JP2002047080A - Ceramics formed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ceramics formed body imparted with antifoulancy wherein, adhesivity of an intermediate layer whose main component is a glaze on a surface of the body to a water-repellent layer is improved. SOLUTION: The water-repellent layer is formed on the intermediate layer whose main component is the glaze 3 containing zirconium silicate 2. The finished ceramics formed body assures an excellent water-repellent property and the water-repellent durability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic molded article such as tableware, tiles, sanitary ware, insulators, etc., which is provided with an antifouling property.

[0002]

2. Description of the Related Art Generally, a glaze is applied to the surface of a ceramic molded body such as a toilet bowl, a basin or a tile to give the ceramic molded body a surface of various colors.
By forming a dense and hydrophilic smooth layer, a hygienic function is exhibited. More recently, a glaze layer on the surface of a ceramic molded body has been required to have an antifouling function in addition to the above-described functions. As an antifouling method for the surface of the ceramic molded body, treatment with a water repellent such as a silicone resin or a fluororesin is performed to impart an antifouling property or to improve a cleaning property.

[0003]

The components of the glaze are divided into a non-crystalline compound serving as a skeleton and a component providing a small amount of color. The non-crystalline compound is generally a glass phase containing silicate as a main component, and components for imparting color are metals such as iron, copper, manganese, cobalt, and titanium, and compounds thereof. These coloring components are dispersed in the glass phase. However, these glazes applied to the surface of the ceramic molded body and the above-mentioned water repellent have poor adhesion, and the water repellent is removed as the number of uses such as washing increases, and the effect of preventing contamination is not maintained for a long time. was there.

[0004]

In order to solve the above-mentioned problems, the present invention provides a ceramic molded body having an intermediate layer mainly composed of glaze formed on a ceramic surface and a water-repellent layer formed on the intermediate layer. Further, the intermediate layer is a ceramic molded body containing zirconium silicate.

According to the above invention, zirconium silicate fine particles are precipitated on the surface of the intermediate layer mainly composed of glaze formed on the ceramic surface, and the zirconium silicate exerts a strong bonding force with the water-repellent layer by the effect of the zirconium silicate. Thereby, durability such as cleaning property and antifouling property can be maintained for a long time.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention can be applied to ceramic molded articles such as tableware, tiles, sanitary ware, and insulators in the form described in each claim.

That is, in the case of the invention described in claim 1,
An intermediate layer mainly composed of glaze is formed on the ceramic surface,
A ceramic molded body having a water-repellent layer formed on the intermediate layer, wherein the intermediate layer is a ceramic molded body containing zirconium silicate.

[0008] The water-repellent layer is mainly in close contact with an active group such as a hydroxyl group existing on the surface of the intermediate layer mainly composed of glaze by chemical bonding. As a result of the investigation, it was found that the zirconium silicate fine particles were superior in the degree of adhesion between the glass phase of the intermediate layer mainly composed of glaze and the zirconium silicate fine particles and the water-repellent layer. Although the detailed reason is unknown, one is presumed to be related to the alkali component in the glass phase of the intermediate layer mainly composed of glaze. That is, for example, when a ceramic molded body provided with a water-repellent layer is used as a product around water, alkali metals and alkaline earth metals in the glass phase elute on the surface over time. At that time, the part of the intermediate layer where the chemical bond is formed with the active group on the surface of the glass phase is locally alkalinized, the bond is cut, and the water repellency is likely to be deteriorated. On the other hand, the surface of the zirconium silicate fine particles has no elution of alkali metal or alkaline earth metal and has a stable bond with the water-repellent layer, so that the water-repellent effect can be maintained for a long time. Another reason is presumed to be related to the density of active groups on the surface of the zirconium silicate fine particles bonded to the water-repellent layer and the strength of the degree of activity. That is, the density of the active groups on the surface of the zirconium silicate fine particles is larger than that on the surface of the glass phase, and the degree of activity is higher, so that a stronger bond with the water-repellent layer can be achieved. Can be.

[0009] Further, according to a second aspect of the present invention, there is provided a ceramic molded body having an intermediate layer mainly composed of glaze formed on a ceramic surface, and a water-repellent layer formed on the intermediate layer.
The intermediate layer has a zirconium silicate content of 5 wt% or more.
0 wt% or less. Preferably, the content is 10 wt% or more and 20 wt% or less.

