WO2021230321A1 - Film, laminate, and method for producing laminate - Google Patents
Film, laminate, and method for producing laminate Download PDFInfo
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- WO2021230321A1 WO2021230321A1 PCT/JP2021/018240 JP2021018240W WO2021230321A1 WO 2021230321 A1 WO2021230321 A1 WO 2021230321A1 JP 2021018240 W JP2021018240 W JP 2021018240W WO 2021230321 A1 WO2021230321 A1 WO 2021230321A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
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Abstract
[Abstract] [Problem] To reduce manufacturing costs while maintaining the performance of a laminate that includes a polyphenylene sulfide layer and a copper layer. [Solution] Provided are: a low-crystallinity high-adhesiveness polyphenylene sulfide film; a laminate L1 that includes a layer A1 formed from said low-crystallinity high-adhesiveness polyphenylene sulfide film, and a layer of a copper foil having low surface roughness; and a laminate L2 that includes a layer A2 formed from a crystalized substance of the low-crystallinity high-adhesiveness polyphenylene sulfide film, and a layer of a copper foil having low surface roughness. Selected drawing: FIG. 1
Description
本発明は、フィルム、積層体、積層体の製造方法に関する。具体的には、新規な低結晶性・高接着性ポリフェニレンスルフィドフィルム、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムからなる層と銅からなる層とを有する積層体（以下、「積層体Ｌ１」）上記積層体Ｌ１を加熱加圧処理して得られる積層体（以下「積層体Ｌ２」）、上記積層体Ｌ２の製造方法に関する。
The present invention relates to a film, a laminate, and a method for manufacturing a laminate. Specifically, a new laminate having a low crystallinity / high adhesive polyphenylene sulfide film, a layer made of the above low crystallinity / high adhesive polyphenylene sulfide film, and a layer made of copper (hereinafter, “laminate L1””. ) The present invention relates to a laminate obtained by heat-pressing the laminate L1 (hereinafter referred to as “laminate L2”), and a method for producing the laminate L2.
ポリフェニレンスルフィド（以下「ＰＰＳ」）はエンジニアリングプラスチックとして知られている。ポリフェニレンスルフィド（ＰＰＳ）は１，４－フェニレン基と硫黄が交互に繰り返される構造を有し、耐熱性に優れた熱可塑性の結晶性樹脂である。ＰＰＳ は高い融点 （２８０℃）を有し、フィラー充填やアロイ化により優れた機械的強度、剛性、寸法安定性を示すことに加えて、熱可塑性樹脂特有の成型加工性をそなえた高耐熱エンジニアリングプラスチックとして、金属や熱硬化性樹脂の代替を中心に用途が拡大している。ＰＰＳ の電気特性は、近年、特に注目されている。交流電圧を印加した際に電気絶縁性の目安となる誘電正接は、他のエンジニアリングプラスチックに比べ格段に小さく、高耐熱性に加え吸水性も低いことから、ＰＰＳは高温高湿下でも優れた絶縁性を示す（非特許文献１）。
Polyphenylene sulfide (hereinafter referred to as "PPS") is known as an engineering plastic. Polyphenylene sulfide (PPS) is a thermoplastic crystalline resin having a structure in which 1,4-phenylene groups and sulfur are alternately repeated and has excellent heat resistance. PPS has a high melting point (280 ° C), and in addition to exhibiting excellent mechanical strength, rigidity, and dimensional stability due to filler filling and alloying, it has high heat-resistant engineering with molding processability peculiar to thermoplastic resins. As a plastic, its applications are expanding mainly as a substitute for metals and thermosetting resins. The electrical characteristics of PPS have received particular attention in recent years. The dielectric loss tangent, which is a measure of electrical insulation when an AC voltage is applied, is much smaller than other engineering plastics, and because it has high heat resistance and low water absorption, PPS has excellent insulation even under high temperature and high humidity. Shows sex (Non-Patent Document 1).
しかし、ＰＰＳフィルムの表面には水酸基（－ＯＨ）やカルボキシル基（－ＣＯＯＨ）などの反応性基が存在しないために、他の熱可塑性樹脂、金属、ガラスなど異種材料に対する接着性に乏しい。ＰＰＳフィルムを異種材料に強固に接着させる手段としては、まず、接着剤が知られている。ポリイミド接着剤を用いてＰＰＳフィルムと銅箔と接着する例（特許文献１）や、特定のエチレン性不飽和単量体をグラフトしたポリオレフィンからなる接着剤を用いてＰＰＳフィルムとポリオレフィンを接着する例（特許文献２）が知られている。しかしながら、このような接着剤を介した接着方法は、接着する材料に合わせて種々の接着剤が必要となり汎用性が乏しい点、接着剤使用に伴いコストが増加する点、接着剤層が製品全体のサイズを大型化する点、接着剤層が製品全体の形状保存性や強度などの性質に影響を与える点などで、問題がある。
However, since the surface of the PPS film does not have reactive groups such as hydroxyl groups (-OH) and carboxyl groups (-COOH), it has poor adhesion to different materials such as other thermoplastic resins, metals, and glass. First, an adhesive is known as a means for firmly adhering a PPS film to a dissimilar material. An example of adhering a PPS film and a copper foil using a polyimide adhesive (Patent Document 1), and an example of adhering a PPS film and a polyolefin using an adhesive made of a polyolefin grafted with a specific ethylenically unsaturated monomer. (Patent Document 2) is known. However, such an adhesive-based bonding method requires various adhesives according to the material to be bonded and is not versatile, the cost increases with the use of the adhesive, and the adhesive layer is the entire product. There are problems in that the size of the product is increased and that the adhesive layer affects the shape preservation and strength of the entire product.
ＰＰＳフィルムを異種材料に強固に接着させる別の手段としては、いわゆる粗面化加工があげられる。この方法では、ＰＰＳフィルムの接着面をあらかじめプラズマ処理やコロナ放電処理などの物理的に処理するか、ＰＰＳフィルムの接着面をあらかじめ酸やアルカリで化学的に処理する（特許文献３）。このような粗面化は接着剤層のような新たな材料層を必要としないため、薄型で精密な構造が求められる積層体の製造に適している。
Another means of firmly adhering the PPS film to different materials is so-called roughening. In this method, the adhesive surface of the PPS film is physically treated in advance by plasma treatment, corona discharge treatment, or the like, or the adhesive surface of the PPS film is chemically treated in advance with an acid or an alkali (Patent Document 3). Since such roughening does not require a new material layer such as an adhesive layer, it is suitable for manufacturing a laminate that requires a thin and precise structure.
特に、ＰＰＳフィルム層と銅箔層を含む積層体は、高周波回路の材料として有用である。このような積層体の製造では、典型的には、あらかじめプラズマ処理したＰＰＳフィルムと銅箔を重ねたものを高温下（典型的にはＰＰＳフィルムの融点：約２８０℃付近かそれ以上の温度）で加圧してＰＰＳフィルム層と銅箔層を密着させる（特許文献４）。しかしながら、この方法では、加熱・加圧のためのエネルギーコストが高くなる傾向にあり、しかも、このような高温下で使用可能な装置は限られている。
In particular, a laminate containing a PPS film layer and a copper foil layer is useful as a material for a high frequency circuit. In the production of such a laminate, typically, a pre-plasma-treated PPS film and a copper foil are laminated at a high temperature (typically, the melting point of the PPS film: a temperature of about 280 ° C. or higher). Pressurize with the PPS film layer and the copper foil layer in close contact with each other (Patent Document 4). However, in this method, the energy cost for heating and pressurizing tends to be high, and moreover, the devices that can be used under such a high temperature are limited.
近年、電子機器の高性能化が進行している一方で、電子機器とその構成部品の低コストかも強く求められている。電子機器に多用されるＰＰＳフィルム層と銅箔層を含む積層体には高性能化と低コスト化が求められているが、本来、性能と製造コストはトレードオフの関係にあるので、このような課題を解決することは容易ではない。
In recent years, while the performance of electronic devices has been increasing, there is a strong demand for low cost of electronic devices and their components. A laminate including a PPS film layer and a copper foil layer, which are often used in electronic devices, is required to have high performance and low cost. However, since performance and manufacturing cost are originally in a trade-off relationship, this is the case. It is not easy to solve various problems.
本発明者は、ＰＰＳフィルム層と銅箔層を含む積層体の耐熱性や誘電特性、剥離強度などの性能を維持したまま、その製造コストを低減するという、難題に挑戦した。本発明者は、既成概念や従来のアプローチにとらわれず、積層体の材料と製造工程を新鮮な視点で見直すことにより、課題解決を試みた。
The present inventor has challenged the difficult problem of reducing the manufacturing cost of the laminate including the PPS film layer and the copper foil layer while maintaining the performance such as heat resistance, dielectric properties, and peel strength. The present inventor tried to solve the problem by reviewing the material and manufacturing process of the laminated body from a fresh viewpoint without being bound by the established concept or the conventional approach.
その結果、本発明者は、従来技術では想定されていなかったＰＰＳフィルムを原料とすることで、この難題を解決した。すなわち本発明では、低結晶性ＰＰＳフィルムを唯一のＰＰＳ材料として使用し、このＰＰＳフィルムに特定の親水化処理を行うことによって、低結晶性・高接着性ポリフェニレンスルフィドフィルムを得た。さらに本発明では、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムと特定の銅箔とを含む積層体を製造した。またさらに本発明では、上記積層体を、加圧下で、従来技術では採用することができなかった比較的穏やかな条件で加圧して、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムを結晶化し、剥離強度が高い積層体を製造した。すなわち本発明は以下のものである。
As a result, the present inventor solved this difficult problem by using a PPS film as a raw material, which was not assumed in the prior art. That is, in the present invention, a low crystallinity PPS film is used as the only PPS material, and the PPS film is subjected to a specific hydrophilization treatment to obtain a low crystallinity and high adhesive polyphenylene sulfide film. Further, in the present invention, a laminate containing the above-mentioned low crystallinity and high adhesive polyphenylene sulfide film and a specific copper foil was produced. Further, in the present invention, the laminate is pressurized under pressure under relatively mild conditions that could not be adopted by the prior art to crystallize the low crystallinity and high adhesive polyphenylene sulfide film. A laminate with high peel strength was produced. That is, the present invention is as follows.
（発明１）ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下であり、少なくとも一方の表面の水接触角が４５°以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルム。
(Invention 1) Low crystallinity and high crystallinity, which contains a polyphenylene sulfide resin as a main component, has a crystallinity of 20% or less measured by an X-ray diffraction method, and has a water contact angle of at least one surface of 45 ° or less. Adhesive polyphenylene sulfide film.
