JP2003292704A - Resin composition and stretched molding - Google Patents
Resin composition and stretched moldingInfo
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- JP2003292704A JP2003292704A JP2002094563A JP2002094563A JP2003292704A JP 2003292704 A JP2003292704 A JP 2003292704A JP 2002094563 A JP2002094563 A JP 2002094563A JP 2002094563 A JP2002094563 A JP 2002094563A JP 2003292704 A JP2003292704 A JP 2003292704A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、２種類の異なるＭ
ＦＲの４−メチル−１−ペンテン系重合体樹脂を特定の
条件で混合させることによって延伸成形性を顕著に向上
させた樹脂組成物に関する。すなわち、高いＭＦＲの４
−メチル−１−ペンテン系重合体樹脂と、低いＭＦＲ値
を有する４−メチル−１−ペンテン系重合体樹脂を特定
の条件で混合した、優れた延伸成形性（優れた溶融流動
性と優れた溶融張力とを両立させた優れた延伸成形性）
を有する樹脂組成物に関する。本発明は、これら樹脂組
成物を含んで構成される延伸成形体に関する。TECHNICAL FIELD The present invention relates to two different types of M
The present invention relates to a resin composition in which a 4-methyl-1-pentene polymer resin of FR is mixed under a specific condition to significantly improve stretch moldability. That is, high MFR 4
-Methyl-1-pentene-based polymer resin and 4-methyl-1-pentene-based polymer resin having a low MFR value were mixed under specific conditions. Excellent stretch moldability (excellent melt flowability and excellent Excellent stretch formability compatible with melt tension)
And a resin composition having The present invention relates to a stretch-molded article containing these resin compositions.
【０００２】[0002]
【従来の技術】４−メチル−１−ペンテン系重合体樹脂
は、高耐熱性、離型性、透明性等の優れた特徴を有する
樹脂として知られている。しかしながら、従来の技術に
よったのでは、市販されている通常の４−メチル−１−
ペンテン系重合体樹脂は、必ずしも、延伸成形性がよい
とはいえず、例えば、延伸フィルムを製造したり、ブロ
ー成形や真空成形を行なったりすることが、同じポリオ
レフィンであるポリエチレンやポリプロピレンと比較し
て困難であるという問題があった。これは、４−メチル
−１−ペンテン系重合体樹脂の機械的強度や溶融張力が
低いことに等に起因している。すなわち、従来の技術に
よる延伸フィルムの成形技術によったのでは、４−メチ
ル−１−ペンテン系重合体樹脂の延伸温度付近での引張
強度が低いために延伸ムラが生じてしまい、厚み精度が
極端に悪くなるという問題があった。また、ブロー成形
にあっては、溶融張力が低いためにパリソンのドローダ
ウンが大きく成形が困難であるという問題があった。さ
らに、真空成形や真空圧空成形においても、シートを加
熱軟化すると、自重でシートが垂れ下がり、成形が困難
であるという問題があった。2. Description of the Related Art A 4-methyl-1-pentene polymer resin is known as a resin having excellent characteristics such as high heat resistance, releasability and transparency. However, according to the conventional technique, commercially available ordinary 4-methyl-1-
Pentene-based polymer resins do not necessarily have good stretch moldability, and for example, it is possible to produce a stretched film, or to perform blow molding or vacuum forming, as compared with polyethylene or polypropylene, which are the same polyolefins. There was a problem that it was difficult. This is due to the low mechanical strength and melt tension of the 4-methyl-1-pentene polymer resin. That is, according to the conventional technique for forming a stretched film, since the tensile strength of the 4-methyl-1-pentene polymer resin near the stretching temperature is low, stretching unevenness occurs and the thickness accuracy is high. There was a problem that it became extremely bad. Further, in the blow molding, there is a problem that the drawdown of the parison is large and the molding is difficult because the melt tension is low. Further, also in vacuum forming and vacuum pressure forming, there is a problem that when the sheet is heated and softened, the sheet hangs down due to its own weight, which makes forming difficult.
【０００３】このような技術的背景から、従来、市販さ
れている通常の４−メチル−１−ペンテン系重合体樹脂
を、高品質の延伸成形体とすべく、種々の検討が行なわ
れてきた。その具体例としては、例えば、特開昭５８−
１９１７３４号や特開平１０−８１７１０号等を挙げる
ことができる。しかしながら、特開昭５８−１９１７３
４号に開示されている技術によったのでは、固体である
４−メチル−１−ペンテン系重合体樹脂に、液体である
炭化水素油を配合するために、混合作業に困難が伴い、
かつ、該ブレンド物を用いてシートを成形する際に押出
機内ホッパー内でブロッキングを起こしやすくなるとい
う問題があった。また、特開平１０−８１７１０号に開
示されている技術は、厚み変動がない平坦なシートを作
製しようとするものであるが、この技術によったので
は、延伸成形時にシートの中央部から延伸されてしま
い、シート端のクリップ部の方に未延伸部が多く残ると
いう問題があった。上記の従来の技術は、４−メチル−
１−ペンテン系重合体樹脂に、添加剤を加えたり、成形
加工方法に工夫を加えるというものであって、本願発明
のごとく、樹脂そのものを改善しようとするものではな
かった。From such a technical background, various studies have been conducted so far to make a commercially available ordinary 4-methyl-1-pentene polymer resin into a high-quality stretch-molded article. . Specific examples thereof include, for example, JP-A-58-58.
191734 and JP-A-10-81710 can be cited. However, JP-A-58-19173
According to the technique disclosed in No. 4, since a solid 4-methyl-1-pentene polymer resin is blended with a liquid hydrocarbon oil, it is difficult to perform a mixing operation.
In addition, there is a problem that blocking tends to occur in the hopper in the extruder when a sheet is formed using the blend. Further, the technique disclosed in Japanese Patent Laid-Open No. 10-81710 is intended to produce a flat sheet having no variation in thickness. According to this technique, the sheet is stretched from the center of the sheet during stretch forming. As a result, a large amount of unstretched portion remains in the clip portion at the sheet end. The above-mentioned conventional technique uses 4-methyl-
It was to add an additive to the 1-pentene polymer resin or to devise a molding processing method, but not to improve the resin itself as in the present invention.
【０００４】[0004]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、４−メチル−１−ペンテン系重合体樹脂本
来の優れた性質（優れた耐熱性、優れた透明性、優れた
離型性等）を維持しつつ、従来の技術によったのでは、
高品質な（高い厚み精度、優れた表面性状等を有する）
延伸成形体を製造することが困難であった、一般的な成
形加工条件においても、高品質な（高い厚み精度、優れ
た表面性状・外観等を有する）延伸成形体を製造するこ
と可能とする、４−メチル−１−ペンテン系重合体樹脂
組成物を提供することにある。The problem to be solved by the present invention is to provide the excellent properties (excellent heat resistance, excellent transparency, excellent release property) inherent in 4-methyl-1-pentene polymer resin. Characteristics, etc.), while using the conventional technology,
High quality (has high thickness accuracy, excellent surface properties, etc.)
It is possible to manufacture a high-quality stretched molded product (having high thickness accuracy, excellent surface properties and appearance, etc.) even under general molding processing conditions where it was difficult to manufacture a stretched molded product. A 4-methyl-1-pentene polymer resin composition is provided.
【０００５】[0005]
【課題を解決するための手段】従来の技術の欄において
も述べたように、市販されている一般的な４−メチル−
１−ペンテン系重合体樹脂では、必ずしも、延伸成形性
がよいとはいえず、延伸フィルムの製造工程において
は、延伸ムラが生じてしまい、厚み精度が極端に悪くな
ったり、ブロー成形の製造工程においては、溶融張力が
低いためにパリソンのドローダウンが大きく成形が困難
であり、真空成形や真空圧空成形の製造工程において
は、シートを加熱軟化すると、自重でシートが垂れ下が
り、成形が困難であるという問題があった。As described in the section of the prior art, commercially available general 4-methyl-
The 1-pentene polymer resin does not necessarily have good stretch moldability, and in the manufacturing process of the stretched film, unevenness in stretching occurs, resulting in extremely poor thickness accuracy or in the blow molding manufacturing process. In, the drawdown of the parison is large due to the low melt tension, making it difficult to form. In the manufacturing process of vacuum forming or vacuum pressure forming, when the sheet is heated and softened, the sheet hangs down by its own weight, making it difficult to form. There was a problem.
