JPS63195284A - Coated steel sheet for enameling - Google Patents
Coated steel sheet for enamelingInfo
- Publication number
- JPS63195284A JPS63195284A JP2722287A JP2722287A JPS63195284A JP S63195284 A JPS63195284 A JP S63195284A JP 2722287 A JP2722287 A JP 2722287A JP 2722287 A JP2722287 A JP 2722287A JP S63195284 A JPS63195284 A JP S63195284A
- Authority
- JP
- Japan
- Prior art keywords
- steel plate
- iron oxide
- steel sheet
- enamel
- steel
- 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.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 104
- 239000010959 steel Substances 0.000 title claims abstract description 104
- 238000004534 enameling Methods 0.000 title claims description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 210000003298 dental enamel Anatomy 0.000 abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005554 pickling Methods 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 150000004767 nitrides Chemical class 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 241000251468 Actinopterygii Species 0.000 abstract 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 235000013980 iron oxide Nutrition 0.000 description 32
- 239000000047 product Substances 0.000 description 18
- 239000003921 oil Substances 0.000 description 17
- 238000007747 plating Methods 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- 230000007547 defect Effects 0.000 description 12
- 230000003746 surface roughness Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000010960 cold rolled steel Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000003449 preventive effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 241001674044 Blattodea Species 0.000 description 1
- 229910000840 Capped steel Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はほうろう用の被覆鋼板に関し、特に自動車、電
機製品等に使用されている通常の普通鋼板をほうろう用
鋼板として使用可能にするとともに、従来のほうろう用
鋼板と同等以上に爪とびゃ泡欠陥及び密着性不良のない
両面若しくは片面はうろう成品の製造を可能にする鋼板
を提供することにある。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a coated steel plate for enameling, and in particular, enables ordinary ordinary steel plates used in automobiles, electrical appliances, etc. to be used as a steel plate for enameling. To provide a steel plate that enables the production of a finished product with enamel on both or one side, which is free from nail and bubble defects and poor adhesion to the same extent or better than conventional steel plates for enameling.
周知の通りほうろう成品の欠陥には、爪飛び、泡及び密
着性不良等があり、はうろう用の鋼板と釉薬の組合せや
前処理が不適当な場合に、欠陥が発生しやすい。As is well known, defects in enamel products include nail skipping, bubbles, and poor adhesion, and defects are likely to occur if the combination of the steel plate for enamel and glaze or the pretreatment is inappropriate.
爪飛びは、焼成時にほうろう釉薬又は焼成炉の雰囲気中
の水分と鉄との反応により生じた水素が鋼中に入り、冷
却時に鋼板とほうろう皮膜の界面に集まり、その水素ガ
スの圧力により、はうろう膜がはね飛ばされて発生した
ものと考えられる。Nail skipping occurs when hydrogen generated by the reaction between the iron and the moisture in the enamel glaze or the atmosphere of the firing furnace enters the steel and collects at the interface between the steel plate and the enamel film during cooling, and the pressure of the hydrogen gas causes It is thought that this was caused by the urostomy membrane being blown off.
そこで耐爪飛性を改善する方法として、鋼中の介在物、
析出物を多くし、その周辺に水素を吸蔵させる方法が従
来から知られており、たとえばＴｉ −Ｃ，Ｔｉ−３お
よびＴｉ−ＲＥＭ−３系で介在物、析出物を作るものと
しては、特開昭４８−２２２号公報、特開昭５２−１３
１９１９号公報および特公昭５４−３４４７号公報など
が、Ｂ−Ｎ系で介在物、析出物を作るものとしては特開
昭５８−１０１３号公報などがある。Therefore, as a method to improve the chipping resistance, inclusions in the steel,
A method of increasing the number of precipitates and occluding hydrogen around them has been known for a long time. Publication No. 48-222, Japanese Patent Publication No. 52-13
1919 and Japanese Patent Publication No. 54-3447, etc., and JP-A-58-1013 which produces inclusions and precipitates in the B--N system.
一方、泡系欠陥にはコツパーヘッドやピンホール等があ
り、これらは主に鋼中（Ｃ）、カーバイドなどが焼成時
に分解し、ＣＯｘガスになり、泡系欠陥になると考えら
れている。その防止策ないしは加工性の向上策として、
溶鋼時又は焼鈍時に脱炭しており、たとえば特開昭５６
−５１５５３号公報又は特開閉５１−６８１３号公報等
がある。On the other hand, foam-based defects include cockroach heads and pinholes, and these are thought to be caused mainly by (C), carbide, etc. in the steel decomposing during firing and turning into COx gas, resulting in foam-based defects. As a preventive measure or a measure to improve processability,
Decarburization occurs during molten steel or annealing, for example, in JP-A-56
-51553, JP-A No. 51-6813, etc.
しかし、泡系欠陥の原因として〔Ｃ〕源以外に、鋼板表
面の介在物も関係している様で、爪飛びと泡欠陥を同時
に完全防止するのは容易ではない。However, in addition to the [C] source, inclusions on the surface of the steel sheet seem to be involved as a cause of bubble defects, and it is not easy to completely prevent nail skipping and bubble defects at the same time.
