JP2010254818A - Propylene-based molding - Google Patents
Propylene-based molding Download PDFInfo
- Publication number
- JP2010254818A JP2010254818A JP2009106915A JP2009106915A JP2010254818A JP 2010254818 A JP2010254818 A JP 2010254818A JP 2009106915 A JP2009106915 A JP 2009106915A JP 2009106915 A JP2009106915 A JP 2009106915A JP 2010254818 A JP2010254818 A JP 2010254818A
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- nucleating agent
- weight
- polymer
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 94
- 238000000465 moulding Methods 0.000 title claims abstract description 25
- 239000002667 nucleating agent Substances 0.000 claims abstract description 69
- 229920001577 copolymer Polymers 0.000 claims abstract description 50
- 238000010828 elution Methods 0.000 claims abstract description 46
- 238000005194 fractionation Methods 0.000 claims abstract description 14
- 230000000630 rising effect Effects 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000012423 maintenance Methods 0.000 abstract 1
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- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 10
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- 239000005977 Ethylene Substances 0.000 description 9
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Abstract
Description
本発明は、プロピレン系成形品、特に長期間の使用もしくは高温下での使用でも外観保持性能に優れた透明成形品とその製造方法に関する。 The present invention relates to a propylene-based molded article, particularly a transparent molded article excellent in appearance retention performance even when used for a long period of time or at a high temperature, and a method for producing the same.
プロピレン系樹脂は、成形加工性、剛性に優れ、またリサイクル性や耐熱性、耐薬品性にも優れていることから、各種の方法で成形加工され、幅広い用途に用いられている。これらの特長を活かすべく、ポリスチレン、ポリエチレンテレフタレート、ポリカーボネートなどに代表される他の透明樹脂からポリプロピレン材料への置き換えも活発であるが、その場合には、ポリプロピレン材料への透明性付与が非常に大きな課題となっている。 Propylene-based resins are excellent in molding processability and rigidity, and are excellent in recyclability, heat resistance, and chemical resistance. Therefore, they are molded by various methods and used in a wide range of applications. In order to take advantage of these features, other transparent resins represented by polystyrene, polyethylene terephthalate, polycarbonate, etc. are actively being replaced with polypropylene materials, but in that case, the provision of transparency to polypropylene materials is very large. It has become a challenge.
透明なプロピレン系成形品を実用に供する際、特に、使い捨てではなく長期間に渡って使用し続ける場合には、その透明な外観を長期間に渡って保持することが必要となる。また、プロピレン系成形品は、その特長である耐熱性を活かして、高温で使用されたり保管されたりすることも多いが、その場合には、高温下でも透明な外観が損なわれないことが強く求められる。 When a transparent propylene-based molded article is put into practical use, it is necessary to keep the transparent appearance for a long period of time, especially when the propylene-based molded article is not disposable but continues to be used for a long period of time. In addition, propylene-based molded products are often used or stored at high temperatures, taking advantage of the heat resistance that is a feature of them, but in that case, the transparent appearance is not impaired even at high temperatures. Desired.
プロピレン系（共）重合体には、単独重合体、ランダム共重合体、ブロック共重合体があるが、剛性や耐熱性、ガスバリヤー性の点ではプロピレン単独重合体が、透明性や耐衝撃性の点ではエチレン、ブテン−１等とプロピレンとのランダム共重合体が、耐熱性、耐衝撃性ではエチレン、ブテン−１等とプロピレンとのブロック共重合体が好適であり、状況に応じて適宜選択的に用いられている。 Propylene-based (co) polymers include homopolymers, random copolymers, and block copolymers. Propylene homopolymers are transparent and impact resistant in terms of rigidity, heat resistance, and gas barrier properties. In view of the above, a random copolymer of ethylene, butene-1, etc. and propylene is preferable, and a block copolymer of ethylene, butene-1, etc., and propylene is preferable in terms of heat resistance and impact resistance. Used selectively.
これらの中で、透明成形品を得るためには、ランダム共重合体が好適である。しかしランダム共重合体を用い、さらにその各種パラメータの最適化を行っても、ポリスチレン、ポリエチレンテレフタレート、ポリカーボネート等には透明性の点ではるかに及ばないのが実情である。 Among these, a random copolymer is suitable for obtaining a transparent molded product. However, even if a random copolymer is used and various parameters thereof are optimized, the actual situation is far below that of polystyrene, polyethylene terephthalate, polycarbonate and the like in terms of transparency.
このため、プロピレン系（共）重合体の改質だけではなく、プロピレン系（共）重合体に対する透明化核剤の活用による透明性の改良が幅広く試みられてきた。透明化核剤としては、ジメチルベンジリデンソルビトール系核剤（例えば、特許文献１参照。）やジメチルジベンジリデンソルビトール系核剤（例えば、特許文献２参照。）に代表される溶解型透明化核剤が最も一般的に使用されている。この種の透明化核剤は、成形加工時の昇温工程でＰＰに溶解して均一分散した後、冷却工程で再析出することにより透明性が発現するという機構を持つ透明化核剤である。 For this reason, not only the modification of the propylene-based (co) polymer but also the improvement of the transparency by utilizing a clearing nucleating agent for the propylene-based (co) polymer has been widely attempted. As the clearing nucleating agent, a solution-type clearing nucleating agent represented by dimethylbenzylidene sorbitol-based nucleating agent (for example, see Patent Document 1) and dimethyldibenzylidene sorbitol-based nucleating agent (for example, see Patent Document 2). Most commonly used. This type of clearing nucleating agent is a clearing nucleating agent having a mechanism in which transparency is manifested by re-precipitation in the cooling step after dissolving and uniformly dispersing in PP in the temperature raising step during the molding process. .
しかしながら、既存の透明化核剤を使用しても、透明性の改良幅は必ずしも十分ではなく、ポリスチレン等の他の樹脂の透明性にはまだ及ばない。また、既存の透明化核剤を使用した成形品では、成形後、長期間が経過したり、成形品が高温下で保持されたりすることにより、透明化核剤成分が、成形品の内部から表面に移行する現象（これをブリードアウト現象という。）が発生する。ブリードアウト現象は、分子量の比較的小さい添加剤において発生しやすいが、この現象が生じると、成形直後には透明であった成形品が曇って見えるようになり、成形品の外観著しく悪化して商品価値が大きく損なわれるため、非常に大きな問題となる。 However, even if an existing clearing nucleating agent is used, the range of improvement in transparency is not always sufficient, and it still does not reach the transparency of other resins such as polystyrene. In addition, in molded products that use existing clearing nucleating agents, the clearing nucleating agent component is removed from the inside of the molded product after a long period of time after molding or when the molded product is held at a high temperature. A phenomenon of shifting to the surface (this is called a bleed-out phenomenon) occurs. The bleed-out phenomenon is likely to occur in additives with a relatively low molecular weight, but when this phenomenon occurs, the molded product that was transparent immediately after molding becomes cloudy and the appearance of the molded product is significantly deteriorated. Since the merchandise value is greatly impaired, it becomes a very big problem.
このように、高い透明性を実現しつつ、長期間の使用もしくは高温下での使用でもブリードアウトによる外観悪化が生じないプロピレン系成形品は存在せず、これらを同時に満たす成形品の開発が強く望まれていた。
In this way, there is no propylene-based molded product that achieves high transparency and does not deteriorate in appearance due to bleed-out even when used for a long time or at high temperatures, and development of molded products that satisfy these simultaneously is strong. It was desired.
本発明の目的は、上記問題点に鑑み、高い透明性と、長期間の使用もしくは高温下での使用でも外観保持性能に優れたプロピレン系成形品を提供することにある。 In view of the above problems, an object of the present invention is to provide a propylene-based molded article having high transparency and excellent appearance retention performance even when used for a long period of time or at a high temperature.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、特定のプロピレン系（共）重合体に対して、特定の透明化核剤を配合したプロピレン系樹脂組成物を成形することにより、透明性と外観保持性能とに優れたプロピレン系成形品が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies in order to solve the above problems, the present inventors mold a propylene-based resin composition in which a specific clearing nucleating agent is blended with a specific propylene-based (co) polymer. As a result, it was found that a propylene-based molded article excellent in transparency and appearance retention performance was obtained, and the present invention was completed.
すなわち、本発明の第１の発明によれば、昇温溶出分別の４０℃溶出成分量が５重量％以下であるプロピレン系（共）重合体１００重量部および分子量が４５０以上の溶解型透明化核剤（Ａ）を０．０１〜２．０重量部を含有するプロピレン系重合体組成物を成形してなることを特徴とするプロピレン系透明成形品が提供される。 That is, according to the first invention of the present invention, 100 parts by weight of a propylene-based (co) polymer having a 40 ° C. elution component amount of 5% by weight or less in temperature rising elution fractionation and a dissolution type transparentization having a molecular weight of 450 or more. Provided is a propylene-based transparent molded article obtained by molding a propylene-based polymer composition containing 0.01 to 2.0 parts by weight of the nucleating agent (A).