The zirconium silicate content is 5 wt.
%, The proportion of zirconium silicate fine particles on the surface of the intermediate layer, which strongly binds to the water-repellent layer, decreases, or the amount of alkali metal or alkaline earth metal eluted from the glass phase increases, resulting in a water-repellent effect. Decrease in the durability of the steel. Further, the content of zirconium silicate is 30%.
If the content exceeds wt%, the ratio of zirconium silicate fine particles on the surface of the intermediate layer, which is strongly bonded to the water-repellent layer, increases, and the durability of the water-repellent effect becomes good. However, poor appearance of the intermediate layer mainly composed of glaze occurs. It is not practical because it impairs the merchantability.

According to a third aspect of the present invention, the water-repellent layer formed on the intermediate layer mainly composed of glaze is a ceramic molded body made of at least one selected from the group of organic silicon compounds.

The organic silicon compound strongly covers the intermediate layer mainly composed of glaze, and exhibits excellent water repellency. Further, it exhibits good water-repellent durability in combination with the effect of zirconium silicate suppressing alkali component elution from the glass phase.

According to a fourth aspect of the present invention, the water-repellent layer formed on the intermediate layer mainly composed of glaze is a ceramic molded body made of at least one selected from the group consisting of alkylsilane compounds.

The alkylsilane compound chemically binds strongly to an active group such as a hydroxyl group present on the surface of the intermediate layer mainly composed of glaze, and suppresses elution of alkali components from zirconium silicate in the glass phase. It shows excellent water repellency durability in combination with the above.

According to a fifth aspect of the present invention, the water-repellent layer formed on the intermediate layer mainly composed of glaze is a ceramic molded body made of at least one selected from the group of organic fluorine compounds.

The organic fluorine compound strongly covers the intermediate layer mainly composed of glaze, and exhibits excellent water and oil repellency. Furthermore, it exhibits good water and oil repellency durability in combination with the effect of zirconium silicate suppressing the elution of alkali components from the glass phase.

According to a sixth aspect of the present invention, the water-repellent layer formed on the intermediate layer mainly composed of glaze is a ceramic molded body made of at least one selected from the group of perfluoroalkylsilane compounds. is there.

The perfluoroalkylsilane compound chemically binds strongly to active groups such as hydroxyl groups present on the surface of the intermediate layer mainly composed of glaze, and elutes alkali components from the zirconium silicate glass phase. It shows good water and oil repellency durability in combination with the suppression effect.

According to a seventh aspect of the present invention, there is provided a ceramic molded article in which an inorganic antibacterial agent is added to an intermediate layer mainly composed of glaze.

[0020] The addition of the inorganic antibacterial agent mainly suppresses bacterial contamination. In addition, due to the synergistic effect with the water-repellent layer, the adhesion of dirt components serving as baits necessary for bacterial growth is reduced, so that the addition of a small amount of the inorganic antibacterial agent provides a sufficient effect. For this reason, the influence on the physical and chemical characteristics of the ceramic molded body is small, and a ceramic molded body having excellent characteristics can be obtained.

Further, as described in claim 8, the ceramic molded body is a ceramic.

Further, it is possible to prevent stains on tableware, sanitary ware, tiles and the like.

The organic silicon compound in the present invention is a silicone compound such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane and methylhydrogenpolysiloxane. Examples include, but are not limited to, alkyd-modified, polyester-modified, acryl-modified, and epoxy-modified silicone compounds.

Examples of the organic fluorine compound include polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, and polychlorotrifluoro. Ethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene / perfluoroalkylvinyl fluoride, vinylidene fluoride / tetrafluoroethylene copolymer, polyvinyl fluoride ether, vinyl fluoride / tetrafluoroethylene copolymer, vinylidene fluoride・ Tetrafluoroethylene ・
Hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer. Fluorine oils such as perfluoropolyethers, perfluoroalkyl polyethers, and ethylene trifluoride polymers. In addition, a fluorine-based surfactant may be used, but the present invention is not limited thereto.

Examples of the alkylsilane compound include trimethylmethoxysilane, trimethylethoxysilane (hereinafter, methoxy may be ethoxy or chloro),
Examples include, but are not limited to, dimethyldimethoxysilane, methyltrimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, and the like.

