The present invention was completed by discovering that it exhibits an excellent deformation recovery property and exhibits an unprecedented characteristic that it can retain its shape even at a high temperature of 121 ° C. or higher.
The present invention provides the following propylene-based resin composition for deformation-recoverable heat-resistant structures and a deformation-recoverable heat-resistant structure comprising the same.
［１］下記成分（Ａ）１〜９９重量部と下記成分（Ｂ）１〜９９重量部（但し、成分（Ａ）と成分（Ｂ）の合計を１００重量部とする）からなるプロピレン系樹脂組成物（Ｘ）を必須成分として含有し、且つ下記特性（ｙ１）〜（ｙ２）を満足することを特徴とする変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）。
（ｙ１）メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）が１．０〜１００ｇ／１０分であること。
（ｙ２）融解ピーク温度（Ｔｍ）が１２１〜１７０℃であること。
成分（Ａ）：下記（ａ１）〜（ａ２）を満足する１種類もしくは２種類以上のプロピレン単独重合体及び／又はプロピレン−α−オレフィン共重合体。
（ａ１）融解ピーク温度（Ｔｍ）が１２１〜１７０℃であること。
（ａ２）メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）が０．１〜５００ｇ／１０分であること。
成分（Ｂ）：下記（ｂ１）を満足する少なくとも１種類のプロピレン−α−オレフィン共重合体。
（ｂ１）プロピレン５１〜９０重量％、エチレン及び／又は炭素数４〜１０のα−オレフィン１０〜４９重量％からなること。
[1] A propylene resin comprising 1 to 99 parts by weight of the following component (A) and 1 to 99 parts by weight of the following component (B) (provided that the total of the component (A) and the component (B) is 100 parts by weight) A propylene-based resin composition (Y) for deformation-recoverable heat-resistant structures, which contains the composition (X) as an essential component and satisfies the following characteristics (y1) to (y2).
(Y1) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 1.0 to 100 g / 10 minutes.
(Y2) Melting peak temperature (Tm) is 121-170 degreeC.
Component (A): One or more propylene homopolymers and / or propylene-α-olefin copolymers satisfying the following (a1) to (a2).
(A1) The melting peak temperature (Tm) is 121 to 170 ° C.
(A2) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.1 to 500 g / 10 minutes.
Component (B): At least one propylene-α-olefin copolymer satisfying the following (b1).
(B1) It is composed of 51 to 90% by weight of propylene, 10 to 49% by weight of ethylene and / or an α-olefin having 4 to 10 carbon atoms.
［２］前記プロピレン系樹脂組成物（Ｘ）の一部または全部は、前記（ａ１）および（ａ２）を満足する成分（Ａ’）１〜９９重量部と、前記（ｂ１）を満足する成分（Ｂ’）１〜９９重量部（但し、（Ａ’）と（Ｂ’）の合計量を１００重量部とする）を、逐次重合して得られるプロピレン系樹脂組成物（Ｘ’）であることを特徴とする前記［１］に記載の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）。
［３］前記プロピレン系樹脂組成物（Ｘ’）がメタロセン系触媒を用いて逐次重合して得られることを特徴とする前記［２］に記載の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）。
［４］前記成分（Ｂ’）は、８３〜９０重量％のプロピレンと１０〜１７重量％のエチレンからなることを特徴とする前記［２］又は［３］に記載の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）。
［５］前記［１］〜［４］のいずれかに記載の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）からなる変形回復性耐熱構造体。
［６］変形回復性耐熱構造体は、押出成形により得られる複数のストランドからなる連続線状体を三次元ランダムループ状に曲がりくねらせて、複数のループの接触部の少なくとも一部が融着してなる立体網目状構造を有する網状構造体であることを特徴とする前記［５］に記載の変形回復性耐熱構造体。
[2] Part or all of the propylene-based resin composition (X) is 1 to 99 parts by weight of the component (A ′) that satisfies the above (a1) and (a2), and the component that satisfies the above (b1) It is a propylene-based resin composition (X ′) obtained by sequentially polymerizing (B ′) 1 to 99 parts by weight (provided that the total amount of (A ′) and (B ′) is 100 parts by weight). The propylene-based resin composition (Y) for deformation-recoverable heat-resistant structures as described in [1] above.
[3] The propylene resin composition for deformation-recoverable heat-resistant structures according to [2], wherein the propylene resin composition (X ′) is obtained by sequential polymerization using a metallocene catalyst. (Y).
[4] The deformation-recoverable heat-resistant structure according to [2] or [3], wherein the component (B ′) comprises 83 to 90% by weight of propylene and 10 to 17% by weight of ethylene. Propylene-based resin composition (Y).
[5] A deformation-recoverable heat-resistant structure comprising the propylene-based resin composition (Y) for a deformation-recoverable heat-resistant structure according to any one of [1] to [4].
[6] The deformation-recoverable heat-resistant structure is formed by twisting a continuous linear body composed of a plurality of strands obtained by extrusion into a three-dimensional random loop, and at least a part of contact portions of the plurality of loops is fused. The deformation-recoverable heat-resistant structure according to [5] above, which is a network structure having a three-dimensional network structure.
本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物は、優れた変形回復性と耐熱性を有する構造体を与える。 The propylene-based resin composition for deformation recovery heat resistant structure of the present invention provides a structure having excellent deformation recovery property and heat resistance.
本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）は、下記成分（Ａ）１〜９９重量部と下記成分（Ｂ）１〜９９重量部（但し、成分（Ａ）と成分（Ｂ）の合計を１００重量部とする）からなるプロピレン系樹脂組成物（Ｘ）を必須成分として含有し、且つ下記特性（ｙ１）〜（ｙ２）を満足することを特徴とする。
（ｙ１）メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）が１．０〜１００ｇ／１０分であること。
（ｙ２）融解ピーク温度（Ｔｍ）が１２１〜１７０℃であること
成分（Ａ）：下記（ａ１）〜（ａ２）を満足する１種類もしくは２種類以上のプロピレン単独重合体および／又はプロピレン−α−オレフィン共重合体。
（ａ１）融解ピーク温度（Ｔｍ）が１２１〜１７０℃であること。
（ａ２）メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）が０．１〜５００ｇ／１０分であること。
成分（Ｂ）：下記（ｂ１）を満足する少なくとも１種類のプロピレン−α−オレフィン共重合体。
（ｂ１）プロピレン５１〜９０重量％、エチレン及び／又は炭素数４〜１０のα−オレフィン１０〜４９重量％からなること。
以下、項目ごとに詳細に説明する。
The propylene resin composition (Y) for deformation-recoverable heat-resistant structure of the present invention comprises 1 to 99 parts by weight of the following component (A) and 1 to 99 parts by weight of the following component (B) (however, the component (A) and the component) A propylene-based resin composition (X) comprising (B) as an essential component) and satisfying the following characteristics (y1) to (y2).
(Y1) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 1.0 to 100 g / 10 minutes.
(Y2) Melting peak temperature (Tm) is 121 to 170 ° C. Component (A): one or more propylene homopolymers and / or propylene-α satisfying the following (a1) to (a2) An olefin copolymer.
(A1) The melting peak temperature (Tm) is 121 to 170 ° C.
(A2) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.1 to 500 g / 10 minutes.
Component (B): At least one propylene-α-olefin copolymer satisfying the following (b1).
(B1) It is composed of 51 to 90% by weight of propylene, 10 to 49% by weight of ethylene and / or an α-olefin having 4 to 10 carbon atoms.
Hereinafter, each item will be described in detail.
［成分（Ａ）または（Ａ’）］
本発明で使用する成分（Ａ）または（Ａ’）は、上記特性（ａ１）、（ａ２）を満足する。
上記各特性などについて、以下、具体的に説明する。なお、成分（Ａ’）は、下記に説明するプロピレン系樹脂組成物（Ｘ’）に由来する。
[Component (A) or (A ′)]
The component (A) or (A ′) used in the present invention satisfies the above characteristics (a1) and (a2).
Each of the above characteristics will be specifically described below. In addition, a component (A ') originates in the propylene-type resin composition (X') demonstrated below.
特性（ａ１）：融解ピーク温度（Ｔｍ）
本発明に使用する成分（Ａ）または（Ａ’）の融解ピーク温度（Ｔｍ）は、１２１〜１７０℃である。
成分（Ａ）または（Ａ’）は、１種類もしくは２種類以上のプロピレン単独重合体および／又はプロピレン−α−オレフィン共重合体からなり、２種類以上の成分からなる場合、２種類以上の成分のブレンド物として、融解ピーク温度が１２１℃〜１７０℃であればよい。
成分（Ａ）または（Ａ’）が２種類以上の組み合わせの例としては、２種類以上のプロピレン単独重合体からなる場合や、２種類以上のプロピレン−α−オレフィン共重合体からなる場合、各々１種類以上のプロピレン単独重合体とプロピレン−α−オレフィン共重合体からなる場合が挙げられる。
融解ピーク温度が１２１℃未満の場合、本発明の樹脂組成物から得られる構造体が１２１℃以上の環境下で形状が保持できるだけの耐熱性を発現することができない。一方、融解ピーク温度が１７０℃を超えるものは、実質的に入手が困難である。
融解ピーク温度の好ましい範囲は、１２５℃〜１７０℃、より好ましくは１３０℃〜１７０℃、更に好ましくは１３５℃〜１７０℃である。
Characteristic (a1): Melting peak temperature (Tm)
The melting peak temperature (Tm) of the component (A) or (A ′) used in the present invention is 121 to 170 ° C.
Component (A) or (A ′) is composed of one or more propylene homopolymers and / or propylene-α-olefin copolymers, and in the case of two or more components, two or more components As a blended product, the melting peak temperature may be 121 ° C to 170 ° C.
Examples of the combination of two or more types of component (A) or (A ′) include a case where the component (A) or (A ′) is composed of two or more types of propylene homopolymers or a case where the component (A) or (A ′) is composed of two or more types of propylene-α-olefin copolymers. Examples include one or more types of propylene homopolymer and propylene-α-olefin copolymer.
When the melting peak temperature is less than 121 ° C., the structure obtained from the resin composition of the present invention cannot exhibit heat resistance sufficient to maintain the shape in an environment of 121 ° C. or higher. On the other hand, those having a melting peak temperature exceeding 170 ° C. are substantially difficult to obtain.
The preferable range of the melting peak temperature is 125 ° C to 170 ° C, more preferably 130 ° C to 170 ° C, and still more preferably 135 ° C to 170 ° C.
特性（ａ２）：メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）
本発明に使用する成分（Ａ）または（Ａ’）のメルトフローレート（ＭＦＲ）は、０．１〜５００ｇ／１０分である。
成分（Ａ）または（Ａ’）は、１種類もしくは２種類以上のプロピレン単独重合体および／又はプロピレン−α−オレフィン共重合体からなり、２種類以上の成分からなる場合、２種類以上の成分のブレンド物として、ＭＦＲが０．１〜５００ｇ／１０分であればよい。
ここで、ＭＦＲは、ＪＩＳ Ｋ７２１０：１９９９のＡ法、条件Ｍ（２３０℃、２．１６ｋｇ荷重）に準拠して測定されるものである。
ＭＦＲが０．１ｇ／１０分未満の場合、本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）のＭＦＲを１．０ｇ／１０分以上にすることが困難となり、成形時の負荷が増したり、成形体の成形自体が困難になる。一方、ＭＦＲが５００ｇ／１０分を超えると、本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）のＭＦＲを１００ｇ／１０分以下にすることが困難になり、成形の安定性、特に、押出成形に用いた場合の成形安定性が損なわれやすくなる。
ＭＦＲの好ましい範囲は、１．０〜５００ｇ／１０分であり、より好ましくは５．０〜２００ｇ／１０分、更に好ましくは５．０〜１００ｇ／１０分である。
Characteristic (a2): Melt flow rate (MFR: 230 ° C., 2.16 kg load)
The melt flow rate (MFR) of the component (A) or (A ′) used in the present invention is 0.1 to 500 g / 10 minutes.
Component (A) or (A ′) is composed of one or more propylene homopolymers and / or propylene-α-olefin copolymers, and in the case of two or more components, two or more components As the blended product, the MFR may be 0.1 to 500 g / 10 minutes.
Here, MFR is measured according to JIS K7210: 1999 method A, condition M (230 ° C., 2.16 kg load).
When the MFR is less than 0.1 g / 10 min, it becomes difficult to make the MFR of the propylene resin composition (Y) for deformation-recoverable heat-resistant structure of the present invention 1.0 g / 10 min or more. The load increases or the molding itself becomes difficult. On the other hand, when the MFR exceeds 500 g / 10 min, it becomes difficult to make the MFR of the propylene resin composition (Y) for deformation-recoverable heat-resistant structure of the present invention 100 g / 10 min or less, and the molding stability In particular, the molding stability when used for extrusion molding tends to be impaired.
The preferable range of MFR is 1.0 to 500 g / 10 minutes, more preferably 5.0 to 200 g / 10 minutes, still more preferably 5.0 to 100 g / 10 minutes.
その他の特性：
本発明に用いられる成分（Ａ）または（Ａ’）は、上記特性（ａ１）および（ａ２）を満足すればよいが、成分（Ａ）または（Ａ’）として、プロピレン−α−オレフィン共重合体を用いる場合、成分（Ａ）または（Ａ’）は、プロピレン含有量が９０重量％より多く、１００重量％未満、α−オレフィン含有量が０重量％より多く、１０重量％未満であることが好ましい。
成分（Ａ）または（Ａ’）としてプロピレン−α−オレフィン共重合体を用いる場合、α−オレフィンとしては、エチレンおよび／又はブテンであることが好ましい。
成分（Ａ）の製造方法は、特に限定されず、市販のプロピレン単独重合体、プロピレン−α−オレフィン共重合体から、適宜選択することができる。具体的には、日本ポリプロ（株）製商標名「ノバテックＰＰ」や、商標名「ウィンテック」が挙げられる。
Other characteristics:
The component (A) or (A ′) used in the present invention only needs to satisfy the above characteristics (a1) and (a2). As the component (A) or (A ′), propylene-α-olefin copolymer When using coalescence, component (A) or (A ′) has a propylene content of more than 90% by weight and less than 100% by weight, and an α-olefin content of more than 0% by weight and less than 10% by weight. Is preferred.
When a propylene-α-olefin copolymer is used as the component (A) or (A ′), the α-olefin is preferably ethylene and / or butene.
The manufacturing method of a component (A) is not specifically limited, It can select suitably from a commercially available propylene homopolymer and a propylene-alpha-olefin copolymer. Specific examples include the trade name “Novatech PP” manufactured by Nippon Polypro Co., Ltd. and the trade name “Wintech”.
［成分（Ｂ）または（Ｂ’）］
本発明で使用する成分（Ｂ）または（Ｂ’）は、上記特性（ｂ１）を満足する１種類もしくは２種類以上プロピレン−α−オレフィン共重合体からなる。
上記特性などについて、以下、具体的に説明する。なお、成分（Ｂ’）は、下記に説明するプロピレン系樹脂組成物（Ｘ’）に由来する。
[Component (B) or (B ′)]
Component (B) or (B ′) used in the present invention is composed of one or more propylene-α-olefin copolymers that satisfy the above characteristic (b1).
