JPH0633470B2 - 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 pigments such as brown and black added to the frit is stapled (glazing in spots), and then a glaze or white 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 a natural stone pattern onto an enamel product by a screen process method, a thermal transfer method, etc., but since the pattern is flat and it is carried out on a separate line from normal enamel construction, equipment, There are many drawbacks such as space and personnel are required, processing cost is high, and surface smoothness, shape and size of enamel products are limited.

[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]

The enamel product of the first invention of the present application, however, has a spotted transparent enamel layer on a base enamel layer provided on a metal substrate, and the transparent enamel layer is formed from the surface portion to the bottom portion of the transparent enamel layer. It is a natural stone tone enamel product characterized in that at least one kind of speckled enamel layer having an area smaller than that of the layer is scattered.

In the method of the second invention of this application, a transparent frit containing 40 to 80% by weight of Pb0 on a basic enamel layer provided on a metal substrate, and a fluidity at the time of firing is smaller than that of the transparent frit. At least one or more frits,
Each is a method for producing a natural stone-like enamel product, which is characterized in that after glazing in the form of spots, it is fired.

In the method of the third invention of this application, 0.3 to ₂ V ₂ O ₅ is added to 100 parts by weight of the frit component for forming the transparent enamel layer on the basic enamel layer provided on the metal substrate.
A natural stone tone enamel characterized in that a transparent frit formed by adding parts by weight and at least one or more types of frit having less fluidity during firing than this transparent frit are glazed and fired, respectively. It is a method of manufacturing a product.

In the method of the fourth invention of this application, 0.3 to 2 of MnO ₃ is added to 100 parts by weight of the frit component for forming the transparent enamel layer on the base enamel layer provided on the metal substrate.
A natural stone tone enamel characterized in that a transparent frit formed by adding parts by weight and at least one or more types of frit having less fluidity during firing than this transparent frit are glazed and fired, respectively. 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 basic enamel layer provided on the metal substrate may have a single-layer structure having only a lower glaze layer or a two-layer structure having a lower glaze and an upper glaze. In the case of a two-layer structure, the upper glaze layer may be fired after the glaze is not baked, but may be fired together with the glazing layer having a punctate pattern provided thereon.

In this invention, the speckled enamel layer does not have to be totally scattered in the transparent enamel layer, and there may be one provided on the base enamel layer which is not covered with the transparent enamel layer, Also, one speckled enamel layer may be provided astride both the transparent enamel layer and the base enamel layer. The speckled enamel layer in the present invention includes streaky ones as well as granular ones.

In the present invention, as a method of glaze-applying the frit, there are a method of scattering the frit itself and a method of forming a glaze (slip) containing the frit as a main ingredient and stapling it with a spray gun.

The transparent flit according to the present invention is made of PbO, V ₂ O.
₅ , due to the components such as MoO _{3 and the} like, the fluidity at the time of firing is larger than that of a normal frit. As the frit having less fluidity during firing than the transparent frit in the present invention, various types of frit such as ordinary transparency, semi-emulsion, color glaze, and matte can be used.

As the transparent frit in the second invention, especially Sb ₂
It is preferable not to contain O ₃ , and if Sb ₂ O ₃ is contained, a pale yellow crystalline substance S at high temperature is obtained.
b ₂ O ₃ -PbO are generated easily transparency and gloss of the enamel layer is lost. Further, the content of PbO is set to 40 to 80% by weight because when it is less than 40%, a sufficient decrease in viscosity cannot be obtained during firing, and when it exceeds 80%, the weather resistance of the enamel layer after firing, This is because the moisture resistance and the chemical resistance are poor and the quality of the product is not preferable.

In the third and fourth inventions, the transparent frit V ₂ O
₅ and MoO ₃ are added in an amount of 0.3 to 2.0 parts by weight when the amount is less than 0.3 parts by weight, the decrease in viscosity during firing is insufficient, and when the amount is more than 2.0 parts by weight after firing. This is because the gloss of the enamel layer becomes dull, the transparency is easily lost, and the material cost is increased.

[Action]

In the enamel product of this invention, the small speckled enamel layer scattered from the surface part to the bottom part of the transparent enamel layer gives a three-dimensional effect and gives an appearance similar to the crystal grains of natural stone, which is Depending on the combination of color and properties such as emulsion, coloring, and transparency of the small speckled enamel layer,
A natural stone tone enamel product with a variety of appearances and textures, similar to the polished skin of natural stone, is obtained.