（発明２）ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下であり、少なくとも一方の表面の水接触角が４５°以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルム からなる層（層Ａ１）、及び、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）、を含み、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの水接触角が４５°以下である少なくとも一方の表面と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが接している、積層体（Ｌ１）。
(Invention 2) Low crystallinity and high crystallinity with polyphenylene sulfide resin as the main component, crystallinity measured by X-ray diffractometry of 20% or less, and water contact angle of at least one surface of 45 ° or less. It contains a layer made of an adhesive polyphenylene sulfide film (layer A1) and a layer made of a copper foil having at least one surface roughness (Rz) of 2 μm or less (layer B), and has the above-mentioned low crystallinity and high adhesiveness. A laminate (L1) in which at least one surface of the polyphenylene sulfide film having a water contact angle of 45 ° or less is in contact with at least one surface of the copper foil having a surface roughness (Rz) of 2 μm or less.
（発明３）ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下であり、少なくとも一方の表面の水接触角が４５°以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化物からなる層（層Ａ２）、及び、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）を含み、上記層Ａ２と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが、密着しており、上記層Ａ２と上記層Ｂとの１８０度剥離試験で測定した剥離強度が１Ｎ／ｃｍ以上を示す、積層体（積層体Ｌ２）。
(Invention 3) Low crystallinity and high crystallinity, which contains a polyphenylene sulfide resin as a main component, has a crystallinity of 20% or less measured by an X-ray diffraction method, and has a water contact angle of at least one surface of 45 ° or less. A layer (layer A2) made of a crystallinized product of an adhesive polyphenylene sulfide film and a layer (layer B) made of a copper foil having at least one surface roughness (Rz) of 2 μm or less are included, and the above layer A2 and the above. At least one surface having a surface roughness (Rz) of 2 μm or less of the copper foil is in close contact with the copper foil, and the peel strength measured by the 180 degree peel test between the layer A2 and the layer B is 1 N / cm or more. Shown, laminated body (laminated body L2).
（発明４）発明３の積層体（Ｌ２）を含む製品。
(Invention 4) A product containing the laminate (L2) of Invention 3.
（発明５）以下の工程１，工程２、工程３を含む、積層体の製造方法。（工程１）まず、ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下である低結晶性ポリフェニレンスルフィドフィルムを用意し、次に、上記低結晶性ポリフェニレンスルフィドフィルムの少なくとも一方の表面をプラズマ処理する工程であって、ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルムを製造する工程。（工程２）上記低結晶性・高接着性ポリフェニレンスルフィドフィルムからなる層（層Ａ１）、及び、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）を含む積層体（積層体Ｌ１）を製造する工程であって、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの水接触角が４５°以下である少なくとも一方の表面と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが接するように、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムと上記銅箔とを重ねる工程。（工程３）上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化物からなる層（層Ａ２）、及び、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）を含み、上記層Ａ２と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが密着しており、上記層Ａ２と上記層Ｂとの１８０度剥離試験で測定した剥離強度が１Ｎ／ｃｍ以上を示す、積層体（積層体Ｌ２）を製造する工程であって、上記積層体Ｌ１を、加圧下で、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化温度以上の温度まで加熱する工程。
(Invention 5) A method for manufacturing a laminated body, which comprises the following steps 1, 2, and 3. (Step 1) First, a low-crystalline polyphenylene sulfide film containing a polyphenylene sulfide resin as a main component and having a crystallinity of 20% or less measured by an X-ray diffractometry is prepared, and then the above-mentioned low-crystalline polyphenylene sulfide is prepared. A step of plasma-treating at least one surface of a film, which comprises a polyphenylene sulfide resin as a main component and has a crystallinity of 20% or less measured by an X-ray diffractometry. The process of manufacturing film. (Step 2) The layer (layer A1) made of the low crystallinity and high adhesive polyphenylene sulfide film and the layer (layer B) made of a copper foil having at least one surface roughness (Rz) of 2 μm or less are included. In the step of manufacturing the laminated body (laminated body L1), at least one surface of the low crystallinity and high adhesive polyphenylene sulfide film having a water contact angle of 45 ° or less and the surface roughness of the copper foil (the surface roughness) ( A step of superimposing the low crystallinity and high adhesive polyphenylene sulfide film and the copper foil so as to be in contact with at least one surface having Rz) of 2 μm or less. (Step 3) A layer (layer A2) made of a crystallinized product of the low crystalline and high adhesive polyphenylene sulfide film, and a layer made of a copper foil having at least one surface roughness (Rz) of 2 μm or less (layer B). ), And the layer A2 and at least one surface of the copper foil having a surface roughness (Rz) of 2 μm or less are in close contact with each other, and are measured by a 180-degree peeling test between the layer A2 and the layer B. In the step of manufacturing a laminated body (laminated body L2) having a peeling strength of 1 N / cm or more, the low crystalline and high adhesive polyphenylene sulfide film is crystallized from the laminated body L1 under pressure. The process of heating to a temperature above the temperature.
本発明によって、従来品と同等以上の性能を有するＰＰＳフィルム層と銅箔層を含む積層体を、低コスト化で製造することができる。
According to the present invention, a laminate including a PPS film layer and a copper foil layer having performance equal to or higher than that of a conventional product can be manufactured at low cost.
［低結晶性・高接着性ＰＰＳフィルム］ 本発明では、出発材料としてポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルム（以下「低結晶性・高接着性ＰＰＳフィルム」）を使用する点を特徴の一つとする。上記低結晶性・高接着性ＰＰＳフィルムは、ポリフェニレンスルフィド樹脂を主な成分とする低結晶性ＰＰＳフィルムの少なくとも一方の表面にプラズマ照射することによって、この表面の他材料面に対する接着性を高めることによって、製造することができる。
[Low crystallinity and high adhesion PPS film] In the present invention, polyphenylene sulfide resin is the main component as a starting material, and the crystallinity measured by the X-ray diffractometry is 20% or less, and the crystallinity is low and high adhesion. One of the features is that a polyphenylene sulfide film (hereinafter referred to as “low crystallinity / high adhesive PPS film”) is used. The low crystallinity and high adhesiveness PPS film enhances the adhesiveness of this surface to other material surfaces by irradiating at least one surface of the low crystallinity PPS film containing polyphenylene sulfide resin as a main component with plasma. Can be manufactured by.
上記結晶化度の測定に用いるＸ線回折法は常法に従う。上記水接触角の測定も、常法に従う。これらの測定方法はすでに確立されており当業者の理解と追試に困難性は無い。後述の実施例で採用した測定方法は常法に従う１例であり測定精度を損なわない範囲で測定条件・測定機器の変更が許容される。
The X-ray diffraction method used for measuring the degree of crystallinity follows a conventional method. The measurement of the water contact angle also follows a conventional method. These measurement methods have already been established, and there is no difficulty in understanding and retesting by those skilled in the art. The measurement method adopted in the examples described later is an example according to a conventional method, and changes in measurement conditions and measurement equipment are permitted as long as the measurement accuracy is not impaired.
上記低結晶性ＰＰＳフィルムに含まれるポリフェニレンスルフィド樹脂としては、公知の直鎖型ポリフェニレンスルフィド樹脂を制限なく使用することができる。「直鎖型ポリフェニレンスルフィド樹脂」はポリフェニレンスルフィドの代表的な類型として当技術分野ではよく知られている（他方の類型は「架橋型ポリフェニレンスルフィド」と呼ばれている）。上記直鎖型ポリフェニレンスルフィド樹脂はｐ－フェニレン単位とスルフィド結合単位が交互に結合したｐ－フェニレンスルフィド単位から実質的になる直鎖状重合体であり、実質的に直鎖状構造をとる限りは少量のｍ－フェニレンスルフィド単位を含むことができる。直鎖型ポリフェニレンスルフィド樹脂の製造方法も周知であって、工業的には、ｐ－ジクロロベンゼンと硫化ナトリウムをＮ－メチル－２－ピロリドン中、２００℃から２５０℃で縮合重合させるフィリップス法、ｐ－ブロムチオフェニレン金属塩を自己縮合重合するダウ・ケミカル法が代表的である。
As the polyphenylene sulfide resin contained in the low crystalline PPS film, a known linear polyphenylene sulfide resin can be used without limitation. "Linear polyphenylene sulfide resin" is well known in the art as a representative type of polyphenylene sulfide (the other type is called "crosslinked polyphenylene sulfide"). The linear polyphenylene sulfide resin is a linear polymer substantially composed of p-phenylene sulfide units in which p-phenylene units and sulfide bond units are alternately bonded, and is substantially linear as long as it has a linear structure. It can contain a small amount of m-phenylene sulfide units. A method for producing a linear polyphenylene sulfide resin is also well known, and industrially, a phillips method in which p-dichlorobenzene and sodium sulfide are condensed and polymerized in N-methyl-2-pyrrolidone at 200 ° C to 250 ° C, p. -A typical Dow chemical method is to self-condensate polymer a bromthiophenylene metal salt.
本発明で用いる低結晶性ＰＰＳフィルムに含まれるポリフェニレンスルフィド樹脂の割合は、一般的には７０重量％以上、好ましくは８０重量％以上、さらに好ましくは９０重量％以上である。上記ポリフェニレンスルフィドの含有量が７０重量％未満では、後述の積層体Ｌ２の耐熱性、周波数特性、温度特性等が低下する。３０重量％未満であれば他の樹脂や添加剤等を含むことができる。上記ポリフェニレンスルフィドは、フィルム成形の点では、溶融粘度が１０００乃至２５０００ポイズ（測定条件：温度３００℃、剪断速度２００（秒）－１）のものが好ましい。好ましい本発明の低結晶性ＰＰＳフィルムは、直鎖型ポリフェニレンスルフィド樹脂からなる非強化型（強化用フィラーを含まない）フィルムである。
The proportion of the polyphenylene sulfide resin contained in the low crystalline PPS film used in the present invention is generally 70% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more. If the content of the polyphenylene sulfide is less than 70% by weight, the heat resistance, frequency characteristics, temperature characteristics, etc. of the laminated body L2 described later are deteriorated. If it is less than 30% by weight, other resins, additives and the like can be contained. The polyphenylene sulfide preferably has a melt viscosity of 1000 to 25,000 poise (measurement conditions: temperature 300 ° C., shear rate 200 (seconds) -1 ) in terms of film molding. The preferred low crystalline PPS film of the present invention is a non-reinforced (non-reinforcing filler-free) film made of a linear polyphenylene sulfide resin.
本発明の低結晶性ＰＰＳフィルムの厚みは特に制限されず、後述の積層体Ｌ２の用途に応じて適宜選択される。本発明の低結晶性ＰＰＳフィルムの厚みは、一般的には１０μｍ以上５００μｍ以下、好ましくは１５μｍ以上３００μｍ以下、より好ましくは２０μｍ以上１００μｍ以下である。
The thickness of the low crystallinity PPS film of the present invention is not particularly limited, and is appropriately selected according to the use of the laminate L2 described later. The thickness of the low crystalline PPS film of the present invention is generally 10 μm or more and 500 μm or less, preferably 15 μm or more and 300 μm or less, and more preferably 20 μm or more and 100 μm or less.
