JPH0976410A - Fluoroplastic film laminated metal strip and production thereof - Google Patents
Fluoroplastic film laminated metal strip and production thereofInfo
- Publication number
- JPH0976410A JPH0976410A JP18238396A JP18238396A JPH0976410A JP H0976410 A JPH0976410 A JP H0976410A JP 18238396 A JP18238396 A JP 18238396A JP 18238396 A JP18238396 A JP 18238396A JP H0976410 A JPH0976410 A JP H0976410A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- metal strip
- film
- tetrafluoroethylene
- layer
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 57
- 239000002184 metal Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920002313 fluoropolymer Polymers 0.000 title abstract 2
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- 239000010410 layer Substances 0.000 claims abstract description 44
- 238000007639 printing Methods 0.000 claims abstract description 41
- 239000012790 adhesive layer Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 14
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 13
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 13
- 238000010030 laminating Methods 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 2
- 238000013461 design Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- 238000003475 lamination Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000004927 fusion Effects 0.000 description 6
- 230000008961 swelling Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910000576 Laminated steel Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フッ素樹脂フィルム積
層金属帯およびその製造方法に関し、特に、印刷層を有
するフッ素樹脂フィルムを金属帯表面に被覆した，意匠
性と密着性が共に優れるフッ素樹脂フィルム積層金属帯
についての提案である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluororesin film-laminated metal strip and a method for producing the same, and more particularly, a fluororesin having a printed layer having a fluororesin film coated on the surface of the metal strip, which is excellent in both design and adhesion. This is a proposal for a film laminated metal strip.
【０００２】[0002]
【従来の技術】一般に、フッ素樹脂フィルムは、耐食性
や耐汚染性、耐付着性、耐熱性、不燃性等の性質に優れ
ていることから、もしステンレス鋼板などに強固にラミ
ネートできれば、該フィルムのかかる特性をステンレス
鋼板のもつ優れた強度や加工性に付加することができる
ので、機能性に優れたラミネート鋼板が得られる。この
ようなラミネート鋼板があれば、パンやケーキ、菓子な
どを焼くために用いる焼型、食品調理器具および食品加
工器具、あるいは電子レンジ内板、炊飯器の内釜やガス
テーブルの天板のような加熱調理器具、さらにはレンジ
フード用素材のような厨房用品用材料等にも広く利用で
き、このような鋼材を工業的に製造する技術の確立が望
まれていた。特に、１枚ずつの切り板にフッ素樹脂フィ
ルムをバッチ式でラミネートする方法は生産性が低くコ
スト高となることから、金属帯に帯状のフッ素樹脂フィ
ルムを連続的にラミネートする技術が求められている。2. Description of the Related Art Generally, a fluororesin film is excellent in properties such as corrosion resistance, stain resistance, adhesion resistance, heat resistance, and nonflammability. Since such characteristics can be added to the excellent strength and workability of the stainless steel sheet, a laminated steel sheet having excellent functionality can be obtained. With such laminated steel sheets, baking molds used for baking bread, cakes, confectionery, food cooking and food processing equipment, microwave oven inner plates, rice cooker inner pots, gas table tops, etc. It can be widely used for various cooking utensils, as well as materials for kitchen products such as materials for range hoods, and it has been desired to establish a technology for industrially producing such steel materials. Particularly, the method of laminating the fluororesin film on each of the cut plates in a batch method is low in productivity and high in cost. Therefore, a technique for continuously laminating the belt-shaped fluororesin film on the metal strip is required. There is.
【０００３】しかしながら、フッ素樹脂フィルムは、表
面張力が小さくかつ、強い非接着性を示すために、接着
剤によるラミネートが難しいという難点があった。この
ような難点を克服する技術として、発明者らは先に、鋼
板表面に、フッ素樹脂と耐熱性樹脂との混合樹脂からな
る下地処理層（接着剤層）を介在させて、熱可塑性フッ
素樹脂フィルムをラミネートしてなるフッ素樹脂フィル
ム被覆鋼板を提案した（特開平５−162243号公報参
照）。この提案の技術によれば、フィルム密着性に優れ
たフッ素樹脂フィルム被覆鋼板を提供することができ
る。However, since the fluororesin film has a small surface tension and exhibits a strong non-adhesive property, it is difficult to laminate it with an adhesive. As a technique for overcoming such a difficulty, the inventors have previously made a thermoplastic fluororesin by interposing an undercoating layer (adhesive layer) made of a mixed resin of a fluororesin and a heat-resistant resin on the surface of a steel sheet. A fluororesin film-coated steel sheet obtained by laminating films has been proposed (see Japanese Patent Laid-Open No. 5-162243). According to the proposed technique, it is possible to provide a fluororesin film-coated steel sheet having excellent film adhesion.
