JP3293084B2 - Heat-resistant non-adhesive pre-coated steel sheet - Google Patents
Heat-resistant non-adhesive pre-coated steel sheetInfo
- Publication number
- JP3293084B2 JP3293084B2 JP2741499A JP2741499A JP3293084B2 JP 3293084 B2 JP3293084 B2 JP 3293084B2 JP 2741499 A JP2741499 A JP 2741499A JP 2741499 A JP2741499 A JP 2741499A JP 3293084 B2 JP3293084 B2 JP 3293084B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- heat
- resistant
- adhesive
- steel sheet
- 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.)
- Expired - Lifetime
Links
Landscapes
- Cookers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、食品調理器具，加熱調
理器具等に適した耐熱非粘着プレコート鋼板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant and non-adhesive precoated steel sheet suitable for food cooking utensils, cooking utensils and the like.
【０００２】[0002]
【従来の技術】フッ素樹脂は、耐熱性，非粘着性，耐汚
染性等の優れた特性を活用し、鋼材との複合材として使
用されている。フッ素樹脂が複合された鋼板は、たとえ
ばパン，ケーキの焼き型，フライパン等の食品調理器
具，電子レンジ内板，電子制御ジャーの内釜，ガステー
ブル用天板等の加熱調理器具として汎用されている。ガ
ステーブルの天板についてみると、その７割程度がフッ
素樹脂塗装製品である。ガステーブルは、家電機器店，
量販店等で販売されているコンロタイプと、予めシステ
ムキッチンに組み込まれるシステムキッチンタイプに大
別される。コンロタイプでは、大半のガステーブルに４
フッ化樹脂プレコート鋼板が使用されている。他方、シ
ステムキッチンタイプでは、耐久性，特に煮こぼれ等の
汚れの拭き取り易さを考慮してプレコート化がほとんど
進められておらず、従来からのポストコート法による４
フッ化樹脂コーティングが施されている。2. Description of the Related Art Fluororesins have been used as composite materials with steel materials by utilizing their excellent properties such as heat resistance, non-adhesion and stain resistance. Fluoroplastic composite steel sheets are widely used as cooking utensils such as food cooking utensils such as bread and cake baking pans and frying pans, microwave oven inner plates, inner pots of electronic control jars, gas table tops, and the like. I have. About the gas table top plate, about 70% is fluororesin coated products. Gas table, home appliance store,
They are broadly divided into stove types sold at mass retailers and the like, and system kitchen types that are pre-installed in the system kitchen. For the stove type, most gas tables have 4
Fluororesin precoated steel sheets are used. On the other hand, in the system kitchen type, pre-coating has hardly been promoted in consideration of durability, particularly ease of wiping off dirt such as boiling over.
Fluororesin coating is applied.
【０００３】システムキッチンタイプのガステーブルで
は、透明なパーフルオロアルキルビニルエーテル−テト
ラフルオロエチレン共重合体（ＰＦＡ）フィルムを着色
耐熱性樹脂層を介して鋼板に積層することにより、透明
ＰＦＡフィルムを透かして着色意匠が観察されるラミネ
ート鋼板、透明なＰＦＡフィルムにグラビア印刷を施
し、印刷面を鋼板側に配置して印刷ＰＦＡフィルムを積
層し、透明ＰＦＡフィルム層を透かして印刷意匠性が得
られるラミネート鋼板が一部で使用され始めている。こ
の場合、システムキッチンに要求される耐久性は、フッ
素樹脂単独からなるＰＦＡフィルムで表面被覆すること
により付与される。In a gas table of a system kitchen type, a transparent perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer (PFA) film is laminated on a steel sheet via a colored heat-resistant resin layer, so that the transparent PFA film can be seen through. Laminated steel sheet where colored design is observed, gravure printing is performed on a transparent PFA film, the printed surface is placed on the steel sheet side, the printed PFA film is laminated, and a printed steel sheet is obtained through the transparent PFA film layer to obtain the printed design Has begun to be used by some. In this case, the durability required for the system kitchen is provided by covering the surface with a PFA film made of a fluororesin alone.
【０００４】[0004]
【発明が解決しようとする課題】ＰＦＡフィルムを鋼板
にラミネートするものでは、フィルム製造の安定性を考
慮すると４０μｍ以上の厚膜が必要である。そのため、
ＰＦＡフィルムの平米単価が被積層材であるＳＵＳ４３
０等のステンレス鋼板の平米単価を超える。また、鋼板
に印刷ＰＦＡフィルムを十分な接着性で積層するために
は、加熱方法，加熱時間等が拘束され、処理が煩雑にな
る。そのため、得られるラミネート鋼板は、従来のコン
ロタイプで使用されている耐熱非粘着プレコート鋼板に
比較して著しく高価になる。しかも、膜厚４０μｍのＰ
ＦＡフィルムを鋼板にラミネートするため、ラミネート
鋼板の表面が非常に疵付き易くなる。たとえば、ＪＩＳ
Ｋ５４００及びＪＩＳ Ｇ３３１２に規定されている
鉛筆硬度で６Ｂ程度になり、爪によっても容易に疵や圧
痕がつけられ、コンロタイプに使用されている耐熱非粘
着プレコート鋼板の鉛筆硬度Ｈに比較して著しく見劣り
する。In the case of laminating a PFA film on a steel sheet, a film having a thickness of 40 μm or more is required in consideration of the stability of film production. for that reason,
The unit price of PFA film is SUS43
Exceeds the flat unit price of stainless steel sheets such as 0. Further, in order to laminate the printed PFA film on the steel plate with sufficient adhesiveness, the heating method, the heating time and the like are restricted, and the processing becomes complicated. Therefore, the resulting laminated steel sheet is significantly more expensive than the heat-resistant non-adhesive pre-coated steel sheet used in the conventional stove type. In addition, a P having a film thickness of 40 μm
Since the FA film is laminated on the steel sheet, the surface of the laminated steel sheet is very easily scratched. For example, JIS
The pencil hardness specified in K5400 and JIS G3312 is about 6B, and scratches and indentations are easily formed by nails. Be inferior.
【０００５】そこで、発明者等は、コスト及び耐疵付き
性を考慮し、従来のコンロタイプで使用されている耐熱
非粘着プレコート鋼板に関し煮こぼれ等の拭取り耐久性
（以下、非粘着耐久性という）を付与すべく鋭意検討し
た。具体的には、耐熱非粘着塗膜に使用されている４フ
ッ化樹脂及び耐熱性樹脂の樹脂種，組成比及び耐熱非粘
着塗膜の膜厚，焼成条件等が非粘着耐久性に及ぼす影響
を調査したが、十分な非粘着耐久性を呈するものは見当
たらなかった。また、良好な塗料塗装性，塗膜外観，非
粘着性を得ることも難しく、従来の耐熱非粘着プレコー
ト鋼板の塗料組成が高いレベルでバランスされたもので
あることを確認するに止まった。[0005] In view of the cost and scratch resistance, the inventors of the present invention have studied the heat-resistant non-adhesive pre-coated steel sheet used in the conventional stove type, which has a wiping durability such as boiling over (hereinafter referred to as a non-adhesive durability). ). Specifically, the effect of the resin type and composition ratio of the tetrafluoride resin and the heat-resistant resin used for the heat-resistant non-adhesive coating film, the film thickness of the heat-resistant non-adhesive coating film, and the firing conditions on the non-adhesive durability However, none of them exhibited sufficient non-adhesive durability. In addition, it was difficult to obtain good paint coatability, coating appearance, and non-adhesion, and it was only confirmed that the paint composition of the conventional heat-resistant and non-adhesive precoated steel sheet was balanced at a high level.
