JPH07118871A - Coated metallic sheet - Google Patents
Coated metallic sheetInfo
- Publication number
- JPH07118871A JPH07118871A JP13904194A JP13904194A JPH07118871A JP H07118871 A JPH07118871 A JP H07118871A JP 13904194 A JP13904194 A JP 13904194A JP 13904194 A JP13904194 A JP 13904194A JP H07118871 A JPH07118871 A JP H07118871A
- Authority
- JP
- Japan
- Prior art keywords
- chemical conversion
- coating film
- coating
- conversion treatment
- metal plate
- 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
Landscapes
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、塗料密着性に優れた
塗装金属板、あるいは更に、食品用容器や調理器具など
に用いられる食品安全性に優れた塗装金属板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated metal sheet having excellent paint adhesion, or a coated metal sheet having excellent food safety used for food containers, cooking utensils and the like.
【０００２】[0002]
【従来の技術】塗装金属板は、めっき鋼板やステンレス
鋼板、アルミニウム合金板等の金属板上に、有機樹脂を
主成分とする塗料を塗装・焼き付けして塗膜を形成した
ものである。2. Description of the Related Art A coated metal plate is a metal plate such as a plated steel plate, a stainless steel plate, or an aluminum alloy plate, on which a paint containing an organic resin as a main component is applied and baked to form a coating film.
【０００３】この塗膜を金属板に強力に密着させる手法
として、金属面にりん酸塩処理やクロメート処理等の化
成処理を施すことが行われ、更に密着性を向上させるた
めにシランカップリング剤やシリカを混入した化成処理
も行われている。As a method for strongly adhering this coating film to a metal plate, a chemical conversion treatment such as phosphate treatment or chromate treatment is performed on the metal surface, and a silane coupling agent is further used to improve the adhesion. Chemical conversion treatment with silica and silica is also performed.
【０００４】しかし、りん酸塩処理やクロメート処理、
あるいはシランカップリング剤処理を施した場合、初期
の密着性は良好であるが水に曝した後に密着性が低下す
る傾向があり、水分を含んだ食品に接する容器には不向
きである。However, phosphate treatment and chromate treatment,
Alternatively, when a silane coupling agent treatment is applied, the initial adhesiveness is good, but the adhesiveness tends to decrease after exposure to water, and it is not suitable for a container in contact with a food containing water.
【０００５】近年、樹脂の開発により、食品容器用に耐
食性を期待するポリプロピレン、ポリエステルやアクリ
ル等の樹脂に加え、弗素樹脂やポリエーテルスルフォン
樹脂、ポリアミドイミド樹脂等の耐熱樹脂も調理用具に
用いられるようになり、中でも湿潤環境下での樹脂密着
性が特に重要となっている。In recent years, due to the development of resins, in addition to resins such as polypropylene, polyester and acrylic, which are expected to have corrosion resistance for food containers, heat resistant resins such as fluororesins, polyether sulfone resins and polyamideimide resins are also used in cooking utensils. In particular, resin adhesion in a wet environment has become particularly important.
【０００６】従来、クロメート処理を施した例として
は、特開平４−９４７６８号公報に記載された技術があ
る。この公報では、ステンレス鋼板又はめっき鋼板の表
面を粗面化した後、適正量のＳｉＯ2 を含むクロメート
皮膜（シリカクロメート皮膜と称している）を形成する
ことを開示している。As an example of the conventional chromate treatment, there is a technique described in Japanese Patent Application Laid-Open No. 4-94768. This publication discloses that after a surface of a stainless steel plate or a plated steel plate is roughened, a chromate film (referred to as a silica chromate film) containing an appropriate amount of SiO 2 is formed.
【０００７】シリカクロメート皮膜は、クロム酸にシリ
カと還元剤を含む液に処理面を浸漬するか或いはこの処
理液を処理面に塗布することによって形成され、これに
よって、耐水性とともに塗膜の密着性が向上するもので
ある。The silica chromate film is formed by immersing the treated surface in a liquid containing silica and a reducing agent in chromic acid, or by coating this treated liquid on the treated surface, whereby water resistance and adhesion of the coating film are achieved. It improves the sex.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、シリカ
クロメート皮膜には処理液中の６価クロムの一部が未還
元のまま残存することがあり、これが食品に溶出し食品
安全性を保証し得ないとの問題が残されていた。However, a part of hexavalent chromium in the treatment liquid may remain unreduced in the silica chromate film, and this may be eluted into foods and food safety cannot be guaranteed. The problem with was left.
