JPH10165315A - Burner net - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain initial good usability for a long time by forming a composite plated film containing a fluorine-contained compound having a particular quantity at a volume rate on a surface so as to provide non-tackiness, impact resistance, damage resistance and heat resistance in a burner net used for gas table oven grill or the like. SOLUTION: A required burner net is provided by forming a composite plated film containing dispersed fluorine compound fine particles of 15% or more at a volume rate on the surface of the burner net. As the fluorine compound fine particles, one or more is selected from the group of fluorine compounds including polytetrafluoroethylene, tetrafluoroethylene/hexafluoropropylene copolymer, polytetrafluoroethylene/parfluoroalkyl vinyl ether copolymer and fluorine graphite. The composite plated film is formed, preferably by making eutectoid of a fluorine compound in a metallic plated base material, and an average particle diameter among the fine particles of this fluorine compound is preferably set to 2μm or lower.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、焼き網に関し、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
施した焼き網に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a grid, and more particularly, to a grid with a composite plating film containing fine particles of a fluorine compound.

【０００２】[0002]

【従来の技術】ガステーブルコンログリルなどに用いら
れる焼き網では、被調理材料から発生する油蒸気ないし
油煙、煮こぼれ汁などにより焼き網が汚染されるため、
恒常的な清掃を必要とするが、油蒸気や煮こぼれ等の汚
染物は、調理時の熱によって凝縮され、さらには炭化さ
れて凝固物となり焼き網にこびり付く。このため、清掃
によりこれらの凝固物を取り除くのは容易でない。した
がって、焼き網は、短期間の繰り返し使用により美観が
劣化するとともに、快適な調理がなしえなくなる。2. Description of the Related Art In a grill used for a gas table stove grill or the like, the grill is contaminated by oil vapor or oil smoke generated from the material to be cooked, spilled soup and the like.
Although regular cleaning is required, contaminants such as oil vapor and boiling spills are condensed by heat during cooking, and further carbonized to solidify and stick to the grill. For this reason, it is not easy to remove these solids by cleaning. Therefore, the grill will deteriorate the aesthetic appearance due to repeated use for a short period of time, and will not be able to cook comfortably.

【０００３】そこで、清掃や凝固物の除去を容易にする
手段として、焼き網の表面に非粘着性を付与することに
より、汚染を軽減したり、汚染の除去を容易化するなど
の手段が種々提案されている。[0003] Therefore, as means for facilitating cleaning and removal of solidified substances, there are various means for reducing contamination and facilitating removal of contamination by imparting non-adhesiveness to the surface of the grid. Proposed.

【０００４】例えば、表面がシリコン樹脂加工された焼
き網（オキツモ（株）製）や、親油性多孔質セラミック
とセラミック樹脂とによって加工した焼き網（大島工業
（株）製）などが製造されている。これらの技術を適用
した焼き網では、使用当初においては、ある程度の非粘
着性が確保されるので、煮こぼれ汁などによる汚れを比
較的容易に除去できる。[0004] For example, grill nets whose surface is processed with silicone resin (manufactured by Okitsumo Co., Ltd.) and grill nets manufactured by using lipophilic porous ceramic and ceramic resin (manufactured by Oshima Industry Co., Ltd.) are manufactured. I have. Since a certain degree of non-adhesiveness is secured at the beginning of use, a grill net to which these techniques are applied can relatively easily remove stains such as boiling water.

【０００５】しかし、これらの技術を適用した皮膜は、
基材に対する付着性が十分でなく、皮膜硬度や強度が十
分でない。よって、汚れ除去のための清掃時に皮膜が傷
付き易く、清掃時の傷により次第に汚染物に対する非粘
着性が低下するという問題がある。[0005] However, a film to which these techniques are applied is
Insufficient adhesion to substrate, insufficient film hardness and strength. Therefore, there is a problem that the film is easily damaged during cleaning for removing dirt, and the non-adhesiveness to contaminants gradually decreases due to the damage during cleaning.

【０００６】[0006]

【発明が解決しようとする課題】本発明は、焼き網にお
ける上記のような問題点に鑑みなされたものであり、優
れた非粘着性とともに耐衝撃性、耐傷付き性、耐熱性な
どを備えることによって、初期の快適な使用性が長期に
わたって維持できる焼き網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 grill net, and has excellent non-adhesiveness, impact resistance, scratch resistance, heat resistance and the like. Accordingly, an object of the present invention is to provide a grill which can maintain initial comfortable usability for a long period of time.