【０００６】[0006]
【課題を解決するための手段】本発明は、このような問
題を解消すべく案出されたものであり、耐熱性樹脂と乳
化重合法で製造されたＰＦＡとの混合物を主成分とする
着色又は透明耐熱非粘着塗膜を最表層に設けることによ
り、システムキッチンタイプに使用でき、優れた非粘着
耐久性を呈する耐熱非粘着プレコート鋼板を得ることを
目的とする。本発明の耐熱非粘着プレコート鋼板は、そ
の目的を達成するため、ポリエーテルスルホン樹脂，ポ
リフェニルスルフィド樹脂，ポリアミドイミド樹脂の少
なくとも１種の耐熱性樹脂を主成分とする着色塗膜が鋼
板表面に形成され、ポリエーテルスルホン樹脂，ポリフ
ェニルスルフィド樹脂，ポリアミドイミド樹脂の少なく
とも１種以上の耐熱性樹脂と乳化重合法で製造した平均
粒径０．０５〜１μｍのパーフルオロアルキルビニルエ
ーテル−テトラフルオロエチレン共重合体を主成分とす
るフッ素樹脂との混合物を主成分とする着色又は透明耐
熱非粘着塗膜が前記着色塗膜の上に形成されていること
を特徴とする。DISCLOSURE OF THE INVENTION The present invention has been devised to solve such a problem, and comprises a coloring material mainly composed of a mixture of a heat-resistant resin and PFA produced by an emulsion polymerization method. Alternatively, by providing a transparent heat-resistant and non-adhesive coating film on the outermost layer, an object is to obtain a heat-resistant and non-adhesive precoated steel sheet which can be used for a system kitchen type and exhibits excellent non-adhesive durability. In order to achieve the object, the heat-resistant non-adhesive precoated steel sheet of the present invention has a colored coating mainly composed of at least one heat-resistant resin such as a polyether sulfone resin, a polyphenyl sulfide resin, and a polyamide-imide resin on the surface of the steel sheet. A perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer having an average particle size of 0.05 to 1 μm formed by emulsion polymerization and at least one kind of heat-resistant resin of polyether sulfone resin, polyphenyl sulfide resin and polyamide imide resin is formed. A colored or transparent heat-resistant and non-adhesive coating mainly composed of a mixture with a fluororesin mainly composed of a polymer is formed on the colored coating.
【０００７】印刷意匠性を組合せた耐熱非粘着プレコー
ト鋼板では、ポリエーテルスルホン樹脂，ポリフェニル
スルフィド樹脂，ポリアミドイミド樹脂の少なくとも１
種の耐熱性樹脂を主成分とする着色塗膜が鋼板表面に形
成され、ポリテトラフルオロエチレン樹脂，パーフルオ
ロアルキルビニルエーテル−テトラフルオロエチレン共
重合体の少なくとも１種以上のフッ素樹脂とアクリル樹
脂，ポリウレタン樹脂，ポリエステル樹脂の少なくとも
１種以上の水溶性又は水分散性樹脂との混合物をベース
とする耐熱性印刷インキ層が前記着色塗膜の上に一部又
は全面に形成され、次いでポリエーテルスルホン樹脂，
ポリフェニルスルフィド樹脂，ポリアミドイミド樹脂の
少なくとも１種以上の耐熱性樹脂を主成分とする透明塗
膜が前記耐熱印刷インキ層の上に形成され、更に、ポリ
エーテルスルホン樹脂，ポリフェニルスルフィド樹脂，
ポリアミドイミド樹脂の少なくとも１種以上の耐熱性樹
脂と乳化重合法で製造した平均粒径０．０５〜１μｍの
パーフルオロアルキルビニルエーテル−テトラフルオロ
エチレン共重合体を主成分とするフッ素樹脂との混合物
を主成分とする透明耐熱非粘着塗膜が前記透明塗膜の上
に形成されている。[0007] A heat-resistant non-adhesive precoated steel sheet having a combination of a printing design property includes at least one of a polyether sulfone resin, a polyphenyl sulfide resin, and a polyamideimide resin.
A colored coating mainly composed of a kind of heat-resistant resin is formed on the surface of the steel sheet, and at least one kind of fluororesin of polytetrafluoroethylene resin, perfluoroalkylvinylether-tetrafluoroethylene copolymer, acrylic resin, polyurethane A heat-resistant printing ink layer based on a mixture of at least one of a resin and a polyester resin with a water-soluble or water-dispersible resin is partially or entirely formed on the colored coating film; ,
A transparent coating mainly composed of at least one heat-resistant resin of a polyphenyl sulfide resin or a polyamide imide resin is formed on the heat-resistant printing ink layer, and a polyether sulfone resin, a polyphenyl sulfide resin,
A mixture of at least one or more heat-resistant resins of a polyamideimide resin and a perfluoroalkylvinylether-tetrafluoroethylene copolymer having a mean particle diameter of 0.05 to 1 μm produced by an emulsion polymerization method and a fluororesin as a main component is prepared. A transparent heat-resistant and non-adhesive coating as a main component is formed on the transparent coating.
【０００８】[0008]
【実施の形態】従来の耐熱非粘着プレコート鋼板では、
ポリエーテルスルホン樹脂，ポリフェニルスルフィド樹
脂，ポリアミドイミド樹脂等の耐熱性樹脂を主成分とす
る着色塗膜を鋼板表面に設け、ポリエーテルスルホン樹
脂，ポリフェニルスルフィド樹脂，ポリアミドイミド樹
脂等の耐熱性樹脂とテトラフルオロエチレン樹脂（以
下，ＰＴＦＥという），ＰＦＡ等の４フッ化樹脂を主成
分とする着色耐熱非粘着塗膜を着色塗膜の上に設けてい
る。高い成形加工性，耐熱非粘着性を発現させる構成と
しては、着色塗膜を形成する耐熱性樹脂としてポリエー
テルスルホン樹脂，着色耐熱非粘着塗膜を形成する耐熱
性樹脂としてポリエーテルスルホン樹脂，４フッ化樹脂
としてＰＴＦＥを使用することが最も一般的である。DESCRIPTION OF THE PREFERRED EMBODIMENTS In a conventional heat-resistant and non-adhesive pre-coated steel sheet,
A colored coating mainly composed of a heat-resistant resin such as a polyether sulfone resin, a polyphenyl sulfide resin, or a polyamide imide resin is provided on a steel sheet surface, and a heat-resistant resin such as a polyether sulfone resin, a polyphenyl sulfide resin, or a polyamide imide resin is provided. And a colored heat-resistant and non-adhesive coating mainly composed of a tetrafluoroethylene resin (hereinafter, referred to as PTFE), a tetrafluoride resin such as PFA, etc., is provided on the colored coating. In order to exhibit high moldability and heat-resistant and non-adhesive properties, polyethersulfone resin is used as a heat-resistant resin for forming a colored coating, polyethersulfone resin is used as a heat-resistant resin for forming a colored heat-resistant and non-adhesive coating, It is most common to use PTFE as the fluorinated resin.