【０００４】一方、最近では、上述したようなガステー
ブルなどの厨房用品は、優れた意匠性が求められてお
り、その要求に応じたラミネート鋼板として、模様を印
刷したフッ素樹脂フィルムを鋼板に被覆した材料が提案
されている。例えば、 ．特開平２−252550号公報では、金属表面に、チキソ
トロピー指数が２〜８のフッ素系樹脂組成物からなるイ
ンキの印刷層を表面に形成したフッ素樹脂フィルムが、
該印刷層を上層にして熱融着された樹脂積層金属、 ．特開平３−5139号公報では、金属表面に、印刷層を
有するフッ素樹脂フィルムが、該印刷層を内側にして熱
融着された樹脂積層金属、 ．特開平３−142237号公報では、フッ素樹脂フィルム
の少なくとも一面にフッ素系樹脂組成物からなる印刷層
を有するフッ素樹脂積層フィルムと、その応用例とし
て、金属板の表面に、フッ素樹脂積層フィルムの印刷層
を内側に向けて重ね、次いで 260〜360 ℃に加熱して熱
融着した樹脂積層金属、 がそれぞれ提案されている。On the other hand, recently, kitchen products such as the gas table as described above are required to have excellent designability, and as a laminated steel plate in accordance with the demand, a fluororesin film having a pattern printed thereon is coated on the steel plate. The proposed material is proposed. For example,. In Japanese Unexamined Patent Publication No. 2-252550, a fluororesin film having a metal surface on which a printed layer of an ink made of a fluororesin composition having a thixotropic index of 2 to 8 is formed,
A resin laminated metal that is heat-fused with the printed layer as an upper layer; In Japanese Patent Laid-Open No. 3139/1993, a resin laminated metal in which a fluororesin film having a printing layer on a metal surface is heat-sealed with the printing layer inside ,. In JP-A-3-142237, a fluororesin laminated film having a printing layer made of a fluororesin composition on at least one surface of a fluororesin film, and an application example thereof, printing of the fluororesin laminated film on a surface of a metal plate It has been proposed that each of the layers be a resin laminated metal in which the layers are stacked inward and then heated to 260 to 360 ° C to be heat-sealed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記の
，，に記載の樹脂積層金属は、いずれも１枚ずつ
の切り板にフッ素樹脂フィルムをバッチ式でラミネート
したものであり、金属帯の表面に帯状のフッ素樹脂フィ
ルムを連続的にラミネートする技術ではない。特に、上
記従来技術にかかる積層構成は、金属表面とフッ素樹脂
フィルムとの密着性が不十分であり、連続的なラミネー
ト方式に適するものではなかった。しかも、上記従来技
術では、用いる印刷インキのフッ素樹脂成分によって
は、ラミネート時（熱融着時）に印刷模様が不鮮明とな
り、意匠性に劣るという欠点があった。However, each of the above-mentioned resin laminated metals described in and is made by laminating a fluororesin film in a batch manner on each one of the cut plates, and the metal strip surface is formed on the surface of the metal strip. It is not a technique for continuously laminating a belt-shaped fluororesin film. In particular, the above-mentioned laminated structure according to the prior art has insufficient adhesion between the metal surface and the fluororesin film and is not suitable for a continuous laminating method. Moreover, the above-mentioned conventional technique has a drawback that the printed pattern becomes unclear during lamination (at the time of heat fusion) depending on the fluororesin component of the printing ink used, resulting in poor design.
【０００６】本発明の目的は、従来技術が抱える上記課
題を解決することにあり、特に、金属帯の表面に、印刷
層を有するフッ素樹脂フィルムを、ロール圧着によって
密着性良く連続ラミネートすることができる技術を確立
し、意匠性と密着性が共に優れるフッ素樹脂フィルム積
層金属帯を提供することにある。An object of the present invention is to solve the above problems of the prior art. In particular, it is possible to continuously laminate a fluororesin film having a printing layer on the surface of a metal strip by roll pressure bonding with good adhesion. It is to establish a technique that can be applied and to provide a fluororesin film-laminated metal strip that is excellent in both design and adhesion.
