JP2005307059A - Poly(4-methyl-1-pentene) resin film - Google Patents
Poly(4-methyl-1-pentene) resin film Download PDFInfo
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本発明は、温度２００℃以上の高い温度で良好な離型性が得られる、ポリ４−メチル−１−ペンテン樹脂フィルムおよび該樹脂フィルムである離型フィルムに関する。 The present invention relates to a poly-4-methyl-1-pentene resin film and a release film which is the resin film, in which good release properties can be obtained at a high temperature of 200 ° C. or higher.
ポリ４−メチル−１−ペンテン（ＰＭＰ）は、２２０〜２４０℃の融点を示し、耐熱性に優れるとともに、機械的特性、耐薬品性、電気絶縁性および離型性などの特性に優れているため、例えばポリ４−メチル−１−ペンテン樹脂フィルムとしてプリント基板用離型フィルム、熱硬化性樹脂用離型フィルム、合成皮革用離型フィルム等の離型フィルム、電線被覆用フィルムなどの用途に広く用いられている（特許２６１９０３４号公報）。 Poly-4-methyl-1-pentene (PMP) has a melting point of 220 to 240 ° C. and is excellent in heat resistance, and is excellent in properties such as mechanical properties, chemical resistance, electrical insulation and releasability. Therefore, for example, as a poly-4-methyl-1-pentene resin film, a release film for a printed circuit board, a release film for a thermosetting resin, a release film such as a release film for synthetic leather, a wire coating film, etc. Widely used (Japanese Patent No. 2619034).
ところで、ポリ４−メチル−１−ペンテン樹脂フィルムは、極めて優れた耐熱性フィルムであるが、２００℃以上の高温においては離型性が不十分となるため、上記用途においてさらなる離型性の向上が望まれていた。しかしながらポリ４−メチル−１−ペンテンに高温での離型性を付与するために、耐熱性に優れるポリフェニレンスルフィド樹脂（ＰＰＳ）（特開平３−３３１４０号公報）やフィラーのブレンドが開示されているが、ポリ４−メチル−１−ペンテンがフィラーや、ＰＰＳとの親和性に乏しいため、高い耐熱性を得るに十分な量をブレンドすると、離型フィルムとして使用した場合にフィルム表面からブレンドした樹脂が脱落してプリント基板などの製品表面に移行して汚染する問題があり、フィラーや耐熱性樹脂のブレンド量を低く抑える必要性から耐熱性の向上にも限度がある。また、フィルム成形に際して厚薄ムラを生じるなど成形性や得られるフィルムの外観も十分なものではない。 By the way, the poly-4-methyl-1-pentene resin film is an extremely excellent heat-resistant film. However, since the releasability becomes insufficient at a high temperature of 200 ° C. or higher, the releasability is further improved in the above applications. Was desired. However, polyphenylene sulfide resin (PPS) excellent in heat resistance (JP-A-3-33140) and a blend of fillers are disclosed in order to impart releasability at high temperature to poly-4-methyl-1-pentene. However, since poly-4-methyl-1-pentene has poor affinity with fillers and PPS, when blended in an amount sufficient to obtain high heat resistance, a resin blended from the film surface when used as a release film Drops and migrates to the surface of products such as printed circuit boards, causing contamination, and there is a limit to improving heat resistance because of the need to keep the blend amount of filler and heat resistant resin low. In addition, the moldability and the appearance of the resulting film are not sufficient, such as unevenness in thickness during film formation.
また、特開平１−２８９８１７号公報には、ポリオレフィンとエステル結合を有しない含フッ素オレフィン化合物とをラジカル開始剤の存在下にグラフト重合させる、撥水撥油性および耐加水分解性に優れる含フッ素ポリオレフィンの製造方法が開示されている。しかしながら、グラフト重合によって得られる含フッ素ポリオレフィンは共重合体であるため、十分な耐熱性が得られない問題がある。
また、特表平１０−５０９９８８号公報には、５０重量％より多い多量の溶融処理可能な熱可塑性フルオロポリマー成分と炭化水素重合体成分からなる組成物が、溶融損傷のような溶融欠陥を生じないことが開示されている。しかしながら、フッ素系樹脂成分の量が多いため炭化水素重合体成分に対する分散性が悪く、離型フィルムとして使用した際に、フィルム表面からプリント基板などの製品表面へフッ素系樹脂が脱落して移行する、汚染の問題がある。
In Japanese Patent Application Laid-Open No. 10-509988, a composition comprising a large amount of thermoplastic fluoropolymer component and hydrocarbon polymer component capable of being melted in a large amount of more than 50% by weight causes melting defects such as melting damage. There is no disclosure. However, since the amount of the fluororesin component is large, the dispersibility with respect to the hydrocarbon polymer component is poor, and when used as a release film, the fluororesin drops and moves from the film surface to the product surface such as a printed circuit board. There is a problem of contamination.