本発明の第２の発明によれば、第１の発明における透明化核剤（Ａ）が下記化学構造式（１）で示される透明化核剤（Ａ）で示されることを特徴とするプロピレン系樹脂組成物を成形してなるプロピレン系透明成形品が提供される。 According to a second invention of the present invention, the clearing nucleating agent (A) in the first invention is represented by a clearing nucleating agent (A) represented by the following chemical structural formula (1). A propylene-based transparent molded product obtained by molding a resin-based resin composition is provided.
本発明の第３の発明によれば、第１または第２の発明における透明化核剤（Ａ）が、下記化学構造式（２）で示されることを特徴とする請求項１記載のプロピレン系透明成形品が提供される。 According to a third aspect of the present invention, the clearing nucleating agent (A) in the first or second aspect is represented by the following chemical structural formula (2), A transparent molded article is provided.
また、本発明の第４の発明によれば、第１から第３いずれかの発明において、プロピレン系（共）重合体における昇温溶出分別の４０℃溶出成分量が１重量％以下であることを特徴とする請求項１または２に記載のプロピレン系透明成形品が提供される。 According to the fourth aspect of the present invention, in any one of the first to third aspects, the 40 ° C. elution component amount of the temperature rising elution fraction in the propylene-based (co) polymer is 1% by weight or less. A propylene-based transparent molded article according to claim 1 or 2 is provided.
本発明の第５の発明によれば、第１から第３のいずれかの発明におけるプロピレン系透明成形品の製造方法が提供される。 According to the fifth aspect of the present invention, there is provided a method for producing a propylene-based transparent molded article according to any one of the first to third aspects.
本発明のプロピレン系透明薄肉成形品は、非常に高い透明性を、長期間の使用もしくは高温下での使用でも維持し続けるという、従来のプロピレン系成形品では実現しえなかった優れた性能を得ることができる。 The propylene-based transparent thin-walled molded product of the present invention has excellent performance that could not be realized with conventional propylene-based molded products, such as maintaining extremely high transparency even during long-term use or use at high temperatures. Obtainable.
本発明は、昇温溶出分別（ＴＲＥＦ）による４０℃溶出成分量が５重量％以下であるプロピレン系（共）重合体１００重量部に対し、前記化学構造式（１）で示される透明化核剤（Ａ）を０．０１〜２．０重量部配合することを特徴とするプロピレン系樹脂組成物を成形してなるプロピレン系成形品である。以下、このような透明薄肉成形品を製造するために用いるプロピレン系樹脂組成物を構成する成分、プロピレン系樹脂組成物の製造方法、薄肉成形品の成形方法について詳細に説明する。 The present invention provides a transparent nucleus represented by the above chemical structural formula (1) with respect to 100 parts by weight of a propylene-based (co) polymer whose elution component amount at 40 ° C. is 5% by weight or less by temperature rising elution fractionation (TREF). A propylene-based molded article formed by molding a propylene-based resin composition, which contains 0.01 to 2.0 parts by weight of the agent (A). Hereinafter, components constituting the propylene-based resin composition used for producing such a transparent thin-walled molded product, a method for producing the propylene-based resin composition, and a molding method for the thin-walled molded product will be described in detail.
［１］プロピレン系樹脂組成物を構成する成分
（１）プロピレン系（共）重合体
本発明で用いられるプロピレン系（共）重合体は、昇温溶出分別の４０℃溶出成分量が５重量％以下でなければならない。ここで言う４０℃溶出成分量とは、比較的低温で有機溶媒に溶解する成分の全重合体に対する比率であり、低結晶性成分が全重合体中に占める割合の指標である。低結晶性成分は、プロピレン系（共）重合体の中で、ポリプロピレン結晶の間に存在しているが、プロピレン系樹脂組成物に配合された透明化核剤等の添加剤成分は、この低結晶性成分を通って、成形品の中を移動すると考えられている。このよういな低結晶性成分が特定の量よりも多くなると、成形品の内部から成形品表面に向かって、低結晶性成分によって形成される、添加剤の移動経路がつながることになる。その結果、成形品内部から表面への添加剤の移行、いわゆるブリードアウトという現象が顕在化して、透明性が大幅に悪化することになる。その限界値が昇温溶出分別の４０℃溶出成分量で５重量％に相当する。この限界値を見出したのは、本発明者らの成果である。
[1] Component constituting propylene-based resin composition (1) Propylene-based (co) polymer The propylene-based (co) polymer used in the present invention has an amount of components eluted at 40 ° C. of 5% by weight for temperature rising elution fractionation. Must be: The 40 ° C. elution component amount referred to here is the ratio of the component dissolved in the organic solvent at a relatively low temperature to the total polymer, and is an index of the ratio of the low crystalline component in the total polymer. The low crystalline component exists in the propylene-based (co) polymer between the polypropylene crystals, but the additive component such as a clearing nucleating agent blended in the propylene-based resin composition is low in this low-crystalline component. It is believed to move through the molded article through the crystalline component. When such a low crystalline component is larger than a specific amount, an additive transfer path formed by the low crystalline component from the inside of the molded product to the surface of the molded product is connected. As a result, the phenomenon of so-called bleed-out of additives from the inside of the molded product to the surface becomes obvious, and the transparency is greatly deteriorated. The limit value corresponds to 5% by weight in the amount of 40 ° C. elution component for temperature rising elution fractionation. The inventors found out this limit value.
昇温溶出分別の４０℃溶出成分量が５重量部以下になれば、ブリードアウトによる透明性の悪化はかなりの程度まで抑制されるが、この値がさらに小さくなれば、さらにブリードアウトの度合いは小さくなるため、より好ましい。本発明者らは、特に、昇温溶出分別の４０℃溶出成分量が１重量部以下になれば、ブリードアウトはほぼ完全に抑制できるため、きわめて好ましいことを見出した。 If the 40 ° C elution component amount of the temperature rising elution fraction is 5 parts by weight or less, the deterioration of transparency due to bleed out is suppressed to a considerable extent, but if this value is further reduced, the degree of bleed out is further increased. Since it becomes small, it is more preferable. The present inventors have found that the bleed-out can be suppressed almost completely if the amount of the 40 ° C. elution component in the temperature elution fractionation is 1 part by weight or less, which is extremely preferable.
なお、本発明において採用している昇温溶出分別（ＴＲＥＦ）とは、以下に示す方法である。すなわち、試料を１４０℃でオルトジクロロベンゼンに溶解し溶液とする。これを１４０℃のＴＲＥＦカラムに導入した後、８℃／分の降温速度で１００℃まで冷却し、引き続き４℃／分の降温速度で４０℃まで冷却後、１０分間保持する。その後、溶媒であるオルトジクロロベンゼンを１ｍＬ／分の流速でカラムに流し、ＴＲＥＦカラム中で４０℃のオルトジクロロベンゼンに溶解している成分を１０分間溶出させ、次に昇温速度１００℃／時間にてカラムを１４０℃までリニアに昇温し、溶出曲線を得る。上記条件に従って得た溶出曲線から４０℃で溶出する成分の全量に対する割合（重量％）を算出し、４０℃溶出成分量とする。用いるカラム、溶媒、温度等の条件は以下の通りである。
カラムサイズ：４．３ｍｍφ×１５０ｍｍ
カラム充填材：１００μｍ表面不活性処理ガラスビーズ
溶媒：オルトジクロロベンゼン
試料濃度：５ｍｇ／ｍＬ
試料注入量：０．２ｍＬ
溶媒流速：１ｍＬ／分
検出器：波長固定型赤外検出器 ＦＯＸＢＯＲＯ社製 ＭＩＲＡＮ １Ａ
測定波長：３．４２μｍ
In addition, the temperature rising elution fractionation (TREF) employ | adopted in this invention is the method shown below. That is, a sample is dissolved in orthodichlorobenzene at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to 40 ° C. at a rate of 4 ° C./min, and held for 10 minutes. Thereafter, orthodichlorobenzene as a solvent is caused to flow through the column at a flow rate of 1 mL / min, and components dissolved in 40 ° C orthodichlorobenzene are eluted in the TREF column for 10 minutes, and then the heating rate is 100 ° C / hour. The column is linearly heated to 140 ° C. to obtain an elution curve. From the elution curve obtained according to the above conditions, a ratio (% by weight) to the total amount of components eluted at 40 ° C. is calculated and used as the 40 ° C. eluted component amount. Conditions such as a column to be used, a solvent, and a temperature are as follows.