【０００６】本明細書においては、市販されている一般
的な４−メチル−１−ペンテン系重合体樹脂について
は、便宜上、『低分子量４−メチル−１−ペンテン系重
合体樹脂』又は『低分子量樹脂』ということがある。こ
こで、『低（い）分子量』とは、あくまでも相対的なも
のであって、絶対的なものではないが、高いＭＦＲ値
（１０〜５００［ｇ／１０分］）を有することを意味す
る。本明細書においては、市販されている一般的なもの
よりも高分子量の４−メチル−１−ペンテン系重合体樹
脂を、便宜上、『高分子量４−メチル−１−ペンテン系
重合体樹脂』又は『高分子量樹脂』ということがある。
ここで、『高（い）分子量』とは、あくまでも相対的な
ものであって、絶対的なものではないが、低いＭＦＲ値
（０．１〜１０［ｇ／１０分］）を有することを意味す
る。[0006] In the present specification, for convenience, commercially available general 4-methyl-1-pentene polymer resins are referred to as "low molecular weight 4-methyl-1-pentene polymer resin" or "low molecular weight 4-methyl-1-pentene polymer resin". Sometimes called "molecular weight resin". Here, “low molecular weight” means having a high MFR value (10 to 500 [g / 10 min]), although it is a relative one and not an absolute one. . In the present specification, a 4-methyl-1-pentene-based polymer resin having a higher molecular weight than a commercially available general resin is referred to as a "high-molecular-weight 4-methyl-1-pentene-based polymer resin" for convenience. Sometimes called "high molecular weight resin".
Here, “high molecular weight” means that it has a low MFR value (0.1 to 10 [g / 10 min]), although it is a relative value and not an absolute value. means.
【０００７】一方、本発明者らは、４−メチル−１−ペ
ンテン系重合体樹脂の延伸成形性を改良すべく、市販さ
れている一般的なものとは異なる、高分子量の４−メチ
ル−１−ペンテン系重合体樹脂を使用して、その延伸成
形加工特性につき、鋭意検討をした。その結果、４−メ
チル−１−ペンテン系重合体樹脂を高分子量とすること
により、延伸成形性は改良された。しかしながら、延伸
成形性の改良の程度と逆相関して、溶融時の流動性が低
下し、成形品表面に肌荒れが生じ、外観が不良となると
いう知見を見い出した。On the other hand, the inventors of the present invention, in order to improve the stretch moldability of 4-methyl-1-pentene polymer resin, have a high molecular weight of 4-methyl-pentene-polymer which is different from general ones commercially available. The 1-pentene polymer resin was used and earnestly studied on its stretch molding processing characteristics. As a result, the stretch moldability was improved by making the 4-methyl-1-pentene polymer resin have a high molecular weight. However, it has been found that, in inverse correlation with the degree of improvement in stretch moldability, the fluidity during melting decreases, the surface of the molded product becomes rough, and the appearance becomes poor.
【０００８】そこで、本発明者らは、これら従来の技術
における問題点と、本発明者らが見い出した知見に鑑
み、市販されている一般的な４−メチル−１−ペンテン
系重合体樹脂（低分子量４−メチル−１−ペンテン系重
合体樹脂）と、市販されている一般的なものよりも高分
子量の４−メチル−１−ペンテン系重合体樹脂（高分子
量４−メチル−１−ペンテン系重合体樹脂）を特定の配
合条件でブレンドすることにより、低分子量４−メチル
−１−ペンテン系重合体樹脂の優れた溶融流動性と、高
分子量４−メチル−１−ペンテン系重合体樹脂の優れた
溶融張力を併せ有するような、すなわち、相乗効果を発
揮するような、樹脂組成物を製造することができるので
はないかという作業仮説に基づき、種々、鋭意検討を進
めた。鋭意検討の結果、その詳細については後述する
が、この作業仮説は、正しいことが実証され、低分子量
樹脂と高子量樹脂を、特定の配合条件でブレンドするこ
とにより、両者の優れた特性のみを発現し、好ましくな
い特性は低減されるという、一種の相乗効果を見い出し
た。Therefore, in view of the problems in these conventional techniques and the findings found by the present inventors, the present inventors have found that a general commercially available 4-methyl-1-pentene polymer resin ( Low molecular weight 4-methyl-1-pentene polymer resin) and higher molecular weight 4-methyl-1-pentene polymer resin (higher molecular weight 4-methyl-1-pentene) than commercially available general resins Of a low-molecular weight 4-methyl-1-pentene polymer resin and a high-molecular weight 4-methyl-1-pentene polymer resin by blending Based on the working hypothesis that it is possible to produce a resin composition that has a superior melt tension, that is, that exhibits a synergistic effect, various studies have been made. As a result of earnest study, the details will be described later, but this working hypothesis has been proved to be correct, and by blending a low molecular weight resin and a high molecular weight resin under specific compounding conditions, only the excellent characteristics of both are expressed. However, they have found a kind of synergistic effect that undesirable characteristics are reduced.
【０００９】すなわち、本発明者らは、鋭意検討を進め
た結果、成分（Ａ）として、ＭＦＲが０．１〜１０［ｇ
／１０分］の範囲にある４−メチル−１−ペンテン系重
合体樹脂と、成分（Ｂ）として、ＭＦＲが１０〜５００
［ｇ／１０分］の範囲にある４−メチル−１−ペンテン
系重合体樹脂とを含んでなる、４−メチル−１−ペンテ
ン系重合体樹脂組成物であって、成分（Ａ）のＭＦＲを
ＭＦＲA、成分（Ｂ）のＭＦＲをＭＦＲBとしたときに、
ＭＦＲAとＭＦＲBとの関係が、数式（１）〜数式（４）
を同時に満足する関係にあることを特徴とする、４−メ
チル−１−ペンテン系重合体樹脂組成物は、低分子量樹
脂の優れた溶融流動性と、高分子量樹脂の優れた溶融張
力を併せ有するという知見を得て、本発明を完成するに
至った。ここで、ＭＦＲは、ＡＳＴＭ Ｄ１２３８に準
じ、荷重５．０ｋｇ、温度２６０℃の条件で測定したメ
ルトフローレートを意味する。That is, as a result of intensive studies, the present inventors have found that the component (A) has an MFR of 0.1 to 10 [g].
/ 10 min] in the range of 4-methyl-1-pentene polymer resin, and the component (B) has an MFR of 10 to 500.
A 4-methyl-1-pentene-based polymer resin composition comprising a 4-methyl-1-pentene-based polymer resin in the range of [g / 10 minutes], wherein the MFR of component (A) is Is MFR A and the MFR of component (B) is MFR B ,
The relationship between MFR A and MFR B is expressed by Equations (1) to (4).
The 4-methyl-1-pentene-based polymer resin composition is characterized by satisfying at the same time, and has excellent melt flowability of low molecular weight resin and excellent melt tension of high molecular weight resin. Based on the finding, the present invention has been completed. Here, MFR means a melt flow rate measured under a load of 5.0 kg and a temperature of 260 ° C. according to ASTM D1238.
【００１０】[0010]
【数２】 [Equation 2]
【００１１】本発明において、成分（Ａ）のＭＦＲをＭ
ＦＲA、成分（Ｂ）のＭＦＲをＭＦＲBとしたときに、Ｍ
ＦＲAとＭＦＲBとの関係は、数式（１）〜数式（４）を
同時に満足する関係にある。本発明において、通常、
〔ＭＦＲB÷ＭＦＲA〕の数値は、好ましくは数式（９）
で表され、より好ましくは数式（８）で表され、より好
ましくは数式（７）で表され、より好ましくは数式
（６）で表され、より好ましくは数式（５）で表され
る。In the present invention, the MFR of the component (A) is M
When FR A and the MFR of component (B) are MFR B , M
The relationship between FR A and MFR B satisfies the expressions (1) to (4) at the same time. In the present invention,
The value of [MFR B ÷ MFR A ] is preferably the numerical formula (9).
Is more preferably represented by formula (8), more preferably represented by formula (7), more preferably represented by formula (6), and more preferably represented by formula (5).
【００１２】[0012]
【数３】 [Equation 3]
【００１３】本発明において、成分（Ａ）と成分（Ｂ）
の組成比は、成分（Ａ）と成分（Ｂ）の合計重量を基準
として、成分（Ａ）が、１〜９９重量％、成分（Ｂ）
が、１〜９９重量％である。In the present invention, the component (A) and the component (B)
The composition ratio of the component (A) is 1 to 99% by weight based on the total weight of the component (A) and the component (B).
Is 1 to 99% by weight.