本発明は上記問題点を解決するものであり、温度２００℃以上の高温で良好な離型性が得られるポリ４−メチル−１−ペンテン樹脂フィルムおよび、該樹脂フィルムである、プリント基板用、熱硬化性樹脂用、および合成皮革用などに有用な離型フィルムを提供することである。 The present invention solves the above-mentioned problems, and is a poly-4-methyl-1-pentene resin film capable of obtaining good releasability at a high temperature of 200 ° C. or higher, and the resin film, for a printed circuit board, It is an object of the present invention to provide a release film useful for thermosetting resins and synthetic leather.
本発明者は、上記問題を解決するべく鋭意研究した結果、特定の粘度を有するポリ４−メチル−１−ペンテン（Ａ）とフッ素系樹脂（Ｂ）を特定の量で組み合わせて得られるポリ４−メチル−１−ペンテン樹脂フィルムが、上記課題を解決できることを見出し、本願発明に到った。 As a result of intensive studies to solve the above problems, the present inventor has obtained a poly-4 obtained by combining poly-4-methyl-1-pentene (A) having a specific viscosity and a fluororesin (B) in a specific amount. The present inventors have found that a methyl-1-pentene resin film can solve the above problems, and have arrived at the present invention.
即ち本発明は、ポリ４−メチル−１−ペンテン（Ａ）７０〜９９質量部と、フッ素系樹脂（Ｂ）３０〜１質量部（ただし、（Ａ）＋（Ｂ）＝１００質量部である）とからなり、ブロッキング力が５０〜３００ｍＮ／ｃｍであることを特徴とする、ポリ４−メチル−１−ペンテン樹脂フィルムおよび該樹脂フィルムである離型フィルムを提供する。
That is, in the present invention, 70 to 99 parts by mass of poly-4-methyl-1-pentene (A) and 30 to 1 part by mass of the fluororesin (B) (provided that (A) + (B) = 100 parts by mass). A poly-4-methyl-1-pentene resin film and a release film which is the resin film are provided, which have a blocking force of 50 to 300 mN / cm.
本発明に係るポリ４−メチル−１−ペンテン樹脂フィルムは、温度２００℃以上の高温での離型性に優れているので、特にプリント基板用離型フィルム、熱硬化性樹脂用離型フィルム、合成皮革用離型フィルムなどの高い温度で使用される離型フィルム用途に好適に使用することができ、また、離型フィルムからプリント基板などの製品表面への移行物による汚染の問題が少ない。また、従来より高い温度での離型性が良好であることから、製品の成形サイクルを短縮でき、生産性を向上できる。 Since the poly-4-methyl-1-pentene resin film according to the present invention is excellent in release properties at a high temperature of 200 ° C. or higher, in particular, a release film for printed circuit boards, a release film for thermosetting resins, It can be suitably used for a release film used at a high temperature, such as a release film for synthetic leather, and there are few problems of contamination due to the transfer from the release film to the product surface such as a printed circuit board. In addition, since the releasability at a higher temperature is better than before, the product molding cycle can be shortened and the productivity can be improved.
以下、本発明に係るポリ４−メチル−１−ペンテン樹脂フィルムおよび該樹脂フィルムからなる離型フィルムについて具体的に説明する。 Hereinafter, the poly-4-methyl-1-pentene resin film according to the present invention and a release film made of the resin film will be specifically described.
本発明のポリ４−メチル−１−ペンテン樹脂フィルムは、ポリ４−メチル−１−ペンテン（Ａ）とフッ素系樹脂（Ｂ）から構成される。 The poly-4-methyl-1-pentene resin film of the present invention is composed of poly-4-methyl-1-pentene (A) and a fluororesin (B).