一般的に入手可能なポリフェニレンスルフィド樹脂フィルムは、ポリフェニレンスルフィド樹脂を溶融押出して得られる原反フィルムを加温下に一軸または二軸延伸して得られ、概ね４０％以上の結晶化度を示す。これに対して、本発明で用いる低結晶性ＰＰＳフィルムは、上記ポリフェニレンスルフィド樹脂を主な成分とする材料を、上記ポリフェニレンスルフィド樹脂の結晶化を抑制した条件でフィルム成形したものである。結晶化を抑制する手段は限定されないが、ポリフェニレンスルフィド樹脂を溶融押出して得られる原反フィルムを無延伸条件で急冷する方法、市販のポリフェニレンスルフィド樹脂フィルムを再溶融して非晶質化する方法、非結晶構造を与えるモノマーを共重合したポリフェニレンスルフィド樹脂をフィルム成形する方法などが挙げられる。製造コストの面で、最初にあげた方法（無延伸・急冷）が好ましい。本発明の低結晶性ＰＰＳフィルムの製造においては、Ｘ線回折法により測定した結晶化度が２０％以下、好ましくは１５％以下、さらに好ましくは５％以下となるように、ポリフェニレンスルフィド樹脂の結晶化を抑制する。
A generally available polyphenylene sulfide resin film is obtained by uniaxially or biaxially stretching a raw film obtained by melt-extruding a polyphenylene sulfide resin under heating and exhibiting a crystallinity of approximately 40% or more. On the other hand, the low crystalline PPS film used in the present invention is a film formed by molding a material containing the polyphenylene sulfide resin as a main component under conditions in which crystallization of the polyphenylene sulfide resin is suppressed. The means for suppressing crystallization is not limited, but a method of quenching a raw film obtained by melt-extruding a polyphenylene sulfide resin under non-stretching conditions, a method of remelting a commercially available polyphenylene sulfide resin film to amorphize it, Examples thereof include a method of film-forming a polyphenylene sulfide resin obtained by copolymerizing a monomer giving an amorphous structure. In terms of manufacturing cost, the first method (non-stretching / quenching) is preferable. In the production of the low crystalline PPS film of the present invention, the crystallinity of the polyphenylene sulfide resin is such that the crystallinity measured by the X-ray diffraction method is 20% or less, preferably 15% or less, and more preferably 5% or less. Suppresses crystallization.
本発明の低結晶性・高接着性ＰＰＳフィルムは、こうして得られた低結晶性ＰＰＳフィルムの少なくとも一方の表面の他材料に対する接着性を向上させたもの、具体的には、上記低結晶性ＰＰＳフィルムの少なくとも一方の表面をプラズマ処理したものである。プラズマ処理装置やプラズマ処理の条件は、得られた低結晶性ＰＰＳフィルムの少なくとも一方の表面の水接触角が４５°以下、好ましくは３５°以下となる条件であれば、制限されない。上記プラズマ処理は、典型的には、上記低結晶性ＰＰＳフィルムをドラム型プラズマ照射装置あるいは平板型プラズマ照射装置に導入し、上記装置においてプラズマを上記低結晶性ＰＰＳフィルムの少なくとも一方の表面に照射する。このプラズマ処理によって、上記表面に水酸基（－ＯＨ）やカルボキシル基（－ＣＯＯＨ）などの反応性基が生成すると推測される。このため、本発明におけるプラズマ処理を一種の親水化処理と位置付けることもできる。得られた低結晶性・高接着性ＰＰＳフィルムは、金属などの他材料、特に銅箔に対して高い接着性を示す。なお、通常、上記プラズマ処理はポリフェニレンスルフィド樹脂の結晶化が進行しない程度の低温下で行うため、上記低結晶性ＰＰＳフィルムの結晶化度は、プラズマ処理を経ても維持される。
The low-crystalline and high-adhesive PPS film of the present invention is one in which the adhesiveness of at least one surface of the thus obtained low-crystalline PPS film to other materials is improved, specifically, the above-mentioned low-crystalline PPS. At least one surface of the film is plasma-treated. The plasma processing apparatus and plasma treatment conditions are not limited as long as the water contact angle of at least one surface of the obtained low crystallinity PPS film is 45 ° or less, preferably 35 ° or less. In the plasma treatment, the low crystalline PPS film is typically introduced into a drum type plasma irradiator or a flat plate type plasma irradiator, and the plasma is applied to at least one surface of the low crystalline PPS film in the apparatus. do. It is presumed that this plasma treatment produces reactive groups such as hydroxyl groups (-OH) and carboxyl groups (-COOH) on the surface. Therefore, the plasma treatment in the present invention can be regarded as a kind of hydrophilization treatment. The obtained low crystallinity and high adhesiveness PPS film exhibits high adhesiveness to other materials such as metal, particularly copper foil. Since the plasma treatment is usually performed at a low temperature at which the crystallization of the polyphenylene sulfide resin does not proceed, the crystallinity of the low crystalline PPS film is maintained even after the plasma treatment.
ドラム型プラズマ照射装置を用いた上プラズマ照射電圧は、一般的には１．０ｋＶ以上４．０ｋＶ以下、好ましくは１．５ｋＶ以上３．５ｋＶ以下、さらに好ましくは１．５ｋＶ以上３．０ｋＶ以下である。同等のプラズマ照射強度が得られる条件で、平板型プラズマ照射装置などの他の方式でプラズマ処理を行うことができる。
The upper plasma irradiation voltage using the drum type plasma irradiation device is generally 1.0 kV or more and 4.0 kV or less, preferably 1.5 kV or more and 3.5 kV or less, and more preferably 1.5 kV or more and 3.0 kV or less. be. Plasma treatment can be performed by another method such as a flat plate type plasma irradiation device under the condition that the same plasma irradiation intensity can be obtained.
本発明の低結晶性・高接着性ＰＰＳフィルムは、熱収縮が抑えられている。本発明の低結晶性・高接着性ＰＰＳフィルムについて以下の方法で求めた縦方向の熱収縮率（％）及び横方向の熱収縮率（％）のいずれもが、１％以下、好ましくは０．５％以下である。
The low crystallinity and high adhesiveness PPS film of the present invention suppresses heat shrinkage. For the low crystallinity and high adhesiveness PPS film of the present invention, both the heat shrinkage rate (%) in the vertical direction and the heat shrinkage rate (%) in the horizontal direction obtained by the following methods are 1% or less, preferably 0. It is less than 5.5%.
（熱収縮率の測定方法）まず、試料フィルムから、正方形（１００ｍｍ×１００ｍｍ×０．０２５ｍｍ）の試験片を切り出し、４辺（縦方向の２辺：ｌ１，ｌ２及び横方向の２辺：ｌ３，ｌ４）の長さ（ｌ１ｂ，ｌ２ｂ，ｌ３ｂ，ｌ４ｂ）を測定する。次に、試験片を２００℃で２ＭＰａ荷重下、１０分間、熱プレスした。熱プレスを終えた試験片の４辺の長さ（ｌ１ａ，ｌ２ａ，ｌ３ａ，ｌ４ａ）を測定する。以下の式に従い、縦方向の熱収縮率（％）と横方向の熱収縮率（％）を算出する。
・縦方向の熱収縮率（％）＝（（ｌ１ｂ－ｌ１ａ）＋（ｌ２ｂ－ｌ２ａ））÷（ｌ１ｂ＋ｌ２ｂ）×１００
・横方向の熱収縮率（％）＝（（ｌ３ｂ－ｌ３ａ）＋（ｌ４ｂ－ｌ４ａ））÷（ｌ３ｂ＋ｌ４ｂ）×１００
本発明の低結晶性・高接着性ＰＰＳフィルムと銅箔とを用いて、より低い製造コストで結晶性ＰＰＳからなる層と銅からなる層とを含む積層体（以下「積層体Ｌ２」）を製造することができる。この積層体Ｌ２は、剥離強度、誘電特性、耐熱性に優れるため、コンデンサ、キャパシター、各種通信機器に用いられる回路基板、伝送ケーブル、アンテナの構成部材として有用である。 (Measurement method of heat shrinkage rate) First, a square (100 mm × 100 mm × 0.025 mm) test piece is cut out from the sample film, and four sides (two sides in the vertical direction: l1, l2 and two sides in the horizontal direction: l3) are cut out. , L4) (l1b, l2b, l3b, l4b) are measured. Next, the test piece was heat-pressed at 200 ° C. under a load of 2 MPa for 10 minutes. The lengths (l1a, l2a, l3a, l4a) of the four sides of the test piece that has been hot-pressed are measured. According to the following formula, the heat shrinkage rate (%) in the vertical direction and the heat shrinkage rate (%) in the horizontal direction are calculated.
-Vertical heat shrinkage rate (%) = ((l1b-l1a) + (l2b-l2a)) ÷ (l1b + l2b) x 100
Lateral heat shrinkage rate (%) = ((l3b-l3a) + (l4b-l4a)) ÷ (l3b + l4b) x 100
Using the low crystalline / high adhesive PPS film of the present invention and a copper foil, a laminated body containing a layer made of crystalline PPS and a layer made of copper (hereinafter referred to as “laminated body L2”) can be obtained at a lower manufacturing cost. Can be manufactured. Since the laminated body L2 is excellent in peel strength, dielectric property, and heat resistance, it is useful as a component of a capacitor, a capacitor, a circuit board used in various communication devices, a transmission cable, and an antenna.
・縦方向の熱収縮率（％）＝（（ｌ１ｂ－ｌ１ａ）＋（ｌ２ｂ－ｌ２ａ））÷（ｌ１ｂ＋ｌ２ｂ）×１００
・横方向の熱収縮率（％）＝（（ｌ３ｂ－ｌ３ａ）＋（ｌ４ｂ－ｌ４ａ））÷（ｌ３ｂ＋ｌ４ｂ）×１００
本発明の低結晶性・高接着性ＰＰＳフィルムと銅箔とを用いて、より低い製造コストで結晶性ＰＰＳからなる層と銅からなる層とを含む積層体（以下「積層体Ｌ２」）を製造することができる。この積層体Ｌ２は、剥離強度、誘電特性、耐熱性に優れるため、コンデンサ、キャパシター、各種通信機器に用いられる回路基板、伝送ケーブル、アンテナの構成部材として有用である。 (Measurement method of heat shrinkage rate) First, a square (100 mm × 100 mm × 0.025 mm) test piece is cut out from the sample film, and four sides (two sides in the vertical direction: l1, l2 and two sides in the horizontal direction: l3) are cut out. , L4) (l1b, l2b, l3b, l4b) are measured. Next, the test piece was heat-pressed at 200 ° C. under a load of 2 MPa for 10 minutes. The lengths (l1a, l2a, l3a, l4a) of the four sides of the test piece that has been hot-pressed are measured. According to the following formula, the heat shrinkage rate (%) in the vertical direction and the heat shrinkage rate (%) in the horizontal direction are calculated.