The above characteristics will be specifically described below. In addition, a component (B ') originates in the propylene-type resin composition (X') demonstrated below.
特性（ｂ１）：プロピレンとα−オレフィンの含有量
本発明に用いられる成分（Ｂ）または（Ｂ’）は、プロピレン５１〜９０重量％、エチレン及び／又は炭素数４〜１０のα−オレフィン１０〜４９重量％からなる。
プロピレン含有量が５１重量％未満の場合、成分（Ａ）または（Ａ’）との相溶性が低下し、変形時に界面が破壊されやすくなるため、本発明の樹脂組成物から得られる構造体の変形回復性が低下しやすくなる。一方、プロピレン含有量が９０重量％を超える場合、成分（Ｂ）または（Ｂ’）が変形時に塑性変形を起こしやすくなるため、本発明の樹脂組成物から得られる構造体の変形回復性が低下しやすくなる。
プロピレン含有量の好ましい範囲は、６０重量％以上９０重量％以下であり、より好ましくは７０重量％以上９０重量％以下であり、更に好ましくは８０重量％以上９０重量％以下、特に好ましくは８３重量％以上９０重量％以下である。
Characteristic (b1): Content of propylene and α-olefin Component (B) or (B ′) used in the present invention is 51 to 90% by weight of propylene, ethylene and / or α-
When the propylene content is less than 51% by weight, the compatibility with the component (A) or (A ′) is reduced, and the interface is easily destroyed during deformation. Therefore, the structure obtained from the resin composition of the present invention Deformability recovery tends to decrease. On the other hand, when the propylene content exceeds 90% by weight, the component (B) or (B ′) is liable to undergo plastic deformation at the time of deformation, so the deformation recovery property of the structure obtained from the resin composition of the present invention is reduced. It becomes easy to do.
The preferred range of the propylene content is 60% by weight or more and 90% by weight or less, more preferably 70% by weight or more and 90% by weight or less, still more preferably 80% by weight or more and 90% by weight or less, and particularly preferably 83% by weight. % To 90% by weight.
その他の特性：
本発明に用いられる成分（Ｂ）または（Ｂ’）は、上記特性（ｂ１）を満足すればよいが、α−オレフィンとしては、エチレンおよび／又はブテンであることが好ましい。
成分（Ｂ）の製造方法は、特に限定されず、市販のプロピレン−α−オレフィン共重合体から、適宜選択することができる。具体的には、エクソンモービル社製商標名「Ｖｉｓｔａｍａｘｘ」や、ダウケミカル社製商標名「Ｖｅｒｓｉｆｙ」や、三井化学社製商標名「タフマーＰＮ」や「ノティオＳＮ」や「タフマーＸＭ」、住友化学社製商標名「タフセレン」等が挙げられる。
Other characteristics:
The component (B) or (B ′) used in the present invention may satisfy the above characteristic (b1), but the α-olefin is preferably ethylene and / or butene.
The manufacturing method of a component (B) is not specifically limited, It can select suitably from a commercially available propylene-alpha-olefin copolymer. Specifically, ExxonMobil brand name “Vistamaxx”, Dow Chemical brand name “Versify”, Mitsui Chemicals brand name “Toughmer PN”, “Notio SN”, “Toughmer XM”, Sumitomo Chemical The brand name “Tough Selenium” manufactured by the company may be mentioned.
［プロピレン系樹脂組成物（Ｘ）］
本発明で使用されるプロピレン系樹脂組成物（Ｘ）は、上記成分（Ａ）および／又は（Ａ’）１〜９９重量部と下記成分（Ｂ）および／又は（Ｂ’）１〜９９重量部からなる。但し、成分（Ａ）および／又は（Ａ’）と、成分（Ｂ）および／又は（Ｂ’）の合計を１００重量部とする。また、成分（Ａ’）および（Ｂ’）は、下記に説明するプロピレン系樹脂組成物（Ｘ’）に由来する。
成分（Ａ）および／又は（Ａ’）が１重量部を下回ると、本発明の樹脂組成物から得られる構造体が高温下、好ましくは１２１℃以上の環境下で形状が保持できるだけの耐熱性を発現することができない。一方、成分（Ａ）および／又は（Ａ’）が９９重量部を上回ると、変形時に塑性変形を起こしやすくなるため、本発明の樹脂組成物から得られる構造体の変形回復性が低下しやすくなる。
プロピレン系樹脂組成物（Ｘ）および／又は（Ｘ’）に占める成分（Ａ）および／又は（Ａ’）の好ましい範囲は、１〜７０重量部であり、より好ましくは１０〜６０重量部、更に好ましくは２０〜５０重量部である。
[Propylene-based resin composition (X)]
The propylene-based resin composition (X) used in the present invention is 1 to 99 parts by weight of the above component (A) and / or (A ′) and 1 to 99 parts by weight of the following components (B) and / or (B ′). Consists of parts. However, the total of the component (A) and / or (A ′) and the component (B) and / or (B ′) is 100 parts by weight. In addition, components (A ′) and (B ′) are derived from the propylene-based resin composition (X ′) described below.
When the component (A) and / or (A ′) is less than 1 part by weight, the structure obtained from the resin composition of the present invention is heat resistant enough to maintain its shape at high temperature, preferably at 121 ° C. or higher. Cannot be expressed. On the other hand, if the component (A) and / or (A ′) exceeds 99 parts by weight, plastic deformation is likely to occur during deformation, and thus the deformation recovery property of the structure obtained from the resin composition of the present invention is likely to be lowered. Become.
A preferred range of the component (A) and / or (A ′) in the propylene-based resin composition (X) and / or (X ′) is 1 to 70 parts by weight, more preferably 10 to 60 parts by weight, More preferably, it is 20-50 weight part.
［プロピレン系樹脂組成物（Ｘ’）］
プロピレン系樹脂組成物（Ｘ）の一部もしくは全部に、前記（ａ１）および（ａ２）を満足する成分（Ａ’）１〜９９重量部と、前記（ｂ１）を満足する成分（Ｂ’）１〜９９重量部（但し、（Ａ’）と（Ｂ’）の合計量を１００重量部とする）を逐次重合して得られるプロピレン系樹脂組成物（Ｘ’）を用いることができる。
プロピレン系樹脂組成物（Ｘ’）の製造方法は、特に限定されないが、例えば、特開２００５−１３２９７９号公報に記載の方法を用いることができ、ここで言及したことで、同公報の全内容が本明細書に取り込まれたものとする。
プロピレン系樹脂組成物（Ｘ’）を製造する触媒は、特に限定されないが、プロピレン系樹脂組成物（Ｘ’）やプロピレン系樹脂組成物（Ｙ）、更にはプロピレン系樹脂組成物（Ｙ）から製造される変形回復性耐熱構造体のベタツキを抑制しやすくなるため、メタロセン触媒を用いることが好ましい。
プロピレン系樹脂組成物（Ｘ’）は、市販品より適宜選択してもよく、市販品の例としては、日本ポリプロ（株）製商標名「ニューコン」、商標名「ウェルネクス」等が挙げられる。
[Propylene-based resin composition (X ′)]
In part or all of the propylene-based resin composition (X), 1 to 99 parts by weight of the component (A ′) satisfying the above (a1) and (a2), and the component (B ′) satisfying the above (b1) A propylene-based resin composition (X ′) obtained by sequentially polymerizing 1 to 99 parts by weight (provided that the total amount of (A ′) and (B ′) is 100 parts by weight) can be used.
The production method of the propylene-based resin composition (X ′) is not particularly limited, but for example, the method described in JP-A-2005-132799 can be used, and all the contents of the publication can be referred to here. Is incorporated herein.
The catalyst for producing the propylene-based resin composition (X ′) is not particularly limited, but from the propylene-based resin composition (X ′), the propylene-based resin composition (Y), and further from the propylene-based resin composition (Y). It is preferable to use a metallocene catalyst because it is easy to suppress stickiness of the produced deformation-recoverable heat-resistant structure.
The propylene-based resin composition (X ′) may be appropriately selected from commercially available products. Examples of commercially available products include Nippon Polypro Co., Ltd. trade name “Newcon”, trade name “Wellnex” and the like. .
［プロピレン系樹脂組成物（Ｙ）］
本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）は、プロピレン系樹脂組成物（Ｘ）および／又は（Ｘ’）を必須成分とし、かつ上記特性（ｙ１）、（ｙ２）を満足するものである。
[Propylene-based resin composition (Y)]
The propylene-based resin composition (Y) for deformation-recoverable heat-resistant structure of the present invention comprises the propylene-based resin composition (X) and / or (X ′) as an essential component, and the above characteristics (y1) and (y2) Is satisfied.
特性（ｙ１）：メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）
本発明のプロピレン系樹脂組成物（Ｙ）のメルトフローレート（ＭＦＲ）は、１．０〜１００ｇ／１０分である。
ここで、ＭＦＲは、ＪＩＳ Ｋ７２１０：１９９９のＡ法、条件Ｍ（２３０℃、２．１６ｋｇ荷重）に準拠して測定されるものである。
ＭＦＲが１．０ｇ／１０分未満の場合、成形時の負荷が増したり、成形体の成形自体が困難になる。一方、ＭＦＲが１００ｇ／１０分を超えると、成形の安定性、特に押出成形に用いた場合の成形安定性が損なわれやすくなる。
プロピレン系樹脂組成物（Ｙ）のメルトフローレート（ＭＦＲ）は、成分（Ａ）および／又は（Ａ’）のＭＦＲを考慮し、成分（Ｂ）および／又は（Ｂ’）のＭＦＲや、プロピレン系樹脂組成物（Ｘ）および／又は（Ｘ’）以外の第三成分のＭＦＲを、適宜選択することにより調整できる。
プロピレン系樹脂組成物（Ｙ）のメルトフローレート（ＭＦＲ）の好ましい範囲は、２．０〜５０ｇ／１０分、更に好ましくは５．０〜３０ｇ／１０分、特に好ましくは５．０〜２０ｇ／１０分である。
Characteristic (y1): Melt flow rate (MFR: 230 ° C., 2.16 kg load)
The melt flow rate (MFR) of the propylene-based resin composition (Y) of the present invention is 1.0 to 100 g / 10 min.
Here, MFR is measured according to JIS K7210: 1999 method A, condition M (230 ° C., 2.16 kg load).
When the MFR is less than 1.0 g / 10 minutes, the load during molding increases, or the molding itself becomes difficult. On the other hand, if the MFR exceeds 100 g / 10 min, the molding stability, particularly the molding stability when used for extrusion molding, tends to be impaired.
The melt flow rate (MFR) of the propylene-based resin composition (Y) takes into account the MFR of the component (A) and / or (A ′), the MFR of the component (B) and / or (B ′), propylene The MFR of the third component other than the system resin composition (X) and / or (X ′) can be adjusted by appropriately selecting.
The preferable range of the melt flow rate (MFR) of the propylene-based resin composition (Y) is 2.0 to 50 g / 10 minutes, more preferably 5.0 to 30 g / 10 minutes, and particularly preferably 5.0 to 20 g / minute. 10 minutes.
特性（ｙ２）：融解ピーク温度（Ｔｍ）
本発明のプロピレン系樹脂組成物（Ｙ）の融解ピーク温度は、１２１〜１７０℃である。
融解ピーク温度が１２１℃未満の場合、本発明のプロピレン系樹脂組成物（Ｙ）から得られる構造体が高温下、好ましくは１２１℃以上の環境下で形状が保持できるだけの耐熱性を発現することができない。一方、融解ピーク温度が１７０℃を超えるものは、実質的に製造が困難である。
融解ピーク温度の好ましい範囲は、１２５〜１７０℃、より好ましくは１３０〜１７０℃、更に好ましくは１３５〜１７０℃である。
Characteristic (y2): Melting peak temperature (Tm)
The melting peak temperature of the propylene-based resin composition (Y) of the present invention is 121 to 170 ° C.
When the melting peak temperature is less than 121 ° C., the structure obtained from the propylene-based resin composition (Y) of the present invention exhibits heat resistance sufficient to maintain its shape at a high temperature, preferably in an environment of 121 ° C. or higher. I can't. On the other hand, those having a melting peak temperature exceeding 170 ° C. are substantially difficult to produce.
The preferable range of the melting peak temperature is 125 to 170 ° C, more preferably 130 to 170 ° C, and still more preferably 135 to 170 ° C.
その他の特性：
本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）は、曲げ弾性率が２０〜５００ＭＰａであることが好ましく、より好ましくは４０〜４００ＭＰａ、更に好ましくは５０〜３００ＭＰａ、特に好ましくは５０〜２５０ＭＰａである。
曲げ弾性率は、成分（Ａ）および／又は（Ａ’）と成分（Ｂ）または（Ｂ’）の組成、配合比や下記その他の成分の配合量などを適宜選択することにより、所望の値に調整することができる。
曲げ弾性率が前記範囲にあれば、柔軟性、変形のしやすさ、変形回復性のバランスを取りやすいので、好ましい。
Other characteristics:
The propylene-based resin composition (Y) for deformation-recoverable heat-resistant structure of the present invention preferably has a flexural modulus of 20 to 500 MPa, more preferably 40 to 400 MPa, still more preferably 50 to 300 MPa, particularly preferably. 50 to 250 MPa.
The flexural modulus is a desired value by appropriately selecting the composition of the component (A) and / or (A ′) and the component (B) or (B ′), the blending ratio, the blending amount of the following other components, and the like. Can be adjusted.
A flexural modulus within the above range is preferable because it is easy to balance flexibility, ease of deformation, and deformation recovery.
また、本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）は、引張降伏応力が、２０ＭＰａ以下が好ましく、より好ましくは１５ＭＰａ以下、更に好ましくは１２ＭＰａ以下であり、特に好ましくは１０ＭＰａ以下であり、最も好ましくは観測されないことである。引張降伏応力が前記範囲にあれば、変形回復性を発現させやすく、好ましい。 In addition, the propylene resin composition (Y) for deformation-recoverable heat-resistant structure of the present invention has a tensile yield stress of preferably 20 MPa or less, more preferably 15 MPa or less, still more preferably 12 MPa or less, and particularly preferably 10 MPa. And most preferably not observed. If the tensile yield stress is within the above range, it is easy to develop deformation recovery properties, which is preferable.
［その他の成分］
本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）は、前述したプロピレン系樹脂組成物（Ｘ）を必須成分とする樹脂組成物であるが、本発明の目的を阻害しない範囲で、その他の樹脂または添加剤等、各種の他の成分を、添加して用いることができる。
[Other ingredients]
The propylene-based resin composition (Y) for deformation-recoverable heat-resistant structure of the present invention is a resin composition containing the above-mentioned propylene-based resin composition (X) as an essential component, but does not impair the object of the present invention. Then, various other components such as other resins or additives can be added and used.