[ポリ４−メチル−１−ペンテン（Ａ）]
本発明で用いられるポリ４−メチル−１−ペンテン（Ａ）は、具体的には、４−メチル−１−ペンテンの単独重合体もしくは４−メチル−１−ペンテンとエチレンまたは炭素原子数３〜２０の他の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−オクテン、１−デセン、１−テトラデセン、１−オクタデセン等との共重合体で、通常、４−メチル−１−ペンテンを８５モル％以上、好ましくは９０モル％以上の量で含む４−メチル−１−ペンテンを主体とした重合体である。
[Poly-4-methyl-1-pentene (A)]
Specifically, poly-4-methyl-1-pentene (A) used in the present invention is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and ethylene or a carbon atom number of 3 A copolymer of 20 other α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, etc. It is a polymer mainly composed of 4-methyl-1-pentene containing 1-pentene in an amount of 85 mol% or more, preferably 90 mol% or more.
ポリ４−メチル−１−ペンテン（Ａ）の、ＡＳＴＭ Ｄ１２３８に準じ、荷重５ｋｇ、温度２６０℃の条件で測定したメルトフローレート（ＭＦＲ）は、用途に応じ種々決定されるが、通常、１〜５０ｇ／１０分、好ましくは２〜４０ｇ／１０分、さらに好ましくは５〜３０ｇ／１０分の範囲である。ポリ４−メチル−１−ペンテン（Ａ）のメルトフローレートが上記のような範囲内にあると、フィルム成形性および得られるフィルムの外観が良好である。また融点は２２０〜２４０℃、好ましくは２３０〜２４０℃の範囲にあるのが好ましい。 The melt flow rate (MFR) of poly-4-methyl-1-pentene (A) measured under conditions of a load of 5 kg and a temperature of 260 ° C. according to ASTM D1238 is variously determined depending on the application, but is usually 1 to The range is 50 g / 10 minutes, preferably 2 to 40 g / 10 minutes, and more preferably 5 to 30 g / 10 minutes. When the melt flow rate of poly-4-methyl-1-pentene (A) is in the above range, the film formability and the appearance of the resulting film are good. The melting point is 220 to 240 ° C, preferably 230 to 240 ° C.
また、このようなポリ４−メチル−１−ペンテン（Ａ）は従来公知の方法で製造することができ、例えば特開昭５９−２０６４１８号公報に記載されているように、触媒の存在下に４−メチル−１−ペンテンと上記のエチレンまたはα−オレフィンを重合することにより得ることができる。 Further, such poly-4-methyl-1-pentene (A) can be produced by a conventionally known method. For example, as described in JP-A-59-206418, in the presence of a catalyst. It can be obtained by polymerizing 4-methyl-1-pentene and the above ethylene or α-olefin.
[フッ素系樹脂（Ｂ）]
本発明で用いられるフッ素系樹脂（Ｂ）としては、融点が２５０〜３２０℃、特に２６０〜３００℃のものが好ましく、具体的には、テトラフルオロエチレンの重合体（ＰＴＦＥ）、またテトラフルオロエチレン−ヘキサフルオロエチレン共重合体（ＦＥＰ）、テトラフルオロエチレン−エチレン共重合体（ＥＴＦＥ）などが例示できる。
[Fluorine resin (B)]
The fluororesin (B) used in the present invention preferably has a melting point of 250 to 320 ° C., particularly 260 to 300 ° C., specifically, a tetrafluoroethylene polymer (PTFE) or tetrafluoroethylene. Examples include hexafluoroethylene copolymer (FEP) and tetrafluoroethylene-ethylene copolymer (ETFE).
これらのフッ素系樹脂（Ｂ）は、温度３００℃、剪断速度１００ｓｅｃ−１の条件下で測定した溶融粘度が１０２〜１０４Ｐａ・ｓ、特に５×１０２〜５×１０３のＰａ・ｓ範囲にあるのが好ましい。溶融粘度がこのような範囲にあると、ポリ４−メチル−１−ペンテン（Ａ）との分散性がよく比較的小量のフッ素系樹脂をポリ４−メチル−１−ペンテンに良好に分散することができ、本発明のポリ４−メチル−１−ペンテン樹脂フィルムを離型フィルム用途に使用した際に、離型フィルムからプリント基板などの製品表面への移行物による汚染の問題が少なく好ましい。 These fluororesins (B) have a melt viscosity of 10 2 to 10 4 Pa · s, particularly 5 × 10 2 to 5 × 10 3 Pa · s, measured at a temperature of 300 ° C. and a shear rate of 100 sec −1. It is preferably in the s range. When the melt viscosity is within such a range, the dispersibility with poly-4-methyl-1-pentene (A) is good and a relatively small amount of fluorine-based resin is well dispersed in poly-4-methyl-1-pentene. When the poly-4-methyl-1-pentene resin film of the present invention is used for a release film, there is little problem of contamination due to the transfer from the release film to the product surface such as a printed circuit board.
