JPH0643257B2 - Plate enamel products - Google Patents
Plate enamel productsInfo
- Publication number
- JPH0643257B2 JPH0643257B2 JP30131487A JP30131487A JPH0643257B2 JP H0643257 B2 JPH0643257 B2 JP H0643257B2 JP 30131487 A JP30131487 A JP 30131487A JP 30131487 A JP30131487 A JP 30131487A JP H0643257 B2 JPH0643257 B2 JP H0643257B2
- Authority
- JP
- Japan
- Prior art keywords
- enamel
- plate
- layer
- product
- bent
- 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 - Fee Related
Links
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- Glass Compositions (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は板状のほうろう製品に関し、さらに詳しくは
曲げ加工に適した板状のほうろう製品に関する。Description: TECHNICAL FIELD The present invention relates to a plate-shaped enamel product, and more particularly to a plate-shaped enamel product suitable for bending.
〔従来の技術〕 従来アルミ板あるいはアルミメツキ鋼板をほうろう加工
後、プレスブレーキ等により曲げ加工すると、折曲部の
ほうろう層にクラツクが大量に発生し、外観が劣るもの
であつた。また鋼板をほうろう加工後曲げ加工した場合
も、前記のクラツクが発生し、このクラツクは鋼板素地
に達するので赤錆が発生し、外観と共に強度上も問題が
あった。このため上記各種金属板を用いて、たとえば外
周に折曲片部を有する浅い箱状のパネル等のように、折
曲部のあるほうろう製品を製作する場合は、先ず金属板
を折曲加工後にほうろう加工していたので、工程が複雑
で生産性が低かつた。[Prior Art] When a conventional aluminum plate or an aluminum plated steel plate is enamel processed and then bent by a press brake or the like, a large amount of cracks are generated in the enamel layer at the bent portion, resulting in a poor appearance. Also, when the steel plate is bent after enameling, the cracks described above occur, and the cracks reach the base material of the steel plate, so that red rust occurs and there is a problem in appearance and strength. Therefore, when using the above-mentioned various metal plates to manufacture an enameled product having a bent portion, such as a shallow box-shaped panel having a bent piece portion on the outer periphery, first, after the metal plate is bent, Since enameled, the process was complicated and the productivity was low.
この発明は上記従来の問題点を解決するもので、ほうろ
う加工を能率よくおこなえ、曲げ加工時において発生す
るクラツクが目立たず、外観のすぐれた曲げ加工品を得
ることができる板状ほうろう製品を提供しようとするも
のである。The present invention solves the above-mentioned conventional problems, and provides a plate-shaped enamel product capable of efficiently performing enamel processing, inconspicuous cracks generated during bending, and obtaining a bent product with an excellent appearance. Is what you are trying to do.
しかしてこの発明のほうろう製品は、少なくとも表面部
がアルミ層から成る金属板の表面に、ＳｉＯ2とＴｉＯ2
とＺｒＯ2の合計を３〜１０重量％、Ｎａ2ＯとＫ2Ｏと
Ｌｉ2Ｏの合計を１５〜２５重量％、ＢａＯとＺｎＯの
合計を５〜２０重量％、Ｐ2Ｏ5とＡｌ2Ｏ3とＳｂ2Ｏ3と
Ｂ2Ｏ3の合計を５０〜８０重量％含有し、かつＰ2Ｏ5と
Ａｌ2Ｏ3とＳｂ2Ｏ3とＢ2Ｏ3の合計に対するＰ2Ｏ5の割
合が８０％以上であるフリツトを用いた、厚さ１０〜５
０μｍのほうろう層を設けたことを特徴とする板状ほう
ろう製品である。However, the enamel product of the present invention has SiO 2 and TiO 2 on the surface of a metal plate having at least a surface portion made of an aluminum layer.