【０００７】[0007]
【課題を解決するための手段】発明者らは、上記の目的
を実現するために鋭意研究をした結果、下記の内容を要
旨構成とする発明を完成するに至った。すなわち、本発
明で提案するものは、金属帯の表面に、４フッ化エチレ
ン−６フッ化プロピレン共重合樹脂（以下、「ＦＥＰ樹
脂」という。）と耐熱性樹脂から主として構成される接
着剤層と、主成分として４フッ化エチレン−パーフルオ
ロアルキルビニルエーテル共重合樹脂（以下、「ＰＦＡ
樹脂」という。）を含む付着量； 0.1〜５ｇ／ｍ2 の印
刷層と、ＰＦＡ樹脂フィルム層とからなる積層構造を設
けたことを特徴とするフッ素樹脂フィルム積層金属帯、
である。なお、上記フッ素樹脂フィルム積層金属帯にお
いて、接着剤層を構成するＦＥＰ樹脂は、樹脂固形分と
して、接着剤の総固形分中に30〜85wt％含有することが
好ましく、接着剤層を構成する耐熱性樹脂は、樹脂固形
分として、接着剤の総固形分中に10〜60wt％含有するこ
とが好ましい。また、上記フッ素樹脂フィルム積層金属
帯において、印刷インキを構成するＰＦＡ樹脂は、印刷
インキの総固形分中に10〜95wt％含有することが好まし
い。Means for Solving the Problems As a result of intensive research aimed at achieving the above-mentioned objects, the inventors have completed an invention having the following contents. That is, what is proposed in the present invention is an adhesive layer mainly composed of a tetrafluoroethylene-6-fluoropropylene copolymer resin (hereinafter referred to as “FEP resin”) and a heat resistant resin on the surface of a metal band. And a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin as a main component (hereinafter referred to as “PFA
"Resin". ), A fluororesin film laminated metal strip having a laminated structure comprising a printed layer of 0.1 to 5 g / m 2 and a PFA resin film layer,
It is. In the above-mentioned fluororesin film-laminated metal strip, the FEP resin forming the adhesive layer is preferably contained in the total solid content of the adhesive in an amount of 30 to 85 wt% as a resin solid content, which constitutes the adhesive layer. The heat-resistant resin is preferably contained as a resin solid content in the total solid content of the adhesive in an amount of 10 to 60 wt%. In the above-mentioned fluororesin film-laminated metal strip, the PFA resin constituting the printing ink is preferably contained in the total solid content of the printing ink in an amount of 10 to 95 wt%.
【０００８】このようなフッ素樹脂フィルム積層金属帯
を製造する方法として、本発明は、必要に応じてリン酸
塩処理、塗布型クロメート処理のいずれかもしくはこれ
らを組み合わせた処理を施した金属帯の表面に、ＦＥＰ
樹脂と耐熱性樹脂から主として構成される接着剤層を塗
布し、次いで、主成分としてＰＦＡ樹脂を含む印刷イン
キを 0.1〜５ｇ／ｍ2 の付着量で印刷したＰＦＡ樹脂フ
ィルムを、その印刷層が下層になるように積層し、その
後、フィルム側のロール温度を 100〜260 ℃としたロー
ルで圧着することにより、連続的にラミネートする方法
を提案する。なお、主成分としてＰＦＡ樹脂を含む印刷
インキをＰＦＡ樹脂フィルムに印刷する際には、ＰＦＡ
樹脂フィルムの印刷面を予め放電加工処理等により活性
化しておくことが望ましい。As a method for producing such a fluororesin film-laminated metal strip, the present invention provides a method for producing a metal strip which has been subjected to either a phosphate treatment, a coating chromate treatment or a combination thereof as required. FEP on the surface
An adhesive layer mainly composed of a resin and a heat-resistant resin is applied, and then a printing ink containing PFA resin as a main component is printed at a deposition amount of 0.1 to 5 g / m 2 to obtain a PFA resin film, We propose a method in which the layers are laminated so as to form a lower layer, and then the layers are continuously laminated by pressure bonding with a roll having a roll temperature on the film side of 100 to 260 ° C. When printing a printing ink containing PFA resin as a main component on a PFA resin film,
It is desirable to activate the printed surface of the resin film in advance by electric discharge machining or the like.
