JPH093660A - Porcelain enameled steel sheet and its production - Google Patents
Porcelain enameled steel sheet and its productionInfo
- Publication number
- JPH093660A JPH093660A JP17685795A JP17685795A JPH093660A JP H093660 A JPH093660 A JP H093660A JP 17685795 A JP17685795 A JP 17685795A JP 17685795 A JP17685795 A JP 17685795A JP H093660 A JPH093660 A JP H093660A
- Authority
- JP
- Japan
- Prior art keywords
- enamel
- steel sheet
- layer
- phase
- porcelain
- 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.)
- Withdrawn
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 47
- 239000010959 steel Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052573 porcelain Inorganic materials 0.000 title abstract 5
- 238000007747 plating Methods 0.000 claims abstract description 32
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 238000005275 alloying Methods 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 4
- 238000005246 galvanizing Methods 0.000 claims abstract description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 82
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 13
- 239000008397 galvanized steel Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000010304 firing Methods 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000000037 vitreous enamel Substances 0.000 abstract description 4
- 238000004534 enameling Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 57
- 239000000047 product Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 229910001000 nickel titanium Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Landscapes
- Coating With Molten Metal (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、密着性を改善したホー
ロー被覆鋼板及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a enamel coated steel sheet having improved adhesion and a method for producing the same.
【０００２】[0002]
【従来の技術】ホーロー製品は、流し台，洗面化粧台，
調理用レンジ等の家庭用品や外壁材，内壁材等の建築用
材料を始めとして広範な分野で使用されている。このホ
ーロー製品は、ガラス質のホーロー層を金属板上に形成
したものであるが、金属板とホーロー層との密着性を改
善するために煩雑なホーロー前処理や高温焼成が採用さ
れている。しかし、ホーロー前処理では廃液処理の問題
があり、高温焼成では製品に変形を発生させること等が
問題とされている。金属板として鋼板を使用したホーロ
ー鋼板では、アルカリ脱脂，酸洗，ニッケル置換処理等
のホーロー前処理後にホーロー掛けし、８００〜９００
℃で焼成している。この焼成によって鋼板とホーロー層
との界面にＦｅ−Ｎｉ−Ｔｉ系の中間層が形成され、ホ
ーロー層に密着性が付与される。なお、Ｔｉは、フリッ
ト成分である。2. Description of the Related Art Enamel products include sinks, vanities,
It is used in a wide range of fields including household products such as cooking stoves and building materials such as outer and inner wall materials. This enamel product has a vitreous enamel layer formed on a metal plate, but complicated enamel pretreatment and high temperature firing are employed to improve the adhesion between the metal plate and the enamel layer. However, the enamel pretreatment has a problem of waste liquid treatment, and the high temperature firing causes a problem such as deformation of the product. For enamel steel plates using steel plates as metal plates, enamel pre-treatment such as alkali degreasing, pickling, nickel substitution treatment, etc.
It is baked at ℃. By this firing, an Fe-Ni-Ti-based intermediate layer is formed at the interface between the steel plate and the enamel layer, and the enamel layer is provided with adhesion. Note that Ti is a frit component.
【０００３】[0003]
【発明が解決しようとする課題】しかし、ホーロー掛け
に先立つアルカリ脱脂，酸洗，ニッケル置換処理等の工
程で多量の廃液が発生する。そのため、廃液処理に多大
のコストがかかり、結果としてホーロー製品のコストを
上昇させる。また、高温で焼成することから、熱歪みに
よって鋼板が変形し易くなる。変形した部品を使用して
製品を組み立てるとき、変形を手作業によって矯正する
ことが要求される。熱歪みに起因する変形を抑制するた
めには、板厚が通常０．７〜０．９ｍｍ程度の厚板を使
用することが必要となり、製品重量が増加する。更に、
鋼板ホーローでは、焼成温度で非ホーロー面がスケール
化すること，鋼板自体の耐食性が不足すること等から、
常に鋼板の両面にホーロー層を形成することが必要とな
る。その結果、不要部に対してもホーロー掛けすること
になり、作業時間が長くなるばかりでなく、フリットの
消費量も多くなる。However, a large amount of waste liquid is generated in the steps of alkali degreasing, pickling, nickel substitution treatment, etc. prior to enamel application. Therefore, the waste liquid treatment requires a great deal of cost, resulting in an increase in the cost of the enamel product. Moreover, since the steel sheet is fired at a high temperature, the steel sheet is easily deformed by thermal strain. When assembling a product using deformed parts, it is required to correct the deformation manually. In order to suppress the deformation caused by thermal strain, it is necessary to use a thick plate having a plate thickness of usually 0.7 to 0.9 mm, which increases the product weight. Furthermore,
In the steel plate enamel, the non-enameled surface is scaled at the firing temperature, and the corrosion resistance of the steel plate itself is insufficient.
