JPS60110884A - Manufacture of enamelware - Google Patents

Abstract

PURPOSE:To simplify a pretreating stage before enameling by immersing a degreased steel sheet substrate for enameling in an aqueous soln. of nickel formate, nickel acetate or nickel citrate, pulling up the substrate, driving and calcining it, coating enamel, and calcining it. CONSTITUTION:A degreased steel sheet substrate for enameling is immersed in an aqueous soln. of nickel formate, nickel acetate or nickel citrate, and it is pulled up, dried and calcined to form a thin layer of org. nickel hemioxide or nickel oxide on the surface of the substrate. Enamel is coated on the org. nickel hemioxide or nickel oxide layer, and after diffusing and infiltrating the enamel into the layer, calcination is carried out.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a simple method for manufacturing enamel articles.

Conventional TFL formation and its problems In the manufacturing method of enamel products, a steel plate base material for enamel processed into the shape of various target objects is subjected to the steps of enamel pretreatment, application of enamel glaze, and drying firing. Ru. During this process, especially the enamel pre-treatment includes degreasing, washing with water, and electroless gi #L tu! using an aqueous nickel sulfate solution. f = =
, )r Rui 71 @ get 1! & 11Z hV
ih - k method - core ■ - drying order 7'L.

The conditions for pickling treatment are concentration 7-10 bi2%, temperature 65%.
~76°C 1 immersion treatment time 5-10 t'L,
Electroless treatment has a concentration of 10 to 16 g/μ, a temperature of 65 hair, and a hair temperature of 75
It is carried out for 5-10 minutes for 1 hour at °C.

Among the various performances that must be ensured when making an enamel product, the adhesion between the steel plate base material for enamel and the enamel layer, and the surface condition of the enamel product (glossy,
The K-enamel pre-treatment process is heavily involved in this process (pinhole formation, citron shavings, etc.). Therefore, managing the conditions for this pretreatment requires a great deal of effort, as it requires fineness and accuracy despite a wide variety of factors such as the ever-changing temperature, temperature, immersion time, aging of the liquid, etc. At the same time, the use of generated water vapor and strong acids led to the deterioration of the working environment.

Purpose of the Invention The present invention aims to improve the adhesion between an enameled steel sheet base material and an enameled layer when made into an enameled product, without impairing the surface condition.
It is an object of the present invention to provide a method for manufacturing an enameled article, which greatly simplifies the process of manufacturing the enameled article, particularly the kneeling step after the pickling treatment with an aqueous sulfuric acid solution in the porous pretreatment.

Structure of the Invention The present invention involves degreasing and washing the layers of steel plates for enamel processed into various desired shapes, immersing them in an aqueous solution of nickel formate, nickel acetate, or nickel citrate, and then removing the layers. Basically, the enamel glaze is applied to a dried or fired product and then fired, and if necessary, the nickel salt aqueous solution may contain water-soluble sugars, starch,
Uniformly dissolves cellulose and synthetic polymer compounds.

There are a few theories about the mechanism of adhesion between the steel sheet layer for enamel and the enamel layer, and there is no established theory, but the general interpretation is that in conventional manufacturing methods, the adhesion mechanism between the enamel layer and the enamel layer is formed on the surface of the base material by electroless treatment. When enamel glaze is applied to a thin porous nickel layer, it penetrates and diffuses, and by firing it, it forms a foothold for anchor-like adhesion between the thin porous nickel layer and the enamel layer, and also improves the layer phase. It is believed that diffusion into the boron-like layer occurs due to alloying of nickel during the electroless treatment of the steel, resulting in closer adhesion.

In addition, for VC with a good surface condition, when a nickel porous layer is formed on the steel plate substrate for enamel,
The formation of a nickel porous layer is extremely effective because it prevents the generation of hydrogen and gas due to contact between the alkaline components in the enamel glaze and the steel.