[ポリ４−メチル−１−ペンテン樹脂フィルム]
本発明のポリ４−メチル−１−ペンテン樹脂フィルムは、ポリ４−メチル−１−ペンテン（Ａ）とフッ素系樹脂（Ｂ）を、ポリ４−メチル−１−ペンテン（Ａ）が７０〜９９質量部、好ましくは８０〜９８質量部に対し、フッ素系樹脂（Ｂ）３０〜１質量部、好ましくは２０〜２質量部（ただし、上記の成分（Ａ）および成分（Ｂ）の合計質量は１００質量部とする）の割合で種々公知の方法、例えばＶ-ブレンダー、リボンブレンダー、ヘンシェルミキサー、タンブラーブレンダーで混合する方法、あるいは前記ブレンダーで混合した後、単軸押し出し機、複軸押し出し機、ニーダー、バンバリーミキサー等で溶融混錬して造粒あるいは紛砕し、次いで、プレス成形、押出成形、インフレーション成形、などの公知の方法でフィルム成形することができる。また、得られたフィルムを延伸することにより、さらに機械的強度を付与したフィルムとしてもよく、効率良く生産するには、インフレーション成形法や押出成形法が好ましい。
[Poly-4-methyl-1-pentene resin film]
The poly-4-methyl-1-pentene resin film of the present invention comprises poly-4-methyl-1-pentene (A) and a fluororesin (B), and poly-4-methyl-1-pentene (A) is 70 to 99. 30 to 1 part by mass, preferably 20 to 2 parts by mass of the fluororesin (B) with respect to 80 parts by mass, preferably 80 to 98 parts by mass. 100 parts by mass) in various proportions of known methods such as V-blender, ribbon blender, Henschel mixer, tumbler blender, or after mixing with the blender, single screw extruder, double screw extruder, It is melt-kneaded with a kneader, Banbury mixer, etc., granulated or pulverized, and then formed into a film by a known method such as press molding, extrusion molding or inflation molding. be able to. Moreover, it is good also as a film which provided the mechanical strength further by extending | stretching the obtained film, and an inflation molding method and an extrusion method are preferable for producing efficiently.
離型フィルムの厚みは、通常１０〜２００μｍ、好ましくは２０〜１００μｍである。このような範囲であれば、フィルムの生産性に優れ、またフィルム成形時にピンホールなどを生じることなく、また十分な強度も得られることから好ましい。
また、ポリ４−メチル−１−ペンテン樹脂フィルムのメルトフローレート（ＭＦＲ）は、用途に応じて異なるが、離型フィルムの場合、通常１〜５０ｇ／１０分、好ましくは２〜４０ｇ／１０分、さらに好ましくは５〜３０ｇ／１０分であり、このような範囲であると、フィルムの成形性および外観が良好であり好ましい。また、融点は離型フィルムとして高い温度での離型性から、２２０℃〜３２０℃、好ましくは２２５℃〜２８０℃の範囲にあるのが好ましい。
The thickness of the release film is usually 10 to 200 μm, preferably 20 to 100 μm. If it is such a range, it is excellent in productivity of a film, and since a sufficient strength is also obtained without producing a pinhole etc. at the time of film forming, it is preferable.
The melt flow rate (MFR) of the poly-4-methyl-1-pentene resin film varies depending on the application, but in the case of a release film, it is usually 1 to 50 g / 10 minutes, preferably 2 to 40 g / 10 minutes. More preferably, it is 5 to 30 g / 10 minutes, and if it is in such a range, the moldability and appearance of the film are good, which is preferable. Moreover, it is preferable that melting | fusing point exists in the range of 220 to 320 degreeC from the mold release property in a high temperature as a release film, Preferably it is 225 to 280 degreeC.