【００１４】本発明において、通常、成分（Ａ）と成分
（Ｂ）の組成比が、成分（Ａ）と成分（Ｂ）の合計重量
を基準として、成分（Ａ）が、５０〜９５重量％、成分
（Ｂ）が、５〜５０重量％であることが好ましい。In the present invention, the composition ratio of the component (A) and the component (B) is usually 50 to 95% by weight of the component (A) based on the total weight of the component (A) and the component (B). The component (B) is preferably 5 to 50% by weight.
【００１５】本発明において、通常、成分（Ａ）と成分
（Ｂ）の組成比が、成分（Ａ）と成分（Ｂ）の合計重量
を基準として、成分（Ａ）が、６０〜９５重量％、成分
（Ｂ）が、５〜４０重量％であることがより好ましい。
本発明は、以下の［１］〜［１５］に記載した事項によ
り特定される。In the present invention, the composition ratio of the component (A) and the component (B) is usually 60 to 95% by weight of the component (A) based on the total weight of the component (A) and the component (B). The component (B) is more preferably 5 to 40% by weight.
The present invention is specified by the matters described in [1] to [15] below.
【００１６】［１］ 成分（Ａ）として、ＭＦＲが０．
１〜１０［ｇ／１０分］の範囲にある４−メチル−１−
ペンテン系重合体樹脂と、成分（Ｂ）として、ＭＦＲが
１０〜５００［ｇ／１０分］の範囲にある４−メチル−
１−ペンテン系重合体樹脂とを含んでなる、４−メチル
−１−ペンテン系重合体樹脂組成物であって、成分
（Ａ）のＭＦＲをＭＦＲA、成分（Ｂ）のＭＦＲをＭＦ
ＲBとしたときに、ＭＦＲAとＭＦＲBとの関係が、数式
（１）〜数式（４）を同時に満足する関係であることを
特徴とする、４−メチル−１−ペンテン系重合体樹脂組
成物（但し、ＭＦＲは、ＡＳＴＭ Ｄ１２３８に準じ、
荷重５．０ｋｇ、温度２６０℃の条件で測定したメルト
フローレートを意味する。）。[1] As the component (A), the MFR is 0.
4-methyl-1- in the range of 1 to 10 [g / 10 min]
Pentene-based polymer resin and 4-methyl-, as component (B), having an MFR in the range of 10 to 500 [g / 10 min].
A 4-methyl-1-pentene polymer resin composition comprising 1-pentene polymer resin, wherein MFR of component (A) is MFR A and MFR of component (B) is MF
When R B , the relationship between MFR A and MFR B is a relationship that simultaneously satisfies formulas (1) to (4), a 4-methyl-1-pentene-based polymer resin Composition (However, MFR is in accordance with ASTM D1238,
It means a melt flow rate measured under the conditions of a load of 5.0 kg and a temperature of 260 ° C. ).
【数４】 [Equation 4]
【００１７】［２］ 成分（Ａ）と成分（Ｂ）の組成比
が、成分（Ａ）と成分（Ｂ）の合計重量を基準として、
成分（Ａ）が、１〜９９重量％、成分（Ｂ）が、１〜９
９重量％であることを特徴とする、［１］に記載した、
４−メチル−１−ペンテン系重合体樹脂組成物。[2] The composition ratio of the component (A) and the component (B) is based on the total weight of the component (A) and the component (B).
Component (A) is 1 to 99% by weight, component (B) is 1 to 9
9% by weight, as described in [1],
4-Methyl-1-pentene polymer resin composition.
【００１８】［３］ 成分（Ａ）と成分（Ｂ）の組成比
が、成分（Ａ）と成分（Ｂ）の合計重量を基準として、
成分（Ａ）が、５０〜９５重量％、成分（Ｂ）が、５〜
５０重量％であることを特徴とする、［１］に記載し
た、４−メチル−１−ペンテン系重合体樹脂組成物。[3] The composition ratio of the component (A) and the component (B) is based on the total weight of the component (A) and the component (B).
Component (A) is 50 to 95% by weight, and component (B) is 5 to 95% by weight.
50% by weight of the 4-methyl-1-pentene polymer resin composition described in [1].
【００１９】［４］ ［１］乃至［３］の何れかに記載
した、４−メチル−１−ペンテン系重合体樹脂組成物を
含んで構成される、延伸成形体。[4] A stretched molded article containing the 4-methyl-1-pentene polymer resin composition described in any one of [1] to [3].
【００２０】［５］ 延伸成形体が、一軸延伸フィル
ム、二軸延伸フィルム、インフレーションフィルム、中
空成形体、射出ブロー成形体、真空成形体、及び、真空
圧空成形体からなる群から選択された何れか一つである
ことを特徴とする、［４］に記載した延伸成形体。[5] Any stretch-molded article is selected from the group consisting of a uniaxially-stretched film, a biaxially-stretched film, an inflation film, a hollow-molded article, an injection blow-molded article, a vacuum-molded article and a vacuum-pneumatic article. The stretched molded article according to [4], characterized in that it is only one.
【００２１】［４］ ［１］乃至［３］ 請求項１乃至
３の何れかに記載した、４−メチル−１−ペンテン系重
合体樹脂組成物を、一軸延伸フィルム成形法、二軸延伸
フィルム成形法、インフレーションフィルム成形法、中
空成形法、射出ブロー成形法、真空成形法、及び、真空
圧空成形法からなる群から選択された何れか一つの延伸
成形方法で成形加工することを特徴とする、延伸成形体
の製造方法。[4] [1] to [3] The 4-methyl-1-pentene polymer resin composition according to any one of claims 1 to 3 is produced by a uniaxially stretched film forming method or a biaxially stretched film. It is characterized in that it is molded by any one stretch-molding method selected from the group consisting of a molding method, an inflation film molding method, a hollow molding method, an injection blow molding method, a vacuum molding method, and a vacuum pressure molding method. And a method for producing a stretch-molded body.
【００２２】［５］ ［１］乃至［３］の何れかに記載
した４−メチル−１−ペンテン系重合体樹脂組成物を含
んで構成される、離型フィルム。[5] A release film comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００２３】［６］ ［１］乃至［３］の何れかに記載
した４−メチル−１−ペンテン系重合体樹脂組成物を含
んで構成される、離型紙。[6] A release paper comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００２４】［７］ ［１］乃至［３］の何れかに記載
した４−メチル−１−ペンテン系重合体樹脂組成物を含
んで構成される、容器。[7] A container comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００２５】［８］ ［１］乃至［３］の何れかに記載
した４−メチル−１−ペンテン系重合体樹脂組成物を含
んで構成される、哺乳ビン。[8] A baby bottle comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００２６】［９］ ［１］乃至［３］の何れかに記載
した４−メチル−１−ペンテン系重合体樹脂組成物を含
んで構成される、農薬容器。[9] A pesticide container comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００２７】［１０］ ［１］乃至［３］の何れかに記
載した４−メチル−１−ペンテン系重合体樹脂組成物を
含んで構成される、実験器具。[10] A laboratory instrument comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００２８】［１１］ ［１］乃至［３］の何れかに記
載した４−メチル−１−ペンテン系重合体樹脂組成物を
含んで構成される、医療用容器。[11] A medical container comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００２９】［１２］ ［１］乃至［３］の何れかに記
載した４−メチル−１−ペンテン系重合体樹脂組成物を
含んで構成される、化粧品容器。[12] A cosmetic container comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００３０】［１３］ ［１］乃至［３］の何れかに記
載した４−メチル−１−ペンテン系重合体樹脂組成物を
含んで構成される、洗剤容器。[13] A detergent container containing the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００３１】［１４］ ［１］乃至［３］の何れかに記
載した４−メチル−１−ペンテン系重合体樹脂組成物を
含んで構成される、食品容器。[14] A food container containing the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【００３２】［１５］ ［１］乃至［３］の何れかに記
載した４−メチル−１−ペンテン系重合体樹脂組成物を
含んで構成される、接着剤容器。[15] An adhesive container comprising the 4-methyl-1-pentene polymer resin composition described in any of [1] to [3].
【発明の実施の形態】本発明は、成分（Ａ）として、Ｍ
ＦＲが０．１〜１０［ｇ／１０分］の範囲にある４−メ
チル−１−ペンテン系重合体樹脂と、成分（Ｂ）とし
て、ＭＦＲが１０〜５００［ｇ／１０分］の範囲にある
４−メチル−１−ペンテン系重合体樹脂とを含んでな
る、４−メチル−１−ペンテン系重合体樹脂組成物であ
って、成分（Ａ）のＭＦＲをＭＦＲA、成分（Ｂ）のＭ
ＦＲをＭＦＲBとしたときに、ＭＦＲ AとＭＦＲBとの関
係が、数式（１）〜数式（４）を同時に満足する関係に
あることを特徴とする、優れた溶融流動性と、優れた溶
融張力を併せ有する、４−メチル−１−ペンテン系重合
体樹脂組成物である。ここで、ＭＦＲは、ＡＳＴＭ Ｄ
１２３８に準じ、荷重５．０ｋｇ、温度２６０℃の条件
で測定したメルトフローレートを意味する。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, M is used as the component (A).