【０００９】[0009]
【作用】本発明のフッ素樹脂フィルム積層金属帯は、金
属帯の表面に、ＦＥＰ樹脂と耐熱性樹脂から主として構
成される接着剤層と、ＰＦＡ樹脂を主成分とする印刷層
と、ＰＦＡ樹脂フィルム層とからなる積層構造を設けた
ことに特徴がある（図１参照）。特に、ＦＥＰ樹脂と耐
熱性樹脂から主として構成される接着剤層を、金属帯と
ＰＦＡ樹脂を主成分とする印刷層の界面に介在させた構
成とすることにより、金属帯の表面にＰＦＡ樹脂フィル
ムを強固に密着させることができるが、ＰＦＡ樹脂やＰ
ＴＦＥ樹脂を用いた場合には強固な密着性が得られな
い。その理由は明らかではないが、ＦＥＰ樹脂の融点が
ＰＦＡ樹脂の融点よりも低いことが有利に作用している
ものと考える。但し、ＦＥＰ樹脂より融点の低い４フッ
化エチレン−エチレン共重合樹脂 (ＥＴＦＥ樹脂) 、フ
ッ化ビニリデン樹脂 (ＰｖｄＦ樹脂)を用いると、熱分
解温度が低いために熱融着時にＰＦＡフィルムの下に気
泡 (ワキ) が発生したり、あるいは強固な密着性が得ら
れない。The fluororesin film-laminated metal strip of the present invention has an adhesive layer mainly composed of an FEP resin and a heat resistant resin, a printing layer containing PFA resin as a main component, and a PFA resin film on the surface of the metal strip. It is characterized in that a laminated structure composed of layers is provided (see FIG. 1). In particular, a PFA resin film is formed on the surface of the metal strip by providing an adhesive layer mainly composed of an FEP resin and a heat-resistant resin at the interface between the metal strip and the printing layer containing PFA resin as a main component. Can be firmly adhered, but PFA resin and P
When TFE resin is used, strong adhesion cannot be obtained. Although the reason is not clear, it is considered that the melting point of the FEP resin is lower than the melting point of the PFA resin, which is advantageous. However, when a tetrafluoroethylene-ethylene copolymer resin (ETFE resin) or a vinylidene fluoride resin (PvdF resin) having a lower melting point than the FEP resin is used, the thermal decomposition temperature is low, so that it is formed under the PFA film at the time of heat fusion. Bubbles are generated, or strong adhesion cannot be obtained.
【００１０】このような接着剤層を構成するＦＥＰ樹脂
は、樹脂固形分として、接着剤の総固形分中に30〜85wt
％含有することが好ましい。この理由は、ＦＥＰ樹脂含
有量が30wt％未満では、接着剤と印刷層あるいはＰＦＡ
樹脂フィルムとの密着性が悪くなり、ＦＥＰ樹脂含有量
が85wt％を超えると、接着剤と金属帯との密着性が悪く
なるからである。一方、耐熱性樹脂は、接着剤と金属帯
との密着性を向上させるために、樹脂固形分として、接
着剤の総固形分中に10〜60wt％含有することが好まし
い。かかる耐熱性樹脂としては、ポリエーテルサルフォ
ン（ＰＥＳ）などを用いることができる。なお、接着剤
層の皮膜硬度の改善や着色等のために、耐熱着色顔料を
添加することができる。The FEP resin constituting such an adhesive layer has a resin solid content of 30 to 85 wt% in the total solid content of the adhesive.
% Is preferably contained. The reason for this is that if the FEP resin content is less than 30 wt%, the adhesive and printing layer or PFA
This is because the adhesiveness with the resin film deteriorates, and when the FEP resin content exceeds 85 wt%, the adhesiveness between the adhesive and the metal strip deteriorates. On the other hand, in order to improve the adhesion between the adhesive and the metal strip, the heat-resistant resin is preferably contained in the total solid content of the adhesive in an amount of 10 to 60 wt% as a resin solid content. As such a heat resistant resin, polyether sulfone (PES) or the like can be used. A heat-resistant coloring pigment can be added for improving the film hardness of the adhesive layer, coloring, and the like.
【００１１】また、上記印刷層を構成するインキの主成
分樹脂として、ＦＥＰ樹脂や４フッ化エチレン−エチレ
ン共重合樹脂（ＥＴＦＥ樹脂）などの低融点フッ素樹脂
を用いると、熱融着時に印刷模様が不鮮明になる。この
点、本発明のフッ素樹脂フィルム積層金属帯は、ＰＦＡ
樹脂を主成分とする印刷インキで印刷層を構成している
ので、熱融着時に印刷模様が不鮮明になることはない。When a low melting point fluororesin such as FEP resin or tetrafluoroethylene-ethylene copolymer resin (ETFE resin) is used as the main component resin of the ink constituting the above-mentioned printing layer, a printed pattern is formed at the time of heat fusion. Becomes unclear. In this respect, the fluororesin film laminated metal strip of the present invention is made of PFA.
Since the printing layer is composed of the printing ink containing resin as a main component, the printed pattern does not become unclear during the heat fusion.
【００１２】このような印刷層は、主成分としてＰＦＡ
樹脂を含む印刷インキの付着量で、0.1〜５ｇ／ｍ2 と
することが必要である。この理由は、インキの付着量が
５ｇ／ｍ2 を超えると、下地の隠蔽効果が大きくなって
インキの色柄が鮮明になるが、インキに含まれる不純物
等により、熱融着時にＰＦＡ樹脂フィルムと印刷層の界
面に気泡が発生する。一方、インキの付着量が 0.1ｇ／
ｍ2 より少ないと、下地の隠蔽効果がなく、印刷層とし
て意匠性がないからである。Such a printing layer contains PFA as a main component.