【０００７】[0007]

【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、焼き網の表
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、基材に対する
付着性、耐衝撃性、耐傷付き性等に優れ、しかも非粘着
性に優れ且つこれを長期にわたって維持できる焼き網が
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、一層撥水・撥油
性、非粘着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 fluorine compound fine particles having a volume fraction of 15% or more were dispersed and contained on the surface of the grid. It has been found that, when a composite plating film is formed, it is possible to obtain a grill which is excellent in adhesion to a substrate, impact resistance, scratch resistance, and the like, is excellent in non-adhesiveness, and can maintain this for a long period of time. 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 excellent water repellency, oil repellency and non-adhesion can be obtained. The present invention has been completed based on these findings, and has the following configuration.

【０００８】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 invention of claim 1 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.

【０００９】請求項２記載の発明は、請求項１記載の焼
き網において、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、ポリ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
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 grid according to the first aspect, the composite plating film is made of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene-perfluoroalkyl vinyl ether. It is characterized by comprising one or more kinds of fluorine compound fine particles selected from a fluorine compound group consisting of a copolymer and fluorinated graphite.

【００１０】請求項３記載の発明は、請求項１又は２記
載の焼き網において、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。The invention according to claim 3 is characterized in that, in the grid according to claim 1 or 2, the composite plating film is one in which a fluorine compound is eutectoid in a metal plating base material.

【００１１】請求項４記載の発明は、請求項３記載の焼
き網において、フッ素化合物微粒子の平均粒子径が２μ
ｍ以下であることを特徴とする。According to a fourth aspect of the present invention, in the grid according to the third aspect, the fluorine compound fine particles have an average particle diameter of 2 μm.
m or less.

【００１２】請求項５記載の発明は、請求項１、２、３
又は４記載の焼き網において、複合めっき皮膜は、１５
０〜３５０℃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。[0012] The invention according to claim 5 is the invention according to claims 1, 2, and 3.
Or, in the grid according to 4, the composite plating film has a thickness of 15
It is characterized by being heat-treated at a temperature of 0 to 350 ° C.

【００１３】請求項６記載の発明は、請求項１、２、
３、４又は５記載の焼き網において、焼き網は、ガステ
ーブルコンログリルに用いられることを特徴とする。[0013] The invention according to claim 6 is the first or second invention.
3. The grill according to 3, 4, or 5, wherein the grill is used for a gas table stove grill.

【００１４】[0014]

【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.

【００１５】本発明においては、基板材である焼き網用
部材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、耐焦げ付き性等の性質を有し、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、基板材である焼き網用部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 grill member, which is a substrate material, is composed of a non-metallic fluorine compound and a matrix metal, the composite plating film has both inherent properties. Becomes In particular,
Derived from fluorine compounds, it has high lubricity, abrasion resistance, antifouling properties, and charring resistance properties, and has particularly excellent durability, heat resistance, chemical resistance, water repellency, and oil repellency. Demonstrate the properties such as. In addition, due to the matrix metal, it has properties such as high hardness, high strength, high thermal conductivity, and high electrical conductivity, and further exhibits excellent adhesion to a grill member, which is a substrate material.

【００１６】また、焼き網は、バーナーやヒーターの極
近傍で使用されるので、高度の耐熱性が要求されるが、
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、しかもフッ素化合物に
起因する非粘着性により、魚を焼いた際の焦げ付き等も
防止できる。Further, since the grill is used very close to a burner or a heater, a high degree of heat resistance is required.
As described above, in the present invention, a metal is used as a matrix, which satisfies this requirement. In addition, due to the non-adhesion caused by the fluorine compound, it is possible to prevent scorching or the like when grilling fish.

【００１７】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が十分に発揮され
ず、魚を焼いた際に焦げ付きが生じる。このような焦げ
付きは、焼き網にとって致命的なものとなる。なぜな
ら、焦げ付きを生じた場合には、焼き魚の焼き網に対す
る身離れ荷重が大きくなり、焼き魚を焼き網から剥がす
場合に、魚の皮部と身部とが分離する。このため、皮部
だけが焼き網に張り付いた状態となって、焼き魚の見栄
えが悪くなる。更に、魚の美味み成分は魚の皮部と身部
との間に多く存在するのに、皮部が焼き網に張り付いた
状態になると、この美味み成分が皮部と共に焼き網に残
存する。この結果、焼き魚の味覚も悪くなる。However, if the addition amount of the fluorine compound is small,
The non-adhesive property of the fluorine compound is not sufficiently exhibited, and burning occurs when the fish is baked. Such scorching is fatal to the grill. This is because when burning occurs, the load on the grilled fish separating from the grill becomes large, and when peeling the grilled fish from the grill, the skin and the body of the fish are separated. For this reason, only the skin is stuck to the grill and the appearance of the grilled fish deteriorates. Furthermore, although a large amount of delicious components of fish exist between the skin and the body of the fish, when the skin is stuck to the grill, the delicious components remain in the grill together with the skin. As a result, the taste of the grilled fish also deteriorates.