4-Me with FR in the range of 0.1-10 [g / 10 min]
Chill-1-pentene polymer resin and component (B)
And the MFR is in the range of 10 to 500 [g / 10 minutes]
4-methyl-1-pentene polymer resin
A 4-methyl-1-pentene polymer resin composition
Then, change the MFR of component (A) to MFRA, Component (B) M
FR to MFRBAnd then MFR AAnd MFRBSeki
The relations in which the clerk simultaneously satisfies the formulas (1) to (4)
Excellent melt flowability and excellent melting
4-methyl-1-pentene-based polymerization that also has melt tension
It is a body resin composition. Where MFR is ASTM D
According to 1238, load 5.0 kg, temperature 260 ℃ conditions
Means the melt flow rate measured in.
【数５】 [Equation 5]
【００３３】以下、本発明に係る４−メチル−１−ペン
テン系重合体組成物について説明する。本発明の４−メ
チル−１−ペンテン系重合体樹脂とは、４−メチルペン
テン−１と他のα−オレフィン、例えば、エチレン、プ
ロピレン、１−ブテン、１−ヘキセン、１−ヘプテン、
１−オクテン、１−デセン、１−テトラデセン、１−ヘ
キサデセン、１−ヘプタデセン、１−オクタデセン、エ
イコセン等の炭素数２乃至２０のα−オレフィンとの共
重合体樹脂である。本発明では、該α−オレフィンとし
ては、この中でも炭素数７〜２０のα−オレフィンが好
ましく、特に炭素数１０〜２０のα−オレフィンが好ま
しい。本発明において使用される４−メチルペンテン−
１系重合体樹脂における上記α−オレフィン由来構造単
位の含有量は、通常０〜２０重量％以下、好ましくは１
〜１０重量％である。The 4-methyl-1-pentene polymer composition according to the present invention will be described below. The 4-methyl-1-pentene polymer resin of the present invention means 4-methylpentene-1 and other α-olefins, for example, ethylene, propylene, 1-butene, 1-hexene, 1-heptene,
It is a copolymer resin with an α-olefin having 2 to 20 carbon atoms such as 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene and eicosene. In the present invention, the α-olefin is preferably an α-olefin having 7 to 20 carbon atoms, and particularly preferably an α-olefin having 10 to 20 carbon atoms. 4-methylpentene used in the present invention
The content of the α-olefin-derived structural unit in the 1-based polymer resin is usually 0 to 20% by weight or less, preferably 1
10 to 10% by weight.
【００３４】本発明において使用される４−メチル−１
−ペンテン系重合体樹脂は、高温ＧＰＣ（ゲル・パーミ
エーション・クロマトグラフィー）試験法により測定さ
れる重量平均分子量（Ｍｗ）が１０万〜５００万のもの
が用いられる。また、ＤＳＣ（示差走査型熱量計）試験
に基づいて測定される融点（Ｔｍ）は、２００〜２５０
℃、好ましくは２２０〜２４０℃のものが用いられる。
さらに、ＡＳＴＭ Ｄ１２３８に準じた荷重５ｋｇ、温
度２６０℃の条件により測定されるＭＦＲ（メルトフロ
ーレート）は０．０５〜５００［ｇ／１０分］である。
その中で、ＭＦＲが０．１〜１０［ｇ／１０分］のもの
が延伸成形性やブロー成形性に好適な高分子量の成分と
なり、ＭＦＲが１０〜５００［ｇ／１０分］のものが流
動性を改良する成分として好ましい。4-methyl-1 used in the present invention
The pentene polymer resin having a weight average molecular weight (Mw) of 100,000 to 5,000,000 measured by a high temperature GPC (gel permeation chromatography) test method is used. Further, the melting point (Tm) measured based on the DSC (Differential Scanning Calorimeter) test is 200 to 250.
C., preferably 220 to 240.degree. C. is used.
Furthermore, the MFR (melt flow rate) measured under a load of 5 kg according to ASTM D1238 and a temperature of 260 ° C. is 0.05 to 500 [g / 10 min].
Among them, those having an MFR of 0.1 to 10 [g / 10 min] are high molecular weight components suitable for stretch moldability and blow moldability, and those having an MFR of 10 to 500 [g / 10 min]. Preferred as a component for improving fluidity.
【００３５】また、本発明において使用される４−メチ
ル−１−ペンテン系重合体樹脂には、本発明の目的を損
わない範囲で、好ましくは全体の１０重量％以下の可塑
剤を含有していてもよい。可塑剤としてはパラフィン
系、ナフテン系、アロマ系等の鉱油類、α−オレフィン
類のオリゴマー、コオリゴマー、エステル系可塑剤、各
種植物油、動物油等を挙げることができる。そのような
可塑剤は延伸成形性をより良くするが、１０％以上含有
すると、４−メチル−１−ペンテン系重合体樹脂の優れ
た特徴である透明性や離型性等が損われる虞がある。The 4-methyl-1-pentene polymer resin used in the present invention preferably contains 10% by weight or less of the total amount of the plasticizer as long as the object of the present invention is not impaired. May be. Examples of the plasticizer include paraffin-based, naphthene-based, aroma-based mineral oils, oligomers of α-olefins, cooligomers, ester-based plasticizers, various vegetable oils, animal oils and the like. Such a plasticizer improves the stretch moldability, but if it is contained in an amount of 10% or more, the transparency and releasability, which are excellent features of the 4-methyl-1-pentene polymer resin, may be impaired. is there.
【００３６】本発明の４−メチル−１−ペンテン系重合
体樹脂には、他の樹脂、例えば、ポリオレフィン類、ポ
リアミド類、ポリエステル類等を全体の３０重量％以下
の割合で含有していても良い。ポリオレフィン類につい
て具体的には、エチレン・プロピレン共重合体、エチレ
ン・ブテン共重合体、エチレン・オクテン共重合体、プ
ロピレン・ブテン共重合体、ブテン系重合体等である。The 4-methyl-1-pentene polymer resin of the present invention may contain other resins such as polyolefins, polyamides and polyesters in an amount of 30% by weight or less based on the total weight. good. Specific examples of the polyolefins include ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / octene copolymers, propylene / butene copolymers, butene-based polymers and the like.
【００３７】本発明の４−メチル−１−ペンテン系重合
体樹脂には、耐熱安定剤、耐候性安定剤、滑剤、核剤、
顔料、染料等、通常、ポリオレフィンに添加して使用さ
れる各種添加剤を本発明の目的を損わない範囲で添加し
てもよい。特に、滑剤は、流動性が改良され、成形品外
観がよくなるので好ましい。The 4-methyl-1-pentene polymer resin of the present invention includes a heat resistance stabilizer, a weather resistance stabilizer, a lubricant, a nucleating agent,
Various additives such as pigments and dyes which are usually used by adding to polyolefin may be added within a range not impairing the object of the present invention. In particular, the lubricant is preferable because the fluidity is improved and the appearance of the molded product is improved.
【００３８】本発明に係る樹脂組成物の製造は、特に限
定されず、ドライブレンドまたは溶融ブレンドのいずれ
の方法にしたがって行なってもよい。例えば、前記樹脂
組成物を構成する成分（Ａ）及び成分（Ｂ）の各成分、
並びに、必要に応じて添加される添加剤を、それぞれ、
所定の割合で別個に押出機に供給し、あるいは、予め各
成分を混合し、押出機に供給して、溶融、混錬して樹脂
組成物を調整することができる。また、引き続き、Ｔ−
ダイ、チューブダイ等の適当な成形用ダイから押出して
フィルムを成形したり、中空成形、射出成形に供するこ
とができる。押出機または射出成形機によって成形する
場合、成形時の加熱温度は、通常、２４０〜３２０℃程
度である。The production of the resin composition according to the present invention is not particularly limited, and may be carried out by either dry blending or melt blending. For example, each component of the component (A) and the component (B) constituting the resin composition,
Also, the additives added as necessary, respectively,
The resin composition can be prepared by separately supplying the components at a predetermined ratio to the extruder, or by mixing the respective components in advance and supplying the components to the extruder to melt and knead the components. In addition, T-
It can be extruded from an appropriate molding die such as a die or a tube die to form a film, or can be subjected to blow molding or injection molding. When molding with an extruder or an injection molding machine, the heating temperature during molding is usually about 240 to 320 ° C.