It is necessary that the amount of the printing ink containing the resin attached is 0.1 to 5 g / m 2 . The reason for this is that when the amount of deposited ink exceeds 5 g / m 2 , the hiding effect of the base becomes large and the color pattern of the ink becomes clear, but due to impurities etc. contained in the ink, the PFA resin film during thermal fusion bonding. And air bubbles are generated at the interface of the print layer. On the other hand, the amount of deposited ink is 0.1 g /
This is because when it is less than m 2 , there is no effect of concealing the underlayer and there is no design as a printing layer.
【００１３】そして、かかるＰＦＡ樹脂成分は、印刷イ
ンキの総固形分中に10〜95wt％含有することが好まし
い。この理由は、ＰＦＡ樹脂成分の含有量が10wt％未満
では、フィルムに施した印刷層が容易に剥がれてしま
い、一方ＰＦＡ樹脂成分の含有量が95wt％を超えると、
同時に添加配合される耐熱着色顔料の含有量が少なくな
り色柄が不鮮明となるからである。The PFA resin component is preferably contained in the printing ink in an amount of 10 to 95 wt% in the total solid content. The reason for this is that if the content of the PFA resin component is less than 10 wt%, the printed layer applied to the film will be easily peeled off, while if the content of the PFA resin component exceeds 95 wt%,
This is because the content of the heat-resistant coloring pigment added and compounded at the same time becomes small and the color pattern becomes unclear.
【００１４】なお、印刷層を構成する他の樹脂成分とし
ては、ＦＥＰ樹脂などのフッ素樹脂、ポリフェニレンサ
ルファイド（ＰＰＳ）やポリエーテルサルフォン（ＰＥ
Ｓ）などの耐熱樹脂を用いることができる。Other resin components constituting the printing layer include fluororesins such as FEP resin, polyphenylene sulfide (PPS) and polyether sulfone (PE).
A heat resistant resin such as S) can be used.
【００１５】このような本発明のフッ素樹脂フィルム積
層金属帯において、ＰＦＡ樹脂フィルムは、メルトフロ
ーが２〜20ｇ／ｍ2 の範囲にあるものを使用することが
できる。そのフィルム厚みは、特に限定するものではな
いが、10〜100 μｍの範囲にあるものが好ましい。In such a fluororesin film-laminated metal strip of the present invention, a PFA resin film having a melt flow of 2 to 20 g / m 2 can be used. The film thickness is not particularly limited, but is preferably in the range of 10 to 100 μm.
【００１６】また本発明において、金属帯は、Al−Zn合
金めっき鋼板、Zn−Fe合金めっき鋼板、Al−Siめっき鋼
板、55％Al−Zn合金めっき鋼板、Zn−Ni合金めっき鋼
板、Alめっき鋼板およびステンレス鋼板等を用いること
ができる。また、金属帯に塗布型クロメート処理を施す
と、金属帯と接着剤の密着性が向上し、結果として金属
帯とフッ素樹脂フィルムの密着性が向上する。In the present invention, the metal strip is an Al-Zn alloy plated steel sheet, a Zn-Fe alloy plated steel sheet, an Al-Si plated steel sheet, a 55% Al-Zn alloy plated steel sheet, a Zn-Ni alloy plated steel sheet, an Al plated sheet. A steel plate, a stainless steel plate, etc. can be used. Further, when the metal band is subjected to the coating chromate treatment, the adhesion between the metal band and the adhesive is improved, and as a result, the adhesion between the metal band and the fluororesin film is improved.
【００１７】次に、本発明にかかるフッ素樹脂フィルム
積層金属帯を製造する方法は、上述したような積層構造
に重ね合わせた積層体を、フィルム側のロール表面温度
を100〜260 ℃、好ましくは 120〜220 ℃にコントロー
ルしたロールで圧着することにより、連続的に熱融着す
ることに特徴がある。特に、フィルム側のロール表面温
度を 100〜260 ℃にコントロールすることは、非常に重
要である。その理由は、このロール表面温度が 100℃未
満では、金属帯の温度を高くして圧着してもフィルムと
金属帯との優れた密着性は得られず、一方、ロール表面
温度が 260℃を超えると、圧着時にフィルムがロール表
面に融着して金属帯の表面から浮き上がるからである。Next, in the method for producing a fluororesin film laminated metal strip according to the present invention, a laminate having the laminated structure as described above is laminated at a film surface roll surface temperature of 100 to 260 ° C., preferably It is characterized by continuous heat fusion by pressure bonding with a roll controlled at 120 to 220 ° C. In particular, it is very important to control the roll surface temperature on the film side to 100 to 260 ° C. The reason for this is that if the roll surface temperature is less than 100 ° C, excellent adhesion between the film and the metal band cannot be obtained even if the temperature of the metal strip is increased and pressure bonding is applied, while the roll surface temperature is less than 260 ° C. If it exceeds, the film will be fused to the roll surface at the time of pressure bonding and float from the surface of the metal strip.
