JP6328951B2 - Melt adhesive film - Google Patents
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Description
本発明は、フッ素樹脂に特有の耐熱性、耐候性、耐薬品性、剥離性、低誘電特性等の優れた特性を有すると共に、異種材料、特に金属材料との溶融接着性が優れる溶融接着性フィルムに関する。 The present invention has excellent properties such as heat resistance, weather resistance, chemical resistance, releasability, low dielectric properties and the like, which are characteristic of fluororesins, and also has excellent melt adhesion with different materials, particularly metal materials. Related to film.
フッ素樹脂は、耐熱性、耐候性、耐薬品性、剥離性、低誘電特性等の優れた特性を有し、成形体に成形されるだけでなく、被覆材料としても使用され、異種材料との積層が検討されてきた。しかしながら、フッ素樹脂の表面エネルギーは小さく、フッ素樹脂と異種材料の接着は困難である。 Fluorocarbon resin has excellent properties such as heat resistance, weather resistance, chemical resistance, peelability, and low dielectric properties, and is not only molded into a molded body but also used as a coating material. Lamination has been considered. However, the surface energy of the fluororesin is small, and it is difficult to bond the fluororesin and a different material.
そこで、金属材料などの基材とフッ素樹脂を積層させる方法として、従来、一般的に、基材上に、基材及びフッ素樹脂の両方との接着性を有する接着層を形成し、その上にフッ素樹脂を積層する方法が検討されてきた。例えば、特許文献１には、（ａ）テトラフルオロエチレン／パーフルオロオレフィン共重合体と、ポリアミドイミド等の非溶融加工性結合剤と、ポリエーテルスルホン等の溶融加工性結合剤とを含むプライマ粉末が基材上に被着されてプライマ層が形成される工程、（ｂ）テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体を含むオーバーコート粉末がプライマ層上に被着されてオーバーコート層が形成される工程、プライマ層とオーバーコート層の両方が被着された後に（c）基材が焼き付けられる工程を含む方法が開示されている。 Therefore, as a method of laminating a base material such as a metal material and a fluororesin, conventionally, an adhesive layer having adhesiveness with both the base material and the fluororesin is generally formed on the base material, and on that, A method of laminating a fluororesin has been studied. For example, Patent Document 1 discloses a primer powder containing (a) a tetrafluoroethylene / perfluoroolefin copolymer, a non-melt processable binder such as polyamideimide, and a melt processable binder such as polyethersulfone. (B) an overcoat powder containing a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer is deposited on the primer layer. And (c) the substrate is baked after both the primer layer and the overcoat layer are deposited.
本発明の発明者は、上述の従来技術の方法を用いて、テトラフルオロエチレン／パーフルオロオレフィン共重合体の１種であるテトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、非溶融加工性結合剤の１種であるポリアミドイミド（ＰＡＩ）、溶融加工性結合剤の１種であるポリフェニレンスルフィド（ＰＰＳ）が、５０／２５／２５の質量比で含まれるプライマ粉末をＳＵＳ基材上に被着させてプライマ層を形成し、その後、テトラフルオロエチレン−フルオロアルキルビニルエーテル共重合体（ＰＦＡ）を含むオーバーコート粉末を当該プライマ層上に被着させてオーバーコート層を形成し、焼き付けを行ってＳＵＳ基材上に離型表面を形成した。そして、当該離型表面の断面を電子顕微鏡で観察した。その結果、従来の一般的な方法では、下記（ａ）及び（ｂ）のメカニズムで、基材とフッ素樹脂とが接着していることが確認された。 The inventor of the present invention uses the above-described prior art method to produce a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), which is one of tetrafluoroethylene / perfluoroolefin copolymers, non-melt processability. A primer powder containing polyamidoimide (PAI), which is one type of binder, and polyphenylene sulfide (PPS), which is one type of melt-processable binder, is coated on a SUS substrate at a mass ratio of 50/25/25. A primer layer is formed, and then an overcoat powder containing a tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA) is deposited on the primer layer to form an overcoat layer, and baking is performed. A release surface was formed on the SUS substrate. And the cross section of the said mold release surface was observed with the electron microscope. As a result, in the conventional general method, it was confirmed that the base material and the fluororesin were adhered by the following mechanisms (a) and (b).