更に、密着性不良は特に両面１回掛はうろうで発生しや
すい、一般に密着性を向上させるためには鋼板の表面粗
度を大きくするか、鋼板と釉薬間の化学結合力を強める
とよい、前者には鋼中にＣｕを０．０２５％以上添加し
たり、酸洗減量を大きくしたり、後者には酸洗後Ｎｉメ
ッキした上に釉薬を塗布する方法がある。しかし、両面
１回掛はうろうでは密着不良が起り易いので、特開昭５
１−１３１１号公報では鋼板の表面粗さとＭｎ量を規制
し、特開昭５７−６３６６１号公報では鋼中成分の（Ｐ
＋Ｓ）／Ｃｕを２．０以下にしている。Furthermore, poor adhesion is particularly likely to occur when both sides are coated once, and in general, to improve adhesion, it is better to increase the surface roughness of the steel plate or strengthen the chemical bond between the steel plate and the glaze. For the former method, there is a method of adding 0.025% or more of Cu to the steel or increasing the weight loss after pickling, and for the latter method, there is a method of applying a glaze on Ni plating after pickling. However, when applying one coat on both sides, poor adhesion is likely to occur.
1-1311, the surface roughness and Mn content of the steel plate are regulated, and JP-A-57-63661 regulates the content of (P) in the steel.
+S)/Cu is 2.0 or less.
一方はうろう用被覆金属製品としてほうろう用フリット
に水溶性又は水分散高分子、酸化剤及び潮解性物質より
なる混合物を鋼板表面に施釉、乾燥したもので、これを
そのまま成形加工し、焼成できるものとして特公昭４９
−４１０８４号公報、更にこれとほぼ類似の特公昭８１
−１２９７４号公報がある。これらはほうろう釉薬を施
釉したままで優れた成形加工ができ、その後焼成すると
ほうろう成品として外観、密着性、耐食性が良好である
としている。On the other hand, a coated metal product for enamel is made by applying a mixture of a water-soluble or water-dispersible polymer, an oxidizing agent, and a deliquescent substance to a frit for enamel on the surface of a steel plate and drying it, which can then be molded and fired as is. As a special public service in 1977
Publication No. 41084, and almost similar to this, Special Publication No. 1981
There is a publication No.-12974. It is said that these products can be molded with excellent enamel glaze as they are, and that when fired afterwards, they produce enamel products with good appearance, adhesion, and corrosion resistance.
上述のように、はうろう用鋼板は通常の普通鋼板とはや
や異なる特別の成分で、特に、介在物が多く、清浄度指
数は普通鋼板の約５倍も高く、またＪＩＳ（：３１３３
はほうろう用鋼板としては脱炭処理鋼板であると規定し
ている。従来技術では、普通鋼板、すなわちＪ、 Ｉ
Ｓ規格に該当するものとしては熱延鋼板（ＪＩＳＧ３１
３１）及び冷延鋼板（ＪｔＳＧ３１４１）を使用して両
面若しくは片面はうろう成品とし、密着性不良が発生し
ないほうろう被覆製品を提供することはできなかった。As mentioned above, steel sheets for crawlers have a special composition that is slightly different from ordinary steel sheets.In particular, they have many inclusions, have a cleanliness index about 5 times higher than ordinary steel sheets, and are compliant with JIS (3133).
stipulates that steel sheets for enameling must be decarburized steel sheets. In the prior art, ordinary steel plates, namely J, I
Hot-rolled steel sheets (JISG31
31) and a cold-rolled steel plate (JtSG3141), it was not possible to provide an enamel-coated product with enamel on both sides or one side, which would not cause poor adhesion.
本発明は、上記はうろう用の鋼板を提供するために普通
鋼板の表面に５０〜１１００人厚の酸化鉄屑を形成する
ことにより、普通鋼板をほうろう用被覆鋼板として提供
することにある。The present invention is to provide a plain steel plate as a coated steel plate for enameling by forming iron oxide scraps having a thickness of 50 to 1100 on the surface of the above-mentioned common steel plate.
一般に、はうろう用鋼板は両面１回掛はうろうの場合完
全脱脂後酸洗、Ｎｉメッキ、中和後、施釉するのが常識
とされており、完全脱脂後酸洗し、油および酸化鉄屑を
完全除去するのが不可欠になっているので本発明の様に
鋼板と釉薬の間に酸化鉄層を付着せしめるのは従来の常
識では考えられない、また、はうろう用に適さない通常
の熱延及び冷延普通鋼板に両面１回掛けほうろうが可能
であるとの従来の技術常識もない。In general, it is common knowledge that steel sheets for glazing are completely degreased, then pickled, Ni-plated, neutralized, and then glazed if both sides are coated once. Since it is essential to completely remove iron scraps, attaching an iron oxide layer between the steel plate and the glaze as in the present invention is unthinkable under conventional wisdom, and is not suitable for glazing. There is also no conventional technical knowledge that it is possible to enamel a hot-rolled or cold-rolled ordinary steel sheet once on both sides.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明が対象とする普通鋼板とはＪＩＳＧ３１３１の熱
間圧延軟鋼板及び銅帯（ＳＰＩＣ，５ＰＩＩＤ、 ５Ｐ
ＩＩＥ等）、ＪＴＳＧ３１４１の冷間圧延鋼板及び銅帯
（ＳＰＣＣ，５ＰＣＤ、ｓｐｃε等）、及びＪＩＳＧ３
３０３のぶりき原板（Ｓ Ｐ Ｂ等）等を含む普通鋼の
鋼板及び銅帯であり、ＪＩＳに３１３３のほうろう用脱
炭鋼及び銅帯（Ｓ Ｐ Ｐ等）、ＪＩＳ規格にない熱間
圧延はうろう用鋼板及び銅帯及び鋳型鋳造のキャップド
鋼の軟鋼板及び銅帯等は含まない。The ordinary steel sheets targeted by the present invention are JIS G3131 hot-rolled mild steel sheets and copper strips (SPIC, 5PIID, 5P).
IIE, etc.), cold rolled steel sheets and copper strips of JTSG3141 (SPCC, 5PCD, spcε, etc.), and JISG3
Steel plates and copper strips made of ordinary steel, including No. 303 tin plate (S P B, etc.), decarburized steel for enameling and copper strips (S P, etc.) under JIS No. 3133, and hot-rolled steel sheets that are not listed in JIS standards. Does not include steel plates and copper strips for crawlers and mild steel plates and copper strips of mold-cast capped steel.