It is always necessary to form enamel layers on both sides of the steel sheet. As a result, an unnecessary portion is hung, which not only prolongs the working time but also increases the consumption of the frit.
【０００４】この点、溶融Ａｌめっき鋼板を原板とする
アルミめっきホーローでは、酸洗，ニッケル置換処理等
の化学的なホーロー前処理は必要とされない。しかし、
付着オイルの除去，アルミ層とホーロー層との密着性改
善等の観点から、アルミめっき表層の酸化皮膜を厚くす
るため、空焼きと称されるホーロー前処理が行われてい
る。すなわち、焼成温度と同程度の５５０〜６００℃で
５〜１０分間加熱する空焼きの後、冷却してホーロー掛
けし、再度５５０〜６００℃の温度に加熱して焼成す
る。そのため、空焼き，焼成と２度の加熱が必要とな
り、熱消費量が多くなる。また、焼成温度は、鋼板ホー
ローに比較して低く、熱歪みによる変形は少ないもの
の、鋼板の板厚が０．６ｍｍ以下になると変形が目立っ
てくる。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、鋼板表面に設けた亜鉛めっき層の合金
化度を調整することにより、従来のホーロー前処理を必
要とせず、しかもホーロー層の密着性を改善したホーロ
ー被覆鋼板を得ることを目的とする。In this respect, an aluminum-plated enamel using a hot-dip Al-plated steel sheet as a base plate does not require a chemical enamel pretreatment such as pickling and nickel replacement. But,
From the viewpoint of removing the adhered oil and improving the adhesion between the aluminum layer and the enamel layer, a enamel pretreatment called air baking is performed to thicken the oxide film on the aluminum plating surface layer. That is, after air-baking for 5 to 10 minutes at 550 to 600 ° C., which is about the same as the firing temperature, it is cooled, enameled, and again heated to a temperature of 550 to 600 ° C. and fired. Therefore, it is necessary to perform air baking and firing and heating twice, resulting in a large amount of heat consumption. Further, the firing temperature is lower than that of the steel plate enamel, and the deformation due to thermal strain is small, but the deformation becomes noticeable when the plate thickness of the steel plate is 0.6 mm or less. The present invention has been devised to solve such a problem, and by adjusting the alloying degree of the galvanized layer provided on the surface of the steel sheet, the conventional enamel pretreatment is not required, and the enamel is not required. The object is to obtain a enamel-coated steel sheet with improved layer adhesion.