（ａ）フッ素樹脂３（ＦＥＰ）粉末、ＰＡＩ５粉末及びＰＰＳ４粉末を含むプライマ粉末がプライマ層（III）としてＳＵＳ基板（IV）上に塗布され（図１）、焼き付けられて、オーバーコート層（V）との親和性が高いフッ素樹脂３（ＦＥＰ）相と、ＳＵＳ基板（IV）との親和性が高いＰＡＩ５相及びＰＰＳ４相とからなるプライマ層（III）が形成された（図２）。（ｂ）その後形成されたオーバーコート層（V）のＰＦＡの一部は、プライマ層（III）のフッ素樹脂３（ＦＥＰ）相と相溶し（図３）、上記されるとおり、ＰＦＡからなるオーバーコート層（V）が、フッ素樹脂３（ＦＥＰ）相、ＰＰＳ４相及びＰＡＩ５相からなるプライマ層（III）を介してＳＵＳ基板（IV）上に形成された。 (A) Primer powder containing fluororesin 3 (FEP) powder, PAI5 powder and PPS4 powder is applied as a primer layer (III) on the SUS substrate (IV) (FIG. 1), baked, and overcoat layer (V ), A primer layer (III) composed of a fluororesin 3 (FEP) phase having a high affinity with the PUS5 phase and a PPS4 phase having a high affinity with the SUS substrate (IV) was formed (FIG. 2). (B) A part of the PFA of the overcoat layer (V) formed thereafter is compatible with the fluororesin 3 (FEP) phase of the primer layer (III) (FIG. 3) and consists of PFA as described above. An overcoat layer (V) was formed on the SUS substrate (IV) through a primer layer (III) composed of a fluororesin 3 (FEP) phase, a PPS 4 phase and a PAI 5 phase.
しかし、上述した従来の一般的な接着は、フッ素樹脂から相分離した結合剤相が基材と結合することによって接着力を得ているため、プライマ層と基材との接着強度を十分に向上させるためには、結合剤樹脂が相当量必要である。例えば、先述の先行技術文献１に開示される方法では、プライマ粉末中のテトラフルオロエチレン／パーフルオロオレフィン共重合体の配合比は、７０質量％以下である。そのため、プライマ層のテトラフルオロエチレン／パーフルオロオレフィン共重合体に由来する特性は損なわれていた。 However, the conventional general adhesion described above has improved adhesive strength between the primer layer and the base material because the binder phase phase-separated from the fluororesin is bonded to the base material to obtain an adhesive force. In order to achieve this, a considerable amount of binder resin is required. For example, in the method disclosed in Prior Art Document 1 described above, the blending ratio of the tetrafluoroethylene / perfluoroolefin copolymer in the primer powder is 70% by mass or less. Therefore, the characteristics derived from the tetrafluoroethylene / perfluoroolefin copolymer of the primer layer have been impaired.
最近、フッ素樹脂に特有の耐熱性、耐候性、耐薬品性、剥離性、低誘電特性等の優れた特性を有すると共に、異種材料、特に銅箔との溶融接着性が優れる溶融接着性フィルムが要求されてきていたが、そのような溶融接着性フィルムは実現されていなかった。
本発明が解決しようとする課題は、フッ素樹脂に特有の耐熱性、耐候性、耐薬品性、剥離性、低誘電特性等の優れた特性を有すると共に、異種材料、特に銅箔との溶融接着性が優れる溶融接着性フィルムの提供である。
Recently, a melt-adhesive film that has excellent properties such as heat resistance, weather resistance, chemical resistance, peelability, and low dielectric properties unique to fluororesins, as well as excellent melt adhesion to dissimilar materials, especially copper foil, has been developed. Although it has been required, such a melt adhesive film has not been realized.
The problem to be solved by the present invention is that it has excellent properties such as heat resistance, weather resistance, chemical resistance, peelability, low dielectric properties, etc. specific to fluororesin, and melt adhesion to dissimilar materials, particularly copper foil The present invention provides a melt-adhesive film having excellent properties.
本発明の発明者は、上記課題を解決するために鋭意検討した結果、フッ素樹脂、液晶ポリマー及びポリエーテルスルホンからなり、液晶ポリマー及びポリエーテルスルホンからなる特定平均粒子径の分散粒子が特定濃度でフッ素樹脂中に分散されている溶融接着性フィルムが、上記特性を有することを見出し、本発明を完成させるに至った。
本発明は、例えば、フッ素樹脂、液晶ポリマー及びポリエーテルスルホンからなる溶融接着性フィルムにおいて、フッ素樹脂、液晶ポリマー及びポリエーテルスルホンの総重量を基準にして、フッ素樹脂８５〜９８質量％、液晶ポリマー１〜１０質量％、ポリエーテルスルホン１〜５質量％からなり、前記液晶ポリマーは全芳香族ポリエステルであり、前記ポリエーテルスルホンは分子端末に官能基を有するポリエーテルスルホンであり、 前記液晶ポリマー及び前記ポリエーテルスルホンからなる分散粒子がフッ素樹脂中に分散する構造を有し、前記分散粒子の平均粒子径が１〜１０μｍであり、 前記溶融接着性フィルムの厚さ方向断面において、１辺が５０μｍの正方形を単位面積とするとき、上記単位面積中の上記分散粒子の個数が１０〜３０個であることが好ましい。
The inventor of the present invention has made extensive studies to solve the above-mentioned problems. As a result, the dispersed particles having a specific average particle diameter composed of a fluororesin, a liquid crystal polymer, and a polyethersulfone, and composed of a liquid crystal polymer and a polyethersulfone have a specific concentration. It has been found that the melt-adhesive film dispersed in the fluororesin has the above properties, and has completed the present invention.