【００１８】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。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, the volume fraction of the fluorine compound particles in the composite plating film needs to be 15% or more.

【００１９】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、基板材である焼き網との接着性
を考慮するとき、複合めっき皮膜中の共析物の体積分率
を６０％以下とするのが好ましく、より好ましくは４５
％以下とするのがよい。However, in a composite plating film composed of a metal and an eutectoid, the larger the volume fraction of the eutectoid, the more
Adhesion and adhesion between the plating layer and the substrate are reduced. Therefore, when considering the adhesiveness between the composite plating film and the grid net as a substrate material, the volume fraction of the eutectoid in the composite plating film is preferably set to 60% or less, more preferably 45% or less.
% Or less.

【００２０】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（ＰＴＦＥ）、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）、ポ
リ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（ＰＦＡ）、フッ化黒鉛が好適に使
用できる。Here, as the fluorine compound, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polytetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), Fluorinated graphite can be suitably used.

【００２１】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 reside in that a fluorine compound is used as a water repellent material for the composite plating film, and that a composite plating film is formed from the fluorine compound (dispersed phase) and the 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.

【００２２】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 electroplating method that 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.

【００２３】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.

【００２４】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、
焼き網用部材の材質、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１〜５０
μｍ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 depending on the material and shape of the grilling member, the type of the matrix metal, and the like.
If it is about μm, it can sufficiently serve as a protective film.
For this reason, the particle diameter of the fluorine compound fine particles may be about 2 μm or less on average, and preferably 1 μm or less on average.
More preferably, coarse particles exceeding 30 μm are not contained in order to ensure uniform dispersion of the fluorine compound in the plating solution and the composite plating film.

【００２５】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.

【００２６】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.

【００２７】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 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.

【００２８】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１〜５０ｍｇ程度とする。めっ
き条件については、基板材である焼き網用部材の材質、
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 to be added to the electrolytic plating solution is usually about 1 to 500 mg, more preferably about 1 to 50 mg, per 1 g of the fluorine compound. Regarding the plating conditions, the material of the grid member, which is the substrate material,
What is necessary is just to determine suitably according to the kind of composite plating solution to be used, etc. Generally, what is necessary is just to employ the solution temperature, pH value, current density, etc. which are usually used in the composite plating method.

【００２９】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.

【００３０】上記で例示した焼き網用部材は、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、焼き網用部材に直接形成してもよ
く、また焼き網の基板材（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板に対し施してもよ
い。また、焼き網用部材又はその基板材に対し、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。[0030] The grilling member exemplified above is usually
Although it is composed of metals such as copper, stainless steel, general steel, aluminum, and aluminum alloy, the composite plating film according to the present invention may be directly formed on a member for a grill, or a substrate material of the grill ( (Before assembly), for example, a metal plate such as copper or aluminum. It is also possible to adopt a method in which a known base plating layer (for example, nickel plating, copper plating, or the like) is formed on the grid member or its substrate material, and then a composite plating film is applied.

【００３１】以上に説明した方法により、本発明にかか
る焼き網が作製できるが、本発明のより好ましい態様と
しては、焼き網用部材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、
一層撥水・撥油性、耐熱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 grill described above can be produced by the above-described method. In a more preferred embodiment of the present invention, after performing the composite plating on the members for the grill, a heating treatment is performed at a predetermined temperature. Good to do. By heat treatment,
This is because a composite plating film having more excellent water / oil repellency and heat resistance can be formed, and the adhesiveness / adhesion to a substrate material or the like can be enhanced.

【００３２】上記加熱処理は、焼き網用部材又は基板材
に複合めっき皮膜を施した後、複合めっき皮膜を１５０
〜３５０℃、より好ましくは２００〜３００℃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、３５０℃を超えると、フッ素
化合物の融点を超えるため、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２００〜３００℃に設定するのがよい。In the heat treatment, a composite plating film is applied to a grilling member or a substrate material, and then the composite plating film is
The heating is performed at a temperature of from 350 to 350 ° C, more preferably from 200 to 300 ° C. If the temperature is lower than 150 ° C., a sufficient heat treatment effect cannot be obtained, and if the temperature exceeds 350 ° C., the melting point of the fluorine compound is exceeded, 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 300 ° C.