【００３９】本発明に係る樹脂組成物は、耐熱性、離型
性、透明性に優れる。かつ、従来知られている樹脂組成
物やシートよりも延伸成形性に優れるともに、さらには
高分子量の４−メチル−１−ペンテン系重合体樹脂より
も、外観の良好な延伸成形体を得られる樹脂組成物であ
る。また、本発明に係る樹脂組成物は、一軸延伸フィル
ム成形、二軸延伸フィルム成形、インフレーションフィ
ルム成形、中空成形、射出ブロー成形、真空成形、真空
圧空成形等することによって得られる離型フィルム、離
型紙、哺乳ビン、農薬容器、実験器具、医療用容器、化
粧品容器、洗剤容器、食品容器、接着剤容器である延伸
成形体やフィルム成形品、押出ラミネート成形品、射出
成形品、より具体的には、食品包装フィルム、鮮度保持
包材、ラップフィルム、離型フィルム、合皮用離型紙、
食品容器、実験器具、医療用容器、化粧品容器、洗剤容
器、食品容器、接着剤容器に好適である。The resin composition according to the present invention is excellent in heat resistance, releasability and transparency. In addition, the stretch-molded product is superior in stretch moldability to a conventionally known resin composition or sheet, and further, a stretch-molded product having a good appearance can be obtained as compared with a high molecular weight 4-methyl-1-pentene polymer resin. It is a resin composition. Further, the resin composition according to the present invention is a release film obtained by uniaxially stretched film molding, biaxially stretched film molding, inflation film molding, hollow molding, injection blow molding, vacuum molding, vacuum pressure molding, etc. Patterns, baby bottles, pesticide containers, laboratory equipment, medical containers, cosmetics containers, detergent containers, food containers, stretch containers and film molded products that are adhesive containers, extrusion laminated molded products, injection molded products, and more specifically Is food packaging film, freshness-keeping packaging material, wrap film, release film, release paper for synthetic leather,
It is suitable for food containers, laboratory equipment, medical containers, cosmetic containers, detergent containers, food containers, and adhesive containers.
【００４０】[0040]
【実施例】本発明の４−メチル−１−ペンテン系重合体
樹脂の樹脂組成物について、下記の例により具体的に説
明するが、本発明は下記の例に何ら限定されるものでは
ない。EXAMPLES The resin composition of the 4-methyl-1-pentene-based polymer resin of the present invention will be specifically described by the following examples, but the present invention is not limited to the following examples.
【００４１】 ＭＦＲ
ＡＳＴＭ Ｄ１２３８に準拠して荷重５ｋｇ、温度２６
０℃の条件で測定した。According to MFR ASTM D1238, load 5 kg, temperature 26
The measurement was performed at 0 ° C.
【００４２】 メルトテンション
ＡＳＴＭ Ｄ３８３５に準じてノズル直径２．０９５ｍ
ｍ、ランド長８ｍｍのノズルより樹脂を押出し、温度３
１０℃、引き取り速度１５ｍ／分の条件にて測定した。
メルトテンションの測定値をブロー成形時のドローダウ
ン性の指標とした。メルトテンション（［ｍＮ］）が大
きいほど、ドローダウンが小さくなりブロー成形しやす
い。 Melt tension : Nozzle diameter of 2.095 m according to ASTM D3835
m, the resin is extruded from a nozzle with a land length of 8 mm, and the temperature is 3
The measurement was performed under the conditions of 10 ° C. and a take-up speed of 15 m / min.
The measured value of melt tension was used as an index of drawdown property during blow molding. The larger the melt tension ([mN]), the smaller the drawdown and the easier the blow molding.
【００４３】 ＨＡＺＥ ＡＳＴＭ Ｄ１００３に準じて、測定した。It was measured according to HASE ASTM D1003.
【００４４】 ブロー成形性
プラコー（株）製ダイレクトブロー成形機（φ６５押出
機）により、１ｍｍ厚の４００ｃｃボトル容器を成形
し、本成形時のドローダウン性にて評価した。
○：ドローダウンが小さく容易にブロー成形できる。
×：ドローダウンが大きくブロー成形が困難である。厚
肉成形不可。 Blow Moldability A direct blow molding machine (φ65 extruder) manufactured by Placo Co., Ltd. was used to mold a 400 mm bottle container having a thickness of 1 mm, and the drawdown property during the main molding was evaluated. ◯: The drawdown is small and blow molding is easy. X: The drawdown is large and blow molding is difficult. Thick molding is not possible.
【００４５】 成形条件 成形条件は以下である。 φ６５押出機シリンダーおよびダイ温度： Ｃ１／Ｃ２／Ｃ３／ＡＤ／Ｄ ３１０℃／３１０℃／３１０℃／３２０℃／３２０℃ Molding Conditions Molding conditions are as follows. φ65 extruder cylinder and die temperature: C1 / C2 / C3 / AD / D 310 ° C / 310 ° C / 310 ° C / 320 ° C / 320 ° C
【００４６】 成形品外観
上記成形条件で４００ｃｃブロー容器を試作して、成形
品の表面平滑性を以下のように評価した。表面平滑性を
表す指標として、ＭＦＲおよびＨＡＺＥを用いた。 Appearance of Molded Article A 400 cc blow container was prototyped under the above-mentioned molding conditions, and the surface smoothness of the molded article was evaluated as follows. MFR and HAZE were used as an index showing surface smoothness.
【００４７】［ＭＦＲ］ＭＦＲは、樹脂組成物を成形加
工品としたときの、表面平滑性の指標の一つである。Ｍ
ＦＲが大きいほど流動性が良好であるため、表面の平滑
性が増す。 [MFR] MFR is one of the indexes of the surface smoothness when the resin composition is used as a molded product. M
The larger the FR, the better the fluidity, and thus the smoothness of the surface increases.
【００４８】［ＨＡＺＥ］ＨＡＺＥは、樹脂組成物を成
形加工品としたときの、表面平滑性の指標の一つであ
る。表面が平滑であると、表面での光の反射（拡散や乱
反射）が少なくなるため、ＨＡＺＥは小さくなる。
○：成形品表面が滑らかであり、容器が透き通ってい
る。
×：成形品表面がざらついており、容器が白く曇ってい
る。 [HAZE] HAZE is one of the indexes of the surface smoothness when the resin composition is used as a molded product. If the surface is smooth, the reflection of light (diffusion or irregular reflection) on the surface decreases, so that the HAZE becomes small. ◯: The surface of the molded product is smooth and the container is transparent. X: The surface of the molded product is rough, and the container is white and cloudy.
