JP2001131775A - Enameled product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an enameled product which exhibits slight increase of surface roughness even when it is used for a long period of time, thereby which is almost free from sticking of stains for an indefinite time and from which the stains can be easily removed by flowing water even when the stains stick on. SOLUTION: The enameled product is obtained by forming a surface enamel layer onto a metal substrate, and the content of antimony oxide in the surface enamel layer is <2 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to enamel products such as bathroom building materials, bathtubs, bathtub aprons, washbasins, washbasin counters, sinks, kitchen panels, kitchen doors and the like which constitute bathroom floors, walls, ceilings and the like.

[0002]

BACKGROUND OF THE INVENTION It is necessary to keep the surface of enamel products hygienic and clean, and to keep their aesthetics high over a long period of time, because enamel products are generally widely used as daily necessities. It is a characteristic. As a method to keep the enamel product surface clean and hygienic in general households since ancient times, apply a detergent such as a surfactant, acid, or alkali to a scourer or brush and rub the enamel product surface strongly. Accordingly, a method of removing the adhered dirt has been adopted. However, this method requires labor such as scrubbing with a scourer or a brush every time dirt adheres. In particular, it is difficult for the elderly to require such labor every time. In recent years, environmental pollution from wastewater containing surfactants has been pointed out,
It is also desirable that the use of surfactants be low in quantity and frequency.

[0003] There are roughly two methods for keeping the surface of enamel products hygienically clean and aesthetically pleasing without using a surfactant and without rubbing with a scourer or brush. One method is a method of forming a surface of an enamel product to which a stain is less likely to be chemically attached. Conventionally, (1) a method of roughening the surface of an enamel product and then coating the surface with a fluororesin Also, there has been proposed a method of (2) coating a siloxane resin containing a fluoroalkyl group on the surface of an enamel product to expose a fluoro group for lowering surface energy to the surface, thereby making it difficult to adhere dirt. In this method, since the heat resistance of the fluoro group-containing material is about 400 degrees or less, it cannot be coated with the resin before sintering the enamel. Requires a step of heating. for that reason,
Although the man-hours increase and the manufacturing cost increases, it can be said that this method is excellent in principle.

Another method is to form a surface of an enamel product to which dirt is hardly physically adhered. The surface is made as smooth as possible to prevent the dirt from being firmly adhered to the surface of the enamel product, and to reduce the amount of running water. Is a method of removing dirt by simple washing. Although this method has been proposed for a long time, it has been observed that dirt accumulates in a conventional enameled product, for example, at a waterline portion or an apron portion of a bathtub that has been used for a long time. It was difficult.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an enamel product which can easily remove dirt on the surface of the enamel product by, for example, flowing water without rubbing it strongly with a scourer or a brush. I do.

[0006]

The present inventor has analyzed the enamel products used for a long time and found that the cause of the long-term loss of smoothness is related to the concentration of antimony oxide in the glaze. I found it. Antimony oxide has an effect of suppressing coloring of iron and the like contained as impurities in the glaze, and is one of the components always contained in general enamel glaze. However, when the concentration of antimony oxide increases, a portion having a high concentration of antimony oxide appears in the glaze as streaks, and there is a difference in the corrosion resistance between this portion and the surrounding portion. It was found that the smoothness was reduced. Thus, by controlling the concentration of antimony oxide, it was possible to develop a glaze that did not decrease in smoothness even after long-term use and did not color.

According to the present invention, there is provided an enameled product having a surface glaze layer formed on a metal substrate, wherein the concentration of antimony oxide contained in the surface glaze layer is less than 2 wt%, preferably 1.5 wt% or less. Preferably on an enamel product characterized by being 1 wt% or less, or on a metal substrate,
An enamel product having a coloring glaze layer formed thereon and further having a surface glaze layer formed thereon, wherein the concentration of antimony oxide in the surface glaze layer is less than 2 wt%, preferably 1.5 wt% or less, More preferably, the present invention provides an enamel product characterized by being 1 wt% or less. By doing so, the occurrence of portions having different corrosion resistance is reduced, and an increase in surface roughness during long-term use is suppressed. Therefore, it is possible to maintain, for a long period of time, the difficulty of getting the dirt that the enamel product has at the beginning of use and the ease of dropping it. In the conventional enameled product, the surface glaze layer contained about 1 to 2% by weight of antimony oxide. For this reason,
If the antimony oxide is used for a long period of time, unevenness is formed due to the difference in corrosion resistance between the portion having a high concentration of antimony oxide and the surrounding portion, the smoothness of the surface is reduced, and dirt is easily adhered or hardly removed. On the other hand, in the surface glaze layer according to the present invention, only a portion where the concentration of antimony oxide is high can be formed only slightly, so that the surface smoothness is less reduced even after long-term use.