The present invention relates to, for example, a melt adhesive film composed of a fluororesin, a liquid crystal polymer, and a polyethersulfone, based on the total weight of the fluororesin, the liquid crystal polymer, and the polyethersulfone. 1 to 10 wt%, polyether sulfone made from 1 to 5 mass%, the liquid crystal polymer is wholly aromatic polyester, the polyether sulfone is a polyethersulfone having a functional group in the molecule terminals, said liquid crystal polymer and the polyether consisting sulfone dispersed particles have a structure dispersed in the fluororesin, the average particle diameter before Symbol dispersed particles is 1 to 10 [mu] m, in the cross section in the thickness direction of the melt adhesive film, one side When a 50 μm square is defined as a unit area, the number of dispersed particles in the unit area is 10 It is preferable that the 30 pieces.
本発明の溶融接着性フィルムは、フッ素樹脂に特有の耐熱性、耐候性、耐薬品性、剥離性、低誘電特性等の優れた特性を有すると共に、異種材料、特に銅箔との溶融接着性が優れる。 The melt-adhesive film of the present invention has excellent properties such as heat resistance, weather resistance, chemical resistance, peelability, and low dielectric properties unique to fluororesins, and melt adhesion to dissimilar materials, particularly copper foil. Is excellent.
本発明の溶融接着性フィルムを構成するフッ素樹脂の具体例は、テトラフルオロエチレン−フルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、エチレン−テトラフルオロエチレン共重合体（ＥＴＦＥ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）、エチレン−クロロトリフルオロエチレンコポリマー（ＥＣＴＦＥ）、テトラフルオロエチレン‐ヘキサフルオロプロピレン‐ビニリデンフロライド共重合体（ＴＨＶ）などの熱溶融性フッ素樹脂である。好ましいフッ素樹脂は、ポリエーテルスルホンのスルホン基と類似する構造であるエーテル基を有するテトラフルオロエチレン−フルオロアルキルビニルエーテル共重合体（ＰＦＡ）である。これらのフッ素樹脂は単独で、又は２種以上を組み合わせて使用される。 Specific examples of the fluororesin constituting the melt adhesive film of the present invention include tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and ethylene-tetrafluoroethylene. Hot-melting fluorine such as copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) Resin. A preferred fluororesin is a tetrafluoroethylene-fluoroalkyl vinyl ether copolymer (PFA) having an ether group having a structure similar to the sulfone group of polyethersulfone. These fluororesins are used individually or in combination of 2 or more types.
フッ素樹脂は、末端基がフッ素化剤によってフッ素化処理された末端基安定化処理フッ素樹脂であっても、フッ素化処理による末端基安定化処理されていないフッ素樹脂あってもよく、両者の混合物であってもよい。好ましいフッ素樹脂は、フッ素化処理による末端基安定化処理されていないフッ素樹脂である。フッ素樹脂の末端基が安定化処理されていないフッ素樹脂は、末端基安定化処理されたフッ素樹脂に比べて、他樹脂との相溶性及び銅箔との濡れ性を改善する。 The fluororesin may be a fluororesin whose end groups are fluorinated with a fluorinating agent, or may be a fluororesin that has not been end group-stabilized by fluorination. It may be. A preferred fluororesin is a fluororesin that has not been subjected to end group stabilization treatment by fluorination treatment. The fluororesin in which the end group of the fluororesin is not subjected to the stabilization treatment improves the compatibility with other resins and the wettability with the copper foil as compared with the fluororesin subjected to the endgroup stabilization treatment.