Column size: 4.3mmφ × 150mm
Column packing material: 100 μm surface inactivated glass beads Solvent: Orthodichlorobenzene Sample concentration: 5 mg / mL
Sample injection volume: 0.2 mL
Solvent flow rate: 1 mL / min Detector: Fixed wavelength type infrared detector MIRAN 1A manufactured by FOXBORO
Measurement wavelength: 3.42 μm
本発明のプロピレン系樹脂組成物で用いられるプロピレン系（共）重合体は、基本的には、昇温溶出分別の４０℃溶出成分量が５重量％以下であれば、プロピレン単独重合体であっても、プロピレン系共重合体（ランダム共重合体、ブロック共重合体）であっても、あるいはこれらの混合物であってもよい。プロピレン系共重合体の例としては、エチレン、ブテン−１、ペンテン−１、ヘキセン−１、オクテン−１等の少なくとも一種のα−オレフィンをコモノマーとして含む、プロピレンとα−オレフィン共重合体（ランダム共重合体、ブロック共重合体）が挙げられる。具体的には、プロピレン−エチレン共重合体、プロピレン−ブテン−１共重合体、プロピレン−ペンテン−１共重合体、プロピレン−ヘキセン−１共重合体、プロピレン−オクテン−１共重合体のような二元共重合体、プロピレン−エチレン−ブテン−１共重合体、プロピレン−エチレン−ヘキセン−１共重合体のような三元共重合体などが挙げられる。 The propylene-based (co) polymer used in the propylene-based resin composition of the present invention is basically a propylene homopolymer if the 40 ° C. elution component amount in the temperature rising elution fractionation is 5% by weight or less. Alternatively, it may be a propylene copolymer (random copolymer, block copolymer) or a mixture thereof. Examples of propylene-based copolymers include propylene and α-olefin copolymers (random) containing at least one α-olefin such as ethylene, butene-1, pentene-1, hexene-1, octene-1 as a comonomer. Copolymer, block copolymer). Specifically, such as propylene-ethylene copolymer, propylene-butene-1 copolymer, propylene-pentene-1 copolymer, propylene-hexene-1 copolymer, propylene-octene-1 copolymer, etc. And terpolymers such as binary copolymers, propylene-ethylene-butene-1 copolymers, and propylene-ethylene-hexene-1 copolymers.
これらの中でも、昇温溶出分別の４０℃溶出成分量を少なくして、ブリードアウトを抑制するためには、プロピレン単独重合体、もしくは、コモノマー含量が低いプロピレン系ランダム共重合体がより好ましい。一方、高い透明性を得るためには、プロピレン単独重合体よりはプロピレン系ランダム共重合体の方が好ましく、プロピレン系ランダム共重合体の中でも、コモノマー含量が高いものの方が一般には好ましい。このように、ブリードアウトの抑制と高い透明性の実現とは相反する関係にある。したがって、コモノマー含量には最適範囲があり、その範囲は使用する触媒系などによって異なるが、一般には０．１〜５重量％が好ましい。 Among these, a propylene homopolymer or a propylene-based random copolymer having a low comonomer content is more preferable in order to reduce the amount of elution component at 40 ° C. in the temperature rising elution fraction and suppress bleed out. On the other hand, in order to obtain high transparency, a propylene-based random copolymer is preferable to a propylene homopolymer, and a propylene-based random copolymer having a high comonomer content is generally preferable. Thus, the suppression of bleed-out and the realization of high transparency are contradictory. Therefore, there is an optimum range for the comonomer content, and the range varies depending on the catalyst system used, but is generally preferably 0.1 to 5% by weight.
本発明で用いられるプロピレン系（共）重合体を得るために用いられる触媒は、特に限定されるものではなく、公知の触媒が使用可能である。例えば、チタン化合物と有機アルミニウムを組み合わせた、いわゆるチーグラー・ナッタ触媒、あるいは、メタロセン触媒（例えば、特開平５−２９５０２２号公報等に記載）が使用できる。 The catalyst used for obtaining the propylene-based (co) polymer used in the present invention is not particularly limited, and a known catalyst can be used. For example, a so-called Ziegler-Natta catalyst or a metallocene catalyst (for example, described in JP-A-5-295022) in which a titanium compound and organoaluminum are combined can be used.
ただし、チーグラー・ナッタ触媒を用いた場合には、昇温溶出分別の４０℃溶出成分量を効果的に低減するという点では困難がある。低結晶性成分が最も少ないプロピレン単独重合体を重合した場合でも、昇温溶出分別の４０℃溶出成分量を、１重量％以下の領域まで低減することはきわめて難しい。 However, when a Ziegler-Natta catalyst is used, there is a difficulty in effectively reducing the amount of the 40 ° C. elution component of the temperature rising elution fractionation. Even when a propylene homopolymer having the least amount of low crystallinity is polymerized, it is extremely difficult to reduce the amount of 40 ° C. elution components in the temperature elution fractionation to a region of 1% by weight or less.
一方、メタロセン触媒を用いた場合には、組成分布が狭いプロピレン系（共）重合体を重合することが可能であるため、低結晶成分の少ないプロピレン系（共）重合体を重合することができる。そのため、プロピレン単独重合体のみならず、ランダム共重合体であっても、昇温溶出分別の４０℃溶出成分量を１重量％より小さくすることさえ容易である。その結果、透明性の出やすい、コモノマー含量が比較的高いランダム共重合体を重合しても、昇温溶出分別の４０℃溶出成分量は増加しないため、ブリードアウト性能も優れることになり、耐ブリードアウト性と透明性とを両立した、きわめて有用なプロピレン系（共）重合体を得ることが可能となる。 On the other hand, when a metallocene catalyst is used, a propylene-based (co) polymer having a narrow composition distribution can be polymerized, so that a propylene-based (co) polymer with a low low crystal component can be polymerized. . Therefore, not only the propylene homopolymer but also a random copolymer, it is easy to even make the amount of the 40 ° C. elution component of the temperature rising elution fraction smaller than 1% by weight. As a result, even if a random copolymer with a relatively high comonomer content, which is easily transparent, is polymerized, the amount of components eluted at 40 ° C. in the temperature elution fractionation does not increase. It is possible to obtain a very useful propylene-based (co) polymer having both bleed-out property and transparency.
本発明で用いられるプロピレン系（共）重合体を得るために用いられる重合プロセスは、特に限定されるものではなく、公知の重合プロセスが使用可能である。例えば、スラリー重合法、バルク重合法、気相重合法等が使用できる。また、これらの重合法の１種または２種以上を組み合わせて多段重合を行って重合することもできる。さらには、２種以上のプロピレン系（共）重合体を機械的に溶融混練することによっても製造することができる。 The polymerization process used for obtaining the propylene-based (co) polymer used in the present invention is not particularly limited, and a known polymerization process can be used. For example, a slurry polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used. Moreover, it can also superpose | polymerize by performing multistage polymerization combining the 1 type (s) or 2 or more types of these polymerization methods. Further, it can also be produced by mechanically melting and kneading two or more types of propylene-based (co) polymers.
本発明で用いられるプロピレン系（共）重合体のメルトフローレート（ＭＦＲ）は、昇温溶出分別の４０℃溶出成分量が５重量％以下であれば、特に制限なく用いることができる。ただし、ＭＦＲが極端に大きくなると、昇温溶出分別の４０℃溶出成分量は一般的には増加する傾向が見られるため好ましくない。また、ＭＦＲが極端に小さくなると、成形加工時の流動性が極端に悪化する結果、成形品の表面状態が乱れてしまい、透明性が大きく損なわれたり、ブリードアウト性能が著しく悪化したりして外観が損なわれる可能性がある。このように、本発明で用いられるプロピレン系（共）重合体のＭＦＲには最適点があるが、その範囲は、成形法や成形品の形状等に依存する。一般的には、ＭＦＲが０．３〜１００程度の範囲にあることが望ましい。 The melt flow rate (MFR) of the propylene-based (co) polymer used in the present invention can be used without particular limitation as long as the amount of components eluted at 40 ° C. is 5% by weight or less. However, if the MFR becomes extremely large, the amount of the 40 ° C. elution component in the temperature rising elution fraction generally tends to increase, which is not preferable. In addition, if the MFR is extremely small, the fluidity during the molding process is extremely deteriorated. As a result, the surface state of the molded product is disturbed, the transparency is greatly impaired, and the bleedout performance is significantly deteriorated. Appearance may be impaired. Thus, the MFR of the propylene-based (co) polymer used in the present invention has an optimum point, but the range depends on the molding method and the shape of the molded product. In general, the MFR is desirably in the range of about 0.3 to 100.
（２）透明化核剤（Ａ）
本発明のプロピレン系樹脂組成物に用いられる透明化核剤（Ａ）は、分子量が４５０以上の溶解型透明化核剤である。既存の溶解型透明化核剤は、分子量が３８６〜４１４程度のものが実用化されているが、これらは、分子量が比較的小さく、プロピレン系樹脂組成物の中で移動しやすかったために、長期間の使用もしくは高温下での使用において、ブリードアウトする傾向を抑制することは難しかった。これに対して、分子量が４５０以上の溶解型透明化核剤を使用することにより、核剤分子がプロピレン系樹脂組成物の中で移動しづらくなるため、長期間の使用もしくは高温下での使用におけるブリードアウトを大きく抑制できるということを、本発明者らは見出した。
(2) Clearing nucleating agent (A)
The clearing nucleating agent (A) used in the propylene-based resin composition of the present invention is a dissolution-type clearing nucleating agent having a molecular weight of 450 or more. Existing dissolution-type transparent nucleating agents having a molecular weight of about 386 to 414 have been put into practical use, but these have a relatively low molecular weight and are easy to move in the propylene-based resin composition, so that they are long. It has been difficult to suppress the tendency to bleed out during period use or use at high temperatures. On the other hand, the use of a solution-type transparent nucleating agent having a molecular weight of 450 or more makes it difficult for the nucleating agent molecules to move in the propylene-based resin composition. The present inventors have found that the bleed-out can be greatly suppressed.