【０００５】[0005]
【課題を解決するための手段】本発明のホーロー被覆鋼
板は、その目的を達成するため、溶融Ｚｎめっき直後の
加熱処理により表面までδ1 相及びζ相を成長させため
っき層をもち、該めっき層の片面又は両面にホーロー層
が形成されていることを特徴とする。このホーロー被覆
鋼板は、溶融亜鉛めっき直後の表面亜鉛層を加熱し、Ｆ
ｅ−Ｚｎ系金属間化合物のうちでδ1 相及びζ相をめっ
き層の表面まで成長させる合金化処理を施し、次いで合
金化亜鉛めっき鋼板のめっき層上の片面又は両面にホー
ロー層を形成することにより製造される。また、焼成温
度３５０〜５５０℃でホーローを焼き付けるとき、鋼板
の熱変形が抑制され、寸法精度の高いホーロー被覆鋼板
が得られる。In order to achieve the object, the enamel coated steel sheet of the present invention has a plating layer in which a δ 1 phase and a ζ phase are grown to the surface by heat treatment immediately after hot dip Zn plating. The enamel layer is formed on one side or both sides of the plating layer. This enamel-coated steel sheet heats the surface zinc layer immediately after hot dip galvanizing,
Among the e-Zn-based intermetallic compounds, an alloying treatment for growing the δ 1 phase and the ζ phase to the surface of the plated layer is performed, and then a enamel layer is formed on one side or both sides of the plated layer of the galvannealed steel sheet. It is manufactured by Further, when the enamel is baked at a firing temperature of 350 to 550 ° C., thermal deformation of the steel plate is suppressed and a enamel-coated steel plate with high dimensional accuracy can be obtained.
【０００６】[0006]
【作用】本発明者等は、従来の問題があるホーロー前処
理を必要とせず、優れたホーロー密着性を得る方法につ
いて種々調査検討した。その結果、溶融亜鉛めっき鋼板
をめっき直後に加熱し、亜鉛めっき層をＦｅ−Ｚｎ系合
金めっき層に変質させた合金化亜鉛めっき鋼板をホーロ
ー原板として使用するとき、ホーロー前処理なしでも優
れた密着性が得られることを見い出した。更に、低温焼
成用フリットを使用すると、熱歪みに起因する製品の変
形も抑制され、板厚が０．２〜０．５ｍｍ程度の薄鋼板
であってもホーロー原板として使用できることが判っ
た。合金化亜鉛めっき鋼板は、通常の亜鉛めっき鋼板を
めっき直後に加熱することによって亜鉛めっき層をＦｅ
−Ｚｎ系合金めっき層に変質させたものである。Ｆｅ−
Ｚｎ系合金としては、表１に示すようにΓ相（Ｆｅ5 Ｚ
ｎ21），δ1 相（ＦｅＺｎ7 ），ζ相（ＦｅＺｎ13），
η相（Ｚｎ）とよばれるものが存在する。本発明では、
これら金属間化合物のうち、亜鉛めっき層のＺｎ相をδ
1 相（ＦｅＺｎ7 ）及びζ相（ＦｅＺｎ13）に変質させ
たものである。このような合金化亜鉛めっき鋼板は、通
常の溶融亜鉛めっき鋼板の製造ラインにおいてめっき直
後の鋼板を加熱することにより連続的に製造される。合
金化Ｚｎめっき鋼板をホーロー用原板として用いる場
合、ホーロー密着性の点からは合金化度（換言すれば、
めっき層中のＦｅ濃度）を高め、表面祖度を大きくする
ことが有利である。反面、ホーロー用製品部材への成形
面からすると、過度に合金化度を高くするとめっき層が
パウダリングし、成形性が低下する。このようなことか
ら、ホーロー用部材の成形度合いによって異なるが、め
っき層中のＦｅ濃度７〜１５重量％程度の合金化度が好
ましい。このとき、加熱条件は、めっき層中のＦｅ濃度
を蛍光Ｘ線等で管理しながら連続的に制御することが好
ましい。The present inventors have conducted various investigations and investigations on a method of obtaining excellent enamel adhesion without the need for the enamel pretreatment which has the conventional problems. As a result, when the galvanized steel sheet is heated immediately after plating and the alloyed galvanized steel sheet in which the galvanized layer is transformed into the Fe-Zn alloy plated layer is used as the enamel base plate, excellent adhesion is obtained without the enamel pretreatment. It has been found that sex can be obtained. Further, it has been found that the use of the frit for low temperature firing suppresses the deformation of the product due to the thermal strain, and even a thin steel plate having a plate thickness of about 0.2 to 0.5 mm can be used as a enamel plate. The galvannealed steel sheet is formed by heating a normal galvanized steel sheet immediately after plating so that the galvanized layer becomes Fe-free.