【０００９】この問題を解決するために、この発明は行
われたもので、湿潤環境に曝されても塗料密着性を失わ
ず、且つ食品安全性が確保される塗装金属板の提供を目
的とする。In order to solve this problem, the present invention has been carried out, and an object thereof is to provide a coated metal plate which does not lose paint adhesion even when exposed to a moist environment and which ensures food safety. To do.
【００１０】[0010]
【課題を解決するための手段】この目的を達成するため
の手段は、金属板上にりん酸及びシリカゾルからなる化
成処理層を形成し、その上に単一層又は複層の塗膜を有
する塗装金属板とその態様とである。その態様として
は、塗膜が耐熱樹脂を主成分とする塗膜である塗装金属
板と、塗膜の最上層が弗素樹脂を含む塗膜である塗装金
属板、及びりん酸とシリカゾルの重量比が、Ｈ3 ＰＯ4
／ＳｉＯ2 として、０．０５以上５以下である塗装金属
板である。Means for achieving this object is to form a chemical conversion treatment layer comprising phosphoric acid and silica sol on a metal plate, and apply a coating having a single-layer or multi-layer coating film thereon. It is a metal plate and its aspect. As its aspect, a coated metal plate in which the coating film is a coating film containing a heat-resistant resin as a main component, a coated metal plate in which the uppermost layer of the coating film is a coating film containing a fluororesin, and a weight ratio of phosphoric acid and silica sol. But H 3 PO 4
/ SiO 2 is a coated metal plate having a value of 0.05 or more and 5 or less.
【００１１】[0011]
【作用】食品容器や調理用具などに用いられる塗装金属
板の塗膜は無害でなければならないことは当然である
が、塗膜と金属板との間に介在する化成処理層の安全性
も又無視することができない。特に、水分を含んだ食品
に直接触れる用途では、塗膜の密着性が低下する傾向に
あり、この傾向を低減するとともに、介在する化成処理
層にも食品安全性が強く求められる。[Function] Naturally, the coating film of a coated metal plate used for food containers and cooking utensils must be harmless, but the safety of the chemical conversion treatment layer interposed between the coating film and the metal plate is also important. Cannot be ignored. In particular, in the case of direct contact with a food containing water, the adhesiveness of the coating film tends to decrease, and this tendency is reduced, and the chemical conversion treatment layer interposed is strongly required to have food safety.
【００１２】りん酸及びシリカゾルからなる化成処理層
は、金属板と塗膜との間の密着力を高め、この密着力は
高温下でも又湿潤環境に置かれても低下することがな
い。その上、この化成処理層の組成はりん酸とシリカで
あり、万一食品に触れても無害である。The chemical conversion treatment layer composed of phosphoric acid and silica sol enhances the adhesion between the metal plate and the coating film, and this adhesion does not decrease even at high temperature or in a humid environment. Moreover, the composition of this chemical conversion treatment layer is phosphoric acid and silica, and is harmless even if it comes into contact with food.
【００１３】この処理層は、りん酸にシリカゾルを混合
した処理液を金属基板表面に塗布した後これを乾燥する
ことにより形成される。This treatment layer is formed by applying a treatment liquid in which phosphoric acid is mixed with silica sol to the surface of the metal substrate and then drying it.
【００１４】りん酸及びシリカゾルからなる化成処理層
が塗膜の密着力を高める機構については、次のように考
えることが出来る。先ずりん酸が金属表面を活性化す
る。同時に、処理層はりん酸とシリカゾルとの縮合反応
により強度の高い化成皮膜を形成し、この皮膜がシラノ
ール基（ＳｉＯＨ）やりん酸基（ＰＯＨ）によって、活
性化された金属表面に強固に密着する。このりん酸とシ
リカゾルとが縮合して出来た皮膜は、シランカップリン
グ剤処理皮膜やりん酸塩皮膜と異なり、沸騰水に浸漬し
ても塗料密着性を低下させることがない。The mechanism by which the chemical conversion treatment layer composed of phosphoric acid and silica sol enhances the adhesion of the coating film can be considered as follows. First, phosphoric acid activates the metal surface. At the same time, the treatment layer forms a high-strength chemical conversion film by the condensation reaction of phosphoric acid and silica sol, and this film firmly adheres to the activated metal surface by silanol groups (SiOH) and phosphoric acid groups (POH). To do. Unlike the silane coupling agent-treated film and the phosphate film, the film formed by the condensation of phosphoric acid and silica sol does not deteriorate the coating adhesion even when immersed in boiling water.
【００１５】こうして出来た化成処理層の上に塗料が塗
布され焼付けられるが、この時、シラノール基やりん酸
基が塗膜と化成皮膜との架橋反応を促進する。A coating material is applied on the thus-formed chemical conversion treatment layer and baked. At this time, silanol groups and phosphoric acid groups accelerate the crosslinking reaction between the coating film and the chemical conversion film.