透明化核剤（Ａ）の分子量は、分子量が４５０以上であれば特に制限はない。分子量が大きくなればなるほど、プロピレン系樹脂組成物の中で移動しづらくなり、よりブリードアウトが生じにくくなることが期待できる。ただし、分子量が極端に大きくなりすぎると、プロピレン系樹脂組成物の中での移動が抑制されすぎて均一に分散されにくくなったり、プロピレン系（共）重合体への溶解性が低下したりして、透明性が十分に発現されにくくなる傾向がある。本発明で規定した、４０℃溶出成分量が５重量％以下という特定のポリプロピレン系（共）に配合する場合であれば、透明化核剤（Ａ）の分子量は４５０〜６００程度の範囲にあることが好ましい。このような特定の分子量の透明化核剤（Ａ）と、４０℃溶出成分量が５重量％以下という特定のポリプロピレン系（共）とを併用することにより、透明化核剤の機能が最大限に発揮されるとともに、比較的分子量が高い透明化核剤であるがためにプロピレン系樹脂組成物の中での移動が抑制されること、および透明化核剤の移動の原因となる４０℃溶出成分量が少ないという理由に起因して、ブリードアウトが非常に少ないという挙動を示す。このように特定の分子量を有する透明化核剤と、４０℃溶出成分量が５重量％以下という特定のポリプロピレン系（共）重合体が密接に関係する原因を両面から解明することができたものである。 The molecular weight of the clearing nucleating agent (A) is not particularly limited as long as the molecular weight is 450 or more. It can be expected that the higher the molecular weight, the more difficult it is to move in the propylene-based resin composition, and the more difficult it is to produce bleed out. However, if the molecular weight is excessively large, movement in the propylene resin composition is suppressed too much and it becomes difficult to disperse uniformly, or the solubility in the propylene (co) polymer may be reduced. Therefore, the transparency tends to be not sufficiently exhibited. In the case of blending with a specific polypropylene system (co-) whose elution component amount of 40 ° C. is 5% by weight or less as defined in the present invention, the molecular weight of the clearing nucleating agent (A) is in the range of about 450 to 600. It is preferable. The combined use of such a clearing nucleating agent (A) with a specific molecular weight and a specific polypropylene system (co-) having an elution component amount of 5 ° C. or less at 40 ° C. maximizes the function of the clearing nucleating agent. 40 ° C. elution, which is a clearing nucleating agent having a relatively high molecular weight, and is prevented from moving in the propylene-based resin composition and causing the clearing nucleating agent to move. Due to the reason that the amount of the component is small, the bleed-out behavior is very small. The reason why the clearing nucleating agent having a specific molecular weight and the specific polypropylene-based (co) polymer whose elution component amount at 40 ° C. is 5% by weight or less is closely related can be clarified from both sides. It is.
本発明のプロピレン系樹脂組成物から成形された各種成形品の特徴は、成形品の大小、肉厚の違いにかかわらず、２０〜４０℃程度の夏の気候、および−３０〜１０℃程度の冬季気温というような気候変動のある環境において、長期間、繰り返して使用しても、透明性の低下、粉吹き現象などに代表される外観不良の発生が特異的に少ないことである。
さらに、その成形品を、煮沸環境や、マイクロ波、放射線照射の照射下というような過酷な環境下に放置したり繰り返して使用しても、透明性等の外観変化は、通常の汎用のプロピレン系（共）重合体に汎用の透明化核剤を配合したプロピレン系樹脂組成物から成形された各種成形品に比較すれば、到底予期し得ないほど少なくなり、非常に優れた品質上の耐久性を有すると言うことができる。
The characteristics of various molded articles molded from the propylene-based resin composition of the present invention are as follows. Regardless of the size of the molded article and the difference in wall thickness, summer climate of about 20-40 ° C. and about −30-10 ° C. Even in repeated use over a long period of time in an environment with a climate change such as winter temperature, the occurrence of poor appearance such as reduced transparency and powder blowing phenomenon is specifically low.
Furthermore, even if the molded product is left in a harsh environment such as a boiling environment, microwaves, or irradiation with radiation, or repeatedly used, the appearance change such as transparency is normal general-purpose propylene. Compared to various molded products molded from a propylene resin composition containing a general-purpose clearing nucleating agent blended with a polymer (co) polymer, it is extremely unpredictable and has excellent quality durability It can be said that it has sex.
このような透明化核剤（Ａ）としては、分子量が４５０以上の溶解型透明化核剤であれば任意に使用できるが、具体的には、例えば、下記化学構造式（１）で示される溶解型透明化核剤が挙げられる。 As such a clearing nucleating agent (A), any solvent-type clearing nucleating agent having a molecular weight of 450 or more can be arbitrarily used. Specifically, for example, it is represented by the following chemical structural formula (1). A dissolution type clarification nucleating agent is mentioned.
化学構造式（１）において、ｎは、０〜２の整数であり、Ｒ１〜Ｒ５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ６は、炭素数が１〜２０のアルキル基である。 In the chemical structural formula (1), n is an integer of 0 to 2, and R 1 to R 5 are the same or different and are each a hydrogen atom or an alkyl group, alkenyl group, or alkoxy group having 1 to 20 carbon atoms. , A carbonyl group, a halogen group and a phenyl group, and R 6 is an alkyl group having 1 to 20 carbon atoms.
また、このような透明化核剤（Ａ）のうち、市販品として入手できる代表的なものは、ミラッドＮＸ８０００Ｊ（ミリケン・アンド・カンパニー）などが挙げられる。その化学構造式は、下記化学構造式（２）の通りである。この透明化核剤の分子量は４８４である。この物質は、前述の特徴に加えて、熱的・化学的にきわめて安定であるため、成形温度においてもほとんど熱分解しないという非常に優れた特徴があるため、分解物が成形品の表面にブリードアウトして外観を悪化させるという問題が生じないため、非常に好ましい。 In addition, representative examples of such a clearing nucleating agent (A) that can be obtained as a commercial product include MIRAD NX8000J (Milliken & Company). Its chemical structural formula is as shown in chemical structural formula (2) below. The molecular weight of this clearing nucleating agent is 484. In addition to the above-mentioned characteristics, this material is extremely stable thermally and chemically, so it has an excellent characteristic that it hardly decomposes at molding temperatures. This is very preferable because it does not cause the problem of deterioration of the appearance due to out.
本発明のプロピレン系樹脂組成物に用いられる透明化核剤（Ａ）の配合量は、プロピレン系（共）重合体１００重量部に対し、０．０１〜２．０重量部であり、好ましくは０．２〜０．５重量部である。０．０１重量部未満では十分な効果が得られ難い。配合量を増加するにつれて、プロピレン系成形品の透明性は良化するが、２．０重量部を超えると透明化核剤が凝集する結果、かえって透明性が低下する可能性があるため望ましくない。また、いかに表面に移行しづらい透明化核剤とはいえ、過剰量の添加はブリードアウトに悪影響を及ぼす可能性もあることから、その意味でも避ける方が望ましい。透明性とブリードアウトのバランスが最も良いのは、０．２〜０．５重量部の範囲である。 The blending amount of the clearing nucleating agent (A) used in the propylene resin composition of the present invention is 0.01 to 2.0 parts by weight, preferably 100 parts by weight of the propylene (co) polymer, 0.2 to 0.5 part by weight. If it is less than 0.01 part by weight, it is difficult to obtain a sufficient effect. As the compounding amount is increased, the transparency of the propylene-based molded product is improved. However, when the amount exceeds 2.0 parts by weight, the transparency nucleating agent aggregates, which is undesirable because the transparency may decrease. . In addition, although it is a clearing nucleating agent that is difficult to migrate to the surface, addition of an excessive amount may adversely affect bleed out, so it is desirable to avoid it in that sense. The best balance between transparency and bleed out is in the range of 0.2 to 0.5 parts by weight.
本発明に用いられる透明化核剤（Ａ）の製造方法としては、特表２００７−５３４８２７号公報等に記載の方法を挙げることができる。市販品としても、容易に入手することができ、例えば、ミラッドＮＸ８０００Ｊ（ミリケン・アンド・カンパニー社製）を挙げることができる。 As a manufacturing method of the clearing nucleating agent (A) used for this invention, the method as described in Japanese translations of PCT publication No. 2007-534827 etc. can be mentioned. Commercially available products can also be easily obtained, and for example, MIRAD NX8000J (Milken & Company) can be mentioned.