本発明の溶融接着性フィルムは、液晶ポリマー（以下、「ＬＣＰ」と言うことがある）を含む。ＬＣＰは、熱溶融状態で液晶性を示すサーモトロピック液晶高分子である。本発明の溶融接着性フィルムを構成するＬＣＰの具体例は、ポリプラスチックス社製ベクトラ、住友化学株式会社製スミカスーパー、ＪＸ日鉱日石エネルギー株式会社製ザイダー、上野製薬株式会社製ＵＥＮＯ ＬＣＰ、東レ株式会社製シベラスなどである。好ましいＬＣＰは、融点が高く、耐熱性に優れるものである。ＬＣＰは、フッ素樹脂と金属材料との積層体を使用する用途では、高温になるところに使用されることが多く、例えば銅箔との接着で使用する場合、その用途は基板が多いため、ハンダ耐熱がひとつの基準とされる。ＬＣＰの用途が共晶ハンダの場合、融点が２４０℃以上のＬＣＰが好ましい。また、剛直な直線上の分子構造を有する全芳香族性ポリエステルが、使用するＬＣＰとして、好ましい。 The melt adhesive film of the present invention contains a liquid crystal polymer (hereinafter sometimes referred to as “LCP”). LCP is a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a hot melt state. Specific examples of the LCP constituting the melt adhesive film of the present invention include Vectra manufactured by Polyplastics, Sumika Super manufactured by Sumitomo Chemical Co., Ltd., Zider manufactured by JX Nippon Oil & Energy Corporation, UENO LCP manufactured by Ueno Pharmaceutical Co., Ltd., Toray Industries, Inc. For example, Siberus Co., Ltd. Preferred LCPs have a high melting point and excellent heat resistance. LCP is often used at high temperatures in applications where a laminate of a fluororesin and a metal material is used. For example, when used for bonding to copper foil, the LCP is often used for soldering. One standard is heat resistance. When the use of LCP is eutectic solder, LCP having a melting point of 240 ° C. or higher is preferable. Further, a wholly aromatic polyester having a rigid linear molecular structure is preferred as the LCP to be used.
全芳香族性ポリエステルは、剛直な直線状の分子構造により、線膨張が小さく、高強度であるという特性を示す。そのため、後述する本発明のフッ素樹脂フィルムの接着構造において、上述のようなＬＣＰ及びポリエーテルスルホンで構成される分散粒子が一旦銅箔表面に引っかかると、熱収縮による変動が小さく、かつ高強度であるため、高いアンカー効果が得られる。また、全芳香族性ポリエステルは融点が高く、フッ素樹脂の融点に近くなるためフッ素樹脂中に分散させる時の熱劣化を抑えることが出来る。 The wholly aromatic polyester has a characteristic of low linear expansion and high strength due to a rigid linear molecular structure. Therefore, in the adhesive structure of the fluororesin film of the present invention to be described later, once the dispersed particles composed of LCP and polyethersulfone as described above are caught on the copper foil surface, the fluctuation due to heat shrinkage is small and the strength is high. Therefore, a high anchor effect can be obtained. Further, the wholly aromatic polyester has a high melting point and is close to the melting point of the fluororesin, so that thermal degradation when dispersed in the fluororesin can be suppressed.
本発明の溶融接着性フィルムは、ポリエーテルスルホンを含む。使用するポリエーテルスルホンの具体例は、ＢＡＳＦジャパン株式会社製ウルトラゾーン、ソルベイアドバンストポリマーズ株式会社レーデル、住友化学株式会社製スミカエクセルなどである。好ましいポリエーテルスルホンは、液晶ポリマーのフッ素樹脂中への分散性の向上と、溶融接着性フィルムの異種材料、特に銅箔との溶融接着性の向上の観点から、分子末端に官能基を有するポリエーテルスルホンである。分子末端に官能基を有するポリエーテルスルホンは、分子末端に官能基を有しないポリエーテルスルホンに比べて、他樹脂との相溶性及び銅箔との接着性がより高い。 The melt adhesive film of the present invention contains polyethersulfone. Specific examples of the polyether sulfone to be used include Ultra Zone manufactured by BASF Japan Ltd., Soldel Advanced Polymers Inc. Radel, Sumika Excel Co., Ltd. manufactured by Sumitomo Chemical Co., Ltd. A preferred polyethersulfone is a polysulfone having a functional group at the molecular end, from the viewpoint of improving the dispersibility of the liquid crystal polymer in the fluororesin and improving the melt adhesion with a different material of the melt adhesive film, particularly copper foil. Ether sulfone. Polyether sulfone having a functional group at the molecular end has higher compatibility with other resins and adhesiveness with copper foil than polyether sulfone having no functional group at the molecular end.