【００１６】実験の結果では、りん酸とシリカゾルとが
共存して脱水縮合すると、塗膜と金属板との密着力は高
まるが、その効果は、両者の重量比が、Ｈ3 ＰＯ4 ／Ｓ
ｉＯ 2 として、０．０５以上５以下の場合に最も大き
い。The results of the experiment show that phosphoric acid and silica sol
When coexisting and dehydration-condensation, the adhesion between the coating film and the metal plate is high.
Maru, but the effect is that the weight ratio of both is H3POFour/ S
iO 2Is the largest when 0.05 or more and 5 or less
Yes.
【００１７】又、化成処理層の量は２mg/m2 好ましくは
５mg/m2 乃至５００mg/m2 が適切である。The amount of the chemical conversion treatment layer is preferably 2 mg / m 2, preferably 5 mg / m 2 to 500 mg / m 2 .
【００１８】なお、上記の化成処理層の作用は、熱可塑
性、熱硬化性にかかわらず一般の耐食有機塗膜に対して
効を奏するのみならず、耐熱樹脂塗膜に対しても同様の
効果をもたらす。The action of the chemical conversion treatment layer described above is effective not only for general corrosion-resistant organic coating films, but also for heat-resistant resin coating films, regardless of thermoplasticity or thermosetting property. Bring
【００１９】言い換えれば、塗膜の主成分として使用で
きる樹脂は、ポリエステル系、アクリル系、エポキシ
系、ウレタン系、塩化ビニル系、ポリエチレン系、ポリ
プロピレン系等の代表的な樹脂はもとより、耐熱性を有
するポリエーテルサルフォン（ＰＥＳ）系、ポリフェニ
レンスルフィド（ＰＰＳ）系、ポリアミドイミド（ＰＡ
Ｉ）系の樹脂などである。In other words, the resin that can be used as the main component of the coating film has heat resistance as well as typical resins such as polyester, acrylic, epoxy, urethane, vinyl chloride, polyethylene and polypropylene. Polyether sulfone (PES) type, polyphenylene sulfide (PPS) type, polyamide imide (PA)
Examples thereof include I) type resins.
【００２０】又、食品の焦げつき、こびりつきなどを防
ぎ、汚れを落ち易くするために、フッ素樹脂がよく用い
られるが、この樹脂は金属板との密着性が得難い。しか
し、りん酸及びシリカゾルからなる化成処理層を介すれ
ば、上記のような他の樹脂と混ぜてフッ素樹脂を含ませ
た塗膜とすることによって良好な密着性が得られる。Further, a fluororesin is often used in order to prevent the food from being scorched or sticky and to easily remove stains, but it is difficult to obtain adhesion of this resin to a metal plate. However, through a chemical conversion treatment layer composed of phosphoric acid and silica sol, good adhesion can be obtained by forming a coating film containing a fluororesin by mixing with the other resin as described above.
【００２１】或いは、塗膜を複層として上記のような樹
脂塗料の上にフッ素系樹脂塗膜を設けることによって、
良好な密着性が得られる。このようにして、密着性と食
品安全性に優れ更に非粘着性及び潤滑性に富んだ塗装鋼
板を得ることができる。含ませるフッ素樹脂の量は、密
着性確保のためには他の樹脂より少なくするのがよい
が、非粘着性や潤滑性を得るためには少なくとも１０wt
％以上必要である。Alternatively, a fluororesin coating film is provided on the above resin paint by using the coating film as a multi-layer,
Good adhesion can be obtained. In this way, it is possible to obtain a coated steel sheet which is excellent in adhesiveness and food safety and is also highly non-adhesive and lubricative. The amount of fluororesin included should be smaller than other resins to ensure adhesion, but at least 10 wt% to obtain non-adhesiveness and lubricity.
% Or more is required.
【００２２】フッ素樹脂としては、四弗化エチレン樹脂
（ＰＴＦＥ）、四弗化エチレン・六弗化プロピレン共重
合樹脂（ＦＥＰ）、四弗化エチレン・パーフロロアルキ
ルビニルエーテル共重合樹脂（ＰＦＡ）の他に、四弗化
エチレン・エチレン共重合樹脂（ＥＴＦＥ）などが用い
られる。Examples of the fluororesin include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin (PFA). In addition, tetrafluoroethylene / ethylene copolymer resin (ETFE) or the like is used.
【００２３】潤滑性に富んだ塗装鋼板では、容器や用具
の成型に際しても曲げや絞り等の加工が容易になる。A coated steel sheet having high lubricity facilitates bending, drawing and the like when molding containers and tools.