【００３３】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焼き
網自体、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、１０〜３
０分程度で充分である。As a heating means, for example, a method in which hot air is applied to the composite plating film, a method in which the grille itself provided with the composite plating film, or a substrate material provided with the composite plating film is put into a heater and heated. Can be illustrated. The heat treatment time is not particularly limited, and can be appropriately set in relation to the heat treatment temperature.
About 0 minutes is enough.

【００３４】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.

【００３５】[0035]

【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.

【００３６】〔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）焼き網（ＳＰＣＣ鋼製で、幅１９０ｍｍ×奥行き
２７０ｍｍの長方形のもの） （ｂ）ＳＰＣＣ鋼板（１００ｍｍ×２００ｍｍ×０．５
ｍｍの平板状のもの）。[Invention Example 1-1] Plating object The following were prepared as plating objects. (A) Grid (made of SPCC steel and rectangular with 190 mm width x 270 mm depth) (b) SPCC steel plate (100 mm x 200 mm x 0.5
mm).

【００３７】尚、焼き網については焼き魚の身離れ荷重
の測定を行った。また、ＳＰＣＣ鋼板についてはフッ素
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、耐薬品性試験、及び耐磨耗
性試験、耐熱焦げ付き試験１及び耐熱焦げ付き試験２の
試料として用いた。これらの結果及び試験方法の詳細に
ついては、後述する。The detachment load of the grilled fish was measured for the grill. For the SPCC steel sheet, the amount of eutectoid fluorine compound was measured, and the contact angle with water was measured by a droplet method using a FACE contact angle meter. It was used as a sample in a chemical test, a wear resistance test, a heat scorch test 1 and a heat scorch test 2. Details of these results and the test method will be described later.

【００３８】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、上記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３
０．０ｍｇ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, the above-mentioned PTFE fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.) are added in an amount of 5% by weight based on the weight of the solution, and a tertiary perfluoroammonium salt (Dai Nippon Ink Chemicals) is added as a surfactant. (Trade name "MegaFac F150", manufactured by Co., Ltd.)
It was added at a rate of 0.0 mg to form a composite electrolytic plating bath.

【００３９】[0039]

【表１】 [Table 1]

【００４０】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（膜厚：３μｍ）を施した。 Formation of Base Plating Film The above-mentioned plating object was used as a cathode, 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 base nickel plating (thickness: 3 μm).

【００４１】[0041]

【表２】 [Table 2]

【００４２】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

【００４３】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焼き網およびＳＰＣＣ鋼板
を、３５０℃の熱風循環式乾燥炉に３０分間入れる方法
で行った。以上のようにして、本発明例１-1にかかる焼
き網等を作製した。 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 grill and the SPCC steel plate subjected to the composite plating in a hot-air circulation drying oven at 350 ° C. for 30 minutes. As described above, a grid and the like according to the present invention example 1-1 were produced.

【００４４】〔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と同様にして焼
き網等を得た。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 to 2.
Except that the content was 5% by weight, a grid and the like were obtained in the same manner as in Invention Example 1-1. Such a processed product is referred to as Invention Example 1-2.

【００４５】〔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と同様にして焼
き網等を得た。このような処理品を、発明例１-3とす
る。[Inventive Example 1-3] The amount of the PTFE fine particles added in the preparation of the composite electrolytic plating bath was 7.
Except that the content was 5% by weight, a grid and the like were obtained in the same manner as in Invention Example 1-1. Such a processed product is referred to as Invention Example 1-3.

【００４６】〔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と同様にして焼き網等を得た。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 grill and the like were obtained in the same manner as in Invention Example 1-1. Such a processed product is referred to as Inventive Example 2.

【００４７】〔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と同様にして焼き網等を得た。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.) was 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 grill and the like were obtained in the same manner as in Invention Example 1-1. Such a processed product is referred to as Inventive Example 3.

【００４８】〔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と同様にして焼き網等を
得た。このような処理品を、発明例４とする。Inventive Example 4 In preparing 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 obtained in the same manner as in Example 1-1 except that was added in an amount of 40.0 mg per 1 g of the fluorinated graphite fine particles. Such a processed product is referred to as Invention Example 4.

【００４９】〔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、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 と同様にして焼き網等を得た。このような処理品
を、発明例５とする。Inventive Example 5 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 described above, a grill and the like were obtained. Such a processed product is referred to as Inventive Example 5.

