JPH1158491A - Mold for extruding resin sheet - Google Patents
Mold for extruding resin sheetInfo
- Publication number
- JPH1158491A JPH1158491A JP9241885A JP24188597A JPH1158491A JP H1158491 A JPH1158491 A JP H1158491A JP 9241885 A JP9241885 A JP 9241885A JP 24188597 A JP24188597 A JP 24188597A JP H1158491 A JPH1158491 A JP H1158491A
- Authority
- JP
- Japan
- Prior art keywords
- resin sheet
- plating
- sheet extrusion
- composite
- composite plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、樹脂シート押出加
工用金型に関し、より詳しくはフッ素化合物微粒子を含
む複合めっき皮膜を施した樹脂シート押出加工用金型に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin sheet extrusion die, and more particularly, to a resin sheet extrusion die provided with a composite plating film containing fine particles of a fluorine compound.
【０００２】[0002]
【従来の技術】近年、産業用機器等においては樹脂シー
トが多用されるようになってきているが、この樹脂シー
トの製造方法としては、樹脂を加熱溶融させて流動状態
とし、これをスクリューで樹脂シート押出加工用金型に
押し込み、更に、仕上げロール、コンベア、引き取りロ
ールを経て、切断機によりシートを切断する方法が一般
的である。この際、上記樹脂シート押出加工用金型とし
て従来型の金型を用いると、金型で滞留した樹脂が熱に
より焦げ付いて固着することにより樹脂流路を塞いだ
り、或いは、焦げ付いた樹脂が製品に混入することによ
り不良品となる等の課題を有していた。2. Description of the Related Art In recent years, resin sheets have been frequently used in industrial equipment and the like. The method of manufacturing the resin sheet is to heat and melt the resin to make it flow, and then use a screw. In general, the sheet is pushed into a resin sheet extrusion die, further cut through a finishing roll, a conveyor, and a take-up roll, and then cut by a cutting machine. At this time, if a conventional mold is used as the resin sheet extrusion processing mold, the resin that has accumulated in the mold is scorched by heat and fixed, thereby blocking the resin flow path, or the scorched resin is a product. There is a problem that the product becomes a defective product by being mixed into the product.
【０００３】このため、上記の不都合が生じた場合に
は、樹脂シート押出加工装置の作動を一旦停止して樹脂
シート押出加工用金型を取り外し、付着した樹脂或いは
焦げ付いた樹脂を金属ヘラや金属ブラシで擦り落として
除去する方法が採られていた。しかし、樹脂が付着或い
は焦げ付く毎に上記の作業を行うのは面倒であり、しか
もこのような作業中は樹脂シート押出加工装置を運転で
きないため、生産性が低下するという課題を有してい
た。[0003] Therefore, when the above-mentioned inconvenience occurs, the operation of the resin sheet extrusion processing apparatus is temporarily stopped, the mold for resin sheet extrusion processing is removed, and the adhered resin or the scorched resin is removed with a metal spatula or a metal spatula. A method of removing by removing with a brush has been adopted. However, it is troublesome to perform the above operation every time the resin adheres or burns, and the resin sheet extrusion processing device cannot be operated during such operation, so that there is a problem that productivity is reduced.
【０００４】そこで、フッ素樹脂（例えば、ポリテトラ
フルオロエチレン）等の撥水性の高い材料で金型面を被
覆するような方法も考えられる。この方法であれば、製
造初期にはフッ素樹脂等の非粘着性の効果が発揮される
ので上記課題を解決できる。しかしながら、フッ素樹脂
の被覆層は強度的に劣るため、長期間使用した場合には
被覆層が徐々に剥がれて、やはり上記のような課題が生
じる。加えて、樹脂被覆層が剥がれた場合には、製造し
ている樹脂シートに混入して、不良品となる等の課題を
有していた。Therefore, a method of coating the mold surface with a highly water-repellent material such as a fluororesin (for example, polytetrafluoroethylene) is also conceivable. According to this method, the above-mentioned problem can be solved because the non-adhesive effect of the fluororesin or the like is exhibited in the early stage of the production. However, since the fluororesin coating layer is inferior in strength, when used for a long period of time, the coating layer gradually peels off, and the above-mentioned problem still arises. In addition, when the resin coating layer comes off, there is a problem that the resin coating layer is mixed into the resin sheet being manufactured and becomes a defective product.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、樹脂シート
押出加工用金型における上記のような問題点に鑑みなさ
れたものであり、優れた非粘着性と耐久性と耐焦げ付き
性とを有する表面被覆層を備えることにより、長期間に
わたり生産性の向上と、不良率の飛躍的低減とを図るこ
とができる樹脂シート押出加工用金型を提供することを
目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems in a resin sheet extrusion die, and has excellent non-adhesiveness, durability and scoring resistance. It is an object of the present invention to provide a resin sheet extrusion processing mold that includes a surface coating layer and can improve productivity and dramatically reduce the defective rate over a long period of time.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意研究を行ったところ、樹脂シート
押出加工用金型の表面に体積分率で１５％以上のフッ素
化合物微粒子が分散含有された複合めっき皮膜を形成す
れば、めっき皮膜と基材との密着性等に優れ、しかも非
粘着性や、耐焦げ付き性に優れ且つこれを長期にわたっ
て維持できる樹脂シート押出加工用金型が得られること
を見いだした。更に、このような複合めっき皮膜を所定
の温度で加熱処理すると、一層非粘着性、耐久性、耐焦
げ付き性に優れた皮膜が得られることを見いだした。本
発明は、これらの知見に基づいて完成されたものであ
り、下記構成を特徴とする。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and found that fine particles of a fluorine compound having a volume fraction of 15% or more were formed on the surface of a resin sheet extrusion die. When a composite plating film is formed in which is dispersed and contained, the metal for resin sheet extrusion processing is excellent in adhesion between the plating film and the base material, and is excellent in non-adhesiveness and sticking resistance, and can maintain this for a long period of time. We found that a mold was obtained. Furthermore, it has been found that when such a composite plating film is subjected to a heat treatment at a predetermined temperature, a film having more non-adhesiveness, durability, and scorching resistance can be obtained. The present invention has been completed based on these findings, and has the following configuration.
【０００７】即ち、請求項１記載の発明は、体積分率で
１５％以上のフッ素化合物を含んでなる複合めっき皮膜
が、表面に施されてなることを特徴とする。That is, the first aspect of the present invention is characterized in that a composite plating film containing a fluorine compound in a volume fraction of 15% or more is applied to the surface.
【０００８】請求項２記載の発明は、請求項１記載の樹
脂シート押出加工用金型において、複合めっき皮膜は、
ポリテトラフルオロエチレン、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、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、フッ化黒鉛、フッ化ピッチよりなるフッ素化合物群
から選択される１種以上のフッ素化合物微粒子を含み構
成されていることを特徴とする。According to a second aspect of the present invention, in the resin sheet extrusion die of the first aspect, the composite plating film is
At least one fluorine compound selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, fluorinated graphite, and fluorinated pitch It is characterized by comprising fine particles.
【０００９】請求項３記載の発明は、請求項１又は２記
載の樹脂シート押出加工用金型において、複合めっき皮
膜は、金属めっき母材中にフッ素化合物が共析されてい
るものであることを特徴とする。According to a third aspect of the present invention, in the resin sheet extrusion die according to the first or second aspect, the composite plating film is one in which a fluorine compound is codeposited in a metal plating base material. It is characterized by.
【００１０】請求項４記載の発明は、請求項３記載の樹
脂シート押出加工用金型において、フッ素化合物微粒子
の平均粒子径が２μｍ以下であることを特徴とする。According to a fourth aspect of the present invention, there is provided the resin sheet extrusion die according to the third aspect, wherein the average particle diameter of the fluorine compound fine particles is 2 μm or less.
【００１１】請求項５記載の発明は、請求項１、２、３
又は４記載の樹脂シート押出加工用金型において、複合
めっき皮膜は、１５０〜３５０℃の温度で加熱処理され
てなるものであることを特徴とする。[0011] The invention according to claim 5 is the invention according to claims 1, 2, and 3.