本発明の溶融接着性フィルムは、液晶ポリマー及びポリエーテルスルホンからなる分散粒子がフッ素樹脂中に分散する構造を有している。フッ素樹脂のＳＰ値は約１３（ＭＪ／ｍ3）、液晶ポリマーのＳＰ値は約２０（ＭＪ／ｍ3）、ポリエーテルスルホンのＳＰ値は約１８（ＭＪ／ｍ3）である。これら３つの樹脂は比較的相溶性が高く、特にＳＰ値が近い液晶ポリマーとポリエーテルスルホンとが共に分散粒子を形成してフッ素樹脂中に分散しており、後述するように、上記分散粒子は、ポリエーテルスルホンからなる小粒子が、液晶ポリエステルからなる大粒子の表面に付着しているような構造をしている。 The melt adhesive film of the present invention has a structure in which dispersed particles composed of a liquid crystal polymer and polyethersulfone are dispersed in a fluororesin. The SP value of the fluororesin is about 13 (MJ / m 3 ), the SP value of the liquid crystal polymer is about 20 (MJ / m 3 ), and the SP value of the polyethersulfone is about 18 (MJ / m 3 ). These three resins have relatively high compatibility, and in particular, a liquid crystal polymer having a close SP value and polyethersulfone form dispersed particles together and dispersed in the fluororesin. As described later, the dispersed particles are In this structure, small particles made of polyethersulfone are attached to the surface of large particles made of liquid crystal polyester.
図４は、本発明の溶融接着性フィルムの厚さ方向断面のＳＥＭ写真である。図４を基に本発明のメカニズムを考察する。図５、図６及び図７は、本発明の溶融接着性フィルムにおいて推察される基材との接着メカニズムを示す図である。図５は、液晶ポリマー１及びポリエーテルスルホン２からなる分散粒子がフッ素樹脂３中に分散する構造を模式的に示している。銅箔（II）表面には、成形時に生じる微細な凹凸が存在する。図５に模式的に
示される本発明の溶融接着性フィルム（I）が溶融され、銅箔（II）に接着されると、上記分散粒子が銅箔（II）の凹部にはまり込む（図６）。銅箔（II）に接着されたフィルムが冷却されると、収縮率が大きいフッ素樹脂３部分が収縮し、上記分散粒子が上記凹部にかみつく（図７）。このアンカー効果により、本発明の溶融接着性フィルム（I）は、銅箔（II）に強固に接着される。従来の一般的な接着では、結合剤樹脂が基材及びフッ素樹脂と面で接着するのに対し、本発明では分散粒子が接着点となり、多数の点で接着する構造となる。
FIG. 4 is an SEM photograph of a cross section in the thickness direction of the melt adhesive film of the present invention. The mechanism of the present invention will be considered based on FIG. 5, 6 and 7 are diagrams showing the adhesion mechanism with the base material presumed in the melt adhesive film of the present invention. FIG. 5 schematically shows a structure in which dispersed particles composed of the liquid crystal polymer 1 and the polyethersulfone 2 are dispersed in the fluororesin 3. On the surface of the copper foil (II), there are fine irregularities generated during molding. When the melt-adhesive film (I) of the present invention schematically shown in FIG. 5 is melted and adhered to the copper foil (II), the dispersed particles fit into the recesses of the copper foil (II) (FIG. 6). ). When the film adhered to the copper foil (II) is cooled, the fluororesin 3 portion having a large shrinkage contracts and the dispersed particles bite into the recesses (FIG. 7). Due to this anchor effect, the melt-adhesive film (I) of the present invention is firmly bonded to the copper foil (II). In the conventional general bonding, the binder resin is bonded to the base material and the fluororesin on the surface, whereas in the present invention, the dispersed particles serve as bonding points, and the bonding is performed at a number of points.
上述のように、アンカー効果を発揮し接着点となる、液晶ポリマー及びポリエーテルスルホンの分散粒子の平均粒子径及び単位面積当たりの分散粒子の個数が、本発明の溶融接着性フィルムにおいて、接着強度に大きく影響する。上記分散粒子の平均粒子径は１〜１０μｍである。上記分散粒子の平均粒子径が小さすぎたり、大きすぎたりすると、銅箔凹部との上記アンカー効果が十分に得られず、溶融接着性フィルムと異種材料との接着力が小さくなる。 As described above, the average particle diameter of the dispersed particles of liquid crystal polymer and polyethersulfone, which exhibits an anchor effect and serves as an adhesion point, and the number of dispersed particles per unit area are the adhesive strength in the melt adhesive film of the present invention. Greatly affects. The average particle diameter of the dispersed particles is 1 to 10 μm. If the average particle diameter of the dispersed particles is too small or too large, the anchor effect with the copper foil recess cannot be sufficiently obtained, and the adhesive force between the melt-adhesive film and the dissimilar material becomes small.