The perfluoroalkylsilane compound is a compound in which some of the alkyl groups of the above-mentioned alkylsilane compound are substituted with a fluorocarbon group.
CF3 (CH2) 2Si (OCH3) 3, CF3 (CF
2) 5 (CH2) 2Si (OCH3) 3, CF3 (CF
2) 7 (CH2) 2Si (OCH3) 3, CF3 (CF
2) 7 (CH2) 2SiCH3 (OCH3) 2, CF3
(CF2) 3 (CH2) 2Si (OCH3) 3, CF3
1 carbon atoms such as (CF2) 7 (CH2) 2SiCl3
To 20 silane compounds, but are not limited thereto.

Examples of the inorganic antibacterial agent in the present invention include silver nitrate, silver sulfate, silver chloride and the like, zeolite supporting silver, copper, zinc or tin, silica gel supporting silver, copper, zinc or tin, silver , Calcium phosphate carrying copper, zinc or tin, hydroxyapatite carrying silver, copper, zinc or tin, zinc oxide carrying silver, copper, zinc or tin, or carrying silver, copper, zinc or tin Zirconium phosphate. More silver,
Examples include, but are not limited to, copper, zinc, or oxides thereof.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described in detail.

(Example 1) The basic component of the glaze is a Zegel type (0.2KnaO, 0.3ZnO, 0.4CaO).
0.5Al2O3 · 2.9SiO2. Zirconium silicate was added thereto and mixed by a ball mill for 24 hours. Approximately 100mm x 100mm x
It was applied to one side of a 10 mm clay body and dried at 80 ° C. for 1 hour. The thickness of the glaze after drying is about 1 mm. afterwards,
The temperature was raised to 1200 ° C. over 6 hours, the temperature was maintained at 1200 ° C. for 1 hour, and then cooled to room temperature over 6 hours to produce a tile-shaped ceramic flat plate. Next, after washing the glaze surface of the ceramic plate with ethanol, a water-repellent layer was formed with absorbent cotton and allowed to stand at 25 ° C. for 24 hours. In addition,
CF3 (CF2) 7 (CH2) 2Si as water-repellent layer
(OCH3) 3 was used. This is used as a test sample.
The added amount of zirconium silicate is 0 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt% of the entire glaze material.
%, 30% by weight, and 40% by weight, which were designated as test samples 1 to 8, respectively.

(Example 2) The basic component of the glaze is a Zegel type (0.2KnaO, 0.3ZnO, 0.4CaO).
0.5Al2O3 · 2.9SiO2. To this, zirconium silicate was added in an amount of 10% by weight of the entire glaze raw material, and hydroxyapatite carrying silver was added in an amount of 1% by weight of the entire glaze raw material, and mixed by a ball mill for 24 hours. The mixed glaze was applied to one side of a clay body of about 100 mm × 100 mm × 10 mm and dried at 80 ° C. for 1 hour. The thickness of the glaze after drying is about 1 mm. Thereafter, the temperature was raised to 1200 ° C. over 6 hours, the temperature was maintained at 1200 ° C. for 1 hour, and then cooled down to room temperature over 6 hours to produce a tile-shaped ceramic flat plate. Next, after washing the glaze surface of the ceramic plate with ethanol, a water-repellent layer was formed with absorbent cotton and allowed to stand at 25 ° C. for 24 hours. The water-repellent layer is made of CF3 (CF2) 7 (CH2) 2Si (OCH3) 3
Was used. This is designated as Test Sample 9.

FIG. 1 is a schematic view showing a cross section of a ceramic molded body according to an embodiment of the present invention. 1 is CF3 (CF
2) A water-repellent layer represented by 7 (CH2) 2Si (OCH3) 3. 2 is zirconium silicate contained in the glaze. 3 is a glaze.

Reference numeral 4 denotes an inorganic antibacterial agent represented by hydroxyapatite carrying silver. 5 is a clay base.

Using these test samples 1 to 8, glaze observation evaluation was performed. The gloss of the glaze surface of each test sample was visually evaluated. 0% zirconium silicate
試 験, when the surface gloss is equivalent to that, and when the surface gloss is slightly inferior, △.
When the gloss was clearly inferior, it was evaluated as x. The results are shown in (Table 1).