【０００９】しかし、この塗膜構成で非粘着耐久性を調
査したところ、６〜７回の繰返し試験で汚染因子を容易
に除去できなくなった。なお、非粘着耐久性は、醤油／
砂糖／卵＝１／１／１の混合液及び牛乳を塗膜表面に載
せて２６０℃の加熱炉に１時間入れ、十分に冷却した
後、汚染因子である醤油／砂糖／卵＝１／１／１の混合
液及び牛乳が塗膜表面に焦げ付かずに繰返し除去できる
回数で評価した。そして、システムキッチンタイプで
は、１０回以上の繰返し除去が可能なことを耐久性有無
の判断基準にした。非粘着耐久性を改善するため、耐熱
性樹脂及び４フッ化樹脂について樹脂種依存性を検討し
たが、樹脂種による顕著な性能向上は検出できなかっ
た。耐熱非粘着塗膜における耐熱性樹脂に対する４フッ
化樹脂の混合比を高くして非粘着耐久性の改善を図った
が、４フッ化樹脂の配合量が増加すると塗料塗装性が極
端に低下し、良好な表面外観が得られなくなった。膜厚
の増大、すなわち塗膜焼成時に塗膜表面に移行する４フ
ッ化樹脂の厚みを大きくした場合でも、表面外観が悪化
するばかりでなく塗膜にワキが発生し易くなり、却って
物理的な汚染因子の吸着により非粘着耐久性が低下する
傾向がみられた。[0009] However, when the non-adhesive durability of this coating film composition was examined, the contamination factor could not be easily removed in 6 to 7 repeated tests. The non-adhesive durability was measured using soy sauce /
The mixed solution of sugar / egg = 1/1/1 and milk were placed on the surface of the coating film and placed in a heating furnace at 260 ° C. for 1 hour, and after sufficiently cooling, soy sauce / sugar / egg = 1/1 as a contaminant. The evaluation was made by the number of times that the mixed solution of / 1 and milk could be repeatedly removed without scorching on the coating film surface. In the system kitchen type, the criterion for judging the durability is based on the fact that it can be repeatedly removed 10 times or more. In order to improve the non-adhesive durability, the dependency of the heat-resistant resin and the tetrafluoride resin on the resin type was examined, but no remarkable improvement in performance due to the resin type was detected. Although the non-adhesive durability was improved by increasing the mixing ratio of the tetrafluororesin to the heat-resistant resin in the heat-resistant and non-adhesive coating film, the paint coatability was extremely reduced when the amount of the tetrafluororesin was increased. , Good surface appearance could not be obtained. Even when the thickness of the film is increased, that is, when the thickness of the tetrafluoride resin migrating to the surface of the coating film when the coating film is baked is increased, not only the surface appearance is deteriorated, but also the coating film is liable to be wrinkled. There was a tendency for the non-adhesive durability to decrease due to adsorption of contamination factors.
【００１０】次いで、従来からコンロタイプに使用され
ている耐熱非粘着プレコート鋼板について、非粘着耐久
性が劣る原因を調査した。この種の鋼板表面に形成され
ている耐熱非粘着塗膜は、光学顕微鏡，ＥＰＭＡ（電子
プローブ微小部分析）等による観察結果から、塗膜表面
に４フッ化樹脂が移行し、着色塗膜側に耐熱性樹脂が配
向した２層構造をもっていることが確認される。塗膜表
面への４フッ化樹脂の移行は、表面張力の小さな４フッ
化樹脂が熱力学的に安定な形態を採ることに依る。しか
し、断面構造の詳細な調査結果から、２コート２ベーク
で形成された塗膜のように明確な２層構造をもつもので
はなく、上層と下層との界面が大きくうねり、部分的に
は耐熱性樹脂中に４フッ化樹脂が浮かんだ海島構造にな
っていることが判った。また、塗膜の表面近傍では、一
部、４フッ化樹脂からなる層が薄く、直下に耐熱性樹脂
層が存在する部分も検出される。この観察結果は、均一
な４フッ化樹脂層が形成されると非粘着耐久性が発現さ
れることを示唆している。Next, the cause of poor non-adhesive durability of a heat-resistant non-adhesive precoated steel sheet conventionally used for a stove type was investigated. The heat-resistant and non-adhesive coating film formed on the surface of this type of steel sheet shows that tetrafluoride resin migrates to the coating film surface, Is confirmed to have a two-layer structure in which the heat-resistant resin is oriented. The transfer of the tetrafluoride resin to the surface of the coating film is based on the fact that the tetrafluoride resin having a small surface tension takes a thermodynamically stable form. However, from the detailed investigation results of the cross-sectional structure, it does not have a clear two-layer structure like a coating film formed by two coats and two bake, and the interface between the upper layer and the lower layer undulates, and the heat resistance is partially high. It has been found that the resin has a sea-island structure in which the tetrafluoride resin is suspended in the conductive resin. Further, in the vicinity of the surface of the coating film, a part of the layer made of tetrafluororesin is thin, and a part in which the heat-resistant resin layer exists immediately below is also detected. This observation result suggests that a non-adhesive durability is exhibited when a uniform tetrafluoride resin layer is formed.
【００１１】４フッ化樹脂層の均一膜化には、耐熱非粘
着塗膜から顔料を除去すること、４フッ化樹脂として溶
融可能なＰＦＡを使用することが考えられる。塗膜に含
まれている顔料は、４フッ化樹脂の表面移行を阻害する
虞れがある。そこで、顔料を含まない樹脂で耐熱非粘着
塗膜を形成し、透明耐熱非粘着層を形成する場合には着
色塗膜で呈色することを検討した。非粘着耐久性は、顔
料無添加により若干向上したが、１０回に満たない繰返
し回数であった。塗膜構造を観察したところ、顔料無添
加により４フッ化樹脂が均一化する傾向は窺がわれた
が、十分な均一化が得られなかった。In order to make the tetrafluoride resin layer uniform, it is conceivable to remove the pigment from the heat-resistant and non-adhesive coating film, or to use a meltable PFA as the tetrafluoride resin. The pigment contained in the coating film may hinder the migration of the tetrafluoride resin to the surface. Therefore, it was studied to form a heat-resistant and non-adhesive coating with a resin containing no pigment, and to form a color with a colored coating when forming a transparent heat-resistant and non-adhesive layer. The non-adhesive durability was slightly improved by the addition of no pigment, but the number of repetitions was less than 10 times. When the structure of the coating film was observed, it was found that the tetrafluoride resin tended to be uniform when no pigment was added, but sufficient uniformity could not be obtained.
【００１２】次いで、顔料無添加に併せＰＦＡを４フッ
化樹脂として使用した。得られた塗膜は、２コート２ベ
ークと見間違うほどの明瞭な２層構造をもっており、４
フッ化樹脂層が十分に均一化されていた。この断面構造
は、ＰＦＡの溶融流動に起因するものと考えられる。と
ころが、非粘着耐久性を調査したところ、繰返し回数が
１０回に満たなかった。すなわち、単に４フッ化樹脂層
を均一化するだけでは、ＰＦＡラミネート鋼板にみられ
る優れた非粘着耐久性が得られないことを示す。更に、
顔料無添加で４フッ化樹脂としてＰＦＡを用いた耐熱非
粘着塗膜について詳細に検討した。塗膜表面を走査型電
子顕微鏡で観察したところ、ＰＦＡが溶融流動可能であ
るものの比較的荒れた塗膜表面になっていた。塗膜表面
の観察結果は、６０度反射で表面光沢が１０前後と低い
ことに良く対応している。Next, PFA was used as a tetrafluoride resin together with no pigment added. The resulting coating film had a clear two-layer structure that was mistaken for two coats and two bake.
The fluorinated resin layer was sufficiently uniform. This cross-sectional structure is considered to be caused by the melt flow of PFA. However, when the non-adhesive durability was investigated, the number of repetitions was less than 10. That is, it is shown that simply making the tetrafluoride resin layer uniform does not provide the excellent non-adhesive durability seen in the PFA laminated steel sheet. Furthermore,
A heat-resistant and non-adhesive coating film using PFA as a tetrafluoride resin without adding a pigment was examined in detail. When the coating film surface was observed with a scanning electron microscope, it was found that the PFA could be melted and flowed, but the coating film surface was relatively rough. The observation result of the coating film surface well corresponds to the low surface gloss of about 10 at 60 degree reflection.