このようにして得られるポリ４−メチル−１−ペンテン樹脂フィルムは、成形性が良好であり、温度２００℃以上の高い温度において離型性が良好である。また、離型フィルムとして使用した際に、配合したフッ素系樹脂が離型フィルム表面から脱落することが少なく、製品表面を汚染しない。 The poly-4-methyl-1-pentene resin film thus obtained has good moldability and good release properties at a high temperature of 200 ° C. or higher. Further, when used as a release film, the blended fluororesin is less likely to fall off from the release film surface and does not contaminate the product surface.
また、本発明におけるポリ４−メチル−１−ペンテン樹脂フィルムには、耐候安定剤、防錆剤、スリップ剤、核剤、顔料、染料などの通常ポリオレフィンに添加して使用される各種配合剤を本発明の目的を損なわない範囲で添加しても良い。 In addition, the poly-4-methyl-1-pentene resin film in the present invention includes various compounding agents used by adding to a normal polyolefin such as a weather resistance stabilizer, a rust inhibitor, a slip agent, a nucleating agent, a pigment, and a dye. You may add in the range which does not impair the objective of this invention.
また、本発明者は、ＡＳＴＭ Ｄ１８９３−６７に準じて測定した温度２００℃でのフィルムのブロッキング力が低いと、高温でのプリント基板からの離型フィルムの離型性が良好であるので、本発明のポリ４−メチル−１−ペンテン樹脂フィルムである離型フィルムの離型性を、ＡＳＴＭ Ｄ１８９３−６７に準じて評価した。すなわちＴダイ付きキャストフィルム成形機で成形した、厚さ５０μｍフィルム２枚を重ね合わせ、表面を鏡面処理した２枚の金属板に挟んで、温度２００℃で５ＭＰａの荷重で３０分間加熱加圧処理した後、室温まで冷却して、フィルムを速度２００ｍｍ／分で剥離した際の平均荷重を測定して求めたブロッキング力で評価した。温度２００℃以上で良好な離型性を得るには、ブロッキング力は、５０〜３００ｍＮ／ｃｍ、さらに５０〜２００ｍＮ／ｃｍであることが好ましい。 In addition, the present inventor has a good release property of a release film from a printed circuit board at a high temperature when the blocking power of the film at a temperature of 200 ° C. measured according to ASTM D1893-67 is low. The releasability of the release film which is the poly-4-methyl-1-pentene resin film of the invention was evaluated according to ASTM D1893-67. In other words, two 50 μm thick films formed on a cast film molding machine with a T-die are stacked and sandwiched between two mirror-finished metal plates, and heated and pressurized for 30 minutes at a temperature of 200 ° C. and a load of 5 MPa. Then, it was cooled to room temperature, and the average load when the film was peeled at a speed of 200 mm / min was measured and evaluated by the blocking force obtained. In order to obtain good releasability at a temperature of 200 ° C. or higher, the blocking force is preferably 50 to 300 mN / cm, more preferably 50 to 200 mN / cm.
[離型フィルム]
本発明のポリ４−メチル−１−ペンテン樹脂フィルムである離型フィルムは、プリント基板用離型フィルム、熱硬化性樹脂用離型フィルム、合成皮革用離型フィルムなど、特に高い温度で使用される離型フィルムに好適に使用できる。
[Release film]
The release film which is the poly-4-methyl-1-pentene resin film of the present invention is used at a particularly high temperature such as a release film for printed circuit boards, a release film for thermosetting resins, and a release film for synthetic leather. It can be suitably used for a release film.
以下、本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。また、各物性値は以下の方法にて評価した。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. Each physical property value was evaluated by the following method.
[ＭＦＲ]
ＡＳＴＭ Ｄ１２３８に準じ、荷重５kg、温度２６０℃の条件で測定した。
[MFR]
According to ASTM D1238, the load was 5 kg and the temperature was 260 ° C.
[溶融粘度]
フッ素系樹脂の溶融粘度は、（株）東洋製機製作所製 キャピログラフ−１Ａを用いて、温度３００℃（フッ素系樹脂の融点＋３０℃）、剪断速度１００ｓｅｃ−１の条件で測定した。
[Melt viscosity]
The melt viscosity of the fluororesin was measured under the conditions of a temperature of 300 ° C. (melting point of fluororesin + 30 ° C.) and a shear rate of 100 sec −1 using Capillograph-1A manufactured by Toyo Seisakusho Co., Ltd.