【００２４】[0024]
【実施例】金属板上に、りん酸とシリカゾルからなる化
成処理液を塗布し、板温が８０℃となる条件で乾燥し
た。その上に塗料を単層もしくは二層塗布し、それぞれ
の塗料に適した条件で焼付けた。Example A chemical conversion treatment liquid consisting of phosphoric acid and silica sol was applied onto a metal plate and dried under the condition that the plate temperature was 80 ° C. A single layer or two layers of coating material was applied thereon and baked under conditions suitable for each coating material.
【００２５】金属板は、各々Ａ：ＳＵＳ３０４，Ｂ：Ａ
ｌ板、Ｃ：Ｚｎ・１３％Ｎｉめっき鋼板、Ｄ：Ａｌ／Ｔ
ｉ二層めっき鋼板、Ｅ：Ｚｎ・５５％Ａｌめっき鋼板、
Ｆ：ＳＵＳ４３０、Ｇ：Ｚｎ・５％Ａｌめっき鋼板であ
る。The metal plates are A: SUS304 and B: A, respectively.
l plate, C: Zn / 13% Ni plated steel plate, D: Al / T
i two-layer plated steel sheet, E: Zn / 55% Al plated steel sheet,
F: SUS430, G: Zn / 5% Al plated steel sheet.
【００２６】これらの供試材について、塗料密着性、食
品安全性を調べ、更に、塗膜特性に応じて耐食性、耐熱
性、潤滑性、非粘着性の各特性を付け加えた。各特性の
試験条件は以下の通りである。With respect to these test materials, paint adhesion and food safety were examined, and further, corrosion resistance, heat resistance, lubricity, and non-adhesive properties were added according to coating film properties. The test conditions for each property are as follows.
【００２７】〔１〕塗料密着性試験 沸騰水に２時間浸漬し、空冷後０Ｔ曲げ試験及び１Ｔ曲
試験を行い、テープ剥離による剥離面積で評価した。評
価は、各々、０Ｔ曲試験で皮膜剥離が無かった場合は
◎、１Ｔ曲試験のみで皮膜剥離が無かった場合は○、１
Ｔ曲試験で皮膜剥離は見られたが剥離面積１０％未満の
場合は△、１Ｔ曲試験で皮膜剥離面積１０％以上の場合
は×、である。[1] Paint Adhesion Test After being immersed in boiling water for 2 hours and air-cooled, a 0T bending test and a 1T bending test were performed, and the peeled area by tape peeling was evaluated. The evaluation is ⊙ when there is no film peeling in the 0T bending test, and ◯ when there is no film peeling only in the 1T bending test.
Film peeling was observed in the T-bend test, but the peeling area was less than 10%, and 1 was the film peeling area in the T-bending test, 10% or more.
【００２８】〔２〕食品安全性試験 ３種類の浸漬液に各々浸漬し、試験後の浸漬液に含まれ
るクロム等の有害重金属量を測定した。浸漬液は、純
水、４％酢酸水溶液、５％食塩水である。各浸漬液とも
液量は供試材の表面積１cm2 当たり２ml、温度は９５
℃、浸漬時間は３０分である。有害重金属量の全溶出量
が１ppm 未満の場合は○、１ppm 以上の場合は×、とし
て評価した。[2] Food Safety Test Each of the three kinds of immersion liquids was dipped, and the amount of harmful heavy metals such as chromium contained in the immersion liquid after the test was measured. The immersion liquid is pure water, 4% acetic acid aqueous solution, and 5% saline. The amount of each immersion liquid is 2 ml per 1 cm 2 of surface area of the test material, and the temperature is 95.
C., immersion time is 30 minutes. When the total amount of harmful heavy metals eluted was less than 1 ppm, it was evaluated as ○, and when it was 1 ppm or more, it was evaluated as ×.
【００２９】〔３〕耐食性試験 ０Ｔ折り曲げを施した試験片についてＪＩＳ Ｚ ２３
７１に基づき１０００時間の塩水噴霧を行い、折り曲げ
部の塗膜を粘着テープを用いて強制的に剥離し剥離率を
調べた。測定は目視により、剥離率５％未満の場合は
◎、５％以上１０％未満は〇、１０％以上２５％未満は
△、２５％以上の場合は×として評価した。[3] Corrosion resistance test Regarding test pieces subjected to 0T bending, JIS Z 23
Based on No. 71, salt water was sprayed for 1000 hours, the coating film at the bent portion was forcibly peeled off using an adhesive tape, and the peeling rate was examined. When the peeling rate was less than 5%, the measurement was evaluated as ⊚, when 5% or more and less than 10% was evaluated as ◯, when 10% or more and less than 25% was evaluated as Δ, and when 25% or more was evaluated as x.