-Zn-based alloy plating layer is transformed. Fe-
As a Zn-based alloy, as shown in Table 1, the Γ phase (Fe 5 Z
n 21 ), δ 1 phase (FeZn 7 ), ζ phase (FeZn 13 ),
There is a so-called η phase (Zn). In the present invention,
Of these intermetallic compounds, the Zn phase of the zinc plating layer
It is one that has been transformed into one phase (FeZn 7 ) and ζ phase (FeZn 13 ). Such an alloyed galvanized steel sheet is continuously manufactured by heating the steel sheet immediately after plating in a normal hot-dip galvanized steel sheet production line. When an alloyed Zn-plated steel sheet is used as a enamel plate, the degree of alloying (in other words, from the viewpoint of enamel adhesion)
It is advantageous to increase the Fe concentration in the plating layer) and increase the surface roughness. On the other hand, in terms of the molding surface of the product member for enamel, if the alloying degree is excessively increased, the plating layer powders and the moldability deteriorates. For this reason, the Fe content in the plating layer is preferably about 7 to 15% by weight, although it depends on the degree of forming of the enamel member. At this time, it is preferable that the heating conditions be controlled continuously while controlling the Fe concentration in the plating layer with fluorescent X-rays or the like.
【０００７】[0007]
【表１】 [Table 1]
【０００８】亜鉛めっき層をδ1 相及びζ相に変質させ
ることにより、熱拡散現象に伴って合金化Ｚｎめっき層
の表面粗さが図１に示すように５〜１５μｍになる。こ
のような表面粗さをもつ合金化亜鉛めっき層上にホーロ
ー層を形成すると、表面粗さに起因するアンカー効果に
よって優れたホーロー密着性が発現する。また、亜鉛め
っき層をδ1 相及びζ相に変質させることにより、めっ
き層の溶融温度は亜鉛めっき層の約４２０℃からδ1 相
の溶融温度（約６２０℃）及びζ相の溶融温度（約４９
５℃）に上昇し、ホーロー焼成が容易になる。しかも、
良好な密着性が付与されるため、Ａｌめっき鋼板で実施
されている空焼き，鋼板ホーローで行われている高温焼
成によりＦｅ−Ｎｉ−Ｔｉ系の中間層を生成させる工程
等が不要となり、低温焼成でも十分に密着性，耐食性及
び耐久性が優れたホーロー鋼板が得られる。このように
前処理不要で密着性が付与されるため、焼成温度範囲が
異なる種々のフリットが適用でき、結果として光沢，鮮
映性等の種々のホーロー性能の付与が可能となる。By converting the zinc plating layer into the δ 1 phase and the ζ phase, the surface roughness of the alloyed Zn plating layer becomes 5 to 15 μm as shown in FIG. 1 due to the thermal diffusion phenomenon. When the enamel layer is formed on the alloyed zinc-plated layer having such surface roughness, excellent enamel adhesion is exhibited due to the anchor effect resulting from the surface roughness. Further, by changing the quality of the galvanized layer into the δ 1 phase and the ζ phase, the melting temperature of the galvanized layer changes from about 420 ° C. of the galvanized layer to the melting temperature of the δ 1 phase (about 620 ° C.) and the melting temperature of the ζ phase ( About 49
(5 ° C), and enamel firing becomes easier. Moreover,
Since good adhesion is imparted, the step of generating an Fe-Ni-Ti-based intermediate layer by air-baking performed on an Al-plated steel sheet or high-temperature firing performed on a steel sheet enamel is unnecessary, and low temperature is achieved. A enamel plate with excellent adhesion, corrosion resistance and durability can be obtained even by firing. In this way, since pretreatment is not required and adhesion is imparted, various frits having different firing temperature ranges can be applied, and as a result, various enamel properties such as gloss and sharpness can be imparted.
