JPH0730462B2 - Natural stone tone enamel product and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an enamel product having a natural stone tone appearance and a method for producing the same.

[Conventional technology]

Generally, enamel products in which the surface of a metal substrate such as iron or stainless steel is covered with an enamel layer are widely used for interior and exterior panels of buildings, various household products such as containers and decorations, etc. Since the enamel layer has a monotonous appearance, the demand for patterned enamel layer is increasing. As this patterned enamel layer, a natural stone tone enamel layer is particularly preferable for building panels, but conventionally, to obtain this enamel layer, a transparent enamel substrate on which a lower glaze and an upper glaze layer are formed is transparent. A method in which a glaze with brown or black pigments added to the frit is stapled (glazing in spots), and then a glaze or milky glaze with a white pigment added to a transparent frit is stapled in a striking pattern and baked. It depends. However, this method has a drawback that individual spots or the boundary line between the spots and the base color is too clear, and a simple punctiform pattern different from natural stone is likely to be formed. In addition to this, there is also a manufacturing method that transfers the natural stone pattern onto the enamel product by the screen process method, heat transfer method, etc. Since it is carried out on a separate line, equipment, space, personnel, etc. are required, resulting in high processing costs, smoothness and shape of the surface of enamel products,
There are many drawbacks such as limited size.

[Problems to be Solved by the Invention]

The present invention solves the above-mentioned conventional problems, and an object thereof is to provide a natural stone tone enamel product having a deep and excellent appearance and a method for producing the same.

[Means for Solving the Problems]

Thus, the enamel product of the first invention of this application is such that an upper glaze enamel layer containing milk frits as a main component is provided on the lower glaze enamel layer provided on the metal substrate, and on this upper glaze enamel layer, In the upper glaze enamel layer, which is composed of a transparent frit and a pigment as a main component and has a lower brightness than the upper glaze enamel layer, and a portion having a lower brightness than the annular part and surrounded by the annular part. It is a natural stone-like enamel product characterized by spotted enamel layers that are recessed in a concave shape.

In addition, the enamel product of the second invention of this application is such that an upper glaze enamel layer containing milk white frits as a main component is provided on the lower glaze enamel layer provided on the metal substrate, and a transparent enamel layer is provided on the upper glaze enamel layer. An annular part having a lower brightness than the upper glaze enamel layer, which is mainly composed of frits and pigments, and a part having a lower brightness than the annular part, which is surrounded by the annular part, and is formed in the upper glaze enamel layer. With scattered spotted enamel layers that are recessed in a concave shape, on the upper glaze enamel layer and the spotted enamel layer, a white small speckled enamel layer having a particle size of 2 mm or less and having a higher brightness than the upper glaze enamel layer. It is a natural stone tone enamel product characterized by being scattered around.

The method of the third invention (Claim 3) of this application is that a lower glaze enamel layer provided on a metal substrate is glazed with an upper glaze prepared by using water as a main component of milky frits and wetted. A method for producing a natural stone tone enamel product, which comprises stapling a glaze formed by preparing a transparent frit and a pigment as a main component with alcohol on the glaze layer of the upper glaze, followed by firing.

The method of the fourth invention (Claim 4) of this application is such that a lower glaze enamel layer provided on a metal substrate is glazed with an upper glaze obtained by preparing water with a milky frit as a main component, and a wet state. On the glaze layer of the above-mentioned glaze, a natural stone-like enamel characterized by stapling a glaze made of alcohol by adding a metal nitrate as a coloring aid with a transparent frit and a pigment as a main component, and then firing It is a method of manufacturing a product.

As the metal substrate in the present invention, an iron plate, a steel plate, a stainless steel plate such as stainless steel, or the like can be used.

In the present invention, the upper glaze enamel layer or the upper glaze for forming the enamel layer may be at least a milky frit, and the brightness of the upper glaze enamel layer after firing is higher than that of the annular portion of the speckled enamel layer. In this case, pigments of various colors other than white may be included.

The particle size of the small speckled enamel layer in the second invention is set to 2 mm or less, because if the particle size exceeds 2 mm, an unnatural appearance will occur when it is glazed on the speckled enamel layer.

As the metal nitrate in the fourth invention, for example, nitrates of cobalt, copper, manganese, nickel, iron, chromium and the like can be used, and the addition amount thereof is the transparent frit.
It is preferably 2.0 parts by weight or less with respect to 0 parts by weight, 2.
If it exceeds 0 parts by weight, the difference in color development between the annular portion and the core portion becomes small, which is not preferable.

[Action]

In the enamel product of this invention, the speckled enamel layer scattered on the upper glaze enamel layer has a concave shape concavely recessed in the upper glaze enamel layer and has a low-lightness nucleus in the center thereof. Since there is a ring-shaped part, and this ring-shaped part is surrounded by an annular part having a higher brightness than the core-shaped part and a lower brightness than the upper glaze enamel layer, the ring-shaped part, the core-shaped part with respect to the upper surface of the upper glazed enamel layer It gives a three-dimensional effect that sinks in the order of, and gives a porous pumice stone surface with a large number of burrows, or a deep natural stone-like appearance similar to Oya stone.