（１）添加剤
本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）には、本発明の効果を妨げない限り、プロピレン系樹脂に添加できる酸化防止剤などの添加剤を、適宜配合することができる。
具体的には、２，６−ジ−ｔ−ブチル−ｐ−クレゾール（ＢＨＴ）、テトラキス［メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン（ＢＡＳＦジャパン社製商品名「ＩＲＧＡＮＯＸ １０１０」）やｎ−オクタデシル−３−（４’−ヒドロキシ−３，５’−ジ−ｔ−ブチルフェニル）プロピオネート（ＢＡＳＦジャパン社製商品名「ＩＲＧＡＮＯＸ １０７６」）で代表されるフェノール系安定剤、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールジホスファイトやトリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイトなどで代表されるホスファイト系安定剤、オレイン酸アミドやエルカ酸アミド等の高級脂肪酸アミドや高級脂肪酸エステルやシリコーンオイルで代表される滑剤、炭素原子数８〜２２の脂肪酸のグリセリンエステルやソルビタン酸エステル、ポリエチレングリコールエステルなどで代表される帯電防止剤、ソルビトール系造核剤（例えば、新日本理化社製商品名「ゲルオールＭＤ」）、芳香族燐酸エステル類（例えば、ＡＤＥＫＡ社製商品名「ＮＡ−２１」や「ＮＡ−１１」）、ミリケン社製商標名「Ｍｉｌｌａｄ」シリーズ、ミリケン社製商標名「Ｈｙｐｅｒｆｏｒｍ」シリーズ、タルク、高密度ポリエチレンなどで代表される造核剤、シリカ、炭酸カルシウム、タルクなどで代表されるブロッキング防止剤や有機過酸化物などで代表される分子量調整剤や架橋助剤、ステアリン酸カルシウムなどの高級脂肪酸金属塩やハイドロタルサイト類に代表される中和剤、光安定剤、紫外線吸収剤、金属不活性剤、過酸化物、充填剤、抗菌防黴剤、蛍光増白剤、防曇剤、着色剤、顔料、天然油、合成油、ワックス、更には用途に応じて有機系、無機系の難燃剤などを、添加してもよく、それらの配合量は、適宜量である。
(1) Additives The propylene-based resin composition for deformation-recoverable heat-resistant structures (Y) of the present invention includes additives such as antioxidants that can be added to the propylene-based resin as long as the effects of the present invention are not hindered. It can mix | blend suitably.
Specifically, 2,6-di-t-butyl-p-cresol (BHT), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (BASF Japan) And trade name “IRGANOX 1010”) and n-octadecyl-3- (4′-hydroxy-3,5′-di-t-butylphenyl) propionate (trade name “IRGANOX 1076” manufactured by BASF Japan). Phenol stabilizers such as bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tris (2,4-di-t-butylphenyl) phosphite Lubricants represented by higher fatty acid amides such as oleic acid amide and erucic acid amide, higher fatty acid esters and silicone oils, Antistatic agent represented by glycerin ester, sorbitan acid ester, polyethylene glycol ester and the like of fatty acid having 8 to 22 carbon atoms, sorbitol nucleating agent (for example, trade name “Gelol MD” manufactured by Shin Nippon Rika Co., Ltd.), aroma Group phosphates (for example, trade names “NA-21” and “NA-11” manufactured by ADEKA), trade names “Millad” series manufactured by Milliken, trade names “Hyperform” manufactured by Milliken, talc, high-density polyethylene Nucleating agents represented by, such as anti-blocking agents represented by silica, calcium carbonate, talc, etc., molecular weight regulators represented by organic peroxides, crosslinking aids, higher fatty acid metal salts such as calcium stearate, Neutralizers, light stabilizers, UV absorbers, metal inertness typified by hydrotalcite , Peroxides, fillers, antibacterial and antifungal agents, fluorescent whitening agents, antifogging agents, colorants, pigments, natural oils, synthetic oils, waxes, and organic and inorganic flame retardants depending on the application May be added, and the blending amount thereof is an appropriate amount.
有機系難燃剤としては、臭素系難燃剤やリン系難燃剤などが挙げられ、必要に応じて、三酸化アンチモンなどの難燃助剤を併用することが好ましい。例えば、臭素系難燃剤の配合量は、所望の難燃性能に応じて、適宜調整すればよいが、本発明のプロピレン系樹脂組成物（Ｙ）中に０．１〜１０重量％配合し、また、難燃助剤は、臭素系難燃剤の１／４〜１／２量程度、配合することを例示できる。さらに、リン系難燃剤の配合量は、所望の難燃性能に応じて、適宜調整すればよいが、本発明のプロピレン系樹脂組成物（Ｙ）中に１〜３０重量％程度、配合することを例示できる。 Examples of organic flame retardants include brominated flame retardants and phosphorus flame retardants, and it is preferable to use a flame retardant aid such as antimony trioxide as necessary. For example, the blending amount of the brominated flame retardant may be appropriately adjusted according to the desired flame retardant performance, but 0.1 to 10% by weight is blended in the propylene based resin composition (Y) of the present invention, Moreover, a flame retardant adjuvant can mix | blend about 1/4 to 1/2 amount of brominated flame retardants. Furthermore, the blending amount of the phosphorus-based flame retardant may be appropriately adjusted according to the desired flame retardant performance. However, about 1 to 30% by weight is blended in the propylene-based resin composition (Y) of the present invention. Can be illustrated.
抗菌剤、制菌剤としては、東亞合成社製商標名「ノバロン」やシナネンゼオミック社製商標名「ゼオミック」や富士ケミカル社製商標名「バクテキラー」や石塚硝子社製商標名「イオンピュア」で例示される銀系抗菌剤、ＡＤＥＫＡ社製商標名「ロイヤルガード」や三菱化学フーズ社製商標名「ワサオーロ」で例示される有機系抗菌剤が挙げられるが、効果の持続性の観点から、銀系抗菌剤の使用が好ましい。抗菌剤、制菌剤の配合量は、所望の抗菌、制菌性能に応じて、適宜調整すればよいが、本発明のプロピレン系樹脂組成物（Ｙ）中に０．１〜１０重量％程度、配合することを例示できる。 As antibacterial and antibacterial agents, the brand name “Novalon” manufactured by Toagosei Co., Ltd., the brand name “Zeomic” manufactured by Sinanen Zeomic Co., the brand name “Bacte Killer” manufactured by Fuji Chemical Co., Ltd., and the brand name “Ion Pure” manufactured by Ishizuka Glass Co., Ltd. Examples include silver antibacterial agents, organic antibacterial agents exemplified by trade name “Royal Guard” manufactured by ADEKA and trade name “Wasaolo” manufactured by Mitsubishi Chemical Foods, Inc. The use of antibacterial agents is preferred. The blending amount of the antibacterial agent and antibacterial agent may be appropriately adjusted according to the desired antibacterial and antibacterial performance, but is about 0.1 to 10% by weight in the propylene resin composition (Y) of the present invention. Can be exemplified.
（２）その他のポリマー
また、本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）には、本発明の効果を妨げない限り、プロピレン系樹脂に添加できるエラストマー、脂環式炭化水素樹脂などの改質剤を、適宜配合することができる。
その他のポリマーは、本発明の効果を妨げない限り、添加量に特に制限は無いが、通常、プロピレン系樹脂組成物（Ｘ）１００重量部に対して、１００重量部以下である。
(2) Other polymers In addition, the propylene resin composition (Y) for deformation-recoverable heat-resistant structure of the present invention has an elastomer, alicyclic carbonization that can be added to the propylene resin as long as the effects of the present invention are not hindered. A modifier such as a hydrogen resin can be appropriately blended.
The amount of the other polymer is not particularly limited as long as the effect of the present invention is not hindered, but is usually 100 parts by weight or less with respect to 100 parts by weight of the propylene-based resin composition (X).
具体的には、エチレン−α−オレフィン共重合体、例えば、低密度ポリエチレン、線状低密度ポリエチレン、高密度ポリエチレン、エチレン系エラストマーやエチレン−酢酸ビニル共重合体などで代表されるポリエチレン系樹脂や、１−ブテン単独重合体、１−ブテン−プロピレン共重合体、１−ブテン−エチレン共重合体等のポリオレフィンを挙げることができる。また、石油樹脂、テルペン樹脂、ロジン系樹脂、クマロンインデン樹脂、並びにそれらの水素添加誘導体等に代表される脂環式炭化水素樹脂や、例えば三井化学社製商品名「アペル」やポリプラスチックス社製商品名「ＴＯＰＡＳ」や日本ゼオン社製商品名「ゼオノア」、「ゼオネックス」に代表される環状オレフィン（共）重合体などを添加してもよい。 Specifically, ethylene-α-olefin copolymers, such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polyethylene-based resins represented by ethylene-based elastomers and ethylene-vinyl acetate copolymers, 1-butene homopolymer, 1-butene-propylene copolymer, 1-butene-ethylene copolymer, and other polyolefins. In addition, alicyclic hydrocarbon resins represented by petroleum resins, terpene resins, rosin resins, coumarone indene resins, and hydrogenated derivatives thereof, for example, trade names “Apel” and polyplastics manufactured by Mitsui Chemicals, Inc. A cyclic olefin (co) polymer represented by the trade name “TOPAS” manufactured by the company, the trade name “ZEONOR” or “ZEONEX” manufactured by ZEON Corporation may be added.
さらに、スチレン系エラストマーを加えることができ、スチレン系エラストマーとしては、市販されているものの中から、適宜選択して使用することもでき、例えば、スチレン−ブタジエンブロック共重合体の水素添加物としてクレイトンポリマージャパン（株）より「クレイトンＧ」として、また、旭化成ケミカルズ社より「タフテック」の商品名で、スチレン−イソプレンブロック共重合体の水素添加物として（株）クラレより「セプトン」の商品名で、スチレン−ビニル化ポリイソプレンブロック共重合体の水素添加物として（株）クラレより「ハイブラー」の商品名で、スチレン−ブタジエンランダム共重合体の水素添加物としてＪＳＲ（株）より「ダイナロン」の商品名で販売されており、これらの商品群より、適宜、選択して用いてもよい。 Further, a styrene-based elastomer can be added, and the styrene-based elastomer can be appropriately selected from commercially available ones. For example, as a hydrogenated product of a styrene-butadiene block copolymer, Kraton “Clayton G” from Polymer Japan Co., Ltd., “Tough Tech” from Asahi Kasei Chemicals, Inc., “Septon” from Kuraray Co., Ltd. as a hydrogenated product of styrene-isoprene block copolymer. As a hydrogenated product of styrene-vinylated polyisoprene block copolymer, Kuraray Co., Ltd. under the trade name “Hibler”, and as a hydrogenated product of styrene-butadiene random copolymer, “Dynalon” from JSR Co., Ltd. The product is sold under the product name. It may be.
［プロピレン系樹脂組成物（Ｙ）の製造方法］
本発明のプロピレン系樹脂組成物（Ｙ）は、上述のプロピレン系樹脂組成物（Ｘ）を構成する成分（Ａ）と成分（Ｂ）、および／または上述のプロピレン系樹脂組成物（Ｘ’）と、必要に応じて、他の添加剤、ポリマー成分をヘンシェルミキサー、Ｖブレンダー、リボンブレンダー、タンブラーブレンダー等で混合し、得ることができる。更に必要に応じて、前記混合工程の後、単軸押出機、多軸押出機、ニーダー、バンバリミキサー等の混練機により溶融混練する方法により得ることもできる。
また、各成分は同時に混合および／又は溶融混練してもよいし、一部をマスターバッチとした上で、混合および／又は溶融混練してもよい。
[Production Method of Propylene Resin Composition (Y)]
The propylene-based resin composition (Y) of the present invention includes the components (A) and (B) constituting the propylene-based resin composition (X) and / or the propylene-based resin composition (X ′). If necessary, other additives and polymer components can be mixed with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender or the like to obtain. Further, if necessary, it can also be obtained by a method of melt-kneading with a kneader such as a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer after the mixing step.
Moreover, each component may be mixed and / or melt-kneaded at the same time, or may be mixed and / or melt-kneaded after making a part of the master batch.
［変形回復性耐熱構造体］
本発明の変形回復性耐熱構造体は、高温下での変形回復性に優れ、且つ高温下、好ましくは１２１℃以上の環境下でも形状が保持できる耐熱性を有する。
構造体の形状、成形方法、用途は、特に制限は無いが、継続した負荷により継続して変形せしめられた後、負荷を除去した際に、変形回復性が求められる用途に用いられる。
例えば、射出成形や、押出成形により、平板や棒状、らせん状、さらには異型断面や中空断面を有する成形体を緩衝用のバネに類する用途に適用する場合や、クッション等の支持体に適用する場合等が挙げられる。
また、芯鞘構造を有したり、サイドバイサイド構造を有する構造体の一構成要素として使用することもできる。
好適な適用形態の例としては、押出成形により得られる複数のストランドからなる連続線状体を三次元ランダムループ状に曲がりくねらせて、複数のループの接触部の少なくとも一部が融着してなる立体網目状構造を有する網状構造体や、特開２０１２−１１２０７２号公報や、特開平５−１６３６５７号公報に例示される繊維集合体からなる構造体などが挙げられる。
[Deformation-resistant heat-resistant structure]
The deformation-recoverable heat-resistant structure of the present invention is excellent in deformation recovery property at high temperatures, and has heat resistance that allows the shape to be maintained at high temperatures, preferably even in an environment of 121 ° C. or higher.
The shape, forming method, and use of the structure are not particularly limited, but are used for applications that require deformation recovery when the load is removed after being continuously deformed by a continuous load.
For example, by injection molding or extrusion molding, a flat body, rod shape, spiral shape, or a molded body having an irregular or hollow cross section is applied to a use similar to a buffer spring, or applied to a support such as a cushion. Cases.
Moreover, it can also be used as one component of the structure which has a core-sheath structure or has a side-by-side structure.
As an example of a suitable application form, a continuous linear body composed of a plurality of strands obtained by extrusion is twisted into a three-dimensional random loop, and at least a part of contact portions of the plurality of loops is fused. Examples thereof include a network structure having a three-dimensional network structure, and a structure made of a fiber assembly exemplified in Japanese Patent Application Laid-Open No. 2012-112072, and Japanese Patent Application Laid-Open No. 5-163657.
特に好適な適用形態としては、押出成形により得られる複数のストランドからなる連続線状体を三次元ランダムループ状に曲がりくねらせて、複数のループの接触部の少なくとも一部が融着してなる立体網目状構造を有する網状構造体が挙げられる。
前記網状構造体は、例えば、ベッド等の寝具、家庭用や車両・船舶・航空機用座席等のクッション材として用いられる場合があり、これらの用途では、長時間にわたり、人が横たわったり、座ったりするため、継続した負荷により継続して変形せしめられる。しかも、負荷を除去した後に、再びクッション材として使用するには、変形が実用上問題ない程度まで回復する必要がある。
更には、自動車のクッションや緩衝部品、暖房機能付与のベッド用クッションなどでは、高温下（例えば７０℃）で負荷がかかるケースがあるため、高温下での変形回復性も求められる。
また、近年、病院などではクッション自体の洗浄、場合によっては滅菌処理を行うニーズがあり、高温下、好ましくは１２１℃以上の蒸気滅菌処理への耐性が求められており、本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物（Ｙ）を適用する変形回復性耐熱構造体としては、特に好適な適用形態であるといえる。
As a particularly preferred application form, a continuous linear body made of a plurality of strands obtained by extrusion molding is twisted into a three-dimensional random loop, and at least a part of contact portions of the plurality of loops is fused. Examples thereof include a network structure having a three-dimensional network structure.
The net-like structure may be used, for example, as a bedding such as a bed, or a cushioning material for a home, vehicle, ship or aircraft seat. In these applications, a person lies down or sits down for a long time. Therefore, it is continuously deformed by the continued load. In addition, after removing the load, in order to use it again as a cushioning material, it is necessary to recover the deformation to such an extent that there is no practical problem.