【０００９】[0009]
実施例１：板厚０．４ｍｍの鋼板に０．１５重量％Ａｌ
−残部Ｚｎの溶融Ｚｎめっきを施し、表面亜鉛層が凝固
しないうちに加熱により合金化処理し、合金化亜鉛めっ
き鋼板を製造した。得られた合金化亜鉛めっき鋼板のめ
っき層は、δ1 相及びζ相で構成されており、合金化に
よるめっき層中の平均Ｆｅ濃度は約１０重量％であっ
た。この合金化亜鉛めっき鋼板をホーロー原板として使
用した。ホーロー掛けには、ＰｂＯ，Ｂ2 Ｏ3 ，ＳｉＯ
2 Ａｌ2 Ｏ3 等を含み軟化点３６５℃，線膨張係数１１
０×１０-7／℃のフリットに懸濁剤，止め薬，水等を添
加したスリップを使用した。ホーロー前処理なしで合金
化亜鉛めっき鋼板に乾燥膜厚が８０μｍとなるようにス
リップを塗布し、軟化点近傍の温度３６０℃に１０分間
加熱し、次いでめっき層の溶融温度以下で焼成する二段
階焼成を施した。２段目の焼成は、４００〜６００℃の
範囲にある各温度で、保持時間を５分及び１０分に設定
した。その結果、めっき層中の平均Ｆｅ濃度は、図２に
示すように焼成によって約１０重量％から２０重量％に
増加した。また、６００℃で焼成されたホーロー被覆鋼
板のめっき層は、δ1 相及びζ相で構成されており、鋼
素地側に僅かにΓ相が析出していた。Example 1: 0.15 wt% Al on a 0.4 mm thick steel plate
-The balance Zn was subjected to hot dip Zn plating, and alloying treatment was performed by heating before the surface zinc layer was solidified to produce an alloyed galvanized steel sheet. The plated layer of the obtained galvannealed steel sheet was composed of δ 1 phase and ζ phase, and the average Fe concentration in the plated layer by alloying was about 10% by weight. This alloyed galvanized steel sheet was used as a enamel plate. For enamel, PbO, B 2 O 3 , SiO
2 including Al 2 O 3 etc., softening point 365 ° C, linear expansion coefficient 11
A slip prepared by adding a suspending agent, a stopper, water, etc. to a 0 × 10 −7 / ° C. frit was used. Two steps of applying a slip to an alloyed galvanized steel sheet without enamel pretreatment so that the dry film thickness becomes 80 μm, heating it to a temperature near the softening point of 360 ° C. for 10 minutes, and then firing at a temperature not higher than the melting temperature of the plating layer. It was baked. In the second-stage firing, the holding time was set to 5 minutes and 10 minutes at each temperature in the range of 400 to 600 ° C. As a result, the average Fe concentration in the plating layer was increased from about 10% by weight to 20% by weight by firing as shown in FIG. Further, the plating layer of the enamel coated steel sheet fired at 600 ° C. was composed of the δ 1 phase and the ζ phase, and a slight Γ phase was precipitated on the steel base side.
【００１０】このときのめっき層中の平均Ｆｅ濃度をホ
ーロー密着性との関係を図３に示す。なお、ホーロー密
着性は、加重３００ｇを約５０ｃｍの高さから落下させ
る衝撃試験によって測定した相対値である。図３にみら
れるように、平均Ｆｅ濃度が１８重量％を超えるとホー
ロー密着性が低下する傾向がみられた。この平均Ｆｅ濃
度は、図２から焼成温度５５０℃以上に相当する。ま
た、６００℃の焼成温度では平均Ｆｅ濃度が２０重量％
近くになり、ホーロー密着性が大幅に低下した。このホ
ーロー密着性の低下は、めっき層自体の加工性がＦｅ含
有量の増加に伴って低下したこと及び鋼素地側に特に加
工性が劣るΓ相が析出したことに起因するものと推察さ
れる。このようにδ1 相及びζ相で構成されためっき層
をもつ合金化亜鉛めっき鋼板をホーロー原板として使用
するとき、ホーロー前処理なしで良好なホーロー密着性
が得られることが判った。このとき、図２及び図３に示
した結果から、めっき層中の平均Ｆｅ濃度が約２０重量
％以下で、鋼素地側に加工性の劣るΓ相が析出しない焼
成条件、具体的には焼成温度５５０℃以下が望ましい。
焼成温度の下限は、焼成後のホーロー層の光沢，耐食性
等の実用性から定められ、焼成温度３５０℃以上で実用
性を満足するホーロー被覆鋼板が得られた。FIG. 3 shows the relationship between the average Fe concentration in the plating layer and the enamel adhesion at this time. The enamel adhesion is a relative value measured by an impact test in which a weight of 300 g is dropped from a height of about 50 cm. As shown in FIG. 3, when the average Fe concentration exceeds 18% by weight, the enamel adhesion tends to decrease. This average Fe concentration corresponds to a firing temperature of 550 ° C. or higher from FIG. Further, at a firing temperature of 600 ° C., the average Fe concentration is 20% by weight.