In the enamel product of the second invention, a white speckled enamel layer gives an impression of being floated, and a colorful and more three-dimensional natural stone tone appearance can be obtained.

Further, in the manufacturing method of the present invention, when stapling a glaze prepared with alcohol on the glaze layer of the upper glaze in a wet state, alcohol has a much smaller surface tension than water, so alcohol is on the glaze layer of the upper glaze. To spread the wet top glaze locally to form a spotted recess, in which the transparent frit and a part of the pigment diffused along with alcohol, and the rest of the pigment was initially stapled. Remain in position. By drying and baking this, a three-dimensional speckled pattern having a low-lightness core portion at the center and recessed in the upper glazed enamel layer can be obtained easily and reliably by one-time stapling.

Further, in the fourth invention, the alcohol content diffusing on the glaze layer of the upper glaze diffuses a part of the metal nitrate which is a coloring aid together with a part of the pigment, and the coloring of the metal nitrate by firing is added. As a result, the color of the annular portion becomes more uniform, and spotted patterns of various colors are formed depending on the type of metal nitrate.

〔Example〕

 Examples and comparative examples of the present invention will be described below.

First of all, as a metal substrate, an SPP enameled steel plate with a thickness of 1.6 mm is used.
The test piece was cut into cm square pieces, subjected to ordinary alkali degreasing, pickling, nickel dip, and neutralizing treatments as pretreatments, and sprayed with general black bottom glaze and then baked.

Next, as the enamel frit, natural and chemical raw materials prepared so as to have the composition shown in Table 1 were put in a melting crucible and placed in an electric furnace at 1300 ° C. (however, frits A to D).
And melted at 1200 ° C. (frit E) for 60 minutes, cooled with water and dried.

Next, using each of the above frits, a mixture prepared at the mixing ratio shown in Table 2 was put into a ball mill together with alumina boulders, crushed for 40 minutes, and passed through a 60 mesh sieve all-pass.
9 types of glaze (slip). The glazes b and c were prepared in water, and the glazes d to j were prepared in the form of slips using ethanol as a medium. Further, the frit A was crushed in a mortar to obtain a granular glaze a for scattering particles having a particle size of 14 to 60 mesh.

An enamel product was manufactured using the above test piece and glaze according to the following combinations and steps.

[Example 1] On one surface of the test piece, a gray glaze b glaze (glaze b) was sprayed with a spray gun to a thickness of about 150 µm, and immediately after that, a spot glaze i glaze was stapled. Was sprayed with a spray gun so that the coated particle diameter of 1 was 3 mm. By stapling the i glaze with a small surface tension prepared with alcohol on the wet glazed coating of b glaze, which is a slurry prepared with water, the alcohol content of the i glaze diffuses on the surface of the b glaze, When the glazed surface was dented in spots, and dried and baked at 800 ° C. for 3 minutes, enamel product 1 as shown in FIGS. 1 and 2 was obtained.

In the figure, 2 is a test piece in which a black lower glaze enamel layer 4 is provided on both sides of an enameled steel plate 3 which is a metal substrate. On the upper glaze enamel layer 5 which is a baked body of b-glaze, spotted enamel layers 6 which are a baked body of i-glaze are scattered. This speckled enamel layer 6 is present in the depression of the upper glaze enamel layer 5 corresponding to the depression of the glaze surface at the time of the glaze, and has a core portion 7 in the center of which a black-brown pigment of low lightness is deposited. However, a light blackish-brown annular portion 8 surrounds the periphery thereof, and has a natural stone-like appearance similar to Otani stone in which nest-like spots are scattered on the gray upper glaze enamel layer 5. The coloring of the annular portion 8 is caused by the dispersion of some fine particles of the black-brown pigment along with the diffusion of alcohol (ethanol) during glaze, and when observed in detail, fine color unevenness (shading) And has a color nearer to the outer side of the annular portion 8 and tends to become slightly lighter in color. The actual size of the particle size Q of the large spotted enamel layer 6 on the left side of the center in FIG. 1 is about 10 mm.

[Example 2] In Example 1, d-glaze was stapled immediately after b glazing, and the glazing firing was performed under the same conditions as in Example 1 except for the above.

As a result, the ring-shaped portion 8 surrounding the core portion 7 has a more uniform light black color than that of the first embodiment because the color development by the copper nitrate in the d-glaze is added to the color development by some fine particles of the black-brown pigment. An enamel product having a brown color and an appearance closer to that of Otani stone was obtained.

[Example 3] In Example 2, after the glaze of d glaze, the granular glaze a (frit A) was sparsely scattered over the whole and baked under the same conditions as in Example 1.

As a result, as shown in FIG. 3, the small speckled enamel layer 9 which is a fired body of the glaze a is scattered on the upper glaze enamel layer 5 and the speckled enamel layer 6, and the white speckled patterns are obtained. Since the enamel layer 9 appears to float, the speckled enamel layer 6 gives the impression of being further depressed, resulting in a enamel product 10 having a deep Oya stone-like appearance. In the figure, the first
The same or corresponding parts as those in the figure are designated by the same reference numerals as those in FIG.