【００１８】[0018]
【実施例】以下に、本発明の実施例を比較例とともに説
明する。 （実施例１〜５）ＰＦＡ樹脂フィルム４に放電加工処理
を施してそのフィルム表面を活性化し、次いでその活性
面に、ＰＦＡ樹脂 (40％) と耐熱着色顔料 (60％) を含
有する印刷インキをその付着量を変えて印刷して印刷層
３を形成し、その後、印刷層３を形成したＰＦＡ樹脂フ
ィルム４を、樹脂組成を変えた接着剤層２を介在させ
て、その印刷層３が下層になるようにステンレス鋼板１
に圧着ロールを用いて熱融着し、フッ素樹脂フィルム積
層金属帯の製品を得た。この時の製造条件を表１に示
す。なお、フッ素樹脂フィルムを熱圧着する際のロール
線圧は0.3kg/cmとし、ステンレス鋼板は、Cr付着量を30
mg/m2 として 150℃×30秒の乾燥を行って塗布型クロメ
ート処理を施したものを用いた。EXAMPLES Examples of the present invention will be described below together with comparative examples. (Examples 1 to 5) A printing ink containing a PFA resin (40%) and a heat-resistant color pigment (60%) on the active surface of the PFA resin film 4 by electric discharge machining to activate the film surface. Is printed by changing the amount of adhesion thereof to form the printing layer 3, and then the PFA resin film 4 on which the printing layer 3 is formed is interleaved with the adhesive layer 2 having a different resin composition to form the printing layer 3. Stainless steel plate 1 to be the lower layer
It was heat-sealed using a pressure bonding roll to obtain a product of a fluororesin film laminated metal strip. Table 1 shows the manufacturing conditions at this time. The roll linear pressure during thermocompression bonding of the fluororesin film was 0.3 kg / cm, and the stainless steel plate had a Cr adhesion amount of 30 kg.
As the mg / m 2 , used was one that was dried at 150 ° C for 30 seconds and subjected to coating type chromate treatment.
【００１９】（比較例１〜４）ＰＦＡ樹脂フィルム４へ
の印刷インキの付着量または圧着ロールの表面温度を本
発明範囲から逸脱したものに設定すること以外は上記実
施例と同様にして、フッ素樹脂フィルム積層金属帯の製
品を得た。この時の製造条件を表１に示す。(Comparative Examples 1 to 4) Fluorine was prepared in the same manner as in the above Examples except that the amount of the printing ink deposited on the PFA resin film 4 or the surface temperature of the pressure roll was set outside the range of the present invention. A resin film laminated metal strip product was obtained. Table 1 shows the manufacturing conditions at this time.
【００２０】（比較例５〜10）接着剤２の樹脂組成を本
発明範囲から逸脱したものに設定すること以外は上記実
施例と同様にして、フッ素樹脂フィルム積層金属帯の製
品を得た。この時の製造条件を表１に示す。(Comparative Examples 5 to 10) Fluororesin film laminated metal strip products were obtained in the same manner as in the above Examples except that the resin composition of the adhesive 2 was set outside the range of the present invention. Table 1 shows the manufacturing conditions at this time.
【００２１】[0021]
【表１】 [Table 1]
【００２２】このようにして得られた製品の外観観察お
よび密着性試験を行った。その結果を表２に示す。この
表に示す結果から明らかなように、本発明にかかるフッ
素樹脂フィルム積層金属帯は、鮮やかな色調の印刷模様
を観察することができ、しかも、フィルム面の膨れやウ
キの発生もなく、密着性に優れるものであった。これに
対し、比較例にかかるフッ素樹脂フィルム積層金属帯
は、模様の色彩がくすんで見え鮮やかさに欠けていた
り、フィルム面に膨れやウキが発生したり、もしくは密
着性の低下を招いた。なお、本実施例において、印刷イ
ンキ中のＰＦＡ樹脂含有量が、本発明範囲（印刷インキ
の総固形分に対して10〜95wt％）を逸脱したものである
と、10wt％未満では印刷層が容易に剥がれたり、95wt％
を超えると印刷層の色柄が不鮮明になったりするという
不具合を生じた。The appearance of the product thus obtained was observed and the adhesion test was conducted. The results are shown in Table 2. As is clear from the results shown in this table, the fluororesin film-laminated metal strip according to the present invention can observe a printed pattern with a vivid color tone, and further, without the occurrence of swelling or blown film surface, adhesion. It was excellent in nature. On the other hand, in the fluororesin film-laminated metal strip according to the comparative example, the color of the pattern was dull and was not visible, the film surface was swollen or blown, or the adhesiveness was deteriorated. In this Example, if the PFA resin content in the printing ink deviates from the range of the present invention (10 to 95 wt% with respect to the total solid content of the printing ink), the printing layer is less than 10 wt%. Easy to peel off, 95wt%
If it exceeds, there is a problem that the color pattern of the printing layer becomes unclear.