[0034]

[Table 1]

Next, test samples 1 to 8 were subjected to a water resistance and durability test. Each test sample is submerged in hot water at 60 ° C.
The contact angle after 50 hours, 100 hours, and 150 hours was measured, and the durability of the water-repellent layer was evaluated based on the change in the contact angle.
The results are shown in (Table 2).

[0036]

[Table 2]

Next, the test sample 9 was tested for its antibacterial performance. Test sample 4 was used as a comparative example.
To each of the test samples 9 and 4, 1 cc of Staphylococcus aureus and Escherichia coli was added dropwise and cultured at 37 ° C for 24 hours. Thereafter, the bacteria were washed out with a sterilized phosphate buffer. The viable cell count in the washed-out liquid was measured by a pour plate method using a cell count medium. The results are shown in (Table 3).

[0038]

[Table 3]

As can be seen from Table 1, test samples 2 to 6 exhibited good gloss similar to test sample 1. Test sample 7 slightly deteriorated in surface gloss. Test sample 8 had clearly deteriorated surface gloss. From these results, good surface gloss can be realized when the added amount of zirconium silicate is 30 wt% or less, more preferably 20 wt% or less.

As is clear from Table 2, water repellency was improved by adding zirconium silicate. When the addition amount of zirconium silicate is particularly 10% to 20%
%, The effect of improving the water repellency is remarkable, but when the amount is 20% or more, the degree of improvement in the water repellency tends to be almost saturated.

As is clear from Table 3, test sample 9 was able to obtain a remarkable antibacterial effect on Staphylococcus aureus and Escherichia coli as compared with test sample 4. When used in combination with a water-repellent layer having good durability, it is possible to obtain a clean ceramic molded body in which the growth of bacteria is suppressed with a small amount of an antibacterial agent. The results of the antibacterial properties shown in Table 3 indicate that no surviving bacteria were detected, and x means that the surviving bacteria were the same as the control.

[0042]

As apparent from the above description, the following effects can be obtained according to the ceramic molded body of the present invention.

According to the first aspect of the present invention, there is provided a ceramic molded body in which an intermediate layer mainly composed of glaze is formed on a ceramic surface, and a water-repellent layer is formed on the intermediate layer. This is a ceramic molded body containing zirconium. The water-repellent layer is mainly in close contact with an active group such as a hydroxyl group existing on the surface of the intermediate layer mainly composed of glaze by chemical bonding. The degree of adhesion between the glass phase of the intermediate layer mainly composed of glaze and the zirconium silicate fine particles and the water-repellent layer is superior to the zirconium silicate fine particles, and the detailed reason is unknown, but one is mainly based on glaze. It is presumed to be related to the alkali component in the glass phase of the intermediate layer. That is, for example, when a ceramic molded body provided with a water-repellent layer is used as a product around water, alkali metals and alkaline earth metals in the glass phase elute on the surface over time. At that time, the part of the intermediate layer where the chemical bond is formed with the active group on the surface of the glass phase is locally alkalinized, the bond is cut, and the water repellency is likely to be deteriorated. On the other hand, the surface of the zirconium silicate fine particles has no elution of alkali metal or alkaline earth metal and has a stable bond with the water-repellent layer, so that the water-repellent effect can be maintained for a long time. Another reason is related to the density of active groups on the surface of the zirconium silicate fine particles bonded to the water repellent layer and the strength of the degree of activity. That is, the density of the active groups on the surface of the zirconium silicate fine particles is larger than that on the surface of the glass phase, and the degree of activity is higher, so that a stronger bond with the water-repellent layer can be achieved. Can be.

According to a second aspect of the present invention, there is provided a ceramic molded body in which an intermediate layer mainly composed of glaze is formed on a ceramic surface, and a water-repellent layer is formed on the intermediate layer.
The intermediate layer has a zirconium silicate content of 5 wt% or more.
0 wt% or less. Preferably, the content is 10 wt% or more and 20 wt% or less. If the content of zirconium silicate is less than 5 wt%, the proportion of zirconium silicate fine particles on the surface of the intermediate layer that strongly binds to the water-repellent layer decreases, or the amount of alkali metal or alkaline earth metal eluted from the glass phase increases. By doing so, the degree of improvement in the durability of the water-repellent effect decreases. On the other hand, if the content of zirconium silicate exceeds 30% by weight, the ratio of zirconium silicate fine particles on the surface of the intermediate layer, which is strongly bonded to the water-repellent layer, increases, and the durability of the water-repellent effect becomes good. This causes poor appearance of the intermediate layer, impairs the merchantability, and is not practical.