And ZrO 2 total 3 to 10 wt%, Na 2 O, K 2 O and Li 2 O total 15 to 25 wt%, BaO and ZnO total 5 to 20 wt%, P 2 O 5 and Al. total 2 O 3 and Sb 2 O 3 and B 2 O 3 and containing 50 to 80 wt%, and P 2 O to the total of P 2 O 5 and Al 2 O 3 and Sb 2 O 3 and B 2 O 3 Thickness of 10 to 5 using a frit whose ratio of 5 is 80% or more
A plate-shaped enamel product characterized by having an enamel layer of 0 μm.
この発明において少なくとも表面部がアルミ層から成る
金属板としては、アルミニウム板またはアルミメツキ鋼
板を用いることができる。このアルミ層のアルミニウム
純度は、ほうろう層との強固な密着力を得るために、８
０％以上とするのが好ましい。またアルミメツキ鋼板の
場合のメツキ層は、耐食性の点から１０μｍ以上の厚さ
とするのが好ましい。In the present invention, an aluminum plate or an aluminum plated steel plate can be used as the metal plate having at least the surface portion made of an aluminum layer. The aluminum purity of this aluminum layer is 8 in order to obtain a strong adhesion with the enamel layer.
It is preferably 0% or more. In the case of an aluminum plated steel plate, the plated layer preferably has a thickness of 10 μm or more from the viewpoint of corrosion resistance.
この発明においては、発明者が研究の結果得た知見に基
づき、ほうろう層形成用のフリツトの各構成成分を限定
しているが、以下その限定理由を説明する。In the present invention, each constituent component of the frit for forming an enamel layer is limited based on the knowledge obtained by the inventor as a result of the research. The reason for the limitation will be described below.
まずＳｉＯ2，ＴｉＯ2，ＺｒＯ2（以下ＲＯ2群と総称す
る）は、結晶化およびほうろうの耐久性向上のための必
須成分であり、ＲＯ2群の総量がフリツト中に占める割
合が３％（重量％。以下同じ）未満であるとほうろう層
の耐酸性が低下し、また１０％を越えるとアルミ層への
ほうろうの密着性が悪くなる。First, SiO 2 , TiO 2 , and ZrO 2 (hereinafter collectively referred to as RO 2 group) are essential components for crystallization and improving the durability of enamel, and the total amount of RO 2 group accounts for 3% in the frit. If it is less than (% by weight; the same applies hereinafter), the acid resistance of the enamel layer is lowered, and if it exceeds 10%, the adhesion of the enamel to the aluminum layer is deteriorated.
次にＮａ2Ｏ，Ｋ2Ｏ，Ｌｉ2Ｏ（以下Ｒ2Ｏ群と総称す
る）の総量が１５％未満だとほうろうの融点が上りアル
ミ層への密着性が低下し、曲げ加工時にほうろう層の剥
離現象を生じやすい。またＲ2Ｏ群が２５％を越えると
熱膨張率が上昇し、ほうろう層焼成時にクラツクを生じ
やすくなるので好ましくない。Next, if the total amount of Na 2 O, K 2 O, and Li 2 O (collectively referred to as R 2 O group below) is less than 15%, the melting point of enamel rises and the adhesion to the aluminum layer decreases, and enameling during bending. A layer peeling phenomenon is likely to occur. If the R 2 O group exceeds 25%, the coefficient of thermal expansion increases, and cracking tends to occur during firing of the enamel layer, which is not preferable.
またＢａＯ，ＺｎＯ（以下ＲＯ群と総称する）の総量が
５％未満だと耐酸性が低下し、２０％を越えるとガラス
構造が軟弱になり耐酸性とともに密着性も低下する。If the total amount of BaO and ZnO (hereinafter collectively referred to as RO group) is less than 5%, the acid resistance decreases, and if it exceeds 20%, the glass structure becomes soft and the acid resistance as well as the adhesion decrease.