It became closer, and the enamel adhesion decreased significantly. It is speculated that this decrease in enamel adhesion is due to the workability of the plating layer itself decreasing with an increase in the Fe content and the precipitation of the Γ phase, which is particularly poor in workability, on the steel substrate side. . As described above, it was found that when the alloyed galvanized steel sheet having the plating layer composed of the δ 1 phase and the ζ phase was used as the enamel base plate, good enamel adhesion was obtained without the enamel pretreatment. At this time, from the results shown in FIG. 2 and FIG. 3, the firing conditions are such that the average Fe concentration in the plating layer is about 20% by weight or less, and the Γ phase having poor workability does not precipitate on the steel base side, specifically, firing. A temperature of 550 ° C or lower is desirable.
The lower limit of the firing temperature is determined by the practicality such as the gloss and corrosion resistance of the enamel layer after the calcination, and the enamel-coated steel sheet satisfying the practicality was obtained at the calcination temperature of 350 ° C or higher.
【００１１】実施例２：板厚０．４ｍｍの鋼板に、約
０．１５重量％−残部Ｚｎの溶融亜鉛めっきを付着量４
５ｇ／ｍ2 で施した。溶融亜鉛めっき層が凝固しないう
ちに加熱し、合金化亜鉛めっき鋼板を製造した。形成さ
れためっき層は、δ1 相及びζ相で構成されており、合
金化によるめっき層中の平均Ｆｅ濃度は約１０重量％，
線膨張係数は１４５×１０-7／℃であった。この合金化
亜鉛めっき鋼板をホーロー原板として使用した。ホーロ
ー掛けには、スリップＩ〜III を使用した。スリップＩ
は、ＰｂＯ，Ｂ2 Ｏ3 ，Ｂｉ2 Ｏ3 ，ＺｎＯ，ＣｕＯ，
Ｆｅ2 Ｏ3，Ｆ2 等を含み軟化点２９５℃，線膨張係数
１４０×１０-7／℃のフリットに懸濁剤，止め薬，水等
を添加することにより調製した。Example 2: A hot-dip galvanized layer having a thickness of 0.4 mm and a balance of Zn of 0.45% by weight was applied to a steel sheet having a thickness of 0.4 mm.
It was applied at 5 g / m 2 . It was heated before the hot-dip galvanized layer solidified to produce an alloyed galvanized steel sheet. The formed plating layer is composed of δ 1 phase and ζ phase, and the average Fe concentration in the plating layer by alloying is about 10% by weight.
The linear expansion coefficient was 145 × 10 -7 / ° C. This alloyed galvanized steel sheet was used as a enamel plate. Slip I to III were used for enameling. Slip I
Is PbO, B 2 O 3 , Bi 2 O 3 , ZnO, CuO,
It was prepared by adding a suspending agent, a stopper, water and the like to a frit containing Fe 2 O 3 , F 2 and the like and having a softening point of 295 ° C. and a linear expansion coefficient of 140 × 10 −7 / ° C.