【００３０】〔４〕潤滑性試験 深絞り加工を行い、限界しわ押さえ圧を測定した。供試
材は、厚さ０．４mm、直径１２０mmの円板であり、深絞
り条件は、ダイス；４０．９mmφ−３mmＲ，ポンチ；４
０mmφ−４mmＲ、しわ押さえ板；４０．５mmφである。
限界しわ押さえ圧２．０トン以上の場合は○、２．０ト
ン未満で１．０トン以上の場合は△、１．０トン未満の
場合は×、として評価した。[4] Lubricity test Deep drawing was carried out and the limit wrinkle pressing pressure was measured. The test material is a disk having a thickness of 0.4 mm and a diameter of 120 mm, and the deep drawing conditions are a die; 40.9 mmφ-3 mmR, punch; 4
0mmφ-4mmR, wrinkle holding plate: 40.5mmφ.
When the limit wrinkle pressing pressure was 2.0 tons or more, it was evaluated as ◯, when less than 2.0 tons and 1.0 tons or more was evaluated as Δ, and when less than 1.0 tons, it was evaluated as x.
【００３１】〔５〕非粘着性試験 ２０℃の雰囲気中で、ゴニオメーター式接触角測定器を
用い、純水を滴下して接触角を測定した。接触角１００
°以上の場合は○、１００°未満９５°以上の場合は
△、９５°未満の場合は×、として評価した。[5] Non-Adhesion Test In a 20 ° C. atmosphere, pure water was added dropwise using a goniometer type contact angle measuring device to measure the contact angle. Contact angle 100
It was evaluated as ◯ when it was more than °, as Δ when it was less than 100 ° and more than 95 °, and as x when it was less than 95 °.
【００３２】〔６〕耐熱性試験 ２６０℃の炉中に３時間保持し、空冷した後０Ｔ曲げ試
験及び１Ｔ曲試験を行い、曲部にテープを貼り付けて塗
膜を強制的に剥離し（以下、テープ剥離と称す）た場合
の皮膜剥離面積から耐熱性を評価した。評価は、各々、
０Ｔ曲試験で皮膜剥離が無かった場合は◎、１Ｔ曲試験
のみで皮膜剥離が無かった場合は○、１Ｔ曲試験で皮膜
剥離面積１０％未満の場合は△、１Ｔ曲試験で皮膜剥離
面積１０％未満の場合は×、である。[6] Heat resistance test After being kept in a furnace at 260 ° C. for 3 hours and air-cooled, a 0T bending test and a 1T bending test are performed, and a tape is attached to the bending portion to forcibly peel off the coating film ( Hereinafter, the heat resistance was evaluated from the film peeling area in the case of tape peeling). The evaluation is
When there is no film peeling in the 0T bending test, ◎ when there is no film peeling only in the 1T bending test, ○ when the film peeling area is less than 10% in the 1T bending test, and the film peeling area is 10 in the 1T bending test. When it is less than%, it is x.
【００３３】調査は、従来技術による耐熱塗装金属板に
ついても行い、この発明の実施例と比較した。 実施例１．約１５μｍの塗膜を一層設け、塗料密着性、
食品安全性に加え、耐食性並びにフッ素樹脂を含む塗膜
については潤滑性と非粘着性の諸特性を調べた。The investigations were also carried out on heat-resistant coated metal sheets according to the prior art and compared with the examples of the present invention. Example 1. A coating film of about 15 μm is provided to improve paint adhesion.
In addition to food safety, the corrosion resistance and coating films containing fluororesin were examined for lubricity and non-adhesive properties.
【００３４】その他の条件及び調査の結果を表１に示
す。Table 1 shows other conditions and the results of the investigation.
【００３５】[0035]
【表１】 [Table 1]
【００３６】発明の実施例では全ての供試材で、塗料密
着性、食品安全性に優れた結果を示すとともに、耐食性
にも優れ、フッ素樹脂を含む塗膜については潤滑性と非
粘着性についても満足な結果を得た。In the examples of the invention, all test materials show excellent results in paint adhesion and food safety, and also have excellent corrosion resistance, and coating films containing a fluororesin show lubricity and non-adhesiveness. Also got a satisfactory result.
【００３７】これに対して、従来例では、化成処理層が
シリカクロメート処理層（N0. １６）の場合はクロムの
溶出が見られて食品安全性に劣り、化成処理層がりん酸
亜鉛処理層（N0. １７）の場合は塗料密着性に劣った。On the other hand, in the conventional example, when the chemical conversion treatment layer is a silica chromate treatment layer (N0.16), chromium elution is observed and the food safety is poor, and the chemical conversion treatment layer is a zinc phosphate treatment layer. In the case of (N0.17), the paint adhesion was poor.