【００２３】[0023]
【表２】 [Table 2]
【００２４】なお、上掲の例における試験項目と試験方
法および判定方法は、次の条件で行った。 ．外観観察 〔ワキ判定〕試験片のフィルム面を観察し、フィルム面
の膨れ（ワキ）およびウキの有無を観察した。評価は、
以下の基準で行った。 Ａ；フィルムの膨れまたはフィルムのウキの発生なし。 Ｂ；直径１mmφ以下の膨れ、またはフィルムのウキの発
生を観察。 Ｃ；直径１mmφ以上の膨れ、またはフィルムの全面ウキ
を観察。 〔意匠性〕試験片のフィルム面を観察し、色柄の鮮明さ
を評価した。評価は、以下の基準で行った。 ○；色柄は鮮明である。 △；色柄は一部不鮮明である。 ×；色柄は不鮮明である。 ．密着性試験 JIS Z 6744の井型エリクセン試験法に準じて行った。こ
の井型エリクセン試験法は、試験片に井型を入れた部分
をエリクセン試験機で６mm押し出した後、押し出し部の
フィルムの切り口をナイフで浮かし、ピンセットでつか
み強制的にフィルムを剥離する方法である。 評価基準 ○：フィルムを浮かすことができない。 △：フィルムを浮かせるが、フィルムの剥離ができな
い。 ×：フィルムを浮かせて、フィルムの剥離ができる。The test items, test methods, and determination methods in the above examples were performed under the following conditions. . Observation of Appearance [Determination of Armpit] The film surface of the test piece was observed, and the presence or absence of swelling (armpit) and fluff on the film surface was observed. Evaluation,
The evaluation was performed according to the following criteria. A: No swelling of the film or generation of blown film. B: Observe swelling with a diameter of 1 mmφ or less, or generation of blown film. C: Observe swelling with a diameter of 1 mm or more, or the entire surface of the film. [Design] The film surface of the test piece was observed and the sharpness of the color pattern was evaluated. The evaluation was performed according to the following criteria. ○: The color pattern is clear. Δ: The color pattern is partially unclear. X: The color pattern is unclear. . Adhesion test The adhesion test was carried out according to the JIS Z 6744 well-type Erichsen test method. This well-type Erichsen test method is a method in which the well-shaped portion of the test piece is extruded by an Erichsen tester by 6 mm, then the cut end of the film at the extruded part is lifted with a knife, grabbed with tweezers, and the film is forcibly peeled off. is there. Evaluation Criteria A: The film cannot be floated. Δ: The film can be floated, but the film cannot be peeled off. X: The film can be lifted and peeled off.
【００２５】[0025]
【発明の効果】以上説明したように、本発明にかかる印
刷層を有するフッ素樹脂フィルム積層金属帯によれば、
意匠性と密着性が共に優れるので、調理加工器具用素
材、厨房設備用素材、電子レンジの内板、ガステーブル
の天板等の幅広い用途に適合する優れた素材を供給する
ことができる。As described above, according to the fluororesin film laminated metal strip having the printing layer according to the present invention,
Because of its excellent design and adhesion, it is possible to supply excellent materials suitable for a wide range of applications such as materials for cooking and processing equipment, materials for kitchen equipment, inner plates of microwave ovens, and top plates of gas tables.
【図１】本発明にかかるフッ素樹脂フィルム積層金属帯
の積層構造を示す断面図である。FIG. 1 is a cross-sectional view showing a laminated structure of a fluororesin film laminated metal strip according to the present invention.
１ 金属帯（鋼板） ２ 接着剤層（接着剤） ３ 印刷層 ４ ＰＦＡ樹脂フィルム層（ＰＦＡ樹脂フィルム） 1 Metal Band (Steel Plate) 2 Adhesive Layer (Adhesive) 3 Printing Layer 4 PFA Resin Film Layer (PFA Resin Film)
Claims (5)
フッ化プロピレン共重合樹脂と耐熱性樹脂から主として
構成される接着剤層と、主成分として４フッ化エチレン
−パーフルオロアルキルビニルエーテル共重合樹脂を含
む付着量；0.1〜５ｇ／ｍ2 の印刷層と、４フッ化エチ
レン−パーフルオロアルキルビニルエーテル共重合樹脂
フィルム層とからなる積層構造を設けたことを特徴とす
るフッ素樹脂フィルム積層金属帯。1. The surface of the metal strip is tetrafluoroethylene-6.