Furthermore, since there are cases where a load is applied at a high temperature (for example, 70 ° C.) in an automobile cushion, a cushioning part, a bed cushion with a heating function, etc., a deformation recovery property at a high temperature is also required.
In recent years, there has been a need in hospitals to clean the cushion itself, and in some cases, sterilization, and resistance to steam sterilization at a high temperature, preferably 121 ° C. or higher, is required. It can be said that it is a particularly suitable application form as a deformation recovery heat resistant structure to which the propylene resin composition (Y) for a heat resistant structure is applied.
上記以外にも、例えば、排水性向上、通気性向上や土砂等の保持を目的に地面に埋設したり、敷設するする土木資材用途、建築資材用途や、産業資材用途などにも、本発明のプロピレン系樹脂組成物（Ｙ）を用いた変形回復性耐熱構造体は、好適に用いることができる。これらの用途においては、例えば、日中屋外で高温環境下になり、尚且つ人、車両、動物などの荷重により変形が付与されることが想定されるが、本発明のプロピレン系樹脂組成物（Ｙ）を用いた変形回復性耐熱構造体を用いることにより、元の形状に容易に復元することが期待される。更には、高温下、好ましくは１２１℃以上での形状保持性に優れるため、スチーム洗浄機での洗浄にも、適応できる。また、本発明のプロピレン系樹脂組成物（Ｙ）を用いた構造体は、柔軟であるため、様々な形状への追随性も有しており、適用範囲の広がりも、期待できる。 In addition to the above, for example, in the use of civil engineering materials, building materials, industrial materials, etc. that are embedded in or laid on the ground for the purpose of improving drainage, improving air permeability and retaining earth and sand, etc. A deformation recoverable heat-resistant structure using the propylene-based resin composition (Y) can be suitably used. In these applications, for example, it is assumed that the outdoor environment is in a high temperature environment during the daytime and is deformed by a load of a person, vehicle, animal, etc., but the propylene resin composition ( By using the deformation-recoverable heat-resistant structure using Y), it is expected to easily restore the original shape. Furthermore, since it has excellent shape retention at high temperatures, preferably at 121 ° C. or higher, it can be applied to cleaning with a steam cleaner. Moreover, since the structure using the propylene-based resin composition (Y) of the present invention is flexible, it has followability to various shapes and can be expected to expand its application range.
前記網状構造体の製造方法としては、公知の方法を適宜採用すればよく、例えば、特開２０１３−０４０４３７号公報や、特開平７−１７３７５３号公報、特許第５４５９４３８号公報、特許第５４５９４３６号公報、特許第５４５４７３３号公報に記載の方法が挙げられるが、これらに限定されるものではない。
また、高温下での負荷がかかる用途に適用する場合には、構造体の形状を保持できる温度以下、好ましくは想定される使用条件温度以上、構造体の形状を保持できる温度以下で、成形された構造体を１０秒乃至１日程度状態調整を行うと、高温下での変形回復性がより向上しやすいので好ましい。
本発明の構造体の場合は、例えば４０℃、５０℃、６０℃、７０℃、８０℃、９０℃、１００℃、１１０℃、１２０℃、１３０℃、１４０℃、１５０℃、１６０℃といった温度条件が例示できる。
As a method for producing the network structure, a known method may be appropriately employed. For example, Japanese Patent Application Laid-Open No. 2013-040437, Japanese Patent Application Laid-Open No. 7-173753, Japanese Patent No. 5549438, and Japanese Patent No. 5559436. Although the method of patent 5454733 is mentioned, it is not limited to these.
In addition, when applied to an application in which a load under high temperature is applied, it is molded at a temperature not higher than a temperature at which the shape of the structure can be maintained, preferably at a temperature not lower than an assumed use condition temperature and not higher than a temperature at which the shape of the structure can be maintained. It is preferable to adjust the state of the structure for about 10 seconds to 1 day since deformation recovery at high temperatures is more likely to be improved.
In the case of the structure of the present invention, for example, temperatures of 40 ° C., 50 ° C., 60 ° C., 70 ° C., 80 ° C., 90 ° C., 100 ° C., 110 ° C., 120 ° C., 130 ° C., 140 ° C., 150 ° C., 160 ° C. Conditions can be exemplified.
また、前記成形体を緩衝用のバネに類する用途に適用する場合や、クッション等の支持体に適用する場合、更には、前記網状構造体をクッション材用途に適用する場合の何れのケースでも、継続した負荷により、継続して変形せしめられる変形形態は、曲げ変形になる。
例えば、前記網状構造体の場合、一見変形形態は、圧縮変形とみられがちだが、網状構造体を構成する各々の線条に着目すれば、変形形態は、曲げ変形である。
したがって、継続した負荷により継続して曲げ変形を行い、その後、負荷を除去した際の変形回復性を評価することにより、前述の例に挙げた各種構造体の変形回復性を十分類推することができる。
In addition, when the molded body is applied to a use similar to a buffer spring, when applied to a support such as a cushion, and further, in any case of applying the network structure to a cushion material, A deformation form that is continuously deformed by a continuous load is a bending deformation.
For example, in the case of the network structure, the seemingly deformed form tends to be seen as a compressive deformation. However, if attention is paid to each filament constituting the network structure, the deformed form is a bending deformation.
Therefore, it is possible to sufficiently analogize the deformation recoverability of the various structures listed in the above example by continuously bending and deforming with the continued load, and then evaluating the deformation recovery when the load is removed. it can.
以下、本発明を実施例によって具体的に説明するが、本発明は、これらの実施例のみに限定されるものではない。
なお、実施例および比較例において使用したプロピレン系樹脂組成物とその構成成分、変形回復性耐熱構造体の諸物性は、下記の評価方法に従って、測定、評価した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
The propylene resin compositions used in the examples and comparative examples, their constituent components, and various physical properties of the deformation-recoverable heat-resistant structure were measured and evaluated according to the following evaluation methods.
［各プロピレン系樹脂の物性］
（１）メルトフローレート（ＭＦＲ、単位：ｇ／１０分）：
ＪＩＳ Ｋ７２１０：１９９９のＡ法、条件Ｍ（２３０℃、２．１６ｋｇ荷重）に準拠して測定した。
（２）融解ピーク温度（融点）（Ｔｍ、単位：℃）：
示差走査熱量計（ＤＳＣ）を用い、一旦２００℃まで温度を上げて、熱履歴を消去した後、１０℃／分の降温速度で４０℃まで温度を降下させ、再び昇温速度１０℃／分にて測定した際の、吸熱ピークトップの温度を融解ピーク温度（融点）（Ｔｍ）とした。
[Physical properties of each propylene resin]
(1) Melt flow rate (MFR, unit: g / 10 minutes):
Measured in accordance with JIS K7210: 1999, Method A, Condition M (230 ° C., 2.16 kg load).
(2) Melting peak temperature (melting point) (Tm, unit: ° C.):
Using a differential scanning calorimeter (DSC), once the temperature was raised to 200 ° C. and the heat history was erased, the temperature was lowered to 40 ° C. at a temperature lowering rate of 10 ° C./min, and the temperature rising rate was 10 ° C./min again. The temperature at the top of the endothermic peak at the time of measurement was taken as the melting peak temperature (melting point) (Tm).
（３）α−オレフィン含有量（単位：重量％）
市販のプロピレン−α−オレフィン共重合体成分（Ｂ）については、メーカーより公表されているカタログ記載の値を用いた。
プロピレン系樹脂組成物（Ｘ’）中の成分（Ａ’）および（Ｂ’）については、前述した特開２００５−１３２９７９号公報に記載の方法にて、測定した。
尚、成分（Ａ’）および（Ｂ’）は、特開２００５−１３２９７９号公報に記載の成分（Ａ）および（Ｂ）に各々対応する。
（４）プロピレン系樹脂組成物（Ｘ’）中の成分（Ａ’）および（Ｂ’）の含有量（単位：重量％）
前述した特開２００５−１３２９７９号公報に記載の方法にて測定した。
尚、成分（Ａ’）および（Ｂ’）は、特開２００５−１３２９７９号公報に記載の成分（Ａ）および（Ｂ）に各々対応する。
(3) α-olefin content (unit: wt%)
About the commercially available propylene-alpha-olefin copolymer component (B), the value of the catalog description published by the manufacturer was used.
The components (A ′) and (B ′) in the propylene-based resin composition (X ′) were measured by the method described in JP-A-2005-132979 described above.
The components (A ′) and (B ′) correspond to the components (A) and (B) described in JP-A-2005-132979, respectively.
(4) Content of the components (A ′) and (B ′) in the propylene-based resin composition (X ′) (unit: wt%)
The measurement was performed by the method described in JP-A-2005-132979 described above.
The components (A ′) and (B ′) correspond to the components (A) and (B) described in JP-A-2005-132979, respectively.
（５）残留歪（単位：％）
（ｉ）試料の調製
プロピレン系樹脂組成物（Ｙ）を、圧縮成形法により、シート状に成形した。
使用したスペーサー：長さ２００ｍｍ、幅２００ｍｍ、厚さ１ｍｍ。
圧縮成形条件：
（ア）予熱工程：予熱時間７分、予熱温度２００℃、予熱時圧力０．１ＭＰａ
（イ）加圧工程：加圧時間３分、加圧時温度２００℃、加圧時圧力８ＭＰａ
（ウ）冷却工程：冷却時間３分、冷却時温度３０℃、冷却時圧力１２ＭＰａ
上述の条件で成形して得られたシートを、２３℃、５０％相対湿度の条件下、４８時間以上状態調整を行った後、また、場合によっては、更にギヤオーブンにて７０℃又は１００℃、１時間の条件で状態調整を行い、更に２３℃、５０％相対湿度の条件下４８時間以上状態調整を行った後、カッターナイフにて切り出し、長さ１４０ｍｍ、幅１０ｍｍ、厚さ１ｍｍの構造体を作製し、下記試験に供した。
（ｉｉ）定変位曲げ試験
長さ２２０ｍｍ、幅１５０ｍｍ、厚さ３ｍｍのガラス板を２枚、１００ｍｍの間隔をあけて作業台上に平行に配置した。
前述の方法で作製した構造体の長さ方向の両端から各々２０ｍｍの位置に標線を付し（即ち、標線間距離１００ｍｍ）、前述のガラス板の向かい合う各々の端部と構造体に付された標線が一致するように構造体を設置し、構造体とガラス板が重なる部分をセロハンテープにて厳重に固定した。厚さ５０ｍｍのスペーサーを介し、構造体が固定されたガラス板を、セロハンテープにて固定された面同士が向かい合い、尚且つガラス板の四隅が重なり合うように重ね合わせた。
この状態で、構造体は、標線間が空間を介して５０ｍｍになるように曲げられた状態となり、元の標線間長さ１００ｍｍに対して５０％の変形量を与えられたことになる。尚、一組のガラス板には１試料につき３枚、１乃至５種類の試料を固定した。
引き続き上記状態のまま、２３℃、５０％相対湿度条件下または４０℃に調整されたギヤオーブン中、もしくは７０℃に調整されたギヤオーブン中で、２２時間状態調整を行い、その後に同条件下でガラス板に張り付けられた構造体の標線近傍を鋭利なハサミまたはカッターナイフで切断、負荷を除去した。
切断された構造体は、直ちに２３℃、５０％相対湿度の恒温恒湿室に運び込み、３０分間状態調整を行った。切断された構造体は、ある程度曲げ変形を残しており、曲げ変形したままの状態で切断された両端の距離を、定規を用いて測定した。この距離をＬ１とした。
また、作業台上で切断された構造体の曲げ変形を作業台と平行になるように延ばし、切断された両端の長さを、定規を用いて測定した。この長さをＬ０とした。
以下の計算式を用いて、残留歪を求めた。残留歪は、変形回復性の指標であり、値が小さいほど変形回復性に優れると言える。
残留歪＝（Ｌ０−Ｌ１）／Ｌ０×１００（％）
(5) Residual strain (unit:%)
(I) Preparation of sample The propylene-based resin composition (Y) was molded into a sheet by a compression molding method.
Spacers used: length 200 mm, width 200 mm,
Compression molding conditions:
(A) Preheating process: preheating
(A) Pressurization step:
(C) Cooling step: Cooling
The sheet obtained by molding under the above-mentioned conditions is subjected to condition adjustment for 48 hours or more under the conditions of 23 ° C. and 50% relative humidity, and in some cases, further, 70 ° C. or 100 ° C. in a gear oven. After adjusting the condition under conditions of 1 hour and further adjusting the condition for 48 hours or more under the conditions of 23 ° C. and 50% relative humidity, the structure is cut out with a cutter knife and has a length of 140 mm, a width of 10 mm, and a thickness of 1 mm. A body was prepared and subjected to the following test.
(Ii) Constant displacement bending test Two glass plates having a length of 220 mm, a width of 150 mm, and a thickness of 3 mm were arranged in parallel on a work table with an interval of 100 mm.
A marked line is attached to each position of 20 mm from both ends in the length direction of the structure manufactured by the above-described method (that is, the distance between marked lines is 100 mm), and the structure is attached to each of the opposite end portions of the glass plate. The structure was placed so that the marked lines coincided with each other, and the portion where the structure and the glass plate overlap was firmly fixed with cellophane tape. The glass plates on which the structures were fixed were overlapped through a spacer having a thickness of 50 mm so that the surfaces fixed with cellophane tape faced each other and the four corners of the glass plates overlapped.
In this state, the structure is bent so that the gap between the marked lines becomes 50 mm through the space, and the deformation amount of 50% is given to the original length between the marked lines of 100 mm. . In addition, 3 sheets per sample and 1 to 5 types of samples were fixed to a set of glass plates.
Then, in the gear oven adjusted to 23 ° C. and 50% relative humidity or 40 ° C. or in the gear oven adjusted to 70 ° C. for 22 hours, the same conditions are applied. Then, the vicinity of the marked line of the structure attached to the glass plate was cut with sharp scissors or a cutter knife to remove the load.
The cut structure was immediately brought into a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity, and the condition was adjusted for 30 minutes. The cut structure remained bent to some extent, and the distance between both ends cut in the bent state was measured using a ruler. This distance was set to L1.
Further, the bending deformation of the structure cut on the workbench was extended so as to be parallel to the workbench, and the lengths of the cut ends were measured using a ruler. This length was defined as L0.
Residual strain was determined using the following formula. Residual strain is an index of deformation recovery, and the smaller the value, the better the deformation recovery.
Residual strain = (L0−L1) / L0 × 100 (%)
（６）曲げ弾性率（単位：ＭＰａ）
射出成形品の曲げ弾性率を、ＪＩＳ Ｋ７１７１に準拠して、測定した。
（７）引張降伏応力（単位：ＭＰａ）
射出成形品の引張降伏応力を、ＪＩＳ Ｋ７１６２に準拠して、測定した。
(6) Flexural modulus (unit: MPa)
The flexural modulus of the injection molded product was measured according to JIS K7171.
(7) Tensile yield stress (unit: MPa)
The tensile yield stress of the injection molded product was measured according to JIS K7162.