（３）その他の添加剤
本発明のプロピレン系樹脂組成物においては、プロピレン系（共）重合体および透明化核剤（Ａ）に加えて、プロピレン系（共）重合体の安定剤などとして使用されている各種酸化防止剤、中和剤、滑剤、紫外線吸収剤、光安定剤等の添加剤を、透明化核剤の機能やブリードアウト性能に悪影響を与えない範囲で配合することができる。
(3) Other additives In the propylene-based resin composition of the present invention, in addition to the propylene-based (co) polymer and the clearing nucleating agent (A), it is used as a stabilizer for the propylene-based (co) polymer. Additives such as various antioxidants, neutralizers, lubricants, ultraviolet absorbers, light stabilizers, and the like can be blended within a range that does not adversely affect the function and bleeding out performance of the clearing nucleating agent.
具体的には、酸化防止剤としては、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−フォスファイト、ジ−ステアリル−ペンタエリスリトール−ジ−フォスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトール−ジ−フォスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレン−ジ−フォスフォナイト、テトラキス（２，４−ジ−ｔ−ブチル−５−メチルフェニル）−４，４’−ビフェニレン−ジ−フォスフォナイト等のリン系酸化防止剤、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、テトラキス［メチレン（３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロシンナメート）］メタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ハイドロキシベンジル）ベンゼン、トリス（３，５−ジ−ｔ−ブチル−４−ハイドロキシベンジル）イソシアヌレート等のフェノール系酸化防止剤、ジ−ステアリル−β，β’−チオ−ジ−プロピオネート、ジ−ミリスチル−β，β’−チオ−ジ−プロピオネート、ジ−ラウリル−β，β’−チオ−ジ−プロピオネート等のチオ系酸化防止剤等が挙げられる。 Specifically, as the antioxidant, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, bis ( 2,4-di-t-butylphenyl) pentaerythritol-diphosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4 Phosphorous antioxidants such as 4,4'-biphenylene-diphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-diphosphonite, 2,6-di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, 1 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate Phenolic antioxidants such as di-stearyl-β, β'-thio-di-propionate, di-myristyl-β, β'-thio-di-propionate, di-lauryl-β, β'-thio-di -Thio antioxidants such as propionate.
中和剤の具体例としては、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウムなどの金属脂肪酸塩、ハイドロタルサイト（商品名：協和化学工業（株）の下記一般式（３）で表されるマグネシウムアルミニウム複合水酸化物塩）、ミズカラック（下記一般式（４）で表されるリチウムアルミニウム複合水酸化物塩）などが挙げられる。 Specific examples of the neutralizing agent include metal fatty acid salts such as calcium stearate, zinc stearate and magnesium stearate, hydrotalcite (trade name: magnesium represented by the following general formula (3) of Kyowa Chemical Industry Co., Ltd.) Aluminum complex hydroxide salt), Mizukarak (lithium aluminum composite hydroxide salt represented by the following general formula (4)), and the like.
Ｍｇ１−ｘＡｌｘ（ＯＨ）２（ＣＯ３）ｘ／２・ｍＨ２Ｏ …（３）
［式中、ｘは、０＜ｘ≦０．５であり、ｍは３以下の数である。］
［Ａｌ２Ｌｉ（ＯＨ）６］ｎＸ・ｍＨ２Ｏ …（４）
［式中、Ｘは、無機または有機のアニオンであり、ｎはアニオン（Ｘ）の価数であり、ｍは３以下である。］
Mg 1-x Al x (OH) 2 (CO 3 ) x / 2 · mH 2 O (3)
[Wherein x is 0 <x ≦ 0.5, and m is a number of 3 or less. ]
[Al 2 Li (OH) 6 ] n X · mH 2 O (4)
[Wherein, X is an inorganic or organic anion, n is the valence of the anion (X), and m is 3 or less. ]
滑剤の具体例としては、既知の滑剤が挙げられるが、オレイン酸アミド、ステアリン酸アミド、エルカ酸アミド、ベヘニン酸アミド等の脂肪酸アミド、ステアリン酸ブチル、シリコーンオイル等が挙げられる。 Specific examples of the lubricant include known lubricants, and examples thereof include fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, and behenic acid amide, butyl stearate, and silicone oil.
紫外線吸収剤としては、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンゾトリアゾール等の紫外線吸収剤等が挙げられる。 Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2 And ultraviolet absorbers such as' -hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole.
光安定剤としては、ｎ−ヘキサデシル−３，５−ジ−ｔ−ブチル−４−ヒドロキシベンゾエート、２，４−ジ−ｔ−ブチルフェニル−３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンゾエート、ビス（２，２，６，６−テトラメチル−４−ピぺリジル）セバケート、コハク酸ジメチル−２−（４−ヒドロキシ−２，２，６，６−テトラメチル−１−ピペリジル）エタノール縮合物、ポリ｛［６−〔（１，１，３，３−テトラメチルブチル）アミノ〕−１，３，５−トリアジン−２，４ジイル］〔（２，２，６，６−テトラメチル−４−ピペリジル）イミノ〕ヘキサメチレン〔（２，２，６，６−テトラメチル−４−ピペリジル）イミノ〕｝、Ｎ，Ｎ’−ビス（３−アミノプロピル）エチレンジアミン−２，４−ビス〔Ｎ−ブチル−Ｎ−（１，２，２，６，６−ペンタメチル−４−ピペリジル）アミノ〕−６−クロロ−１，３，５−トリアジン縮合物等の光安定剤を挙げることができる。 Examples of the light stabilizer include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4 ′. -Hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl) succinate ) Ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl] [(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N′-bis (3-aminopropyl) ethylenediamine-2,4- Bis [N-butyl-N- ( , Mention may be made of a light stabilizer such as 2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate.
さらに、下記化学構造式（５）や下記一般式（６）で表されるアミン系酸化防止剤、５，７−ジ−ｔ−ブチル−３−（３，４−ジ−メチル−フェニル）−３Ｈ−ベンゾフラン−２−ワン等のラクトン系酸化防止剤、下記化学構造式（７）等のビタミンＥ系酸化防止剤を挙げることができる。 Further, an amine-based antioxidant represented by the following chemical structural formula (5) or the following general formula (6), 5,7-di-t-butyl-3- (3,4-di-methyl-phenyl)- Examples thereof include lactone antioxidants such as 3H-benzofuran-2-one and vitamin E antioxidants such as the following chemical structural formula (7).
さらに、その他に、透明化核剤の機能やブリードアウト性能に悪影響を与えない範囲で、帯電防止剤、脂肪酸金属塩等の分散剤、有機化酸化物、顔料や染料等の着色剤、その他の添加剤を配合することができる。さらに、高密度ポリエチレン、低密度ポリエチレン、線形低密度ポリエチレン、オレフィン系エラストマー、非オレフィン系エラストマー、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリレート共重合体、天然樹脂のような各種熱可塑性樹脂を１〜３０重量％をポリマーブレンドすることも可能である。 In addition, antistatic agents, dispersants such as fatty acid metal salts, organic oxides, colorants such as pigments and dyes, etc., as long as they do not adversely affect the function and bleeding out performance of the clearing nucleating agent Additives can be blended. Furthermore, various thermoplastics such as high density polyethylene, low density polyethylene, linear low density polyethylene, olefin elastomer, non-olefin elastomer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate copolymer, natural resin It is also possible to polymer blend 1-30% by weight of the resin.
［２］プロピレン樹脂組成物の製造方法
本発明のプロピレン系樹脂組成物は、プロピレン系（共）重合体、透明化核剤（Ａ）および必要に応じて用いる他の添加剤を、ヘンシェルミキサー、スーパーミキサー、リボンブレンダー等に投入して混合した後、通常の単軸押出機、二軸押出機、バンバリーミキサー、プラベンダー、ロール等で１６０〜２８０℃の温度範囲で溶融混練することにより得ることができる。
[2] Propylene resin composition production method The propylene resin composition of the present invention comprises a propylene-based (co) polymer, a clearing nucleating agent (A), and other additives used as needed, a Henschel mixer, Obtained by melting and kneading in a temperature range of 160 to 280 ° C. with a normal single screw extruder, twin screw extruder, Banbury mixer, plastic bender, roll, etc. Can do.