【００４９】［実施例１］ 樹脂組成物の調製
成分（Ａ）として、ＭＦＲ＝０．１［ｇ／１０分］の４
−メチル−１−ペンテン・１−ヘキサデセン共重合体樹
脂粉末（１−ヘキサデセン含有量：６．０重量％、粉末
の粒子直径約２００μｍ）８０重量部と、成分（Ｂ）と
して、ＭＦＲ＝１００［ｇ／１０分］の４−メチル−１
−ペンテン・１−ヘキサデセン共重合体樹脂粉末（１−
ヘキサデセン含有量：６．０重量％、粉末の粒子直径約
３ｍｍ）２０重量部の比率で配合し（ＭＦＲB／ＭＦＲA
＝１０００）、さらに、この成分（Ａ）と成分（Ｂ）か
らなる樹脂組成物１００重量部に対して、造粒時の熱分
解を抑制する目的で耐熱安定剤であるヒンダードフェノ
ール系化合物のテトラキス〔メチレン−３（３，５−ジ
−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピ
オネート〕メタン（チバガイギー（株）製、商品名：イ
ルガノックス１０１０）０．１０重量部、フェノールア
クリレート系化合物の２−［１−（２−ヒドロキシ−
３，−５−ジ−ｔｅｒｔ−ペンチルフェニル）エチル］
−４，６−ジ−ｔｅｒｔ−ペンチルフェニルアクリレー
ト（住友化学（株）製、商品名：スミライザーＧｓ
（Ｆ））０．１０重量部、トリス（２，４−ジ−ｔｅｒ
ｔ−ブチルフェニル）ホスファイト（チバガイギー
（株）製、商品名：イルガフォス１６８）０．１０重量
部の比率で配合し、ヘンシェルミキサーを用いて高速で
１分間混合した。 樹脂組成物の評価
得られた樹脂組成物を二軸押出機で３００℃溶融混練
し、押出成形してペレットを得た。このペレットにてＭ
ＦＲの測定、メルトテンションの測定、ブロー成形性の
評価、成形品外観の評価を行なった。結果を表−１に示
す。 Example 1 Preparation of Resin Composition As the component (A), 4 of MFR = 0.1 [g / 10 min]
-Methyl-1-pentene / 1-hexadecene copolymer resin powder (1-hexadecene content: 6.0% by weight, particle diameter of powder: about 200 μm) 80 parts by weight, and as component (B), MFR = 100 [ g / 10 min] 4-methyl-1
-Pentene / 1-hexadecene copolymer resin powder (1-
Hexadecene content: 6.0% by weight, powder particle diameter of about 3 mm) and blended at a ratio of 20 parts by weight (MFR B / MFR A
= 1000), and further, for 100 parts by weight of the resin composition comprising the component (A) and the component (B), a hindered phenol-based compound that is a heat-resistant stabilizer for the purpose of suppressing thermal decomposition during granulation. Tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (manufactured by Ciba-Geigy Co., Ltd., trade name: Irganox 1010) 0.10 parts by weight, 2 of phenol acrylate compound -[1- (2-hydroxy-
3, -5-Di-tert-pentylphenyl) ethyl]
-4,6-Di-tert-pentylphenyl acrylate (Sumitomo Chemical Co., Ltd., trade name: Sumilizer Gs
(F)) 0.10 parts by weight, tris (2,4-di-ter)
t-Butylphenyl) phosphite (manufactured by Ciba-Geigy Co., Ltd., trade name: Irgafos 168) was mixed at a ratio of 0.10 parts by weight and mixed at a high speed for 1 minute using a Henschel mixer. Evaluation of Resin Composition The obtained resin composition was melt-kneaded at 300 ° C. with a twin-screw extruder and extrusion-molded to obtain pellets. M in this pellet
The FR was measured, the melt tension was measured, the blow moldability was evaluated, and the appearance of the molded product was evaluated. The results are shown in Table-1.
【００５０】［実施例２］ 樹脂組成物の調製
成分（Ａ）として、ＭＦＲ＝０．１［ｇ／１０分］の４
−メチル−１−ペンテン・１−ヘキサデセン共重合体樹
脂粉末（１−ヘキサデセン含有量：６．０重量％、粉末
の粒子直径約２００μｍ）７０重量部と、成分（Ｂ）と
して、ＭＦＲ＝１００［ｇ／１０分］の４−メチル−１
−ペンテン・１−ヘキサデセン共重合体樹脂粉末（１−
ヘキサデセン含有量：６．０重量％、粉末の粒子直径約
３ｍｍ）３０重量部の比率で配合し（ＭＦＲB／ＭＦＲA
＝１０００）、さらに、実施例１と全く同様に、耐熱安
定剤を配合し、実施例１と全く同様に、樹脂組成物を調
製した。 樹脂組成物の評価
実施例１と全く同様に評価を行なった。結果を表−１に
示す。 Example 2 Preparation of Resin Composition As the component (A), 4 of MFR = 0.1 [g / 10 min] was used.
70 parts by weight of -methyl-1-pentene / 1-hexadecene copolymer resin powder (1-hexadecene content: 6.0% by weight, particle diameter of the powder is about 200 μm) and MFR = 100 [ g / 10 min] 4-methyl-1
-Pentene / 1-hexadecene copolymer resin powder (1-
Hexadecene content: 6.0% by weight, powder particle diameter of about 3 mm, blended in a ratio of 30 parts by weight (MFR B / MFR A
= 1000), and in the same manner as in Example 1, a heat-resistant stabilizer was added, and a resin composition was prepared in exactly the same manner as in Example 1. Evaluation of Resin Composition Evaluation was performed in exactly the same manner as in Example 1. The results are shown in Table-1.
【００５１】［実施例３］ 樹脂組成物の調製
成分（Ａ）として、ＭＦＲ＝１［ｇ／１０分］の４−メ
チル−１−ペンテン・１−ヘキサデセン共重合体樹脂粉
末（１−ヘキサデセン含有量：６．０重量％、粉末の粒
子直径約２００μｍ）８０重量部と、成分（Ｂ）とし
て、ＭＦＲ＝２５［ｇ／１０分］の４−メチル−１−ペ
ンテン・１−ヘキサデセン共重合体粉末（１−ヘキサデ
セン含有量：６．０重量％、粉末の粒子直径約３ｍｍ）
２０重量部の比率で配合し（ＭＦＲB／ＭＦＲA＝２
５）、さらに、実施例１と全く同様に、耐熱安定剤を配
合し、実施例１と全く同様に、樹脂組成物を調製した。 樹脂組成物の評価
実施例１と全く同様に評価を行なった。結果を表−１に
示す。 Example 3 As a component (A) for preparing a resin composition , 4-methyl-1-pentene / 1-hexadecene copolymer resin powder (containing 1-hexadecene) having MFR = 1 [g / 10 min] Amount: 6.0% by weight, 80 parts by weight of powder particle diameter (about 200 μm), and 4-methyl-1-pentene / 1-hexadecene copolymer having MFR = 25 [g / 10 min] as the component (B). Powder (1-hexadecene content: 6.0% by weight, particle diameter of powder is about 3 mm)
Blended in a ratio of 20 parts by weight (MFR B / MFR A = 2
5) Furthermore, a heat stabilizer was added in exactly the same manner as in Example 1, and a resin composition was prepared in exactly the same manner as in Example 1. Evaluation of Resin Composition Evaluation was performed in exactly the same manner as in Example 1. The results are shown in Table-1.
【００５２】［実施例４］ 樹脂組成物の調製
成分（Ａ）として、ＭＦＲ＝５［ｇ／１０分］の４−メ
チル−１−ペンテン・１−ヘキサデセン共重合体樹脂粉
末（１−ヘキサデセン含有量：６．０重量％、粉末の粒
子直径約２００μｍ）８０重量部と、成分（Ｂ）とし
て、ＭＦＲ＝２５［ｇ／１０分］の４−メチル−１−ペ
ンテン・１−ヘキサデセン共重合体粉末（１−ヘキサデ
セン含有量：６．０重量％、粉末の粒子直径約３ｍｍ）
２０重量部の比率で配合し（ＭＦＲB／ＭＦＲA＝５）、
さらに、実施例１と全く同様に、耐熱安定剤を配合し、
実施例１と全く同様に、樹脂組成物を調製した。 樹脂組成物の評価
実施例１と全く同様に評価を行なった。結果を表−１に
示す。 Example 4 As a component (A) for preparing a resin composition , 4-methyl-1-pentene / 1-hexadecene copolymer resin powder (containing 1-hexadecene) having MFR = 5 [g / 10 min] Amount: 6.0% by weight, 80 parts by weight of powder particle diameter (about 200 μm), and 4-methyl-1-pentene / 1-hexadecene copolymer having MFR = 25 [g / 10 min] as the component (B). Powder (1-hexadecene content: 6.0% by weight, particle diameter of powder is about 3 mm)
Blended in a ratio of 20 parts by weight (MFR B / MFR A = 5),
Furthermore, in the same manner as in Example 1, a heat stabilizer was blended,
A resin composition was prepared in exactly the same manner as in Example 1. Evaluation of Resin Composition Evaluation was performed in exactly the same manner as in Example 1. The results are shown in Table-1.
【００５３】［比較例１］ 樹脂組成物の調製
成分（Ａ）として、４−メチル−１−ペンテン系重合体
樹脂１００重量部に対し、熱分解を抑制する目的で耐熱
安定剤であるヒンダードフェノール系化合物のテトラキ
ス〔メチレン−３（３，５−ジ−ｔｅｒｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート〕メタン（チバ
ガイギー（株）製、商品名：イルガノックス１０１０）
０．１０重量部、フェノールアクリレート系化合物の２
−［１−（２−ヒドロキシ−３，−５−ジ−ｔｅｒｔ−
ペンチルフェニル）エチル］−４，６−ジ−ｔｅｒｔ−
ペンチルフェニルアクリレート（住友化学（株）製、商
品名：スミライザーＧｓ（Ｆ））０．１０重量部、トリ
ス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファ
イト（チバガイギー（株）製、商品名：イルガフォス１
６８）０．１０重量部の比率で配合したＭＦＲ＝１［ｇ
／１０分］の４−メチル−１−ペンテン・１−ヘキサデ
セン共重合体樹脂粉末（１−ヘキサデセン含有量：６．
０重量％、粉末の粒子直径約３ｍｍ）を配合し、樹脂組
成物を調製した。 樹脂組成物の評価
実施例１と全く同様に評価を行なった。結果を表−１に
示す。 Comparative Example 1 As a component (A) for preparing a resin composition, 100 parts by weight of a 4-methyl-1-pentene polymer resin was used as a heat-resistant stabilizer for the purpose of suppressing thermal decomposition. Phenol compound tetrakis [methylene-3 (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionate] methane (manufactured by Ciba-Geigy Co., Ltd., trade name: Irganox 1010)
0.10 parts by weight of phenol acrylate compound 2
-[1- (2-hydroxy-3, -5-di-tert-
Pentylphenyl) ethyl] -4,6-di-tert-
Pentyl phenyl acrylate (Sumitomo Chemical Co., Ltd., trade name: Sumilizer Gs (F)) 0.10 parts by weight, tris (2,4-di-tert-butylphenyl) phosphite (Ciba Geigy Co., Ltd., trade name : Irgafoss 1
68) MFR mixed at a ratio of 0.10 parts by weight = 1 [g
/ 10 min] 4-methyl-1-pentene / 1-hexadecene copolymer resin powder (1-hexadecene content: 6.