（８）耐熱性
前述の試料の調製の項で得られた長さ１４０ｍｍ、幅１０ｍｍ、厚さ１ｍｍの構造体（状態調整条件は２３℃、５０％相対湿度）に、長さ方向の両端から、各々２０ｍｍの位置に標線を付した（即ち標線間距離１００ｍｍ）。
前記構造体の端部をクリップで挟み、ぶら下げた状態で１００℃もしくは１２１℃に調整されたギヤオーブン中に投入し、１５分間状態調整を行った。
前記状態調整終了後、ギヤオーブンから取り出し、直ちに２３℃、５０％相対湿度の恒温恒湿室に運び込み、溶融していない構造体について、直ちに標線間の長さ（Ｌ２）を測定した。
前記状態調整中に収縮したものは、Ｌ２が１００ｍｍ未満となり、膨張もしくは自重で垂れたものは、Ｌ２が１００ｍｍより大きくなる。前記状態調整で溶融したものについては、耐熱性なしとし、溶融しなかったものについては、元の標線間距離１００ｍｍからの変化量（％）の絶対値を耐熱性の指標とし、その値が小さいものほど、耐熱性が良好であるとした。
(8) Heat resistance The structure 140 mm long, 10 mm wide and 1 mm thick obtained in the preparation of the sample described above (conditions are adjusted at 23 ° C. and 50% relative humidity) from both ends in the length direction. , Each marked with a marked line at a position of 20 mm (that is, the distance between marked lines is 100 mm).
The end of the structure was sandwiched between clips and placed in a gear oven adjusted to 100 ° C. or 121 ° C. in a suspended state, and the state was adjusted for 15 minutes.
After completion of the condition adjustment, it was taken out from the gear oven, immediately brought into a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity, and the length (L2) between the marked lines was immediately measured for the unmelted structure.
Those that contract during the condition adjustment have an L2 of less than 100 mm, and those that sag due to expansion or dead weight have an L2 greater than 100 mm. For those melted by the above-mentioned condition adjustment, there was no heat resistance, and for those not melted, the absolute value of the amount of change (%) from the original distance between the marked lines of 100 mm was used as the heat resistance index, and the value was The smaller the value, the better the heat resistance.
［プロピレン系樹脂組成物（Ｘ’）の構成成分］
下記製造例（Ｘ’−１）〜（Ｘ’−２）で得られた樹脂を用いた。
[Components of Propylene Resin Composition (X ′)]
Resins obtained in the following production examples (X′-1) to (X′-2) were used.
（製造例Ｘ’−１）
（ｉ）予備重合触媒の調製
（珪酸塩の化学処理）
１０リットルの撹拌翼の付いたガラス製セパラブルフラスコに、蒸留水３．７５リットル、続いて濃硫酸（９６％）２．５ｋｇをゆっくりと添加した。５０℃で、さらにモンモリロナイト（水澤化学社製ベンクレイＳＬ；平均粒径＝２５μｍ、粒度分布＝１０〜６０μｍ）を１ｋｇ分散させ、９０℃に昇温し、６．５時間その温度を維持した。５０℃まで冷却後、このスラリーを減圧濾過し、ケーキを回収した。
このケーキに蒸留水を７リットル加え再スラリー化後、濾過した。この洗浄操作を、洗浄液（濾液）のｐＨが、３．５を超えるまで実施した。回収したケーキを窒素雰囲気下１１０℃で終夜乾燥した。乾燥後の重量は、７０７ｇであった。
(Production Example X′-1)
(I) Preparation of prepolymerized catalyst (chemical treatment of silicate)
To a 10-liter glass separable flask with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 25 μm, particle size distribution = 10-60 μm) was dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake.
7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5. The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g.
（珪酸塩の乾燥）
先に化学処理した珪酸塩は、キルン乾燥機により乾燥を実施した。
仕様及び乾燥条件は以下の通りである。
回転筒：円筒状、内径５０ｍｍ、加温帯５５０ｍｍ（電気炉）
かき上げ翼付き回転数：２ｒｐｍ
傾斜角：２０／５２０
珪酸塩の供給速度：２．５ｇ／分
ガス流速：窒素 ９６リットル／時間
向流乾燥温度：２００℃（粉体温度）
(Drying silicate)
The silicate previously chemically treated was dried with a kiln dryer.
Specifications and drying conditions are as follows.
Rotating cylinder: Cylindrical, inner diameter 50 mm, heating zone 550 mm (electric furnace)
Rotating speed with lifting blade: 2rpm
Tilt angle: 20/520
Silicate supply rate: 2.5 g / min Gas flow rate: Nitrogen 96 liters / hour Countercurrent drying temperature: 200 ° C. (powder temperature)
（触媒の調製）
撹拌および温度制御装置を有する内容積１６リットルのオートクレーブを窒素で充分置換した。乾燥珪酸塩２００ｇを導入し、混合ヘプタン１１６０ｍｌ、さらにトリエチルアルミニウムのヘプタン溶液（０．６０Ｍ）８４０ｍｌを加え、室温で攪拌した。１時間後、混合ヘプタンにて洗浄し、珪酸塩スラリーを２，０００ｍｌに調製した。
次に、先に調製した珪酸塩スラリーに、トリイソブチルアルミニウムのヘプタン溶液（０．７１Ｍ／Ｌ）９．６ｍｌを添加し、２５℃で１時間反応させた。並行して、（ｒ）−ジクロロ［１，１’−ジメチルシリレンビス｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ジルコニウム２，１８０ｍｇ（０．３ｍＭ）と混合ヘプタン８７０ｍｌに、トリイソブチルアルミニウムのヘプタン溶液（０．７１Ｍ）３３．１ｍｌを加えて、室温にて１時間反応させた混合物を、珪酸塩スラリーに加え、１時間攪拌後、混合ヘプタンを追加して５，０００ｍｌに調製した。
(Preparation of catalyst)
An autoclave with an internal volume of 16 liters equipped with a stirring and temperature control device was thoroughly replaced with nitrogen. 200 g of dry silicate was introduced, 1160 ml of mixed heptane and 840 ml of a heptane solution of triethylaluminum (0.60 M) were added, and the mixture was stirred at room temperature. After 1 hour, the mixture was washed with mixed heptane to prepare 2,000 ml of silicate slurry.
Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the silicate slurry prepared above and reacted at 25 ° C. for 1 hour. In parallel, (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium 2,180 mg (0.3 mM) and mixed heptane 870 ml Then, 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added, and the mixture reacted at room temperature for 1 hour was added to the silicate slurry. After stirring for 1 hour, 5,000 ml was added with mixed heptane. Prepared.
（予備重合／洗浄）
続いて、槽内温度を４０℃に昇温し、温度が安定したところで、プロピレンを１００ｇ／時間の速度で供給し、温度を維持した。４時間後プロピレンの供給を停止し、さらに２時間維持した。
予備重合終了後、残モノマーをパージし、撹拌を停止させ約１０分間静置後、上澄みを２，４００ｍｌデカントした。続いて、トリイソブチルアルミニウム（０．７１Ｍ／Ｌ）のヘプタン溶液９．５ｍｌ、さらに混合ヘプタンを５，６００ｍｌ添加し、４０℃で３０分間撹拌し、１０分間静置した後に、上澄みを５，６００ｍｌ除いた。さらにこの操作を３回繰り返した。
最後の上澄み液の成分分析を実施したところ、有機アルミニウム成分の濃度は、１．２３ｍｍоｌ／Ｌ、Ｚｒ濃度は８．６×１０−６ｇ／Ｌであり、仕込み量に対する上澄み液中の存在量は、０．０１６％であった。続いて、トリイソブチルアルミニウム（０．７１Ｍ／Ｌ）のヘプタン溶液を１７０ｍｌ添加した後に、４５℃で減圧乾燥を実施した。触媒１ｇ当たりポリプロピレンを２．０ｇ含む予備重合触媒が得られた。
この予備重合触媒を用いて、以下の手順に従ってプロピレン−エチレンブロック共重合体の製造を行った。
(Prepolymerization / washing)
Subsequently, the temperature in the tank was raised to 40 ° C., and when the temperature was stabilized, propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours.
After completion of the prepolymerization, the remaining monomer was purged, the stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then the supernatant was decanted to 2,400 ml. Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 5,600 ml of mixed heptane were further added, stirred at 40 ° C. for 30 minutes, allowed to stand for 10 minutes, and then the supernatant was added to 5,600 ml. Excluded. This operation was further repeated 3 times.
When the component analysis of the supernatant liquid was performed, the concentration of the organoaluminum component was 1.23 mmol / L, the Zr concentration was 8.6 × 10 −6 g / L, and the abundance in the supernatant with respect to the amount charged. Was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure. A prepolymerized catalyst containing 2.0 g of polypropylene per 1 g of catalyst was obtained.
Using this prepolymerized catalyst, a propylene-ethylene block copolymer was produced according to the following procedure.
（ｉｉ）第一重合工程
攪拌羽根を有する横型反応器（Ｌ／Ｄ＝６、内容積１００リットル）を十分に乾燥し、内部を窒素ガスで十分に置換した。ポリプロピレン粉体床の存在下、回転数３０ｒｐｍで攪拌しながら、反応器の上流部に上記の方法で調製した予備重合触媒を（予備重合パウダーを除いた固体触媒量として）０．５６８ｇ／ｈｒ、トリイソブチルアルミニウムを１５．０ｍｍｏｌ／ｈｒで連続的に供給した。反応器の温度を６５℃、圧力を２．１ＭＰａＧに保ち、且つ反応器内気相部のエチレン／プロピレンモル比が０．０７、水素濃度が１００ｐｐｍになるように、モノマー混合ガスを連続的に反応器内に流通させ、気相重合を行った。
反応によって生じた重合体パウダーは、反応器内の粉体床量が一定になるように、反応器下流部より連続的に抜き出した。この時、定常状態になった際の重合体抜き出し量は１０．０ｋｇ／ｈｒであった。
第一重合工程で得られたプロピレン−エチレンランダム共重合体を分析したところ、ＭＦＲは６．０ｇ／１０分、エチレン含有量は２．２ｗｔ％であった。
(Ii) First polymerization step A horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade was sufficiently dried, and the inside was sufficiently replaced with nitrogen gas. While stirring at a rotation speed of 30 rpm in the presence of a polypropylene powder bed, 0.568 g / hr of the prepolymerized catalyst prepared as described above (as the amount of solid catalyst excluding the prepolymerized powder) in the upstream part of the reactor, Triisobutylaluminum was continuously fed at 15.0 mmol / hr. The monomer mixed gas is continuously reacted so that the reactor temperature is maintained at 65 ° C., the pressure is maintained at 2.1 MPaG, the ethylene / propylene molar ratio in the reactor gas phase is 0.07, and the hydrogen concentration is 100 ppm. It was made to distribute | circulate in a container and vapor phase polymerization was performed.
The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, the amount of the polymer extracted when the steady state was reached was 10.0 kg / hr.
When the propylene-ethylene random copolymer obtained in the first polymerization step was analyzed, the MFR was 6.0 g / 10 min and the ethylene content was 2.2 wt%.
（ｉｉｉ）第二重合工程
攪拌羽根を有する横型反応器（Ｌ／Ｄ＝６、内容積１００リットル）に、第一工程より抜き出したプロピレン−エチレンランダム共重合体を連続的に供給した。回転数２５ｒｐｍで攪拌しながら、反応器の温度を７０℃、圧力を２．０ＭＰａＧに保ち、且つ反応器内気相部のエチレン／プロピレンモル比が０．４５３、水素濃度が３３０ｐｐｍになるように、モノマー混合ガスを連続的に反応器内に流通させ、気相重合を行った。
反応によって生じた重合体パウダーは、反応器内の粉体床量が一定になるように、反応器下流部より連続的に抜き出した。この時、重合体抜き出し量が１７．９ｋｇ／ｈｒになるように活性抑制剤として酸素を供給し、第二重合工程での重合反応量を制御した。活性は３１．４ｋｇ／ｇ−触媒であった。
こうして得られたプロピレン系樹脂（Ｘ’−１）の各種分析結果を表１に示す。
(Iii) Second polymerization step The propylene-ethylene random copolymer extracted from the first step was continuously supplied to a horizontal reactor (L / D = 6, internal volume 100 liters) having a stirring blade. While stirring at a rotational speed of 25 rpm, the temperature of the reactor is maintained at 70 ° C., the pressure is maintained at 2.0 MPaG, and the ethylene / propylene molar ratio in the gas phase in the reactor is 0.453, and the hydrogen concentration is 330 ppm. A monomer mixed gas was continuously passed through the reactor to carry out gas phase polymerization.
The polymer powder produced by the reaction was continuously extracted from the downstream portion of the reactor so that the amount of the powder bed in the reactor was constant. At this time, oxygen was supplied as an activity inhibitor so that the amount of polymer extracted was 17.9 kg / hr, and the polymerization reaction amount in the second polymerization step was controlled. The activity was 31.4 kg / g-catalyst.
Various analysis results of the propylene resin (X′-1) thus obtained are shown in Table 1.
得られたプロピレン系樹脂（Ｘ’−１）１００重量部に、添加剤（酸化防止剤）として、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネ−ト］メタン（商品名「ＩＲＧＡＮＯＸ１０１０」、ＢＡＳＦジャパン株式会社製）０．０５重量部、ホスファイト系酸化防止剤であるトリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（商品名「ＩＲＧＡＦＯＳ １６８」、ＢＡＳＦジャパン株式会社製）０．０５重量部を、ヘンシェルミキサーに投入し、７５０ｒｐｍで１分間室温で高速混合した後、スクリュー口径２５ｍｍのテクノベル社製ＫＺＷ−２５押出機にて、スクリュー回転数２５０ｒｐｍ、吐出量１５ｋｇ／ｈｒ、押出機温度２００℃で溶融混練し、ストランドダイから押し出された溶融樹脂を、冷却水槽で冷却固化させながら引き取り、ストランドカッターを用いてストランドを直径約２ｍｍ、長さ約３ｍｍに切断することでプロピレン系樹脂組成物（Ｘ’−１）を得た。 To 100 parts by weight of the resulting propylene resin (X′-1), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) was used as an additive (antioxidant). ) Propionate] methane (trade name “IRGANOX1010”, manufactured by BASF Japan Ltd.) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (product), which is a phosphite antioxidant 0.05 parts by weight of “IRGAFOS 168” (manufactured by BASF Japan Ltd.) was charged into a Henschel mixer, mixed at 750 rpm for 1 minute at room temperature, and then KZW-25 extruder manufactured by Technobel with a screw diameter of 25 mm. , Melt kneading at a screw speed of 250 rpm, a discharge rate of 15 kg / hr, an extruder temperature of 200 ° C., and pressing from a strand die The molten resin, take-off while cooled and solidified in a cooling water tank, a diameter of about 2mm strands using a strand cutter, to obtain by cutting a length of about 3mm propylene resin composition (X'-1).