［３］透明成形品
本発明の成形品は、上記のプロピレン系樹脂組成物を、公知の射出成形機、押出成形機、フィルム成形機、ブロー成形機、繊維成形機等各種の成形機により成形することにより得られるものである。特に、高い透明性を発現しつつ、ブリードアウトを抑制するためには、成形時の冷却工程において冷却条件を強化することが望ましい。これにより、成形の表面に強固なスキン層が形成されて、透明化核剤が表面に移行するのを妨げることによって、より効果的にブリードアウトによる透明性の悪化を抑制することができる。また、冷却を強化することにより、成形品が内部まで急激に冷却固化される結果、結晶のサイズが小さくなり、透明性がより改良されるという効果もある。冷却の強化は、金型や冷却ロールに通水する冷却水の温度を制御することにより実現できる。望ましい冷却水の温度は６０℃以下であるが、３０℃以下とすることがより好ましい。
[3] Transparent molded product The molded product of the present invention is obtained by molding the above-mentioned propylene-based resin composition by various molding machines such as a known injection molding machine, extrusion molding machine, film molding machine, blow molding machine, and fiber molding machine. It is obtained by doing. In particular, in order to suppress bleed-out while exhibiting high transparency, it is desirable to enhance the cooling conditions in the cooling process during molding. Thereby, a strong skin layer is formed on the surface of molding, and the transparency nucleating agent is prevented from moving to the surface, so that the deterioration of transparency due to bleed out can be more effectively suppressed. Further, by strengthening the cooling, the molded product is rapidly cooled and solidified to the inside. As a result, there is an effect that the crystal size is reduced and the transparency is further improved. Enhanced cooling can be realized by controlling the temperature of the cooling water flowing through the mold or cooling roll. Desirable cooling water temperature is 60 ° C. or lower, and more preferably 30 ° C. or lower.
具体的には、食品容器（プリン容器、ゼリー容器、ヨーグルト容器、その他のデザート容器、惣菜容器、茶碗蒸し容器、インスタントラーメン容器、米飯容器、レトルト容器、弁当容器等）、飲料容器（飲料ボトル、チルドコーヒー容器、ワンハンドカップ容器、その他の飲料容器等）、キャップ（ペットボトルキャップ、１ピースキャップ、２ピースキャップ、インスタントコーヒーのキャップ、調味料キャップ、化粧品容器キャップ等）、医薬品容器（輸液バッグ、血液バッグ、プレフィルドシリンジ、キット製剤、目薬容器、薬液容器、薬剤容器、液体の長期保存容器、プレススルーパッケージ、ストリップパッケージ、分包、プラスチックバイアル等）、その他各種容器（インク容器、化粧品容器、シャンプー容器、洗剤容器等）、医療用器具（ディスポーザブルシリンジおよびその部品、カテーテル・チューブ、真空採血管、手術用不織布、血液用フィルター、血液回路などのディスポーザブル器具、人工肺、人工肛門などの人工臓器類の部品、ダイアライザー、試験管、検査キット、縫合糸、湿布基材、歯科用材料の部品、整形外科用材料の部品、コンタクトレンズのケース等）、日用品（衣装ケース、バケツ、洗面器、バス・トイレタリー用品、筆記用具、文房具、コンテナ、玩具、調理器具、その他各種ケース等）、自動車部品（インパネ、バンパー、灯体等）、電気・電子部品（各種電気機器の部材・筐体、半導体搬送容器、光学部品、各種情報メディアケース、太陽電池封止材等）、建材、産業資材品、フィルム、繊維、シート、などが挙げられる。 Specifically, food containers (pudding containers, jelly containers, yogurt containers, other dessert containers, side dish containers, tea bowl steamers, instant noodle containers, cooked rice containers, retort containers, lunch boxes, etc.), beverage containers (beverage bottles, chilled containers, etc.) Coffee containers, one-hand cup containers, other beverage containers, etc.), caps (plastic bottle caps, 1-piece caps, 2-piece caps, instant coffee caps, seasoning caps, cosmetic container caps, etc.), pharmaceutical containers (infusion bags, blood) Bags, prefilled syringes, kit formulations, eye drops containers, drug containers, drug containers, liquid long-term storage containers, press-through packages, strip packages, sachets, plastic vials, etc., and other various containers (ink containers, cosmetic containers, shampoo containers) , Detergent containers, etc.) Medical devices (Disposable syringes and parts thereof, catheters and tubes, vacuum blood collection tubes, surgical nonwoven fabrics, blood filters, disposable devices such as blood circuits, parts of artificial organs such as artificial lungs and colostomy, dialyzers, test tubes , Inspection kits, sutures, poultice base materials, parts for dental materials, parts for orthopedic materials, contact lens cases, etc., daily necessities (costume cases, buckets, washbasins, bath / toiletries, writing utensils, stationery, etc. , Containers, toys, cooking utensils, other cases, etc.), automotive parts (instruments, bumpers, lamps, etc.), electrical / electronic parts (members / housing for various electrical equipment, semiconductor transport containers, optical parts, various information media) Case, solar cell sealing material, etc.), building materials, industrial materials, films, fibers, sheets, and the like.
中でも、透明性、および長期間の使用もしくは高温下での使用でも外観を保持できるという特徴を活かすことのできる用途として、長期保管される食品・飲料・医薬品・化粧品等の容器、長期間使用される日用品・工業材料部品・建材・産業資材品等の物品、高温滅菌を施される食品・飲料・医薬品等の容器・医療器具、高温物を充填する食品・飲料等の容器・器具、レトルト・電子レンジ・食器乾燥機・食器洗浄機等の高温環境下で使用される食品・飲料・調味料等の容器・調理器具・食器類、使用環境が高温下となる自動車・電気・電子部品等の工業用品・産業資材部品などに特に好適である。 Above all, as a use that can make use of the characteristics of transparency and long-term use or the appearance can be maintained even at high temperatures, containers such as food, beverages, pharmaceuticals, and cosmetics that are stored for a long time are used for a long time. Goods such as daily necessities, industrial material parts, building materials, industrial materials, containers / medical equipment for food / beverages / pharmaceuticals that are subjected to high-temperature sterilization, containers / equipment for food / beverages that are filled with high-temperature materials, retorts, etc. Containers / cooking utensils / tableware for food, beverages, seasonings, etc. used in high-temperature environments such as microwave ovens, dish dryers, dishwashers, etc. It is particularly suitable for industrial articles and industrial material parts.
以下、実施例により、本発明をさらに詳細に説明するが、本発明は、これらの記載により何ら限定されるものではない。なお、各実施例および比較例において、用いた物性測定は以下の方法で行い、プロピレン系（共）重合体、透明化核剤および他の添加剤（酸化防止剤、中和剤など）としては以下のものを使用した。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these description. In each example and comparative example, the physical properties used were measured by the following methods, and as propylene-based (co) polymers, clearing nucleating agents and other additives (antioxidants, neutralizing agents, etc.) The following were used.
１．試験方法
（１）昇温溶出分別（ＴＲＥＦ）
前述の方法にしたがって４０℃溶出成分量を測定し、重量％で表した。この数値が小さいほど、結晶性の低い成分が小さいことになり、ブリードアウトによる外観の悪化が生じにくい方向となる。
1. Test method (1) Temperature rising elution fractionation (TREF)
According to the method described above, the amount of components eluted at 40 ° C. was measured and expressed in weight%. The smaller this value, the smaller the component with low crystallinity, and the direction of appearance deterioration due to bleed-out is less likely to occur.
（２）メルトフローレート（ＭＦＲ）
ＪＩＳ Ｋ７１２０：１９９９、２３０℃ ２．１６ｋｇ荷重に準拠して測定した。
(2) Melt flow rate (MFR)
Measured according to JIS K7120: 1999, 230 ° C. 2.16 kg load.
（３）エチレン含量
１３Ｃ−ＮＭＲにより、エチレン含有量、およびブテン−１含有量を測定した。その測定条件は以下の通りである。
機種：日本電子（株）製ＧＳＸ−４００
溶媒：ｏ−ジクロルベンゼン：重ベンゼン＝４：１（体積比）
濃度：１００ｍｇ／ｍｌ
温度：１３０℃
パルス角：９０°
パルス間隔：１５秒
積算回数：５，０００回以上
(3) Ethylene content
The ethylene content and the butene-1 content were measured by 13 C-NMR. The measurement conditions are as follows.
Model: GSX-400 manufactured by JEOL Ltd.
Solvent: o-dichlorobenzene: heavy benzene = 4: 1 (volume ratio)
Concentration: 100 mg / ml
Temperature: 130 ° C
Pulse angle: 90 °
Pulse interval: 15 seconds Integration count: 5,000 times or more
（４）ヘーズ
東芝機械製ＩＳ１００ＧＮ射出成形機により、成形温度２２０℃、金型温度３０℃で１００ｍｍ×１００ｍｍ×１ｍｍｔのシート状試験片を作成し、ＪＩＳ Ｋ７１０５：１９８１に準拠して測定した。この値が小さいほど透明であることを意味し、一般には高透明・高光沢な成形品としての外観意匠性が高いことになる。
(4) Haze A sheet-shaped test piece of 100 mm × 100 mm × 1 mmt was prepared at a molding temperature of 220 ° C. and a mold temperature of 30 ° C. using an IS100GN injection molding machine manufactured by Toshiba Machine and measured according to JIS K7105: 1981. It means that it is transparent so that this value is small, and generally the external appearance design property as a highly transparent and highly glossy molded product will be high.