なお、これらほうろう用鋼板、鋼帯を本発明方法により
ほうろう用の被覆処理を行なうと、従来のほうろう用鋼
板には見られないような爪飛び、泡欠陥が少ないほうろ
う成品が得られるが、本発明法は普通鋼板を従来同等も
しくはそれ以上の品質のほうろう用の鋼板とすることを
目的とするので、上記はうろう用鋼板、銅帯は本発明の
対象外とした。よって、本発明にいう普通鋼板とは、広
義には、爪飛び、泡欠陥防止及び密着性不良対策が講ぜ
られていない鋼板を指す。Furthermore, when these enameled steel plates and steel strips are coated for enameling using the method of the present invention, enameled products with less nail skipping and bubble defects, which are not seen in conventional enameled steel plates, can be obtained. Since the purpose of the invention method is to convert ordinary steel plates into steel plates for enameling with the same or higher quality than conventional steel plates, the above-mentioned steel plates for enameling and copper strips are excluded from the scope of the present invention. Therefore, in a broad sense, the ordinary steel sheet referred to in the present invention refers to a steel sheet in which measures are not taken to prevent nail skipping, bubble defects, and poor adhesion.
上記普通鋼板の成分範囲はＪＩＳ規格に表示されており
、Ｃ： ０．１５％以下、Ｍｎ ： ０．６０％以下、
Ｐ ： ０．０５０％以下、Ｓ ： ０．０５０％以下
で、更に、Ｃｕは０．０８％以下、ＡＩは０．０８％以
下、Ｔｉは０．１０％以下とする。Ｃｕは一般に０．０
８％超ではＣｕ原囚の表面疵が発生しやすくなり、更に
、コスト高になるので、０．０８％以下にした。又、Ａ
Ｉを０．０８％以下にする理由はもともとＡＩ脱酸する
場合ＡＩ金含有不可避であり、目的に対する影響を調査
した結果、０．０８％迄は特に悪影響はないが、０．０
８％超では経済的に問題が生じる。The composition range of the above-mentioned ordinary steel sheet is shown in the JIS standard, C: 0.15% or less, Mn: 0.60% or less,
P: 0.050% or less, S: 0.050% or less, Cu: 0.08% or less, AI: 0.08% or less, and Ti: 0.10% or less. Cu is generally 0.0
If it exceeds 8%, surface flaws will easily occur on the Cu raw material, and furthermore, the cost will increase, so it is set to 0.08% or less. Also, A
The reason for setting I to 0.08% or less is that when deoxidizing AI, it is unavoidable that AI contains gold, and as a result of investigating the effect on the purpose, up to 0.08% there is no particular adverse effect, but 0.0
If it exceeds 8%, economic problems will arise.
Ｔｉを０．１０％以下にする理由は上記のＡＩと同様に
Ｔｉ脱酸の他にＮ、Ｃと結合し、窒化物、炭化物とし、
非時効性の他に加工性を向上するために添加されるが、
本願発明のほうろう性に対する影響は０，１０％迄は特
に悪影響はないが、０．１０％超ではコスｉ・高になる
。The reason for setting Ti to 0.10% or less is that in addition to deoxidizing Ti, it combines with N and C to form nitrides and carbides, similar to the above AI.
In addition to being anti-aging, it is added to improve processability.
The effect of the present invention on enamelability is not particularly bad up to 0.10%, but when it exceeds 0.10%, the cost i becomes high.
一般にほうろう用鋼板を用いた両面１回掛けの通常の製
造工程ではほうろうを焼成する際、まず鋼板表面に酸化
が起り、ついで、はうろう釉薬が溶融し、酸化鉄がほう
ろう中に溶解し、焼成終了時に酸化鉄層が消滅して、は
うろう層と鋼板が密着する。その際酸化鉄の過不足が密
着に大きな影響を及ぼすと考えられている。しかし、適
正な酸化鉄の厚みは不明であり、かつ、はうろう釉薬の
すきまや、加熱温度、昇温速度や雰囲気等が異なりその
コントロールは極めて難しい、従って、安定した密着性
を有するほうろう用鋼板を作ることは困難である。また
、通常の冷延普通鋼板（５ＰＣＣ等）では粗度を大きく
し、Ｃｕ添加やＮｉメッキをしても密着性のよいものを
作る事は極めて難しい。In general, in the normal manufacturing process using a steel plate for enameling, in which both sides are coated once, when the enamel is fired, oxidation occurs first on the surface of the steel plate, then the enamel glaze melts, and iron oxide dissolves in the enamel. At the end of firing, the iron oxide layer disappears and the wax layer and steel plate come into close contact. At this time, excess or deficiency of iron oxide is thought to have a significant effect on adhesion. However, the appropriate thickness of iron oxide is unknown, and it is extremely difficult to control the gap in the enamel glaze, heating temperature, heating rate, atmosphere, etc. Therefore, it is difficult to use enamel with stable adhesion. It is difficult to make steel plates. Furthermore, it is extremely difficult to make a normal cold-rolled steel sheet (such as 5PCC) with good adhesion even if the roughness is increased and Cu is added or Ni plated.
そこで本発明は前もって少くとも普通鋼板の表面に適正
な厚みで、均一な酸化鉄屑を前もって生成させた点に大
きな特徴を有するものである。Therefore, the present invention has a major feature in that uniform iron oxide scraps are generated in advance at least on the surface of an ordinary steel plate with an appropriate thickness.