[融点]
ＤＳＣ装置（Ｓｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔｓ社製）を使用し、空気中、樹脂の融点より３０℃高い温度まで１０℃／分で昇温した後、３分間保持し、次いで１０℃／分で室温まで降温した後、測定速度１０℃／分で樹脂の融点より３０℃高い温度まで昇温したときの、融解に基づく吸熱ピーク温度を融点とした。
[Melting point]
After using a DSC apparatus (manufactured by Seiko Instruments), raising the temperature in air to 30 ° C. higher than the melting point of the resin at 10 ° C./min, holding for 3 minutes, and then lowering the temperature to 10 ° C./min to room temperature The endothermic peak temperature based on melting when the temperature was raised to a temperature 30 ° C. higher than the melting point of the resin at a measurement rate of 10 ° C./min was defined as the melting point.
[引張降伏強度]
Ｔダイ付きキャストフィルム成形機（モダンマシナリー社製 キャストフィルム製造装置：Ｅ−５０）で、シリンダー温度３００℃で厚さ５０μｍのフィルムを成形した。得られたフィルムのＭＤ（押出方向）方向およびＴＤ方向（押出方向の直角方向）の引張降伏強度を、ＡＳＴＭ Ｄ８８２に準じて測定した。
[Tensile yield strength]
A film having a thickness of 50 μm was formed at a cylinder temperature of 300 ° C. using a cast film molding machine with a T-die (cast film manufacturing apparatus: E-50 manufactured by Modern Machinery Co., Ltd.). The tensile yield strength in the MD (extrusion direction) direction and the TD direction (perpendicular direction to the extrusion direction) of the obtained film was measured according to ASTM D882.
[引張降伏伸び]
Ｔダイ付きキャストフィルム成形機（モダンマシナリー社製 キャストフィルム製造装置：Ｅ−５０）で、シリンダー温度３００℃で厚さ５０μｍのフィルムを成形した。得られたフィルムのＭＤ（押出方向）方向およびＴＤ方向（押出方向の直角方向）の引張降伏伸びを、ＡＳＴＭ Ｄ８８２に準じて測定した。
[Tensile yield elongation]
A film having a thickness of 50 μm was formed at a cylinder temperature of 300 ° C. using a cast film molding machine with a T-die (cast film manufacturing apparatus: E-50 manufactured by Modern Machinery Co., Ltd.). The tensile yield elongation in the MD (extrusion direction) direction and the TD direction (perpendicular direction to the extrusion direction) of the obtained film was measured according to ASTM D882.
[引張破壊伸び]
Ｔダイ付きキャストフィルム成形機（モダンマシナリー社製 キャストフィルム製造装置：Ｅ−５０）で、シリンダー温度３００℃で厚さ５０μｍのフィルムを成形した。得られたフィルムの、ＭＤ（押出方向）方向およびＴＤ方向（押出方向の直角方向）の引張破壊伸びを、ＡＳＴＭ Ｄ８８２に準じて測定した。
[Tensile fracture elongation]
A film having a thickness of 50 μm was formed at a cylinder temperature of 300 ° C. using a cast film molding machine with a T-die (cast film manufacturing apparatus: E-50 manufactured by Modern Machinery Co., Ltd.). The tensile elongation at break in the MD (extrusion direction) direction and the TD direction (perpendicular direction to the extrusion direction) of the obtained film was measured according to ASTM D882.
[ブロッキング力]
ＡＳＴＭ Ｄ１８９３−６７に準じて、Ｔダイ付きキャストフィルム成形機でシリンダー温度３００℃で成形した厚さ５０μｍのフィルムから切り出した、７ｃｍ×２４ｃｍのフィルム２枚を重ね合わせ、表面を鏡面処理した２枚の金属板の挟んで、温度２００℃、５ＭＰａの荷重で３０分間加熱加圧処理した後、室温まで冷却して、インテスコ社製ＭＯＤＥＬ２００５型精密万能材料試験機の剥離試験用治具に加熱加圧処理したフィルムをセットし、速度２００ｍｍ／分で２枚のフィルムを剥離した際の平均荷重を測定してブロッキング力を求めた。
[Blocking power]
In accordance with ASTM D1893-67, two 7cm x 24cm films cut from a 50μm thick film molded at a cylinder temperature of 300 ° C by a cast film molding machine with a T-die, and two mirror-finished surfaces After being heated and pressed at a temperature of 200 ° C. and a load of 5 MPa for 30 minutes, it was cooled to room temperature and heated and pressed on a peeling test jig of a MODEL2005 precision universal material testing machine manufactured by Intesco. The processed film was set, and the average load when the two films were peeled off at a speed of 200 mm / min was measured to determine the blocking force.