【００１３】次いで、非粘着耐久試験の過程で、焦付き
を生じさせない汚染因子の容易な除去が困難になり始め
た段階で、塗膜の表面形態を同様に観察したところ、汚
染因子が焦げ付き始めた部位で耐熱非粘着塗膜の表面一
部が欠落していることが検出された。この観察結果か
ら、ＰＦＡの部分的な欠落により、汚染因子の焦付きが
生じることが判った。ＰＦＡの欠落は、ＰＦＡの粒子形
態を制御することにより抑制できる。塗膜に添加される
ＰＦＡは、通常、懸濁重合法で調製されている。懸濁重
合では、水中に懸濁しているＰＦＡが重合し、液滴が相
互に衝突して合体することから、平均粒径が数μｍの異
形粒子になる。数μｍの平均粒径は、塗料製造上では比
較的取り扱い易い粒径であるが、異形粒子に起因する塗
膜の欠陥等によって欠落し易い。Next, in the process of the non-adhesion durability test, when it became difficult to easily remove the contaminants that did not cause scorching, the surface morphology of the coating film was similarly observed. It was detected that part of the surface of the heat-resistant and non-adhesive coating film was missing at the site where the heat-resistant and non-adhesive coating film was missing. From this observation result, it was found that the partial loss of PFA resulted in the burning of contaminants. Lack of PFA can be suppressed by controlling the particle morphology of PFA. PFA to be added to a coating film is usually prepared by a suspension polymerization method. In suspension polymerization, PFA suspended in water is polymerized, and droplets collide with each other and coalesce, resulting in irregular shaped particles having an average particle size of several μm. The average particle size of several μm is a particle size that is relatively easy to handle in the production of paint, but is likely to be missing due to defects in the coating film caused by irregular shaped particles.
【００１４】そこで、本発明においては、乳化重合法で
調製したＰＦＡを使用する。乳化重合では、ミセルの中
でのみ重合反応が生じるため、ミセルの形態、換言すれ
ば球形を維持したままでＰＦＡ粒子が成長する。その結
果、球形の樹脂粒子が得られる。乳化重合法で調製され
た平均粒径０．０５〜１μｍのＰＦＡ樹脂粒子を耐熱性
樹脂に配合するとき、非粘着耐久性に優れた塗膜が形成
される。優れた非粘着耐久性は、耐熱非粘着塗膜の上層
を形成するＰＦＡ層が最密充填形態を採り、ＰＦＡの溶
融流動が僅かに生じるだけで緻密で健全な塗膜が形成さ
れる結果と推察される。具体的には、繰返し回数１０
回，更には２０回を超える優れた非粘着耐久性を呈す
る。Therefore, in the present invention, PFA prepared by an emulsion polymerization method is used. In emulsion polymerization, a polymerization reaction occurs only in micelles, so that PFA particles grow while maintaining the micelle morphology, in other words, a spherical shape. As a result, spherical resin particles are obtained. When a PFA resin particle having an average particle size of 0.05 to 1 μm prepared by an emulsion polymerization method is mixed with a heat-resistant resin, a coating film having excellent non-adhesive durability is formed. Excellent non-adhesive durability is due to the fact that the PFA layer which forms the upper layer of the heat-resistant non-adhesive coating adopts a close-packed form, and a dense and sound coating is formed only by a slight melt flow of PFA. Inferred. Specifically, the number of repetitions 10
And excellent non-adhesive durability more than 20 times.
【００１５】最密充填形態を採る塗膜を形成する上で
は、ＰＦＡ樹脂粒子の平均粒径を０．０５〜１μｍの範
囲に調整することが必要である。ＰＦＡ樹脂粒子の粒径
は、重合開始剤，界面活性剤濃度等の重合条件によって
調整される。平均粒径が０．０５μｍ未満では、塗料化
の際にチクソトロピー性が高くなり過ぎ、ロールコート
法で鋼板表面への塗装が困難になる。逆に１μｍを超え
る平均粒径では、最密充填形態での空隙が大きくなり過
ぎ、非粘着耐久性が低下する傾向がみられる。これに対
し、従来の懸濁重合で調製したＰＦＡ樹脂粒子は、異形
粒子であるため最密充填形態を採れず、溶融流動しても
緻密な塗膜が形成されない。緻密さ，健全さに欠ける塗
膜がＰＦＡの部分的な欠落を発生させ、汚染因子の焦付
きになるものと推察される。In order to form a coating film in a close-packed form, it is necessary to adjust the average particle size of the PFA resin particles to a range of 0.05 to 1 μm. The particle size of the PFA resin particles is adjusted by polymerization conditions such as a polymerization initiator and a surfactant concentration. When the average particle size is less than 0.05 μm, the thixotropy becomes excessively high during coating, and it becomes difficult to coat the steel sheet surface by the roll coating method. Conversely, if the average particle size exceeds 1 μm, the voids in the close-packed form tend to be too large, and the non-adhesive durability tends to decrease. On the other hand, PFA resin particles prepared by conventional suspension polymerization are irregular-shaped particles, so that they cannot take the form of close packing, and do not form a dense coating film even when melted and flowed. It is presumed that the coating film lacking in denseness and soundness causes partial loss of PFA, which may cause the contamination factor to be burned.
【００１６】本発明に従って塗装される鋼板としては、
必要に応じてリン酸塩処理、塗布型クロメート処理等を
施した５５％Ａｌ−Ｚｎめっき鋼板、Ａｌめっき鋼板、
ステンレス鋼板等が使用される。まず、塗装原板に耐熱
性樹脂からなる着色塗料を塗布し、焼き付ける。着色塗
料の成分である耐熱性樹脂には、ポリエーテルスルホン
樹脂、ポリフェニルスルフィド樹脂、ポリアミドイミド
樹脂の少なくとも一種以上の樹脂が使用される。着色塗
料は、鋼板素地の隠蔽及び耐熱非粘着塗膜との組合せで
色調を付与するため、酸化チタン，カーボンブラック，
酸化クロム，酸化鉄等の耐熱性に優れた着色顔料が配合
される。必要に応じて防錆顔料、体質顔料等を配合して
も良い。透明な耐熱非粘着塗膜では、着色塗膜で色調及
び意匠外観を発現させるため、アルミナ粉等のメタリッ
ク顔料を配合して意匠性を向上させることもできる。The steel sheet coated according to the present invention includes:
55% Al-Zn plated steel sheet, Al plated steel sheet which has been subjected to phosphate treatment,
A stainless steel plate or the like is used. First, a colored paint made of a heat-resistant resin is applied to the original coating plate and baked. As the heat-resistant resin which is a component of the coloring paint, at least one kind of resin such as polyether sulfone resin, polyphenyl sulfide resin and polyamideimide resin is used. The coloring paint is used to cover the steel plate base and to provide a color tone in combination with the heat-resistant and non-adhesive coating film.
A coloring pigment excellent in heat resistance such as chromium oxide and iron oxide is blended. If necessary, a rust preventive pigment, an extender pigment and the like may be added. In the case of a transparent heat-resistant and non-adhesive coating film, a metallic pigment such as alumina powder can be blended to improve the design property in order to develop a color tone and a design appearance with a colored coating film.
【００１７】着色塗膜層は、乾燥塗膜厚さで２〜２０μ
ｍとなるように鋼板表面に塗布される。耐熱性樹脂を溶
剤に溶解した塗料をロールコート法，カーテンフロー法
等で鋼板に塗布し、含有する耐熱性樹脂の中で最も融点
の高い樹脂の融点を超える温度で焼き付ける。着色塗膜
の上面にポリエーテルスルホン樹脂，ポリフェニルスル
フィド樹脂，ポリアミドイミド樹脂の少なくとも１種以
上の耐熱性樹脂と乳化重合法で調製した平均粒径０．０
５〜１μｍのＰＦＡ粒子との混合物を主成分とする着色
又は透明耐熱非粘着塗膜を形成する。着色耐熱非粘着塗
膜の場合、必要な塗膜色調を付与するため酸化チタン，
カーボンブラック，酸化クロム，酸化鉄等の耐熱性に優
れた着色顔料，体質顔料等を配合する。また、意匠性向
上のためにアルミ粉等のメタリック顔料を配合しても良
い。The colored coating layer has a dry coating thickness of 2 to 20 μm.
m is applied to the steel sheet surface. A paint prepared by dissolving a heat-resistant resin in a solvent is applied to a steel sheet by a roll coating method, a curtain flow method, or the like, and baked at a temperature exceeding the melting point of the resin having the highest melting point among the heat-resistant resins contained therein. On the upper surface of the colored coating film, at least one kind of heat-resistant resin such as polyether sulfone resin, polyphenyl sulfide resin, and polyamide imide resin and an average particle size of 0.0 prepared by an emulsion polymerization method.