（製造例Ｘ’−２）
（ｉ）予備重合触媒の調製
（珪酸塩の化学処理）
１０リットルの撹拌翼の付いたガラス製セパラブルフラスコに、蒸留水３．７５リットル、続いて濃硫酸（９６％）２．５ｋｇをゆっくりと添加した。５０℃で、更にモンモリロナイト（水澤化学社製ベンクレイＳＬ；平均粒径＝５０μｍ）を１ｋｇ分散させ、９０℃に昇温し、６．５時間その温度を維持した。５０℃まで冷却後、このスラリーを減圧濾過し、ケーキを回収した。このケーキに蒸留水を７リットル加え再スラリー化後、濾過した。この洗浄操作を、洗浄液（濾液）のｐＨが、３．５を超えるまで実施した。
回収したケーキを窒素雰囲気下１１０℃で終夜乾燥した。乾燥後の重量は７０７ｇであった。化学処理した珪酸塩をキルン乾燥機でＸ’−１と同様に乾燥した。
(Production Example X′-2)
(I) Preparation of prepolymerized catalyst (chemical treatment of silicate)
To a 10-liter glass separable flask with a stirring blade, 3.75 liters of distilled water was added slowly followed by 2.5 kg of concentrated sulfuric acid (96%). At 50 ° C., 1 kg of montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL; average particle size = 50 μm) was further dispersed, heated to 90 ° C., and maintained at that temperature for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake to reslurry it, and then filtered. This washing operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5.
The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 707 g. The chemically treated silicate was dried in the same manner as X′-1 with a kiln dryer.
（触媒の調製）
内容積３リットルの撹拌翼のついたガラス製反応器に、上記で得た乾燥珪酸塩２００ｇを導入し、混合ヘプタン１，１６０ｍｌ、更にトリエチルアルミニウムのヘプタン溶液（０．６０Ｍ）８４０ｍｌを加え、室温で撹拌した。１時間後、混合ヘプタンにて洗浄し、珪酸塩スラリーを２．０リットルに調製した。
次に、調製した珪酸塩スラリーにトリイソブチルアルミニウムのヘプタン溶液（０．７１Ｍ／Ｌ）９．６ｍｌを添加し、２５℃で１時間反応させた。並行して、〔（ｒ）−ジクロロ［１，１´−ジメチルシリレンビス｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ジルコニウム〕（合成は、特開平１０−２２６７１２号公報実施例に従って実施した）２，１８０ｍｇ（３ｍｍｏｌ）と混合ヘプタン８７０ｍｌに、トリイソブチルアルミニウムのヘプタン溶液（０．７１Ｍ）を３３．１ｍｌ加えて、室温にて１時間反応させた混合物を、珪酸塩スラリーに加え、１時間撹拌した。
(Preparation of catalyst)
200 g of the dried silicate obtained above was introduced into a glass reactor equipped with a stirring blade having an internal volume of 3 liters, mixed with 1,160 ml of mixed heptane and further 840 ml of a heptane solution of triethylaluminum (0.60 M), Stir with. After 1 hour, the mixture was washed with mixed heptane to prepare a silicate slurry at 2.0 liters.
Next, 9.6 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added to the prepared silicate slurry and reacted at 25 ° C. for 1 hour. In parallel, [(r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] zirconium] (the synthesis is disclosed in JP-A-10-226712) 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) was added to 2,180 mg (3 mmol) and 870 ml of mixed heptane (performed according to the Examples), and the mixture reacted at room temperature for 1 hour was treated with a silicate slurry And stirred for 1 hour.
（予備重合）
続いて、窒素で充分置換を行った内容積１０リットルの撹拌式オートクレーブに、ｎ−ヘプタン２．１リットルを導入し、４０℃に保持した。そこに先に調製した触媒スラリーを導入した。温度が４０℃に安定したところでプロピレンを１００ｇ／時間の速度で供給し、温度を維持した。４時間後プロピレンの供給を停止し、更に２時間維持した。予備重合終了後、残モノマーをパージし、撹拌を停止させ約１０分間静置後、上澄み約３リットルをデカントした。
続いてトリイソブチルアルミニウム（０．７１Ｍ／Ｌ）のヘプタン溶液９．５ｍｌ、更に混合ヘプタンを５．６リットル添加し、４０℃で３０分間撹拌し、１０分間静置した後に、上澄みを５．６リットル除いた。更にこの操作を３回繰り返した。
最後の上澄み液の成分分析を実施したところ、有機アルミニウム成分の濃度は、１．２３ｍｍоｌ／Ｌ、Ｚｒ濃度は８．６×１０−６ｇ／Ｌであり、仕込み量に対する上澄み液中の存在量は０．０１６％であった。続いて、トリイソブチルアルミニウム（０．７１Ｍ／Ｌ）のヘプタン溶液１７０ｍｌを添加した後に、４５℃で減圧乾燥した。
この操作により、触媒１ｇ当たりポリプロピレン２．１ｇを含む予備重合触媒が得られた。
(Preliminary polymerization)
Subsequently, 2.1 liters of n-heptane was introduced into a stirring autoclave having an internal volume of 10 liters that had been sufficiently replaced with nitrogen, and maintained at 40 ° C. The catalyst slurry prepared previously was introduced there. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 100 g / hour to maintain the temperature. After 4 hours, the supply of propylene was stopped and maintained for another 2 hours. After completion of the prepolymerization, the remaining monomer was purged, stirring was stopped and the mixture was allowed to stand for about 10 minutes, and then about 3 liters of the supernatant was decanted.
Subsequently, 9.5 ml of a heptane solution of triisobutylaluminum (0.71 M / L) and 5.6 liters of mixed heptane were added, and the mixture was stirred at 40 ° C. for 30 minutes and allowed to stand for 10 minutes. Removed liters. This operation was further repeated 3 times.
When the component analysis of the supernatant liquid was performed, the concentration of the organoaluminum component was 1.23 mmol / L, the Zr concentration was 8.6 × 10 −6 g / L, and the abundance in the supernatant with respect to the amount charged. Was 0.016%. Subsequently, 170 ml of a heptane solution of triisobutylaluminum (0.71 M / L) was added, followed by drying at 45 ° C. under reduced pressure.
By this operation, a prepolymerized catalyst containing 2.1 g of polypropylene per 1 g of catalyst was obtained.
（ｉｉ）第一重合工程
図１は、実施例で用いた重合装置のフローシートである。
攪拌羽根を有する横型重合器５（Ｌ／Ｄ＝５．２、内容積：５０ｍ３）に、予め保有量４５ｖｏｌ％になるようにベッドポリマー量を制御し、反応温度は、触媒がフィードされるリアクター上流部分を５９℃、パウダー抜出される部分を６５℃と設定し、その間の温度を６３℃と設定した。反応圧力２．０５ＭＰａＧ、攪拌速度１９．５ｒｐｍの条件を維持しながら、配管２から反応器の気相部ガス組成がエチレン／プロピレン＝０．０６になるように混合ガスを連続的に供給し、更に反応器の気相中の水素濃度を水素／プロピレン＝０．０００６４モル比に維持するように、水素ガスを連続的に供給して、予備重合処理した上記触媒を０．１２ｋｇ／ｈ（予備重合ポリマー量除く）、有機アルミニウム化合物としてトリイソブチルアルミニウムを１ｋｇ／ｈ一定となるように配管１より供給した。生成ポリマーすなわちプロピレン−エチレンランダム共重合体成分（Ａ’）の分子量（ＭＦＲ）を調整した。
(Ii) First Polymerization Step FIG. 1 is a flow sheet of the polymerization apparatus used in the examples.
The amount of bed polymer is controlled in advance in a horizontal polymerization vessel 5 (L / D = 5.2, internal volume: 50 m 3 ) having a stirring blade so that the holding amount is 45 vol%, and the reaction temperature is fed by the catalyst. The upstream part of the reactor was set to 59 ° C., the part from which the powder was extracted was set to 65 ° C., and the temperature in between was set to 63 ° C. While maintaining the reaction pressure of 2.05 MPaG and the stirring speed of 19.5 rpm, the mixed gas was continuously supplied from the
反応熱は、配管３から供給される原料プロピレンの気化熱により除去した。重合器から排出される未反応ガスは、配管４を通して反応器系外で冷却、凝縮させて重合器５に還流した。本重合で得られたプロピレン−エチレンランダム共重合体成分（Ａ’）は、重合体の保有レベルが反応容積の４５ｖｏｌ％となるように配管６を通して重合器５から間欠的に抜き出し、第２重合工程の重合器１１に供給した。ガス遮断槽７からプロピレン−エチレンランダム共重合体成分（Ａ’）の一部を抜き出して、分析用試料とした。
第一重合工程で得られたプロピレン−エチレンランダム共重合体を分析したところ、ＭＦＲは４６ｇ／１０分、エチレン含有量は１．９５ｗｔ％であった。
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the
When the propylene-ethylene random copolymer obtained in the first polymerization step was analyzed, the MFR was 46 g / 10 min and the ethylene content was 1.95 wt%.
（ｉｉｉ）第二重合工程
攪拌羽根を有する横型重合器１１（Ｌ／Ｄ＝５．２、内容積：５０ｍ３）に、第１重合工程からのプロピレン−エチレンランダム共重合体成分（Ａ’）を配管８から間欠的にそれぞれ供給し、プロピレンとエチレンの共重合を行った。
反応条件は、攪拌速度１８ｒｐｍ、反応温度７０℃、反応圧力１．９５ＭＰａＧであり、気相中のガス組成エチレン／プロピレン＝０．３８、水素／エチレン＝０．００１２モル比となるように調整した。反応器中の未反応ガスは、未反応ガス抜き出し配管１３から抜き出され、循環経路を通して、原料循環ガス供給配管１５から再供給される。プロピレン−エチレンランダム共重合体成分（Ｂ’）の重合量を調整するための重合活性抑制剤として、酸素／窒素混合ガス（酸素濃度２１ｗｔ％）を配管１２より１０Ｌ／ｈで供給した。
(Iii) Second polymerization step A propylene-ethylene random copolymer component (A ′) from the first polymerization step is added to a horizontal polymerization vessel 11 (L / D = 5.2, internal volume: 50 m 3 ) having a stirring blade. Were intermittently supplied from the
The reaction conditions were a stirring speed of 18 rpm, a reaction temperature of 70 ° C., a reaction pressure of 1.95 MPaG, and the gas composition in the gas phase was adjusted to be ethylene / propylene = 0.38 and hydrogen / ethylene = 0.0012 molar ratio. . Unreacted gas in the reactor is extracted from the unreacted
反応熱は、配管１４から供給される原料プロピレンの気化熱により除去した。重合器から排出される未反応ガスは、配管１３を通して反応器系外で冷却、凝縮させて重合器１１に還流した。
第２重合工程で生成されたプロピレン系樹脂（Ｘ’−２）は、重合体の保有レベルが反応容積の５５ｖｏｌ％となるように、配管１８を通して重合器１１から間欠的に抜き出した。
このとき、重合されたプロピレン系樹脂（Ｘ’−２）の一部を抜き出して、分析用試料とした。このとき、プロピレン系樹脂（Ｘ’−２）の生産量は、６．０ｔ／ｈであった。
こうして得られたプロピレン系樹脂（Ｘ’−２）の各種分析結果を、表１に示す
The reaction heat was removed by the heat of vaporization of the raw material propylene supplied from the
The propylene-based resin (X′-2) produced in the second polymerization step was intermittently extracted from the
At this time, a part of the polymerized propylene resin (X′-2) was extracted and used as a sample for analysis. At this time, the production amount of the propylene-based resin (X′-2) was 6.0 t / h.
Various analysis results of the propylene-based resin (X′-2) thus obtained are shown in Table 1.
得られたプロピレン系樹脂（Ｘ’−２）１００重量部に、添加剤（酸化防止剤）としてテトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネ−ト］メタン（商品名「ＩＲＧＡＮＯＸ１０１０」、ＢＡＳＦジャパン株式会社製）０．０５重量部、フォスファイト系酸化防止剤であるトリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト（商品名「ＩＲＧＡＦＯＳ １６８」、ＢＡＳＦジャパン株式会社製）０．０５重量部を、ヘンシェルミキサーに投入し、７５０ｒｐｍで１分間室温で高速混合した後、スクリュー口径２５ｍｍのテクノベル社製ＫＺＷ−２５押出機にて、スクリュー回転数２５０ｒｐｍ、吐出量１５ｋｇ／ｈｒ、押出機温度２００℃で溶融混練し、ストランドダイから押し出された溶融樹脂を、冷却水槽で冷却固化させながら引き取り、ストランドカッターを用いてストランドを直径約２ｍｍ、長さ約３ｍｍに切断することでプロピレン系樹脂組成物（Ｘ’−２）を得た。 Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) as an additive (antioxidant) was added to 100 parts by weight of the obtained propylene-based resin (X′-2). Propionate] methane (trade name “IRGANOX1010”, manufactured by BASF Japan Ltd.) 0.05 part by weight, tris (2,4-di-t-butylphenyl) phosphite (trade name) which is a phosphite antioxidant “IRGAFOS 168” (manufactured by BASF Japan Ltd.), 0.05 parts by weight, was charged into a Henschel mixer and mixed at a high speed at 750 rpm for 1 minute at room temperature. It is melt-kneaded at a screw speed of 250 rpm, a discharge rate of 15 kg / hr, and an extruder temperature of 200 ° C. The molten resin was taken out while being cooled and solidified in a cooling water tank, and the strand was cut into a diameter of about 2 mm and a length of about 3 mm using a strand cutter to obtain a propylene-based resin composition (X′-2). .
［成分（Ａ）］
（Ａ−１）日本ポリプロ社製、商標名「ウィンテック ＷＦＷ４Ｍ」（メタロセン触媒によるプロピレンを９０重量％超含むプロピレン−α−オレフィン共重合体、ＭＦＲ７ｇ／１０分、融点１３５℃）
（Ａ−２）日本ポリプロ社製、商標名「ウィンテック ＷＦＸ４Ｍ」（メタロセン触媒によるプロピレンを９０重量％超含むプロピレン−α−オレフィン共重合体、ＭＦＲ７ｇ／１０分、融点１２５℃）
（Ａ−３）日本ポリプロ社製、商標名「ノバテックＰＰ ＦＸ８８７７」（プロピレンを９０重量％超含むプロピレン−α−オレフィン共重合体、ＭＦＲ７ｇ／１０分、融点１３５℃）
[Component (A)]
(A-1) Made by Nippon Polypro Co., Ltd., trade name “Wintech WFW4M” (propylene-α-olefin copolymer containing more than 90% by weight of propylene by metallocene catalyst, MFR 7 g / 10 min, melting point 135 ° C.)
(A-2) Made by Nippon Polypro Co., Ltd., trade name “Wintech WFX4M” (propylene-α-olefin copolymer containing more than 90% by weight of propylene by metallocene catalyst, MFR 7 g / 10 min, melting point 125 ° C.)
(A-3) manufactured by Nippon Polypro Co., Ltd., trade name “Novatec PP FX8877” (propylene-α-olefin copolymer containing more than 90% by weight of propylene, MFR 7 g / 10 min, melting point 135 ° C.)