Alternatively, in the resin sheet extrusion die according to 4, the composite plating film is obtained by heat-treating at a temperature of 150 to 350 ° C.
【００１２】[0012]
【実施の形態】本発明の構成要素を順次説明し、この説
明を通して本発明の実施の形態を明らかにする。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The components of the present invention will be sequentially described, and the embodiments of the present invention will be clarified through this description.
【００１３】本発明においては、樹脂シート押出加工用
金型の表面に形成された複合めっき皮膜は、非金属であ
るフッ素化合物とマトリックス金属とから成るので、両
者の固有の性質を兼ね備えたものとなる。具体的には、
フッ素化合物に由来し、高度の潤滑性、耐磨耗性、防汚
性、非粘着性等の性質を有し、更に、特に優れた耐久
性、耐熱性、耐薬品性、撥水性、撥油性等の性質を発揮
する。加えて、マトリックス金属に由来して、高硬度、
高強度、高熱伝導性、高電導性等の性質を備え、更に、
基板材に対する優れた密着性を発揮する。In the present invention, since the composite plating film formed on the surface of the resin sheet extrusion die comprises a non-metallic fluorine compound and a matrix metal, the composite plating film has both of the inherent properties of both. Become. In particular,
Derived from fluorine compounds, has high lubricity, abrasion resistance, antifouling properties, non-adhesive properties, etc., and also has particularly excellent durability, heat resistance, chemical resistance, water repellency, oil repellency Demonstrate the properties such as. In addition, high hardness,
With properties such as high strength, high thermal conductivity, high conductivity,
Demonstrates excellent adhesion to substrate materials.
【００１４】また、樹脂シート押出加工用金型は、樹脂
が固着したり、焦げ付いたりするような厳しい環境で使
用されるので、高度の非粘着性、耐久性、耐焦げ付き性
等が要求されるが、上記の如く本発明においては金属を
マトリックスとしているので、この要求は満たされる。Further, since the resin sheet extrusion die is used in a severe environment where the resin is fixed or scorched, it is required to have a high degree of non-adhesion, durability, scoring resistance and the like. However, as described above, in the present invention, a metal is used as a matrix, so that this requirement is satisfied.
【００１５】但し、フッ素化合物の添加量が少ないと、
フッ素化合物の特性である非粘着性等が十分に発揮され
ない。そこで、本発明者らが実験したところ、フッ素化
合物微粒子の体積分率が１５％以上であると、上記の不
都合を十分に解消できることを見出した。よって、複合
めっき皮膜中のフッ素化合物粒子の体積分率としては、
１５％以上である必要がある。However, if the addition amount of the fluorine compound is small,
Non-adhesiveness, which is a characteristic of fluorine compounds, is not sufficiently exhibited. Thus, the present inventors have conducted an experiment and found that the above-mentioned inconvenience can be sufficiently solved if the volume fraction of the fluorine compound fine particles is 15% or more. Therefore, as the volume fraction of the fluorine compound particles in the composite plating film,
It needs to be 15% or more.
【００１６】但し、金属と共析物とからなる複合めっき
皮膜においては、共析物の体積分率が大きくなるほど、
めっき層と基材との接着性・密着性が低下する。よっ
て、複合めっき皮膜と、基板材である樹脂シート押出加
工用金型との接着性を考慮するとき、複合めっき皮膜中
の共析物の体積分率は１５〜６０％とするのが好まし
く、より好ましくは２５〜４５％とするのがよい。However, in a composite plating film comprising a metal and an eutectoid, as the volume fraction of the eutectoid increases,
Adhesion and adhesion between the plating layer and the substrate are reduced. Therefore, when considering the adhesiveness between the composite plating film and the resin sheet extrusion die as a substrate material, the volume fraction of the eutectoid in the composite plating film is preferably set to 15 to 60%, More preferably, it is good to be 25-45%.
【００１７】ここで、フッ素化合物しては、ポリテトラ
フルオロエチレン（以下、ＰＴＦＥという）、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
（以下、ＦＥＰという）、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（以下、Ｐ
ＦＡという）、フッ化黒鉛、フッ化ピッチが好適に使用
できる。Here, fluorine compounds include polytetrafluoroethylene (hereinafter, referred to as PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter, referred to as FEP), and tetrafluoroethylene-perfluoroalkylvinyl ether copolymer. Coalescence (hereinafter P
FA), fluorinated graphite and fluorinated pitch can be suitably used.
【００１８】本発明の特徴は、複合めっき皮膜の撥水材
としてフッ素化合物を使用する点、及びこのフッ素化合
物（分散相）とめっき材（マトリックス相）とで複合め
っき皮膜を形成する点にある。このことから、めっき材
（母材）は、好適な被覆性を有しかつフッ素化合物をマ
トリックス中に取り込めるものであればよい。よって、
本発明では、金属めっき材以外の母材を使用することも
可能であるが、本発明効果を十分に発揮させるために
は、金属めっき材を用いるのが好ましく、この場合の被
覆手段としては、電解めっき法や無電解めっき法が好適
である。The features of the present invention are that a fluorine compound is used as a water repellent material for a composite plating film, and that a composite plating film is formed from this fluorine compound (dispersed phase) and a plating material (matrix phase). . For this reason, the plating material (base material) only needs to have a suitable covering property and be capable of incorporating a fluorine compound into the matrix. Therefore,
In the present invention, it is possible to use a base material other than the metal plating material, but in order to sufficiently exhibit the effects of the present invention, it is preferable to use a metal plating material, in this case, as a coating means, An electrolytic plating method or an electroless plating method is suitable.
【００１９】本発明で好適に使用できる電解めっき法と
しては、例えば特開平４−３２９８９７号公報に記載の
方法があげられる。また、無電解めっき法としては、例
えば特開昭４９−２７４４３号公報に記載の方法があげ
られる。これらのめっき法であると、フッ素化合物の微
粒子を金属マトリックス相中に分散し共析させることが
できる。よって、非金属であるフッ素化合物固有の性質
とマトリックス金属の性質とを併せもった好適な複合め
っき皮膜が得られる。As an electrolytic plating method which can be suitably used in the present invention, for example, a method described in JP-A-4-329897 can be mentioned. Examples of the electroless plating method include a method described in JP-A-49-27443. According to these plating methods, fine particles of a fluorine compound can be dispersed in a metal matrix phase and co-deposited. Therefore, it is possible to obtain a suitable composite plating film having both the properties of the non-metallic fluorine compound and the properties of the matrix metal.
【００２０】複合めっき皮膜の形成方法を、電解めっき
法を例にして具体的に説明する。電解めっき法を用いる
場合、金属めっき液としては、例えば、ニッケル、銅、
亜鉛、スズ、鉄、鉛、カドミウム、クロム、貴金属類お
よびそれらの合金を塩の形態で用いる。これらのめっき
液は、各種の組成のものが知られており、本発明では、
公知のめっき液の何れをも使用することができる。The method for forming the composite plating film will be specifically described with reference to an electrolytic plating method as an example. When using the electrolytic plating method, as the metal plating solution, for example, nickel, copper,
Zinc, tin, iron, lead, cadmium, chromium, precious metals and their alloys are used in the form of salts. These plating solutions are known to have various compositions, and in the present invention,
Any of the known plating solutions can be used.