In a preferred aspect of the present invention, the surface glaze layer has a concentration of antimony oxide of 0.001 watts.
Provided is an enamel product characterized by at least t%, preferably at least 0.01 wt%, more preferably at least 0.1 wt%. By adding a trace amount of antimony oxide to the surface glaze layer, the glaze layer is no longer colored and becomes a completely transparent layer, so that the color tone can be easily controlled. Antimony is oxidized from trivalent to pentavalent during firing, and has an effect of suppressing coloring by reducing iron contained as an impurity in the surface glaze layer.

By making the surface of the enamel product unprecedentedly smooth, it is difficult for dirt to adhere firmly. As a result, even if it adheres, it can be lifted up by contact with water, and the raised dirt can be removed. It will be removed by running water. Further, by providing a configuration in which a colored design layer is provided as a lower layer, it is possible to impart design properties with a particulate pigment or an emulsifier.

In a preferred embodiment of the invention, the second glaze layer is transparent. By doing so, the design of the first glaze layer can be used, and the color tone can be easily controlled.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. However, the present invention is not limited to the following description. In one embodiment of the enamel product of the present invention, a lower glaze is formed on a metal substrate, a colorable glaze layer is formed thereon, and a transparent surface glaze layer is formed on the surface. . Here, in the surface glaze layer,
Antimony oxide less than 2 wt%, preferably 1.5 wt%
%, More preferably 1% by weight or less. Further, the second glaze layer contains antimony oxide in an amount of 0.001% by weight or more, preferably 0.01% by weight or more, and more preferably 0.1% by weight or more.

The method for producing the above enameled product includes, for example, a step of forming a coloring glaze layer by applying a coloring glaze raw material containing a pigment or an emulsifier to a metal base material and then baking it to form a fine vitrified layer. It can be performed through a step of firing after applying the frit-like glaze material on the colored glaze layer. . here,
As the fine vitrified frit-like glaze raw material, a glaze raw material mixture composed of silica sand, borax, soda ash, etc. is used.
It can be obtained by melting at a high temperature of 0 ° C. or higher. As a method of applying the glaze raw material, a general method such as a wet method such as spray coating, dip coating, spin coating, and roll coating, a dry method such as a hot dry lacing method, and a dry glazing method can be used. The firing temperature varies depending on the glaze composition and metal substrate,
It is fired at a temperature of about 300-1100 ° C.

[0013] In another embodiment of the enamel product of the present invention, a lower glaze is formed on a metal substrate, and a colorable glaze layer is formed thereon. Here, antimony oxide is less than 2 wt% in the surface glaze layer, preferably 1.
The content is set to 5 wt% or less, more preferably 1 wt% or less. Further, in the surface glaze layer, antimony oxide is 0.001 wt% or more, preferably 0.01 wt%.
As described above, it is more preferably 0.1% by weight or more.

The method for producing the above enameled product includes, for example, a transparent vitrified frit-like glaze raw material containing no pigment or emulsifier, and a pigment / emulsifier which can be dissolved in glass at a firing temperature. Can be carried out through a step of applying the mixture to a metal substrate and a step of firing. here,
As the fine vitrified frit-like glaze raw material, a glaze raw material mixture composed of silica sand, borax, soda ash, etc. is used.
It can be obtained by melting at a high temperature of 0 ° C. or higher. As a method of applying the glaze raw material, a general method such as a wet method such as spray coating, dip coating, spin coating, and roll coating, a dry method such as a hot dry lacing method, and a dry glazing method can be used. The firing temperature varies depending on the glaze composition and metal substrate,
It is fired at a temperature of about 300-1100 ° C.

The metal substrate may be, for example, iron (steel plate, casting)
A substrate, a stainless steel substrate, an aluminum substrate, a copper substrate, or the like, on which a lower glaze is applied, a substrate having an oxide film on the surface by an acid treatment, an annealing treatment, or the like can be preferably used. .