-Vertical heat shrinkage rate (%) = ((l1b-l1a) + (l2b-l2a)) ÷ (l1b + l2b) x 100
Lateral heat shrinkage rate (%) = ((l3b-l3a) + (l4b-l4a)) ÷ (l3b + l4b) x 100
Using the low crystalline / high adhesive PPS film of the present invention and a copper foil, a laminated body containing a layer made of crystalline PPS and a layer made of copper (hereinafter referred to as “laminated body L2”) can be obtained at a lower manufacturing cost. Can be manufactured. Since the laminated body L2 is excellent in peel strength, dielectric property, and heat resistance, it is useful as a component of a capacitor, a capacitor, a circuit board used in various communication devices, a transmission cable, and an antenna.
上記積層体Ｌ２は、上記低結晶性・高接着性ＰＰＳフィルムからなる層（以下「層Ａ１」）と銅からなる層（以下「層Ｂ」）とを含む積層体（以下「積層体Ｌ１」）を加熱・加圧することによって製造することができる。上記積層体Ｌ１は、上記積層体Ｌ２の中間体として位置づけられる。
The laminate L2 is a laminate (hereinafter “laminate L1”) including a layer made of the low crystallinity and high adhesive PPS film (hereinafter “layer A1”) and a layer made of copper (hereinafter “layer B”). ) Can be manufactured by heating and pressurizing. The laminated body L1 is positioned as an intermediate of the laminated body L2.
［積層体Ｌ１］ 本発明では、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムと銅箔とを重ねて、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムからなる層（層Ａ１）及び銅箔からなる層（層Ｂ）を含む積層体（積層体Ｌ１）を製造する。
[Laminated body L1] In the present invention, the low crystalline / high adhesive polyphenylene sulfide film and the copper foil are laminated, and the layer (layer A1) made of the low crystalline / high adhesive polyphenylene sulfide film and the copper foil are used. A laminated body (laminated body L1) including a layer (layer B) is produced.
上記銅箔の上記低結晶性・高接着性ポリフェニレンスルフィドフィルムと接する面は、より平滑、すなわちその表面粗さがより小さい程、上記層Ａ１と上記層Ｂとの密着性が向上することが分かっている。ポリフェニレンスルフィドフィルムと銅箔とを接着剤を介して接着する場合や、溶融状態のポリフェニレンスルフィドフィルムに銅箔を被覆する場合には、ポリフェニレンスルフィドフィルムに接する銅箔面の表面粗さが大きいほど高い接着強度が得られるが、驚くべきことに、本発明ではこの逆である。
It was found that the surface of the copper foil in contact with the low crystallinity and high adhesive polyphenylene sulfide film is smoother, that is, the smaller the surface roughness thereof, the better the adhesion between the layer A1 and the layer B. ing. When the polyphenylene sulfide film and the copper foil are bonded via an adhesive, or when the copper foil is coated on the molten polyphenylene sulfide film, the larger the surface roughness of the copper foil surface in contact with the polyphenylene sulfide film, the higher the surface roughness. Adhesive strength is obtained, but surprisingly, the opposite is true in the present invention.
そこで、本発明では、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下、好ましくは少なくとも一方の表面粗さ（Ｒｚ）が１．５μｍ以下である銅箔を用いる。上記表面粗さ（Ｒｚ）の測定は常法に従う。表面粗さ（Ｒｚ）の測定方法はすでに確立されており当業者の理解と追試に困難性は無い。後述の実施例で採用した測定方法は常法に従う１例であり測定精度を損なわない範囲で測定条件・測定機器の変更が許容される。
Therefore, in the present invention, a copper foil having at least one surface roughness (Rz) of 2 μm or less, preferably at least one surface roughness (Rz) of 1.5 μm or less is used. The surface roughness (Rz) is measured according to a conventional method. The method for measuring the surface roughness (Rz) has already been established, and there is no difficulty in understanding and retesting by those skilled in the art. The measurement method adopted in the examples described later is an example according to a conventional method, and changes in measurement conditions and measurement equipment are permitted as long as the measurement accuracy is not impaired.
上記積層体Ｌ１において、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの水接触角が４５°以下である少なくとも一方の表面と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが接している。
In the laminated body L1, at least one surface of the low crystallinity and high adhesive polyphenylene sulfide film having a water contact angle of 45 ° or less and at least one surface of the copper foil having a surface roughness (Rz) of 2 μm or less. Is in contact with the surface of.
ここで使用する銅箔としては、表面粗さが上述の条件を満たすものであれば、電解銅箔や圧延銅箔などの公知の銅箔を制限なく使用することができる。さらに、キャリア箔付銅箔やニッケル層等を備えた銅箔等も使用することができる。また、上記銅箔にあらかじめ表面処理してもよい。上記銅箔の厚みは特に制限されないが、一般的には５μｍ以上５０μｍ以下、好ましくは１０μｍ以上５０μｍ以下、さらに好ましくは１０μｍ以上３０μｍ以下の範囲にある。
As the copper foil used here, known copper foils such as electrolytic copper foils and rolled copper foils can be used without limitation as long as the surface roughness satisfies the above conditions. Further, a copper foil with a carrier foil, a copper foil provided with a nickel layer, or the like can also be used. Further, the copper foil may be surface-treated in advance. The thickness of the copper foil is not particularly limited, but is generally in the range of 5 μm or more and 50 μm or less, preferably 10 μm or more and 50 μm or less, and more preferably 10 μm or more and 30 μm or less.
積層体Ｌ１を構成する層Ａ１と層Ｂのそれぞれの数（層数）は特に制限されない。上記低結晶性・高接着性ポリフェニレンスルフィドフィルムと銅箔との積層手段は常法に従う。一般的には真空プレス機を用いる。
The number (number of layers) of each of the layers A1 and B constituting the laminated body L1 is not particularly limited. The means for laminating the low crystallinity and high adhesive polyphenylene sulfide film and the copper foil is according to a conventional method. Generally, a vacuum press is used.
［積層体Ｌ２］ 本発明では、さらに、積層体Ｌ１を、加圧下に、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化温度以上の温度まで加熱して、積層体Ｌ２を製造する。上記加熱によって、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムに含まれるポリフェニレンスルフィドが結晶化する。したがって、本発明の積層体Ｌ２は、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化物からなる層（層Ａ２）、及び、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）を含み、上記層Ａ２と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが強固に密着している。
[Laminated body L2] In the present invention, the laminated body L1 is further heated to a temperature equal to or higher than the crystallization temperature of the low crystalline and high adhesive polyphenylene sulfide film under pressure to produce the laminated body L2. By the heating, the polyphenylene sulfide contained in the low crystalline and high adhesive polyphenylene sulfide film is crystallized. Therefore, the laminate L2 of the present invention is a layer (layer A2) made of a crystallinized product of the low crystalline and high adhesive polyphenylene sulfide film, and a copper foil having at least one surface roughness (Rz) of 2 μm or less. A layer (layer B) made of the above layer (layer B) is included, and the layer A2 and at least one surface having a surface roughness (Rz) of 2 μm or less of the copper foil are firmly adhered to each other.
本発明の積層体Ｌ２の、１８０度剥離試験で測定した剥離強度は、１Ｎ／ｃｍ以上、好ましくは４Ｎ／ｃｍ以上を示す。上記１８０度剥離試験は常法に従う。１８０度剥離試験の測定方法はすでに確立されており当業者の理解と追試に困難性は無い。後述の実施例で採用した測定方法は常法に従う１例であり測定精度を損なわない範囲で測定条件・測定機器の変更が許容される。
The peel strength of the laminated body L2 of the present invention measured in the 180 degree peel test is 1 N / cm or more, preferably 4 N / cm or more. The 180-degree peeling test follows a conventional method. The measuring method of the 180 degree peeling test has already been established, and there is no difficulty in understanding and retesting by those skilled in the art. The measurement method adopted in the examples described later is an example according to a conventional method, and changes in measurement conditions and measurement equipment are permitted as long as the measurement accuracy is not impaired.
積層体Ｌ２の製造は、具体的には、上記層Ａ１と上記層Ｂとが隙間がなく密着するように上記積層体Ｌ１を押圧した状態で、上記積層体Ｌ１を上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化温度以上の温度まで加熱する。このような加圧・加熱を行う装置は適宜選択できるが、典型的には、真空プレス機を用いる。上記押圧力としては、上記層Ａ１と上記層Ｂとが隙間がなく密着する限り制限されないが、一般的には １ＭＰａ以上６ＭＰａ以下、好ましくは２ＭＰａ以上５ＭＰａ以下であればよい。上記所定温度の基準となる上記結晶化温度は、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの主成分であるポリフェニレンスルフィド樹脂の結晶化温度を指す。ポリフェニレンスルフィド樹脂、典型的には直鎖状ポリフェニレンスルフィド樹脂の結晶化温度は１２０℃から１３０℃までの範囲にある。必要最小のエネルギーコストで上記低結晶性・高接着性ポリフェニレンスルフィドフィルムからなる層（層Ａ１）を十分に結晶化させるためには、上記所定温度は概ね１３０℃以上２３０℃以下、好ましくは１４０℃以上２００℃以下、さらに好ましくは１５０℃以上１９０℃以下の範囲で選ばれる。この温度が高いほどエネルギーコストは高くなるがより高い結晶化が達成される傾向にある。
Specifically, in the production of the laminated body L2, the laminated body L1 is pressed with the laminated body L1 so that the layer A1 and the layer B are in close contact with each other without a gap, and the laminated body L1 is subjected to the low crystallinity and high adhesion. Heat to a temperature above the crystallization temperature of the polyphenylene sulfide film. A device for performing such pressurization / heating can be appropriately selected, but a vacuum press machine is typically used. The pressing force is not limited as long as the layer A1 and the layer B are in close contact with each other without a gap, but generally, the pressing force may be 1 MPa or more and 6 MPa or less, preferably 2 MPa or more and 5 MPa or less. The crystallization temperature, which is a reference of the predetermined temperature, refers to the crystallization temperature of the polyphenylene sulfide resin which is the main component of the low crystalline and high adhesive polyphenylene sulfide film. The crystallization temperature of the polyphenylene sulfide resin, typically the linear polyphenylene sulfide resin, ranges from 120 ° C to 130 ° C. In order to sufficiently crystallize the layer (layer A1) made of the low crystalline and high adhesive polyphenylene sulfide film at the minimum energy cost, the predetermined temperature is generally 130 ° C. or higher and 230 ° C. or lower, preferably 140 ° C. It is selected in the range of 200 ° C. or higher, more preferably 150 ° C. or higher and 190 ° C. or lower. The higher the temperature, the higher the energy cost, but the higher the crystallization tends to be achieved.