In the manufacturing method of the present invention, the transparent frit has a large fluidity at the time of firing due to the action of PbO, V ₂ O ₅ , MoO _{3 and the} like contained in the transparent frit, so that a molten pool that greatly spreads is formed on the base enameled layer. , The frit having less fluidity than this transparent frit is melted and solidified in a state scattered over the surface from the bottom of the molten pool according to the size and specific gravity of the particles, and the amorphous enamel layer has an amorphous milk An enamel product having a natural stone-like texture in which turbid spots, colored spots, transparent spots and the like are mixed in a non-uniform manner can be obtained by the enamel glaze firing process.

〔Example〕

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

First, as an enamel substrate, an SPP enamel steel plate with a thickness of 1.6 mm is cut into 15 cm square pieces, and as a pretreatment, ordinary alkali degreasing, pickling, nickel dip, and neutralization treatments are applied to each, and a general black base A test piece was obtained by applying glaze and firing.

Next, as the enamel frit, the transparent frits A to D ₂ shown in Table 1 (however, only the frit A is a normal frit having a small fluidity during firing), the opaque frits E to G shown in Table 2, and the glaze A are shown. And E glaze were mixed and melted at a weight ratio of 60:40 to prepare a semi-emulsion frit H. Among these frits, the frits B _{1 to} B ₄ are low melting point PbO frits, and thus the raw materials to be mixed are melted in a chamotte crucible at 1200 ° C. for 30 minutes using an electric furnace, and then rapidly cooled in a water tank and dried. The other frits were similarly melted at 1300 ° C. for 60 minutes, rapidly cooled in a water tank and dried. If necessary, a dry type flakes may be used by using a water-cooled roll after melting.

And using the above Furitsuto, those formulated with Formulation proportions shown in Table 3 was charged with alumina cobblestone to a ball mill and milled for 40 minutes, 60 mesh screen nine glaze sieve allpass X ₁ and those to X ₉ (Slip).

Next, the above-mentioned frits and glazes were tested for their flow diffusion characteristics during firing by the following method.

Frit's Flow Diffusion Characteristic Test Method A stencil sheet with a cutout hole having a diameter of 10 mm was placed on an enameled steel plate, and 0.5 g of fritted particles in a particle size range of 24 mesh pass and 9 mesh was scattered in the cut hole,
After removing the pattern paper, it is baked in an electric furnace at 800 ° C. for 3 minutes. After cooling, the maximum and minimum diameters of circular enamel layers are measured with a caliper, and the average value is used as the fluid diffusion diameter, and the fluid diffusion characteristics are evaluated by the size.

Flow diffusion characteristic test method of glaze A glaze containing 0.5 g of solid content is spray-coated on the surface of the enameled steel plate in the cutout hole with a spray gun, and other firing, cooling and measurement are performed in the same manner as in the case of the frit. Conduct and evaluate flow diffusion characteristics.

As a result of the above-mentioned test, the relationship between the fluid diffusion diameters of the frits and the glaze (the fluidity) was as follows, and the typical fluid diffusion diameters of the frits and the glaze were as shown in Table 4.

B ₅ > B ₄ > B ₃ = X ₅ > C ₂ > B ₂ ≧ D ₂ ≧ X ₆ ≧ C
₃ ≧ X ₇ > C ₁ > B ₁ > C ₄ > D ₁ ≧ A ≧ E = F = H ≧
X ₄ ≧ X ₃ ≧ X ₉ ≧ X ₁ = X ₂ > G ≧ X ₈ Using the above enamel substrate, frits and glaze, enamel products were manufactured by the following combinations and steps.

[Example 1] As shown in Fig. 1 (a), on one lower glaze enamel layer 2 of a test piece 3 in which black lower glaze enamel layer 2 was provided on both sides of a metal enamel steel plate 1 , The granular frits B ₂ are scattered in an appropriate amount, and then the granular frits E and A
Were scattered in the same manner and baked at 800 ° C. for 3 minutes. By this firing, the frit B ₂ having a large fluidity is melted and is sunk into the lower glaze enamel layer 2 and diffused to the surroundings to form a molten pool, and most of the frits A and E are melted by being taken in the molten pool. did.

As shown in FIGS. 1 (b) and 2, the obtained enamel product 4 has small spots of the frit A extending from the bottom of the transparent enamel layer 5 in which the molten pool is solidified by the frit B ₂ to the surface. -Shaped transparent enamel layer 6 and the small speckled milky enamel layer 7 of the frit E are scattered in a speckled manner, and some of the speckled transparent enamel layer 6 and speckled milky-white enamel layer 7 are directly underglaze enamel. It had a natural stone-like appearance with a depth that was scattered on Layer 2.