0% by weight and powder particle diameter of about 3 mm) were mixed to prepare a resin composition. Evaluation of Resin Composition Evaluation was performed in exactly the same manner as in Example 1. The results are shown in Table-1.
【００５４】［比較例２］ 樹脂組成物の調製
成分（Ａ）として、ＭＦＲ＝５［ｇ／１０分］の４−メ
チル−１−ペンテン・１−ヘキサデセン共重合体樹脂粉
末（１−ヘキサデセン含有量：６．０重量％、粉末の粒
子直径約２００μｍ）８０重量部と、成分（Ｂ）とし
て、ＭＦＲ＝１０［ｇ／１０分］の４−メチル−１−ペ
ンテン・１−ヘキサデセン共重合体樹脂粉末（１−ヘキ
サデセン含有量：６．０重量％、粉末の粒子直径約３ｍ
ｍ）２０重量部の比率で配合し（ＭＦＲB／ＭＦＲA＝
２）、さらに、実施例１と全く同様に、耐熱安定剤を配
合し、実施例１と全く同様に、樹脂組成物を調製した。 樹脂組成物の評価
実施例１と全く同様に評価を行なった。結果を表−１に
示す。 Comparative Example 2 As a component (A) for preparing a resin composition , 4-methyl-1-pentene / 1-hexadecene copolymer resin powder (containing 1-hexadecene) having MFR = 5 [g / 10 min] Amount: 6.0 wt%, 80 parts by weight of powder particle diameter (about 200 μm), and 4-methyl-1-pentene / 1-hexadecene copolymer with MFR = 10 [g / 10 min] as component (B) Resin powder (1-hexadecene content: 6.0% by weight, powder particle diameter about 3 m
m) compounded at a ratio of 20 parts by weight (MFR B / MFR A =
2) Furthermore, a heat stabilizer was blended in the same manner as in Example 1 to prepare a resin composition in the same manner as in Example 1. Evaluation of Resin Composition Evaluation was performed in exactly the same manner as in Example 1. The results are shown in Table-1.
【００５５】［比較例３］ 樹脂組成物の調製
成分（Ｂ）として、４−メチル−１−ペンテン系重合体
樹脂１００重量部に対し、熱分解を抑制する目的で耐熱
安定剤であるヒンダードフェノール系化合物のテトラキ
ス〔メチレン−３（３，５−ジ−ｔｅｒｔ−ブチル−４
−ヒドロキシフェニル）プロピオネート〕メタン（チバ
ガイギー（株）製、商品名：イルガノックス１０１０）
０．２５重量部、ペンタエリスリトール−テトラキス−
（３−ドデシルチオプロピオネート）（シプロ化成
（株）製、商品名：シーノックス４１２Ｓ）０．５０重
量部の比率で配合したＭＦＲ＝２５［ｇ／１０分］の４
−メチル−１−ペンテン・１−ヘキサデセン共重合体樹
脂粉末（１−ヘキサデセン含有量：６．０重量％、粉末
の粒子直径約３ｍｍ）を配合し、樹脂組成物を調製し
た。 樹脂組成物の評価
実施例１と全く同様に評価を行なった。結果を表−１に
示す。 [Comparative Example 3] As a component (B) for preparing a resin composition, 100 parts by weight of a 4-methyl-1-pentene polymer resin was used as a heat stabilizer for the purpose of suppressing thermal decomposition. Phenol compound tetrakis [methylene-3 (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionate] methane (manufactured by Ciba-Geigy Co., Ltd., trade name: Irganox 1010)
0.25 part by weight, pentaerythritol-tetrakis-
(3-dodecylthiopropionate) (manufactured by Cypro Kasei Co., Ltd., trade name: Seanox 412S), MFR = 25 [g / 10 min] 4 blended at a ratio of 0.50 part by weight.
-Methyl-1-pentene / 1-hexadecene copolymer resin powder (1-hexadecene content: 6.0% by weight, particle diameter of powder of about 3 mm) was mixed to prepare a resin composition. Evaluation of Resin Composition Evaluation was performed in exactly the same manner as in Example 1. The results are shown in Table-1.
【００５６】[0056]
【表−１】 [Table-1]
【００５７】[0057]
【発明の効果】本発明の効果は、４−メチル−１−ペン
テン系重合体樹脂本来の優れた性質（優れた耐熱性、優
れた透明性、優れた離型性等）を維持しつつ、従来の技
術においては、高品質な（高い厚み精度、優れた表面性
状等を有する）延伸成形体を製造することが困難であっ
た、一般的な成形加工条件においても、高品質な（高い
厚み精度、優れた表面性状・外観等を有する）延伸成形
体を製造すること可能とする、４−メチル−１−ペンテ
ン系重合体樹脂組成物を提供することができる。すなわ
ち、本発明に係る樹脂組成物は、４−メチル−１−ペン
テン系重合体樹脂本来の優れた性質（優れた耐熱性、優
れた透明性、優れた離型性等）を維持しつつ、従来の技
術における４−メチル−１−ペンテン系重合体樹脂とは
対照的に、優れた延伸成形性（高いメルトテンション）
と優れた溶融流動性を併せ有するため、高品質な（高い
厚み精度、優れた表面性状・外観等を有する）延伸成形
体を製造することを可能とする。本発明に係る樹脂組成
物は、一軸延伸フィルム成形、二軸延伸フィルム成形、
インフレーションフィルム成形、中空成形、射出ブロー
成形、真空成形、真空圧空成形において、一般的な成形
加工条件で成形加工しても、高品質な（高い厚み精度、
優れた表面性状・外観等を有する）延伸成形体を製造す
ることを可能とする。本発明に係る樹脂組成物を含んで
構成される延伸成形体の具体例としては、例えば、離型
フィルム、離型紙、哺乳ビン、農薬容器、実験器具、医
療用容器、化粧品容器、洗剤容器、食品容器、接着剤容
器、フィルム成形品、押出ラミネート成形品、射出成形
品、食品包装フィルム、鮮度保持包材、ラップフィル
ム、離型フィルム、合皮用離型紙等を挙げることができ
る。The effect of the present invention is that while maintaining the original excellent properties of the 4-methyl-1-pentene polymer resin (excellent heat resistance, excellent transparency, excellent releasability, etc.), In the conventional technology, it was difficult to produce a high-quality stretched molded product (having high thickness accuracy, excellent surface properties, etc.). It is possible to provide a 4-methyl-1-pentene-based polymer resin composition capable of producing a stretched molded article (having accuracy, excellent surface properties, appearance, etc.). That is, the resin composition according to the present invention, while maintaining the original excellent properties of the 4-methyl-1-pentene polymer resin (excellent heat resistance, excellent transparency, excellent releasability, etc.), Excellent stretch formability (high melt tension), in contrast to the 4-methyl-1-pentene polymer resin in the prior art
And excellent melt fluidity, it is possible to produce a high-quality stretched molded product (having high thickness accuracy, excellent surface properties and appearance, etc.). The resin composition according to the present invention, uniaxially stretched film molding, biaxially stretched film molding,
Inflation film molding, hollow molding, injection blow molding, vacuum molding, vacuum pressure molding, even if molding under general molding conditions, high quality (high thickness accuracy,
It is possible to produce a stretch-molded article (having excellent surface properties and appearance). Specific examples of the stretched molded article containing the resin composition according to the present invention include, for example, release films, release papers, baby bottles, pesticide containers, laboratory equipment, medical containers, cosmetic containers, detergent containers, Examples thereof include food containers, adhesive containers, film molded products, extrusion laminated molded products, injection molded products, food packaging films, freshness-keeping packaging materials, wrap films, release films, and release paper for synthetic leather.