上記層Ａ２は、熱履歴において、従来の結晶性ポリフェニレンスルフィド層、すなわち、結晶性ポリフェニレンスルフィドフィルムと称して市販されているフィルムからなる層とは、異なる。現在の分析技術では上記層Ａ２と従来の結晶性ポリフェニレンスルフィド層との違いをポリフェニレンスルフィドの分子構造あるいは配向性などで表現することは困難であるが、ほとんどの高分子化合物に関してその熱履歴の差が化合物の何らかの性状に差異を与えることが分かっている。したがって上記層Ａ２を有する積層体Ｌ２は、従来の結晶性ポリフェニレンスルフィドからなる層と銅からなる層を有する積層体のいずれとも異なる物品である。
The layer A2 is different from the conventional crystalline polyphenylene sulfide layer, that is, a layer made of a commercially available film called a crystalline polyphenylene sulfide film, in terms of thermal history. With the current analytical technology, it is difficult to express the difference between the above layer A2 and the conventional crystalline polyphenylene sulfide layer by the molecular structure or orientation of polyphenylene sulfide, but the difference in the thermal history of most polymer compounds. Is known to make a difference in some properties of the compound. Therefore, the laminated body L2 having the layer A2 is an article different from both the conventional laminated body having a layer made of crystalline polyphenylene sulfide and a layer made of copper.
本発明の積層体Ｌ２の従来品に対する有利性は、製造コストと製造設備にある。従来品の製造では、結晶性ポリフェニレンスルフィドフィルムと銅箔との熱プレス工程でポリフェニレンスルフィドフィルムの融点（約２８０℃）付近の温度まで加熱する必要があったが、本発明では、熱プレス温度はこれよりはるかに低い。このため、積層体Ｌ２の製造におけるコストは従来よりも低減され、本発明の積層体Ｌ２は耐熱性が比較的劣る機器でも製造できる。
The advantages of the laminated body L2 of the present invention over the conventional product are in the manufacturing cost and the manufacturing equipment. In the production of the conventional product, it was necessary to heat the polyphenylene sulfide film to a temperature near the melting point (about 280 ° C.) in the heat pressing process of the crystalline polyphenylene sulfide film and the copper foil. Much lower than this. Therefore, the cost in manufacturing the laminated body L2 is lower than before, and the laminated body L2 of the present invention can be manufactured even with a device having relatively inferior heat resistance.
より平滑な銅箔とポリフェニレンスルフィドフィルムを含む積層体を回路基板として用いた場合には、伝送損失を小さくできる点で有利である。本発明の積層体Ｌ２を構成する銅箔層Ｂと結晶性ポリフェニレンスルフィドフィルム層Ａ２との界面では、上述の積層体Ｌ１に用いた銅箔のより小さな表面粗さが維持されている。このため、本発明の積層体Ｌ２は特に高周波回路基板用銅張積層体の材料として優れる。
When a laminate containing a smoother copper foil and a polyphenylene sulfide film is used as a circuit board, it is advantageous in that transmission loss can be reduced. At the interface between the copper foil layer B constituting the laminate L2 of the present invention and the crystalline polyphenylene sulfide film layer A2, the smaller surface roughness of the copper foil used for the laminate L1 described above is maintained. Therefore, the laminate L2 of the present invention is particularly excellent as a material for a copper-clad laminate for a high-frequency circuit board.
［製品］ 剥離強度や耐熱性、誘電特性の点で、本発明の積層体Ｌ２は従来品、すなわち、結晶性ポリフェニレンスルフィドフィルムと銅箔とを積層させて得られる積層体と同等以上の性能を有する。このため、本発明の積層体Ｌ２は、結晶性ポリフェニレンスルフィドフィルムと銅箔とを積層させて得られる積層体がこれまで適用されてきたあらゆる分野で、従来品に置き換わることができる。本発明の積層体Ｌ２は、例えば、コンデンサ、キャパシター、各種通信機器に用いられる回路基板、基地局に用いられる回路基板、車載ミリ波レーダーに用いられる回路基板、伝送ケーブル、アンテナの構成部材として用いることができ、中でも高周波に対応する構成部材として有用である。
[Product] In terms of peel strength, heat resistance, and dielectric properties, the laminate L2 of the present invention has performance equal to or higher than that of a conventional product, that is, a laminate obtained by laminating a crystalline polyphenylene sulfide film and a copper foil. Have. Therefore, the laminate L2 of the present invention can replace the conventional product in all fields to which the laminate obtained by laminating the crystalline polyphenylene sulfide film and the copper foil has been applied. The laminated body L2 of the present invention is used, for example, as a component of a capacitor, a capacitor, a circuit board used for various communication devices, a circuit board used for a base station, a circuit board used for an in-vehicle millimeter-wave radar, a transmission cable, and an antenna. It is possible, and above all, it is useful as a component corresponding to high frequency.
[Product] In terms of peel strength, heat resistance, and dielectric properties, the laminate L2 of the present invention has performance equal to or higher than that of a conventional product, that is, a laminate obtained by laminating a crystalline polyphenylene sulfide film and a copper foil. Have. Therefore, the laminate L2 of the present invention can replace the conventional product in all fields to which the laminate obtained by laminating the crystalline polyphenylene sulfide film and the copper foil has been applied. The laminated body L2 of the present invention is used, for example, as a component of a capacitor, a capacitor, a circuit board used for various communication devices, a circuit board used for a base station, a circuit board used for an in-vehicle millimeter-wave radar, a transmission cable, and an antenna. It is possible, and above all, it is useful as a component corresponding to high frequency.
［実施例１～１０，比較例１～１０］
（材料） 本発明の例及び比較品の製造には以下の材料を用いた。＊は本発明の条件を外れる比較品を表す。 [Examples 1 to 10, Comparative Examples 1 to 10]
(Material) The following materials were used for the production of the example of the present invention and the comparative product. * Represents a comparative product that does not meet the conditions of the present invention.
（材料） 本発明の例及び比較品の製造には以下の材料を用いた。＊は本発明の条件を外れる比較品を表す。 [Examples 1 to 10, Comparative Examples 1 to 10]
(Material) The following materials were used for the production of the example of the present invention and the comparative product. * Represents a comparative product that does not meet the conditions of the present invention.
・低結晶性ＰＰＳフィルム（Ｆ１）：ｐ－フェニレンスルフィド単位からなる直鎖状ポリフェニレンスルフィドを溶融押出したフィルムを急冷して得られた結晶化度０％の直鎖型・非強化ＰＰＳからなる無延伸フィルム。厚み２５μｍ。
-Low crystalline PPS film (F1): A linear non-reinforced PPS having a crystallinity of 0% obtained by quenching a film obtained by melt-extruding a linear polyphenylene sulfide composed of p-phenylene sulfide units. Stretched film. Thickness 25 μm.
・低結晶性ＰＰＳフィルム（Ｆ２）：ｐ－フェニレンスルフィド単位からなる直鎖状ポリフェニレンスルフィドを溶融押出したフィルムを急冷して得られた結晶化度１３．９％の直鎖型・非強化ＰＰＳからなる無延伸フィルム。厚み２５μｍ。
Low crystalline PPS film (F2): From a linear non-reinforced PPS having a crystallinity of 13.9% obtained by quenching a film obtained by melt-extruding a linear polyphenylene sulfide composed of p-phenylene sulfide units. Non-stretched film. Thickness 25 μm.
・低結晶性ＰＰＳフィルム（Ｆ３＊）：ｐ－フェニレンスルフィド単位からなる直鎖状ポリフェニレンスルフィドを溶融押出したフィルムを急冷して得られた結晶化度２８．４％の直鎖型・非強化ＰＰＳからなる無延伸フィルム。厚み２５μｍ。
Low crystalline PPS film (F3 *): A linear non-reinforced PPS having a crystallinity of 28.4% obtained by quenching a film obtained by melt-extruding a linear polyphenylene sulfide composed of p-phenylene sulfide units. Non-stretched film consisting of. Thickness 25 μm.
・結晶性ＰＰＳフィルム（比較品、Ｆ４＊）：市販の、直鎖状・フィラー非配合タイプのＰＰＳフィルム。結晶化度約５０％、厚み２５μｍ。
・ Crystalline PPS film (comparative product, F4 *): Commercially available linear PPS film without filler. Crystallinity is about 50% and thickness is 25 μm.
・銅箔（Ｍ１）：厚み３０μｍの圧延銅箔。表面粗さＲｚ：１．２μｍ
・銅箔（比較品、Ｍ２＊）：厚み３０μｍの圧延銅箔。表面粗さＲｚ：２．２μｍ
（低結晶性・高接着性ポリフェニレンスルフィドフィルムの製造） ドラム型プラズマ照射装置を用い、表１に示す条件で上記ＰＰＳフィルムの片面をプラズマ処理した。こうして本発明の低結晶性・高接着性ポリフェニレンスルフィドフィルムとその比較品を製造した。表１中、「－」は処理を行わなかったことを示す。得られたポリフェニレンスルフィドフィルムの水接触角と熱収縮率を表１に示す。
-Copper foil (M1): Rolled copper foil with a thickness of 30 μm. Surface roughness Rz: 1.2 μm
-Copper foil (comparative product, M2 *): Rolled copper foil with a thickness of 30 μm. Surface roughness Rz: 2.2 μm
(Manufacturing of low crystallinity and high adhesive polyphenylene sulfide film) One side of the PPS film was plasma-treated under the conditions shown in Table 1 using a drum-type plasma irradiation device. In this way, the low crystallinity and high adhesive polyphenylene sulfide film of the present invention and its comparative product were manufactured. In Table 1, "-" indicates that no processing was performed. Table 1 shows the water contact angle and the heat shrinkage of the obtained polyphenylene sulfide film.
・銅箔（比較品、Ｍ２＊）：厚み３０μｍの圧延銅箔。表面粗さＲｚ：２．２μｍ
（低結晶性・高接着性ポリフェニレンスルフィドフィルムの製造） ドラム型プラズマ照射装置を用い、表１に示す条件で上記ＰＰＳフィルムの片面をプラズマ処理した。こうして本発明の低結晶性・高接着性ポリフェニレンスルフィドフィルムとその比較品を製造した。表１中、「－」は処理を行わなかったことを示す。得られたポリフェニレンスルフィドフィルムの水接触角と熱収縮率を表１に示す。
-Copper foil (M1): Rolled copper foil with a thickness of 30 μm. Surface roughness Rz: 1.2 μm
-Copper foil (comparative product, M2 *): Rolled copper foil with a thickness of 30 μm. Surface roughness Rz: 2.2 μm
(Manufacturing of low crystallinity and high adhesive polyphenylene sulfide film) One side of the PPS film was plasma-treated under the conditions shown in Table 1 using a drum-type plasma irradiation device. In this way, the low crystallinity and high adhesive polyphenylene sulfide film of the present invention and its comparative product were manufactured. In Table 1, "-" indicates that no processing was performed. Table 1 shows the water contact angle and the heat shrinkage of the obtained polyphenylene sulfide film.