［プロピレン−α−オレフィン共重合体（Ｂ）］
（Ｂ−１）エクソンモービル社製、商標名「Ｖｉｓｔａｍａｘｘ ６２０２」（プロピレン−エチレン共重合体、ＭＦＲ２０ｇ／１０分、エチレン含有量１５重量％）
（Ｂ−２）エクソンモービル社製、商標名「Ｖｉｓｔａｍａｘｘ ６１０２」（プロピレン−エチレン共重合体、ＭＦＲ３ｇ／１０分、エチレン含有量１６重量％）
（Ｂ−３）エクソンモービル社製、商標名「Ｖｉｓｔａｍａｘｘ ３０００」（プロピレン−エチレン共重合体、ＭＦＲ８ｇ／１０分、エチレン含有量１１重量％）
[Propylene-α-olefin copolymer (B)]
(B-1) manufactured by ExxonMobil, trade name “Vistamaxx 6202” (propylene-ethylene copolymer, MFR 20 g / 10 min,
(B-2) manufactured by ExxonMobil, trade name “Vistamaxx 6102” (propylene-ethylene copolymer, MFR 3 g / 10 min,
(B-3) manufactured by ExxonMobil, trade name “Vistamaxx 3000” (propylene-ethylene copolymer, MFR 8 g / 10 min,
［その他樹脂成分］
（ＰＥ−１）日本ポリエチレン社製、商標名「カーネル ＫＳ５７１」（メタロセン触媒によるエチレン−α−オレフィン共重合体、ＭＦＲ１２ｇ／１０分（但し１９０℃、２．１６ｋｇ荷重）、密度０．９０７ｇ／ｃｍ３）
（ＰＥ−２）日本ポリエチレン社製、商標名「カーネル ＫＳ３４０Ｔ」（メタロセン触媒によるエチレン−α−オレフィン共重合体、ＭＦＲ３．５ｇ／１０分（但し１９０℃、２．１６ｋｇ荷重）、密度０．８８ｇ／ｃｍ３）
（Ｃ−１）三井化学社製、商標名「タフマーＢＬ ２４８１Ｍ」（１−ブテン系重合体、ＭＦＲ９ｇ／１０分、融点５８℃）
（Ｃ−２）クレイトンポリマー社製、商標名「クレイトン Ｇ１６５７ＭＯ」（スチレン−ブタジエンブロック共重合体の水素添加物）
[Other resin components]
(PE-1) manufactured by Nippon Polyethylene Co., Ltd., trade name “Kernel KS571” (ethylene-α-olefin copolymer with metallocene catalyst, MFR 12 g / 10 minutes (190 ° C., 2.16 kg load), density 0.907 g / cm 3 )
(PE-2) manufactured by Nippon Polyethylene Co., Ltd., trade name “Kernel KS340T” (ethylene-α-olefin copolymer with metallocene catalyst, MFR 3.5 g / 10 minutes (190 ° C., 2.16 kg load), density 0.88 g / Cm 3 )
(C-1) Trade name “Tuffmer BL 2481M” manufactured by Mitsui Chemicals, Inc. (1-butene polymer, MFR 9 g / 10 min, melting point 58 ° C.)
(C-2) Trade name “Clayton G1657MO” (hydrogenated product of styrene-butadiene block copolymer) manufactured by Kraton Polymer Co., Ltd.
［実施例１］
製造例Ｘ’−１で得られたプロピレン系樹脂組成物（Ｘ’−１）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−１）５０重量％をヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−１）とした。φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１）ペレットを得た。
得られたペレットを、成形温度を２３０℃に変更した以外は、前述と同様の方法で圧縮成形法によりシート状に成形し、７０℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表２にまとめた。
[Example 1]
50% by weight of the propylene-based resin composition (X′-1) obtained in Production Example X′-1 and 50% by weight of the propylene-α-olefin copolymer (B-1) were blended in a Henschel mixer, Propylene resin composition (X-1) was obtained. Using a single screw extruder of φ30 mm, melt kneading was performed under conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min to obtain propylene resin composition (Y-1) pellets.
The obtained pellet was molded into a sheet by a compression molding method in the same manner as described above except that the molding temperature was changed to 230 ° C., and the structure was prepared by the above method without adjusting the state at 70 ° C. for 1 hour. Got.
The evaluation results of the obtained structure are summarized in Table 2.
［実施例２］
製造例Ｘ’−２で得られたプロピレン系樹脂組成物（Ｘ’−２）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−２）５０重量％をヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−２）とした。更に、エルカ酸アミドを、（Ｘ−２）１００重量部に対して、０．１５重量部配合し、ヘンシェルミキサーにてブレンドした後に、φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練しプロピレン系樹脂組成物（Ｙ−２）ペレットを得た。
得られたペレットを、成形温度を２３０℃に変更した以外は、前述と同様の方法で圧縮成形法によりシート状に成形し、７０℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表２にまとめた。変形回復性（残留歪）、耐熱性は、実施例１とほぼ同等であったが、構造体が滑りやすくなり、構造体同士を接触させた際の軋みや引っ掛かり感が少なくなった。
[Example 2]
50% by weight of the propylene-based resin composition (X′-2) obtained in Production Example X′-2 and 50% by weight of the propylene-α-olefin copolymer (B-2) were blended with a Henschel mixer, It was set as the propylene-type resin composition (X-2). Furthermore, 0.15 parts by weight of erucic acid amide was blended with 100 parts by weight of (X-2), blended with a Henschel mixer, and then discharged at a cylinder temperature of 200 ° C. using a φ30 mm single screw extruder. The mixture was melt-kneaded under conditions of an amount of 6 kg / min to obtain propylene-based resin composition (Y-2) pellets.
The obtained pellet was molded into a sheet by a compression molding method in the same manner as described above except that the molding temperature was changed to 230 ° C., and the structure was prepared by the above method without adjusting the state at 70 ° C. for 1 hour. Got.
The evaluation results of the obtained structure are summarized in Table 2. The deformation recovery property (residual strain) and heat resistance were almost the same as in Example 1, but the structures were slippery and less squeezed or caught when the structures were brought into contact with each other.
［実施例３］
実施例１において、圧縮成形法により得られたシートを７０℃１時間の状態調整を行った以外は、実施例１と同様な操作を行った。
評価結果を表２にまとめた。実施例１に比べて、４０℃および７０℃の変形回復性（残留歪）が更に改善された。
[Example 3]
In Example 1, the same operation as in Example 1 was performed except that the state of the sheet obtained by the compression molding method was adjusted at 70 ° C. for 1 hour.
The evaluation results are summarized in Table 2. Compared to Example 1, the deformation recoverability (residual strain) at 40 ° C. and 70 ° C. was further improved.
［実施例４］
実施例２において、圧縮成形法により得られたシートを７０℃１時間の状態調整を行った以外は、実施例２と同様な操作を行った。
評価結果を表２にまとめた。実施例２に比べて、４０℃および７０℃の変形回復性（残留歪）が更に改善された。
[Example 4]
In Example 2, the same operation as in Example 2 was performed, except that the state of the sheet obtained by the compression molding method was adjusted at 70 ° C. for 1 hour.
The evaluation results are summarized in Table 2. Compared to Example 2, deformation recoverability (residual strain) at 40 ° C. and 70 ° C. was further improved.
［比較例１］
本発明のプロピレン系樹脂組成物（Ｙ）以外の樹脂組成物として、ＰＥ−１を用いて、成形温度を２３０℃に変更した以外は、前述と同様の方法で圧縮成形法によりシート状に成形し、７０℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表２にまとめた。本発明のプロピレン系樹脂組成物（Ｙ）を用いたものに比べ、７０℃での変形回復性（残留歪）が大幅に悪化し、耐熱性に関しても、大幅に劣るものであった。
[Comparative Example 1]
The resin composition other than the propylene-based resin composition (Y) of the present invention is molded into a sheet by a compression molding method in the same manner as described above, except that PE-1 is used and the molding temperature is changed to 230 ° C. And the structure was obtained by the above-mentioned method, without adjusting the state for 1 hour at 70 ° C.
The evaluation results of the obtained structure are summarized in Table 2. Compared to the one using the propylene-based resin composition (Y) of the present invention, the deformation recovery property (residual strain) at 70 ° C. was greatly deteriorated, and the heat resistance was also significantly inferior.
［実施例５］
実施例４において、圧縮成形法により得られたシートを１００℃１時間の状態調整を行った以外は、実施例４と同様な操作を行った。
評価結果を表３にまとめた。実施例４に比べて、４０℃および７０℃の変形回復性（残留歪）が更に改善された。
[Example 5]
In Example 4, the same operation as in Example 4 was performed, except that the state of the sheet obtained by the compression molding method was adjusted at 100 ° C. for 1 hour.
The evaluation results are summarized in Table 3. Compared to Example 4, the deformation recoverability (residual strain) at 40 ° C. and 70 ° C. was further improved.
［実施例６］
製造例Ｘ’−１で得られたプロピレン系樹脂組成物（Ｘ’−１）をプロピレン系樹脂組成物（Ｙ−３）とした。
プロピレン系樹脂組成物（Ｙ−３）を、前述の方法で圧縮成形法によりシート状に成形し、７０℃又は１００℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表３にまとめた。
[Example 6]
The propylene resin composition (X′-1) obtained in Production Example X′-1 was used as the propylene resin composition (Y-3).
The propylene-based resin composition (Y-3) was molded into a sheet shape by the compression molding method by the above method, and the structure was obtained by the above method without adjusting the state at 70 ° C. or 100 ° C. for 1 hour.
The evaluation results of the obtained structure are summarized in Table 3.
［実施例７］
実施例６において、圧縮成形法により得られたシートを１００℃１時間の状態調整を行った以外は、実施例６と同様な操作を行った。
評価結果を表３にまとめた。実施例６に比べて、４０℃および７０℃の変形回復性（残留歪）が更に改善された。
[Example 7]
In Example 6, the same operation as in Example 6 was performed, except that the state of the sheet obtained by the compression molding method was adjusted at 100 ° C. for 1 hour.
The evaluation results are summarized in Table 3. Compared to Example 6, the deformation recoverability (residual strain) at 40 ° C. and 70 ° C. was further improved.
［実施例８］
製造例Ｘ’−２で得られたプロピレン系樹脂組成物（Ｘ’−２）をプロピレン系樹脂組成物（Ｙ−４）とした。
プロピレン系樹脂組成物（Ｙ−４）を、前述の方法で圧縮成形法によりシート状に成形し、７０℃又は１００℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表３にまとめた。
[Example 8]
The propylene resin composition (X′-2) obtained in Production Example X′-2 was used as the propylene resin composition (Y-4).
The propylene-based resin composition (Y-4) was molded into a sheet shape by the compression molding method by the above method, and the structure was obtained by the above method without adjusting the state at 70 ° C. or 100 ° C. for 1 hour.
The evaluation results of the obtained structure are summarized in Table 3.
［実施例９］
実施例８において、圧縮成形法により得られたシートを１００℃１時間の状態調整を行った以外は、実施例８と同様な操作を行った。
評価結果を表３にまとめた。実施例８に比べて、４０℃および７０℃の変形回復性（残留歪）が更に改善された。
[Example 9]
In Example 8, the same operation as in Example 8 was performed, except that the state of the sheet obtained by the compression molding method was adjusted at 100 ° C. for 1 hour.
The evaluation results are summarized in Table 3. Compared to Example 8, deformation recoverability (residual strain) at 40 ° C. and 70 ° C. was further improved.
［実施例１０］
製造例Ｘ’−２で得られたプロピレン系樹脂組成物（Ｘ’−２）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−３）５０重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−３）とした。φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−５）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、７０℃又は１００℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表３にまとめた。
[Example 10]
50% by weight of the propylene resin composition (X′-2) obtained in Production Example X′-2 and 50% by weight of the propylene-α-olefin copolymer (B-3) were blended using a Henschel mixer. And a propylene resin composition (X-3). Using a single screw extruder of φ30 mm, melt kneading was performed under the conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min to obtain propylene resin composition (Y-5) pellets.
The obtained pellets were formed into a sheet by the compression molding method by the above-described method, and the structure was obtained by the above-described method without adjusting the state at 70 ° C. or 100 ° C. for 1 hour.
The evaluation results of the obtained structure are summarized in Table 3.
［実施例１１］
実施例１０において、圧縮成形法により得られたシートを７０℃１時間の状態調整を行った以外は、実施例１０と同様な操作を行った。
評価結果を表３にまとめた。実施例１０に比べて、４０℃および７０℃の変形回復性（残留歪）が更に改善された。
[Example 11]
In Example 10, the same operation as in Example 10 was performed, except that the state of the sheet obtained by the compression molding method was adjusted at 70 ° C. for 1 hour.
The evaluation results are summarized in Table 3. Compared to Example 10, the deformation recoverability (residual strain) at 40 ° C. and 70 ° C. was further improved.
［実施例１２］
実施例１１において、圧縮成形法により得られたシートを１００℃１時間の状態調整を行った以外は、実施例１１と同様な操作を行った。
評価結果を表３にまとめた。実施例１１に比べて、７０℃の変形回復性（残留歪）が更に改善された。
[Example 12]
In Example 11, the same operation as in Example 11 was performed, except that the state of the sheet obtained by the compression molding method was adjusted at 100 ° C. for 1 hour.
The evaluation results are summarized in Table 3. Compared to Example 11, the deformation recoverability (residual strain) at 70 ° C. was further improved.
［比較例２］
本発明のプロピレン系樹脂組成物（Ｙ）以外の樹脂組成物として、Ｂ−２を用いて、前述の方法で圧縮成形法によりシート状に成形し、７０℃又は１００℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表４にまとめた。７０℃での変形回復性（残留歪）を測定することができず、また、耐熱性が大幅に劣るものであった。
[Comparative Example 2]
As a resin composition other than the propylene-based resin composition (Y) of the present invention, using B-2, it is molded into a sheet by the compression molding method as described above, and is adjusted at 70 ° C. or 100 ° C. for 1 hour. Without doing so, a structure was obtained by the method described above.
The evaluation results of the obtained structure are summarized in Table 4. The deformation recovery property (residual strain) at 70 ° C. could not be measured, and the heat resistance was significantly inferior.
［比較例３］
本発明のプロピレン系樹脂組成物（Ｙ）以外の樹脂組成物として、Ａ−１を用いて、前述と同様の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表４にまとめた。比較例１に比べ、４０℃および７０℃での変形回復性（残留歪）および耐熱性に優れるものであったが、本発明のプロピレン系樹脂組成物（Ｙ）を用いたものに比べ、柔軟性が大幅に劣るものであった。
[Comparative Example 3]
As a resin composition other than the propylene-based resin composition (Y) of the present invention, A-1 is used to form a sheet by a compression molding method in the same manner as described above, and the state is adjusted at 100 ° C. for 1 hour. A structure was obtained by the method described above.
The evaluation results of the obtained structure are summarized in Table 4. Compared to Comparative Example 1, it was excellent in deformation recovery (residual strain) and heat resistance at 40 ° C. and 70 ° C., but more flexible than that using the propylene-based resin composition (Y) of the present invention. The property was significantly inferior.
［実施例１３］
成分（Ａ）として（Ａ−１）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−２）５０重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−４）とした。φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−８）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表４にまとめた。
[Example 13]
As component (A), 50% by weight of (A-1) and 50% by weight of propylene-α-olefin copolymer (B-2) were blended with a Henschel mixer to produce a propylene resin composition (X-4). It was. Using a single screw extruder of φ30 mm, melt kneading was performed under conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min to obtain propylene resin composition (Y-8) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structure are summarized in Table 4.