[Example 2] over spray in FIG. 3 (a) to show white thickness of about 150μm glaze X ₁ is a base color glaze to the top of the lower glaze enamel layer 2 of one of the test piece 3 as, 800 The base having the upper glaze enamel layer 8 formed by firing at ℃ for 3 minutes was used as a patterned base, and the appropriate amount of granular frits B ₄ was scattered on the upper glaze enamel layer 8, and further the granular frits A, E and H were formed.
And fired at 800 ° C. for 3 minutes.

As a result, the frit B ₄ having good fluidity largely melts and flows to form a large spotted transparent enamel layer 9 as shown in FIGS.
The small speckled transparent enamel layer 6 of Frit E, the small speckled milky enamel layer 7 of Frit H and the small speckled semi-emulsion enamel layer 10 of Frit H float on the surface of the transparent enamel layer 9 in the form of natural stone crystals. It was possible to obtain an enamel product 11 having a three-dimensional deep natural stone-like appearance by sinking.

[Example 3] In Example 2, the glaze X was used instead of the fritted B _4.
5 , glaze X ₄ in place of flit A, glaze X _{1 in place} of flit E, and glaze X in place of frit H
_As shown in FIG. 5 (a), ₉ was stapled onto the upper glaze enamel layer 8 in a staple shape in this order, and then dried and fired. The firing conditions were the same as in Example 2.

The obtained enamel product 12 is, as shown in FIG.
Although the pattern is slightly different from that of Example 2 by scattering, a small speckled transparent enamel layer 1 of glaze X ₄ is formed on the surface to the bottom of the transparent enamel layer 13 which is a fired body of glaze X _{5 having} high fluidity.
4, glaze X ₁ small speckled milky white enamel layer 15, glaze X
_It had a natural stone-like appearance similar to that of Example 2 in which the speckled semi-emulsion enamel layer 16 of 9 was scattered.

[Fourth Embodiment] In the second embodiment, a frit B is used instead of the flit B _4.
2 was scattered, and the others were glazed and fired under the same conditions as in Example 2.

Since the flow diffusion diameter of the fritted B ₂ during firing is reduced by about 40% compared to the fritted B ₄ , the overall pattern is small, but an enamel product with a natural stone appearance similar to that of Example 2 is obtained. Was given.

In Example 5 Example 2, instead of Furitsuto B _4, the Furitsuto B ₃ the flow diffusion diameter during firing is an intermediate value of Furitsuto B ₄ and B ₂ handouts, others under the same conditions as in Example 2 When glazing and firing were performed, an enamel product having an intermediate pattern pattern of Examples 2 and 4 was obtained.

[Example 6] In Example 2, the frit B was formed on the upper glaze layer 8.
Instead of ₄ , glaze X ₅ was stapled with a spray gun, and frits A, E, and H were scattered on it in the same manner as in Example 2, and baking was performed after drying. The obtained enamel product was tested. It had an appearance similar to that of Example 3.

[Embodiment 7] In Embodiment 2, instead of the flit B ₄ , the flit C _{3 is used.}
When the glaze firing was performed under the same conditions as in Example 2, the frits C ₃ showed a fluidity close to that of the frits B ₃ in Example 5, and the transparent enamel layer in the obtained enamel product was the same as that in Example 2. 5 has a shape close to 5, but MnO ₂
Since it has a transparent light brown color due to its coloring property, a natural stone-like appearance in which a crystal grain pattern of a stone of a different kind from that of Example 5 appeared was obtained.

In Example 8 Example 7, instead of Furitsuto C _3, the Furitsuto C ₂ to half region (upper top glaze enamel layer 8) of the test piece 3, to spread these Furitsuto C ₁ in the remaining half of the region, the When the frits A, E, and H were scattered on the upper portion (all areas) and fired, the diffusion diameter of the transparent enamel layer was larger than that in Example 7 depending on the fluidity of the frits C _{1 to} C ₃ during firing. Was reduced in the order of C ₂ > C ₃ > C ₁ , but an enamel product having an appearance generally similar to that of Example 7 was obtained.

[Embodiment 9] In Embodiment 7, a flit D is used instead of the flit C _{3.
When the} glazed firing was performed under the same conditions as in Example 7, except that No. ₂ was scattered, an enamel product having an appearance very similar to the scattered region of the fritted C ₂ in Example 8 was obtained.