【００３８】実施例２．耐熱樹脂を主成分とする塗料を
用い、一層又は二層の塗膜を設け、塗料密着性、食品安
全性に加え、耐食性並びにフッ素樹脂を含む塗膜につい
ては潤滑性と非粘着性の諸特性を調べた。Example 2. A single or double-layered coating is prepared using a paint that contains heat-resistant resin as the main component. In addition to paint adhesion and food safety, corrosion resistance and various properties of a fluororesin-containing coating are lubricity and non-adhesiveness. I checked.
【００３９】その他の条件及び調査の結果について、一
層塗膜の場合を表２に、二層塗膜の場合を表３に各々示
す。Regarding other conditions and the results of the investigation, Table 2 shows the case of a one-layer coating film and Table 3 shows the case of a two-layer coating film.
【００４０】[0040]
【表２】 [Table 2]
【００４１】この発明の実施例では、全ての供試材が耐
熱性、塗料密着性、食品安全性を満足した。特に、化成
処理層のＨ3 ＰＯ4 ／ＳｉＯ2 が０．０５〜５の範囲
で、付着量が５mg/m2 以上の供試材（No. ２１乃至３
５、N0. ３９、４０）では、極めて優れた耐熱性と塗料
密着性を示した。In the examples of the present invention, all the test materials satisfied heat resistance, paint adhesion and food safety. In particular, in the H 3 range PO 4 / SiO 2 is 0.05 to 5 in the chemical conversion treatment layer, the adhesion amount is 5 mg / m 2 or more test material (No. 21 to 3
5, No. 39, 40) showed extremely excellent heat resistance and paint adhesion.
【００４２】これに対して、従来例では、化成処理層が
シリカクロメート処理層の場合はクロムの溶出が見られ
食品安全性に問題があり、りん酸亜鉛処理層の場合は耐
熱性と塗料密着性に劣り、シランカップリング剤処理層
では塗料密着性に劣っていた。On the other hand, in the conventional example, when the chemical conversion treatment layer is the silica chromate treatment layer, chromium elution is observed and there is a problem in food safety, and in the case of the zinc phosphate treatment layer, heat resistance and paint adhesion. Inferior in adhesion, and in the silane coupling agent-treated layer, inferior in paint adhesion.
【００４３】[0043]
【表３】 [Table 3]
【００４４】二層塗膜の場合でも、この発明の実施例で
は、全ての供試材が耐熱性、塗料密着性、食品安全性を
満足した。Even in the case of the two-layer coating film, in the examples of the present invention, all the test materials satisfied the heat resistance, the paint adhesion and the food safety.
【００４５】又、最上層塗膜に弗素系樹脂を含む供試材
（No. ５１、５２）は第一層にフッ素樹脂含有の有無に
かかわらず、潤滑性、非粘着性ともに満足な結果が得ら
れた。Further, the test materials (No. 51, 52) containing the fluorine-based resin in the uppermost coating film showed satisfactory results in both lubricity and non-adhesiveness regardless of the presence or absence of the fluorine resin in the first layer. Was obtained.
【００４６】なお、ここに示した実施例に用いた金属板
の他に、冷延鋼板やチタン板、他のステンレス鋼板、銅
板等が用いられ、めっき鋼板としては亜鉛めっき鋼板、
アルミニウムめっき鋼板、ニッケルめっき鋼板、クロム
めっき鋼板、コバルトめっき鋼板、或いはこれらの合金
めっき鋼板や複層めっき鋼板等が用いられる。In addition to the metal plates used in the examples shown here, cold rolled steel plates, titanium plates, other stainless steel plates, copper plates, etc. are used.
Aluminum-plated steel sheet, nickel-plated steel sheet, chrome-plated steel sheet, cobalt-plated steel sheet, or their alloy-plated steel sheet or multi-layer plated steel sheet is used.
【００４７】りん酸は、正りん酸、無水りん酸、あるい
はこれらの水溶液のいずれの形態の物でも使用出来る。The phosphoric acid can be used in the form of orthophosphoric acid, phosphoric anhydride, or an aqueous solution thereof.
【００４８】シリカゾルは、市販されているものを使用
出来る。この実施例では、平均粒径１２ｎｍ（比表面積
２００m2/g）の乾式製法によるシリカゾルを使用した。
粒径は５乃至１００ｎｍのものが適当で、乾式法で製造
されたものでも湿式法によるものでもよい。Commercially available silica sol can be used. In this example, a dry-process silica sol having an average particle diameter of 12 nm (specific surface area 200 m 2 / g) was used.