A colored or transparent heat-resistant and non-adhesive coating film containing a mixture of 5-1 μm PFA particles as a main component is formed. In the case of a colored heat-resistant and non-adhesive coating film, titanium oxide,
A coloring pigment with excellent heat resistance, such as carbon black, chromium oxide, and iron oxide, an extender pigment, and the like are blended. Further, a metallic pigment such as aluminum powder may be blended for improving the design.
【００１８】塗料に占めるフッ化樹脂の割合が高くなる
と、非粘着耐久性が向上する。しかし、塗料中の溶解成
分である耐熱性樹脂量が減少するため、塗料のロールコ
ート適性が低下し、硬度低下に起因した塗膜疵も発生し
易くなる。そこで、非粘着耐久性，塗膜硬度等の塗膜特
性と塗料特性とをバランスさせるため、耐熱性樹脂と乳
化重合ＰＦＡとの配合比を好ましくは４０：６０〜８
０：２０（更に好ましくは５０：５０〜７０：３０）の
範囲に設定する。耐熱非粘着塗膜は、乾燥塗膜厚さで２
〜２０μｍとなるように鋼板表面に塗布される。使用さ
れる塗料は、溶剤に溶解する耐熱性樹脂を含むためロー
ルコート法で塗布できるが、溶剤に溶解しない４フッ化
樹脂を含むためチクソトロピー性を呈する。したがっ
て、トップフィードフルリバース方式のロールコート法
による塗装が好ましい。塗布された塗料は、塗料に含ま
れている耐熱性樹脂及びＰＦＡの中で最も融点の高い樹
脂の融点を超える温度で焼き付けられる。When the proportion of the fluorinated resin in the paint increases, the non-adhesive durability is improved. However, since the amount of the heat-resistant resin, which is a dissolved component in the coating material, is reduced, the suitability of the coating material for roll coating is reduced, and a coating film flaw due to a decrease in hardness is likely to occur. Therefore, in order to balance coating properties such as non-adhesive durability and coating hardness with coating properties, the mixing ratio of the heat-resistant resin to the emulsion-polymerized PFA is preferably from 40:60 to 8%.
0:20 (more preferably 50:50 to 70:30). The heat-resistant and non-adhesive coating has a dry coating thickness of 2
It is applied to the surface of the steel sheet so as to have a thickness of about 20 μm. The paint to be used can be applied by a roll coating method because it contains a heat-resistant resin that dissolves in a solvent, but exhibits thixotropic properties because it contains a tetrafluoride resin that does not dissolve in a solvent. Therefore, coating by a roll coating method of a top feed full reverse system is preferable. The applied paint is baked at a temperature exceeding the melting point of the resin having the highest melting point among the heat-resistant resin and PFA contained in the paint.
【００１９】印刷意匠を組み合わせた塗装では、耐熱性
着色塗装が施された鋼板に耐熱性印刷インキ層をグラビ
アオフセット法で印刷する。グラビアオフセット印刷に
はプレコート鋼板製造用の連続塗装設備を使用し、ロー
ルコーターのアプリケーターロールをオフセットロール
に置き換え、グラビアロールを配置するだけで必要な製
造ラインが構築される。その結果、高価な印刷ＰＦＡフ
ィルムを使用する必要がなくなり、鋼板に印刷ＰＦＡフ
ィルムを十分な接着性で積層するために必要で煩雑な処
理が省略される。したがって、低い製造コストで印刷意
匠を付けた耐熱非粘着プレコート鋼板が安価かつ簡便に
製造できる。In the coating in which the printing design is combined, a heat-resistant printing ink layer is printed on a steel sheet on which a heat-resistant coloring coating has been applied by a gravure offset method. For gravure offset printing, continuous coating equipment for the production of precoated steel sheets is used, the applicator roll of the roll coater is replaced with offset rolls, and the necessary production line is constructed simply by placing gravure rolls. As a result, it is not necessary to use an expensive printed PFA film, and complicated and necessary processing for laminating the printed PFA film on the steel plate with sufficient adhesiveness is omitted. Therefore, a heat-resistant and non-adhesive precoated steel sheet provided with a printing design at low manufacturing cost can be manufactured inexpensively and easily.
【００２０】グラビアオフセット印刷に使用される耐熱
性印刷インキは、ポリテトラフルオロエチレン樹脂，パ
ーフルオロアルキルビニルエーテル−テトラフルオロエ
チレン共重合体の少なくとも１種以上のフッ素樹脂とア
クリル樹脂，ポリウレタン樹脂，ポリエステル樹脂の少
なくとも１種以上の水溶性又は水分散性樹脂との混合物
をベースとする水性印刷インキ組成物である。印刷イン
キの一成分である４フッ化樹脂は顔料の分散性が悪く、
４フッ化樹脂単独では適正なグラビアオフセット印刷性
が得られない、この点、アクリル樹脂，ポリウレタン樹
脂，ポリエステル樹脂の少なくとも１種以上の水溶性又
は水分散性樹脂を混合してインキ化することによって顔
料の分散性が格段に改善され、優れたグラビアオフセッ
ト印刷適性を得ることができる。４フッ化樹脂と水溶性
又は水分散性樹脂との配合比は、水溶性又は水分散性樹
脂の量が増加するほど耐熱性が低下するため、重量比で
９９：１〜９５：５の範囲に調整することが好ましい。The heat-resistant printing ink used for gravure offset printing includes at least one kind of fluororesin such as polytetrafluoroethylene resin, perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer, acrylic resin, polyurethane resin and polyester resin. An aqueous printing ink composition based on a mixture with at least one water-soluble or water-dispersible resin. Tetrafluoride resin, a component of printing ink, has poor pigment dispersibility,
Proper gravure offset printability cannot be obtained with tetrafluororesin alone. In this regard, at least one water-soluble or water-dispersible resin of acrylic resin, polyurethane resin, or polyester resin is mixed to form an ink. The dispersibility of the pigment is significantly improved, and excellent gravure offset printing suitability can be obtained. The mixing ratio of the tetrafluororesin to the water-soluble or water-dispersible resin is in the range of 99: 1 to 95: 5 by weight, because the heat resistance decreases as the amount of the water-soluble or water-dispersible resin increases. It is preferable to adjust to.
【００２１】４フッ化樹脂と水溶性又は水分散性樹脂と
を混合した樹脂組成物に、酸化チタン，カーボンブラッ
ク，酸化クロム，酸化鉄等の耐熱性が良好な顔料を分散
させ、必要に応じて顔料分散剤等の添加剤を用いてイン
キ化する。調製されたインキは、意匠性を考慮して通常
０．５〜１０μｍの厚みで着色塗膜表面の一部又は全面
にグラビアオフセット印刷される。印刷後に乾燥、必要
に応じて焼き付け処理する。A pigment having good heat resistance such as titanium oxide, carbon black, chromium oxide or iron oxide is dispersed in a resin composition obtained by mixing a tetrafluoride resin and a water-soluble or water-dispersible resin. To form an ink using additives such as a pigment dispersant. The prepared ink is usually gravure offset printed with a thickness of 0.5 to 10 μm on a part or the entire surface of the colored coating film in consideration of design properties. After printing, it is dried and, if necessary, baked.