（積層体Ｌ１の製造） 表２、表３に示す組み合わせで、ＰＰＳフィルムと銅箔を、ＰＰＳフィルムのプラズマ処理された面が銅箔表面に接するように、積層した。本発明の積層Ｌ１とその比較品が得られた。
(Manufacturing of Laminated Body L1) In the combinations shown in Tables 2 and 3, the PPS film and the copper foil were laminated so that the plasma-treated surface of the PPS film was in contact with the copper foil surface. The laminated L1 of the present invention and a comparative product thereof were obtained.
（積層体Ｌ２の製造） 本発明の積層Ｌ１とその比較品を真空プレス機に設置し、以下の条件で加圧下に加熱した。こうして本発明の積層Ｌ２とその比較品が得られた。得られた積層体Ｌ２の剥離強度、誘電率、誘電正接を表２、表３に示す。
・加圧条件：加熱開始から終了まで４ＭＰａに保持した。
・加熱条件：７０℃から７分間で１６０℃まで昇温し、１６０℃で５分間保持した。
(Manufacturing of Laminated Body L2) The laminated body L1 of the present invention and its comparative product were installed in a vacuum press and heated under pressure under the following conditions. In this way, the laminated L2 of the present invention and a comparative product thereof were obtained. Tables 2 and 3 show the peel strength, dielectric constant, and dielectric loss tangent of the obtained laminated body L2.
-Pressurization condition: The pressure was maintained at 4 MPa from the start to the end of heating.
-Heating conditions: The temperature was raised from 70 ° C. to 160 ° C. in 7 minutes and kept at 160 ° C. for 5 minutes.
・加圧条件：加熱開始から終了まで４ＭＰａに保持した。
・加熱条件：７０℃から７分間で１６０℃まで昇温し、１６０℃で５分間保持した。
(Manufacturing of Laminated Body L2) The laminated body L1 of the present invention and its comparative product were installed in a vacuum press and heated under pressure under the following conditions. In this way, the laminated L2 of the present invention and a comparative product thereof were obtained. Tables 2 and 3 show the peel strength, dielectric constant, and dielectric loss tangent of the obtained laminated body L2.
-Pressurization condition: The pressure was maintained at 4 MPa from the start to the end of heating.
-Heating conditions: The temperature was raised from 70 ° C. to 160 ° C. in 7 minutes and kept at 160 ° C. for 5 minutes.
（測定方法） 上記結晶度、水接触角、表面粗さ（Ｒｚ）、剥離強度、熱収縮率は以下の方法で測定した。
(Measurement method) The crystallinity, water contact angle, surface roughness (Rz), peel strength, and heat shrinkage were measured by the following methods.
＜結晶化度＞
・測定機：試料水平型Ｘ線回折装置
・電圧：３０ｋＶ
・電流：２０ｍＡ
・ステップ幅：０．０２°
・測定速度：２°／ｍｉｎ
・ＸＲＤ測定により確認されたピークを結晶質部分と非晶質部分に分け、以下の式に従い、そのピーク面積比から結晶化度を算出した。
結晶化度＝（結晶質部分のピーク面積）／（全体のピーク面積）×１００
＜水の接触角＞
・測定機：接触角・濡れ性測定機
・滴下水量：２μＬ
・サンプル数（Ｎ）：５
・測定方法：２μＬの蒸留水をシリンジにてゆっくりとフィルム表面へ滴下し、滴下後から３秒後の接触角をＣＣＤカメラで観察して測定した。実測値の平均値を水接触角として採用した。 <Crystallinity>
・ Measuring machine: Sample horizontal X-ray diffractometer ・ Voltage: 30 kV
・ Current: 20mA
・ Step width: 0.02 °
・ Measurement speed: 2 ° / min
The peak confirmed by XRD measurement was divided into a crystalline part and an amorphous part, and the crystallinity was calculated from the peak area ratio according to the following formula.
Crystallinity = (peak area of crystalline part) / (overall peak area) x 100
<Water contact angle>
・ Measuring machine: Contact angle ・ Wetting property measuring machine ・ Dropping water volume: 2 μL
-Number of samples (N): 5
-Measuring method: 2 μL of distilled water was slowly dropped onto the film surface with a syringe, and thecontact angle 3 seconds after the dropping was observed with a CCD camera for measurement. The average value of the measured values was adopted as the water contact angle.
・測定機：試料水平型Ｘ線回折装置
・電圧：３０ｋＶ
・電流：２０ｍＡ
・ステップ幅：０．０２°
・測定速度：２°／ｍｉｎ
・ＸＲＤ測定により確認されたピークを結晶質部分と非晶質部分に分け、以下の式に従い、そのピーク面積比から結晶化度を算出した。
結晶化度＝（結晶質部分のピーク面積）／（全体のピーク面積）×１００
＜水の接触角＞
・測定機：接触角・濡れ性測定機
・滴下水量：２μＬ
・サンプル数（Ｎ）：５
・測定方法：２μＬの蒸留水をシリンジにてゆっくりとフィルム表面へ滴下し、滴下後から３秒後の接触角をＣＣＤカメラで観察して測定した。実測値の平均値を水接触角として採用した。 <Crystallinity>
・ Measuring machine: Sample horizontal X-ray diffractometer ・ Voltage: 30 kV
・ Current: 20mA
・ Step width: 0.02 °
・ Measurement speed: 2 ° / min
The peak confirmed by XRD measurement was divided into a crystalline part and an amorphous part, and the crystallinity was calculated from the peak area ratio according to the following formula.
Crystallinity = (peak area of crystalline part) / (overall peak area) x 100
<Water contact angle>
・ Measuring machine: Contact angle ・ Wetting property measuring machine ・ Dropping water volume: 2 μL
-Number of samples (N): 5
-Measuring method: 2 μL of distilled water was slowly dropped onto the film surface with a syringe, and the
＜表面粗さ＞
・測定機：表面粗さ測定機
・触針材質：ダイヤモンド
・触針先端半径：５μｍ
・測定力：４ｍＮ
・低域カットオフ値：８μｍ
・高域カットオフ値：２．５ｍｍ
・評価長さ：７．５ｍｍ
・測定間隔：１．５μｍ
・測定速度：０．５ｍｍ／ｓ
・区間数：３
・記録本数：５本
・粗さ曲線の最大山高さと最大谷深さとの和：Ｒｚ（粗さ曲線の最大高さ）の値を、表面粗さとして採用した。 <Surface roughness>
・ Measuring machine: Surface roughness measuring machine ・ Needle material: Diamond ・ Needle tip radius: 5 μm
・ Measuring force: 4mN
・ Low frequency cutoff value: 8 μm
・ High frequency cutoff value: 2.5 mm
・ Evaluation length: 7.5 mm
・ Measurement interval: 1.5 μm
・ Measurement speed: 0.5 mm / s
・ Number of sections: 3
-Number of records: 5-The sum of the maximum peak height and the maximum valley depth of the roughness curve: The value of Rz (maximum height of the roughness curve) was adopted as the surface roughness.
・測定機：表面粗さ測定機
・触針材質：ダイヤモンド
・触針先端半径：５μｍ
・測定力：４ｍＮ
・低域カットオフ値：８μｍ
・高域カットオフ値：２．５ｍｍ
・評価長さ：７．５ｍｍ
・測定間隔：１．５μｍ
・測定速度：０．５ｍｍ／ｓ
・区間数：３
・記録本数：５本
・粗さ曲線の最大山高さと最大谷深さとの和：Ｒｚ（粗さ曲線の最大高さ）の値を、表面粗さとして採用した。 <Surface roughness>
・ Measuring machine: Surface roughness measuring machine ・ Needle material: Diamond ・ Needle tip radius: 5 μm
・ Measuring force: 4mN
・ Low frequency cutoff value: 8 μm
・ High frequency cutoff value: 2.5 mm
・ Evaluation length: 7.5 mm
・ Measurement interval: 1.5 μm
・ Measurement speed: 0.5 mm / s
・ Number of sections: 3
-Number of records: 5-The sum of the maximum peak height and the maximum valley depth of the roughness curve: The value of Rz (maximum height of the roughness curve) was adopted as the surface roughness.
＜剥離強度＞
・測定機：高速剥離試験機
・試験速度：１２０ｍｍ／ｍｉｎ
・試験：積層体から、長さ１５０ｍｍ、幅１０ｍｍの試験片を切り出した。この試験片について１８０°剥離強度（Ｍ／ｃｍ）を測定した。
・判定：剥離強度から層間接着性を３段階（特に良い＋＋＋：４Ｎ／ｃｍ以上、許容できる＋：１Ｎ／ｃｍ以上４Ｎ／ｃｍ未満、不良－：１Ｎ／ｃｍ未満）で判定した。 <Peeling strength>
・ Measuring machine: High-speed peeling tester ・ Test speed: 120 mm / min
-Test: A test piece having a length of 150 mm and a width of 10 mm was cut out from the laminated body. 180 ° peel strength (M / cm) was measured for this test piece.
Judgment: The interlayer adhesiveness was judged from the peel strength in three stages (particularly good +++: 4N / cm or more, acceptable +: 1N / cm or more and less than 4N / cm, defective −: less than 1N / cm).
・測定機：高速剥離試験機
・試験速度：１２０ｍｍ／ｍｉｎ
・試験：積層体から、長さ１５０ｍｍ、幅１０ｍｍの試験片を切り出した。この試験片について１８０°剥離強度（Ｍ／ｃｍ）を測定した。
・判定：剥離強度から層間接着性を３段階（特に良い＋＋＋：４Ｎ／ｃｍ以上、許容できる＋：１Ｎ／ｃｍ以上４Ｎ／ｃｍ未満、不良－：１Ｎ／ｃｍ未満）で判定した。 <Peeling strength>
・ Measuring machine: High-speed peeling tester ・ Test speed: 120 mm / min
-Test: A test piece having a length of 150 mm and a width of 10 mm was cut out from the laminated body. 180 ° peel strength (M / cm) was measured for this test piece.
Judgment: The interlayer adhesiveness was judged from the peel strength in three stages (particularly good +++: 4N / cm or more, acceptable +: 1N / cm or more and less than 4N / cm, defective −: less than 1N / cm).