［実施例１４］
成分（Ａ）として（Ａ−１）２５重量％と、プロピレン−α−オレフィン共重合体（Ｂ−２）７５重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−５）とした。φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−９）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表４にまとめた。
[Example 14]
As component (A), 25% by weight of (A-1) and 75% by weight of propylene-α-olefin copolymer (B-2) were blended in a Henschel mixer to produce a propylene resin composition (X-5). It was. Using a single screw extruder of φ30 mm, melt kneading was performed under conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min to obtain propylene-based resin composition (Y-9) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structure are summarized in Table 4.
［実施例１５］
成分（Ａ）として（Ａ−１）２５重量％と、プロピレン−α−オレフィン共重合体（Ｂ−３）７５重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−６）とした。φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１０）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表４にまとめた。
[Example 15]
As a component (A), 25% by weight of (A-1) and 75% by weight of a propylene-α-olefin copolymer (B-3) were blended with a Henschel mixer to obtain a propylene resin composition (X-6). It was. Using a single screw extruder of φ30 mm, melt kneading was performed under the conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min to obtain propylene resin composition (Y-10) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structure are summarized in Table 4.
［実施例１６］
成分（Ａ）として（Ａ−２）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−３）５０重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−７）とした。φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１１）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、７０℃又は１００℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表４にまとめた。
[Example 16]
As a component (A), 50% by weight of (A-2) and 50% by weight of a propylene-α-olefin copolymer (B-3) are blended with a Henschel mixer to obtain a propylene resin composition (X-7). It was. Using a single screw extruder of φ30 mm, melt kneading was performed under conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min to obtain propylene-based resin composition (Y-11) pellets.
The obtained pellets were formed into a sheet by the compression molding method by the above-described method, and the structure was obtained by the above-described method without adjusting the state at 70 ° C. or 100 ° C. for 1 hour.
The evaluation results of the obtained structure are summarized in Table 4.
［実施例１７］
実施例１６において、圧縮成形法により得られたシートを１００℃１時間の状態調整を行った以外は、実施例１６と同様な操作を行った。
評価結果を表４にまとめた。実施例１６に比べて、４０℃および７０℃の変形回復性（残留歪）が更に改善された。
[Example 17]
In Example 16, the same operation as in Example 16 was performed, except that the state of the sheet obtained by the compression molding method was adjusted at 100 ° C. for 1 hour.
The evaluation results are summarized in Table 4. Compared to Example 16, deformation recoverability (residual strain) at 40 ° C. and 70 ° C. was further improved.
［実施例１８］
成分（Ａ）として（Ａ−３）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−３）５０重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−８）とした。φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１２）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表４にまとめた。
[Example 18]
As a component (A), 50% by weight of (A-3) and 50% by weight of a propylene-α-olefin copolymer (B-3) were blended with a Henschel mixer to produce a propylene resin composition (X-8). It was. Using a single screw extruder of φ30 mm, melt kneading was performed under conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min to obtain propylene-based resin composition (Y-12) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structure are summarized in Table 4.
［実施例１９］
製造例Ｘ’−２で得られたプロピレン系樹脂組成物（Ｘ’−２）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−３）５０重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−３）とした。更に、リン酸−２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ナトリウム塩系造核剤（ＡＤＥＫＡ社製商品名「アデカスタブＮＡ−１１ＳＦ」）を、プロピレン系樹脂組成物（Ｘ−３）１００重量部に対して、０．１重量部配合し、ヘンシェルミキサーにてブレンドした後に、φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１３）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表５にまとめた。
[Example 19]
50% by weight of the propylene resin composition (X′-2) obtained in Production Example X′-2 and 50% by weight of the propylene-α-olefin copolymer (B-3) were blended using a Henschel mixer. And a propylene resin composition (X-3). Furthermore, phosphoric acid-2,2′-methylenebis (4,6-di-tert-butylphenyl) sodium salt nucleating agent (trade name “ADEKA STAB NA-11SF” manufactured by ADEKA) was added to the propylene resin composition ( X-3) 0.1 part by weight is blended with 100 parts by weight, blended with a Henschel mixer, and melted using a φ30 mm single screw extruder at a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min. The mixture was kneaded to obtain propylene-based resin composition (Y-13) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structures are summarized in Table 5.
［実施例２０］
製造例Ｘ’−１で得られたプロピレン系樹脂組成物（Ｘ’−１）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−３）５０重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−９）とした。φ３０ｍｍの単軸押出機を用いてシリンダー温度２３５℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１４）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表５にまとめた。
[Example 20]
50% by weight of the propylene resin composition (X′-1) obtained in Production Example X′-1 and 50% by weight of the propylene-α-olefin copolymer (B-3) were blended using a Henschel mixer. A propylene resin composition (X-9) was obtained. Using a single screw extruder of φ30 mm, melt kneading was performed under conditions of a cylinder temperature of 235 ° C. and a discharge rate of 6 kg / min to obtain propylene-based resin composition (Y-14) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structures are summarized in Table 5.
［実施例２１］
製造例Ｘ’−１で得られたプロピレン系樹脂組成物（Ｘ’−１）５０重量％と、プロピレン−α−オレフィン共重合体（Ｂ−３）５０重量％を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−９）とした。更に、有機過酸化物（化薬アクゾ社製商品名「パーカドックス１４−４０Ｃ」）を、プロピレン系樹脂組成物（Ｘ−９）１００重量部に対して、０．０７５重量部配合し、ヘンシェルミキサーにてブレンドした後に、φ３０ｍｍの単軸押出機を用いてシリンダー温度２３５℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１５）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表５にまとめた。
[Example 21]
50% by weight of the propylene resin composition (X′-1) obtained in Production Example X′-1 and 50% by weight of the propylene-α-olefin copolymer (B-3) were blended using a Henschel mixer. A propylene resin composition (X-9) was obtained. Furthermore, 0.075 parts by weight of organic peroxide (trade name “Parkadox 14-40C” manufactured by Kayaku Akzo Co., Ltd.) is blended with 100 parts by weight of the propylene resin composition (X-9). After blending with a mixer, the mixture was melt-kneaded using a single screw extruder with a diameter of 30 mm at a cylinder temperature of 235 ° C. and a discharge rate of 6 kg / min to obtain propylene-based resin composition (Y-15) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structures are summarized in Table 5.
［実施例２２］
製造例Ｘ’−２で得られたプロピレン系樹脂組成物（Ｘ’−２）５０重量部と、プロピレン−α−オレフィン共重合体（Ｂ−３）４０重量部を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−１０）とした。更に、その他の樹脂成分として（Ｃ−１）を、１０重量部配合し、ヘンシェルミキサーにてブレンドした後に、φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１６）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表５にまとめた。
[Example 22]
50 parts by weight of the propylene-based resin composition (X′-2) obtained in Production Example X′-2 and 40 parts by weight of the propylene-α-olefin copolymer (B-3) were blended using a Henschel mixer. A propylene resin composition (X-10) was obtained. Furthermore, after blending 10 parts by weight of (C-1) as another resin component and blending with a Henschel mixer, using a single screw extruder of φ30 mm under conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min. The mixture was melt-kneaded to obtain propylene resin composition (Y-16) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structures are summarized in Table 5.
［実施例２３］
製造例Ｘ’−２で得られたプロピレン系樹脂組成物（Ｘ’−２）７７重量部と、プロピレン−α−オレフィン共重合体（Ｂ−３）２０重量部を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−１１）とした。更に、その他の樹脂成分として（ＰＥ−１）を、３重量部配合し、ヘンシェルミキサーにてブレンドした後に、φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１７）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表５にまとめた。
[Example 23]
77 parts by weight of the propylene-based resin composition (X′-2) obtained in Production Example X′-2 and 20 parts by weight of the propylene-α-olefin copolymer (B-3) were blended with a Henschel mixer. A propylene resin composition (X-11) was obtained. Furthermore, after blending 3 parts by weight of (PE-1) as another resin component and blending with a Henschel mixer, a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min were used using a φ30 mm single screw extruder. Melt-kneading was performed to obtain propylene-based resin composition (Y-17) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structures are summarized in Table 5.
［実施例２４］
製造例Ｘ’−２で得られたプロピレン系樹脂組成物（Ｘ’−２）５０重量部と、プロピレン−α−オレフィン共重合体（Ｂ−３）４０重量部を、ヘンシェルミキサーにてブレンドし、プロピレン系樹脂組成物（Ｘ−１０）とした。更に、その他の樹脂成分として（ＰＥ−２）を、１０重量部配合し、ヘンシェルミキサーにてブレンドした後に、φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１８）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、１００℃１時間の状態調整を行い、前述の方法で構造体を得た。
得られた構造体の評価結果を表５にまとめた。
[Example 24]
50 parts by weight of the propylene-based resin composition (X′-2) obtained in Production Example X′-2 and 40 parts by weight of the propylene-α-olefin copolymer (B-3) were blended using a Henschel mixer. A propylene resin composition (X-10) was obtained. Furthermore, after blending 10 parts by weight of (PE-2) as another resin component and blending with a Henschel mixer, a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min were used using a φ30 mm single screw extruder. The mixture was melt-kneaded to obtain propylene resin composition (Y-18) pellets.
The obtained pellets were molded into a sheet shape by the compression molding method by the above-described method, the state was adjusted at 100 ° C. for 1 hour, and the structure was obtained by the above-described method.
The evaluation results of the obtained structures are summarized in Table 5.
［比較例４］
本発明のプロピレン系樹脂組成物（Ｙ）以外の樹脂組成物として、（Ａ−１）５０重量％と、（Ｃ−２）５０重量％を、ヘンシェルミキサーにてブレンドした後に、φ３０ｍｍの単軸押出機を用いてシリンダー温度２００℃、吐出量６ｋｇ／分の条件で溶融混練し、プロピレン系樹脂組成物（Ｙ−１９）ペレットを得た。
得られたペレットを、前述の方法で圧縮成形法によりシート状に成形し、７０℃又は１００℃１時間の状態調整を行わず、前述の方法で構造体を得た。
得られた構造体の評価結果を表５にまとめた。本発明のプロピレン系樹脂組成物（Ｙ）を用いたものに比べ４０℃および７０℃での変形回復性（残留歪）および耐熱性に劣るものであった。
[Comparative Example 4]
As a resin composition other than the propylene-based resin composition (Y) of the present invention, after blending 50% by weight of (A-1) and 50% by weight of (C-2) with a Henschel mixer, a uniaxial φ30 mm Using an extruder, the mixture was melt-kneaded under the conditions of a cylinder temperature of 200 ° C. and a discharge rate of 6 kg / min to obtain propylene resin composition (Y-19) pellets.
The obtained pellets were formed into a sheet by the compression molding method by the above-described method, and the structure was obtained by the above-described method without adjusting the state at 70 ° C. or 100 ° C. for 1 hour.
The evaluation results of the obtained structures are summarized in Table 5. It was inferior in deformation recovery (residual strain) and heat resistance at 40 ° C. and 70 ° C. compared to those using the propylene-based resin composition (Y) of the present invention.
［比較例５］
比較例４において、圧縮成形法により得られたシートを１００℃１時間の状態調整を行った以外は、比較例４と同様な操作を行った。
評価結果を表５にまとめた。本発明のプロピレン系樹脂組成物（Ｙ）を用い、１００℃１時間の状態調整を行ったものに比べ、４０℃および７０℃の変形回復性（残留歪）が劣るものであった。
[Comparative Example 5]
In Comparative Example 4, the same operation as in Comparative Example 4 was performed, except that the state of the sheet obtained by the compression molding method was adjusted at 100 ° C. for 1 hour.
The evaluation results are summarized in Table 5. Compared to the case where the propylene-based resin composition (Y) of the present invention was used for condition adjustment at 100 ° C. for 1 hour, the deformation recoverability (residual strain) at 40 ° C. and 70 ° C. was inferior.
本発明の変形回復性耐熱構造体用プロピレン系樹脂組成物は、柔軟で、高温下での変形回復性に優れ、且つ高温下、好ましくは１２１℃以上の環境下でも、形状が保持できる耐熱性を有するため、優れた変形回復性と耐熱性を有する変形回復性耐熱構造体を提供でき、産業上の利用可能性が高い。 The propylene-based resin composition for deformation-recoverable heat-resistant structures of the present invention is flexible, excellent in deformation recovery at high temperatures, and heat-resistant so that the shape can be maintained at high temperatures, preferably even in an environment of 121 ° C. or higher. Therefore, it is possible to provide a deformation recovery heat-resistant structure having excellent deformation recovery and heat resistance, and the industrial applicability is high.
１ 触媒成分供給配管
２ 原料混合ガス供給配管
３ 原料プロピレン供給配管
４ 未反応ガス抜出し配管
５ 攪拌羽根を有する横型重合器（第１重合工程）
６ 重合体抜出し配管
７ ガス遮断槽（脱ガス槽）
８ 重合体供給配管
９ 凝縮機
１０ 圧縮機
１１ 攪拌羽根を有する横型重合器（第２重合工程）
１２ 活性抑制剤添加用配管
１３ 未反応ガス抜出し配管
１４ 原料プロピレン供給配管
１５ 原料循環ガス供給配管
１６ 凝縮機
１７ 圧縮機
１８ 重合体抜出し配管
DESCRIPTION OF
6
8 Polymer supply pipe 9
12 Pipe for adding
Claims (6)
（ｙ１）メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）が１．０〜１００ｇ／１０分であること。
（ｙ２）融解ピーク温度（Ｔｍ）が１２１〜１７０℃であること。
成分（Ａ）：下記（ａ１）〜（ａ２）を満足する１種類もしくは２種類以上のプロピレン単独重合体及び／又はプロピレン−α−オレフィン共重合体。
（ａ１）融解ピーク温度（Ｔｍ）が１２１〜１７０℃であること。
（ａ２）メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）が０．１〜５００ｇ／１０分であること。
成分（Ｂ）：下記（ｂ１）〜（ｂ２）を満足する少なくとも１種類のプロピレン−α−オレフィン共重合体。
（ｂ１）プロピレン５１〜９０重量％、エチレン及び／又は炭素数４〜１０のα−オレフィン１０〜４９重量％からなること。
（ｂ２）メルトフローレート（ＭＦＲ：２３０℃、２．１６ｋｇ荷重）が３〜２０ｇ／１０分であること。 1 to 99 parts by weight of the following component (A) and 1 to 99 parts by weight of the following component (B) (provided that the total of the component (A) and the component (B) is 100 parts by weight) ( X) (provided that the propylene resin composition (X) does not contain a syndiotactic propylene resin) as an essential component, and satisfies the following characteristics (y1) to (y2): A propylene-based resin composition for deformation-recoverable heat-resistant structures.
(Y1) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 1.0 to 100 g / 10 minutes.
(Y2) Melting peak temperature (Tm) is 121-170 degreeC.
Component (A): One or more propylene homopolymers and / or propylene-α-olefin copolymers satisfying the following (a1) to (a2).
(A1) The melting peak temperature (Tm) is 121 to 170 ° C.
(A2) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 0.1 to 500 g / 10 minutes.
Component (B): at least one propylene-α-olefin copolymer satisfying the following (b1) to (b2) .
(B1) It is composed of 51 to 90% by weight of propylene, 10 to 49% by weight of ethylene and / or an α-olefin having 4 to 10 carbon atoms.
(B2) The melt flow rate (MFR: 230 ° C., 2.16 kg load) is 3 to 20 g / 10 minutes.
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