【００２２】耐熱性印刷インキ層の上に耐熱性樹脂を主
成分とする透明塗膜が設けられる。耐熱性樹脂として
は、ポリエーテルスルホン樹脂，ポリフェニルスルフィ
ド樹脂，ポリアミドイミド樹脂の少なくとも１種以上の
樹脂が使用される。透明塗膜は、耐熱性印刷インキ中の
４フッ化樹脂と透明耐熱非粘着塗膜中の４フッ化樹脂と
を隔離する作用を呈する。透明塗膜は、その上に形成さ
れる透明耐熱非粘着塗膜と相俟って、着色塗膜及びグラ
ビアオフセット印刷による印刷意匠を外観上保護する作
用も呈することから、透明であることが要求される。た
だし、着色塗膜及び印刷柄を隠蔽しない限り、透明塗膜
の塗料に種々の添加剤が必要に応じて添加される。ま
た、塗料中に微量のアルミ粉，着色顔料等を配合するこ
とによって、着色塗膜及び印刷柄との組合せで意匠性を
向上させることも可能である。On the heat-resistant printing ink layer, a transparent coating mainly composed of a heat-resistant resin is provided. As the heat-resistant resin, at least one resin selected from the group consisting of polyethersulfone resin, polyphenylsulfide resin, and polyamideimide resin is used. The transparent coating has an effect of isolating the tetrafluoride resin in the heat-resistant printing ink from the tetrafluoride resin in the transparent heat-resistant non-adhesive coating. The transparent coating film is required to be transparent because it has the effect of protecting the appearance of the colored coating film and the printing design by gravure offset printing together with the transparent heat-resistant and non-adhesive coating film formed thereon. Is done. However, various additives are added as needed to the paint of the transparent coating as long as the coloring coating and the printed pattern are not hidden. Further, by blending a trace amount of aluminum powder, a coloring pigment or the like into the paint, it is also possible to improve the design property in combination with the colored coating film and the printed pattern.
【００２３】透明塗膜層は、乾燥塗膜厚さが１〜１０μ
ｍとなるように塗布される。耐熱性樹脂を溶剤に溶解し
た塗料をロールコート法，カーテンフロー法等で塗装
し、含有する耐熱性樹脂の中で最も融点の高い樹脂の融
点を超える温度で焼き付ける。透明塗膜の上面には、印
刷意匠性を組合せない場合と同様にして透明耐熱非粘着
塗膜が設けられる。すなわち、ポリエーテルスルホン樹
脂，ポリフェニルスルフィド樹脂，ポリアミドイミド樹
脂の少なくとも１種以上の耐熱性樹脂と乳化重合法で調
製した平均粒径０．０５〜１μｍのＰＦＡとの混合物を
主成分とする透明耐熱非粘着塗膜を透明塗膜の上に設け
る。この場合にもアルミ粉等のメタリック顔料を透明耐
熱非粘着塗膜に分散させ、印刷意匠性を更に向上させる
こともできる。The transparent coating layer has a dry coating thickness of 1 to 10 μm.
m. A paint obtained by dissolving a heat-resistant resin in a solvent is applied by a roll coating method, a curtain flow method, or the like, and baked at a temperature exceeding the melting point of the resin having the highest melting point among the heat-resistant resins contained therein. On the upper surface of the transparent coating film, a transparent heat-resistant and non-adhesive coating film is provided in the same manner as in the case where the printing design is not combined. That is, a transparent material mainly comprising a mixture of at least one kind of heat-resistant resin of polyether sulfone resin, polyphenyl sulfide resin and polyamide imide resin and PFA having an average particle size of 0.05 to 1 μm prepared by an emulsion polymerization method. A heat-resistant and non-adhesive coating is provided on the transparent coating. Also in this case, a metallic pigment such as aluminum powder can be dispersed in the transparent heat-resistant and non-adhesive coating film to further improve the print design.
【００２４】[0024]
【実施例】板厚０．４５ｍｍのＳＵＳ４３０ステンレス
鋼板を脱脂した後、塗布型クロメート処理を施し、実施
例１〜４及び比較例１０〜１３ではカーボンブラックを
配合した着色塗膜を乾燥膜厚８μｍでロールコートし、
実施例５〜９及び比較例１４〜１８ではカーボンブラッ
ク及びアルミ粉を配合した着色塗膜を乾燥膜厚１２μｍ
でロールコートし、何れも着色塗膜も３００℃で焼き付
けた。形成された着色塗膜の上に、表１及び２に示す耐
熱非粘着塗膜をロールコートし、４００℃で焼付けた。
なお、実施例１〜４及び比較例１０〜１３では、カーボ
ンブラック及びアルミ粉を配合した乾燥膜厚１２μｍの
耐熱非粘着塗膜、実施例５〜９及び比較例１４〜１８で
は乾燥膜厚５μｍの透明耐熱非粘着塗膜を形成した。ま
た、耐熱非粘着塗膜には、何れも耐熱性樹脂と４フッ化
樹脂とを重量比５０：５０で配合した塗料を使用した。
なお、実施例７〜９及び比較例１６〜１８では、着色塗
膜をロールコートして焼き付けた後、酸化チタンを配合
した耐熱性印刷インキ（ＰＴＦＥ／水性ポリウレタン樹
脂＝９５重量部／５重量部）を表面被覆率８５％でグラ
ビアオフセット印刷し、２００℃で乾燥し、透明塗膜
（ＰＥＳ）を乾燥膜厚３μｍでロールコートして３００
℃で焼き付け、その上に透明耐熱非粘着塗膜を設けた。EXAMPLE After a SUS430 stainless steel plate having a thickness of 0.45 mm was degreased, it was subjected to a coating type chromate treatment. In Examples 1 to 4 and Comparative Examples 10 to 13, a colored coating film containing carbon black was dried to a thickness of 8 μm. Roll coat with
In Examples 5 to 9 and Comparative Examples 14 to 18, a colored coating film containing carbon black and aluminum powder was dried at a thickness of 12 μm.
, And each of the colored coating films was baked at 300 ° C. The heat-resistant and non-adhesive coating films shown in Tables 1 and 2 were roll-coated on the formed colored coating films and baked at 400 ° C.
In Examples 1 to 4 and Comparative Examples 10 to 13, a heat-resistant and non-adhesive coating film having a dry film thickness of 12 μm containing carbon black and aluminum powder was used. In Examples 5 to 9 and Comparative Examples 14 to 18, a dry film thickness of 5 μm was used. Was formed. As the heat-resistant and non-adhesive coating film, a coating material in which a heat-resistant resin and a tetrafluoride resin were mixed at a weight ratio of 50:50 was used.
In Examples 7 to 9 and Comparative Examples 16 to 18, a heat-resistant printing ink (PTFE / aqueous polyurethane resin = 95 parts by weight / 5 parts by weight) containing titanium oxide after roll coating and baking the colored coating film was used. ) Is gravure offset printed at a surface coverage of 85%, dried at 200 ° C., and roll-coated with a transparent coating film (PES) at a dry film thickness of 3 μm to obtain
C., and a transparent heat-resistant and non-adhesive coating was provided thereon.