The enamel products which can be used in the present invention are not limited to the following, but include, for example, bathroom building materials constituting bath floors, walls, ceilings, etc., bathtubs, bathtub aprons, washbasins, These include washbasins, sinks, kitchen panels, kitchen doors, etc. For example, dirt based on metal soap or the like adhering to a bathroom floor or bathroom wall, scale dirt in a bathtub apron, oily dirt in a bathtub draft line, or slimy dirt at the bottom of a bathtub can be easily cleaned by running water from a shower or the like. . In addition, dirt can be removed from a kitchen bag, a kitchen door, a wash counter, or the like by simply wiping with water. Further, the sink, the basin bowl and the like can be cleaned by a simple method such as wiping with water, or after collecting water in the bowl, and then removing the collected water. When the present invention is applied to the bottom of a bathtub, it is preferable to apply a macroscopic unevenness treatment such as embossing to a metal base material before glaze because it prevents slippage.

[0017]

【Example】

[Table 1]

Comparative Example 1 A glaze raw material having the composition shown in Table 1 was melted at 1100 to 1400 ° C. using an electric furnace, and rapidly cooled in water to obtain a glass frit. 2 kg of the obtained glass frit, an emulsifier (antimony oxide), a few g of a pigment and 4 kg of cobblestone were put into a 6-liter pottery pot.
The powder was pulverized by a ball mill so as to pass through a 150 mesh sieve to obtain a powdery glaze. The glaze powder obtained here is designated as glaze A.

[0019]

[Table 2] Antimony oxide was added to the glaze raw material having the composition shown in Table 2 so as to have a concentration of 2 wt%.
It was melted at 00 ° C. and quenched in water to obtain a glass frit. 2 kg of obtained glass frit and 4 kg of cobblestone are
The mixture was placed in a pot made of ceramic having a volume of 6 liters, and pulverized by a ball mill so as to pass through a 150 mesh sieve to obtain a powdery glaze. The glaze powder obtained here is used for glaze B
And Next, the lower glaze was wet-glazed on a 100 × 100 mm cast iron plate-shaped test piece, fired at 800 to 1100 ° C., and the glaze A was dry-glazed in a hot state, and 800 to 1100
℃, and then glaze B is dry-glazed in a hot state.
An enamel sample was obtained by baking at 00 to 1100 ° C. This enamel sample was boiled with 5 wt% NaO
An accelerated test sample was obtained by immersing in an H aqueous solution for 3 hours. With respect to the obtained enamel sample and accelerated test sample, the surface roughness was measured with an atomic force microscope (AFM; De).
manufactured by Hitachi Instruments, Nano S
Cope III) was used to measure the surface roughness in the range of 100 × 100 μm. Ra = 2.9n for enamel sample
m, Ra = 27 nm in the accelerated test sample. FIGS. 1 (a1) and (a2) show enlarged views of the surface obtained by the respective atomic force microscope (AFM) observations. Furthermore, an electron probe microanalyzer (EPMA; JEOL,
FIG. 2A shows a backscattered electron composition image of the surface of the enamel sample observed by JXA-8900RL). A portion having a high concentration of antimony oxide (a streak-like white portion in the photograph) is formed in the enamel sample, and this portion forms a convex portion after the accelerated test, increasing the surface roughness.

Comparative Example 1 A glaze raw material having the composition shown in Table 2 was melted at 1100 to 1400 ° C. using an electric furnace, and rapidly cooled in water to obtain a glass frit. 2 kg of the obtained glass frit and 4 kg of cobble stone were put into a 6-liter pottery pot and pulverized by a ball mill so as to pass through a 150-mesh sieve to obtain a powdery glaze. The glaze powder obtained here is designated as glaze C. Next, 100 × 1
The lower glaze is wet-glazed on a 00 mm cast iron plate specimen,
After firing at 800 to 1100 ° C, the glaze A is dry-glazed in the hot state, fired at 800 to 1100 ° C, and further, the glaze C is dry-glazed in the hot state and fired at 800 to 1100 ° C. A sample was obtained. In the obtained enamel sample, a little yellow coloring was observed in the glaze C layer. The enamel sample was immersed in a boiled 5 wt% NaOH aqueous solution for 3 hours to obtain an accelerated test sample. For the obtained enamel sample and accelerated test sample,
When evaluated in the same manner as in Comparative Example 1, the surface roughness was Ra = 1.6 nm for the enamel sample and Ra = 1.6 nm for the accelerated test sample.
It was 10 nm.