液晶ポリマー及びポリエーテルスルホンからなる上記分散粒子は、溶融接着性フィルムの厚さ方向断面において、１辺が５０μｍの正方形を単位面積としたとき、前記単位面積中に１０〜３０個となるようにフッ素樹脂中に分散している。上記分散粒子が基材との接着点となるため、上記分散粒子の数が少なすぎると、溶融接着性フィルムと異種材料との接着力が小さくなる。上記分散粒子の数があまりにも多い溶融接着性フィルムの作製は困難である。 In the thickness direction cross section of the melt adhesive film, the dispersed particles composed of the liquid crystal polymer and the polyether sulfone have 10 to 30 particles per side when a square having a side of 50 μm is defined as a unit area. Dispersed in fluororesin. Since the dispersed particles serve as adhesion points with the base material, if the number of the dispersed particles is too small, the adhesive force between the melt-adhesive film and the dissimilar material is reduced. It is difficult to produce a melt-adhesive film having too many dispersed particles.
フッ素樹脂、液晶ポリマー及びポリエーテルスルホンの総重量を基準にして、液晶ポリマーの好ましい配合量は１〜１０質量％、ポリエーテルスルホンの好ましい配合量は１〜５質量％である。液晶ポリマーとポリエーテルスルホンとを合わせた好ましい配合量は２〜１５質量％である。先述のように、液晶ポリマー及びポリエーテルスルホンは、アンカー効果を発揮する上記分散粒子の構成成分であり、その分散粒子の平均粒子径及び単位面積当たりの分散粒子の個数が、接着強度に大きく影響する。上述した範囲で配合することにより、液晶ポリマー及びポリエーテルスルホンの分散粒子径が１〜１０μｍであり、溶融接着性フィルムの厚さ方向断面において、一辺が５０μｍの正方形を単位面積とするときの単位面積中の分散粒子の数を１０〜３０個に容易に調整することが出来る。液晶ポリマーとポリエーテルスルホンの配合量が多すぎると、上記分散粒子径及び分散粒子の数を調整することが困難になり、上記分散粒子径は大きく、分散粒子の数は少なくなり、銅箔凹部とのアンカー効果が十分に得られなくなる。液晶ポリマーとポリエーテルスルホンの配合量がさらに多くなると、その接着構造は従来技術と何ら変わらないものとなり、十分な接着力が得られない上に、溶融接着性フィルムのフッ素樹脂に由来する特性が損なわれる。 Based on the total weight of the fluororesin, the liquid crystal polymer and the polyethersulfone, the preferred blending amount of the liquid crystal polymer is 1 to 10% by weight, and the preferred blending amount of the polyethersulfone is 1 to 5% by weight. A preferable blending amount of the liquid crystal polymer and the polyether sulfone is 2 to 15% by mass. As described above, the liquid crystal polymer and polyethersulfone are constituents of the above dispersed particles that exhibit the anchor effect, and the average particle diameter of the dispersed particles and the number of dispersed particles per unit area greatly affect the adhesive strength. To do. By blending in the above-mentioned range, the dispersed particle size of the liquid crystal polymer and the polyethersulfone is 1 to 10 μm, and the unit when the unit area is a square having a side of 50 μm in the cross section in the thickness direction of the melt-adhesive film The number of dispersed particles in the area can be easily adjusted to 10-30. If the blending amount of the liquid crystal polymer and the polyethersulfone is too large, it becomes difficult to adjust the dispersed particle size and the number of dispersed particles, the dispersed particle size is large, the number of dispersed particles is small, and the copper foil recesses are reduced. The anchor effect cannot be obtained sufficiently. When the blending amount of liquid crystal polymer and polyethersulfone is further increased, the adhesive structure becomes the same as that of the prior art, and sufficient adhesive force cannot be obtained, and the characteristics derived from the fluororesin of the melt adhesive film are Damaged.
本発明の溶融接着性フィルムは、フッ素樹脂、液晶ポリマー及びポリエーテルスルホンからなる組成物を押出成形、プレス成形など任意の成形方法で成形して得られる。 The melt-adhesive film of the present invention can be obtained by molding a composition comprising a fluororesin, a liquid crystal polymer and polyethersulfone by any molding method such as extrusion molding or press molding.