【００２１】めっき液に添加するフッ素化合物の粒子径
は、特に限定されるものではない。但し、好ましくはめ
っき皮膜厚よりも小さい微粒子を使用するのがよい。皮
膜全体の膜厚よりも大幅に直径の大きい粒子を用いた場
合、摩擦等の外力を受けてめっき面から粒子が脱落し易
くなるからである。ここで、複合めっき皮膜の厚さは、
樹脂シート押出加工用金型の材質、形状、マトリックス
金属の種類などにより適当に設定することができるが、
通常１〜５０μｍ程度であれば充分に保護皮膜の役割を
果たし得る。このことから、フッ素化合物微粒子の粒径
としては、平均２μｍ以下程度とすればよく、好ましく
は平均１μｍ以下とし、より好ましくは、めっき液中お
よび複合めっき皮膜中におけるフッ素化合物の分散の均
一性を確保するために、３０μｍを超える粗大粒子を含
まないようにする。The particle size of the fluorine compound added to the plating solution is not particularly limited. However, it is preferable to use fine particles smaller than the thickness of the plating film. This is because, when particles having a diameter significantly larger than the film thickness of the entire film are used, the particles are likely to fall off the plating surface due to external force such as friction. Here, the thickness of the composite plating film is
It can be set appropriately according to the material, shape, type of matrix metal, etc. of the resin sheet extrusion die,
Usually, if it is about 1 to 50 μm, it can sufficiently serve as a protective film. From this, the particle diameter of the fluorine compound fine particles may be about 2 μm or less on average, preferably 1 μm or less on average, and more preferably, the uniformity of dispersion of the fluorine compound in the plating solution and the composite plating film. In order to ensure this, do not include coarse particles exceeding 30 μm.
【００２２】めっき液中に添加するフッ素化合物の添加
量は、特に限定されるものではなく、要求される着色程
度や撥水性、撥油性などを考慮して適当に設定する。通
常、２００ｇ／Ｌ（リットル）程度以下、好ましくは１
〜１００ｇ／Ｌ程度に添加すれば充分に目的を達成する
ことができる。The amount of the fluorine compound to be added to the plating solution is not particularly limited, and is appropriately set in consideration of the required degree of coloring, water repellency, oil repellency and the like. Usually, about 200 g / L (liter) or less, preferably 1 g / L
If the amount is added to about 100 g / L, the object can be sufficiently achieved.
【００２３】複合めっき皮膜に含め得るその他の添加物
としては、特に制限されない。例えば複合めっき溶液に
界面活性剤や一次光沢剤、二次光沢剤、或いは公知の染
料、顔料を補助着色剤として添加することができるが、
このうち、特に界面活性剤の添加が推奨される。なぜな
ら、フッ素化合物は、撥水性が非常に高く濡れにくいの
で、界面活性剤により電解めっき溶液に対するフッ素化
合物等の濡れ性を改善して、フッ素化合物等をめっき液
に均一に分散する必要があるからである。Other additives that can be included in the composite plating film are not particularly limited. For example, a surfactant or a primary brightener, a secondary brightener, or a known dye or pigment can be added as an auxiliary colorant to the composite plating solution,
Of these, the addition of a surfactant is particularly recommended. This is because the fluorine compound has a very high water repellency and is hard to wet, so it is necessary to improve the wettability of the fluorine compound and the like to the electrolytic plating solution with a surfactant and to uniformly disperse the fluorine compound and the like in the plating solution. It is.
【００２４】電解めっき溶液に添加する界面活性剤は、
電解めっき液のｐＨ域でカチオン性を示すものでなけれ
ばならず、このような界面活性剤としては、例えば水溶
性のカチオン系、非イオン系およびめっき液のｐＨ値に
おいてカチオン性を示す両性界面活性剤がある。具体的
には、カチオン系界面活性剤としては、第４級アンモニ
ウム塩、第２アミンおよび第３アミン類などが使用で
き、非イオン系界面活性剤としては、ポリエチレンイミ
ン系、エステル系のものなどが使用でき、両性界面活性
剤としては、カルボン酸系、スルホン酸系のものが使用
できる。これらの界面活性剤のうち、分子中にＣ−Ｆ結
合を有するフッ素系界面活性剤が特に好適に使用でき
る。The surfactant to be added to the electrolytic plating solution is as follows:
The surfactant must exhibit cationicity in the pH range of the electrolytic plating solution. Examples of such a surfactant include a water-soluble cationic type, a nonionic type, and an amphoteric interface exhibiting cationicity at the pH value of the plating solution. There are activators. Specifically, quaternary ammonium salts, secondary amines and tertiary amines can be used as the cationic surfactant, and polyethylene imine-based, ester-based surfactants and the like as the nonionic surfactant. And carboxylic acid-based and sulfonic acid-based surfactants can be used as the amphoteric surfactant. Among these surfactants, fluorine surfactants having a CF bond in the molecule can be particularly preferably used.
【００２５】電解めっき液中への界面活性剤の添加量
は、フッ素化合物１ｇに対し、通常１〜５００ｍｇ程度
であり、より好ましくは１〜１００ｍｇ程度とする。め
っき条件については、基板材である樹脂シート押出加工
用金型の材質、使用する複合めっき液の種類などに応じ
て適宜決定すればよく、一般には複合めっき法において
通常用いられている液温、ｐＨ値、電流密度などを採用
すればよい。The amount of the surfactant added to the electrolytic plating solution is usually about 1 to 500 mg, more preferably about 1 to 100 mg, per 1 g of the fluorine compound. The plating conditions may be appropriately determined according to the material of the resin sheet extrusion die as the substrate material, the type of the composite plating solution to be used, and the like. Generally, the solution temperature generally used in the composite plating method, What is necessary is just to employ | adopt pH value, electric current density, etc.
【００２６】上述の如く、フッ素化合物等は撥水性に富
むため、めっき処理の進行中はめっき液を常に攪拌し、
フッ素化合物等をめっき液中に均一に分散させた状態で
めっきを行うことが好ましい。攪拌方法については、特
に限定されないので、通常の機械的攪拌手段、例えばス
クリュー攪拌、マグネチックスターラーによる攪拌など
の方法を使用すればよい。As described above, since the fluorine compound and the like are rich in water repellency, the plating solution is constantly stirred while the plating process is in progress.
Plating is preferably performed in a state where a fluorine compound or the like is uniformly dispersed in the plating solution. There is no particular limitation on the stirring method, and any ordinary mechanical stirring means such as a screw stirring method or a magnetic stirring method may be used.
【００２７】上記で例示した樹脂シート押出加工用金型
は、通常、銅、ステンレス鋼、一般鋼、アルミニウム、
アルミニウム合金などの金属類から構成されるが、本発
明にかかる複合めっき皮膜は、樹脂シート押出加工用金
型に直接形成してもよく、また基板材（組立て前のも
の）である、例えば銅、アルミニウムなどの金属、樹脂
類、炭素材からなる基板材上に、公知の下地めっき層
（例えば、ニッケルめっき、銅めっきなど）を形成した
後、複合めっき皮膜を施す方法を採用するのもよい。The resin sheet extrusion die exemplified above is usually made of copper, stainless steel, general steel, aluminum,
Although composed of metals such as aluminum alloys, the composite plating film according to the present invention may be formed directly on a resin sheet extrusion die, or may be a substrate material (before assembly) such as copper. It is also possible to adopt a method of forming a known base plating layer (for example, nickel plating, copper plating, etc.) on a substrate material made of a metal such as aluminum, a resin, or a carbon material, and then applying a composite plating film. .
【００２８】また、樹脂シート押出加工用金型として
は、丸型ダイと平型ダイとがあるが、本発明はいずれの
ものにも適応しうる。上記丸型ダイによる樹脂シートの
作製方法としては、大口径の丸型ダイから樹脂を薄肉厚
パイプとして押し出し、これを直ちに丸型ダイに取り付
けられたカッターでパイプを切り開き、更に、平らに広
げて冷却するような方法がある。一方、上記平型ダイに
よる樹脂シートの作製方法としては、幅広の平型ダイか
ら樹脂をそのまま平坦なシートとして押し出す方法があ
る。また、平型ダイの種類としては、その形状によりＴ
型ダイ（マニホールドダイ）と、魚尾型ダイとがある。As the mold for resin sheet extrusion processing, there are a round die and a flat die, but the present invention can be applied to any of them. As a method for producing a resin sheet using the above-mentioned round die, a resin is extruded from a large-diameter round die as a thin-walled pipe, and this is immediately cut open by a cutter attached to the round die, and further spread flat. There is a way to cool. On the other hand, as a method for producing a resin sheet using the flat die, there is a method of extruding a resin as it is from a wide flat die as a flat sheet. In addition, as for the type of flat die, depending on its shape, T
There are a die (manifold die) and a fishtail die.