In the present invention, a porous thin layer of nickel is easily and uniformly formed by the electroless treatment of a steel plate base material for an enameled material, which has been carried out in the conventional manufacturing method of an enameled product. As a method to omit the pickling treatment and to replace this f'L, the steel plate base material for enamel that has been degreased and washed with water is immersed in an aqueous solution of nickel formate, nickel acetate, or nickel citrate, and then pulled out and dried. By firing the wood, a thin layer of organic hemi-nickel oxide or nickel oxide is formed, and this surface is coated with VC enamel glaze.
By drying and firing, the same steel plate base material for enamel and enamel can be produced by forming a nickel porous layer through pickling treatment and electroless treatment, which were performed in the enamel pre-treatment in the conventional manufacturing method of enamel products. It is possible to ensure the adhesion of the quality layer and the surface condition.

According to the method for manufacturing an enameled product of the present invention, a degreased steel plate base material for enameled enamel is immersed at room temperature, pulled up, and dried without necessarily controlling the exact concentration of the special VC liquid. The labor involved in pre-processing for firing can be greatly reduced, and furthermore, it is possible to prevent accidental eating due to steam and acid VC and to prevent deterioration of the quality of the working environment.

In addition, the nickel formate used in the present invention, j! l'
When a steel plate for pouring is immersed in an aqueous solution of nickel or nickel citrate and then pulled up, if you want to form a thin layer of organic hemi nickel oxide or nickel oxide that is more uniform and thick, add a small amount of water. It is preferable to uniformly dissolve sugars, starch, cellulose, or synthetic polymer compounds such as polyacrylic acid, polyvinyl alcohol, and ethylene glycol in the aqueous solution, thereby increasing the adhesion effect.

The concentration of the aqueous solution of nickel formate acetate or nickel citrate used in the present invention is not limited to that, and the concentration of the aqueous solution of nickel formate or nickel citrate used in the present invention is not limited to the concentration of the required organic nickel hemioxide or &J
- It may be determined based on the thickness of the dioxygen oxide layer. However, when using nickel citrate, the solubility is 15g/1
00CC, and if the amount of nickel that is simply immersed in this solution and pulled up is insufficient, or if you want to attach more nickel to nickel formate or nickel acetate, water-soluble saccharides may be used. By uniformly dissolving small amounts of starch, cellulose, and synthetic polymer compounds, a uniform adhesion can be ensured.

Description of Examples Example 1 A steel plate base material for enamel using the degreasing and water washing method, 100 x 100 mm in size and 0.6 mm in thickness, was immersed in an aqueous solution of nickel acetate [N1(CH3COO)2] at a nominal concentration. Pull up,
After firing at 500°C for 2 minutes, nickel (=j amount of deposited (calculated as amount of metallic nickel)
I met. The same steel plate substrate Me for enamel used as in Section 2 was used as a sample for comparison with enamel, and the enamel pretreatment carried out in the conventional manufacturing method of enamel products, i.e., sulfuric acid aqueous solution concentration 7%.
, Pickled at a liquid temperature of 70°C and immersed for 5 minutes, and after washing with water, the concentration of nickel sulfate heptahydrate was 1 og/I! ,,temperature 7o''
Electroless treatment was performed under conditions where C1 immersion time was changed to 5, 10.15 minutes, and after washing with water, neutralization, and drying, the amount of nickel deposited was determined using the same method as above, and the results are shown in column A of Table 1. I got it.

To measure the amount of nickel, cut the central part of the specimen into 3 x 3 pieces using the following method, place 7 L in a beaker, and add a mixture of concentrated nitric acid and water at a weight ratio of 1:1. 2
After adding cc and no longer smoking, add 10 cc of a mixed solution of concentrated hydrochloric acid and water at a weight ratio of 1:5, and then pull out the cut pieces and wash with an appropriate amount of water. Next, A7mo, :=7 water 30
cc, 20% ammonium persulfate solution 10 CC 1 dimethylglyoxime ethanol saturated solution S Add CC, total... f 2
After adjusting the volume to 00 cc, a portion of this P solution was color-compared using a photoelectric photometer against a predetermined calibration curve.

Enamel glazes a and b having the compositions shown in the following pc were applied to each of the enamel pretreated steel plate base materials produced by VC coating as described above, and dried at 160"C for 10 minutes. For 015 minutes, the enamel product (sample) according to the present invention and the comparative product were produced by firing the enamel product (sample) according to the present invention for 6 minutes at 720"C. Steel plate base 4/4
The adhesion of the Polow question was determined by the PEI adhesion test specified by ASTM.
The surface condition was determined in terms of gloss, pinholes, and repellency, and the results in column B in Table 1 were obtained.