次にＰ2Ｏ5，Ａｌ2Ｏ3，Ｓｂ2Ｏ3，Ｂ2Ｏ3（以下Ｒ2Ｏ3
群と総称する）の総量が５０％未満だとほうろうの密着
性が低下し、曲げ加工時に剥離を生じやすく、また８０
％を越えると熱膨張率が上昇し、焼成時にクラツクを生
じやすくなるので好ましくない。またＲ2Ｏ3群中のＰ2
Ｏ5の占める割合が８０％未満だと、曲げ加工時のクラ
ツクが目立つようになるので好ましくない。Next, P 2 O 5 , Al 2 O 3 , Sb 2 O 3 , B 2 O 3 (hereinafter R 2 O 3
If the total amount of the enamel is less than 50%, the adhesiveness of the enamel is deteriorated and peeling is apt to occur during bending.
If it exceeds%, the coefficient of thermal expansion increases and cracking is likely to occur during firing, which is not preferable. In addition, P 2 in the R 2 O 3 group
If the proportion of O 5 is less than 80%, cracking during bending becomes conspicuous, which is not preferable.
またこの発明においてほうろう層の厚さは１０〜５０μ
ｍに限定してあるが、この厚さが１０μｍ未満だとほう
ろう外観に素地が透けて見える欠陥が生じやすく、５０
μｍを越えると曲げ加工時にクラツクが目立ちやすくな
り、いずれも外観品質が悪化するので好ましくない。In the present invention, the thickness of the enamel layer is 10 to 50 μm.
Although it is limited to m, if the thickness is less than 10 μm, the enamel appearance is apt to have a defect in which the substrate can be seen through.
If it exceeds .mu.m, cracks are likely to be noticeable during bending and the quality of appearance is deteriorated, which is not preferable.
この発明の板状ほうろう製品においては、ほうろう層を
形成するフリツトはその各成分比率の組合せにより、５
００〜５６０℃という低温の焼成温度で溶け不足なく溶
融して１０〜５０μｍの薄い層厚のほうろう層を容易に
形成する。得られるほうろう層は耐酸性およびアルミ層
に対する密着性がすぐれ、焼成後の板状ほうろう製品の
曲げ加工時における剥離がほとんど生じない。そしてこ
のほうろう層の厚さは５０μｍ以下と薄いので、第１図
に示すように金属板１の表面側に設けられたほうろう層
２は、曲げ加工によつて伸びを受けるためクラツク３は
生じるものの、ほうろう層厚が薄く引張強度も小さいの
でクラツク３の開口寸法Ａが１０〜３０μｍと微細であ
るため、肉眼で見たときクラツクが目立たない。これに
対して第２図に示すようにほうろう層２の厚さが５０〜
１００μｍと厚い従来の板状ほうろう製品においては、
曲げ加工時にはほうろう層が厚い分だけほうろう層表面
の伸び量および引張強度が増加して、クラツク数が減少
するため、クラツク３の開口寸法Ａが、５０〜１００μ
ｍと大きく、肉眼で見たときクラツクが目立ち、外観が
劣るものである。In the plate-shaped enamel product of the present invention, the frit forming the enamel layer has a ratio of 5 depending on the combination of the respective components.
The enamel layer having a thin layer thickness of 10 to 50 μm is easily formed by melting at a low firing temperature of 00 to 560 ° C. without insufficient melting. The obtained enamel layer has excellent acid resistance and excellent adhesion to the aluminum layer, and peeling hardly occurs during bending of the plate-shaped enamel product after firing. Since the thickness of this enamel layer is as thin as 50 μm or less, the enamel layer 2 provided on the front surface side of the metal plate 1 as shown in FIG. Since the enamel layer is thin and the tensile strength is small, the opening dimension A of the crack 3 is as fine as 10 to 30 μm, so that the crack is not noticeable with the naked eye. On the other hand, as shown in FIG.
In the conventional plate-shaped enamel products with a thickness of 100 μm,
At the time of bending, the amount of cracks decreases as the amount of cracks increases and the amount of elongation of the surface of the enamel layer increases by the thickness of the enamel layer. Therefore, the opening dimension A of the crack 3 is 50 to 100 μm.
m is large, the crack is noticeable with the naked eye, and the appearance is inferior.