【００２９】以上に説明した方法により、本発明にかか
る樹脂シート押出加工用金型が作製できるが、本発明の
より好ましい態様としては、樹脂シート押出加工用金型
に対し複合めっきを施した後、所定の温度で加熱処理を
行うのがよい。加熱処理により、一層耐久性、撥水性に
優れた複合めっき皮膜と成すことができ、また基板材等
に対する接着性・密着性を高めることができるからであ
る。The resin sheet extrusion die according to the present invention can be manufactured by the method described above. A more preferred embodiment of the present invention is that the resin sheet extrusion die is subjected to composite plating. The heat treatment is preferably performed at a predetermined temperature. By the heat treatment, a composite plating film having more excellent durability and water repellency can be formed, and the adhesiveness / adhesion to a substrate material or the like can be enhanced.
【００３０】上記加熱処理は、樹脂シート押出加工用金
型に複合めっき皮膜を施した後、複合めっき皮膜を１５
０〜４００℃、より好ましくは２００〜３５０℃の温度
で加熱することにより行う。１５０℃未満であると、充
分な加熱処理効果が得れず、４００℃を超えると、フッ
素化合物が分解するため、皮膜の劣化や変色や褪色の恐
れが生じるので好ましくない。このことから、安全かつ
確実に加熱処理効果を引き出すためには、加熱処理温度
を２００〜３５０℃に設定するのがよい。In the above heat treatment, after the composite plating film is applied to the resin sheet extrusion die, the composite plating film is
The heating is performed at a temperature of 0 to 400 ° C, more preferably 200 to 350 ° C. If the temperature is lower than 150 ° C., a sufficient heat treatment effect cannot be obtained, and if the temperature is higher than 400 ° C., the fluorine compound is decomposed, which may cause deterioration, discoloration or fading of the film. For this reason, in order to safely and surely bring out the heat treatment effect, it is preferable to set the heat treatment temperature to 200 to 350 ° C.
【００３１】加熱手段としては、例えば熱風を複合めっ
き皮膜に当てる方法や、複合めっき皮膜の施された樹脂
シート押出加工用金型自体、又は複合めっき皮膜の施さ
れた基板材を加熱器に入れて加熱する方法が例示でき
る。また、加熱処理時間は、特に限定されるものではな
く、加熱処理温度との関連で適当に設定することができ
るが、通常、１０〜３０分程度で充分である。As the heating means, for example, a method in which hot air is applied to the composite plating film, a resin sheet extrusion die itself provided with the composite plating film, or a substrate material provided with the composite plating film is put into a heater. Heating method. Further, the heat treatment time is not particularly limited and can be appropriately set in relation to the heat treatment temperature, but usually about 10 to 30 minutes is sufficient.
【００３２】なお、加熱処理により撥水性や基材に対す
る密着性が顕著に向上するのは、複合めっき皮膜自体の
熱的改質、界面活性剤の除去（熱分解、蒸発、昇華など
による）による濡れ性の低下などによるものと推考され
る。また、皮膜自体の熱的改質によると推察されるが、
加熱処理によって、基材に対する皮膜の接着性や密着性
が大幅に向上することが経験的に確認されている。The remarkable improvement in water repellency and adhesion to the substrate due to the heat treatment is due to thermal reforming of the composite plating film itself and removal of the surfactant (by thermal decomposition, evaporation, sublimation, etc.). It is presumed to be due to a decrease in wettability. It is also presumed that the film itself is due to thermal reforming,
It has been empirically confirmed that the heat treatment significantly improves the adhesion and adhesion of the film to the substrate.
【００３３】[0033]
【実施例】以下、本発明を適用した発明例および比較例
に基づいて、本発明の内容を具体的に説明する。EXAMPLES The contents of the present invention will be specifically described below based on examples of the present invention and comparative examples.
【００３４】〔発明例１-1〕めっき対象物 めっき対象物として、下記ものを用意した。 （ａ）ＳＵＳ４３０テストピース （ｂ）樹脂シート押出加工用金型（材質はＳＡＣＭ６４
５） 図１に示すように、樹脂シート押出加工用金型１ａは、
複軸樹脂押出機１の樹脂排出口に形成されており、より
具体的には、図２に示すように、マニホールド６を有す
る樹脂流路７を有している。この樹脂流路７の下流側に
は樹脂をシート状にして排出するダイリップ２が設けら
れており、このダイリップ２の上方には樹脂の厚みを調
製するための厚み調製ボルト３が設けられている。更
に、上記樹脂流路７の中間位置には樹脂の流量を調整す
る制限バー５が設けられており、この制限バー５はボル
ト４によって上下する構造である。なお、金型１ａは上
下が分割できる構造となっている（図２中Ａ−Ａ線で示
す）。電解めっきを行う場合には金型上下を分割して、
樹脂が接する面をアノードと平行になるように固定して
めっきを行った。また、このとき、ボルト４や制限バー
５ははずしておき、制限バーの樹脂が接する面にもめっ
きを施した。無電解めっきを行う場合にも、金型上下と
制限バーを分割して、めっき槽に入れて全面をめっきし
た。ただし、ボルトにはめっきを行わなかった。樹脂と
接しない部分にマスキングをしてめっき皮膜を形成しな
いことも可能であるが、マスキング処理は手間がかか
り、かえってコスト高となるため、今回は行わなかっ
た。[Invention Example 1-1] Plating Object The following was prepared as a plating object. (A) SUS430 test piece (b) Mold for resin sheet extrusion processing (material is SACM64
5) As shown in FIG. 1, the resin sheet extrusion die 1a is
It is formed at a resin outlet of the double-screw resin extruder 1, and more specifically, has a resin flow path 7 having a manifold 6 as shown in FIG. 2. A die lip 2 for discharging the resin in a sheet shape is provided downstream of the resin flow path 7, and a thickness adjusting bolt 3 for adjusting the thickness of the resin is provided above the die lip 2. . Further, a restriction bar 5 for adjusting the flow rate of the resin is provided at an intermediate position of the resin flow path 7, and the restriction bar 5 is structured to be moved up and down by bolts 4. The mold 1a has a structure that can be divided into upper and lower parts (shown by the line AA in FIG. 2). When performing electrolytic plating, separate the top and bottom of the mold,
Plating was performed with the surface in contact with the resin fixed so as to be parallel to the anode. At this time, the bolt 4 and the restriction bar 5 were removed, and the surface of the restriction bar in contact with the resin was plated. Also in the case of performing electroless plating, the upper and lower portions of the mold and the restriction bar were divided and put in a plating tank, and the entire surface was plated. However, no plating was applied to the bolts. Although it is possible to mask portions not in contact with the resin and not form a plating film, the masking process is time-consuming and rather expensive, and was not performed this time.
【００３５】尚、ＳＵＳ４３０テストピースについて
は、フッ素化合物の共析量の測定と、FACE接触角計を用
い液滴法による水に対する接触角の測定とを行い、更
に、基材に対する接着力（密着力）試験、衝撃性変形試
験の試料として用いた。また、樹脂シート押出加工用金
型については、樹脂押出機を実際に運転した場合に、樹
脂の焦げ付き及び金型内部の閉塞の有無について調べ
た。これらの結果及び試験方法の詳細については、後述
する。For the SUS430 test piece, the eutectoid amount of the fluorine compound was measured, and the contact angle with water was measured by a droplet method using a FACE contact angle meter. Force) used as a sample for the test and the impact deformation test. In addition, regarding the mold for resin sheet extrusion processing, when the resin extruder was actually operated, the presence or absence of scorching of the resin and clogging of the inside of the mold were examined. Details of these results and the test method will be described later.