【００２５】使用した各樹脂の成分及び得られた塗膜の
特性を表１（本発明例）及び表２（比較例）に示す。表
中、ＰＥＳはポリエーテルスルホン樹脂，ＰＰＳはポリ
フェニレンスルフィド樹脂，ＰＡＩはポリアミドイミド
樹脂，ＰＴＦＥはポリテトラフルオロエチレン樹脂，Ｐ
ＦＡはパーフルオロアルキルビニルエーテル−テトラフ
ルオロエチレン共重合体を示す。塗膜密着性は基盤目密
着性試験で、耐熱性は３００℃に３００時間加熱した後
の基盤目密着性試験で調査した。非粘着耐久性は、醤油
／砂糖／卵＝１／１／１の混合液及び牛乳を塗膜表面に
０．５ｍｌ滴下し、２６０℃の加熱炉に１時間入れ、十
分に冷却した後で塗膜表面に対する醤油／砂糖／卵＝１
／１／１の混合液及び牛乳の焦げつき状況により判断し
た。そして、醤油／砂糖／卵＝１／１／１の混合液及び
牛乳が焦げ付くことなく除去できる回数で評価した。シ
ステムキッチンタイプでは、１０回以上の繰返し除去が
可能なことを非粘着耐久性有無の判断基準とした。Table 1 (Example of the present invention) and Table 2 (Comparative Example) show the components of each resin used and the properties of the obtained coating film. In the table, PES is a polyether sulfone resin, PPS is a polyphenylene sulfide resin, PAI is a polyamideimide resin, PTFE is a polytetrafluoroethylene resin, P
FA represents a perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer. The coating film adhesion was examined by a substrate adhesion test, and the heat resistance was examined by a substrate adhesion test after heating at 300 ° C. for 300 hours. For non-adhesive durability, 0.5 ml of a mixture of soy sauce / sugar / egg and milk was dropped on the surface of the coating film, placed in a heating furnace at 260 ° C. for 1 hour, cooled sufficiently, and then coated. Soy sauce / sugar / egg for membrane surface = 1
Judgment was made based on the state of scorching of the mixed solution of / 1/1 and milk. Then, the evaluation was made by the number of times that the mixture of soy sauce / sugar / egg = 1/1/1 and milk could be removed without burning. In the system kitchen type, the ability to remove repeatedly 10 or more times was used as a criterion for determining the non-adhesive durability.
【００２６】表１から明らかなように、着色塗膜及び耐
熱非粘着塗膜が本発明で規定した条件を満足するもので
は、外観，塗膜密着性，耐熱性，非粘着耐久性の何れも
優れていた。これに対し、着色塗膜及び耐熱非粘着塗膜
が本発明で規定した条件を満足しないと、表２に示すよ
うに、得られた塗装鋼板は、外観，塗膜密着性，耐熱
性，非粘着耐久性の何れか一つ又は複数が劣っていた。As is clear from Table 1, when the colored coating film and the heat-resistant and non-adhesive coating film satisfy the conditions specified in the present invention, all of the appearance, coating film adhesion, heat resistance and non-adhesive durability are obtained. It was excellent. On the other hand, when the colored coating film and the heat-resistant and non-adhesive coating film do not satisfy the conditions specified in the present invention, as shown in Table 2, the obtained coated steel sheet has an appearance, coating film adhesion, heat resistance, One or more of the adhesive durability was inferior.
【００２７】 [0027]
【００２８】 [0028]
【００２９】[0029]
【発明の効果】以上に説明したように、本発明の耐熱非
粘着プレコート鋼板は、塗膜に耐熱非粘着性を付与する
４フッ化樹脂成分として乳化重合法で調製された平均粒
径０．０５〜１μｍのＰＦＡを使用しているため、汚染
因子の焦付きを生じさせる欠陥分がなく、緻密で均一な
４フッ化樹脂層が形成される。したがって、得られたプ
レコート鋼板は、４フッ化樹脂本来の非粘着性を長期間
にわたって維持し、システムキッチンタイプのガステー
ブル天板，食品調理器具，加熱調理器具等の厨房機器は
勿論、優れた非粘着耐久性や意匠性を活用して各種内装
材，ケーシング材等として広範な分野に使用される。As described above, the heat-resistant and non-adhesive precoated steel sheet of the present invention has an average particle diameter of 0.1 as prepared by an emulsion polymerization method as a tetrafluoride resin component for imparting heat-resistant and non-adhesive properties to a coating film. Since PFA with a thickness of 0.5 to 1 μm is used, a dense and uniform tetrafluoride resin layer is formed without any defect that causes the deposition of a contaminant. Therefore, the obtained pre-coated steel sheet maintains the original non-adhesiveness of the tetrafluoride resin for a long period of time, and is excellent in kitchen appliances such as a system kitchen type gas table top plate, food cooking utensils, heating cooking utensils and the like. It is used in a wide range of fields as various interior materials, casing materials, etc., utilizing its non-adhesive durability and design.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ３２Ｂ 27/00 Ｂ３２Ｂ 27/00 Ａ 27/20 27/20 Ａ 27/30 27/30 Ｄ 27/34 27/34 Ｃ０９Ｄ 127/18 Ｃ０９Ｄ 127/18 129/00 129/00 // Ａ４７Ｊ 36/02 Ａ４７Ｊ 36/02 Ｂ Ｆ２４Ｃ 15/10 Ｆ２４Ｃ 15/10 Ｂ (72)発明者 輿石 謙二 千葉県市川市高谷新町７番１号 日新製 鋼株式会社技術研究所内 (56)参考文献 特開 平10−264296（ＪＰ，Ａ) 特開 平10−264295（ＪＰ，Ａ) 特開 平10−86274（ＪＰ，Ａ) 特開 平２−108531（ＪＰ，Ａ) 特開 平２−89633（ＪＰ，Ａ) 特開 平８−208931（ＪＰ，Ａ) 特開 平９−71747（ＪＰ，Ａ) 特開 平８−113756（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 15/08 B05D 7/00 - 7/24 C09D 127/00 - 127/24 Continued on the front page (51) Int.Cl. 7 Identification code FI B32B 27/00 B32B 27/00 A 27/20 27/20 A 27/30 27/30 D 27/34 27/34 C09D 127/18 C09D 127 / 18 129/00 129/00 // A47J 36/02 A47J 36/02 B F24C 15/10 F24C 15/10 B (72) Inventor Kenji Koshiishi 7-1 Takayashinmachi, Ichikawa-shi, Chiba Prefecture Nisshin Steel Co., Ltd. (56) References JP-A-10-264296 (JP, A) JP-A-10-264295 (JP, A) JP-A-10-86274 (JP, A) JP-A-2-108531 (JP) JP-A-2-89633 (JP, A) JP-A-8-208931 (JP, A) JP-A-9-71747 (JP, A) JP-A-8-113756 (JP, A) (58) Surveyed field (Int.Cl. 7 , DB name) B32B 15/08 B05D 7 /00-7/24 C09D 127/00-127/24
Claims (2)
ルスルフィド樹脂，ポリアミドイミド樹脂の少なくとも
１種の耐熱性樹脂を主成分とする着色塗膜が鋼板表面に
形成され、ポリエーテルスルホン樹脂，ポリフェニルス
ルフィド樹脂，ポリアミドイミド樹脂の少なくとも１種
以上の耐熱性樹脂と乳化重合法で製造した平均粒径０．
０５〜１μｍのパーフルオロアルキルビニルエーテル−
テトラフルオロエチレン共重合体を主成分とするフッ素
樹脂との混合物を主成分とする着色又は透明耐熱非粘着
塗膜が前記着色塗膜の上に形成されている耐熱非粘着プ
レコート鋼板。1. A colored coating mainly composed of at least one heat-resistant resin such as a polyether sulfone resin, a polyphenyl sulfide resin and a polyamide imide resin is formed on the surface of a steel sheet, and the polyether sulfone resin and the polyphenyl sulfide resin are formed. , A polyamideimide resin and at least one heat-resistant resin and an average particle size of 0.1 produced by an emulsion polymerization method.
0.5-1 μm perfluoroalkyl vinyl ether
A heat-resistant and non-adhesive precoated steel sheet, wherein a colored or transparent heat-resistant and non-adhesive coating mainly composed of a mixture with a fluororesin mainly containing a tetrafluoroethylene copolymer is formed on the colored coating.