【００５０】〔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 と同様にして焼き網等を得た。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, 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.
A grill and the like were obtained in the same manner as 1-1. Such a processed product is referred to as Invention Example 6.

【００５１】〔発明例７〕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。Invention Example 7 Preparation of Electroless Nickel Plating Bath An electroless nickel plating bath having the composition shown in Table 3 was prepared .

【００５２】[0052]

【表３】 [Table 3]

【００５３】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。In 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.

【００５４】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.

【００５５】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 Undercoat Plating Film The above-mentioned object to be plated was used as a cathode, immersed in a wood bath containing a composition solution shown in Table 2, 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.

【００５６】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 was adjusted to a solution temperature of 90 ° C. and a pH of 4.6 under stirring with a screw to obtain a film thickness of 3 μm.
Electroless plating was carried out until the following conditions were reached to form a base electroless nickel plating film.

【００５７】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
様にして焼き網等を得た。このような処理品を、発明例
７とする。 Formation of Composite Plating Film The plating object (undercoated nickel 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 grid net and the like were obtained 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 7.

【００５８】〔比較例１〕発明例1-1 と同様の焼き網お
よびＳＰＣＣ鋼板にエッチングプライマーをエアースプ
レーにて塗布して下地層（膜厚：３μｍ）を形成した
後、ＰＴＦＥフッ素樹脂塗料をアースプレーにて塗布し
てフッ素樹脂塗膜（膜厚：１０μｍ）を形成した。更
に、これらを１００℃で５分間予備乾燥した後、３５０
℃で３０分間加熱処理して焼き網等を得た。このような
処理品を、比較例１とする。Comparative Example 1 An undercoat layer (thickness: 3 μm) was formed by applying an etching primer to the same grid and SPCC steel sheet as in Inventive Example 1-1 by air spray, and then applying a PTFE fluororesin paint. It was applied with an earth spray to form a fluororesin coating film (film thickness: 10 μm). Furthermore, after pre-drying them at 100 ° C. for 5 minutes,
A heating treatment was performed at 30 ° C. for 30 minutes to obtain a grid. Such a processed product is referred to as Comparative Example 1.

【００５９】〔比較例２〕発明例１と同様にして下地層
（膜厚：３μｍ）を形成した後、表４に示す組成のニッ
ケルワット浴（即ち、フッ素化合物と界面活性剤とが添
加されていない浴）を用い、電解ニッケルめっきを行っ
た。めっき操作条件は、スクリュー攪拌下、液温５０
℃、電流密度４Ａ／ｄｍ² とし、膜厚が１０μｍとなる
まで行った。更に、表５に示す組成のサージェント浴を
用い、電解クロムめっきを行った。めっき操作条件は、
スクリュー攪拌下、液温５０℃、ｐＨ３．０、電流密度
２０Ａ／ｄｍ² とし、膜厚が０．２μｍとなるまで行っ
た。その後、水洗し、更に１００℃で５分間乾燥して、
焼き網等を得た。このような処理品を、比較例２とす
る。Comparative Example 2 An underlayer (thickness: 3 μm) was formed in the same manner as in Inventive Example 1, and a nickel watt bath having the composition shown in Table 4 (that is, a fluorine compound and a surfactant were added). The bath was not subjected to electrolytic nickel plating. The plating operation conditions were as follows: a screw temperature of 50 and a liquid temperature of 50.
C., the current density was 4 A / dm ^2, and the process was performed until the film thickness became 10 μm. Further, electrolytic chromium plating was performed using a Sargent bath having the composition shown in Table 5. The plating operation conditions are:
The operation was performed under screw stirring until the liquid temperature was 50 ° C., the pH was 3.0, the current density was 20 A / dm ² , and the film thickness was 0.2 μm. After that, it is washed with water and dried at 100 ° C. for 5 minutes.
A grill was obtained. Such a processed product is referred to as Comparative Example 2.

【００６０】[0060]

【表４】 [Table 4]

【００６１】[0061]

【表５】 [Table 5]

【００６２】〔比較例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１．７
重量％とした以外は、上記発明例１-1と同様にして焼き
網等を得た。このような処理品を、比較例３とする。こ
こで、各種試験は、次のようにして行った。[Comparative Example 3] The addition amount of the PTFE fine particles in the preparation of the composite electrolytic plating bath was 1.7 with respect to the solution weight.
Except that the amount was changed to% by weight, a grid and the like were obtained in the same manner as in Invention Example 1-1. Such a processed product is referred to as Comparative Example 3. Here, the various tests were performed as follows.