＜熱収縮率＞
フィルムから、正方形（１００ｍｍ×１００ｍｍ×０．０２５ｍｍ）の試験片を切り出し、４辺（縦方向の２辺：ｌ１，ｌ２及び横方向の２辺：ｌ３，ｌ４）の長さ（ｌ１ｂ，ｌ２ｂ，ｌ３ｂ，ｌ４ｂ）を測定した。次に、試験片を２００℃で２ＭＰａ荷重下、１０分間、熱プレスした。熱プレスを終えた試験片の４辺の長さ（ｌ１ａ，ｌ２ａ，ｌ３ａ，ｌ４ａ）を測定した。以下の式に従い、縦方向の熱収縮率（％）と横方向の熱収縮率（％）を算出した。
・縦方向の熱収縮率（％）＝（（ｌ１ｂ－ｌ１ａ）＋（ｌ２ｂ－ｌ２ａ））÷（ｌ１ｂ＋ｌ２ｂ）×１００
・横方向の熱収縮率（％）＝（（ｌ３ｂ－ｌ３ａ）＋（ｌ４ｂ－ｌ４ａ））÷（ｌ３ｂ＋ｌ４ｂ）×１００
（評価） 表２に示すように、本発明の積層体Ｌ２（実施例６～１０）は、比較的低温で熱プレスして得られたにも関わらず、良好な剥離強度と誘電特性を示す。結晶化度あるいは水接触角が本発明の要件を満たさないポリフェニレンスルフィドフィルムを用いた積層体Ｌ２の比較品（比較例７～１０）と、銅箔の表面粗さが本発明の要件を満たさない（大きすぎる）積層体Ｌ２の比較品（比較例５、比較例６）とでは、ポリフェニレンスルフィド層と銅箔層との剥離強度が低く、実用性に劣る。 <Heat shrinkage rate>
A square (100 mm × 100 mm × 0.025 mm) test piece is cut out from the film and has a length (l1b, l2b, l1b, l2b, 4 sides (2 sides in the vertical direction: l1, l2 and 2 sides in the horizontal direction: l3, l4)). l3b, l4b) were measured. Next, the test piece was heat-pressed at 200 ° C. under a load of 2 MPa for 10 minutes. The lengths (l1a, l2a, l3a, l4a) of the four sides of the test piece that had been hot-pressed were measured. The heat shrinkage rate (%) in the vertical direction and the heat shrinkage rate (%) in the horizontal direction were calculated according to the following formulas.
-Vertical heat shrinkage rate (%) = ((l1b-l1a) + (l2b-l2a)) ÷ (l1b + l2b) x 100
Lateral heat shrinkage rate (%) = ((l3b-l3a) + (l4b-l4a)) ÷ (l3b + l4b) x 100
(Evaluation) As shown in Table 2, the laminate L2 (Examples 6 to 10) of the present invention exhibits good peel strength and dielectric properties even though it was obtained by hot pressing at a relatively low temperature. .. A comparative product of a laminate L2 using a polyphenylene sulfide film whose crystallinity or water contact angle does not meet the requirements of the present invention (Comparative Examples 7 to 10) and the surface roughness of a copper foil do not meet the requirements of the present invention. Compared with the comparative products (Comparative Example 5 and Comparative Example 6) of the (too large) laminated body L2, the peel strength between the polyphenylene sulfide layer and the copper foil layer is low, and the practicality is inferior.
フィルムから、正方形（１００ｍｍ×１００ｍｍ×０．０２５ｍｍ）の試験片を切り出し、４辺（縦方向の２辺：ｌ１，ｌ２及び横方向の２辺：ｌ３，ｌ４）の長さ（ｌ１ｂ，ｌ２ｂ，ｌ３ｂ，ｌ４ｂ）を測定した。次に、試験片を２００℃で２ＭＰａ荷重下、１０分間、熱プレスした。熱プレスを終えた試験片の４辺の長さ（ｌ１ａ，ｌ２ａ，ｌ３ａ，ｌ４ａ）を測定した。以下の式に従い、縦方向の熱収縮率（％）と横方向の熱収縮率（％）を算出した。
・縦方向の熱収縮率（％）＝（（ｌ１ｂ－ｌ１ａ）＋（ｌ２ｂ－ｌ２ａ））÷（ｌ１ｂ＋ｌ２ｂ）×１００
・横方向の熱収縮率（％）＝（（ｌ３ｂ－ｌ３ａ）＋（ｌ４ｂ－ｌ４ａ））÷（ｌ３ｂ＋ｌ４ｂ）×１００
（評価） 表２に示すように、本発明の積層体Ｌ２（実施例６～１０）は、比較的低温で熱プレスして得られたにも関わらず、良好な剥離強度と誘電特性を示す。結晶化度あるいは水接触角が本発明の要件を満たさないポリフェニレンスルフィドフィルムを用いた積層体Ｌ２の比較品（比較例７～１０）と、銅箔の表面粗さが本発明の要件を満たさない（大きすぎる）積層体Ｌ２の比較品（比較例５、比較例６）とでは、ポリフェニレンスルフィド層と銅箔層との剥離強度が低く、実用性に劣る。 <Heat shrinkage rate>
A square (100 mm × 100 mm × 0.025 mm) test piece is cut out from the film and has a length (l1b, l2b, l1b, l2b, 4 sides (2 sides in the vertical direction: l1, l2 and 2 sides in the horizontal direction: l3, l4)). l3b, l4b) were measured. Next, the test piece was heat-pressed at 200 ° C. under a load of 2 MPa for 10 minutes. The lengths (l1a, l2a, l3a, l4a) of the four sides of the test piece that had been hot-pressed were measured. The heat shrinkage rate (%) in the vertical direction and the heat shrinkage rate (%) in the horizontal direction were calculated according to the following formulas.
-Vertical heat shrinkage rate (%) = ((l1b-l1a) + (l2b-l2a)) ÷ (l1b + l2b) x 100
Lateral heat shrinkage rate (%) = ((l3b-l3a) + (l4b-l4a)) ÷ (l3b + l4b) x 100
(Evaluation) As shown in Table 2, the laminate L2 (Examples 6 to 10) of the present invention exhibits good peel strength and dielectric properties even though it was obtained by hot pressing at a relatively low temperature. .. A comparative product of a laminate L2 using a polyphenylene sulfide film whose crystallinity or water contact angle does not meet the requirements of the present invention (Comparative Examples 7 to 10) and the surface roughness of a copper foil do not meet the requirements of the present invention. Compared with the comparative products (Comparative Example 5 and Comparative Example 6) of the (too large) laminated body L2, the peel strength between the polyphenylene sulfide layer and the copper foil layer is low, and the practicality is inferior.
［実施例１１～１５］
（低結晶性・高接着性ポリフェニレンスルフィドフィルムの製造）
ｐ―フェニレンスルフィド単位からなる直鎖状ポリフェニレンスルフィドを溶融押出したフィルムを急冷して得られた結晶化度０％の無延伸ＰＰＳフィルム（Ｆ５）の片面を以下の表４の条件でプラズマ処理した。本発明の低結晶性・高接着性ポリフェニレンスルフィドフィルムＰＰＳ１０が得られた。フィルムＰＰＳ１０の性質を表４に示す。 [Examples 11 to 15]
(Manufacturing of low crystallinity and high adhesive polyphenylene sulfide film)
One side of an unstretched PPS film (F5) having a crystallinity of 0% obtained by melt-extruding a linear polyphenylene sulfide composed of p-phenylene sulfide units was subjected to plasma treatment under the conditions shown in Table 4 below. .. The low crystallinity and high adhesive polyphenylene sulfide film PPS10 of the present invention was obtained. The properties of the film PPS 10 are shown in Table 4.
（低結晶性・高接着性ポリフェニレンスルフィドフィルムの製造）
ｐ―フェニレンスルフィド単位からなる直鎖状ポリフェニレンスルフィドを溶融押出したフィルムを急冷して得られた結晶化度０％の無延伸ＰＰＳフィルム（Ｆ５）の片面を以下の表４の条件でプラズマ処理した。本発明の低結晶性・高接着性ポリフェニレンスルフィドフィルムＰＰＳ１０が得られた。フィルムＰＰＳ１０の性質を表４に示す。 [Examples 11 to 15]
(Manufacturing of low crystallinity and high adhesive polyphenylene sulfide film)
One side of an unstretched PPS film (F5) having a crystallinity of 0% obtained by melt-extruding a linear polyphenylene sulfide composed of p-phenylene sulfide units was subjected to plasma treatment under the conditions shown in Table 4 below. .. The low crystallinity and high adhesive polyphenylene sulfide film PPS10 of the present invention was obtained. The properties of the film PPS 10 are shown in Table 4.
別途、以下の表５に示す銅箔Ｍ２～Ｍ５を用意した。
Separately, the copper foils M2 to M5 shown in Table 5 below were prepared.
（積層体Ｌ１の製造） 表６に示す組み合わせで、低結晶性・高接着性ＰＰＳフィルム：ＰＰＳ１０）と上記銅箔Ｍ２～Ｍ５のいずれかを、ＰＰＳフィルムのプラズマ処理された面が上記銅箔表面に接するように積層した。こうして本発明の積層Ｌ１が得られた。
(Manufacturing of laminated body L1) In the combination shown in Table 6, low crystallinity and high adhesiveness PPS film: PPS10) and any of the above copper foils M2 to M5 are used, and the plasma-treated surface of the PPS film is the above copper foil. It was laminated so as to be in contact with the surface. In this way, the laminated L1 of the present invention was obtained.
（積層体Ｌ２の製造） 本発明の積層Ｌ１を真空プレス機に設置し、表６に示す条件で加圧下に加熱した。こうして本発明の積層Ｌ２が得られた。得られた積層体Ｌ２の剥離強度、誘電率、誘電正接を表６に示す。剥離強度の判定方法は実施例６～１０，比較例５～１０と同じである。
(Manufacturing of laminated body L2) The laminated body L1 of the present invention was installed in a vacuum press and heated under pressure under the conditions shown in Table 6. In this way, the laminated L2 of the present invention was obtained. Table 6 shows the peel strength, the dielectric constant, and the dielectric loss tangent of the obtained laminated body L2. The method for determining the peel strength is the same as in Examples 6 to 10 and Comparative Examples 5 to 10.
（評価） 表６に示すように、低結晶性・高接着性ポリフェニレンスルフィドフィルムＰＰＳ１０を、上記Ｍとは厚さや表面粗さが異なる銅箔と積層した積層体Ｌ２場合は、特に高い剥離強度と良好な誘電特性を示す。すなわち実施例１２～１５で製造した積層体の剥離強度は、「特に良い＋＋＋」と判定されるための基準値：「４Ｎ／ｃｍ」を大きく上回る。実施例１１～１５によって、本発明の低結晶性・高接着性ポリフェニレンスルフィドフィルムは少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である広範な銅箔と強固に密着し、その結果、有用な積層体Ｌ２が得られることが理解できる。
(Evaluation) As shown in Table 6, in the case of the laminated body L2 in which the low crystallinity and high adhesive polyphenylene sulfide film PPS10 is laminated with a copper foil having a thickness and surface roughness different from those of M, the peel strength is particularly high. Shows good dielectric properties. That is, the peel strength of the laminates produced in Examples 12 to 15 greatly exceeds the reference value: "4N / cm" for determining "particularly good +++". According to Examples 11 to 15, the low crystallinity and high adhesive polyphenylene sulfide film of the present invention firmly adheres to a wide range of copper foil having a surface roughness (Rz) of 2 μm or less on at least one of them, and as a result, it is useful. It can be understood that the laminated body L2 can be obtained.