[Example 4] In Example 1, when e-glaze was used in place of i-glaze, and the other conditions were the same as in Example 1, and glazed and baked, part of nickel nitrate in e-glaze diffused and developed a color. , Annular part 8
(See FIG. 1) was greenish brown, and a natural stone tone enamel product having a color tone slightly different from that of Example 2 was obtained.

[Example 5] In Example 1, when f-glaze was used in place of i-glaze and the other conditions were the same as in Example 1, and the baking was performed under the same conditions, part of manganese nitrate in f-glaze diffused and developed a color. The annular portion 8 was light reddish brown, and an enamel product having an appearance similar to that of Example 1 was obtained.

[Example 6] In Example 1, g-glaze was used instead of i-glaze, and the glaze firing was performed under the same conditions as in Example 1 except for the above.

As shown in FIG. 4, the obtained enamel product 11 had a glazed enamel composition with low viscosity at high temperature, so that the blue core 7 had a larger diameter than the other examples, and the width of The narrow annular portion 8 was surrounded, and the annular portion 8 had a natural stone-like appearance with a pale blue color due to the coloring of cobalt nitrate.

[Example 7] In Example 1, the amount of h-glaze containing a large amount of metal nitrate was added to i.
When glazed firing was performed under the same conditions as in Example 1 except for using the glaze, the color of the annular portion 8 was closer to that of the core portion 7 than in Example 1, and the natural stone tone enameled enamel The product is obtained.

[Example 8] In Example 3, instead of scattering the granular glaze a, c
When stapling was performed with a spray gun using a glaze, an enamel product having an appearance similar to that of Example 3 was obtained.

[Comparative Example] In Example 1, when j-glaze having an excessively large amount of metal nitrate added was used instead of i-glaze, and the glazed firing was performed under the same conditions as in Example 1, the coloring of the annular portion became dark. As a result, the difference in color tone between the core and the core became small, and a part of the spotted enamel layer had a defect of foaming, and only a poor appearance was obtained.

EFFECTS OF THE INVENTION As described above, according to the present invention, a natural stone tone enamel product having a porous and deep appearance can be obtained. In addition, a single stapling operation can surely and easily form a speckled enamel layer having a low brightness at the center and a concave shape depressed in the upper glazed enamel layer, resulting in low production cost.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a partially enlarged plan view of an enamel product showing a first embodiment of the present invention, FIG. 2 is a sectional view taken along the line AA of FIG. 1, and FIG. 3 is a third view of the present invention. An embodiment corresponding to FIG. 1 is shown, and FIG. 4 is a view corresponding to FIG. 1 showing a sixth embodiment of the present invention. 1 ... Enamel product, 3 ... Enameled steel plate, 4 ... Lower glaze enameled layer, 5 ... Upper glaze enameled layer, 6 ... Spotted enameled layer, 7 ... Core part, 8 ... Annular part, 9 …… Small speckled enamel layer, 10 …… enamel products, 11 …… enamel products.

Claims (4)

[Claims] 1. An upper glaze enamel layer containing an opalescent frit as a main component is provided on a lower glaze enamel layer provided on a metal substrate,
On this upper glaze enamel layer, a transparent frit and a pigment are used as a main component, and an annular portion having a lower lightness than the upper glaze enamel layer, and a nucleus portion surrounded by the annular portion and having a lower lightness than the annular portion. A natural stone tone enamel product, characterized in that spotted enamel layers which are recessed in a concave shape are scattered in the upper glaze enamel layer. 2. An upper glaze enamel layer containing an opalescent frit as a main component is provided on a lower glaze enamel layer provided on a metal substrate,
On this upper glaze enamel layer, a transparent frit and a pigment are used as a main component, and an annular portion having a lower lightness than the upper glaze enamel layer, and a nucleus portion surrounded by the annular portion and having a lower lightness than the annular portion. Consists of scattered spotted enamel layer concavely recessed in the upper glaze enamel layer, on the upper glaze enamel layer and the spotted enamel layer, the particle size 2mm or less than the upper glaze enamel layer A natural stone tone enamel product characterized by interspersing white, speckled enamel layers of high brightness. 3. A lower glaze enamel layer provided on a metal substrate is glazed with an upper glaze obtained by preparing water with a milky frit as a main component, and the glaze layer of the upper glaze in a wet state is transparent. A method for producing a natural stone tone enamel product, which comprises stapling a glaze prepared from alcohol with frits and pigments as the main ingredients and then firing. 4. A lower glaze enamel layer provided on a metal substrate is glazed with an upper glaze obtained by preparing water with a milky frit as a main component, and the glaze layer of the upper glaze in a wet state is transparent. A method for producing a natural stone-like enamel product, which comprises stapling a glaze prepared by adding a metal nitrate as a coloring aid, a frit and a pigment as a main ingredient, and a metal nitrate as a color-forming aid, and then baking the staple.