以下、実施例により本発明が詳細に説明されるが、本発明はこれらの実施例に限定されない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
実施例１〜８及び比較例１〜７
フッ素樹脂（三井デュポンフロロケミカル社製PFA 340-J）、液晶ポリマー（ポリプラスチックス社製LCP A950、融点２８０℃）、ポリエーテルスルホン（BASF社製E-2020P）を、表１及び２に示される配合比で、ローラミキサ型混練装置（東洋精機製作所製ラボプラストミル モデル 30C120 ）に投入し、ローラ回転数３０ｒｐｍ、温度３６０℃で１０分間混練した。その後、得られた樹脂（組成物）を当該混練装置から取り出し、３４０℃で熱プレスして、厚さ０．１ｍｍ、５０ｍｍ画の溶融接着性フィルム試料を作製した。
Examples 1-8 and Comparative Examples 1-7
Tables 1 and 2 show the fluororesin (PFI 340-J made by Mitsui DuPont Fluorochemical), liquid crystal polymer (LCP A950 made by Polyplastics, melting point 280 ° C.), and polyethersulfone (E-2020P made by BASF). The mixture ratio was charged into a roller mixer type kneading apparatus (Laboplast Mill Model 30C120 manufactured by Toyo Seiki Seisakusho) and kneaded for 10 minutes at a roller rotation speed of 30 rpm and a temperature of 360 ° C. Thereafter, the obtained resin (composition) was taken out from the kneading apparatus and hot-pressed at 340 ° C. to prepare a melt-adhesive film sample having a thickness of 0.1 mm and 50 mm.
溶融接着性フィルムと銅箔の接着強度の測定
得られた溶融接着性フィルム試料を１８μｍの厚さの両面圧延銅箔で挟み込み、３４０℃で加熱・圧着し、銅箔付き試料を得た。上記銅箔付き試料の接着強度を、島津製作所製オートグラフで１８０°剥離試験により測定した。その結果を表１及び２に示す。
Measurement of adhesive strength between melt-adhesive film and copper foil The obtained melt-adhesive film sample was sandwiched between 18 μm-thick double-sided rolled copper foils and heated and pressure-bonded at 340 ° C. to obtain a sample with copper foil. The adhesive strength of the sample with copper foil was measured by a 180 ° peel test using an autograph manufactured by Shimadzu Corporation. The results are shown in Tables 1 and 2.
溶融接着性フィルム中の分散粒子の平均粒子径と分散密度の測定
上記溶融接着性フィルム試料の厚さ方向断面を走査型電子顕微鏡（ＳＥＭ）で撮影した（倍率：１０００倍、撮影範囲：２６０μｍ×１１０μｍ）。その断面ＳＥＭ写真上で任意の５０μｍ角の範囲に観察される分散粒子の同一方向で最大幅を計測し、分散粒子の粒子径を算術平均して平均粒子径を求めた。中心が上記断面ＳＥＭ写真上にある全ての分散粒子の個数を計測した。その結果を表１及び２に示す。
Measurement of Average Particle Size and Dispersion Density of Dispersed Particles in Melt Adhesive Film The cross section in the thickness direction of the melt adhesive film sample was photographed with a scanning electron microscope (SEM) (magnification: 1000 times, photographing range: 260 μm × 110 μm). The maximum width was measured in the same direction of the dispersed particles observed in an arbitrary 50 μm square range on the cross-sectional SEM photograph, and the average particle size was obtained by arithmetically averaging the particle sizes of the dispersed particles. The number of all dispersed particles having the center on the cross-sectional SEM photograph was counted. The results are shown in Tables 1 and 2.
溶融接着性フィルム中の分散粒子の組成の確認
分散粒子の組成については以下の方法にて確認した。フィルム断面にカーボンを蒸着し、ＳＥＭ上でエネルギー分散型Ｘ線分析装置（ＥＤＸ）を用いて観察した。ポリエーテルスルホンはＳ原子、フッ素樹脂に関してはＦ原子によるスペクトルを確認し、それぞれの原子の存在位置からポリエーテルスルホン及びフッ素樹脂を同定した。どちらも確認されないものを液晶ポリマーと判断した。
Confirmation of composition of dispersed particles in melt adhesive film The composition of dispersed particles was confirmed by the following method. Carbon was vapor-deposited on the film cross section, and observed on an SEM using an energy dispersive X-ray analyzer (EDX). Polyether sulfone confirmed the spectrum by S atom and F atom about fluororesin, and identified polyether sulfone and fluororesin from the position of each atom. Those in which neither was confirmed were judged as liquid crystal polymers.
上記溶融接着性フィルム試料の厚さ方向の断面ＳＥＭ写真と、ＥＤＸの結果から、液晶ポリマー及びポリエーテルスルホンからなる分散粒子は、ポリエーテルスルホンからなる小粒子が、液晶ポリエステルからなる大粒子の表面に付着しているような構造をした粒子の状態で、フッ素樹脂中に分散していることが確認できた。 From the cross-sectional SEM photograph of the thickness direction of the above melt adhesive film sample and the result of EDX, the dispersed particles composed of liquid crystal polymer and polyethersulfone are the small particles composed of polyethersulfone and the surface of large particles composed of liquid crystalline polyester. It was confirmed that it was dispersed in the fluororesin in a state of particles having a structure adhering to the resin.