【００６３】（１）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。(1) 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.

【００６４】（２）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。(2) 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.

【００６５】（３）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。(3) Impact deformation test An impact deformation test (JIS K5400) using a 20 ° C. DuPont method
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.

【００６６】（４）耐薬品性試験 前記JIS K5400 の密着力試験法（碁盤目テープ法）を応
用して行った。具体的には、皮膜面に１ｃｍ² 当たり１
００個の碁盤目を入れた試料を必要枚数用意し、それぞ
れを下記a 〜f の薬品または食品に浸漬し、４時間毎に
試料を取り出して、皮膜の変色の有無を目視によって観
察した。また、浸漬累積時間が９６時間を経過した時点
において、碁盤目の上からセロファン粘着テープを張り
付け、剥がす方法により碁盤目の剥がれ個数ｙを測定し
た。薬品または食品が皮膜の接着性（密着安定性）に及
ぼす影響の程度は、剥がれ個数の多少（ｙ／１００）で
評価した。なお、皮膜の変色の観察および粘着テープの
張り付けは、試料を水洗し風乾した後に行った。 (a）ラッカーシンナー (b）界面活性剤（商標“ファミリーフレッシュ”花王
(株) 製） (c）カレー（商標“ククレカレー辛口”ハウス食品
(株) 製） (d）こいくち醤油（キッコーマン (株) 製） (e）台所用漂白剤（商標“キッチンハイター”花王
(株) 製）を１５％濃度に薄めたもの (f）台所用漂白剤（商標“キッチンハイター”花王
(株) 製）の原液（１００％濃度）(4) Chemical resistance test The test was conducted by applying the adhesion test method (cross-cut tape method) of JIS K5400. Specifically, 1 cm ² per cm ²
A required number of samples each having 00 cross-cuts were prepared, each was immersed in the following chemicals or foods a to f, and the samples were taken out every four hours and visually observed for discoloration of the film. At the time when the accumulated immersion time passed 96 hours, a cellophane adhesive tape was applied from above the grid and the number y of the grids peeled was measured by a method of peeling off. The degree of the effect of the drug or food on the adhesiveness (adhesion stability) of the film was evaluated based on the number of peeled pieces (y / 100). The observation of discoloration of the film and the attachment of the adhesive tape were performed after the sample was washed with water and air-dried. (a) Lacquer thinner (b) Surfactant (trademark "Family Fresh" Kao
(C) Curry (trademark “Kukure Curry Dry” House Foods)
(D) Koikuchi soy sauce (Kikkoman Co., Ltd.) (e) Bleaching agent for kitchen (trademark "Kitchen Highter" Kao)
(F) 15% diluted (f) Kitchen bleach (trade name "Kitchen Highter" Kao)
Stock solution (100% concentration)

【００６７】（５）耐磨耗性試験 先端にナイロンたわしを取付けた棒を６００ｒｐｍで回
転させながら、加重５００ｇで皮膜面に１分間押しつけ
た後、傷の有無を肉眼で調べた。(5) Abrasion Resistance Test While a rod with a nylon scrubber attached to the tip was rotated at 600 rpm and pressed against the film surface with a load of 500 g for 1 minute, the presence or absence of scratches was visually examined.

【００６８】（６）耐焦げ付き性試験 試験１（中温加熱） 下記g 〜h の食品及び調味料２ccを試料の皮膜面に乗
せ、２００℃で１時間加熱し食品等を焦げ付かせた後、
室温に戻してから指先で炭化物を軽く圧迫して、焦げ付
き程度（焼き網用部材に対する固着程度）を調べた。 試験２（高温加熱） 下記g 〜h の食品及び調味料２ccを試料の皮膜面に乗
せ、ガスコンロを用い試料の下側から直火を当てて食品
等を焦げ付かせ、室温に戻してから指先で炭化物を軽く
圧迫して、焦げ付き程度（焼き網用部材に対する固着程
度）を調べた。 (g）カレー（商標“ククレカレー辛口”ハウス食品
(株) 製）。 (h）卵、醤油、砂糖を１：１：２で混合したもの。 なお、耐焦げ付き性は、撥水性や撥油性の良否に影響さ
れると考えられる。(6) Scoring resistance test Test 1 (Medium temperature heating) Foods of the following g to h and 2 cc of seasonings are placed on the film surface of the sample, heated at 200 ° C. for 1 hour, and the foods are scorched.
After returning to room temperature, the carbide was lightly pressed with a fingertip, and the degree of scorching (the degree of fixation to the grill member) was examined. Test 2 (High temperature heating) Put 2 cc of foods and seasonings of the following g to h on the film surface of the sample, apply a direct fire from the bottom of the sample using a gas stove to burn the food etc., return to room temperature, and then fingertip Then, the carbide was lightly pressed, and the degree of scorching (the degree of adhesion to the grill member) was examined. (g) Curry (trademark “Kukure Curry Dry” house food)
Co., Ltd.). (h) A mixture of egg, soy sauce and sugar in a ratio of 1: 1: 2. The scoring resistance is considered to be affected by the quality of water repellency and oil repellency.