【００１２】スリップIIは、ＰｂＯ，Ｂ2 Ｏ3 ，ＳｉＯ
2 ，Ａｌ2 Ｏ3 等を含み軟化点３６５℃，線膨張係数１
１０×１０-7／℃のフリットに懸濁剤，止め薬，水等を
添加することにより調製した。スリップIII は、Ｐ2 Ｏ
5 ，Ａｌ2 Ｏ3 ，Ｓｂ2 Ｏ，Ｎａ2 Ｏ，Ｂ2 Ｏ3 ，Ｌｉ
2 Ｏ等を含み軟化点４８３℃，線膨張係数１２０×１０
-7／℃のフリットに懸濁剤，止め薬，水等を添加するこ
とにより調製した。ホーロー前処理なしで合金化亜鉛め
っき鋼板に乾燥膜厚が８０μｍとなるように各スリップ
Ｉ〜III を塗布した。焼成は、それぞれのフリットの軟
化点近傍の温度に１０分間加熱し、次いで表２に示す各
温度で焼成した。焼成後のホーロー被覆鋼板について、
実施例１と同じ衝撃試験でホーロー密着性を調査した。
そして、ホーロー層の剥離が５％以下のものを◎，５〜
１０％程度剥離したものを○，１０〜５０％程度剥離し
たものを△，５０％以上剥離したものを×として評価し
た。また、ホーロー層の光沢を、７５度鏡面反射率で測
定した。これら調査結果を、表２に併せ示す。Slip II is made of PbO, B 2 O 3 , SiO
2 , including Al 2 O 3 etc., softening point 365 ℃, linear expansion coefficient 1
It was prepared by adding a suspending agent, a stopper, water and the like to a 10 × 10 −7 / ° C. frit. Slip III is P 2 O
5 , Al 2 O 3 , Sb 2 O, Na 2 O, B 2 O 3 , Li
Including 2 O, softening point 483 ℃, linear expansion coefficient 120 × 10
It was prepared by adding a suspending agent, a stopper, water, etc. to a frit at -7 / ° C. Each of the slips I to III was applied to a galvannealed steel sheet without enamel pretreatment so that the dry film thickness was 80 μm. The firing was performed by heating to a temperature near the softening point of each frit for 10 minutes, and then firing at each temperature shown in Table 2. Regarding the enamel coated steel sheet after firing,
The same impact test as in Example 1 was conducted to investigate the enamel adhesion.
And, if the peeling of the enamel layer is 5% or less, ◎, 5
About 10% peeling was evaluated as ◯, about 10 to 50% peeling was evaluated as Δ, and 50% or more peeling was evaluated as x. Further, the gloss of the enamel layer was measured by a 75 ° specular reflectance. The results of these investigations are also shown in Table 2.
【００１３】[0013]
【表２】 [Table 2]
【００１４】表２から明らかなように、本発明に従って
得られたホーロー被覆鋼板では、ホーロー前処理を施さ
なくても、優れたホーロー密着性が得られていた。しか
し、焼成温度が低い比較例１２では、ホーロー密着性が
不足しており、また光沢も著しく低いものであった。他
方、焼成温度が高い比較例１３〜１５では、合金化亜鉛
めっき層中のＦｅ濃度が適正量を超え、めっき層の加工
性が著しく低下していた。その結果として、ホーロー密
着性が劣っていた。As is clear from Table 2, the enamel coated steel sheet obtained according to the present invention had excellent enamel adhesion even without enamel pretreatment. However, in Comparative Example 12 in which the firing temperature was low, the enamel adhesion was insufficient, and the gloss was remarkably low. On the other hand, in Comparative Examples 13 to 15 where the firing temperature was high, the Fe concentration in the alloyed zinc plating layer exceeded the appropriate amount, and the workability of the plating layer was significantly reduced. As a result, the enamel adhesion was poor.