本発明者等は、酸化鉄層の厚みを、酸化前肩の重量測定
と偏光解析装置で測定し、酸化鉄の厚みを求めた。また
、低温度（５７０℃以下）での酸化鉄相は一般にＦｅ＋
ＯｉとＦｅｚＯｚ相からなると言われているが、Ｆｅ＝
Ｏｎ相が主体と考え重量増加分をＦｅ＝Ｏｎの比重で割
って上記厚みを得た。The present inventors determined the thickness of the iron oxide layer by measuring the weight of the shoulder before oxidation and using an ellipsometer. In addition, the iron oxide phase at low temperatures (below 570°C) is generally Fe+
It is said to consist of Oi and FezOz phases, but Fe=
Considering that the On phase was the main component, the above thickness was obtained by dividing the weight increase by the specific gravity of Fe=On.
その結果、酸化鉄層の厚みは５０〜１１００人の範囲が
最適であることが判明した。As a result, it was found that the optimal thickness of the iron oxide layer is in the range of 50 to 1,100.
酸化鉄層の厚みを５０〜１１００人に限定した理由は、
５０人未満では酸化鉄層が薄すぎて密着性が悪くなる。The reason for limiting the thickness of the iron oxide layer to 50 to 1100 people is
If there are fewer than 50 people, the iron oxide layer will be too thin and the adhesion will be poor.
この原因は焼成時に鋼板とほうろう層の界面にＳｉＯ□
と酸化鉄の反応物即ち珪酸鉄がわずかしか出来ないため
と考えられる。一方、酸化鉄屑が１１００人超で６密着
性が低下する。この原因は焼成時にほうろう中に酸化鉄
膜が完全に溶解せず、はうろう層と鋼板の界面に未溶解
の酸化鉄が残存しているためと推定される。The reason for this is that SiO□ is present at the interface between the steel plate and the enamel layer during firing.
This is thought to be due to the fact that only a small amount of iron silicate, a reaction product of iron oxide, is produced. On the other hand, when the amount of iron oxide scrap exceeds 1,100, 6 adhesion decreases. The reason for this is presumed to be that the iron oxide film is not completely dissolved in the enamel during firing, and undissolved iron oxide remains at the interface between the enamel layer and the steel plate.
酸化鉄層が５０〜１１００人厚さにした鋼板をほうろう
掛けして焼成するとほうろう中に酸化鉄膜が適度に溶解
し、はうろう層と鋼板の界面に珪酸鉄が生成し、これが
ほうろう層と鋼板との接着剤としての役割をして密着性
を向上しているものと思われる。When a steel plate with an iron oxide layer of 50 to 1100 mm thick is enameled and fired, the iron oxide film dissolves in the enamel, and iron silicate is generated at the interface between the enamel layer and the steel plate, which forms the enamel layer. It is thought that it acts as an adhesive between the steel plate and the steel plate, improving adhesion.
上述のように普通鋼板の表面にこれら酸化鉄層を形成さ
せるには一般に、電気炉、熱風炉、赤外線炉、ガス炉、
高周波炉、直接通電、レーザービーム等により酸化雰囲
気中で酸化させる。酸化温度は約５０〜６００℃で数秒
〜数１０分位で、高温酸化になる程短時間で行う０弱酸
化雰囲気で酸化させる場合は当然、高温度でかつ長時間
で行うことができる。As mentioned above, in order to form these iron oxide layers on the surface of ordinary steel sheets, electric furnaces, hot blast furnaces, infrared furnaces, gas furnaces,
Oxidize in an oxidizing atmosphere using a high frequency furnace, direct current, laser beam, etc. The oxidation temperature is about 50 to 600° C. for several seconds to several tens of minutes, and when oxidizing is carried out in a weakly oxidizing atmosphere, the oxidation can be carried out at a high temperature and for a long time.
酸化膜の作用、効果は上述した如くほうろう層の鋼板へ
の密着性の向上にあるが、その他の効果として、泡及び
爪とび防止の向上もある。即ち、鋼板表面を酸化すると
炭化物、窒化物、硫化物等が酸化され、ガス化し、鋼板
表面の酸化膜中に泡原因となる成分（Ｃ、Ｎ 、 Ｓ等
）が減少するので泡が発生しにくい。又爪とびの原因は
鉄と釉薬中の水分との反応で発生した水素によって生じ
るので鋼板表面を酸化鉄膜でマスクすればこの反応は起
らない、これは介在物の少ない（一般に０．０５％未満
）、通常の熱延及び冷延普通鋼板では特に爪とびが発生
しやすいので上の酸化処理は極めて有効である。The action and effect of the oxide film is to improve the adhesion of the enamel layer to the steel plate as described above, but other effects include improved prevention of bubbles and nail skipping. In other words, when the steel plate surface is oxidized, carbides, nitrides, sulfides, etc. are oxidized and gasified, and bubble-causing components (C, N, S, etc.) are reduced in the oxide film on the steel plate surface, so bubbles are generated. Hateful. Also, the cause of nail skipping is caused by hydrogen generated by the reaction between iron and moisture in the glaze, so if the surface of the steel plate is masked with an iron oxide film, this reaction will not occur. %), the above oxidation treatment is extremely effective since nail skipping is particularly likely to occur in ordinary hot-rolled and cold-rolled steel sheets.
次に本発明のほうろう用の被覆鋼板は両面１回掛けほう
ろうを行う際、酸化鉄層の上層にＮｉメッキを行うか、
ないしはＮｉメッキ後その上層にさび止め油を塗布する
。その後それらの上層にほうろう釉薬を塗布、乾燥後焼
成すると各種はうろう特性が向上する。Next, when the coated steel plate for enameling of the present invention is enameled once on both sides, the upper layer of the iron oxide layer is plated with Ni, or
Or apply rust preventive oil to the upper layer after Ni plating. After that, an enamel glaze is applied to the top layer of each piece, and when it is dried and fired, the enamel properties of each type are improved.