【００３６】複合電解めっき浴の調製 表１に示す組成のスルファミン酸ニッケル浴を作製し、
この溶液に、ＰＴＦＥ微粒子（粒子径：２μｍ以下、ダ
イキン工業（株）製）を、溶液重量に対し５重量％添加
し、さらに界面活性剤として第３級パーフルオロアンモ
ニウム塩（大日本インキ化学（株）製、商標“メガファ
ックＦ１５０”）をＰＴＦＥ微粒子１ｇ当たり３０．０
ｍｇの割合で添加して、複合電解めっき浴と成した。Preparation of composite electrolytic plating bath A nickel sulfamate bath having the composition shown in Table 1 was prepared.
To this solution, PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) are added at 5% by weight based on the weight of the solution, and a tertiary perfluoroammonium salt (Dai Nippon Ink Chemical ( Co., Ltd., trade name "MegaFac F150") was added at 30.0 g / g of PTFE fine particles.
mg of the composite electrolytic plating bath.
【００３７】[0037]
【表１】 [Table 1]
【００３８】下地めっき皮膜の形成 上記めっき対象物をカソードとし、表２に示す組成液の
入ったウッド浴に漬け、液温２５℃、電流密度１０Ａ／
ｄｍ2 、めっき時間２分という条件で、予めめっき対象
物に下地ニッケルめっきを施した。 Formation of Base Plating Film The above-mentioned plating object was used as a cathode and immersed in a wood bath containing a composition solution shown in Table 2 at a solution temperature of 25 ° C. and a current density of 10 A /
Under the conditions of dm 2 and plating time of 2 minutes, the object to be plated was preliminarily plated with nickel.
【００３９】[0039]
【表２】 [Table 2]
【００４０】複合めっき皮膜の形成 めっき対象物（下地ニッケルめっきを施したもの）を、
ＰＴＦＥ微粒子５．０重量％を分散した前記複合電解め
っき浴に浸漬し、めっき浴を常にスクリュー攪拌しつ
つ、液温５０℃、ｐｈ４．２、電流密度２Ａ／ｄｍ2 の
条件で、膜厚１０μｍとなるまで複合めっきを行った。 Formation of Composite Plating Film The plating object (undercoated nickel plating) was
The PTFE fine particles were immersed in the composite electrolytic plating bath in which 5.0% by weight of the PTFE particles were dispersed, and the plating bath was constantly screw-stirred, and at a liquid temperature of 50 ° C., a ph of 4.2 and a current density of 2 A / dm 2 , a film thickness of 10 μm. Composite plating was performed until
【００４１】加熱処理 上記複合めっきを施したものに対し、３５０℃・３０分
間の加熱処理を行った後、常温で１時間放置した。加熱
処理は、複合めっきを施したＳＵＳ４３０テストピース
及び樹脂シート押出加工用金型を、３５０℃の熱風循環
式乾燥炉に３０分間入れる方法で行った。このようにし
て、表面処理がなされたテストピース及び樹脂シート押
出加工用金型を得た。 Heat Treatment The composite plate was subjected to a heat treatment at 350 ° C. for 30 minutes and then left at room temperature for 1 hour. The heat treatment was performed by placing the SUS430 test piece subjected to the composite plating and the resin sheet extrusion processing mold in a hot air circulating drying oven at 350 ° C. for 30 minutes. Thus, a surface-treated test piece and a resin sheet extrusion die were obtained.
【００４２】〔発明例１-2〕複合電解めっき浴の調製に
おけるＰＴＦＥ微粒子の添加量を、溶液重量に対し２．
５重量％とした以外は、上記発明例１-1と同様にして表
面処理がなされたテストピース及び樹脂シート押出加工
用金型を得た。このような処理品を、発明例１-2とす
る。[Inventive Example 1-2] In the preparation of the composite electrolytic plating bath, the addition amount of the PTFE fine particles was set at 2.
A test piece and a resin sheet extrusion die were surface-treated in the same manner as in Inventive Example 1-1 except that the content was changed to 5% by weight. Such a processed product is referred to as Invention Example 1-2.
【００４３】〔発明例１-3〕複合電解めっき浴の調製に
おけるＰＴＦＥ微粒子の添加量を、溶液重量に対し７．
５重量％とした以外は、上記発明例１-1と同様にして表
面処理がなされたテストピース及び樹脂シート押出加工
用金型を得た。このような処理品を、発明例１-3とす
る。[Inventive Example 1-3] In the preparation of the composite electrolytic plating bath, the addition amount of the PTFE fine particles was 7.
A test piece and a resin sheet extrusion die were surface-treated in the same manner as in Inventive Example 1-1 except that the content was changed to 5% by weight. Such a processed product is referred to as Invention Example 1-3.
【００４４】〔発明例２〕複合電解めっき浴の調製にお
いて、ＰＴＦＥ微粒子の代わりに、ＦＥＰ微粒子（粒子
径２μｍ以下、ダイキン工業（株）製）を５重量％用
い、且つ界面活性剤（商標“メガファックＦ１５０”）
をＦＥＰ微粒子１ｇ当たり６５．０ｍｇの割合で添加
し、更に熱処理条件を２５０℃で３０分とした以外は、
上記発明例１-1と同様にして表面処理がなされたテスト
ピース及び樹脂シート押出加工用金型を得た。このよう
な処理品を、発明例２とする。[Inventive Example 2] In preparing the composite electrolytic plating bath, 5% by weight of FEP fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) was used instead of PTFE fine particles, and a surfactant (trademark “ Mega Fuck F150 ")
Was added at a rate of 65.0 mg per 1 g of FEP fine particles, and the heat treatment was performed at 250 ° C. for 30 minutes.
A test piece and a resin sheet extrusion die were subjected to surface treatment in the same manner as in Inventive Example 1-1. Such a processed product is referred to as Inventive Example 2.
【００４５】〔発明例３〕複合電解めっき浴の調製にお
いて、ＰＴＦＥ微粒子の代わりに、ＰＦＡ微粒子（粒子
径２μｍ以下、ダイキン工業（株）製）を５重量％用
い、且つ界面活性剤（商標“メガファックＦ１５０”）
をＰＦＡ微粒子１ｇ当たり３０．０ｍｇの割合で添加
し、更に熱処理条件を２５０℃で３０分とした以外は、
上記発明例１-1と同様にして表面処理がなされたテスト
ピース及び樹脂シート押出加工用金型を得た。このよう
な処理品を、発明例３とする。Invention Example 3 In the preparation of the composite electrolytic plating bath, 5% by weight of PFA fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) were used instead of PTFE fine particles, and a surfactant (trademark “ Mega Fuck F150 ")
Was added at a rate of 30.0 mg per 1 g of PFA fine particles, and the heat treatment conditions were changed to 250 ° C. for 30 minutes.
A test piece and a resin sheet extrusion die were subjected to surface treatment in the same manner as in Inventive Example 1-1. Such a processed product is referred to as Inventive Example 3.
【００４６】〔発明例４〕複合電解めっき浴の調製にお
いて、ＰＴＦＥ微粒子の代わりに、フッ化黒鉛微粒子
（粒子径１μｍ以下、旭硝子（株）製）を５重量％用
い、且つ界面活性剤（商標“メガファックＦ１５０”）
をフッ化黒鉛微粒子１ｇ当たり４０．０ｍｇの割合で添
加した以外は、上記発明例１-1と同様にして表面処理が
なされたテストピース及び樹脂シート押出加工用金型を
得た。このような処理品を、発明例４とする。Inventive Example 4 In the preparation of the composite electrolytic plating bath, 5% by weight of fluorinated graphite fine particles (particle size: 1 μm or less, manufactured by Asahi Glass Co., Ltd.) was used instead of PTFE fine particles, and a surfactant (trademark) was used. "Mega Fuck F150")
Was added at a ratio of 40.0 mg per 1 g of the fluorinated graphite fine particles to obtain a test piece and a resin sheet extrusion die, which had been subjected to a surface treatment in the same manner as in Invention Example 1-1. Such a processed product is referred to as Invention Example 4.