このようにこの発明の板状ほうろう製品は曲げ加工時の
ほうろう層に生じるクラツクが微細であるので、たとえ
ばコイル状の平板にほうろうを焼付けたものに、ロール
フオーミングその他により曲げ加工を施してパネル等の
曲げ加工製品を能率よく製造できる。As described above, since the plate-shaped enamel product of the present invention has fine cracks generated in the enamel layer during bending, for example, a coil-shaped flat plate to which enamel is baked is bent by roll forming or the like to form a panel. Bending products such as can be manufactured efficiently.
また上釉層の焼成温度が低いため、上釉薬中に配合した
発色顔料の熱分解量が少なく安定性が向上するので、鮮
かな発色を有するほうろう層やマイカ片を分散したメタ
リツク調のほうろう層等で被覆された美麗な外観を有し
曲げ加工可能な板状ほうろう製品を得ることもできる。In addition, since the firing temperature of the upper glaze layer is low, the amount of thermal decomposition of the coloring pigment compounded in the upper glaze is small and the stability is improved. It is also possible to obtain a plate-shaped enamel product which has a beautiful appearance and is bendable.
以下この発明の実施例および比較例を説明する。 Examples and comparative examples of the present invention will be described below.
先ず第１表に示す構成比率の各化合物から成るＲＯ2群
〜Ｒ2Ｏ3群を、第２表に示す６種類の組成比で含有する
フリツトを、実施例のほうろう層形成用のフリツトとし
て用い、またＲＯ2群〜Ｒ2Ｏ3群の組成比が本発明の限
定範囲を越える７種類のフリツトを比較例用のフリツト
として用いた。First, a frit containing RO 2 group to R 2 O 3 group consisting of the compounds having the compositional ratios shown in Table 1 at six compositional ratios shown in Table 2 was used as a frit for forming an enamel layer of the example. Seven types of frits having the composition ratios of the RO 2 group to the R 2 O 3 group exceeding the limited range of the present invention were used as the frits for the comparative examples.
これらのフリツト１００部に対し、添加剤として顔料を
５５部、分散剤を３部加えて、ミルに投入し、９０分間
粉砕後１５０メツシユふるいでオールパスしたものを釉
薬として用いた。To 100 parts of these frits, 55 parts of a pigment and 3 parts of a dispersant were added as additives, put into a mill, milled for 90 minutes, all-passed through a 150 mesh sieve, and used as a glaze.
そして金属板としては、純度８５％のアルミニウムを厚
さ５０μｍの厚さに鋼板表面にメツキして成るアルミメ
ツキ鋼板を用い、このアルミ層の上に上記各釉薬を施釉
して５５０℃で焼成し、厚さ４０μｍのほうろう層を形
成し、板状ほうろう製品試料を得た。Then, as the metal plate, an aluminum plated steel plate formed by plating aluminum having a purity of 85% to a thickness of 50 μm on the surface of the steel plate is used, and each of the above glazes is glazed on the aluminum layer and baked at 550 ° C., A enamel layer having a thickness of 40 μm was formed to obtain a plate-shaped enamel product sample.
得られた試料については、平板のままで下記に記す特性
試験をおこなつたのち、プレスプレーキを用いて曲げ半
径２mmＲで直角曲げをおこない、曲げ部分におけるほう
ろう層の外観を目視観察し、その後１年間屋外曝露後の
曲げ部分におけるほうろう層の外観を同様に目視観察し
た。これらの試験あるいは観察結果は第２表に示す通り
であつた。The obtained sample was subjected to the characteristic test described below on a flat plate and then bent at right angles with a bending radius of 2 mmR using a pre-spray to visually observe the appearance of the enamel layer at the bent portion. The appearance of the enamel layer in the bent portion after annual outdoor exposure was also visually observed. The results of these tests or observations are shown in Table 2.