According to a third aspect of the present invention, the water-repellent layer formed on the intermediate layer mainly composed of glaze is a ceramic molded body made of at least one selected from the group of organic silicon compounds. The organosilicon compound strongly coats the middle layer mainly composed of glaze and expresses excellent water repellency,
Further, it exhibits good water-repellent durability in combination with the effect of zirconium silicate suppressing alkali component elution from the glass phase.

According to a fourth aspect of the present invention, the water-repellent layer formed on the intermediate layer mainly composed of glaze is a ceramic molded body made of at least one selected from the group consisting of alkylsilane compounds. Alkylsilane compounds are
Excellent water repellency with strong binding chemically to active groups such as hydroxyl groups present on the surface of the intermediate layer mainly composed of glaze, and the effect of suppressing the elution of alkali components from the glass phase of zirconium silicate Is shown.

According to a fifth aspect of the present invention, the water-repellent layer formed on the intermediate layer mainly composed of glaze is a ceramic molded body made of at least one selected from the group consisting of organic fluorine compounds. The organofluorine compound strongly coats the middle layer mainly composed of glaze, exhibits excellent water and oil repellency, and further suppresses the elution of alkali components from the zirconium silicate glass phase. Shows good water and oil repellency durability.

According to a sixth aspect of the present invention, the water-repellent layer formed in the form of an intermediate layer mainly composed of glaze is a ceramic molded body made of at least one selected from the group of perfluoroalkylsilane compounds. . The perfluoroalkylsilane compound chemically bonds strongly to active groups such as hydroxyl groups present on the surface of the intermediate layer mainly composed of glaze,
In addition, it exhibits good water and oil repellency durability in combination with the effect of zirconium silicate suppressing alkali component elution from the glass phase.

According to a seventh aspect of the present invention, there is provided a ceramic molded article in which an inorganic antibacterial agent is added to a glaze. The addition of the inorganic antibacterial agent mainly suppresses bacterial contamination. In addition, due to the synergistic effect with the water-repellent layer, the adhesion of the dirt component serving as bait necessary for bacterial growth is reduced, so that a small amount of the inorganic antibacterial agent can be expected to have a sufficient effect. For this reason, the influence on the physical and chemical characteristics of the ceramic molded body is small, and a ceramic molded body having excellent characteristics can be obtained.

Further, as described in claim 8, the ceramic molded body is a ceramic. Thus, it is possible to prevent stains on tableware, sanitary ware, tiles, and the like.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a cross section of a ceramic molded body according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Water-repellent layer 2 Zirconium silicate 3 Glaze 4 Inorganic antibacterial agent 5 Clay base

Continued on the front page (72) Inventor Mitsuyo Yamatomi 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (8)

[Claims] 1. A ceramic molded body having an intermediate layer mainly composed of glaze formed on a ceramic surface and a water-repellent layer formed on the intermediate layer, wherein the intermediate layer contains zirconium silicate. Ceramic molded body. 2. The ceramic compact according to claim 1, wherein the content of zirconium silicate is 5% by weight or more and 30% by weight or less. 3. The ceramic molded article according to claim 1, wherein the water-repellent layer formed on the intermediate layer mainly composed of glaze is made of at least one selected from the group consisting of organic silicon compounds. 4. The ceramic molded article according to claim 1, wherein the water-repellent layer formed on the intermediate layer mainly composed of glaze is made of at least one selected from the group consisting of alkylsilane compounds. 5. The ceramic molded article according to claim 1, wherein the water-repellent layer formed on the intermediate layer mainly composed of glaze is made of at least one selected from the group consisting of organic fluorine compounds. 6. The ceramic molded body according to claim 1, wherein the water-repellent layer formed on the intermediate layer mainly composed of glaze is at least one selected from the group of perfluoroalkylsilane compounds. 7. The ceramic molded body having an intermediate layer mainly composed of glaze formed on a ceramic surface, wherein the glaze contains an inorganic antibacterial agent. Ceramic molded body. 8. The ceramic molded body according to claim 1, wherein the ceramic molded body is a ceramic.