[剥離性]
流動開始温度８０℃のエポキシ系接着剤を３０μｍの厚さで塗布した、厚さ２５μｍのポリイミド製フィルムを、厚さ３５μｍの銅箔（三井金属（株）製、ＳＱ−ＶＬＰ）に接着するプリント基板を製造するに際し、上記エポキシ系接着剤を塗布したポリイミド製フィルムの上に本発明のポリ４−メチル−１−ペンテン重合体組成物からなる厚さ５０μｍの離型フィルムを重ねて、表面を鏡面処理した２枚の金属板で挟んで、温度２００℃、圧力３０ｋｇ／ｃｍ２で３０分間加圧熱処理してエポキシ系接着剤を熱硬化させた。次いで室温まで冷却後、離型フィルムの端を持って剥離した際の剥離性を、容易に剥離できる；○、剥離時の抵抗が大きい；△、剥離困難；×、として評価した。
[Peelability]
A print that adheres a 25 μm thick polyimide film coated with an epoxy adhesive with a flow starting temperature of 80 ° C. to a thickness of 30 μm to a 35 μm thick copper foil (SQ-VLP manufactured by Mitsui Kinzoku Co., Ltd.) When manufacturing a substrate, a 50 μm-thick release film composed of the poly-4-methyl-1-pentene polymer composition of the present invention is overlaid on the polyimide film coated with the epoxy adhesive, and the surface is covered. The epoxy adhesive was thermally cured by sandwiching between two mirror-treated metal plates and pressurizing and heat treating at a temperature of 200 ° C. and a pressure of 30 kg / cm 2 for 30 minutes. Next, after cooling to room temperature, the peelability at the time of peeling with the edge of the release film can be easily peeled; ○, resistance at peeling is large; Δ, difficult to peel;
[実施例１]
４−メチル−１−ペンテンとデセン−１との共重合体〔デセン−１含量：３質量％、ＭＦＲ：５ｇ／１０分、融点：２３５℃、以下「ＰＭＰ（１）」と略す〕９５質量部と、フッ素系樹脂として、テトラフルオロエチレンとエチレンの共重合体（旭硝子（株）製 グレード名：Ｃ−５５ＡＰ）〔融点：２７０℃、溶融粘度：１．５×１０３Ｐａ・ｓ〕５質量部とを４５ｍｍφ二軸押し出し機でシリンダー温度２９０℃で溶融混合し、ペレットを造粒した。次いでこのペレットを４０ｍｍφのＴダイ付きキャストフィルム成形機でシリンダー温度３００℃にてフィルム成形し、厚さ５０μｍのフィルムを得た。
得られたフィルムの機械物性値、ブロッキング力、剥離性の評価結果を表１に示す。
[Example 1]
Copolymer of 4-methyl-1-pentene and decene-1 [Decene-1 content: 3 mass%, MFR: 5 g / 10 min, melting point: 235 ° C., hereinafter abbreviated as “PMP (1)”] 95 mass Part and a copolymer of tetrafluoroethylene and ethylene (manufactured by Asahi Glass Co., Ltd., grade name: C-55AP) [melting point: 270 ° C., melt viscosity: 1.5 × 10 3 Pa · s] 5 The mass part was melt-mixed at a cylinder temperature of 290 ° C. with a 45 mmφ biaxial extruder to granulate the pellets. Next, this pellet was film-formed at a cylinder temperature of 300 ° C. by a cast film molding machine with a 40 mmφ T-die to obtain a film having a thickness of 50 μm.
Table 1 shows the evaluation results of mechanical properties, blocking power, and peelability of the obtained film.