（５）高温ブリードアウト
東芝機械製ＩＳ１００ＧＮ射出成形機により、成形温度２２０℃、金型温度３０℃で１００ｍｍ×１００ｍｍ×１ｍｍｔのシート状試験片を作成し、それを、１００℃のギヤオーブンにて５時間加熱した。その後、室温２３℃、相対湿度５０％の恒温室内にて２４時間冷却した後に、ＪＩＳ Ｋ７１０５：１９８１に準拠してヘーズを測定した。得られた値と、（４）で得られたヘーズの値との差をもって、高温使用下におけるブリードアウトの指標とした。この値が大きいほど、高温で使用した際に透明性が大きく悪化することを意味する。概して言えば、この値が５を超えると、ブリードアウトによる透明性の悪化が顕著となり、実用上の問題になる可能性が高い。
(5) High-temperature bleed-out A sheet-shaped test piece of 100 mm × 100 mm × 1 mmt was produced at a molding temperature of 220 ° C. and a mold temperature of 30 ° C. by using an IS100GN injection molding machine manufactured by Toshiba Machine, and this was performed in a gear oven at 100 ° C. Heated for 5 hours. Then, after cooling for 24 hours in a constant temperature room with a room temperature of 23 ° C. and a relative humidity of 50%, haze was measured according to JIS K7105: 1981. The difference between the obtained value and the haze value obtained in (4) was used as a bleed-out indicator under high temperature use. A larger value means that transparency is greatly deteriorated when used at a high temperature. Generally speaking, when this value exceeds 5, deterioration of transparency due to bleed-out becomes remarkable, and there is a high possibility that it becomes a practical problem.
（６）常温ブリードアウト
東芝機械製ＩＳ１００ＧＮ射出成形機により、成形温度２２０℃、金型温度３０℃で１００ｍｍ×１００ｍｍ×１ｍｍｔのシート状試験片を作成し、それを、４０℃のギヤオーブンにて１００日間加熱した。その後、室温２３℃、相対湿度５０％の恒温室内にて２４時間冷却した後に、その外観を目視で観察した。成形品に曇りが全く見られない場合は「◎」、曇りがわずかに見られる場合は「○」、曇りがかなり見られる場合は「△」、曇りが非常に顕著に見られる場合は「×」とした。この指標は、夏季に想定される室内外での最高温度付近で３ヶ月間以上保管された場合に、ブリードアウトによる透明性の悪化がどの程度あるかを示すものである。
(6) Room temperature bleed out Using a Toshiba Machine IS100GN injection molding machine, a sheet-shaped test piece of 100 mm × 100 mm × 1 mmt was prepared at a molding temperature of 220 ° C. and a mold temperature of 30 ° C., and this was made in a gear oven at 40 ° C. Heated for 100 days. Then, after cooling for 24 hours in a constant temperature room at 23 ° C. and 50% relative humidity, the appearance was visually observed. “◎” when the molded product does not show any cloudiness, “◯” when the cloudiness is slightly observed, “△” when the cloudiness is considerably observed, “X” when the cloudiness is very noticeable. " This index shows the degree of deterioration of transparency due to bleed-out when stored for more than 3 months near the maximum indoor and outdoor temperature expected in summer.
２．プロピレン系（共）重合体、透明化核剤および他の添加剤
（１）プロピレン系（共）重合体
（ｉ）プロピレン単独重合体１（ＨＰＰ−１）：ノバテックＭＡ１Ｑ（日本ポリプロ社製）。チーグラー・ナッタ触媒、ＭＦＲ２５ｇ／１０分、ＴＲＥＦ４０℃溶出成分２．８重量％。
（ｉｉ）プロピレン−エチレンランダム共重合体１（ＲＰＰ−１）：ノバテックＭＧ０３ＢＱ（日本ポリプロ社製）。チーグラー・ナッタ触媒、エチレン濃度２．３重量％、ＭＦＲ３０ｇ／１０分、ＴＲＥＦ４０℃溶出成分４．９重量％。
（ｉｉｉ）プロピレン−エチレンランダム共重合体２（ＲＰＰ−２）：ウィンテックＷＭＧ０３Ｐ（日本ポリプロ社製）。メタロセン触媒、エチレン濃度０．８重量％、ＭＦＲ３０ｇ／１０分、ＴＲＥＦ４０℃溶出成分０．２重量％。
（ｉｖ）プロピレン−エチレンランダム共重合体３（ＲＰＰ−３）：ウィンテックＷＳＸ０２Ｐ（日本ポリプロ社製）。メタロセン触媒、エチレン濃度３．２重量％、ＭＦＲ２５ｇ／１０分、ＴＲＥＦ４０℃溶出成分０．３重量％。
（ｖ）プロピレン−エチレンランダム共重合体４（ＲＰＰ−４）：ノバテックＭＸ０３Ｑ（日本ポリプロ社製）。チーグラー・ナッタ触媒、エチレン濃度３．８重量％、ＭＦＲ３０ｇ／１０分、ＴＲＥＦ４０℃溶出成分１１．３重量％。
2. Propylene-based (co) polymer, clearing nucleating agent and other additives (1) Propylene-based (co) polymer (i) Propylene homopolymer 1 (HPP-1): Novatec MA1Q (manufactured by Nippon Polypro). Ziegler-Natta catalyst, MFR 25 g / 10 min, TREF 40 ° C. Elution component 2.8% by weight.
(Ii) Propylene-ethylene random copolymer 1 (RPP-1): Novatec MG03BQ (manufactured by Nippon Polypro). Ziegler-Natta catalyst, ethylene concentration 2.3 wt%, MFR 30 g / 10 min, TREF 40 ° C. elution component 4.9 wt%.
(Iii) Propylene-ethylene random copolymer 2 (RPP-2): Wintech WMG03P (manufactured by Nippon Polypro). Metallocene catalyst, ethylene concentration 0.8 wt%, MFR 30 g / 10 min, TREF 40 ° C. eluted component 0.2 wt%.
(Iv) Propylene-ethylene random copolymer 3 (RPP-3): Wintech WSX02P (manufactured by Nippon Polypro). Metallocene catalyst, ethylene concentration 3.2 wt%, MFR 25 g / 10 min, TREF 40 ° C. elution component 0.3 wt%.
(V) Propylene-ethylene random copolymer 4 (RPP-4): Novatec MX03Q (manufactured by Nippon Polypro). Ziegler-Natta catalyst, ethylene concentration 3.8 wt%, MFR 30 g / 10 min, TREF 40 ° C. eluting component 11.3 wt%.
（２）透明化核剤
（ｉ）ミラッドＮＸ８０００Ｊ（ミリケン・アンド・カンパニー社製）：透明化核剤（Ａ）相当品で、下記化学構造式（２）で表される化合物。分子量４８４。
(2) Clearing nucleating agent (i) Mirad NX8000J (Milken & Company): A compound represented by the following chemical structural formula (2), which is equivalent to the clearing nucleating agent (A). Molecular weight 484.
（ｉｉ）ゲルオールＭＤ（新日本理化（株）社製）：ジメチルベンジリデンソルビトール系透明化核剤：透明化核剤（Ａ）に相当しない透明化核剤。分子量３８６。
（ｉｉｉ）ミラッド３９８８（ミリケン・アンド・カンパニー社製）：ジメチルベンジリデンソルビトール系透明化核剤：透明化核剤（Ａ）に相当しない透明化核剤。分子量４１４。
(Ii) Gerol MD (manufactured by Shin Nippon Rika Co., Ltd.): Dimethylbenzylidene sorbitol-based clearing nucleating agent: a clearing nucleating agent not corresponding to the clearing nucleating agent (A). Molecular weight 386.
(Iii) Mirad 3988 (manufactured by Milliken & Company): dimethylbenzylidene sorbitol-based clearing nucleating agent: a clearing nucleating agent not corresponding to the clearing nucleating agent (A). Molecular weight 414.
（３）酸化防止剤
（ｉ）ヒンダードフェノール系酸化防止剤：イルガノックス１０１０（ＩＲ１０１０；チバ社製）；テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシルフェニル）プロピオネート］メタン
（ｉｉ）リン系酸化防止剤：イルガフォス１６８（ＩＦ１６８；チバ社製）；トリス（２，４−ジ−ｔｅｒｔ−ブチルフェノール）フォスファイト
(3) Antioxidant (i) Hindered phenol antioxidant: Irganox 1010 (IR1010; manufactured by Ciba); Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-] Hydroxylphenyl) propionate] methane (ii) phosphorus antioxidant: Irgafos 168 (IF168; manufactured by Ciba); Tris (2,4-di-tert-butylphenol) phosphite
（４）中和剤
（ｉ）ステアリン酸カルシウム（ＣＡＳＴ；日油（株）社製）
(4) Neutralizing agent (i) Calcium stearate (CAST; manufactured by NOF Corporation)
（実施例１〜５、比較例１〜９）
プロピレン系（共）重合体、透明化核剤および他の添加剤（酸化防止剤、中和剤）を表１に記載の配合割合（重量部）で準備し、スーパーミキサーでドライブレンドした後、３５ミリ径の２軸押出機を用いて溶融混練した。ダイ出口部温度２００℃でダイから押し出しペレット化し、得られたペレットを用いて物性を測定した。その結果を表１に示す。
(Examples 1-5, Comparative Examples 1-9)
After preparing a propylene-based (co) polymer, a clearing nucleating agent and other additives (antioxidant, neutralizing agent) at a blending ratio (parts by weight) shown in Table 1, and dry blending with a super mixer, Melt kneading was performed using a 35 mm diameter twin screw extruder. Extrusion pelletization was performed from the die at a die outlet temperature of 200 ° C., and physical properties were measured using the obtained pellets. The results are shown in Table 1.