Composition of enamel glaze a #1563-B frit (manufactured by Nippon Ferro (1) 100
Front part (white emulsion type) Frog's eye clay 3 II Ultrafine powder stored sand 2 II Magnesium carbonate 0.25 # Sodium nitrite 0.25 times 7μ Water 45 mμ The milling was carried out for 3 hours using a ball mill.

Composition of enamel glaze b: Low melting white emulsion type enamel frit (JP-A-58-642
Enamel frit with a softening point of 630°C based on 42)
100 parts by weight Frog's eye clay 4 Sodium nitrite 0.1 Ultrafine silica sand 1 Sodium aluminate 0.2 Water 64 Side J Note that milling was carried out for 3 hours using a ball mill.

The gloss was measured at an angle of 46 using a Nippon Denshoku Kogyo variable angle gloss meter.
°, and the gloss level was 84.0%.

From the results in Table 1, it can be seen that the specimen produced by the manufacturing method of the present invention has a nickel-coated steel plate on the steel plate for enamel compared to the comparative product.
It can be seen that when the amount is 1.2 Qn-g/dytf or more, the same or better adhesion and surface condition can be ensured.Example 2 Nickel citrate [Ni3(C6H50□)2@14H]
The same operation as in Example 1 was carried out for various concentration aqueous solutions of [20] and a solution prepared by adding 6.10 parts by weight of unsheathed fructose to a 16% by weight aqueous nickel citrate solution.
In the table, A per 1°2.3 of the enamel product according to the present invention.
11&(The results of nickel citrate aqueous solution concentration 16%
Regarding the solution to which 5.1σ parts by weight of unrefined sucrose of Noriko was added, -C obtained the results in column A for f4,6 in Table 2. Furthermore, the aqueous solution concentration of nickel citrate is 5, 10,
For 15% by weight, the steel plate base material for enamel shown in Example 1 was immersed, pulled up, and dried for 10 minutes at 200T (Akira 6, 7.8 in Table 2) to obtain the amount of nickel shown in column A. I got it. Each of these specimens was treated in the same manner as in Example 1, and the results shown in column B of Table 2 were obtained.

(Hereinafter in the margin) Effects of the Invention As explained in 2, when using the method of manufacturing an enameled article according to the present invention, there is a reduction in profiteering of steel sheets for porcelain and interlayers of the enameled material compared to enameled articles made using the conventional manufacturing method. Surface conditions such as adhesion, gloss, pinholes, and repellency are
If the amount of nickel metal deposited on the steel plate base material 2 is equivalent to that of conventional enamel pretreatment, there will be no play of color. This greatly simplifies the enamel pre-treatment process, significantly reduces the labor required for enamel pre-treatment management, further stabilizes quality, and eliminates the use of steam and strong acids. , corrosion of equipment and equipment, and improvements in the working environment will be noticeable.

Although only an example of the use of wet glaze is shown above, the nickel oxide layer formed on the porous steel plate in the manufacturing method of the present invention can be applied by electrostatic V coating, dry glaze, etc.
1. It can also be applied to powder electrostatic coating, electrophoretic coating, etc.

Name of agent Patent attorney Toshio Nakao and 1 other person Procedural amendment 1988 F Month Riq' [1 Description of the case 1988 Patent Application No. 2189162 Name of the invention Manufacturing method of enamel article 3 Amending Address: 1006 Kadoma, Kadoma City, Osaka Name (5)
82) Matsushita Electric Industrial Co., Ltd. Representative Toshihiko Yamashita 4 Agent 571 Address iJi 1006 Oaza Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. 6 Amendment zJ Elephant 6, Details of Amendment, Page 1 First, insert "1 Sulfuric acid treatment-Water washing," between "Degreasing-Water washing," and "Nickel sulfate" in line 19.

Claims (1)

[Claims] A method for producing an enameled article, which involves immersing a degreased porous steel plate base material in an aqueous solution of nickel formate, nickel acetate, or nickel citrate, pulling it out, drying or firing it, applying an enamel glaze, and firing it.