(a)ほうろう外観 目視によりほうろう層の状態を観察した。各符号の内容
は次の通りである。(a) Appearance of enamel The state of the enamel layer was visually observed. The contents of each code are as follows.
［溶け］ ○＝完全溶融 △＝半溶融 ［クラツク］ ○＝クラツクなし ×＝クラツクあり (b)耐酸性 ＪＩＳＲ−４３０１「ほうろう製品の品質基準」により
判定した。（１０％クエン酸１５分スポツト） (c)密着性 ＪＩＳＺ−２２４７「エリクセン試験方法」により試験
をおこなつた。（エリクセン、３mm絞り、凹） ○印は
剥離なしを、×印は剥離ありを示す。[Melting] ○ = Complete melting △ = Semi-melting [Cracking] ○ = No cracking × = Cracking (b) Acid resistance Judged according to JIS R-4301 "Quality standards for enameled products". (10% citric acid spot for 15 minutes) (c) Adhesion The test was conducted according to JIS Z-2247 "Erichsen test method". (Erichsen, 3 mm aperture, concave) O indicates no peeling, X indicates peeling.
(d)曲げ加工品のほうろう外観 目視により曲げ部分のほうろう層の状態を観察した。(d) Bone enamel appearance of the bent product The state of the enamel layer in the bent portion was visually observed.
次に前記実施例５のフリツト組成において、Ｒ2Ｏ3群中
のＰ2Ｏ5の比率を第３表のように８０％以上の範囲（実
施例７，８）および７０％以下の範囲（比較例８，９）
で変えたほかは、前記実施例５と同条件でほうろう製品
試料を作成し、これらの試料に対して前記実施例と同様
な特性試験（一部省略）をおこなつた結果を第３表に示
す。Next, in the frit composition of Example 5, the ratio of P 2 O 5 in the R 2 O 3 group is 80% or more (Examples 7 and 8) and 70% or less (Table 7). Comparative Examples 8 and 9)
Table 3 shows the results obtained by preparing enamel product samples under the same conditions as in Example 5 and performing characteristic tests (partially omitted) similar to those in Example above on these samples except that the above was changed. Show.
第２表および第３表から明らかなように、比較例のもの
はいずれも曲げ加工品の曲げ部分におけるクラツクが目
立ち、外観が劣るものであるが、実施例によれば上記ク
ラツクが目立たず外観がすぐれた曲げ加工品を得ること
ができ、さらに耐酸性、密着性などの点においてもすぐ
れた板状ほうろう製品が得られることが判る。 As is clear from Tables 2 and 3, the cracks in the bent parts of the bent products are conspicuous and the appearance is inferior in all of the comparative examples. However, according to the examples, the cracks are not conspicuous and the appearance is poor. It can be seen that a bent product having excellent properties can be obtained, and a plate-shaped enamel product having excellent acid resistance and adhesion is also obtained.
以上説明したようにこの発明によれば、ほうろう加工を
平板状態において能率よくおこなうことができ、曲げ加
工時において発生するクラツクが目立たず、外観のすぐ
れた曲げ加工品を得ることできる板状ほうろう製品が提
供される。As described above, according to the present invention, a plate-shaped enamel product capable of efficiently performing enamel working in a flat plate state, a crack generated during bending is not conspicuous, and a bent product having an excellent appearance can be obtained. Will be provided.
第１図はこの発明の板状ほうろう製品の曲げ加工状態を
示す略示拡大断面図、第２図は従来の板状ほうろう製品
の第１図相当図である。 １……金属板、１……ほうろう層。FIG. 1 is an enlarged schematic cross-sectional view showing a bending state of a plate-shaped enamel product of the present invention, and FIG. 2 is a view corresponding to FIG. 1 of a conventional plate-shaped enamel product. 1 ... Metal plate, 1 ... Enamel layer.