[Example 10] In Example 8, half the area of the test piece 3 (on the upper glaze layer 8) was exposed and the other area was covered with a ferrite rubber sheet, and the glaze X was applied to the exposed surface with a spray gun. ₆ was stapled with a particle size of 1 to 3 mm. Next, the remaining half area of the test piece 3 is exposed to cover the area after the glaze, and the exposed surface is stapled with the drug application X ₇ in the same manner as described above, and this application of the glaze X ₇ and the glaze X ₆
The glazes X ₄ , X ₁ , and X ₉ were stapled with a spray gun in the same manner as above, and then baked. As a result, when using the glaze X ₆ , the flow diffusion diameter of the transparent enamel layer was slightly larger than that of X ₇ , but the enamel appearance similar to those of Examples 8 and 9 was obtained.

In Example 11 Example 2, after the sixth diagram spray hooking a white glaze X ₁ as a base color glaze (a), the a semi-dry state, the fluidity on the upper釉施glaze 17 The frits B ₃ were scattered, the frits A, E, and H were further scattered, and then dried and baked.

As a result, the upper glaze layer 17 where the frit B ₃ having good fluidity diffuses at a high temperature to form the transparent enamel layer 18
However, since it is spread by the flow of the frit, the upper glaze enamel layer 8 after firing becomes locally thin, and the lower glaze color (black) appears slightly transparent, but generally it is the same as in Example 2. An enameled enamel product 19 was obtained. In the figure, the same parts as those in FIG. 3 are designated by the same reference numerals as those in FIG.

In Example 12 Example 11, after Suteitsupuru stamped by a spray gun glaze _{X 5} instead of Furitsuto _{B 3,} glaze _X 4, X
Similarly Suteitsupuru beating in the order of _1, X _9, was baked after drying, enamel products enamel appearance similar natural stone tone as in Example 11 were obtained.

On the Example 13 Figure 7 one of the lower glaze enamel layer 2 of the test piece 3 (a), the then multiplied sprayed glaze X ₂ is Ivory color glaze to a thickness of about 150 [mu] m, 800 ° C. And baked for 3 minutes to form the upper glaze enamel layer 20. The glaze X ₃ is a brown glaze thereon and Suteitsupuru beating as Suteitsupuru particle diameter is 1 to 3 mm, after which sprinkle the Furitsuto B _4, was sprinkle Furitsuto A, E, and H. Next, fritted G, which is a matte fritted material for forming a matte portion, was scattered and fired.

The resulting enamel product 21 has a distinctive look, as shown in FIG. 7 (b) and FIG. 8, Furitsuto B Suteitsupuru hook portion of the glaze X ₃ brown, flowing diffuse during sintering
_{4, a} speckled brown enamel layer 22 having a brown streak shape is formed, which is covered with a transparent enamel layer 23 of fritted B ₄ to form a pattern similar to a flower pattern,
Furthermore, a small speckled matte enamel layer 2 with flit G
4, the speckled transparent enamel layer 6, the speckled milky white enamel layer 7, and the speckled semi-emulsion enamel layer 10 similar to those in the second embodiment are scattered in a speckled manner to express stone crystal grains. ,
It had a natural stone-like texture.

In Example 14 Example 2, after sprinkle the Furitsuto B ₄ glaze X ₁ on the upper glaze enamel layer 8 was glazed fired, spread these Furitsuto F of colored glaze instead of Furitsuto A, E, Furitsuto H the glaze X ₈ is a mat glaze instead of, the sprinkle was Furitsuto is lightly Suteitsupuru striking weaken the air pressure of the spray gun so as not to scatter, and calcined after drying.

As a result, the ivory-colored small speckled enamel layer by the frit F, which replaces the frit E representing the crystal grains of stone, shows a color and texture closer to that of natural stone, and a matte glaze that replaces the frit H as compared with Example 2. The speckled enamel layer due to X ₈ became slightly yellowish gray and became matt due to the influence of fritted B ₄ , and a enamel product having a more natural stone appearance was obtained.

[Comparative Example 1] In Example 2, frit B ₁ containing a small amount of PbO and Sb ₂ O ₃ instead of frit B ₄ was scattered, and the other conditions were the same as in Example 2, and the glaze firing was performed. The flow diffusion diameters of B ₁ , A, E, and H are not so different, and the transparent enameled layer due to the flit B ₁ has a small diameter, so that it does not include other small speckled patterns and is scattered only to such an extent that they partially overlap. Further, since the transparent enameled layer portion produces a yellow compound oxide Sb ₂ O ₃ -PbO and becomes a yellow matte, the pattern as a whole has no depth and a natural stone-like appearance was not obtained.