Ｎｉメッキは一般に両面１回掛けほうろうを行う場合、
必須の処理で、数％のＮ１５Ｏ＜水溶液（ｐＨが約２．
５〜３．０）を約７０℃にし、数分間浸漬してメッキ処
理し、その後中和、屹燥するか、ないしは更に密着性を
向上するため、その上層にさび止油を塗布する。酸化鉄
層の上にＮｉメッキした場合通常の鋼板表面にＮｉメッ
キした場合に比ベメッすむ。Generally, when Ni plating is applied once on both sides and enameled,
This is an essential treatment in which several percent of N15O<aqueous solution (with a pH of about 2.
5 to 3.0) is heated to about 70° C. and immersed for several minutes for plating treatment, and then neutralized and dried, or in order to further improve adhesion, an anti-rust oil is applied to the top layer. When Ni plating is applied on the iron oxide layer, it is much better than when Ni plating is applied on the surface of a normal steel plate.
Ｎｉメッキの効果はほうろう成品の欠陥防止に効果があ
るが、特に焼成時の酸化を押え、かつ、はうろう層と鋼
板界面の珪酸鉄中に拡散してほうろう膜の鋼板への密着
性を向上する。The effect of Ni plating is effective in preventing defects in enamel products, but in particular it suppresses oxidation during firing, and also diffuses into the iron silicate at the interface between the enamel layer and the steel plate, improving the adhesion of the enamel film to the steel plate. improves.
上述した塗油の作用、効果はほうろう釉薬が焼成の昇温
時に約５００〜６００℃で軟化、溶融する迄の低温度で
油が分解、燃焼し、釉薬中の水分及び酸素を蒸発、除去
することにより、前記飛飛び及び泡の発生を減少又は防
止できると考えられる。The action and effect of the oil anointing mentioned above is that the oil decomposes and burns at a low temperature until the enamel glaze softens and melts at approximately 500 to 600 degrees Celsius when the temperature rises during firing, and the water and oxygen in the glaze are evaporated and removed. It is thought that this can reduce or prevent the occurrence of the above-mentioned spattering and bubbles.
その塗油量は片面当り３．０ｇ／ｇ＊”以下が適正であ
る。塗油量が片面当り３．０ｇ／ｍ”超では、焼成時に
油の燃焼、分解ガスが大量に発生し、はうろう釉薬が鋼
板上から浮上し、剥離したり、部分的に浮上して釉引け
が起り易くなり、又コスト高になる。The appropriate amount of oil to be applied is 3.0 g/g*" or less per side. If the amount of oil applied is more than 3.0 g/m" per side, oil will burn during firing and a large amount of decomposed gas will be generated. The waxy glaze floats up from the steel plate and peels off, or partially floats up, making it easy for the glaze to fade and to increase costs.
なお上記のさび止め油として、ＪＩＳでＮＰ−０〜１１
及びＮＰ１８〜２０の１５種類に整理され、これらの中
には通常、防錆油、潤滑油、機械油等と呼称しているも
のが含まれ、又気化性さび止め剤も効果があると考えら
れる。塗油は一般にスプレィ、ロールコータ−５浸漬、
フローコーター、はけ塗り等で行う、長尺物ではスプレ
ィで、塗布後ロールで塗布量を均一にする。また、少量
で均一塗布する場合には、静電塗装などで行う。In addition, as the above-mentioned rust preventive oil, NP-0 to 11 according to JIS
and NP18 to 20, and these include what are usually called rust preventive oils, lubricating oils, machine oils, etc., and volatile rust inhibitors are also thought to be effective. It will be done. Oil application is generally spray, roll coater 5 immersion,
Apply with a flow coater, brush, etc. For long items, use a spray, and after application use a roll to even out the amount of application. In addition, when uniformly applying a small amount, use electrostatic painting or the like.
鋼板の表面粗度に関しては、従来のほうろう用鋼板では
１（ＩＩａｘで７〜２０μ糟である。本発明の普通鋼板
はこの表面粗さ範囲の他に上限約６０μ鴎であっても、
すぐれたほうろう被覆を形成可能にする。特に好ましい
鋼板の表面粗度の範囲は、Ｒｍａｘで１５〜６０μ論で
ある０表面粗度の調整方法として、一般に酸洗、ダルロ
ール圧延、研摩（グラインダー、ベーパー、ショツトブ
ラスト、放電加工等）及び研削等で行う、ここで、表面
粗度Ｒｍａｘは、鋼板表裏面のＬ及びＣ方向のＲｍａｘ
の平均値で表示することにする。Regarding the surface roughness of the steel plate, conventional steel plates for enameling have a surface roughness of 1 (7 to 20 μm in IIax).
Enables formation of excellent enamel coating. A particularly preferred range of surface roughness for steel sheets is Rmax of 15 to 60μ.0 Surface roughness adjustment methods generally include pickling, dull roll rolling, polishing (grinder, vapor, shot blasting, electrical discharge machining, etc.) and grinding. Here, the surface roughness Rmax is Rmax in the L and C directions of the front and back surfaces of the steel plate.
We will display the average value.
一方、上記Ｒｍａｘの範囲に相当する１インチ当りのピ
ーク数、ＰＰＩは約２２３〜１０．４ビ一ク／インチで
、中心線平均粗さＲａは、約０．７〜６２μ鴎である。On the other hand, the number of peaks per inch (PPI) corresponding to the range of Rmax is about 223 to 10.4 peaks/inch, and the center line average roughness Ra is about 0.7 to 62 μm.