Claims (1)
板の表面に、ＳｉＯ2とＴｉＯ2とＺｒＯ2の合計を３〜
１０重量％、Ｎａ2ＯとＫ2ＯとＬｉ2Ｏの合計を１５〜
２５重量％、ＢａＯとＺｎＯの合計を５〜２０重量％、
Ｐ2Ｏ5とＡｌ2Ｏ3とＳｂ2Ｏ3とＢ2Ｏ3の合計を５０〜８
０重量％含有し、かつＰ2Ｏ5とＡｌ2Ｏ3とＳｂ2Ｏ3とＢ
2Ｏ3の合計に対するＰ2Ｏ5の割合が８０％以上であるフ
リツトを用いた、厚さ１０〜５０μｍのほうろう層を設
けたことを特徴とする板状ほうろう製品。1. A total of 3 to 3 of SiO 2 , TiO 2, and ZrO 2 is formed on the surface of a metal plate having at least a surface portion made of an aluminum layer.
10% by weight, the total of Na 2 O, K 2 O and Li 2 O is 15 to
25% by weight, the total of BaO and ZnO is 5 to 20% by weight,
The total of P 2 O 5 , Al 2 O 3 , Sb 2 O 3 and B 2 O 3 is 50 to 8
0 wt% and contains P 2 O 5 , Al 2 O 3 , Sb 2 O 3 and B
A plate-like enamel product, which is provided with a enamel layer having a thickness of 10 to 50 μm using a frit having a ratio of P 2 O 5 to the total of 2 O 3 of 80% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30131487A JPH0643257B2 (en) | 1987-11-27 | 1987-11-27 | Plate enamel products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30131487A JPH0643257B2 (en) | 1987-11-27 | 1987-11-27 | Plate enamel products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01141835A JPH01141835A (en) | 1989-06-02 |
| JPH0643257B2 true JPH0643257B2 (en) | 1994-06-08 |
Family
ID=17895360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30131487A Expired - Fee Related JPH0643257B2 (en) | 1987-11-27 | 1987-11-27 | Plate enamel products |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643257B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016063561A1 (en) * | 2014-10-24 | 2016-04-28 | イビデン株式会社 | Coated metal substrate |
| WO2016063560A1 (en) * | 2014-10-24 | 2016-04-28 | イビデン株式会社 | Method for producing coated metal substrate |
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|---|---|---|---|---|
| EP0916624B1 (en) * | 1997-11-11 | 2001-07-25 | Kawasaki Steel Corporation | Porcelain-enameled steel sheets and frits for enameling |
| EP0999191A1 (en) * | 1998-11-03 | 2000-05-10 | Corning Incorporated | Glasses compatible with aluminium |
| US6214471B1 (en) | 1998-11-03 | 2001-04-10 | Corning Incorporated | Glasses compatible with aluminum |
| JP2008308393A (en) * | 2007-06-18 | 2008-12-25 | Noritake Co Ltd | Lead-free low softening point glass, lead-free low softening point glass composition, lead-free low softening point glass paste, and fluorescent display tube |
| JP2017095286A (en) * | 2014-02-25 | 2017-06-01 | 東罐マテリアル・テクノロジー株式会社 | Glaze for aluminum enamel |
| CN105386051B (en) * | 2014-09-09 | 2018-06-26 | 中国科学院金属研究所 | A kind of method for improving the resistance to liquid metal corrosion of martensite heat-resistant steel |
| JP7426029B2 (en) * | 2020-10-01 | 2024-02-01 | 啓二郎 茂 | Aluminum and aluminum alloy appliances and their manufacturing method |
-
1987
- 1987-11-27 JP JP30131487A patent/JPH0643257B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016063561A1 (en) * | 2014-10-24 | 2016-04-28 | イビデン株式会社 | Coated metal substrate |
| WO2016063560A1 (en) * | 2014-10-24 | 2016-04-28 | イビデン株式会社 | Method for producing coated metal substrate |
| JPWO2016063561A1 (en) * | 2014-10-24 | 2017-08-03 | イビデン株式会社 | Coated metal substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01141835A (en) | 1989-06-02 |
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