Example 2 An antimony oxide was added to a glaze raw material having the composition shown in Table 2 so as to have a concentration of 1 wt%, melted at 1100 to 1400 ° C. using an electric furnace, and rapidly cooled in water to obtain a glass. I got a frit. 2 kg of the obtained glass frit and 4 kg of cobble stone were put into a 6-liter pottery pot and pulverized by a ball mill so as to pass through a 150-mesh sieve to obtain a powdery glaze. The glaze powder obtained here is designated as glaze D. Next, 100 × 10
Wet glaze on a 0 mm cast iron plate-shaped test piece with
After firing at 00 to 1100 ° C, the glaze A is dry-glazed in the hot state and fired at 800 to 1100 ° C, and the glaze D is dry-glazed in the hot state and fired at 800 to 1100 ° C. A sample was obtained. The enamel sample was immersed in a boiled 5 wt% NaOH aqueous solution for 3 hours to obtain an accelerated test sample. When the obtained enamel sample and accelerated test sample were evaluated in the same manner as in Comparative Example 1, the surface roughness was Ra =
It was 2.4 nm, and Ra = 7.5 nm in the accelerated test sample.

(Example 3) A material prepared by adding antimony oxide to a glaze raw material having the composition shown in Table 2 so as to have a concentration of 0.5 wt% was used.
It melted at 1100-1400 degreeC using an electric furnace, and was quenched in water to obtain a glass frit. 2 kg of the obtained glass frit and 4 kg of cobble stone were put into a 6-liter pottery pot and pulverized by a ball mill so as to pass through a 150-mesh sieve to obtain a powdery glaze. The glaze powder obtained here is designated as glaze E. Next, 100x
The lower glaze is wet-glazed on a 100 mm cast iron plate-shaped test piece, fired at 800 to 1100 ° C, and then the glaze A is dry-glazed in a hot state, fired at 800 to 1100 ° C, and further heated in a hot state. An enamel sample was obtained by dry-glazing Glaze E and firing at 800-1100 ° C. The enamel sample was immersed in a boiled 5 wt% NaOH aqueous solution for 3 hours to obtain an accelerated test sample. When the obtained enamel sample and the accelerated test sample were evaluated in the same manner as in Comparative Example 1, the surface roughness was R
a = 2.2 nm, and Ra = 5.8 nm in the accelerated test sample. FIGS. 1 (b1) and (b2) show enlarged views of the surface obtained by each atomic force microscope (AFM) observation. In addition, an electronic probe microanalyzer (EP
MA; JEOL, JXA-8900RL). A reflected electron composition image of the surface of the enamel sample observed by JXA-8900RL is shown in FIG.

(Example 4) A material obtained by adding antimony oxide to a glaze raw material having the composition shown in Table 2 so as to have a concentration of 0.1 wt% was used.
It melted at 1100-1400 degreeC using an electric furnace, and was quenched in water to obtain a glass frit. 2 kg of the obtained glass frit and 4 kg of cobble stone were put into a 6-liter pottery pot and pulverized by a ball mill so as to pass through a 150-mesh sieve to obtain a powdery glaze. The glaze powder obtained here is designated as glaze F. Next, 100x
The lower glaze is wet-glazed on a 100 mm cast iron plate-shaped test piece, fired at 800 to 1100 ° C, and then the glaze A is dry-glazed in a hot state, fired at 800 to 1100 ° C, and further heated in a hot state. An enamel sample was obtained by dry-glazing Glaze F and firing at 800 to 1100 ° C. The enamel sample was immersed in a boiled 5 wt% NaOH aqueous solution for 3 hours to obtain an accelerated test sample. When the obtained enamel sample and the accelerated test sample were evaluated in the same manner as in Comparative Example 1, the surface roughness was R
a = 4.5 nm, and Ra = 12 nm in the accelerated test sample.