本発明の低結晶性・高接着性ポリフェニレンスルフィドフィルム、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムからなる層Ａ１と銅箔層Ｂからなる層を含む本発明の積層体Ｌ１、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化物からなる層Ａ２及び銅箔層Ｂを含む本発明の積層体Ｌ２は、高性能で製造コストが低減された電気・電子・通信デバイスの材料として、有用である。
The low crystallinity / high adhesive polyphenylene sulfide film of the present invention, the laminate L1 of the present invention including the layer A1 made of the low crystallinity / high adhesive polyphenylene sulfide film and the copper foil layer B, the low crystallinity -The laminate L2 of the present invention containing the layer A2 made of a crystallinized product of a highly adhesive polyphenylene sulfide film and the copper foil layer B is useful as a material for electric / electronic / communication devices having high performance and reduced manufacturing cost. be.
１ 低結晶性・高接着性ポリフェニレンスルフィドフィルム
１００ 水接触角が４５°以下である表面
１０１ 低結晶性・高接着性ポリフェニレンスルフィドフィルムからなる、層Ａ１
１０２ 低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化物からなる層Ａ２
２ 銅箔
２００ 表面粗さ（Ｒｚ）が２μｍ以下である表面
２０１ 層Ｂ
３ 積層体Ｌ１
４ 積層体Ｌ２ 1 Low crystallinity / high adhesivepolyphenylene sulfide film 100 Surface 101 having a water contact angle of 45 ° or less Layer A1 made of low crystallinity / high adhesive polyphenylene sulfide film
102 Layer A2 composed of crystals of low crystalline and high adhesive polyphenylene sulfide film
2Copper foil 200 Surface 201 layer B with a surface roughness (Rz) of 2 μm or less
3 Laminated body L1
4 Laminated body L2
１００ 水接触角が４５°以下である表面
１０１ 低結晶性・高接着性ポリフェニレンスルフィドフィルムからなる、層Ａ１
１０２ 低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化物からなる層Ａ２
２ 銅箔
２００ 表面粗さ（Ｒｚ）が２μｍ以下である表面
２０１ 層Ｂ
３ 積層体Ｌ１
４ 積層体Ｌ２ 1 Low crystallinity / high adhesive
102 Layer A2 composed of crystals of low crystalline and high adhesive polyphenylene sulfide film
2
3 Laminated body L1
4 Laminated body L2
Claims (5)
- ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下であり、少なくとも一方の表面の水接触角が４５°以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルム。 Low crystallinity and high adhesive polyphenylene sulfide with polyphenylene sulfide resin as the main component, crystallinity measured by X-ray diffraction method of 20% or less, and water contact angle of at least one surface of 45 ° or less. the film.
- ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下であり、少なくとも一方の表面の水接触角が４５°以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルム からなる層（層Ａ１）、
及び、
少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）、を含み、
上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの水接触角が４５°以下である少なくとも一方の表面と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが接している、
積層体（Ｌ１）。 Low crystallinity and high adhesive polyphenylene sulfide with polyphenylene sulfide resin as the main component, crystallinity measured by X-ray diffraction method of 20% or less, and water contact angle of at least one surface of 45 ° or less. Layer consisting of film (layer A1),
as well as,
A layer (layer B) made of copper foil having at least one surface roughness (Rz) of 2 μm or less is included.
At least one surface of the low crystallinity and high adhesive polyphenylene sulfide film having a water contact angle of 45 ° or less is in contact with at least one surface of the copper foil having a surface roughness (Rz) of 2 μm or less. Yes,
Laminated body (L1). - ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下であり、少なくとも一方の表面の水接触角が４５°以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルム の結晶化物からなる層（層Ａ２）、及び、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）を含み、
上記層Ａ２と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが、密着しており、
上記層Ａ２と上記層Ｂとの１８０度剥離試験で測定した剥離強度が１Ｎ／ｃｍ以上を示す、
積層体（積層体Ｌ２）。 Low crystallinity and high adhesive polyphenylene sulfide with polyphenylene sulfide resin as the main component, crystallinity measured by X-ray diffraction method of 20% or less, and water contact angle of at least one surface of 45 ° or less. It contains a layer made of crystallinized film (layer A2) and a layer made of copper foil having at least one surface roughness (Rz) of 2 μm or less (layer B).
The layer A2 and at least one surface of the copper foil having a surface roughness (Rz) of 2 μm or less are in close contact with each other.
The peel strength measured by the 180 degree peel test between the layer A2 and the layer B is 1 N / cm or more.
Laminated body (laminated body L2). - 請求項３に記載の積層体（Ｌ２）を含む製品。 A product containing the laminate (L2) according to claim 3.
- 以下の工程１，工程２、工程３を含む、積層体の製造方法。
（工程１）
まず、ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下である低結晶性ポリフェニレンスルフィドフィルムを用意し、次に、上記低結晶性ポリフェニレンスルフィドフィルムの少なくとも一方の表面をプラズマ処理する工程であって、ポリフェニレンスルフィド樹脂を主な成分とし、Ｘ線回折法により測定した結晶化度が２０％以下である、低結晶性・高接着性ポリフェニレンスルフィドフィルムを製造する工程。
（工程２）
上記低結晶性・高接着性ポリフェニレンスルフィドフィルムからなる層（層Ａ１）、及び、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）を含む積層体（積層体Ｌ１）を製造する工程であって、
上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの水接触角が４５°以下である少なくとも一方の表面と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが接するように、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムと上記銅箔とを重ねる工程。
（工程３）
上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化物からなる層（層Ａ２）、及び、少なくとも一方の表面粗さ（Ｒｚ）が２μｍ以下である銅箔からなる層（層Ｂ）を含み、上記層Ａ２と、上記銅箔の表面粗さ（Ｒｚ）が２μｍ以下である少なくとも一方の表面とが密着しており、上記層Ａ２と上記層Ｂとの１８０度剥離試験で測定した剥離強度が１Ｎ／ｃｍ以上を示す、積層体（積層体Ｌ２）を製造する工程であって、
上記積層体Ｌ１を、加圧下で、上記低結晶性・高接着性ポリフェニレンスルフィドフィルムの結晶化温度以上の温度まで加熱する工程。 A method for manufacturing a laminated body, which comprises the following steps 1, 2, and 3.
(Step 1)
First, a low crystalline polyphenylene sulfide film containing a polyphenylene sulfide resin as a main component and having a crystallinity of 20% or less measured by an X-ray diffractometry is prepared, and then at least one of the above low crystalline polyphenylene sulfide films is prepared. A low-crystalline and highly adhesive polyphenylene sulfide film having a polyphenylene sulfide resin as a main component and a crystallinity of 20% or less measured by an X-ray diffractometry is produced in the step of plasma-treating the surface of the above. Process.
(Step 2)
A laminate (layer B) including a layer (layer A1) made of the low crystallinity and high adhesive polyphenylene sulfide film and a layer (layer B) made of a copper foil having at least one surface roughness (Rz) of 2 μm or less. It is a process of manufacturing body L1).
At least one surface of the low crystallinity / high adhesive polyphenylene sulfide film having a water contact angle of 45 ° or less is in contact with at least one surface of the copper foil having a surface roughness (Rz) of 2 μm or less. The step of superimposing the low crystallinity and high adhesive polyphenylene sulfide film and the copper foil on the surface.
(Step 3)
A layer (layer A2) made of a crystallinized product of the low crystalline / high adhesive polyphenylene sulfide film and a layer (layer B) made of a copper foil having at least one surface roughness (Rz) of 2 μm or less are included. The layer A2 and at least one surface of the copper foil having a surface roughness (Rz) of 2 μm or less are in close contact with each other, and the peeling strength measured by the 180-degree peeling test between the layer A2 and the layer B is high. It is a step of manufacturing a laminated body (laminated body L2) showing 1 N / cm or more.
A step of heating the laminate L1 under pressure to a temperature equal to or higher than the crystallization temperature of the low crystalline and high adhesive polyphenylene sulfide film.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0353934A (en) * | 1989-07-21 | 1991-03-07 | Kureha Chem Ind Co Ltd | Press-molding laminate constituted of polyphenylene sulfide and metallic plate, case molded with this laminate and manufacture of laminate and case |
| JP2008115417A (en) * | 2006-11-02 | 2008-05-22 | Toray Ind Inc | Method for producing metallized film, and metallized film |
| JP2010030308A (en) * | 2009-10-28 | 2010-02-12 | Hitachi Engineering & Services Co Ltd | Method for manufacturing aramid polyphenylen sulfide laminate without using adhesive |
| JP2013018226A (en) * | 2011-07-13 | 2013-01-31 | Daicel Pack Systems Ltd | Method for manufacturing integral molding, and integral molding |
| JP2013223985A (en) * | 2012-04-23 | 2013-10-31 | Adoweru:Kk | Film for electric insulation |
| JP2019188789A (en) * | 2017-05-08 | 2019-10-31 | 学校法人金沢工業大学 | Manufacturing method of bonded article, bonded article, and bonding object |
| WO2021020289A1 (en) * | 2019-07-30 | 2021-02-04 | 東レ株式会社 | Polyarylene sulfide resin film, metal layered product, production method for polyarylene sulfide resin film, and production method for metal layered product |
| JP2021020354A (en) * | 2019-07-26 | 2021-02-18 | 学校法人金沢工業大学 | Method for manufacturing joining object, joining object and object to be joined |
-
2021
- 2021-05-13 TW TW110117197A patent/TW202146534A/en unknown
- 2021-05-13 JP JP2022522199A patent/JPWO2021230321A1/ja active Pending
- 2021-05-13 WO PCT/JP2021/018240 patent/WO2021230321A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0353934A (en) * | 1989-07-21 | 1991-03-07 | Kureha Chem Ind Co Ltd | Press-molding laminate constituted of polyphenylene sulfide and metallic plate, case molded with this laminate and manufacture of laminate and case |
| JP2008115417A (en) * | 2006-11-02 | 2008-05-22 | Toray Ind Inc | Method for producing metallized film, and metallized film |
| JP2010030308A (en) * | 2009-10-28 | 2010-02-12 | Hitachi Engineering & Services Co Ltd | Method for manufacturing aramid polyphenylen sulfide laminate without using adhesive |
| JP2013018226A (en) * | 2011-07-13 | 2013-01-31 | Daicel Pack Systems Ltd | Method for manufacturing integral molding, and integral molding |
| JP2013223985A (en) * | 2012-04-23 | 2013-10-31 | Adoweru:Kk | Film for electric insulation |
| JP2019188789A (en) * | 2017-05-08 | 2019-10-31 | 学校法人金沢工業大学 | Manufacturing method of bonded article, bonded article, and bonding object |
| JP2021020354A (en) * | 2019-07-26 | 2021-02-18 | 学校法人金沢工業大学 | Method for manufacturing joining object, joining object and object to be joined |
| WO2021020289A1 (en) * | 2019-07-30 | 2021-02-04 | 東レ株式会社 | Polyarylene sulfide resin film, metal layered product, production method for polyarylene sulfide resin film, and production method for metal layered product |
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| JPWO2021230321A1 (en) | 2021-11-18 |
| TW202146534A (en) | 2021-12-16 |
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