表１から明らかなように、実施例１は、本発明に規定の範囲にあるプロピレン単独重合体の１００重量部に対して、当該透明化核剤（Ａ）を０．６重量部配合したものである。透明性が良好である上、高温ブリードアウト、常温ブリードアウトともに良好であることがわかる。 As is apparent from Table 1, Example 1 was obtained by blending 0.6 parts by weight of the clearing nucleating agent (A) with respect to 100 parts by weight of the propylene homopolymer in the range specified in the present invention. It is. It can be seen that the transparency is good and that both the high temperature bleed out and the room temperature bleed out are good.
実施例２は、使用したプロピレン系単独重合体は実施例１と同じであるが、透明化核剤（Ａ）の配合量を０．３重量部としたものである。透明性は実施例１とほぼ同等であるが、高温ブリードアウトが実施例１よりも良化していることがわかる。このように透明化核剤（Ａ）の配合量を最適化することによって、透明性とブリードアウトのバランスを取ることが可能であることがわかる。 In Example 2, the propylene-based homopolymer used is the same as that in Example 1, but the blending amount of the clearing nucleating agent (A) is 0.3 parts by weight. Although the transparency is almost the same as that of Example 1, it can be seen that the high temperature bleed out is improved as compared with Example 1. Thus, it turns out that it is possible to balance transparency and bleed-out by optimizing the blending amount of the clearing nucleating agent (A).
実施例３は、本発明に規定の範囲内にあるプロピレン−エチレンランダム共重合体１の１００重量部に対して、当該透明化核剤（Ａ）を０．３重量部配合したものである。実施例１および２に比べて透明性が良好である。また、高温ブリードアウトはわずかに悪化するもの許容範囲内であり、常温ブリードアウトは悪化が見られないことがわかる。 In Example 3, 0.3 parts by weight of the clearing nucleating agent (A) is blended with 100 parts by weight of the propylene-ethylene random copolymer 1 within the range specified in the present invention. Compared with Examples 1 and 2, the transparency is good. Further, it can be seen that the high temperature bleed out slightly deteriorates and is within an allowable range, and the normal temperature bleed out does not deteriorate.
実施例４は、本発明に規定の範囲内にあるプロピレン系（共）重合体として、メタロセン触媒で重合した、プロピレン−エチレンランダム共重合体２を使用し、その１００重量部に対して、当該透明化核剤（Ａ）を０．３重量部配合したものである。メタロセン触媒を使用することにより、ランダム共重合体でありながら、ＴＲＥＦ４０℃溶出成分は０．２重量％と著しく小さい値を実現している。その結果、ブリードアウト性能は、高温、常温ともにきわめて良好である。また、透明性も、チーグラー・ナッタ触媒を用いて重合された実施例１〜３に比べて、非常に良好であることがわかる。 Example 4 uses a propylene-ethylene random copolymer 2 polymerized with a metallocene catalyst as a propylene-based (co) polymer within the range specified in the present invention. It contains 0.3 parts by weight of the clearing nucleating agent (A). By using a metallocene catalyst, the TREF 40 ° C. elution component achieves a remarkably small value of 0.2% by weight while being a random copolymer. As a result, the bleed-out performance is very good at both high temperature and normal temperature. Moreover, it turns out that transparency is also very favorable compared with Examples 1-3 polymerized using the Ziegler-Natta catalyst.
実施例５は、本発明に規定の範囲内にあるプロピレン系（共）重合体として、メタロセン触媒を用いて、実施例４よりもコモノマー含量の高い、プロピレン−エチレンランダム共重合体３を使用し、その１００重量部に対して、当該透明化核剤（Ａ）を０．３重量部配合したものである。メタロセン触媒を使用することにより、コモノマー含量を実施例４よりも増加したにもかかわらず、ＴＲＥＦ４０℃溶出成分がほとんど増加していないことがわかる。その結果、ブリードアウト性能は、高温、常温ともにきわめて良好である。また、透明性も、コモノマー含量を増加した効果により、実施例４に比べて、さらにひときわ良好であることがわかる。 Example 5 uses a propylene-ethylene random copolymer 3 having a comonomer content higher than that of Example 4 using a metallocene catalyst as a propylene-based (co) polymer within the range specified in the present invention. The clearing nucleating agent (A) is blended in an amount of 0.3 part by weight per 100 parts by weight. It can be seen that by using the metallocene catalyst, the TREF 40 ° C. elution component is hardly increased even though the comonomer content is increased as compared with Example 4. As a result, the bleed-out performance is very good at both high temperature and normal temperature. It can also be seen that the transparency is much better than Example 4 due to the effect of increasing the comonomer content.
比較例１は、本発明に規定の範囲外にあるプロピレン系（共）重合体として、プロピレン−エチレンランダム共重合体４を使用し、その１００重量部に対して、当該透明化核剤（Ａ）を０．３重量部配合したものである。ＴＲＥＦ４０℃溶出成分が著しく多く、その結果、ブリードアウト性能も、高温、常温ともに大幅に劣ることがわかる。 Comparative Example 1 uses propylene-ethylene random copolymer 4 as a propylene-based (co) polymer outside the range specified in the present invention, and 100 parts by weight of the clearing nucleating agent (A ) 0.3 parts by weight. It can be seen that the TREF 40 ° C. elution component is remarkably large, and as a result, the bleed-out performance is greatly inferior at both high temperature and normal temperature.
比較例２〜５は、本発明に規定の範囲内にあるプロピレン系（共）重合体１００重量部に対して、分子量が小さく本発明の範囲外にある透明化核剤を添加したものである。同じプロピレン系（共）重合体を用いた実施例に比べて、ブリードアウト性、透明性がともに劣ることがわかる。 In Comparative Examples 2 to 5, a clearing nucleating agent having a small molecular weight and outside the scope of the present invention is added to 100 parts by weight of the propylene-based (co) polymer within the range specified in the present invention. . It can be seen that both the bleed-out property and the transparency are inferior to those using the same propylene-based (co) polymer.
比較例６〜９は、本発明に規定の範囲内にあるプロピレン系（共）重合体１００重量部に対して、分子量が比較例２〜５に用いた透明化核剤よりは大きいものの、実施例よりは小さく本発明の範囲外にある透明化核剤を添加したものである。比較例２〜５よりはブリードアウト性にわずかに優れるものの、実施例に比べれば、ブリードアウト性、透明性が及ばないことがわかる。 Comparative Examples 6 to 9 were carried out although the molecular weight was larger than that of the transparent nucleating agent used in Comparative Examples 2 to 5 with respect to 100 parts by weight of the propylene-based (co) polymer within the range specified in the present invention. A clarification nucleating agent that is smaller than the example and outside the scope of the present invention is added. Although the bleed-out property is slightly better than Comparative Examples 2 to 5, it can be seen that the bleed-out property and transparency are not as good as those of Examples.
本発明のプロピレン系成形品は、非常に高い透明性を、長期間の使用もしくは高温下での使用でも維持し続けるという、従来のプロピレン系成形品では実現しえなかった優れた性能を得ることができる。これらの特徴から、長期間にわたって使用される容器・日用品・工業材料部品・建材・産業資材品等の物品、高温滅菌を施される容器・調理器具・医療器具、高温物が充填される容器や器具、高温環境下で使用される容器・食器類・工業用品・産業資材用部品などに代表される幅広い用途にきわめて有用である。 The propylene-based molded product of the present invention obtains excellent performance that could not be realized with conventional propylene-based molded products, such as maintaining extremely high transparency even during long-term use or use at high temperatures. Can do. Because of these characteristics, containers such as containers, daily necessities, industrial material parts, building materials, industrial materials, etc. used for a long period of time, containers subjected to high temperature sterilization, cooking utensils, medical instruments, containers filled with high temperature materials, It is extremely useful for a wide range of applications such as appliances, containers used in high-temperature environments, tableware, industrial products, and parts for industrial materials.
Claims (5)
A method for producing a propylene-based transparent molded article according to any one of claims 1 to 4.
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Cited By (4)
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| JP2015140421A (en) * | 2014-01-30 | 2015-08-03 | 日本ポリプロ株式会社 | Propylene-based resin composition for injection molding and molded article |
| JP2015183065A (en) * | 2014-03-24 | 2015-10-22 | 日本ポリプロ株式会社 | Thermoformed body |
| RU2623430C2 (en) * | 2012-10-11 | 2017-06-26 | Абу Даби Полимерс Ко. Лтд (Бороудж) Л.Л.С | Nucleied polypropylene composition for containers |
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