[Comparative Example 2] In Example 2, instead of the flit B ₄ , V ₂ O ₅ was added to a half region of the test piece 3 (on the upper glaze layer 8).
Frit C ₄ containing a large amount of MoO was added to the other half of the area.
₃ Frits D ₁ having a small content were scattered, and frits A, E, and H were scattered on this (all areas) and fired. In the obtained enamel product, the burned part of the fritted C ₄ was opaque and lost in a pale yellow color, and there was no depth on the surface due to opacity, and a V ₂ O ₅ type crystalline substance was generated to cause flow during baking. And the diffusion diameter is smaller than that of the other speckled spots of other flits. On the other hand, since the flow diffusivity of the fired part of the frit D ₁ is not much different from that of the other flits, it forms a small transparent enamel layer and forms other small spots. It was not possible to include the pattern, and in each case, only the appearance of a monotonous pattern with no depth was obtained.

[Comparative Example 3] In Example 2, instead of the fritted B ₄ , fritted B ₅ having a large PbO content was scattered, and the other conditions were the same as in Example 2, and the glaze firing was performed. In the obtained enamel product, the small speckled enamel layer due to the frit B ₅ had a feeling that it was largely fluidized and diffused as compared with Example 2, but when left to stand after baking, the small speckled enamel layer part was fogged, Moreover, the test result by the acid resistance test of JIS-R4301 "Quality standard of enamel products" which is a standard of the weather resistance test was C grade, which was inferior in quality. The acid resistance of the enamel product of Example 2 was Class A.

[Effects of the Invention] As described above, according to the present invention, an enamel product having a deep natural stone-like appearance can be obtained by an economical and easy-to-install enamel glaze firing process.

[Brief description of drawings]

FIG. 1 is a process explanation (cross section) showing a first embodiment of the present invention.
2 and 3 are also plan views of enamel products, FIG. 3 is a view corresponding to FIG. 1 showing a second embodiment of the present invention, FIG. 4 is a view corresponding to FIG. 2, and FIG. FIG. 6 is a view corresponding to FIG. 1 showing a third embodiment, FIG. 6 is a view corresponding to FIG. 1 showing an eleventh embodiment of the present invention, and FIG. 7 is a view corresponding to FIG. 1 showing a thirteenth embodiment of the present invention. FIG. 8 is a view equivalent to FIG. 1 ... Enameled steel plate, 2 ... Lower glaze enameled layer, 4 ... Enameled product, 5 ... Transparent enameled layer, 6 ... Small speckled transparent enameled layer, 7 ... Small speckled milky white enameled layer, 8 ...
… Glazed enamel layer, 9 …… Transparent enamel layer, 10 …… Spotted semi-emulsion enamel layer, 11 …… Enamel product, 12
...... Enamel products, 13 ...... Transparent enamel layer, 14 ......
Small speckled transparent enameled layer, 15 ... Small speckled milky white enameled layer, 16 ... Small speckled semi-milky enameled layer, 17 ...
Top glaze layer, 18 ... Transparent enamel layer, 19 ... Enamel product, 20 ... Top glaze layer, 21 ... Enamel product, 22 ... Spotted enamel layer, 23 ... Spotted transparent enamel layer , 24 …… A small speckled matte enamel layer.

Claims (4)

[Claims] 1. A speckled transparent enamel layer is provided on a base enamel layer provided on a metal substrate, and the speckled transparent enamel layer has a smaller area from the surface portion to the bottom portion of the transparent enamel layer. A natural stone tone enamel product characterized by having at least one enamel layer scattered. 2. A transparent frit containing 40 to 80% by weight of PbO and at least one frit having a fluidity during firing which is smaller than that of the transparent frit on a base enamel layer provided on a metal substrate. A method for producing a natural stone-like enamel product, characterized in that each of them is glazed in the form of spots and then fired. 3. A transparent composition prepared by adding 0.3 to ₂ parts by weight of V ₂ O ₅ to 100 parts by weight of a frit component for forming a transparent enamel layer on a base enamel layer provided on a metal substrate. A method for producing a natural stone tone enamel product, which comprises glazing a frit and at least one frit having a fluidity less than that of the transparent frit at the time of firing, and then firing the glaze. 4. A transparent frit obtained by adding 0.3 to 2 parts by weight of MoO ₃ to 100 parts by weight of a frit component for forming a transparent enamel layer on a base enamel layer provided on a metal substrate. A method for producing a natural stone-like enamel product, characterized in that at least one kind of frit having a lower fluidity at the time of baking than this transparent frit is glazed in a dotted pattern and then baked.