A particle size of 5 to 100 nm is suitable, and it may be manufactured by a dry method or a wet method.
【００４９】化成処理液は、化成処理層の付着量に応じ
て濃度を調節されたりん酸水溶液と所定量のシリカゾル
とを混合、攪拌し、均一な溶液とすることにより調製す
ることができる。The chemical conversion treatment liquid can be prepared by mixing and stirring a phosphoric acid aqueous solution whose concentration is adjusted according to the amount of the chemical conversion treatment layer adhered and a predetermined amount of silica sol to form a uniform solution.
【００５０】化成処理に際しては、必要に応じて、アル
カリや溶剤による脱脂、アルカリや酸によるエッチン
グ、或いはブラッシングやショットブラストによる表面
研削等、公知の前処理を施せばよい。In the chemical conversion treatment, known pretreatments such as degreasing with an alkali or a solvent, etching with an alkali or an acid, or surface grinding by brushing or shot blasting may be performed, if necessary.
【００５１】化成処理液の塗布にはスプレーの他にロー
ルコート、カーテンフローコート、静電塗布等の方法を
用いることができる。乾燥は水分を蒸発させればよく、
その温度は５０乃至１５０℃が適当である。In addition to spraying, a method such as roll coating, curtain flow coating or electrostatic coating can be used for coating the chemical conversion treatment liquid. Drying can be done by evaporating water,
A suitable temperature is 50 to 150 ° C.
【００５２】塗料組成物としては、上記の耐熱樹脂を単
独或いは混合して主成分とし、これに顔料、充填材、界
面活性剤や消泡剤等の添加剤、溶剤、分散媒等を要求性
能、塗装作業性等を考慮して適宜調合して用いればよ
い。In the coating composition, the above-mentioned heat-resistant resins are used alone or as a main component, and pigments, fillers, additives such as surfactants and defoamers, solvents, dispersion media, etc. are required. It may be used by appropriately mixing it in consideration of coating workability and the like.
【００５３】塗装方法には、化成処理液の場合と同様、
スプレーの他にロールコート、カーテンフローコート、
静電塗布等の方法を用いることができ、乾燥焼付けには
熱風加熱炉や赤外線加熱炉、誘導加熱炉等を用いること
が出来る。塗膜厚は、塗膜の色調即ち隠蔽性が重視され
る場合には５μm 以上、隠蔽性を問題にしない場合には
０．５μm 以上あれば充分である。The coating method is the same as in the case of the chemical conversion treatment liquid.
In addition to spray, roll coat, curtain flow coat,
A method such as electrostatic coating can be used, and a hot air heating furnace, an infrared heating furnace, an induction heating furnace, or the like can be used for dry baking. The thickness of the coating film is 5 μm or more when the color tone of the coating film, that is, the hiding property is important, and 0.5 μm or more when the hiding property is not a problem.
【００５４】[0054]
【発明の効果】以上に述べてきたように、この発明によ
れば、密着力に富み耐水性があり且つ無害なりん酸・シ
リカゾルの化成処理層を用いて、金属基板を塗膜層で被
覆している。このため、この塗装金属板は食品に無害で
あるとともに塗膜の耐水密着性に優れ、耐熱樹脂塗膜で
被覆すれば耐熱耐水密着性に優れ、更に塗膜層に弗素系
樹脂を含ませることによって潤滑性や非粘着性にも優れ
たものになる。このように、食品用容器や調理器具など
のプレコート金属板に求められる特性の全てを満たすこ
の発明の効果は大きい。As described above, according to the present invention, the metal substrate is coated with the coating layer by using the chemical conversion treatment layer of the phosphoric acid / silica sol which is rich in adhesiveness, has water resistance and is harmless. is doing. For this reason, this coated metal plate is harmless to foods and has excellent water-resistant adhesion of the coating film. If it is coated with a heat-resistant resin coating film, it also has excellent heat-resistant and water-resistant adhesiveness. It also has excellent lubricity and non-adhesiveness. As described above, the effect of the present invention is large, which satisfies all the properties required for a precoated metal plate such as a food container or a cooking utensil.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大沢 健次 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 (72)発明者 岡田 敏彦 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 (72)発明者 吉田 安秀 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenji Osawa Inventor, Marunouchi 1-2-2 Marunouchi, Chiyoda-ku, Tokyo Japan Steel Pipe Co., Ltd. (72) Toshihiko Okada Marunouchi 1-2-2, Chiyoda-ku, Tokyo Inside the Steel Pipe Corporation (72) Inventor Yasuhide Yoshida 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Inside Nihon Steel Pipe Corporation
Claims (4)
し、上層に一層又は複層の塗膜を有する塗装金属板にお
いて、下層の化成処理層がりん酸及びシリカゾルからな
る化成処理液を塗布した後、これを乾燥させて形成した
層であることを特徴とする塗装金属板。1. A coated metal plate having a chemical conversion treatment layer as a lower layer on a metal plate and a coating film of one or more layers as an upper layer, wherein the lower chemical conversion treatment layer comprises a chemical conversion treatment liquid containing phosphoric acid and silica sol. A coated metal plate, which is a layer formed by drying after coating.