【００４７】〔発明例５〕複合電解めっき浴の調製にお
いて、ＰＴＦＥ微粒子の代わりに、フッ化ピッチ微粒子
（粒子径２μｍ以下、大阪ガス（株）製）を５重量％用
い、且つ界面活性剤（商標“メガファックＦ１５０”）
をフッ化ピッチ微粒子１ｇ当たり２５．０ｍｇの割合で
添加し、更に熱処理条件を２５０℃で３０分とした以外
は、上記発明例１-1と同様にして表面処理がなされたテ
ストピース及び樹脂シート押出加工用金型を得た。この
ような処理品を、発明例５とする。[Invention Example 5] In preparing a composite electrolytic plating bath, 5% by weight of pitch fluoride fine particles (particle size: 2 μm or less, manufactured by Osaka Gas Co., Ltd.) were used instead of PTFE fine particles, and a surfactant ( Trademark "MegaFac F150")
Was added at a ratio of 25.0 mg / g of fluorinated pitch fine particles, and the heat treatment was performed at 250 ° C. for 30 minutes, except that the test piece and the resin sheet were surface-treated in the same manner as in Invention Example 1-1. An extrusion die was obtained. Such a processed product is referred to as Inventive Example 5.
【００４８】〔発明例６〕複合電解めっき浴の調製にお
いて、ＰＴＦＥ微粒子の代わりに、ＰＴＦＥ微粒子（粒
子径２μｍ以下、ダイキン工業（株）製）を２．５重量
％とＦＥＰ微粒子（粒子径２μｍ以下、ダイキン工業
（株）製）を２．５重量％との混合微粒子を用い、且つ
界面活性剤（商標“メガファックＦ１５０”）を［ＰＴ
ＦＥ微粒子使用量（ｇ）×３０．０＋ＦＥＰ使用量
（ｇ）×６５．０］ｍｇで算出される量だけ用い、更に
熱処理条件を２５０℃で３０分としたこと以外は、発明
例1-1 と同様にして表面処理がなされたテストピース及
び樹脂シート押出加工用金型を得た。このような処理品
を、発明例６とする。Inventive Example 6 In the preparation of the composite electrolytic plating bath, 2.5% by weight of PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) and FEP fine particles (particle size: 2 μm) were used instead of PTFE fine particles. Hereinafter, fine particles mixed with 2.5% by weight of Daikin Industries, Ltd.) were used, and the surfactant (trade name “MegaFac F150”) was changed to [PT
Invention Example 1-1 except that only the amount calculated by using the amount of FE fine particles (g) × 30.0 + the amount of FEP (g) × 65.0] mg was used, and the heat treatment was performed at 250 ° C. for 30 minutes. In the same manner as in the above, a test piece and a resin sheet extrusion die subjected to a surface treatment were obtained. Such a processed product is referred to as Invention Example 6.
【００４９】〔発明例７〕複合電解めっき浴の調製にお
いて、ＰＴＦＥ微粒子の代わりに、ＰＴＦＥ微粒子（粒
子径２μｍ以下、ダイキン工業（株）製）を１．２５重
量％、ＰＦＡ微粒子（粒子径２μｍ以下、ダイキン工業
（株）製）を１．２５重量％、及びＦＥＰ微粒子（粒子
径２μｍ以下、ダイキン工業（株）製）を２．５重量％
の混合微粒子を用い、且つ、界面活性剤（商標“メガフ
ァックＦ１５０”）を［ＰＴＦＥ使用量（ｇ）×３０．
０＋ＰＦＡ使用量（ｇ）×３０．０＋ＦＥＰ使用量
（ｇ）×６５．０］ｍｇで出される量だけ用い、更に熱
処理条件を２５０℃で３０分としたこと以外は、発明例
1-1 と同様にして表面処理がなされたテストピース及び
樹脂シート押出加工用金型を得た。このような処理品
を、発明例７とする。Inventive Example 7 In the preparation of the composite electrolytic plating bath, 1.25% by weight of PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) and PFA fine particles (particle size: 2 μm) were used instead of PTFE fine particles. Hereinafter, 1.25% by weight of Daikin Industries, Ltd.) and 2.5% by weight of FEP fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.)
And a surfactant (trade name “MegaFac F150”) [PTFE used amount (g) × 30.
0 + PFA used amount (g) × 30.0 + FEP used amount (g) × 65.0] mg, except that the heat treatment conditions were 250 ° C. for 30 minutes.
In the same manner as in 1-1, a test piece and a resin sheet extrusion die subjected to surface treatment were obtained. Such a processed product is referred to as Invention Example 7.
【００５０】〔発明例８〕無電解ニッケルめっき浴の調製 表３に示す組成の無電解ニッケルめっき浴を作製した。Inventive Example 8 Preparation of Electroless Nickel Plating Bath An electroless nickel plating bath having the composition shown in Table 3 was prepared .
【００５１】[0051]
【表３】 [Table 3]
【００５２】無電解ニッケル−ＰＴＦＥ複合めっき浴の
調製 表３に示す組成の無電解ニッケルめっき浴を作製し、こ
の溶液に、ＰＴＦＥ微粒子（粒子径：２μｍ以下、ダイ
キン工業（株）製）を、溶液重量に対し５重量％添加
し、さらに界面活性剤として第３級パーフルオロアンモ
ニウム塩（大日本インキ化学（株）製、商標“メガファ
ックＦ１５０”）をＰＴＦＥ微粒子１ｇ当たり３０．０
ｍｇの割合で添加して、無電解ニッケル−ＰＴＦＥ複合
めっき浴と成した。The electroless nickel-PTFE composite plating bath
An electroless nickel plating bath having the composition shown in Preparation Table 3 was prepared , and PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) were added to this solution in an amount of 5% by weight based on the weight of the solution. A tertiary perfluoroammonium salt (manufactured by Dainippon Ink and Chemicals, Inc., trade name “MegaFac F150”) as an activator is added at 30.0 g / g of PTFE fine particles.
mg electroless nickel-PTFE composite plating bath.
【００５３】上記無電解ニッケルめっき浴、無電解ニッ
ケル−ＰＴＦＥ複合めっき浴及び発明例1-1 に示す表２
のウッド浴を用いて、下記に示す下地めっき皮膜と複合
めっき皮膜とを順に形成した。尚、下地めっき皮膜の形
成は、下地ニッケルストライクめっき処理と、下地無電
解ニッケルめっき処理とから構成されている。The above electroless nickel plating bath, electroless nickel-PTFE composite plating bath and Table 2 shown in Invention Example 1-1
, A base plating film and a composite plating film shown below were formed in order. The formation of the base plating film includes a base nickel strike plating process and a base electroless nickel plating process.
【００５４】下地めっき皮膜の形成 上記めっき対象物をカソードとし、表２に示す組成液の
入ったウッド浴に漬け、液温２５℃、電流密度１０Ａ／
ｄｍ2 、めっき時間２分という条件で、予めめっき対象
物に下地ニッケルストライクめっき処理を施した。 Formation of Base Plating Film The above-mentioned plating object was used as a cathode and immersed in a wood bath containing a composition solution shown in Table 2 at a solution temperature of 25 ° C. and a current density of 10 A /
Under the conditions of dm 2 and plating time of 2 minutes, the object to be plated was preliminarily subjected to a nickel strike plating treatment.
【００５５】次いで、めっき対象物を、表３に示す組成
液の入った無電解ニッケルめっき浴に浸漬し、スクリュ
ー攪拌下、液温９０℃、ｐＨ４．６とし、膜厚が３μｍ
となるまで無電解めっきを行って、下地無電解ニッケル
めっき皮膜を形成した。Next, the object to be plated was immersed in an electroless nickel plating bath containing a composition solution shown in Table 3, and the solution temperature was adjusted to 90 ° C., pH 4.6 under screw stirring, and the film thickness was 3 μm.
Electroless plating was carried out until the following conditions were reached to form a base electroless nickel plating film.