An adhesive layer mainly composed of a fluorinated propylene copolymer resin and a heat-resistant resin, and a printing layer having an adhesion amount containing a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin as a main component; 0.1 to 5 g / m 2 A fluororesin film laminated metal strip having a laminated structure comprising a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin film layer.
ン−６フッ化プロピレン共重合樹脂は、樹脂固形分とし
て、接着剤の総固形分中に30〜85wt％含有することを特
徴とする請求項１に記載のフッ素樹脂フィルム積層金属
帯。2. The tetrafluoroethylene-6-fluoropropylene copolymer resin constituting the adhesive layer is contained as a resin solid content in the total solid content of the adhesive in an amount of 30 to 85 wt%. The fluororesin film-laminated metal strip according to claim 1.
樹脂固形分として、接着剤の総固形分中に10〜60wt％含
有することを特徴とする請求項１に記載のフッ素樹脂フ
ィルム積層金属帯。3. The heat-resistant resin that constitutes the adhesive layer,
The fluororesin film-laminated metal strip according to claim 1, wherein the resin solid content is 10 to 60 wt% in the total solid content of the adhesive.
レン−パーフルオロアルキルビニルエーテル共重合樹脂
は、印刷インキの総固形分中に10〜95wt％含有すること
を特徴とする請求項１に記載のフッ素樹脂フィルム積層
金属帯。4. The tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin constituting the printing ink is contained in an amount of 10 to 95 wt% in the total solid content of the printing ink. Fluororesin film laminated metal strip.
フッ化プロピレン共重合樹脂と耐熱性樹脂から主として
構成される接着剤層を塗布し、次いで、主成分として４
フッ化エチレン−パーフルオロアルキルビニルエーテル
共重合樹脂を含む印刷インキを 0.1〜５ｇ／ｍ2 の付着
量で印刷した４フッ化エチレン−パーフルオロアルキル
ビニルエーテル共重合樹脂フィルムを、その印刷層が下
層になるように積層し、その後、フィルム側のロール温
度を 100〜260 ℃としたロールで圧着することにより、
連続的にラミネートすることを特徴とするフッ素樹脂フ
ィルム積層金属帯の製造方法。5. Tetrafluoroethylene-6 on the surface of the metal strip.
An adhesive layer mainly composed of fluorinated propylene copolymer resin and heat resistant resin is applied, and then 4
The printing layer is a lower layer of a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin film obtained by printing a printing ink containing a fluorinated ethylene-perfluoroalkyl vinyl ether copolymer resin at an adhesion amount of 0.1 to 5 g / m 2. So that the film side roll temperature is 100 to 260 ℃
A method for producing a fluororesin film-laminated metal strip, which comprises laminating continuously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18238396A JPH0976410A (en) | 1995-07-11 | 1996-07-11 | Fluoroplastic film laminated metal strip and production thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17520795 | 1995-07-11 | ||
| JP7-175207 | 1995-07-11 | ||
| JP18238396A JPH0976410A (en) | 1995-07-11 | 1996-07-11 | Fluoroplastic film laminated metal strip and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0976410A true JPH0976410A (en) | 1997-03-25 |
Family
ID=26496542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18238396A Pending JPH0976410A (en) | 1995-07-11 | 1996-07-11 | Fluoroplastic film laminated metal strip and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0976410A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012076079A (en) * | 2011-11-29 | 2012-04-19 | Asahi Glass Co Ltd | Method for manufacturing laminate |
| JP2019038248A (en) * | 2017-08-25 | 2019-03-14 | ▲徳▼亞樹脂股▲ふん▼有限公司ＴＯＡ ＲＥＳＩＮ Ｃｏｒｐｏｒａｔｉｏｎ Ｌｉｍｉｔｅｄ | Thermal transfer structure having weather resistance and method therefor |
-
1996
- 1996-07-11 JP JP18238396A patent/JPH0976410A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012076079A (en) * | 2011-11-29 | 2012-04-19 | Asahi Glass Co Ltd | Method for manufacturing laminate |
| JP2019038248A (en) * | 2017-08-25 | 2019-03-14 | ▲徳▼亞樹脂股▲ふん▼有限公司ＴＯＡ ＲＥＳＩＮ Ｃｏｒｐｏｒａｔｉｏｎ Ｌｉｍｉｔｅｄ | Thermal transfer structure having weather resistance and method therefor |
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