フロントページの続き Ｆターム(参考） 3E033 BA30 CA07 CA18 FA02 FA03 FA04 4F071 AA21 AA88 AH04 AH05 BB05 BB07 BB08 BB09 BB13 BC01 4J002 BB171 BB172 GG01 GG02Continued front page F-term (reference) 3E033 BA30 CA07 CA18 FA02 FA03 FA04 4F071 AA21 AA88 AH04 AH05 BB05 BB07 BB08 BB09 BB13 BC01 4J002 BB171 BB172 GG01 GG02
Claims (9)
０［ｇ／１０分］の範囲にある４−メチル−１−ペンテ
ン系重合体樹脂と、 成分（Ｂ）として、ＭＦＲが１０〜５００［ｇ／１０
分］の範囲にある４−メチル−１−ペンテン系重合体樹
脂とを含んでなる、４−メチル−１−ペンテン系重合体
樹脂組成物であって、 成分（Ａ）のＭＦＲをＭＦＲA、成分（Ｂ）のＭＦＲを
ＭＦＲBとしたときに、 ＭＦＲAとＭＦＲBとの関係が、数式（１）〜数式（４）
を同時に満足する関係にあることを特徴とする、４−メ
チル−１−ペンテン系重合体樹脂組成物（但し、ＭＦＲ
は、ＡＳＴＭ Ｄ１２３８に準じ、荷重５．０ｋｇ、温
度２６０℃の条件で測定したメルトフローレートを意味
する。）。 【数１】 1. The component (A) has an MFR of 0.1 to 1.
4-methyl-1-pentene polymer resin in the range of 0 [g / 10 min], and MFR of 10 to 500 [g / 10 as the component (B).
Min.] 4-methyl-1-pentene-based polymer resin, which is a 4-methyl-1-pentene-based polymer resin composition, wherein MFR of component (A) is MFR A , component MFR of (B) when the MFR B, the relationship between the MFR a and MFR B is formula (1) to equation (4)
4-methyl-1-pentene-based polymer resin composition (provided that MFR is satisfied.
Means a melt flow rate measured under a load of 5.0 kg and a temperature of 260 ° C. according to ASTM D1238. ). [Equation 1]
分（Ａ）と成分（Ｂ）の合計重量を基準として、成分
（Ａ）が、１〜９９重量％、成分（Ｂ）が、１〜９９重
量％であることを特徴とする、請求項１に記載した、４
−メチル−１−ペンテン系重合体樹脂組成物。2. The composition ratio of the component (A) and the component (B) is 1 to 99% by weight of the component (A) and the component (B) based on the total weight of the component (A) and the component (B). 4) according to claim 1, characterized in that 4) is 1 to 99% by weight.
-Methyl-1-pentene polymer resin composition.
分（Ａ）と成分（Ｂ）の合計重量を基準として、成分
（Ａ）が、５０〜９５重量％、成分（Ｂ）が、５〜５０
重量％であることを特徴とする、請求項１に記載した、
４−メチル−１−ペンテン系重合体樹脂組成物。3. The composition ratio of the component (A) and the component (B) is 50 to 95% by weight of the component (A) based on the total weight of the component (A) and the component (B). ) Is 5 to 50
%, According to claim 1, characterized in that
4-Methyl-1-pentene polymer resin composition.
−メチル−１−ペンテン系重合体樹脂組成物を含んで構
成される、延伸成形体。4. The 4 according to any one of claims 1 to 3.
-A stretched molded article containing a methyl-1-pentene polymer resin composition.
延伸フィルム、インフレーションフィルム、中空成形
体、射出ブロー成形体、真空成形体、及び、真空圧空成
形体からなる群から選択された何れか一つであることを
特徴とする、請求項４に記載した延伸成形体。5. The stretched molded product is any one selected from the group consisting of a uniaxially stretched film, a biaxially stretched film, an inflation film, a hollow molded product, an injection blow molded product, a vacuum molded product, and a vacuum pressure molded product. The stretch-formed product according to claim 4, characterized in that it is one.
−メチル−１−ペンテン系重合体樹脂組成物を、一軸延
伸フィルム成形法、二軸延伸フィルム成形法、インフレ
ーションフィルム成形法、中空成形法、射出ブロー成形
法、真空成形法、及び、真空圧空成形法からなる群から
選択された何れか一つの延伸成形方法で成形加工するこ
とを特徴とする、延伸成形体の製造方法。6. The 4 according to claim 1.
-Methyl-1-pentene polymer resin composition, uniaxially stretched film molding method, biaxially stretched film molding method, inflation film molding method, blow molding method, injection blow molding method, vacuum molding method, and vacuum pressure molding A method for producing a stretch-molded article, which comprises molding by any one stretch-molding method selected from the group consisting of
メチル−１−ペンテン系重合体樹脂組成物を含んで構成
される、離型フィルム。7. The method according to any one of claims 1 to 3,
A release film comprising a methyl-1-pentene polymer resin composition.
メチル−１−ペンテン系重合体樹脂組成物を含んで構成
される、離型紙。8. The method according to any one of claims 1 to 3,
A release paper comprising a methyl-1-pentene polymer resin composition.
メチル−１−ペンテン系重合体樹脂組成物を含んで構成
される、容器。9. The method according to any one of claims 1 to 3,
A container comprising a methyl-1-pentene polymer resin composition.
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|---|---|---|---|
| JP2002094563A JP3894822B2 (en) | 2002-03-29 | 2002-03-29 | Resin composition and stretched molded body |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002094563A JP3894822B2 (en) | 2002-03-29 | 2002-03-29 | Resin composition and stretched molded body |
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| Publication Number | Publication Date |
|---|---|
| JP2003292704A true JP2003292704A (en) | 2003-10-15 |
| JP3894822B2 JP3894822B2 (en) | 2007-03-22 |
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|---|---|---|---|
| JP2002094563A Expired - Lifetime JP3894822B2 (en) | 2002-03-29 | 2002-03-29 | Resin composition and stretched molded body |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010024300A (en) * | 2008-07-16 | 2010-02-04 | Mitsui Chemicals Inc | Olefin polymer composition, film and laminate produced using the composition and mold release film formed from the film or laminate |
| WO2013099876A1 (en) * | 2011-12-27 | 2013-07-04 | 三井化学株式会社 | 4-methyl-1-pentene (co)polymer composition, and film and hollow molded body, each of which is formed from 4-methyl-1-pentene (co)polymer composition |
| WO2020116368A1 (en) * | 2018-12-04 | 2020-06-11 | 三井化学株式会社 | Resin composition containing 4-methyl-1-pentene copolymer, and film for capacitors |
-
2002
- 2002-03-29 JP JP2002094563A patent/JP3894822B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010024300A (en) * | 2008-07-16 | 2010-02-04 | Mitsui Chemicals Inc | Olefin polymer composition, film and laminate produced using the composition and mold release film formed from the film or laminate |
| WO2013099876A1 (en) * | 2011-12-27 | 2013-07-04 | 三井化学株式会社 | 4-methyl-1-pentene (co)polymer composition, and film and hollow molded body, each of which is formed from 4-methyl-1-pentene (co)polymer composition |
| JPWO2013099876A1 (en) * | 2011-12-27 | 2015-05-07 | 三井化学株式会社 | 4-methyl-1-pentene (co) polymer composition, film comprising the composition and hollow molded article |
| KR101567269B1 (en) | 2011-12-27 | 2015-11-06 | 미쓰이 가가쿠 가부시키가이샤 | 4-methyl-1-pentene (co)polymer composition, and film and hollow molded body, each of which is formed from 4-methyl-1-pentene (co)polymer composition |
| US9902847B2 (en) | 2011-12-27 | 2018-02-27 | Mitsui Chemicals, Inc. | 4-methyl-1-pentene (co)polymer composition, and film and hollow molded product composed of the composition |
| WO2020116368A1 (en) * | 2018-12-04 | 2020-06-11 | 三井化学株式会社 | Resin composition containing 4-methyl-1-pentene copolymer, and film for capacitors |
| JPWO2020116368A1 (en) * | 2018-12-04 | 2021-10-14 | 三井化学株式会社 | A resin composition containing a 4-methyl-1-pentene copolymer and a film for a capacitor. |
| JP7182644B2 (en) | 2018-12-04 | 2022-12-02 | 三井化学株式会社 | Resin composition containing 4-methyl-1-pentene copolymer, and capacitor film |
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|---|---|
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