[0024]

[Table 3]

Table 3 summarizes the results of the examples of the present invention.
Shown in Thus, it can be seen that by setting the concentration of antimony oxide to less than 2 wt%, an increase in surface roughness after the accelerated test can be suppressed. In addition, coloring does not occur due to the addition of antimony oxide.

[0026]

According to the present invention, even when used for a long time,
Since the increase in surface roughness is small, it is possible to provide an enamel product in which dirt is hardly adhered forever and even if dirt is adhered, the dirt is easily removed by running water.

[Brief description of the drawings]

FIG. 1 is a diagram showing a state of a surface of an enamel sample observed by an atomic force microscope (AFM). (A1) Conventional enamel surface (Comparative Example 1) (a2) Conventional accelerated enamel surface test (Comparative Example 1) (b1) Enamel surface of the present invention (Example 3) (b2) Enamel surface of the present invention After accelerated test (Example 3)

FIG. 2 is an electron probe microanalyzer (EPM)
The reflected electron composition image of the surface of the enamel sample observed in A). (A) Conventional enamel surface (Comparative Example 1) (b) Enamel surface of the present invention (Example 3)

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shin Hayakawa 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka

Claims (22)

[Claims] 1. An enamel product having a surface glaze layer formed on a metal substrate, wherein the concentration of antimony oxide in the surface glaze layer is less than 2 wt%. 2. An enamel product having a surface glaze layer formed on a metal substrate, wherein the concentration of antimony oxide in the surface glaze layer is 1.5 wt% or less. 3. An enamel product having a surface glaze layer formed on a metal substrate, wherein the concentration of antimony oxide in the surface glaze layer is 1 wt% or less. 4. An enamel product having a surface glaze layer formed on a metal substrate, wherein the concentration of antimony oxide in the surface glaze layer is 0.001 wt% or more. The enamel product described. 5. An enamel product having a surface glaze layer formed on a metal substrate, wherein the concentration of antimony oxide in the surface glaze layer is 0.01 wt% or more. The enamel product described. 6. An enamel product having a surface glaze layer formed on a metal substrate, wherein the concentration of antimony oxide in the surface glaze layer is 0.1 wt% or more. The enamel product described. 7. An enamel product in which a colorable glaze layer is formed on a metal substrate and a surface glaze layer is further formed thereon, wherein the surface glaze layer has an antimony oxide concentration of 2 wt. % Enamel product. 8. An enamel product having a colorable glaze layer formed on a metal substrate and further having a surface glaze layer formed thereon, wherein the surface glaze layer has an antimony oxide concentration of 1%. An enamel product having a content of 0.5 wt% or less. 9. An enamel product having a colorable glaze layer formed on a metal substrate and a surface glaze layer formed thereon, wherein the surface glaze layer has an antimony oxide concentration of 1 wt. % Or less. 10. An enamel product having a colorable glaze layer formed on a metal substrate and further having a surface glaze layer formed thereon, wherein the antiglare oxide concentration in said surface glaze layer is zero. 10. The enamel product according to any one of claims 7 to 9, wherein the content is 0.001 wt% or more. 11. An enamel product in which a colorable glaze layer is formed on a metal substrate and a surface glaze layer is further formed thereon, wherein the concentration of antimony oxide in the surface glaze layer is zero. The enamel product according to any one of claims 7 to 9, wherein the content is 0.01% by weight or more. 12. An enamel product having a colorable glaze layer formed on a metal base material and a surface glaze layer formed thereon, wherein the surface glaze layer has an antimony oxide concentration of 0%. The enamel product according to any one of claims 7 to 9, wherein the content is 0.1 wt% or more. 13. The enamel product according to claim 7, wherein the coloring glaze layer contains an emulsifier and a pigment. 14. The enamel product according to claim 7, wherein the surface glaze layer is transparent. 15. The enamel product according to claim 1, wherein the enamel product is a bathtub. 16. The enamel product according to claim 1, wherein the enamel product is a wash basin. 17. The enamel product according to claim 1, wherein the enamel product is a building material for a bathroom. 18. The enamel product according to claim 1, wherein the enamel product is a kitchen panel. 19. The enamel product according to claim 1, wherein the enamel product is a wash counter. 20. The enamel product according to claim 1, wherein the enamel product is a bathtub apron. 21. The enamel product according to claim 1, wherein the enamel product is a sink. 22. The enamel product according to claim 1, wherein the enamel product is a kitchen door.