る請求項１記載の塗装金属板。2. The coated metal plate according to claim 1, wherein the coating film is a coating film containing a heat-resistant resin as a main component.
る請求項１又は２記載の塗装金属板。3. The coated metal plate according to claim 1, wherein the uppermost layer of the coating film is a coating film containing a fluororesin.
Ｏ4 ／ＳｉＯ2 として、０．０５以上５以下である請求
項１、２又は３記載の塗装金属板。4. The weight ratio of phosphoric acid and silica sol is H 3 P.
The coated metal plate according to claim 1, 2 or 3, wherein O 4 / SiO 2 is 0.05 or more and 5 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13904194A JPH07118871A (en) | 1993-08-31 | 1994-06-21 | Coated metallic sheet |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21576493 | 1993-08-31 | ||
| JP5-215764 | 1993-08-31 | ||
| JP13904194A JPH07118871A (en) | 1993-08-31 | 1994-06-21 | Coated metallic sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07118871A true JPH07118871A (en) | 1995-05-09 |
Family
ID=26471955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13904194A Pending JPH07118871A (en) | 1993-08-31 | 1994-06-21 | Coated metallic sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118871A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265708A (en) * | 2005-03-25 | 2006-10-05 | Nichias Corp | Chemical conversion film-coated steel sheet and method for producing the same |
| KR101459854B1 (en) * | 2012-12-24 | 2014-11-07 | 주식회사 포스코 | Composition for metal surface treatment comprising silica-sol and its coated steel sheet |
-
1994
- 1994-06-21 JP JP13904194A patent/JPH07118871A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265708A (en) * | 2005-03-25 | 2006-10-05 | Nichias Corp | Chemical conversion film-coated steel sheet and method for producing the same |
| KR101459854B1 (en) * | 2012-12-24 | 2014-11-07 | 주식회사 포스코 | Composition for metal surface treatment comprising silica-sol and its coated steel sheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS582596A (en) | Surface treatment for heat exchanger made of aluminum | |
| JP2004524957A (en) | Corrosion resistant coating for glazing effect | |
| JP3075117B2 (en) | Painted metal plate for sliding plate and method for producing the same | |
| JPH05500327A (en) | Non-stick coating system with two thin basecoats where the first basecoat is a polysiloxane | |
| EP0489036B1 (en) | Non-stick coating system with thin undercoat of polyamide imide, polyarylene sulfide or polyether sulfone | |
| JPH07118871A (en) | Coated metallic sheet | |
| JP2004122409A (en) | Clear coating stainless steel sheet | |
| JP2011235457A (en) | Metal coating material | |
| JP2003033995A (en) | Heat resistant non-sticky coated metal plate excellent in wear resistance and coating material for heat resistant non-sticky coating | |
| JP3477174B2 (en) | Non-chromate type surface treated metal sheet and method for producing the same | |
| JPH0847669A (en) | Resin-coated metal material having excellent weather resistance and contamination resistance | |
| JP2010042617A (en) | Aluminum coating material excellent in water repellency and dust adhesion resistance | |
| JP2001219122A (en) | Article with fluororesin coating film and manufacturing method there for | |
| JPS61138567A (en) | Production of heat resistant coated steel plate excellent in nonadhesive properties | |
| JP2000279880A (en) | Stainless steel plate coated with transparent fluoroplastic coating with high wear resistance, finger printing-proofness, and excellent design property | |
| JPH08281867A (en) | Heat-resistant painted metal panel | |
| JP2003138382A (en) | Metal surface treating agent for bonding substrate and treatment method therefor | |
| JPS607946B2 (en) | Manufacturing method of highly durable painted metal plate | |
| JP2745385B2 (en) | Film-coated metal plate | |
| JP4280658B2 (en) | Clear painted stainless steel sheet with excellent coating adhesion | |
| JPH079223U (en) | Food container | |
| WO2015151509A1 (en) | Coated steel sheet, method for producing same and member for cooking utensils | |
| JP6656051B2 (en) | Painted stainless steel plate | |
| JPH0858015A (en) | Stainless steel panel having heat-resistant film and production thereof | |
| JP2579487B2 (en) | White chromate treatment method with excellent surface properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20020702 |