先ず、熱延鋼板を対象にした場合では、熱延鋼板表面を
ショット又は塩酸々洗を行うことによりスケールを完全
に除去し且つ表面粗度を所望の値に調整するか、又は該
表面を塩酸々洗−シヨツトによって、上記同様の処理を
行う、また、冷延鋼板の場合は、必要によりスキンバス
又はショットで表面粗度を調整する。First, in the case of hot-rolled steel sheets, the surface of the hot-rolled steel sheet is shot or washed with hydrochloric acid to completely remove scale and adjust the surface roughness to the desired value, or the surface is washed with hydrochloric acid. The same treatment as above is carried out using a washing shot, and in the case of a cold-rolled steel sheet, the surface roughness is adjusted using a skin bath or a shot as necessary.
上記処理後に行う、本発明の特徴とする酸化鉄の形成は
いかなる工程で行なってもよい。The formation of iron oxide, which is a feature of the present invention, may be performed in any step after the above treatment.
なお鋼板の表面粗度は酸化鉄表面にほとんど同じ値で残
存する。すなわち、鋼板表面の深い四部の残留歪が局部
的に大きくなっているため、深い凹部では酸化が促進さ
れ、凹部が若干平担化される傾向があるが、鋼板全体と
しての■度ＲＩＩａｘは酸化前後でほとんど変わりない
。また、酸化鉄形成後に粗度計、光学顕微鏡或いは電子
盟微鏡により鋼板地鉄の酸化鉄との界面の粗さを測定す
ることができる。ホーロー掛は工程である脱脂−水洗一
酸洗一水洗一中和一乾燥一施釉一乾燥一焼成一空冷の工
程中で行う場合は施釉前の乾燥後引続いて酸化を行うこ
とが好ましい。Note that the surface roughness of the steel plate remains at almost the same value as the iron oxide surface. In other words, because the residual strain in the deep four parts of the steel sheet surface is locally large, oxidation is promoted in the deep recesses and the recesses tend to become slightly flattened, but the degree RIIax of the steel sheet as a whole is There is almost no difference between before and after. Further, after the formation of iron oxide, the roughness of the interface between the steel plate base iron and the iron oxide can be measured using a roughness meter, an optical microscope, or an electron microscope. When enameling is performed during the steps of degreasing, water washing, pickling, water washing, neutralization, drying, glazing, drying, firing, and air cooling, it is preferable to carry out oxidation after drying before glazing.
また、Ｎｉメッキを行う場合は、酸洗後の水洗の後にＮ
ｉメッキし、更にさび止め油を塗布する場合は施釉する
前に塗油する。In addition, when Ni plating is performed, N
If you want to apply anti-rust oil after plating, apply the oil before glazing.
本発明において、酸化処理した鋼板は白板、パネル等の
平板のま−で使用されるか、曲げ、プレス加工、溶接等
を行って各用途別の成形品に加工される。このような加
工が加えられても、プレス部品等の、極めて薄い酸化鉄
層は剥離しにく−１たとえ、一部が剥離しても、その後
のＮｉメッキ、塗油等により、鋼板の粗度の凹部が埋め
られているので、実際上、問題はない。In the present invention, the oxidized steel plate is used as a flat plate such as a white plate or a panel, or it is processed into molded products for various uses by bending, press working, welding, etc. Even if such processing is applied, the extremely thin iron oxide layer of pressed parts etc. is difficult to peel off.1 Even if a part of the iron oxide layer peels off, the subsequent Ni plating, oiling, etc. will prevent the roughness of the steel plate. There is no problem in practice, since the recesses have been filled in.
はうろう釉薬は溶融後急冷破砕されたガラス質（フリッ
ト）に浮遊剤、着色剤、水を加えてボールミル等で、約
２００メツシユに微粉砕したもの（スリップ）で、これ
らの成分は、はうろう成分ないしはその用途により異な
り、更に種々の添加物を加えることがある。The floating glaze is made by adding a flotation agent, a coloring agent, and water to a glassy material (frit) that is melted, then rapidly cooled and crushed, and then finely ground (slip) to about 200 mesh pieces using a ball mill, etc. It varies depending on the wax component or its use, and various additives may be added.
施釉はスプレィ、浸漬、静電スプレィ、電気泳動法等が
あり、鋼板の片面又は両面に行う。施釉後、室温〜１０
０℃位で数１０分乾燥し、約８００〜９２０℃の炉で焼
成するか、連続炉で乾燥、焼成、冷却を行ない、はうろ
う成品に仕上げる。Glazing can be done by spraying, dipping, electrostatic spraying, electrophoresis, etc. on one or both sides of the steel plate. After glazing, room temperature ~10
The product is dried at about 0°C for several tens of minutes, then fired in a furnace at about 800 to 920°C, or dried, fired, and cooled in a continuous furnace to produce a smooth product.
本発明の製品から製造されるほうろう成品は、耐食性、
耐熱性、耐摩耗性、耐薬品性、豊かな色彩等に優れ、ス
トーブ、レンジ、ボール、ポット、炊飯器、流し台、建
築用パネル、白板、等に用いられる。Enamel products produced from the products of the present invention have corrosion resistance,
It has excellent heat resistance, abrasion resistance, chemical resistance, rich color, etc., and is used for stoves, ranges, bowls, pots, rice cookers, sinks, architectural panels, white boards, etc.
以上、普通鋼板に１回掛けほうろうをする場合について
説明した。一方、２回掛けほうろうについては下釉にＣ
ｏｏ 、 ＮｉＯ等を添加し、鋼板との密着性を高めて
いるので本発明の酸化鉄皮膜があると更に密着性を向上
する。又、下釉にはＰ２ａｓ。The case where enameling is performed once on an ordinary steel plate has been described above. On the other hand, for double-glazed enamel, C is applied to the lower glaze.
oo, NiO, etc. are added to improve the adhesion to the steel plate, so the presence of the iron oxide film of the present invention further improves the adhesion. Also, P2as is used for the lower glaze.