【００６９】（７）焼き魚の身離れ荷重試験 焼き網の上にカレイの一夜干し１匹（体長：約２０ｃ
ｍ）を載置し、ガステーブルコンロ（大阪ガス（株）
製、１０−６３７型）のグリルにセットした後、両面焼
きで５分間加熱した。加熱後、焼き魚を焼き網上に載置
した状態で、ガステーブルコンロから焼き網を取り出
し、凧糸で焼き魚を２個所固定する。そして、凧糸にテ
ンションゲージを付けて焼き魚を持ち上げ、焼き魚が焼
き網から剥がれる際の指示値を測定した。尚、焼き魚の
身離れ荷重とは、テンションゲージの指示値から焼き魚
を剥がした後の焼き魚の自重を減じたときの値をいう。
この試験は、各試料につき５回ずつ繰り返し行った。表
６及び表７に作製条件を一覧表示し、各種試験結果を表
８〜表１０に一覧表示する。(7) Separation load test of grilled fish One fish dried overnight on flatfish (body length: about 20c)
m) on a gas stove (Osaka Gas Co., Ltd.)
, 10-637) and heated for 5 minutes by baking on both sides. After heating, the grilled fish is taken out from the gas stove while the grilled fish is placed on the grill, and two grilled fishes are fixed with a kite string. The grilled fish was lifted by attaching a tension gauge to the kite string, and the indicated value when the grilled fish was peeled off the grill was measured. The detached load of the grilled fish refers to a value obtained by subtracting the weight of the grilled fish after peeling the grilled fish from the indicated value of the tension gauge.
This test was repeated five times for each sample. The production conditions are listed in Tables 6 and 7, and the results of various tests are listed in Tables 8 to 10.

【００７０】[0070]

【表６】 [Table 6]

【００７１】[0071]

【表７】 [Table 7]

【００７２】[0072]

【表８】 [Table 8]

【００７３】[0073]

【表９】 [Table 9]

【００７４】[0074]

【表１０】 [Table 10]

【００７５】試験結果 表８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２、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 8, the test results of the eutectoid amount 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 each of the examples of the present invention had a larger contact angle than Comparative Examples 2 and 3, and had extremely good water repellency.

【００７６】また、表８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、耐薬品性に
関して、本発明例は、比較例１に比べて基材に対する接
着性、耐衝撃変形性、耐薬品性に優れていることが確認
された。なお、表８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、本発明例ではいずれ
も０／１００であったので、単に０／１００とし、比較
例１についてのみ、各結果を注１に記載した。また、表
８の耐薬品性試験は、前記ａ〜ｆの薬品をそれぞれ用い
て行った結果を示すものであるが、本発明例ではいずれ
も０／１００であったので、単に０／１００とし、比較
例１についてのみ、各結果を注２に記載した。Further, as shown in Table 8, with respect to poor adhesion, impact deformation resistance and chemical resistance of the composite plating film to the substrate, the present invention example exhibited better adhesiveness to the substrate than Comparative Example 1. It was confirmed that it had excellent impact deformation resistance and chemical resistance. Note that the adhesion test in Table 8 shows the results of the tests performed under the conditions 1 to 3 above. In the present invention, the results were all 0/100. Only for, each result is described in Note 1. The chemical resistance test shown in Table 8 shows the results obtained by using the chemicals a to f described above. In the present invention, the chemical resistance was 0/100. Each result is described in Note 2 only for Comparative Example 1.

【００７７】更に、表９に示すように、複合めっき皮膜
の耐磨耗性試験および耐熱焦げ付き性試験において、本
発明例は比較例に比べ、耐磨耗性、耐熱焦げ付き性に優
れることが確認された。Further, as shown in Table 9, in the abrasion resistance test and the heat resistance test of the composite plating film, it was confirmed that the present invention example was superior to the comparative example in the wear resistance and the heat resistance resistance. Was done.