【００１５】[0015]
【発明の効果】以上に説明したように、本発明において
は、δ1 相及びζ相を主体とする合金化めっき層をもつ
鋼板をホーロー原板とすることにより、ホーロー前処理
を必要とすることなく、密着性に優れたホーロー層が形
成される。その結果、従来のホーロー前処理で発生して
いた廃液の処理が不要になり、また低温焼成が可能であ
ることからホーロー被覆鋼板の熱歪みによる変形が抑制
され、ホーロー原板として薄鋼板を使用することも可能
になる。更に、合金化亜鉛めっき鋼板は、優れた耐食性
を呈することから、ホーロー被覆を片面だけに施すこと
もできる。このようにして得られたホーロー被覆鋼板
は、その優れた長所を活用して外装材，内装材，厨房用
家具，調理用器具等として広範な用途に使用される。As described above, in the present invention, the enamel pretreatment is required by using the steel plate having the alloyed plating layer mainly composed of the δ 1 phase and the ζ phase as the enamel base plate. Without forming a enamel layer having excellent adhesion. As a result, it is not necessary to treat the waste liquid generated in the conventional enamel pretreatment, and since low temperature firing is possible, deformation due to thermal strain of the enamel coated steel sheet is suppressed, and a thin steel sheet is used as the enamel base plate. It also becomes possible. Furthermore, since the alloyed galvanized steel sheet exhibits excellent corrosion resistance, the enamel coating can be applied to only one surface. The enamel coated steel sheet thus obtained is used in a wide range of applications as exterior materials, interior materials, kitchen furniture, cooking utensils, etc. by utilizing its excellent advantages.
【図面の簡単な説明】[Brief description of drawings]
【図１】 合金化溶融亜鉛めっき鋼板のめっき層の表面
粗さ[Fig. 1] Surface roughness of coating layer of galvannealed steel sheet
【図２】 めっき層中の平均Ｆｅ濃度に及ぼす焼成温度
の影響FIG. 2 Effect of firing temperature on average Fe concentration in plating layer
【図３】 めっき層中の平均Ｆｅ濃度とホーロー密着性
との関係FIG. 3 Relationship between average Fe concentration in plated layer and enamel adhesion
Claims (3)
面までδ1 相及びζ相を成長させためっき層をもち、該
めっき層の片面又は両面にホーロー層が形成されている
ホーロー被覆鋼板。1. A enamel coated steel sheet having a enamel layer formed on one or both sides of the enamel layer having a δ 1 phase and a ζ phase grown to the surface by heat treatment immediately after hot dip Zn plating.
し、Ｆｅ−Ｚｎ系金属間化合物のうちでδ1 相及びζ相
をめっき層の表面まで成長させる合金化処理を施し、次
いで合金化亜鉛めっき鋼板のめっき層上の片面又は両面
にホーロー層を形成することを特徴とするホーロー被覆
鋼板及びその製造方法。2. A surface zinc layer immediately after hot dip galvanizing is heated, and an alloying treatment for growing a δ 1 phase and a ζ phase among Fe—Zn intermetallic compounds to the surface of the plated layer is performed, and then alloying is performed. A enamel-coated steel sheet, which comprises forming a enamel layer on one or both surfaces of a galvanized steel sheet, and a method for producing the same.
焼き付ける請求項１記載の製造方法。3. The manufacturing method according to claim 1, wherein the enamel is baked at a baking temperature of 350 to 550 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17685795A JPH093660A (en) | 1995-06-20 | 1995-06-20 | Porcelain enameled steel sheet and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17685795A JPH093660A (en) | 1995-06-20 | 1995-06-20 | Porcelain enameled steel sheet and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH093660A true JPH093660A (en) | 1997-01-07 |
Family
ID=16021044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17685795A Withdrawn JPH093660A (en) | 1995-06-20 | 1995-06-20 | Porcelain enameled steel sheet and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH093660A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0964078A1 (en) * | 1998-06-12 | 1999-12-15 | Enamels and Ceramic Coatings International C.V. | Enamelling of zinc or zinc-alloy precoated steel surfaces |
-
1995
- 1995-06-20 JP JP17685795A patent/JPH093660A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0964078A1 (en) * | 1998-06-12 | 1999-12-15 | Enamels and Ceramic Coatings International C.V. | Enamelling of zinc or zinc-alloy precoated steel surfaces |
| WO1999066103A1 (en) * | 1998-06-12 | 1999-12-23 | Enamels And Ceramic Coatings International C.V. | Enamelling of zinc or zinc-alloy precoated steel surfaces |
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