【００５６】複合めっき皮膜の形成 めっき対象物（下地ニッケルめっきを施したもの）を、
ＰＴＦＥ微粒子５．０重量％を分散した前記無電解ニッ
ケル−ＰＴＦＥ複合めっき浴に浸漬し、めっき浴を常に
スクリュー攪拌しつつ、液温９０℃、ｐｈ５．１の条件
で、膜厚１０μｍとなるまで複合めっきを行った。この
ようにして、無電解めっきを施す他は、発明例1-1 と同
様にして表面処理がなされたテストピース及び樹脂シー
ト押出加工用金型を得た。このような処理品を、発明例
８とする。 Formation of Composite Plating Film The object to be plated (the one subjected to nickel base plating) was
Immerse in the electroless nickel-PTFE composite plating bath in which 5.0% by weight of PTFE fine particles are dispersed, and constantly stir the plating bath with a screw until the film thickness becomes 10 μm at a liquid temperature of 90 ° C. and a ph of 5.1. Composite plating was performed. In this way, a test piece and a resin sheet extrusion die were surface-treated in the same manner as in Invention Example 1-1 except that electroless plating was performed. Such a processed product is referred to as Invention Example 8.
【００５７】〔比較例１〕発明例1-1 と同様のＳＵＳ４
３０テストピースに、実施例1-1 と同様のニッケルウッ
ド浴を用いて下地ニッケルストライクめっきを行った
後、めっき対象物を、前記表１に示す組成液の入ったス
ルファミン酸ニッケルめっき浴に浸漬し、スクリュー攪
拌下、液温５０℃、電流密度４Ａ／ｄｍ2 の条件下で、
膜厚が１０μｍとなるまで電解ニッケルめっきを行っ
た。このような処理品を、比較例１とする。Comparative Example 1 SUS4 similar to Invention Example 1-1
30 test pieces were subjected to base nickel strike plating using the same nickel wood bath as in Example 1-1, and the object to be plated was immersed in a nickel sulfamate plating bath containing the composition solution shown in Table 1 above. Then, under screw stirring, at a liquid temperature of 50 ° C. and a current density of 4 A / dm 2 ,
Electrolytic nickel plating was performed until the film thickness became 10 μm. Such a processed product is referred to as Comparative Example 1.
【００５８】〔比較例２〕複合電解めっき浴の調製にお
けるＰＴＦＥ微粒子の添加量を、溶液重量に対し１．７
重量％とした以外は、上記発明例１-1と同様にして表面
処理がなされたテストピース及び樹脂シート押出加工用
金型を得た。このような処理品を、比較例２とする。こ
こで、各種試験は、次のようにして行った。[Comparative Example 2] The addition amount of the PTFE fine particles in the preparation of the composite electrolytic plating bath was 1.7 with respect to the weight of the solution.
A test piece and a resin sheet extrusion die were surface-treated in the same manner as in Invention Example 1-1 except that the content was changed to wt%. Such a processed product is referred to as Comparative Example 2. Here, the various tests were performed as follows.
【００５９】（１）フッ素化合物共析量の測定試験 ＳＵＳ４３０テストピースを、重量比が１：１の硝酸水
溶液に浸漬して、めっき皮膜を溶解させた後、メンプラ
ンフィルター（平均穴径：０．２μｍ）を用いて濾過
し、更に８０℃で１時間デシケータ中で乾燥冷却した
後、重量分析にて測定した。(1) Measurement test of eutectoid content of fluorine compound A SUS430 test piece was immersed in an aqueous nitric acid solution having a weight ratio of 1: 1 to dissolve the plating film. .2 μm), dried and cooled in a desiccator at 80 ° C. for 1 hour, and measured by gravimetric analysis.
【００６０】（２）接触角試験 ＦＡＣＥ接触角測定装置（協和界面科学 (株) 製、CA-A
型）を用い、液滴法により試料（皮膜面）に対する水の
接触角を測定した。なお、撥水性の良否は、接触角の大
小で評価できる。(2) Contact angle test FACE contact angle measuring device (CA-A, manufactured by Kyowa Interface Science Co., Ltd.)
), And the contact angle of water to the sample (film surface) was measured by a droplet method. The quality of the water repellency can be evaluated by the magnitude of the contact angle.
【００６１】（３）接着性試験 JIS K5400 の密着力試験法（碁盤目テープ法）に準じて
行った。具体的には、皮膜面に１ｃｍ2 当たり１００個
の碁盤目を入れた試料を３通り用意し、それぞれ、(1）
２５０℃で２時間放置、(2）−１０℃で２時間放置、
(3）２００℃で１時間放置後、−１０℃で１時間放置す
るサイクルを１０回繰り返す、という操作を加えた。そ
の後、試料を室温に戻し、セロファン粘着テープを碁盤
目の上に張り、これを剥がした。そして、テープに付着
した碁盤目の剥がれ個数ｘを目視で読み取り、剥がれ個
数ｘ／１００で接着力の良否を評価した。(3) Adhesion test The adhesion test was carried out according to the adhesion test method (cross-cut tape method) of JIS K5400. Specifically, three samples having 100 grids per cm 2 on the film surface were prepared, and each of the samples was (1)
Leave at 250 ° C for 2 hours, (2) Leave at -10 ° C for 2 hours,
(3) An operation of repeating a cycle of standing at 200 ° C. for 1 hour and then standing at −10 ° C. for 1 hour 10 times was added. Thereafter, the sample was returned to room temperature, a cellophane adhesive tape was placed on a grid, and this was peeled off. Then, the number x of the grids peeled off on the tape was visually read, and the adhesive strength was evaluated based on the number x / 100 of the peelings.
【００６２】（４）耐衝撃変形性試験 ２０℃デュポン方式による衝撃変形試験（JIS K5400 ）
を行って試料を変形させ、変形した部分の皮膜の損傷を
調べた。耐衝撃変形試験の条件は、５００ｇの重りを５
００ｍｍの落下高さから落とすというものである。(4) Impact deformation test An impact deformation test using a 20 ° C. DuPont method (JIS K5400)
Was performed to deform the sample, and the damage of the film at the deformed portion was examined. The conditions of the shock deformation test are as follows.
Dropping from a drop height of 00 mm.
【００６３】（５）運転試験 上記発明例１〜８及び比較例１、２の方法で作製した樹
脂シート押出加工用金型を、図１に示すように、複軸樹
脂押出機１に取り付け、可塑剤であるジ−２−エチルヘ
キシルフタレートを３０ｗｔ％含むポリ塩化ビニルを１
時間に３０ｋｇの速度でホッパ１ｂより連続投入して、
ポリ塩化ビニル樹脂のシートをＴ型ダイより押し出し、
更に仕上げロール８、コンベア９、及び引取ロール１０
を介して切断機１１に搬送し、この切断機１１でシート
を切断することにより、樹脂シート（幅６００ｍｍ×長
さ１０００ｍｍ）を作製した。尚、この際、加熱温度は
１２０℃であり、また、作製した樹脂シートはスタッカ
１２により搬送される。そして、複軸樹脂押出機を２４
時間連続運転し、その場合に樹脂の焦げ付き及び金型内
部の閉塞の有無について調べた。(5) Operation Test The resin sheet extrusion processing dies prepared by the methods of Invention Examples 1 to 8 and Comparative Examples 1 and 2 were attached to a double-screw resin extruder 1 as shown in FIG. 1 polyvinyl chloride containing 30 wt% of di-2-ethylhexyl phthalate as a plasticizer
Continuously feed from the hopper 1b at a speed of 30 kg per hour,
Extruding a sheet of polyvinyl chloride resin from a T-die,
Further, a finishing roll 8, a conveyor 9, and a take-up roll 10
Then, the sheet was conveyed to a cutting machine 11, and the sheet was cut by the cutting machine 11 to prepare a resin sheet (600 mm in width × 1000 mm in length). At this time, the heating temperature is 120 ° C., and the produced resin sheet is transported by the stacker 12. Then, the double-screw resin extruder is set to 24
It was operated continuously for a time, and in that case, the presence or absence of scorching of the resin and blockage of the inside of the mold were examined.
【００６４】表４及び表５に作製条件を一覧表示し、各
種試験結果を表６及び表７に一覧表示する。The production conditions are listed in Tables 4 and 5, and the results of various tests are listed in Tables 6 and 7.