【００７８】また、表１０に示すように、焼き魚の身離
れ荷重試験結果において、本発明例は何れも比較例に比
べて焼き魚の身離れ荷重が小さく、しかも繰り返し行っ
ても身離れ荷重の増大が抑制されており、極めて良好で
あることが確認された。したがって、焼き魚を焼き網か
ら容易に剥がすことができると共に、焼き網の汚れも容
易に除去することができ、しかもそれらの効果が長期に
わたって維持される。Further, as shown in Table 10, in the results of the detachment load test of the grilled fish, in each of the present invention examples, the detachment load of the grilled fish was smaller than that of the comparative example. Was suppressed, and it was confirmed that it was extremely good. Therefore, the grilled fish can be easily removed from the grill and the stains on the grill can be easily removed, and their effects are maintained for a long time.

【００７９】[0079]

【発明の効果】本発明においては、基板材である焼き網
用部材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 grid member, which is a substrate material, is composed of a non-metallic fluorine compound and a matrix metal.
Demonstrates high lubricity, abrasion resistance, heat resistance, chemical resistance, water repellency, oil repellency, etc. derived from the characteristics of fluorine compounds, and high hardness, high hardness derived from the characteristics of matrix metals It has properties such as strength, high thermal conductivity, and high heat resistance. Furthermore,
Since the composite plating film has good adhesiveness and adhesion to the substrate, peeling of the film due to a difference in thermal expansion coefficient between the substrate and the film is unlikely to occur.

【００８０】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、魚を焼い
た際の焦げ付きを防止できる。Further, the volume fraction of the fine particles of the fluorine compound 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, it is possible to prevent burning when the fish is grilled.

【００８１】更に、フッ素化合物等を部材表面にコーテ
ィング法で被覆してなる従来品では、プレコート法、ポ
ストコート法の何れを採用した場合であっても、部材ま
たは基材板の角部分に十分な塗膜を施し難いため、塗膜
厚の薄い角部から塗膜が剥離し易いが、金属めっき法を
用いる本発明によれば、部材または部材となるべき基板
材の角部にも均一の厚さの皮膜を形成できる。よって、
角部からの皮膜の剥離がない。Further, in the case of a conventional product in which a fluorine compound or the like is coated on the surface of a member by a coating method, even if the pre-coating method or the post-coating method is employed, the corner portion of the member or the base plate is sufficiently covered. Although it is difficult to apply a coating film, the coating film is easily peeled off from a thin corner portion of the coating film thickness, but according to the present invention using the metal plating method, the corner portion of the member or the substrate material to be the member is also uniform. A thick film can be formed. Therefore,
There is no peeling of the film from the corners.

【００８２】以上に述べたように、本発明によれば、魚
を焼いた際の焦げ付きや皮膜の剥離を防止できるので、
焼き網にとって致命的な欠陥である焼き魚の見栄えの低
下や焼き魚の味覚の低下というような問題が生じことな
く、且つ、このような快適な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 scorching and peeling of the film when grilling fish.
An excellent effect that the problems such as a decrease in the appearance of grilled fish and a decrease in taste of grilled fish, which are fatal defects for the grill, do not occur, and such comfortable usability can be maintained for a long time. To play.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 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焼き
網。1. A grill which is provided with a composite plating film containing at least 15% by volume of a fluorine compound on a surface thereof. 【請求項２】 前記複合めっき皮膜は、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、ポリ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
載の焼き網。2. The composite plating film is made of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, polytetrafluoroethylene-
2. The grid according to claim 1, comprising one or more kinds of fine particles of a fluorine compound selected from the group consisting of a perfluoroalkylvinyl ether copolymer and a fluorinated graphite. 【請求項３】 前記複合めっき皮膜は、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、請求項
１又は２記載の焼き網。3. The grid according to claim 1, wherein the composite plating film has a fluorine compound co-deposited in a metal plating base material. 【請求項４】 前記フッ素化合物微粒子の平均粒子径が
２μｍ以下である、請求項３記載の焼き網。4. The grid according to claim 3, wherein the fluorine compound fine particles have an average particle size of 2 μm or less. 【請求項５】 前記複合めっき皮膜は、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、請求項１、２、３又は４記載の焼き網。5. The composite plating film according to claim 1, wherein the composite plating film has a thickness of 150 to 350.
5. The grid according to claim 1, wherein the grid is heat-treated at a temperature of ° C. 【請求項６】 前記焼き網は、ガステーブルコンログリ
ルに用いられる、請求項１、２、３、４又は５記載の焼
き網。6. The grill according to claim 1, wherein the grill is used for a gas table stove grill.