表１の結果から、実施例１〜８の溶融接着性フィルムと銅箔との接着強度は十分に高かった。ここで、必要とされる接着強度は、９Ｎ/ｃｍ以上である。分散粒子の平均粒子径が１０μｍ以上であり、分散粒子の数が１０個以下である比較例１及び４の溶融接着性フィルムと銅箔との接着強度は低かった。分散粒子の数が少なすぎる比較例２及び３の溶融接着性フィルムと銅箔の接着強度も低かった。フッ素樹脂のみからなる比較例５の溶融接着性フィルム、液晶ポリマーのみからなる比較例６の溶融接着性フィルム、ポリエーテルスルホンのみからなる比較例７の溶融接着性フィルムと銅箔との接着強度も低く、それぞれの樹脂単体での銅箔への接着性は低いことが分かった。 From the results of Table 1, the adhesive strength between the melt adhesive films of Examples 1 to 8 and the copper foil was sufficiently high. Here, the required adhesive strength is 9 N / cm or more. The adhesive strength between the melt-adhesive film of Comparative Examples 1 and 4 and the copper foil, in which the average particle diameter of the dispersed particles was 10 μm or more and the number of dispersed particles was 10 or less, was low. The adhesive strength between the melt adhesive films of Comparative Examples 2 and 3 and the copper foil was too low. The adhesive strength between the melt adhesive film of Comparative Example 5 made only of fluororesin, the melt adhesive film of Comparative Example 6 made only of liquid crystal polymer, the melt adhesive film of Comparative Example 7 made only of polyethersulfone and the copper foil It was found that the adhesiveness to the copper foil with each resin alone was low.
本発明の溶融接着性フィルムは、フッ素樹脂製のものと異種材料、特に銅箔が接着される際の媒体として好適に使用される。 The melt-adhesive film of the present invention is suitably used as a medium when a material different from that made of a fluororesin, particularly a copper foil, is bonded.
１…液晶ポリマー、２…ポリエーテルスルホン、３…フッ素樹脂、４…ＰＰＳ、５…ＰＡＩ、（I）…溶融接着性フィルム、（II）…溶融接着性フィルム、（III）…プライマ層、（IV）…ＳＵＳ基板、（V）…オーバーコート層 DESCRIPTION OF SYMBOLS 1 ... Liquid crystal polymer, 2 ... Polyether sulfone, 3 ... Fluorine resin, 4 ... PPS, 5 ... PAI, (I) ... Melt adhesive film, (II) ... Melt adhesive film, (III) ... Primer layer, IV) ... SUS substrate, (V) ... Overcoat layer
Claims (1)
フッ素樹脂、液晶ポリマー及びポリエーテルスルホンの総重量を基準にして、フッ素樹脂８５〜９８質量％、液晶ポリマー１〜１０質量％、ポリエーテルスルホン１〜５質量％からなり、
前記液晶ポリマーは全芳香族ポリエステルであり、前記ポリエーテルスルホンは分子端末に官能基を有するポリエーテルスルホンであり、
前記液晶ポリマー及び前記ポリエーテルスルホンからなる分散粒子がフッ素樹脂中に分散する構造を有し、前記分散粒子の平均粒子径が１〜１０μｍであり、
前記溶融接着性フィルムの厚さ方向断面において、１辺が５０μｍの正方形を単位面積とするとき、上記単位面積中の上記分散粒子の個数が１０〜３０個である溶融接着性フィルム。 In the melt adhesive film made of fluororesin, liquid crystal polymer and polyethersulfone,
Based on the total weight of the fluororesin, the liquid crystal polymer and the polyethersulfone, the fluororesin consists of 85 to 98 mass%, the liquid crystal polymer 1 to 10 mass%, the polyethersulfone 1 to 5 mass%,
The liquid crystal polymer is a wholly aromatic polyester, and the polyethersulfone is a polyethersulfone having a functional group at a molecular terminal,
Said liquid crystal polymer and dispersed particles composed of the polyethersulfone has a structure dispersed in the fluororesin, the average particle diameter before Symbol dispersed particles is 1 to 10 [mu] m,
In the cross section in the thickness direction of the melt-adhesive film, the melt-adhesive film in which the number of the dispersed particles in the unit area is 10 to 30 when a square having a side of 50 μm is a unit area.
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