【００６５】[0065]
【表４】 [Table 4]
【００６６】[0066]
【表５】 [Table 5]
【００６７】[0067]
【表６】 [Table 6]
【００６８】[0068]
【表７】 [Table 7]
【００６９】試験結果 表６に示すように、フッ素化合物の共析量試験結果につ
いて、本発明例は何れも共析量が１５〜４５％と良好で
あり、且つ、複合めっき皮膜の接触角試験結果におい
て、本発明例は何れも比較例１〜３よりも接触角が大き
く、極めて良好な撥水性を有することが確認された。 Test Results As shown in Table 6, the results of the eutectoid amount test of the fluorine compound were as good as 15 to 45% in all of the examples of the present invention, and the contact angle test of the composite plating film was carried out. As a result, it was confirmed that all of the examples of the present invention had a larger contact angle than Comparative Examples 1 to 3 and had extremely good water repellency.
【００７０】また、表６に示すように、複合めっき皮膜
の基材に対する接着不良性、耐衝撃変形性に関して、本
発明例は、基材に対する接着性、耐衝撃変形性に優れて
いることが確認された。なお、表６の接着性試験は、前
記１〜３の条件で行った結果を示すものであるが、本発
明例及び比較例ともに接着不良が認められなかったの
で、単に０／１００と表示している。As shown in Table 6, with respect to the poor adhesion and the impact deformation resistance of the composite plating film to the substrate, the example of the present invention is excellent in the adhesion to the substrate and the impact deformation resistance. confirmed. The adhesion test in Table 6 shows the results of the tests performed under the conditions 1 to 3 above. However, since no poor adhesion was observed in both the present invention and the comparative examples, it was simply indicated as 0/100. ing.
【００７１】更に、表７に示すように、運転試験結果に
おいて、比較例１では運転１時間後に樹脂の焦げ付き、
金型内部の閉塞が発生して、運転不能となり、比較例２
では運転３時間後に樹脂の焦げ付き、金型内部の閉塞が
発生して、運転不能となったのに対して、本発明例は何
れも２４時間運転後であっても、樹脂の焦げ付き、金型
内部の閉塞が発生せず、円滑に連続運転できることが確
認された。Further, as shown in Table 7, in the operation test results, in Comparative Example 1, the resin was scorched one hour after the operation.
Comparative Example 2
In 3 hours after the operation, the resin was scorched and the inside of the mold was blocked, and the operation became impossible. On the other hand, in the examples of the present invention, even after the operation was performed for 24 hours, the resin was scorched and the mold was not operated. It was confirmed that there was no internal blockage and continuous operation was possible smoothly.
【００７２】[0072]
【発明の効果】本発明においては、基板材である樹脂シ
ート押出加工用金型の表面に形成された複合めっき皮膜
は、非金属であるフッ素化合物とマトリックス金属とか
ら成るので、フッ素化合物の特性に由来し、高度の潤滑
性、耐磨耗性、耐熱性、耐薬品性、撥水性、撥油性等の
性質を発揮し、マトリックス金属の特性に由来して、高
硬度、高強度、高熱伝導性、高耐熱性等の性質を併せ持
つ。更に、複合めっき皮膜は、基材に対する接着性・密
着性が良いので、基材と皮膜の熱膨張率の違いに起因す
る皮膜の剥離が生じ難い。According to the present invention, the composite plating film formed on the surface of the resin sheet extrusion die, which is a substrate material, comprises a non-metallic fluorine compound and a matrix metal. Demonstrates high lubricity, abrasion resistance, heat resistance, chemical resistance, water repellency, oil repellency, etc., and high hardness, high strength, and high thermal conductivity due to the properties of matrix metal Has properties such as heat resistance and high heat resistance. Furthermore, since the composite plating film has good adhesion and adhesion to the substrate, peeling of the film due to a difference in the coefficient of thermal expansion between the substrate and the film is unlikely to occur.
【００７３】また、フッ素化合物微粒子の体積分率を１
５％以上に規制しているので、フッ素化合物の特性であ
る非粘着性が十分に発揮される。したがって、樹脂シー
ト押出加工用金型への固着、焦げ付きを防止できる。Further, the volume fraction of the fluorine compound fine particles is set to 1
Since the content is regulated to 5% or more, the non-adhesive property of the fluorine compound is sufficiently exhibited. Therefore, sticking and scorching to the resin sheet extrusion die can be prevented.
【００７４】以上に述べたように、本発明によれば、樹
脂シート押出加工用金型への固着、焦げ付きを防止で
き、且つ、このような優れた使用性が長期にわたって維
持することができるといった優れた効果を奏する。As described above, according to the present invention, it is possible to prevent sticking and scorching to the resin sheet extrusion die and maintain such excellent usability over a long period of time. It has excellent effects.
【図１】樹脂シートを作製する際の作製工程を示す説明
図である。FIG. 1 is an explanatory view showing a production process when producing a resin sheet.
【図２】樹脂シート押出加工用金型の断面図である。FIG. 2 is a cross-sectional view of a resin sheet extrusion die.
１ａ：樹脂シート押出加工用金型 ２：ダイリップ ７：樹脂流路 1a: Mold for resin sheet extrusion processing 2: Die lip 7: Resin channel
Claims (5)
含んでなる複合めっき皮膜が、表面に施されてなる樹脂
シート押出加工用金型。1. A resin sheet extrusion die having a composite plating film containing at least 15% by volume of a fluorine compound on a surface thereof.
オロエチレン、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、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、フッ化黒
鉛、フッ化ピッチよりなるフッ素化合物群から選択され
る１種以上のフッ素化合物微粒子を含み構成されてい
る、請求項１記載の樹脂シート押出加工用金型。2. A fluorine compound comprising polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, fluorinated graphite, and fluorinated pitch. The resin sheet extrusion processing mold according to claim 1, wherein the mold comprises one or more kinds of fluorine compound fine particles selected from the group.
中にフッ素化合物が共析されているものである、請求項
１又は２記載の樹脂シート押出加工用金型。3. The resin sheet extrusion processing die according to claim 1, wherein the composite plating film has a fluorine compound co-deposited in a metal plating base material.
２μｍ以下である、請求項３記載の樹脂シート押出加工
用金型。4. The resin sheet extrusion processing die according to claim 3, wherein the average particle diameter of the fluorine compound fine particles is 2 μm or less.
℃の温度で加熱処理されてなるものであることを特徴と
する、請求項１、２、３又は４記載の樹脂シート押出加
工用金型。5. The composite plating film according to claim 1, wherein the composite plating film has a thickness of 150 to 350.
The resin sheet extrusion die according to claim 1, wherein the die is subjected to a heat treatment at a temperature of ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9241885A JPH1158491A (en) | 1997-08-22 | 1997-08-22 | Mold for extruding resin sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9241885A JPH1158491A (en) | 1997-08-22 | 1997-08-22 | Mold for extruding resin sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1158491A true JPH1158491A (en) | 1999-03-02 |
Family
ID=17081004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9241885A Pending JPH1158491A (en) | 1997-08-22 | 1997-08-22 | Mold for extruding resin sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1158491A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6460831B2 (en) | 1996-11-29 | 2002-10-08 | Fuji Bc Engineering Co., Ltd. | Cutting liquid coater |
| JP2007145016A (en) * | 2005-11-02 | 2007-06-14 | Asahi Kasei Chemicals Corp | Film made of polyphenylene ether resin and its production method |
| JP2010111127A (en) * | 2003-08-28 | 2010-05-20 | Kawata Mfg Co Ltd | Foaming extruder |
-
1997
- 1997-08-22 JP JP9241885A patent/JPH1158491A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6460831B2 (en) | 1996-11-29 | 2002-10-08 | Fuji Bc Engineering Co., Ltd. | Cutting liquid coater |
| JP2010111127A (en) * | 2003-08-28 | 2010-05-20 | Kawata Mfg Co Ltd | Foaming extruder |
| JP2007145016A (en) * | 2005-11-02 | 2007-06-14 | Asahi Kasei Chemicals Corp | Film made of polyphenylene ether resin and its production method |
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