[実施例２]
フッ素系樹脂Ｃ−５５ＡＰを１０質量部、すなわちＰＭＰ（１）の配合量を９０質量部とした以外は、実施例１と同様にしてペレットを造粒した。また、実施例１と同様にして厚さ５０μｍのフィルムを得た。得られたフィルムの機械物性値、ブロッキング力、剥離性の評価結果を表１に示す。
[Example 2]
Pellets were granulated in the same manner as in Example 1 except that 10 parts by mass of the fluororesin C-55AP, that is, the blending amount of PMP (1) was 90 parts by mass. A film having a thickness of 50 μm was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of mechanical properties, blocking power, and peelability of the obtained film.
[実施例３]
フッ素系樹脂Ｃ−５５ＡＰを２０質量部、すなわちＰＭＰ（１）の配合量を８０質量部とした以外は、実施例１と同様にしてペレットを造粒した。また、実施例１と同様にして厚さ５０μｍのフィルムを得た。得られたフィルムの機械物性値、ブロッキング力、剥離性の評価結果を表１に示す。
[Example 3]
Pellets were granulated in the same manner as in Example 1 except that 20 parts by mass of the fluororesin C-55AP, that is, the amount of PMP (1) was 80 parts by mass. A film having a thickness of 50 μm was obtained in the same manner as in Example 1. Table 1 shows the evaluation results of mechanical properties, blocking power, and peelability of the obtained film.
[比較例１]
フッ素系樹脂Ｃ−５５ＡＰを４０質量部、すなわちＰＭＰ（１）の配合量を６０質量部とした以外は、実施例１と同様にしてペレットを造粒した。また、実施例１と同様にして厚さ５０μｍのフィルムを成形したが、フィルムの厚薄ムラが大きく、また外観が良好なフィルムを得ることができなかった。評価結果を表１に示す。
[Comparative Example 1]
Pellets were granulated in the same manner as in Example 1 except that 40 parts by mass of the fluororesin C-55AP, that is, the amount of PMP (1) was 60 parts by mass. Further, a film having a thickness of 50 μm was formed in the same manner as in Example 1. However, a film with a large thickness unevenness and a good appearance could not be obtained. The evaluation results are shown in Table 1.
[比較例２]
フッ素系樹脂Ｃ−５５ＡＰを０質量部、すなわちＰＭＰ（１）の配合量を１００質量部とした以外は、実施例１と同様にしてペレットを造粒した。また、実施例１と同様にして厚さ５０μｍのフィルムを得た。得られたフィルムの離型性を評価したところ、剥離時にフィルムが破れて破損したフィルムが離型面に残り、離型が困難であった。評価結果を表１に示す。
[Comparative Example 2]
Pellets were granulated in the same manner as in Example 1 except that the fluorine-based resin C-55AP was 0 parts by mass, that is, the amount of PMP (1) was 100 parts by mass. A film having a thickness of 50 μm was obtained in the same manner as in Example 1. When the releasability of the obtained film was evaluated, the film was broken and damaged at the time of peeling, and the film remaining on the release surface was difficult to release. The evaluation results are shown in Table 1.
本発明のポリ４−メチル−１−ペンテン樹脂フィルムは、プリント基板用離型フィルム、熱硬化性樹脂用離型フィルム、合成皮革用離型フィルム等の高い温度で使用する離型フィルムに好適に使用できる。また高い温度での離型性が良好であることから、製品の成形サイクルを短縮でき、生産性を向上できることから、工業的価値は極めて高い。
The poly-4-methyl-1-pentene resin film of the present invention is suitable for a release film used at a high temperature, such as a release film for printed circuit boards, a release film for thermosetting resins, and a release film for synthetic leather. Can be used. Moreover, since the releasability at a high temperature is good, the molding cycle of the product can be shortened and the productivity can be improved, so that the industrial value is extremely high.
Claims (4)
A release film which is the poly-4-methyl-1-pentene resin film according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2004127490A JP2005307059A (en) | 2004-04-23 | 2004-04-23 | Poly(4-methyl-1-pentene) resin film |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004127490A JP2005307059A (en) | 2004-04-23 | 2004-04-23 | Poly(4-methyl-1-pentene) resin film |
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| JP2005307059A true JP2005307059A (en) | 2005-11-04 |
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| JP2004127490A Withdrawn JP2005307059A (en) | 2004-04-23 | 2004-04-23 | Poly(4-methyl-1-pentene) resin film |
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