＾１２ｏｘ 、 ＺｒＯ□量を多くしているので、溶融
時の釉薬の流動性を良くし、ガスの放出をはかり、その
後上釉を下釉より低温度で焼成するため、泡欠陥や爪と
びが発生しにくい。The large amounts of ^12ox and ZrO□ improve the fluidity of the glaze during melting and release gas, and then the upper glaze is fired at a lower temperature than the lower glaze, which eliminates bubble defects and nail skipping. Hard to occur.
以上の様に本発明によれば普通鋼板でもほうろう特性が
極めて良好であった。この場合、Ｎｉメッキは不要であ
る。As described above, according to the present invention, even ordinary steel sheets had extremely good enameling properties. In this case, Ni plating is not necessary.
（実施例１）
第１表の成分（重量％）の２．０ｍｍ厚みの普通の熱延
鋼板（ＳＰＩＩＣ）を塩酸々洗した鋼板及び０．８１１
ＩＩｌ厚みの冷延鋼板（ＳＰＣＣと５ＰＣＥ＞を０．５
〜１．２％調質圧延又はショット後１００ｘ １５０ｅ
ｓ”に剪断し、脱脂、硫酸々洗で鋼板表裏面の粗度をＲ
ｍａｘで約７〜６１μ−に調整後、炉温か３５０℃、５
００℃及び７００℃の電気加熱炉中で１秒〜２０分間酸
化し、Ｎｉメッキし、その上層に第２表のフリットを主
成分とする釉薬を鋼板の両面に約１３０μｒ＠施釉し、
１００℃で３０分間乾燥を行った後焼成した。(Example 1) A steel plate obtained by washing an ordinary hot rolled steel plate (SPIIC) with a thickness of 2.0 mm with the ingredients (wt%) in Table 1 and 0.811
IIl thickness cold rolled steel plate (SPCC and 5PCE>0.5
~1.2% after temper rolling or shot 100x 150e
The roughness of the front and back surfaces of the steel plate is Rized by shearing it to s'', degreasing it, and washing it with sulfuric acid.
After adjusting the max to about 7 to 61μ-, the furnace temperature was 350℃, 5
Oxidize in an electric heating furnace at 00°C and 700°C for 1 second to 20 minutes, plate with Ni, and apply a glaze mainly composed of the frit shown in Table 2 on both sides of the steel plate for about 130 μr @ on the upper layer,
After drying at 100°C for 30 minutes, it was fired.
なお比較品には、酸化処理を行っていないもの（通常の
両面１回掛処理）および酸化鉄厚さが本発明範囲外のも
のを示す。Comparative products include those that were not subjected to oxidation treatment (normal double-sided treatment once) and those whose iron oxide thickness was outside the range of the present invention.
第１図には炉温３００℃、５００℃及び７００℃中での
鋼板表面の昇温曲線を示す、参考のため第３表の酸化条
件で炉温３５０℃装入時間３０秒は第１図で鋼板表面温
度が約９０℃に達しな後（図中Ｘ印）直ちに炉外に出し
、大気中で空冷したものである。Figure 1 shows the temperature rise curves of the steel plate surface at furnace temperatures of 300°C, 500°C and 700°C.For reference, Figure 1 shows the oxidation conditions in Table 3 and the charging time of 30 seconds at a furnace temperature of 350°C. Immediately after the surface temperature of the steel plate reached approximately 90°C (marked with an X in the figure), it was taken out of the furnace and air-cooled in the atmosphere.
第３表に両面１回掛けに本発明品を適用した例を示した
が、酸化処理により普通鋼板はほうろう特性が向上した
ことを明らかにしている。Table 3 shows an example in which the product of the present invention was applied to double-sided coating once, and it is clear that the enamel properties of ordinary steel sheets were improved by oxidation treatment.
以下余日
（実施例２）
第１表の成分（重量％）の２．０ｍｍ厚みの普通の熱延
鋼板を塩酸々洗した鋼板及び０．８論−厚の通常の冷延
鋼板を０．５〜１．２％調質圧延又はショットし、１５
０ｘ １００ｍ５２のサンプルに剪断後アルカリ液で脱
脂し、１０％硫酸液中で数分間酸洗して粗度を調整した
後中和し、炉温か３５０℃、５００℃及び７００℃の電
気加熱炉中で１秒〜３分間酸化し、Ｎｉメッキ後後火火
点５５〜２１０℃さび止め油を塗油量を変えて均一に塗
油した。The rest of the day (Example 2) A steel plate obtained by washing a 2.0 mm thick ordinary hot rolled steel plate with the ingredients (wt%) shown in Table 1 and a 0.8 mm thick ordinary cold rolled steel plate. 5-1.2% temper rolled or shot, 15
After shearing a sample of 0x 100m52, it was degreased with an alkaline solution, pickled in a 10% sulfuric acid solution for several minutes to adjust the roughness, neutralized, and heated in an electric heating furnace at a furnace temperature of 350°C, 500°C, and 700°C. After oxidizing for 1 second to 3 minutes, and after Ni plating, a rust preventive oil with a flash point of 55 to 210° C. was applied uniformly in varying amounts.
その後第２表のフリットを主成分とする釉薬（スリップ
）をスプレィで施釉し、室温〜５０℃範囲で３０分間乾
燥した後焼成、空冷後各種はうろう特性を測定し、その
結果を第４表及び第５表に示す。Afterwards, a glaze (slip) containing the frit shown in Table 2 as the main component was applied by spraying, dried for 30 minutes at room temperature to 50°C, fired, and after air cooling, the floating properties of each type were measured. It is shown in Table and Table 5.
なお、第４表の比較品には酸化鉄厚さが本発明範囲外の
ものと従来法のＮｉメッキ後片面３ｇ／ｍ２以上塗油し
たものを示す。The comparative products in Table 4 include those whose iron oxide thickness is outside the range of the present invention and those coated with oil of 3 g/m2 or more on one side after Ni plating using the conventional method.
第５表の比較品には、酸化、Ｎｉメッキ後塗油量の多い
ものを示す。The comparative products in Table 5 include those with a large amount of oil applied after oxidation and Ni plating.
第４表及び第５表から明らかなようにほうろう釉薬を施
釉する前に５０〜１１００人の酸化鉄層を有する鋼板に
ほうろう掛けした製品′はコツパーヘッド、爪飛びがな
く、密着性も良好であった。As is clear from Tables 4 and 5, the products made by enameling a steel plate with a layer of 50 to 1,100 iron oxides before applying the enamel glaze had no crack heads or chipped nails, and had good adhesion. there were.
これに反し、普通の冷延鋼板を従来の製造法である脱脂
、酸洗、Ｎｉメッキ、適量塗油、施釉し。On the other hand, ordinary cold-rolled steel sheets are processed using conventional manufacturing methods such as degreasing, pickling, Ni plating, applying an appropriate amount of oil, and glazing.
はうろう掛けしたものは密着性が悪い。更に酸化膜厚が
５０μ輪未満又は１１００μｍ超のものはほうろう膜の
密着性が悪い。又、塗油量が片面当り３．Ｏｇ／ｌａ２
超では釉引けが発生する。The adhesiveness of the hanging material is poor. Furthermore, if the oxide film thickness is less than 50 μm or more than 1100 μm, the adhesion of the enamel film is poor. Also, the amount of oil applied per side is 3. Og/la2
When using super, glaze fading occurs.
なお、密着性は８０％以上を全ての実施例において合格
の目安にしている。It should be noted that adhesion of 80% or more was set as a criterion for passing in all Examples.
本発明にかかわるほうろう用被覆鋼板は普通鋼板（例え
ば５ＰＣＣ）で、はうろう特性が従来のほうろう用鋼板
と比較して同等程度にほうろう欠陥を防止できるので、
その経済的効果、作業効果が極めて大きい。The coated steel plate for enameling according to the present invention is a normal steel plate (for example, 5PCC), and its enamel properties can prevent enamel defects to the same degree as conventional steel plates for enameling.
The economic and operational effects are extremely large.
第１図は、０ 、８ ｍｍ Ｘ １００ｍｍ Ｘ １５
０ｍｍの寸法の試料について酸化時間（炉内保持時間）
、酸化温度（鋼板表面温度）および炉温の関係を示すグ
ラフである。Figure 1 is 0.8 mm x 100 mm x 15
Oxidation time (furnace holding time) for a sample with a size of 0 mm
, is a graph showing the relationship between oxidation temperature (steel plate surface temperature) and furnace temperature.
Claims (1)
することを特徴とするほうろう用の被覆鋼板。1. A coated steel sheet for enameling, characterized by having an iron oxide layer with a thickness of 50 to 1100 Å on the surface of the ordinary steel sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62027222A JPH0660421B2 (en) | 1987-02-10 | 1987-02-10 | Coated steel plate for enamel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62027222A JPH0660421B2 (en) | 1987-02-10 | 1987-02-10 | Coated steel plate for enamel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63195284A true JPS63195284A (en) | 1988-08-12 |
| JPH0660421B2 JPH0660421B2 (en) | 1994-08-10 |
Family
ID=12215070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62027222A Expired - Lifetime JPH0660421B2 (en) | 1987-02-10 | 1987-02-10 | Coated steel plate for enamel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0660421B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008035528A1 (en) | 2006-09-19 | 2008-03-27 | Nippon Steel Corporation | Works for enameling and enameled products |
| US9073114B2 (en) | 2006-09-27 | 2015-07-07 | Nippon Steel & Sumitomo Metal Corporation | Enameling steel sheet, excellent in fishscale resistance and method of producing the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218970B (en) * | 2011-04-12 | 2013-05-08 | 浙江开尔新材料股份有限公司 | Enamel decorative board for art paintings and processing method thereof |
| JP2013124410A (en) * | 2011-12-16 | 2013-06-24 | Nippon Telegr & Teleph Corp <Ntt> | Method of suppressing generation of hydrogen on surface of steel |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5216517A (en) * | 1975-07-30 | 1977-02-07 | Mitsubishi Heavy Ind Ltd | Process for coating metal surface |
-
1987
- 1987-02-10 JP JP62027222A patent/JPH0660421B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5216517A (en) * | 1975-07-30 | 1977-02-07 | Mitsubishi Heavy Ind Ltd | Process for coating metal surface |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008035528A1 (en) | 2006-09-19 | 2008-03-27 | Nippon Steel Corporation | Works for enameling and enameled products |
| EP2065482A1 (en) * | 2006-09-19 | 2009-06-03 | Nippon Steel Corporation | Works for enameling and enameled products |
| US8236111B2 (en) | 2006-09-19 | 2012-08-07 | Nippon Steel Corporation | Product for enameling and enameled product |
| EP2065482A4 (en) * | 2006-09-19 | 2015-04-22 | Nippon Steel & Sumitomo Metal Corp | Works for enameling and enameled products |
| US9073114B2 (en) | 2006-09-27 | 2015-07-07 | Nippon Steel & Sumitomo Metal Corporation | Enameling steel sheet, excellent in fishscale resistance and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0660421B2 (en) | 1994-08-10 |
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