ルスルフィド樹脂，ポリアミドイミド樹脂の少なくとも
１種の耐熱性樹脂を主成分とする着色塗膜が鋼板表面に
形成され、ポリテトラフルオロエチレン樹脂，パーフル
オロアルキルビニルエーテル−テトラフルオロエチレン
共重合体の少なくとも１種以上のフッ素樹脂とアクリル
樹脂，ポリウレタン樹脂，ポリエステル樹脂の少なくと
も１種以上の水溶性又は水分散性樹脂との混合物をベー
スとする耐熱性印刷インキ層が前記着色塗膜の上に一部
又は全面に形成され、次いでポリエーテルスルホン樹
脂，ポリフェニルスルフィド樹脂，ポリアミドイミド樹
脂の少なくとも１種以上の耐熱性樹脂を主成分とする透
明塗膜が前記耐熱印刷インキ層の上に形成され、更に、
ポリエーテルスルホン樹脂，ポリフェニルスルフィド樹
脂，ポリアミドイミド樹脂の少なくとも１種以上の耐熱
性樹脂と乳化重合法で製造した平均粒径０．０５〜１μ
ｍのパーフルオロアルキルビニルエーテル−テトラフル
オロエチレン共重合体を主成分とするフッ素樹脂との混
合物を主成分とする透明耐熱非粘着塗膜が前記透明塗膜
の上に形成されている耐熱非粘着プレコート鋼板。2. A colored coating mainly composed of at least one heat-resistant resin such as a polyether sulfone resin, a polyphenyl sulfide resin, or a polyamide imide resin is formed on the surface of a steel sheet, and a polytetrafluoroethylene resin, a perfluoroalkyl Heat-resistant printing ink layer based on a mixture of at least one fluororesin of vinyl ether-tetrafluoroethylene copolymer and at least one water-soluble or water-dispersible resin of acrylic resin, polyurethane resin and polyester resin Is formed partially or entirely on the colored coating film, and then a transparent coating film containing as a main component at least one heat-resistant resin of a polyether sulfone resin, a polyphenyl sulfide resin, or a polyamideimide resin is formed. Formed on the printing ink layer,
Polyethersulfone resin, polyphenyl sulfide resin, polyamideimide resin and at least one heat-resistant resin and an average particle size of 0.05 to 1 μm produced by an emulsion polymerization method.
m is a heat-resistant and non-adhesive precoat in which a transparent heat-resistant and non-adhesive coating mainly composed of a mixture with a fluororesin whose main component is a perfluoroalkylvinyl ether-tetrafluoroethylene copolymer is formed on the transparent coating steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2741499A JP3293084B2 (en) | 1999-02-04 | 1999-02-04 | Heat-resistant non-adhesive pre-coated steel sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2741499A JP3293084B2 (en) | 1999-02-04 | 1999-02-04 | Heat-resistant non-adhesive pre-coated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000218731A JP2000218731A (en) | 2000-08-08 |
| JP3293084B2 true JP3293084B2 (en) | 2002-06-17 |
Family
ID=12220443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2741499A Expired - Lifetime JP3293084B2 (en) | 1999-02-04 | 1999-02-04 | Heat-resistant non-adhesive pre-coated steel sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3293084B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003062930A (en) * | 2001-08-30 | 2003-03-05 | Nisshin Steel Co Ltd | Non-tacky precoating metal sheet |
| JP4667852B2 (en) * | 2004-12-17 | 2011-04-13 | 日新製鋼株式会社 | Heat-resistant non-adhesive pre-coated metal plate and manufacturing method thereof |
| US20070036900A1 (en) * | 2005-08-12 | 2007-02-15 | Yuqing Liu | Process for improving the corrosion resistance of a non-stick coating on a substrate |
| EP1960457B1 (en) * | 2005-12-05 | 2012-04-11 | Solvay SA | Process for dispersing solid particles in particulate polymers |
| JP6316317B2 (en) * | 2013-12-26 | 2018-04-25 | 阪本 順 | LAMINATE MANUFACTURING METHOD AND LAMINATE MANUFACTURING APPARATUS |
| KR102021683B1 (en) * | 2015-03-13 | 2019-09-16 | 다이킨 고교 가부시키가이샤 | Paint Compositions and Coated Articles |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0289633A (en) * | 1988-05-20 | 1990-03-29 | Sumitomo Electric Ind Ltd | Fluororesin covered matter |
| JPH02108531A (en) * | 1988-10-19 | 1990-04-20 | Nippon Steel Corp | Coated metal sheet excellent in nonadhesive property and far infrared ray radiation property |
| JPH08113756A (en) * | 1994-10-14 | 1996-05-07 | Du Pont Mitsui Fluorochem Co Ltd | Production of article having surface of water-repellent fluorine-containing resin |
| JP3728702B2 (en) * | 1995-02-02 | 2005-12-21 | オカモト株式会社 | Method for producing fluororesin film laminated steel sheet with adhesive and printing ink and printed pattern |
| JPH0971747A (en) * | 1995-07-03 | 1997-03-18 | Zojirushi Corp | Printing ink and print structure formed therewith |
| JP3351995B2 (en) * | 1996-07-22 | 2002-12-03 | 日新製鋼株式会社 | Heat-resistant non-adhesive design steel sheet and method for producing the same |
| JPH10264295A (en) * | 1997-03-27 | 1998-10-06 | Nisshin Steel Co Ltd | Heat resistant non-adhesive designed steel sheet and its manufacture |
| JPH10264296A (en) * | 1997-03-27 | 1998-10-06 | Nisshin Steel Co Ltd | Heat resistant designed steel sheet and its manufacture |
-
1999
- 1999-02-04 JP JP2741499A patent/JP3293084B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000218731A (en) | 2000-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR960015755B1 (en) | Coated substrate with a multi-layer non-stick coating | |
| EP2001949B1 (en) | Non-stick finish | |
| US7695807B2 (en) | Non-stick finish | |
| US5880205A (en) | Universal primer for non-stick finish | |
| US20070036900A1 (en) | Process for improving the corrosion resistance of a non-stick coating on a substrate | |
| KR100346796B1 (en) | fluorin resin coated product and process for producing the same | |
| JPS632306B2 (en) | ||
| JP6387153B2 (en) | Surface coating method showing three-dimensional pattern texture | |
| JPWO2011048965A1 (en) | Coated article manufacturing method and coated article | |
| US11963633B2 (en) | Cooking utensil | |
| CN113873924A (en) | Method for manufacturing cookware comprising thermochromic composite coating and cookware manufactured by the method | |
| CN110249012A (en) | Substrate coated with wear-resistant and scratch-resistant non-sticking lining | |
| JP2001218684A (en) | Member for cooking utensil and cooking utensil | |
| JP3293084B2 (en) | Heat-resistant non-adhesive pre-coated steel sheet | |
| JP3367508B2 (en) | Fluororesin coating and manufacturing method thereof | |
| WO1991002773A1 (en) | Non-stick coating system with thin undercoat of polyamide imide, polyarylene sulfide or polyether sulfone | |
| JPH08322732A (en) | Cooking pot | |
| WO1997039073A1 (en) | Universal primer for non-stick finish | |
| KR101805736B1 (en) | Surface Coating Method Having Improved Durability with Flouride Resin | |
| JP3351995B2 (en) | Heat-resistant non-adhesive design steel sheet and method for producing the same | |
| JP2001219122A (en) | Article with fluororesin coating film and manufacturing method there for | |
| WO2020110515A1 (en) | Coating composition and coated article | |
| JP3962153B2 (en) | Food heating processing equipment with improved antifouling properties | |
| JP2005262465A (en) | Heat-resistant non-tacky precoated metal sheet | |
| JP2000167977A (en) | Heat-resistant non-adhesive design steel plate and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20020312 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080405 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090405 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090405 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100405 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100405 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110405 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110405 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120405 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130405 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140405 Year of fee payment: 12 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |