JP2003165786A - Glaze composition and stainproof pottery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glaze composition capable of forming a glaze layer whose surface is resistant to adhesion of a stain, which has excellent removability of a stuck stain, and which has also an excellent appearance and suitably usable for hygienic pottery. <P>SOLUTION: The glaze composition contains glaze forming components which form the glaze layer when burned. The composition does not contain a zirconium component but contains a phosphorus component and a tin component as follows. The composition contains glaze forming components whose contents are determined so that a sintered compact, which comprises, in terms of an oxide, SiO<SB>2</SB>of 55.0-67.0 wt.%, Al<SB>2</SB>O<SB>3</SB>of 7.0-15.0 wt.%, SnO<SB>2</SB>of 0.5-8.0 wt.%, P<SB>2</SB>O<SB>5</SB>of 0.5-10.0 wt.%, an arbitrary divalent metal oxide of 10.0-20.0 wt.%, and an arbitrary monovalent metal oxide of 2.0-10.0 wt.%, is formed at the time of burning. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glaze composition for forming a glaze layer having excellent antifouling properties and an excellent appearance, and a sintered body of the glaze composition on the surface of a base material such as sanitary ware. The present invention relates to an antifouling ceramics having a glaze layer formed thereon.

[0002]

2. Description of the Related Art Conventionally, a ceramic is coated with a glaze on the surface of a base material in order to give a beautiful appearance and prevent the adhesion of dirt due to the dirt stress applied over time and to easily remove the adhered dirt. After that, it is baked to form a glaze layer. The formation of the glaze layer on such ceramics is used not only for general ceramics but also for sanitary ceramics such as toilet bowls and washbasins.

[0003]

However, when a glaze layer is formed on the surface of a ceramic body with a general glaze, stains are less likely to adhere to the surface than when the ceramic body is exposed, and the stain removability is improved. Although it is also improved, the surface of such a glaze layer has irregularities on the surface due to undissolved substances in the glaze or zirconium silicate crystals blended as an emulsion It is unavoidable that some adhesion of dirt is unavoidable, and it cannot be said that the dirt removability is sufficiently improved, and it may be difficult to remove dirt that has once adhered.

In order to improve the antifouling property of such a glaze layer, it has been attempted to form a transparent glaze layer consisting only of an amorphous material, but the appearance is only obtained with such a transparent glaze layer. It is difficult to improve, and actually, it is necessary to form a colored or emulsified glaze layer on the lower side of the transparent glaze layer, and it is necessary to form two glaze layers, which is troublesome. It was such a thing.

The present invention has been made in view of the above points, and it is possible to form a glaze layer in which dirt is unlikely to adhere to the surface, and the adhered dirt is excellently removed, and which has a good appearance. A glaze composition suitable for use in sanitary ware,
Another object of the present invention is to provide an antifouling porcelain provided with a glaze layer formed of this glaze composition.

[0006]

The glaze composition according to the present invention is a glaze composition containing a glaze-forming component that forms a glaze layer during firing, which does not contain a zirconium component and contains a phosphorus component and a tin component. It is characterized by containing.

[0007] At this time, 55.
And 0 to 67.0% by weight of SiO _2, and Al ₂ O ₃ of 7.0 to 15.0 wt%, 0.5 to 8.0 wt% of SnO
_2, and P ₂ O ₅ of 0.5 to 10.0 wt%, 10.0
20.0% by weight of any divalent metal oxide, 2.0-
A glaze-forming component whose composition is determined so as to form a sintered body composed of 10.0% by weight of any monovalent metal oxide is included.

In addition, the total amount of glaze-forming components in terms of oxide
In contrast, the silicon component is SiO₂Converted to 55.0 to 67.
0% by weight, aluminum component is Al₂O₃Converted to 7.0
15.0% by weight, tin component SnO₂Converted to 0.5
8.0 wt%, phosphorus component P₂O _FiveConverted to 0.5-10.
0% by weight of any divalent metal component in terms of oxide 10.
0-20.0 wt%, oxide conversion of any monovalent metal component
It is preferable to contain 2.0 to 10.0% by weight in total.

Furthermore, the total amount of glaze-forming components in terms of oxide is
In contrast, the silicon component is SiO₂Converted to 55.0 to 67.
0% by weight, aluminum component is Al₂O₃Converted to 7.0
15.0% by weight, tin component SnO₂3.0-
6.0 wt%, phosphorus component P₂O _Five0.5-5.0 in conversion
Weight%, 15.0% of any divalent metal component in terms of oxide
~ 20.0 wt%, convert any monovalent metal component to oxide
It is preferable that the content is 2.0 to 5.0% by weight.

Further, it contains a calcium component and a zinc component as arbitrary divalent metal components, and the calcium component is 7.0 to 15.0 weight in terms of CaO with respect to the total amount of glaze-forming components in terms of oxide. %, Zinc component in terms of ZnO 2.
It is preferable to contain 0 to 7.0% by weight.

Further, it contains a calcium component and a zinc component as arbitrary divalent metal components, and the calcium component is 1 in terms of CaO with respect to the total amount of glaze-forming components in terms of oxide.
0.0 to 15.0% by weight, zinc component in terms of ZnO 2.
It is preferable to contain 0 to 7.0% by weight.

Further, it is also preferable to contain a magnesium component as an arbitrary divalent metal component in an amount of 0.1 to 2.0% by weight in terms of MgO, based on the total weight of the glaze-forming components in terms of oxide.

Further, it contains a sodium component and a potassium component as arbitrary monovalent metal components, and the sodium component is 0.1 to 5% in terms of Na ₂ O based on the total amount of glaze-forming components in terms of oxide. It is preferable to contain 0% by weight and a potassium component of 1.0 to 5.0% by weight in terms of K ₂ O.

Further, it is also preferable to contain a lithium component as an arbitrary monovalent metal component in an amount of 0.1 to 5.0% by weight in terms of LiO _{2 based on} the total amount of glaze-forming components in terms of oxide.

Calcium hydrogen phosphate is preferably used as a raw material containing a phosphorus component for preparing the glaze composition.

It is also preferable to use bone ash as a raw material containing a phosphorus component for preparing a glaze composition.

It is also preferable to use hydroxyapatite as a raw material containing a phosphorus component for preparing a glaze composition.

It is also preferable to use calcium metaphosphate as a raw material containing a phosphorus component for preparing a glaze composition.

Furthermore, it is also preferable to use tricalcium phosphate as a raw material containing a phosphorus component for preparing the glaze composition.

As a raw material for the emulsion, it is preferable to contain a titanium component in an amount of 0.1 to 8 parts by weight in terms of TiO _{2 with} respect to the total amount of glaze-forming components in terms of oxide.

Further, it is also preferable that, as an emulsion material, 0.1 to 8 parts by weight of CeO _{2 in} terms of CeO _{2 of a} cerium component which does not form a frit is contained with respect to the total amount of glaze-forming components in terms of oxide.

As the coloring material, it is preferable that the pigment is contained in an amount of 0.1 to 8 parts by weight based on the total amount of the glaze-forming components.

Further, it is preferable to contain a tin pigment.

Further, as the coloring material, cobalt compound, manganese compound, nickel compound, uranium compound, chromium compound, iron compound, copper compound, gold compound, antimony compound, arsenic acid compound, molybdenum compound, tungsten compound and vanadium compound are selected. It is preferable to contain at least one of the above, and the total content thereof is 0.1 to 5 parts by weight in terms of a mixing ratio with respect to the total amount of the glaze-forming components in terms of oxide.

Further, as a part or all of the glaze-forming component, it is preferable to contain a frit obtained by previously vitrifying the raw material constituting the glaze-forming component and then crushing the raw material.

Further, as a raw material containing a silicon component for preparing a glaze composition, it is preferable to use a fine powder which does not contain particles having a particle size of 30 μm or more.

As a raw material containing a tin component for preparing a glaze composition, the median diameter is 0.2 to 4.0 μm.
It is preferable to use the fine powder.

As a raw material containing a phosphorus component for preparing a glaze composition, the median diameter is 1.0 to 5.0 μm.
It is preferable to use the fine powder.

Further, an emulsion material raw material containing at least one of a titanium component and a cerium component is blended, and the median diameter of the emulsion material raw material is 0.1 to 2.0 μm.
It is also preferable to use a fine powder.

The median diameter of the entire glaze-forming component is preferably 3 to 5 μm.

Of the raw materials for the glaze-forming component, at least one raw material containing a silicon component, a raw material containing a tin component, and a raw material containing a phosphorus component is pulverized in advance to a predetermined particle size, and then the remaining glaze-forming component. It is preferable to add the above raw material and grind until the entire glaze-forming component has a predetermined particle size.

Further, among the raw materials of the glaze-forming component, the raw material containing the silicon component is pulverized in advance until the median diameter becomes 5 μm or less, and then the remaining raw materials of the glaze-forming component are added so that the entire glaze-forming component has a predetermined particle size. It is preferable to grind until it becomes.

Further, among the raw materials of the glaze-forming component, the raw material containing the tin component is pulverized in advance until the median diameter becomes 1.5 to 2 μm, and the remaining raw materials of the glaze-forming component are added,
It is preferable to grind the entire glaze-forming component to a predetermined particle size.

Of the raw materials for the glaze-forming component, the raw material containing the phosphorus component is crushed in advance to a median diameter of 3 to 5 μm, and the remaining raw materials for the glaze-forming component are added to the whole glaze-forming component to a predetermined particle size. It is also preferable to grind until it becomes.

Of the raw materials of the glaze-forming component, the raw material containing the silicon component, the raw material containing the tin component and the raw material containing the phosphorus component are pulverized in advance until the total median diameter becomes 5 μm or less, and then the remaining glaze-forming component is formed. Add ingredients ingredients,
It is also preferable to grind until the entire glaze-forming component has a predetermined particle size.

Of the raw materials for the glaze-forming component, the raw material containing the silicon component is pulverized in advance until the median diameter becomes 5 μm or less, and the remaining raw materials for the glaze-forming component are added to make the median diameter of the entire glaze-forming component. It is also preferable to pulverize to 3 to 5 μm.

Of the raw materials for the glaze-forming component, the raw material containing the tin component is crushed in advance until the median diameter becomes 1.5 to 2 μm, and then the remaining raw materials for the glaze-forming component are added,
It is also preferable to grind until the median diameter of the entire glaze-forming component becomes 3 to 5 μm.

Of the raw materials for the glaze-forming component, the raw material containing the phosphorus component is crushed in advance to a median diameter of 3 to 5 μm, and the remaining raw materials for the glaze-forming component are added to the median diameter of the entire glaze-forming component. It is also preferable to grind until it becomes 3 to 5 μm.

Of the raw materials for the glaze-forming component, the raw material containing the silicon component, the raw material containing the tin component, and the raw material containing the phosphorus component are pulverized in advance until the total median diameter becomes 5 μm or less, and then the remaining glaze-forming component. It is also preferable to add the above raw material and grind until the median diameter of the entire glaze-forming component becomes 3 to 5 μm.

Further, it is preferable to grind the raw material of the glaze-forming component using a ball mill made of alumina balls.

Further, it is also preferable to pulverize the raw material of the glaze-forming component with a ball mill consisting of alumina balls and a container whose inner lining is made of alumina.

In the antifouling ceramics according to the present invention, a layer made of the above glaze composition is formed on the surface of the base material of the ceramics, and the layer of the glaze composition has a maximum temperature of 1150 to 1250.
It is characterized in that a glaze layer is formed on the surface of the base material by firing at 8 ° C. for 8 hours or more.

At this time, ZrSiO ₄ crystals do not exist,
It is preferable to form a glaze layer in which SnO ₂ crystals and Ca ₃ (PO ₄ ) ₂ crystals are present.

Further, since ZrSiO ₄ crystals do not exist, Ca
It is also preferable to form a glaze layer in which SnSiO ₅ crystals and Ca ₃ (PO ₄ ) ₂ crystals are present.

Further, since ZrSiO ₄ crystals do not exist, Ca
It is also preferable to form a glaze layer in which SnSiO ₅ crystals, SnO ₂ crystals and Ca ₃ (PO ₄ ) ₂ crystals are present.

Furthermore, the thickness of the glaze layer is 0.2 to 1.2 mm.
It is preferable to form it.

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

The glaze composition of the present invention contains a glaze-forming component for forming a glaze layer, and is mixed with water or various binders in order to improve the applicability on the surface of the base material of the sanitary ware. May be.

The glaze-forming component is composed of a silicon component, an aluminum component, a tin component, a phosphorus component, an arbitrary divalent metal component and an arbitrary monovalent metal component, and contains a zirconium component. It is something that should not be done.

The antifouling glaze for sanitary ware having such components has a high stain resistance and stain removability of the glaze layer obtained by coating and firing the glaze composition, and is excellent on the surface of the glaze layer. The luster appears.

When the above components do not contain a silicon component, an aluminum component, a divalent metal component or a monovalent metal component, it is possible to form a glossy and durable glaze layer on sanitary ware. It will be difficult. If the tin component or phosphorus component is not contained, the glaze layer becomes transparent without clouding, and when used in sanitary ware, the base material becomes transparent, which is not preferable in appearance. . Further, when a zirconium component is contained, an emulsified glaze layer can be obtained, but the antifouling performance is significantly reduced.

The amount of these glaze-forming components blended depends on the glaze form.
Glaze-forming component when all components are converted as oxides
The silicon component is SiO with respect to the total amount.₂Converted from 55.0
67.0% by weight, aluminum component as Al₂O₃In conversion
7.0 to 15.0% by weight, tin component SnO₂In conversion
0.5-8.0% by weight, phosphorus component P₂O_FiveConverted to 0.5
~ 10.0 wt%, convert any divalent metal component to oxide
10.0-20.0% by weight, any monovalent metal component
It is preferable to contain 2.0 to 10.0% by weight in terms of oxide.
Good That is, the baking formed by baking the glaze composition.
Oxides in the sintered body (glaze layer) based on the total weight of the sintered body
Converted to SiO₂Is 55.0 to 67.0% by weight, Al₂O₃
Is 7.0 to 15.0% by weight, SnO₂Is 0.5 to 8.0
% By weight, P₂O _Five0.5-10.0% by weight, any divalent
Metal oxide of 10.0 to 20.0% by weight, any monovalent
To contain 2.0 to 10.0% by weight of the metal oxide of
It is preferred to have the composition determined.

The glaze composition having such a composition has high stain resistance and stain removability of the glaze layer obtained by coating and firing the glaze composition, and the surface of the glaze layer exhibits good gloss. It is something to put out.

Of the above-mentioned components, if the content of the silicon component in terms of oxide is less than 55.0% by weight, the antifouling property cannot be sufficiently obtained in the glaze layer, and the milky white of the glaze layer is obtained. The appearance may be deteriorated due to a decrease in degree or an increase in the amount of bubbles generated. On the contrary, when the content of silicon component in terms of oxide exceeds 67.0% by weight, the antifouling property of the glaze layer is deteriorated, and the amount of bubbles is increased to deteriorate the appearance.

When the content of the aluminum component in terms of oxide is less than 7.0% by weight, the antifouling property of the glaze layer cannot be sufficiently obtained, and the amount of bubbles generated in the glaze layer increases. On the contrary, if this content exceeds 15.0% by weight, the antifouling property of the glaze layer cannot be sufficiently obtained, and the effect of improving the opacification degree of the glaze layer by incorporating the tin component is suppressed. I will end up.

If the amount of tin component converted to oxide is less than 0.5% by weight, it becomes difficult to sufficiently improve the milkiness of the glaze layer, and the content is 8.0% by weight.
If it exceeds, the antifouling property of the glaze layer cannot be sufficiently obtained.

If the amount of the phosphorus component converted to oxide is less than 0.5% by weight, it becomes difficult to sufficiently improve the milkiness of the glaze layer, and the content exceeds 10.0% by weight. And the antifouling property of the glaze layer cannot be obtained sufficiently.

If the content of the optional divalent metal component in terms of oxide is less than 10.0% by weight, the compatibility of the components during firing of the glaze composition deteriorates and crystallization is caused, resulting in antifouling property. It cannot be obtained sufficiently and the surface gloss is not obtained sufficiently. Conversely, if this content is 20.0% by weight
If it exceeds, the flow at the time of melting at a high temperature becomes large, the vertical surface sags, and the amount of bubbles generated increases.

If the content of any monovalent metal in terms of oxide is less than 2.0% by weight, the miscibility of the components during baking of the glaze composition deteriorates and crystallization occurs, resulting in sufficient antifouling properties. However, when the content exceeds 10.0% by weight, the flow at the time of melting at high temperature becomes large and the vertical surface becomes In addition, the amount of bubbles is increased and the amount of bubbles is increased, and the glaze layer may be penetrated.

Still more preferably, the amount of the glaze-forming component is 55.0 to 67.0 in terms of SiO ₂ with respect to the total amount of the glaze-forming component when all the glaze-forming components are converted to oxides. % By weight, aluminum component is Al
7.0 to 15.0% by weight calculated as ₂ O ₃ , SnO as tin component
₂ 3.0 to 6.0 wt% in terms of 0.5 to 5.0 wt% of phosphorus component in terms _of P ₂ O _5, in terms of oxide of any divalent metal component from 15.0 to 20. 0% by weight, and an arbitrary monovalent metal component is contained in an amount of 2.0 to 5.0% by weight in terms of oxide. That is, in the sintered body (glaze layer) formed by firing the glaze composition, SiO ₂ is 55.0 to 67.0 wt% in terms of oxide, Al based on the total weight of the sintered body. ₂ O ₃
Of 7.0 to 15.0 wt% and SnO ₂ of 3.0 to 6.0
Wt%, P ₂ O ₅ is 0.5 to 5.0 wt%, the metal oxide of any divalent is 15.0 to 20.0 wt%, a metal oxide of any monovalent 2.0 It has a composition determined to contain 5.0% by weight.

By doing so, the amount of bubbles generated in the glaze layer formed is further reduced, and the occurrence of penetration in the glaze layer is further suppressed.

The content of the tin component is 3.0 to 6.0% by weight in terms of SnO ₂ , and the content of the phosphorus component in terms of P ₂ O ₅ is 0.5 to 5.0% by weight. As a result, the glaze layer has a sufficient opacification degree, has a small amount of bubbles, and has a beautiful appearance.

Further, if the content of any divalent metal component is 10.0 to 20.0% by weight in terms of oxide as described above, a good glaze layer can be obtained. When the content is less than 15.0% by weight, antifouling property and gloss tend to be slightly deteriorated, and when the content is more than 20.0% by weight, the amount of bubbles is slightly increased. It is seen, and the flow at the time of melting at a high temperature becomes large and the vertical surface sags, which is not suitable for products with a vertical surface. Therefore, in order to form a more favorable glaze layer, the content of any divalent metal component in terms of oxide is 15.0.
It is preferable that the content be ˜20.0% by weight.

Further, if the content of the arbitrary monovalent metal component is 2.0 to 10.0% by weight in terms of oxide as described above, a good glaze layer can be obtained, but it is more preferable. In order to form such a glaze layer, it is preferable that the content of any monovalent metal component in terms of oxide is 2.0 to 5.0% by weight. When the content of the arbitrary monovalent metal component is 5.0% by weight or less as described above, it is possible to further suppress the generation of a flow at the time of melting at high temperature during the formation of the coating film, and thus the undulation of the coating surface. The appearance can be further improved by suppressing the occurrence of the like.

Further, as the optional divalent metal component, a calcium component, a zinc component, a magnesium component or the like can be contained. In particular, a calcium component as an arbitrary divalent metal component is contained in an amount of 7.0-15.0 wt% in terms of CaO based on the total amount of glaze-forming components in terms of oxide, and a zinc component in terms of oxide is used for glaze. When the content of ZnO is 2.0 to 7.0% by weight based on the total amount of the forming components, the glaze layer is more excellent in antifouling property and gloss, and the amount of bubbles generated can be further reduced. At this time, if the content of the calcium component in terms of CaO is less than 7.0% by weight, the compatibility of the components during firing of the glaze composition is deteriorated, crystallization is likely to occur, and the antifouling property is slightly lowered, When this content exceeds 15.0% by weight, the antifouling property is slightly lowered, and the amount of bubbles generated tends to be slightly increased. If the content of the zinc component in terms of ZnO is less than 2.0% by weight, the compatibility of the components during firing of the glaze composition is deteriorated, crystallization is likely to occur, and the antifouling property and gloss are slightly deteriorated. However, when the content exceeds 7.0% by weight, the antifouling property is slightly lowered, and the amount of bubbles generated tends to be slightly increased.

Further, it is particularly preferable that a calcium component as an arbitrary divalent metal component is 10.0 to 15.0% by weight in terms of CaO with respect to the total amount of glaze-forming components in terms of oxide.
When the zinc component is contained in an amount of 2.0 to 7.0% by weight in terms of ZnO based on the total amount of glaze-forming components in terms of oxide, the antifouling property and gloss are further excellent, and the amount of bubbles generated is further increased. It can be reduced. At this time, the content of the calcium component in terms of CaO is 7.0 to 15.
If the content is 0% by weight, a good glaze layer can be obtained, but if the content is less than 10.0% by weight, the antifouling property and gloss tend to be slightly deteriorated. When the content exceeds 15.0% by weight, the amount of bubbles generated is slightly increased, and the flow at the time of melting at high temperature becomes large and the vertical surface sags, resulting in products with vertical surfaces. Is not suitable for. Therefore, in order to form a better glaze layer, it is preferable that the calcium component is 10.0 to 15.0 wt% in terms of CaO with respect to the total amount of glaze-forming components in terms of oxide.

When the calcium component and the zinc component are contained within the above ranges, a magnesium component can be further contained as an arbitrary divalent metal component. The content of the magnesium component is an oxide. It is preferably 0.1 to 2.0 wt% in terms of MgO with respect to the total amount of glaze-forming components in terms of conversion. MgO of magnesium component
If the content in terms of conversion is less than 0.1% by weight, the antifouling property of the glaze layer is slightly deteriorated, and if it exceeds 2.0% by weight, the compatibility of the components during firing of the glaze composition deteriorates and crystals are obtained. There is a tendency for stain resistance and gloss to slightly deteriorate.

As the arbitrary monovalent metal component, a sodium component, a potassium component, a lithium component or the like can be used. In particular, a sodium component as an arbitrary monovalent metal component is contained in an amount of 0.1 to 5.0% by weight in terms of Na ₂ O based on the total amount of glaze-forming components in terms of oxide, and a potassium component is used in terms of oxide in terms of glaze. 0.1 to 5.0% by weight in terms of K ₂ O based on the total amount of forming components
By containing, the antifouling property and the gloss are further excellent, and the amount of bubbles generated can be further reduced. At this time, the content of sodium component and potassium component is 0.1 in terms of the above oxide.
If the amount is less than 10% by weight, the compatibility of the components during baking of the glaze composition is deteriorated, crystallization is likely to occur, and the effect of improving antifouling property and gloss cannot be sufficiently obtained. Further, if the content of these exceeds 5.0% by weight, the flow at the time of melting at a high temperature becomes large, the vertical surface sags, and the amount of bubbles generated increases, and the glaze layer There is also a tendency for penetration to occur. In addition, better results can be obtained when there is no difference in the compounding amount of the sodium component and the potassium component in terms of oxide.

Furthermore, the lithium component is further converted into oxide.
Li based on the total amount of glaze-forming components ₂0.1 in O conversion
If the content is 5.0% by weight, the tendency of penetration of the glaze layer is further improved.
Can be reduced to Oxidation of lithium content
If you do not see 0.1% by weight in terms of material, such penetration
Sufficient suppression effect is not obtained, and more than 5.0% by weight
In some cases, the flow at the time of melting at high temperature becomes large and the vertical surface becomes flat.
And the amount of bubbles generated increases.

Here, the glaze-forming components in the glaze composition other than the phosphorus component do not necessarily have to be mixed as a single oxide or an oxide of a single metal. For example, a silicon component or various metal components shown below can be used. It may be compounded as a compound such as an oxide containing a plurality of kinds of metals and silicon, an oxide of silicon alone or a carbonate which produces an oxide of a single metal when heated. Specifically, feldspar, silica stone, lime, dolomite, zinc white, glazed clay, wollastonite, nepheline cyanite, alumina, kaolin, tin oxide powder, etc. are used as the raw material of the glaze-forming component, and these raw materials are appropriately used. A glaze composition can be prepared by using the composition in the proportion of. Therefore, the amount of each component in the glaze-forming component is the total amount of the glaze-forming component in terms of oxide as described above, that is, the glaze-forming component is a mixture of a single oxide of metal and silicon that constitutes this glaze-forming component. It is defined based on the total amount of glaze-forming components when converted virtually, and the blending amount of each component is also defined in terms of a single oxide of metal and silicon.

In addition, calcium hydrogen phosphate (CaHPO ₄ ) can be used as a raw material for the phosphorus component in the glaze composition. In this case, when baking the glaze composition, calcium hydrogen phosphate reacts with other components to vitrify to form opalescent glass, which causes phase separation,
As a result, a glaze layer having a transparent feeling and excellent in antifouling property is formed.

Bone ash (main component is Ca ₃ (PO ₄ ) ₂ ) can also be used as a raw material for the phosphorus component. In this case, bone ash can partially react with other compositions during firing of the glaze composition, and promote vitrification of the glaze composition,
The resulting glaze layer tends to have a slightly improved antifouling property and gloss.

Hydroxyapatite (Ca ₅ (PO ₄ ) ₃ (OH)) can also be used as a raw material for the phosphorus component. In this case, the baking temperature is set to 130 when baking the glaze composition.
When the temperature is 0 ° C or lower, hydroxyapatite does not decompose or reacts with other components, and contributes to opacification of the glaze layer as crystals. In order to obtain the sufficient opacifying effect, it is preferable that the content of hydroxyapatite is 0.1% by weight or more in terms of P ₂ O _{5 based on the} total amount of glaze-forming components in terms of oxide. Also, since this hydroxyapatite exists as crystals in the glaze layer, in order to maintain sufficient antifouling performance and suppress the generation of bubbles, the content is P _{2 with} respect to the total amount of glaze-forming components in terms of oxide. 5.0% by weight in terms of O ₅
The following is preferable.

Calcium metaphosphate (Ca (PO ₃ ) ₂ ) can also be used as the raw material for the phosphorus component. In this case, at the time of firing the glaze composition, calcium metaphosphate reacts with other components to vitrify to form opalescent glass, which causes phase separation, and thus has excellent transparency and stain resistance. A glaze layer is formed. However, when the raw material containing calcium metaphosphate is wet-milled with a mill or the like when preparing the glaze composition, the viscosity increases and the time required for the pulverization increases, so that such an increase in viscosity is suppressed. The content of calcium metaphosphate is P ₂ O _{5 with} respect to the total amount of glaze-forming components in terms of oxide.
It is preferably 3.0% by weight or less in terms of conversion. Further, in order to sufficiently obtain the effect of containing calcium metaphosphate, the content thereof is preferably 0.1% by weight or more in terms of P ₂ O _{5 with} respect to the total amount of glaze-forming components in terms of oxide.

Further, tricalcium phosphate (Ca ₃ (PO ₄ ) ₂ ) can be used as a raw material for the phosphorus component. In this case, tricalcium phosphate does not decompose or react with other components during firing of the glaze composition, and contributes to opacification of the glaze layer as crystals. In order to obtain the sufficient opacifying effect, the content of tricalcium phosphate is 0.1% by weight in terms of P ₂ O _{5 based on the} total amount of glaze-forming components in terms of oxide.
The above is preferable. Although this tricalcium phosphate is present as crystals in the glaze layer, it is more effective in maintaining the antifouling performance of the glaze layer than in the case of hydroxyapatite, and the content of tricalcium phosphate is When the content of the glaze-forming component in terms of oxide is 10% by weight or less in terms of P ₂ O ₅ , the antifouling property of the glaze layer can be sufficiently maintained.

As a raw material for the glaze-forming component, a compound containing silicon, phosphorus, or metal as described above is heated and melted and then solidified to be vitrified (amorphous), and further obtained by pulverization. It is also possible to use a frit. At this time, the glaze-forming component may be composed only of such a frit, or the frit may constitute a part of the glaze-forming component.

In addition to the above-mentioned glaze-forming components, an emulsion material, a coloring material and the like can be added to the glaze composition.

The emulsion material is added to improve the opalescence of the glaze layer, and a titanium component such as titanium oxide (TiO ₂ ) or a cerium component such as cerium oxide (CeO ₂ ) can be used. .

When a titanium component is used as the emulsifying material, the amount of Ti based on the total amount of the glaze-forming component in terms of oxide is
It is preferable to contain 0.1 to 8.0% by weight in terms of O ₂ , and if the content is less than 0.1% by weight, it will be difficult to sufficiently improve the opacification degree of the glaze layer. If it exceeds 0.0% by weight, the antifouling property of the glaze layer tends to be slightly lowered.

When a cerium component is used as the emulsifying agent, the opacification degree can be further improved as compared with the case where titanium oxide is used. The case of cerium component, the total amount of the glaze-forming component in terms of oxide, in terms of CeO ₂ 0.
It is preferable to add 1 to 8.0% by weight, and if the content is less than 0.1% by weight, it becomes difficult to sufficiently improve the milkiness of the glaze layer, and the amount exceeds 8.0% by weight. In this case, the antifouling property of the glaze layer tends to be slightly reduced. When a cerium component such as cerium oxide is used, if it is added to the glaze composition in a fritted state, the effect of improving the milkiness of the glaze layer cannot be obtained. Therefore, the ingredient is not fritted.

As the coloring material, a pigment can be blended. Appropriate pigments are used, and for example, colored compounds such as metal oxides and carbonates are used for kaolin, quartz,
Examples include finely pulverized products obtained by mixing with other inorganic compounds such as tin oxide and firing at a constant temperature. It is preferable to use tin-based pigments because the stability of color increases. At this time, it is preferable that the pigment is contained in an amount of 0.1 to 8.0% by weight based on the actual total amount of the glaze-forming component, and if the amount is less than 0.1, the glaze layer is sufficiently colored. If it exceeds 8.0% by weight, the antifouling performance of the glaze layer tends to be slightly lowered.

As the colorant, a cobalt compound,
Manganese compound, nickel compound, uranium compound,
It is also possible to directly blend one or more compounds selected from chromium compounds, iron compounds, copper compounds, gold compounds, antimony compounds, arsenic acid compounds, molybdenum compounds, tungsten compounds and vanadium compounds. The total content of these compounds is preferably 0.1 to 5.0% by weight based on the total amount of glaze-forming components in terms of oxide, and the content is less than 0.1. If not, it will be difficult to sufficiently color the glaze layer, and if it exceeds 5.0% by weight, bubbles may be generated in the glaze layer.
There is also a tendency that the antifouling performance is slightly lowered.

The glaze composition is prepared by mixing a raw material for the above glaze-forming components, an emulsifying agent, a coloring agent, and the like, which are blended as necessary, in a predetermined amount, and adding water if necessary, and crushing the mixture.
Further, it can be prepared by adjusting the water content or blending an appropriate binder or peptizer as necessary.

In preparing the glaze composition, it is preferable to use, as the raw material containing the silicon component, the raw material containing the tin component and the raw material containing the phosphorus component, which have been subjected to particle size adjustment in advance, before crushing, When blending an emulsion with titanium oxide or cerium oxide as an emulsion,
It is preferable to use those whose particle size is adjusted in advance.

For example, in the case of raw materials containing a silicon component such as feldspar and silica stone, it is preferable to use finely powdered materials in which particles having a particle size of 30 μm or more have been removed by previously pulverizing and classifying these raw materials. .

Further, in the case of a raw material containing a tin component such as tin oxide powder, it is preferable to use a fine powder having a median diameter of 0.2 to 4.0 μm. Further, in the case of a raw material containing a phosphorus component such as bone ash powder, it is preferable to use a material adjusted to a fine powder having a median diameter of 1.0 to 5.0 μm.

In the case of an emulsion material such as titanium oxide powder and cerium oxide powder, the median diameter is 0.1 to 2.0.
It is preferable to use a fine powder having a size of μm.

Here, the median diameter is the particle diameter corresponding to 50% of the cumulative curve in the particle size distribution, and is also called the 50% average particle diameter (D50). In the present specification, the median diameter is derived based on the weight-based particle size distribution. In this case, the total weight of particles having a particle size larger than the value of the median diameter and the total weight of particles having a smaller particle size than the value of the median diameter are used. Becomes equal to the weight.

As described above, the raw material containing a silicon component, the raw material containing a tin component, the raw material containing a phosphorus component, or an emulsifying material such as a titanium oxide powder or a cerium oxide powder, the particle size of which is previously adjusted as described above. The use of such a product can further improve the antifouling property of the glaze layer.

At this time, the grain size of 3 in the raw material containing the silicon component.
If particles of 0 μm or more are contained, the effect of improving the antifouling property as described above cannot be obtained. Further, if the median diameter of the raw material containing the tin component exceeds 4.0 μm, the above-described antifouling effect cannot be obtained, while if the median diameter is less than 0.2 μm, the antifouling property is improved. Not only the effect cannot be obtained, but the milkiness of the glaze layer may decrease. In addition, the median diameter of the raw material containing the phosphorus component is 5.
If it exceeds 0 μm, the effect of improving antifouling property as described above cannot be obtained. On the other hand, if the median diameter is less than 1.0 μm, not only the effect of improving antifouling property cannot be obtained, but also the glaze layer There is also a risk that the milkiness will decrease. Further, if the median diameter of the raw material containing an emulsion component such as titanium oxide or cerium oxide exceeds 2.0 μm, the effect of improving the antifouling property as described above cannot be obtained, while the median diameter is 0.1 μm.
If it is less than m, the milkiness of the glaze layer may decrease.

Further, it is preferable to pulverize each raw material so that the entire median diameter of the glaze-forming component becomes 3 to 5 μm. Within this particle size range, the antifouling property and luster of the glaze layer are further improved, and outside this range, such antifouling property and luster improving effect cannot be obtained.

When the glaze composition is prepared by pulverizing the raw material of the glaze-forming component, of the raw materials of the glaze-forming component, a raw material containing a silicon component, a raw material containing a tin component, and a raw material containing a phosphorus component are prepared. After crushing at least one of the raw materials to a predetermined particle size in advance, it is preferable to add the remaining raw material of the glaze-forming component, and to grind until the entire glaze-forming component has a predetermined particle size, in this case, the glaze layer The antifouling property can be further improved. In particular, when using a raw material containing a silicon component or a raw material containing a tin component or a phosphorus component that has not been subjected to particle size adjustment in advance, first obtain a raw material containing a silicon component or a raw material containing a tin component or a phosphorus component in a predetermined particle size as described above. It is preferable to grind up to.

When only the raw material containing the silicon component is previously pulverized, the median diameter of the raw material containing the silicon component is 5 μm.
It is preferable to grind until the following. Even when the median diameter at this time exceeds 5 μm, the raw material containing the silicon component is pulverized by adding the other raw material and then pulverizing, so that the antifouling property of the glaze layer can be improved. The median diameter of the raw material containing the silicon component in advance is 5 μm
Grinding to the following level reduces the amount of bubbles generated in the glaze layer, improves the opalescence, and allows the glaze layer to have a further improved appearance. At this time, it is preferable to pulverize the raw material containing the silicon component as finely as possible, but if the median diameter is made too small, the time required for the pulverization will take too long, and the production efficiency of the glaze composition will decrease. It is preferable to carry out pulverization in the range of 1 μm or more in diameter.

When only the raw material containing the tin component is previously pulverized, the median diameter of the raw material containing the tin component is 1.5.
It is preferable to grind until it becomes ~ 2 μm. At this time, even when the median diameter exceeds 2 μm, the raw material containing the tin component is pulverized by adding the other raw material and then pulverizing, so that the antifouling property of the glaze layer can be improved in advance. The median diameter of the raw material containing tin is 1.5-
By pulverizing to 2 μm, not only the antifouling property but also the milkiness of the glaze layer is improved, and the glaze layer having a further improved appearance can be formed. When the median diameter of the raw material containing the tin component is less than 1.5 μm, such an effect of improving the opacification cannot be obtained.

When only the raw material containing the phosphorus component is previously pulverized, the median diameter of the raw material containing the phosphorus component is 3 to 5
It is preferable to grind until it becomes μm. At this time, even if the median diameter exceeds 5 μm, the raw material containing the phosphorus component is pulverized by adding the other raw material and then pulverizing, so that the antifouling property of the glaze layer can be improved.
If the median diameter of the raw material containing the phosphorus component is 3 to 5 μm in advance, not only the antifouling property but also the milkiness of the glaze layer is improved, and a glaze layer with a further improved appearance can be formed. it can. Further, when the median diameter of the raw material containing the phosphorus component is less than 3 μm, such an effect of improving the milkiness cannot be obtained.

When all of the raw material containing the silicon component, the raw material containing the tin component and the raw material containing the phosphorus component are previously pulverized, the raw material containing the silicon component, the raw material containing the tin component and the raw material containing the phosphorus component. Is preferably pulverized in advance until the total median diameter becomes 5 μm or less. Even if the median diameter at this time is more than 5 μm, the raw material containing the silicon component, the raw material containing the tin component and the phosphorus component are pulverized by adding the other raw material and then pulverizing, and the antifouling of the glaze layer is prevented. However, the amount of bubbles generated in the glaze layer can be reduced and the opalescence can be improved by pulverizing the median diameter to 5 μm or less in advance to form a glaze layer with an improved appearance. You can At this time, it is preferable to grind the raw material containing the silicon component, the raw material containing the tin component and the raw material containing the phosphorus component as finely as possible, but if the median diameter is made too small, the time required for the pulverization takes too long, and the glaze composition The median diameter is 1
It is preferable to perform pulverization in the range of μm or more.

Then, as described above, the raw material containing the silicon component, the raw material containing the tin component, or the raw material containing the phosphorus component is pulverized in advance to a predetermined particle size, and the rest of the raw materials are added to make the median diameter of the entire glaze-forming component. By pulverizing to 3 to 5 μm, the antifouling property, gloss and opacification can be further improved.

The raw material of the glaze-forming component as described above can be crushed using a ball mill. As such a ball mill, a ball or a container whose inner lining is made of silica, alumina, or the like can be used. In particular, if the lining of the ball or the ball and the container is made of alumina, it is prevented that the lining of the ball or the container made of alumina having high hardness is ground in the crushing process, and the ball or the container is configured. It is possible to prevent the substance to be contained in the glaze composition. On the other hand, for example, when a ball or container lining is made of silica, silica is an essential component of the glaze-forming component, and the amount to be ground is small, so that almost the desired composition is obtained. Although a glaze composition having the above can be obtained, the particles generated by grinding the lining of the ball or the container have a large particle size, and therefore the antifouling property may be slightly reduced.

The water contained in the glaze composition is added in order to improve the coatability of the glaze composition, and should be contained in an amount necessary for obtaining good coatability. Although it is good, for example, solid content 1 in the glaze composition
About 40 parts by weight can be contained with respect to 00 parts by weight. Further, the binder can be contained when it is necessary to improve the film forming property, and the material thereof is not particularly limited as long as it is volatilized during heating and firing.

When the glaze composition thus prepared is used, a glaze layer having a high antifouling property and a good appearance can be formed on the surface of the base material of the sanitary ware.

When forming a glaze layer on the surface of the base material of sanitary ware, first, the glaze composition is applied to the surface of the base material by spray coating or the like to form a layer of the glaze composition on the surface of the base material, and the ceramic is heated and baked. After being melted, it is solidified.

The maximum heating temperature during firing is 1150.
The temperature is preferably ˜1250 ° C., and in this temperature range, a glaze layer having good gloss and antifouling property can be formed. If the maximum temperature during firing does not fall within this range, the gloss and antifouling properties tend to decrease, and if it exceeds this range, the fluidity of the glaze composition increases and it flows over the surface of the base material, and the glaze layer forms. There is a possibility that some parts will not be formed.

The firing time is preferably 8 hours or more at the maximum temperature under the above-mentioned maximum temperature condition, and in this case, the amount of bubbles generated in the glaze layer can be further reduced. The longer the firing time, the more the amount of bubbles generated can be reduced. However, in order to ensure good productivity, 24
It is preferable that the time is not more than the time.

A roller hearth, a tunnel kiln, or the like can be used for heating and baking the glaze composition. The roller hearth is formed by forming a plurality of rollers for transportation inside the furnace, and the ceramics supplied to the inside of the furnace are heated while being conveyed on the rollers and led out of the furnace. A tunnel kiln has a tunnel-shaped furnace equipped with a carriage for transportation that can travel inside the furnace. The ceramics supplied in the furnace are placed on the carriage and the carriage runs. Is heated while being conveyed in the furnace, and is discharged to the outside of the furnace. These roller hearths and tunnel kilns have a high treatment efficiency because they can be heated and fired by successively introducing ceramics into the furnace. When heating and firing with a roller hearth, the heating time at the maximum temperature is preferably 8 hours or more as described above in order to reduce the amount of bubbles generated, but when performing heating and firing with a tunnel kiln The heating time is preferably 10 hours or more.

When the glaze layer is formed by heating and baking the layer of the glaze composition, it is preferable that the thickness of the glaze layer formed after baking be 0.2 to 1.2 mm. Forms a good glaze layer with a high concealing property on the surface of the base ceramic body. When the thickness of the glaze layer is less than 0.2 mm, the hiding property of the surface of the base material of the ceramic is not sufficient and the base material can be seen through. If the thickness exceeds 1.2 mm, the glaze composition before firing When the layer is dried, fine cracks are likely to occur, and the so-called drag bald (part) is formed in the glaze layer formed after firing.
There is a possibility that a defect called "ing" may occur and the surface of the substrate is exposed.

The glaze layer thus formed is subjected to X-ray diffraction measurement.
When measured by the standard method, SnO₂Conclusion
Crystal and CaSnSiO_FiveOut of crystals (tin sphene)
When a diffraction peak due to one or both is observed
Both Ca₃(PO_Four)₂Crystal and Ca_Five(PO_Four)₃(O
H) Diffraction peak due to one or both of the crystals
Are observed and are caused by crystals other than these crystals.
No diffraction peak was observed and SnO₂Crystal, CaSnSi
O_FiveCrystal, Ca₃(PO_Four)₂Crystal and Ca_Five(PO _Four)
₃The existence of crystals other than (OH) crystals is not confirmed.
is there. Therefore, this glaze layer constitutes the entire glaze layer.
Most of the components to be dissolved are compatible and become amorphous,
SnO₂Crystal and CaSnSiO_FiveOf crystal (tin sphene)
One or both crystallizes, and Ca₃(PO_Four)₂crystal
And Ca_Five(PO_Four)₃One or both of the (OH) crystals are bonded
Crystallized and milky, which makes the glaze layer milky white
Is made. At this time, crystals are generated in the glaze layer
, The surface of which is ZrSiO_FourWhen using a composition containing
It does not have unevenness like that of the
It has excellent properties and gloss.

[0107]

EXAMPLES The present invention will be described in detail below with reference to examples.

Example 1 As a raw material of a glaze-forming component,
Kamado feldspar, silica stone powder, rat lime, dolomite, zinc white, raw frog eye clay, tin oxide powder and bone ash were used. As a raw material containing silicon components, Kamado feldspar and silica stone powder, particle size is 30μ
Particles containing 2% of particles of m or more were used, and tin oxide powder having a median diameter of 4.1 μm was used. The bone ash used had a median diameter of 4.1 μm.

Then, using a ball mill in which both the lining of the container and the balls are made of silica, the above-mentioned respective raw materials are charged in predetermined amounts into the container of the ball mill, and 40% to 100 parts by weight of the solid content of these raw materials is used. Add parts by weight of water, rotate this ball mill for 8 hours to pulverize the raw materials,
A glaze composition containing a glaze-forming component having a composition represented by A in Table 1 below as an oxide was prepared. The median diameter of the glaze-forming component in this glaze composition was 5.1 μm as measured by an X-ray transmission particle size analyzer.

This glaze composition was spray-coated on the surface of a dried sanitary ware body to form a layer of the glaze composition, and this sanitary ware was baked in a tunnel kiln at a maximum temperature of 1200 ° C. for 16 hours. Then, a glaze layer having a thickness of 0.6 mm was formed on the surface of the sanitary ware body.

(Examples 2 to 9 and Comparative Examples 1 to 15) In the same manner as in Example 1 except that the blending amount of the raw materials and the pulverizing time of the raw materials were changed, the respective Examples and Comparative Examples were converted into oxides. Contains a glaze-forming component having a composition shown in B to X in Table 1 and the median diameter of the glaze-forming component is 5.1 μm.
Was prepared.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Examples 10 to 13) A glaze composition was prepared in the same manner as in Example 1 except that the bone ash as the phosphorus component raw material was changed to calcium hydrogen phosphate, calcium hydroxide, calcium metaphosphate or tricalcium phosphate.

Then, using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Examples 14 to 17) Titanium oxide powder having a particle size of 2.2 μm or cerium oxide powder having a particle size of 2.2 μm was put into the glaze raw material put in the mill in the same manner as in Example 1, A ground glaze composition having a ground median diameter of 5.1 μm was prepared.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

Then, using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Examples 18 and 19) A predetermined amount of a commercially available iron-based pigment (manufactured by Kawamura Chemical Co., Ltd .; "gray") was put into the glaze raw material put in the mill in the same manner as in Example 1, and pulverized. A ground glaze composition having a median diameter of 5.1 μm was prepared.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

Example 20 A predetermined amount of manganese dioxide powder was put into the glaze raw material put in the mill in the same manner as in Example 1 to prepare a ground glaze composition having a ground median diameter of 5.1 μm.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

Then, using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

Example 21 Crushed glass frit
(Nippon Frit Co., Ltd .; Part No. PN-54321; SiO ₂
70% by weight, Al₂O₃14% by weight, Na₂O16 weight
%) And the raw materials were mixed in a predetermined ratio, and then the same as in Example 1.
The median diameter crushed by the ball mill is 5.1μm
Crushed raw material of 30 parts by weight of glass frit
Mix 60 parts by weight of crushed raw material and mix with glass frit and powder.
The composition of the glaze-forming component consisting of crushed raw materials is expressed in oxide equivalent.
A glaze composition to be A and B of 1 was prepared.

Then, using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Embodiment 22) As the raw material containing silicon component, Kamado feldspar and silica stone powder, particles having a particle size of 30 μm or more removed by pulverization and classification were used. Otherwise in the same manner as in Example 1, a glaze composition having a median diameter of the glaze-forming component of 5.1 μm was prepared.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Examples 23 to 24) Tin oxide powder, which is a raw material containing a tin component, had a median diameter of 3.2 μm and a particle diameter of 0.2 μm.
A glaze composition in which the median diameter of the glaze-forming component was 5.1 μm was prepared in the same manner as in Example 3 except that the glaze composition was used.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

Example 25 A glaze composition was prepared in the same manner as in Example 1 except that the median diameter was adjusted to 4.3 μm as the bone ash powder which was a raw material containing a phosphorus component.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

Examples 26 to 27 Titanium oxide powder and cerium oxide powder, which are emulsion materials, have a median diameter of 1.8.
A glaze composition was prepared in the same manner as in Example 14 except that the glaze-forming component had a median diameter of 5.1 μm.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Examples 28 to 29) Glaze compositions were prepared in the same manner as in Example 2 except that the median diameter of the glaze-forming component was adjusted to 4.3 μm and 2.8 μm by changing the grinding time. .

Then, using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Examples 30 to 33) One or both of a raw material containing a silicon component, a raw material containing a tin component, and a phosphorus component were preliminarily prepared with 20% by weight of water in the same ball mill as in Example 1 for 1 hour. After pulverizing and adjusting the median diameter of these raw materials to the particle diameter shown in Table 3, the remaining raw material and water are added to a ball mill to adjust the content of water to 40 parts by weight with respect to 100 parts by weight of the solid content of the raw materials. And further pulverized with a ball mill, and the composition of the glaze-forming component in terms of oxide is B in Table 1.
A glaze composition having a median diameter of 5.1 μm having the composition shown in 1 was prepared.

Then, using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Example 34) A raw material containing a silicon component was used.
After preliminarily grinding with 20% by weight of water in the same ball mill as in Example 1 for 4 hours to adjust the median diameter to 5.0 μm, the remaining raw material and water were added to the ball mill to adjust the water content to the solid content of the raw material. 40 parts by weight per 100 parts by weight,
Further, the mixture was pulverized for 7 hours with a ball mill to prepare a glaze composition having a median diameter of 5.0 μm and having a composition of the glaze-forming components as oxides shown in B of Table 1.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Examples 35 and 36) A raw material containing a tin component was preliminarily pulverized with 20% by weight of water in the same ball mill as in Example 1 for 3 hours or 6 hours to obtain a median diameter of 1.
After adjusting to 8 μm or 1.3 μm, the remaining raw material and water were added to the ball mill to make the content of water 40 parts by weight with respect to 100 parts by weight of the solid content of the raw material, and further pulverization was performed in the ball mill for 7 hours. A glaze composition having a median diameter of 4.9 μm and having a composition shown in B of Table 1 as an oxide conversion of the glaze-forming component was prepared.

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Examples 37, 38) One or both of a raw material containing a silicon component, a raw material containing a tin component, and a phosphorus component were preliminarily ground with 20% by weight of water in the same ball mill as in Example 1 for 4 hours. After adjusting the median diameter to 4.1 μm, the remaining raw material and water are added to the ball mill to make the water content 40 parts by weight with respect to 100 parts by weight of the raw material solid content, and further pulverized for 7 hours by the ball mill. This was performed to prepare a glaze composition having a median diameter of 5.0 μm and having a composition of the glaze-forming component in terms of oxide as shown in B of Table 1.

(Examples 39 and 40) In Example 39, a ball mill whose container lining is made of alumina and whose balls are made of silica is used. In Example 40, a ball mill whose lining and balls are both made of alumina is used. Using. Otherwise in the same manner as in Example 2, a glaze composition having the composition of the glaze-forming component in terms of oxide as shown in B of Table 1 and having a median diameter of the glaze-forming component of 5.1 μm was prepared. .

Using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

(Example 41, Comparative Example 16) In Example 41, 3 parts by weight of a tin-based pigment (manufactured by Nisto Sangyo Co., Ltd .; "gray") was added to the glaze composition obtained in Example 2. To prepare a glaze composition.

In Comparative Example 16, a glaze composition was prepared by further adding 3 parts by weight of the above tin-based pigment to the glaze composition obtained in Comparative Example 1.

Then, using this glaze composition, a glaze layer having a thickness of 0.6 mm was formed on the surface of the base material of the sanitary ware in the same manner as in Example 1.

[0148]

[Table 1]

(Evaluation) The following evaluations were performed for each of the examples and comparative examples.

Evaluation of antifouling property A sanitary porcelain having a glaze layer formed thereon was dipped in a 5% alkaline aqueous solution at a liquid temperature of 60 ° C for 45 hours, and then written on the surface with a water-based ink, and the handwriting was recorded with a waste cloth. I wiped it off. As a result, the case where the writing trace was completely wiped off was evaluated as "⊚", the case where the writing trace was slightly left but hardly visible was evaluated as "○", and the one where the writing trace was clearly visible was evaluated as "x".

Gloss evaluation Visually observing the glaze layer, and the one having a gloss better than that of Comparative Example 15, which is a conventional product, was marked with "⊚",
Those with similar gloss were evaluated as “◯”, and those with poor gloss were evaluated as “x”.

Evaluation of bubble generation amount The glaze layer was visually observed, and when the amount of bubble generation was smaller than that of Comparative Example 15 which is a conventional product, “⊚” was given,
Those having the same amount of bubble generation were evaluated as “◯”, and those having a large amount of bubble generation were evaluated as “x”.

Evaluation of opalescence: The glaze layer is visually observed, and the one having a higher opacification than that of Comparative Example 15 which is a conventional product is "◎", and the one having the same opacification is "○". "," Those having low milkiness were evaluated as "x".

The above results are shown in Tables 2-4.

[0155]

[Table 2]

[0156]

[Table 3]

[0157]

[Table 4]

[0158]

[Table 5]

According to the results shown above, Examples 1 to 41
On the other hand, the glaze layer had a high antifouling property and a good gloss, and the amount of bubbles generated in the glaze layer and the opalescence were as good as those of the conventional product.

On the other hand, in Comparative Example 15 which is a conventional product containing ZrO ₂ and Comparative Example 16 in which ZrO ₂ is added, a good result can be obtained in terms of gloss, bubble generation amount and opacification degree. However, the antifouling property was low. Further, Comparative Examples 2 and 9 containing a large amount of the silicon component have poor antifouling properties and a large amount of air bubbles, and Comparative Example 1 having a small content of the silicon component has poor antifouling properties, a large amount of bubbles and poor gloss. Met. In Comparative Example 4 in which the content of the aluminum component is large, the antifouling property is poor, the amount of bubbles is large, and the content of the aluminum component is small in Comparative Example 3
However, the antifouling property was poor and the amount of bubbles was large. In Comparative Example 12 containing a large amount of tin component, the antifouling property was poor,
In Comparative Example 11 in which the content of the tin component was small, the milkiness was deteriorated. Further, in Comparative Example 9 in which the content of the divalent metal component is small, the antifouling property is poor and the gloss is also poor.
Further, in Comparative Example 10 in which the content of the divalent metal component was large, the antifouling property was poor and the amount of bubbles generated was large. Further, Comparative Example 7 having a low content of the monovalent metal acid component has poor antifouling property and poor gloss, and Comparative Example 8 having a high content of the monovalent metal component has poor antifouling property. There were many bubbles, and further, penetration was observed in the glaze layer.

In all of Examples 1 to 24, the same good evaluation was obtained, but among them, the RO content was 15
Slightly improved antifouling properties can be seen in Examples 1, 2, 7 and 9 than in Examples 3 to 6 and Example 8 in which the content of RO is 20. The amount of bubbles generated was lower in the other examples than in the examples 4 and 8 in which the weight percentage was exceeded. Further, in comparison with Examples 4, 5, 6 and 8 in which the content of the calcium component was less than 10% by weight, the other examples were improved in not only the amount of bubbles generated but also the antifouling property. . Further, in Example 8 in which the content of the R ₂ O component exceeded 5% by weight, the amount of bubbles generated was slightly larger and the opalescence was slightly lower than those in the other Examples.

Further, in Examples 2 to 4, 7 and 8 in which the content of the tin component was less than 3% by weight, the amount of bubbles generated was slightly larger than that of Examples 1 and 9 and the milkiness was also slightly lower. .

Further, in Example 6 in which the content of the tin component exceeded 6% by weight, the antifouling property was slightly reduced as compared with Examples 1 and 9.

In Examples 4, 5, 6 and 8 in which the content of the phosphorus component exceeds 5% by weight, other Examples 1, 2, 3,
A slight decrease in antifouling property was observed as compared with Nos. 7 and 9.

Also, in the case of Examples 10 to 13 using calcium hydrogen phosphate, hydroxyapatite, calcium metaphosphate, tricalcium phosphate as the phosphorus component raw material,
The same evaluation as in Example 1 having the same composition was obtained.

Further, Example 1 was prepared in which 1.8 parts by weight of titanium oxide and cerium oxide were blended as an emulsion in the glaze-forming component.
Also in the cases of 4 to 17, the same evaluation as in Example 1 having the same composition was obtained.

Further, also in the case of Examples 18 and 19 in which 1.8 parts by weight of zircon pigment was blended in the glaze-forming component for coloring, the same evaluation as in Example 1 having the same composition was obtained.

Also, in the case of Example 20 in which 5 parts by weight of manganese dioxide was blended in the glaze-forming component for coloring, the same evaluation as in Example 1 having the same composition was obtained.

Further, even in the case of Example 21 in which a frit was contained in the glaze-forming component, Example 1 having the same composition
The same evaluation as was obtained.

The particle size of the raw material containing the silicon component is 30
In Example 22 in which particles having a size of μm or more were previously removed,
The antifouling property superior to that of Example 1 having the same composition was obtained.

In Examples 23 and 24 in which the particle diameter of the raw material containing the tin component was changed, the median diameter was 0.2 to
In Example 23 in which the range was 4.0 μm, better antifouling property was obtained than in Example 3 having the same composition. On the other hand, in Example 24 in which the median diameter was less than 0.2 μm, the evaluation results were the same as in Example 3 having the same composition, and the opalescence was slightly lower than that in Example 3.

In Examples 28 and 29 in which the particle size of the entire glaze-forming component was changed, the median size was 3.0 to 5.0.
In Example 28 adjusted to the range of μm, the antifouling property is superior to Example 2 having the same composition, and the median diameter is 3.
In Example 29 having a thickness of less than 0 μm, the same evaluation result as that of Example 2 was obtained.

Example 3 in which at least one of the raw material containing the silicon component and the raw material containing the tin component was crushed in advance.
In Nos. 0 to 38, antifouling properties superior to those in Example 2 having the same composition were obtained. In particular, in Examples 34 to 38 in which the median diameter of the entire glaze-forming component was adjusted to a suitable range, the gloss was also improved, and further, Example 38 in which a raw material containing a tin component was pre-ground to adjust the particle size to a suitable range. , 41 also improved opalescence.

Further, in Example 39 in which the container lining as a ball mill was changed to alumina, and in Example 40 in which both the lining and the balls were changed to alumina, more protective than Example 2 in which the same composition was adjusted. The dirtiness is further improved,
In addition, comparing Example 39 with Example 40, Example 4
0 was more improved in antifouling property.

In addition, in Example 41 containing the tin-based pigment, a colored glaze layer was formed, and the same evaluation result as that of Example 2 having the same composition except that the tin-based pigment was not contained was obtained. Was obtained. Further, the antifouling property was improved as compared with Comparative Example 16 in which the conventional product contained a pigment.

(X-ray Diffraction Measurement) Example 1, Example 10,
Regarding the glaze layers in 11, 12, 13 and Comparative Example 15, X-ray diffraction measurement was performed on a lump sample. At this time, CuK _α rays were used as the X-ray source. As a result, in Examples 1 and 13, the crystals measured by X-ray diffraction were only CaSnSiO ₅ crystals, SnO ₂ crystals, and Ca ₃ (PO ₄ ) ₂ crystals, and the remaining components were amorphized. Moreover, the presence of these crystals provides a high opacification degree and a smooth surface, which has high stain resistance and gloss.

In Examples 10 and 12, the crystals measured by X-ray diffraction were SnO ₂ crystals and CaSnSiO ₅
It was found that they were only crystals, and the remaining components were amorphized. The phosphorus component is considered to be opalescent vitrified in combination with other components. The so-called phase-separated state is produced to give whiteness, which helps the opalescence of SnO ₂ crystals and CaSnSiO ₅ crystals. Also in this case, as in the first embodiment,
It has a high degree of opalescence, and has a smooth surface, which has high stain resistance and gloss.

In Example 11, the crystals measured by X-ray diffraction measurement were SnO ₂ crystals and CaSnSiO ₅ crystals.
It was found that only the (Ca ₅ (PO ₄ ) ₃ (OH)) crystal was present, and the remaining components were amorphized. Also in this case, as in Example 1, the opalescence is high, and the surface is formed smooth, so that the antifouling property and the gloss are high.

On the other hand, in Comparative Example 15, zirconium silicate crystals were formed, and the zirconium silicate crystals formed an uneven surface although the opalescence was good as shown in the above evaluation results. Therefore, the antifouling property becomes low.

[0180]

As described above, the glaze composition according to the present invention is a glaze composition containing a glaze-forming component that forms a glaze layer during firing, does not contain a zirconium component, and is converted into oxide by firing. 55.0 to 67.0 wt% SiO ₂ and 7.0 to 15.0 wt% Al ₂ O
₃ , 0.5 to 8.0 wt% SnO ₂ , and 0.5 to 1
0.0 wt% P ₂ O ₅ , 10.0 to 20.0 wt% any divalent metal oxide, and 2.0 to 10.0 wt% any monovalent metal oxide. Since it contains a glaze-forming component whose composition has been determined so as to form a sintered body consisting of, when a glaze layer is formed by firing this glaze composition, dirt is unlikely to adhere to the surface It is possible to form a good glaze layer having excellent removability, good opacification degree, and reduced amount of bubbles generated.

In addition, the total amount of glaze-forming components in terms of oxide
In contrast, the silicon component is SiO₂Converted to 55.0 to 67.
0% by weight, aluminum component is Al₂O₃Converted to 7.0
15.0% by weight, tin component SnO₂Converted to 0.5
8.0 wt%, phosphorus component P₂O _FiveConverted to 0.5-10.
0% by weight of any divalent metal component in terms of oxide 10.
0-20.0 wt%, oxide conversion of any monovalent metal component
By adding 2.0 to 10.0 wt% in total,
A glaze layer is formed by baking the glaze composition of
And, it is hard for dirt to adhere to the surface and removes dirt that has adhered
It has excellent opacity, good opacities, and the amount of bubbles generated.
It is possible to form a good glaze layer with reduced
Of.

The total amount of glaze-forming components in terms of oxide is
In contrast, the silicon component is SiO₂Converted to 55.0 to 67.
0% by weight, aluminum component is Al₂O₃Converted to 7.0
15.0% by weight, tin component SnO₂3.0-
6.0 wt%, phosphorus component P₂O _Five0.5-5.0 in conversion
Weight%, 15.0% of any divalent metal component in terms of oxide
~ 20.0 wt%, convert any monovalent metal component to oxide
If the content is 2.0 to 5.0% by weight, the acquisition cost is high.
A glaze layer that reduces the amount of raw materials containing tin components
Keeps good opalescence and keeps stain resistance, gloss and bubbles
It is possible to form a glaze layer with a further improved production amount.
Of.

Further, it contains a calcium component and a zinc component as arbitrary divalent metal components, and the calcium component is 7.0 to 15.0 wt% in terms of CaO with respect to the total amount of glaze-forming components in terms of oxide. %, Zinc component in terms of ZnO 2.
When the content is 0 to 7.0% by weight, it is possible to obtain a glaze layer which is further excellent in antifouling property and gloss and in which the amount of bubbles generated is further reduced.

[0184] Further, it contains a calcium component and a zinc component as arbitrary divalent metal components, and the calcium component is 1 in terms of CaO with respect to the total amount of glaze-forming components in terms of oxide.
0.0 to 15.0% by weight, zinc component in terms of ZnO 2.
When the content is 0 to 7.0% by weight, it is possible to obtain a glaze layer which is further excellent in antifouling property and gloss and in which the amount of bubbles generated is further reduced.

Further, when a magnesium component is contained as an arbitrary divalent metal component in an amount of 0.1 to 2.0% by weight in terms of MgO with respect to the total weight of the glaze-forming component in terms of oxide, The antifouling property, the gloss and the amount of bubbles generated can be maintained in good condition.

[0186] Further, by containing a sodium component and a potassium component as the metal component of any monovalent, relative to the glaze-forming component total amount in terms of oxides, the sodium component in terms of Na ₂ O 0.1-5. By adding 0% by weight and 1.0 to 5.0% by weight of potassium component in terms of K ₂ O, it is possible to obtain a glaze layer having more excellent antifouling property and gloss.

Furthermore, when a lithium component as an arbitrary monovalent metal component is contained in an amount of 0.1 to 5.0 wt% in terms of LiO _{2 with} respect to the total amount of glaze-forming components in terms of oxide, the glaze layer is formed. It is possible to prevent the occurrence of penetration and maintain the antifouling property, gloss and the amount of bubbles generated in a good state.

When calcium hydrogen phosphate is used as the raw material containing the phosphorus component for preparing the glaze composition, the antifouling property, the gloss and the amount of bubbles generated can be maintained in good condition. .

When bone ash is used as a raw material containing a phosphorus component for preparing a glaze composition, the antifouling property, luster and amount of air bubbles can be maintained in good condition.

When hydroxyapatite is used as a raw material containing a phosphorus component for preparing a glaze composition, the antifouling property, gloss and the amount of air bubbles can be maintained in good condition.

When calcium metaphosphate is used as a raw material containing a phosphorus component for preparing a glaze composition, the antifouling property, gloss and the amount of air bubbles can be maintained in good condition.

When tricalcium phosphate is used as a raw material containing a phosphorus component for preparing a glaze composition,
The antifouling property, the gloss and the amount of bubbles generated can be maintained in good condition.

When the titanium component is contained as an emulsifying material raw material in an amount of 0.1 to 8 parts by weight in terms of TiO _{2 with} respect to the total amount of glaze-forming components in terms of oxide, antifouling properties, gloss and bubbles are obtained. The generated amount and opalescence can be maintained in good condition.

Further, when a cerium component which does not form a frit is contained as an emulsion material in an amount of 0.1 to 8 parts by weight based on the total amount of glaze-forming components in terms of oxide, antifouling properties, gloss and bubbles are generated. The amount and opalescence can be maintained in good condition.

When a pigment is contained as a coloring material in an amount of 0.1 to 8 parts by weight with respect to the total amount of the glaze-forming components, the glaze layer is colored, and the stain resistance, gloss and bubble generation amount, and opacification degree are increased. And the coloring can be maintained in a good state.

When a tin-based pigment is contained, a glaze layer colored with the pigment can be formed, and at the same time,
It is possible to maintain the antifouling property, gloss, amount of air bubbles and opalescence of the glaze layer in good condition.

The coloring material is selected from cobalt compounds, manganese compounds, nickel compounds, uranium compounds, chromium compounds, iron compounds, copper compounds, gold compounds, antimony compounds, arsenic acid compounds, molybdenum compounds, tungsten compounds and vanadium compounds. If at least one of the above is contained, and the total amount of the contents is 0.1 to 5 parts by weight with respect to the total amount of the glaze-forming components,
The glaze layer can be colored and at the same time, the antifouling property, gloss and amount of air bubbles, opalescence and coloring can be maintained in good condition.

When a frit obtained by vitrifying a raw material constituting the glaze-forming component in advance and then pulverizing it is contained as a part or the whole of the glaze-forming component, even if the frit is used as a raw material in this way. The antifouling property, gloss, opacification degree and amount of bubbles generated can be maintained in good condition.

Further, if a fine powder which does not contain particles having a particle size of 30 μm or more is used as the raw material containing the silicon component for preparing the glaze composition, the antifouling property of the glaze layer can be further improved. It is a thing.

As a raw material containing a tin component for preparing a glaze composition, the median diameter is 0.2 to 4.0 μm.
The use of the finely powdered product of (1) makes it possible to further improve the antifouling property of the glaze layer and maintain a good opalescence.

As a raw material containing a phosphorus component for preparing a glaze composition, the median diameter is 1.0 to 5.0 μm.
The use of the finely powdered product of (1) makes it possible to further improve the antifouling property of the glaze layer and maintain a good opalescence.

Further, an emulsion material raw material containing at least one of a titanium component and a cerium component is blended, and the median diameter of this emulsion material raw material is 0.1 to 2.0 μm.
The use of the finely powdered product of (1) makes it possible to further improve the antifouling property of the glaze layer and maintain a good opalescence.

When the median diameter of the entire glaze-forming component is 3 to 5 μm, the antifouling property and gloss of the glaze layer can be further improved.

Of the raw materials for the glaze-forming component, at least one raw material containing a silicon component, a raw material containing a tin component, and a raw material containing a phosphorus component is pulverized in advance to a predetermined particle size, and then the remaining glaze-forming component. By adding the above raw material and pulverizing the entire glaze-forming component to a predetermined particle size, the antifouling property of the glaze layer can be further improved.

Further, among the raw materials of the glaze-forming component, the raw material containing the silicon component was crushed in advance until the median diameter became 5 μm or less, and the remaining raw material of the glaze-forming component was added to make the entire glaze-forming component have a predetermined particle size. If it is pulverized to a certain extent, a glaze layer having further excellent antifouling property can be obtained.

[0206] Of the raw materials for the glaze-forming component, the raw material containing the tin component was crushed in advance to a median diameter of 1.5 to 2 µm, and the remaining raw materials for the glaze-forming component were added.
When the entire glaze-forming component is pulverized to have a predetermined particle size, a glaze layer having an antifouling property and an improved milkiness can be obtained.

Further, among the raw materials of the glaze-forming component, the raw material containing the phosphorus component is crushed in advance until the median diameter becomes 3 to 5 μm, and the remaining raw materials of the glaze-forming component are added.
When the entire glaze-forming component is pulverized to have a predetermined particle size, a glaze layer having an antifouling property and an improved milkiness can be obtained.

Of the raw materials of the glaze-forming component, the raw material containing the silicon component, the raw material containing the tin component and the raw material containing the phosphorus component were pulverized in advance until the total median diameter became 5 μm or less, and then the remaining glaze-forming component was formed. Add ingredients ingredients,
By crushing the entire glaze-forming component to a predetermined particle size, a glaze layer having an excellent antifouling property can be obtained. Further, among the raw materials for the glaze-forming component, a raw material containing a silicon component has a median diameter of 5 μm in advance. After pulverizing to the following, add the rest of the ingredients for the glaze-forming component and pulverize until the median diameter of the entire glaze-forming component is 3 to 5 μm, further improving the antifouling property, gloss and opalescence of the glaze layer. Is what you can do.

[0209] Of the raw materials for the glaze-forming component, the raw material containing the tin component was previously crushed to a median diameter of 1.5 to 2 µm, and the remaining raw materials for the glaze-forming component were added.
By pulverizing until the median diameter of the entire glaze-forming component becomes 3 to 5 μm, the antifouling property, gloss and opacification degree of the glaze layer can be further improved.

Of the raw materials for the glaze-forming component, the raw material containing the phosphorus component was pulverized in advance to a median diameter of 3 to 5 μm, and the remaining raw materials for the glaze-forming component were added to the median diameter of the entire glaze-forming component. When the particle size is 3 to 5 μm, the antifouling property, gloss and opacification degree of the glaze layer can be further improved.

Of the raw materials for the glaze-forming component, the raw material containing the silicon component, the raw material containing the tin component, and the raw material containing the phosphorus component were pulverized in advance until the total median diameter became 5 μm or less, and then the remaining glaze-forming component. When the raw material of (1) is added and the mixture is pulverized until the median diameter of the entire glaze-forming component becomes 3 to 5 μm, the antifouling property, gloss and opacification degree of the glaze layer can be further improved.

Further, when the raw material of the glaze-forming component is pulverized by using a ball mill made of alumina balls, it is possible to suppress the inclusion of particles having a large particle size generated by the grinding of the ball mill during the pulverization and to further prevent the stain resistance. A glaze layer having excellent properties can be formed.

Further, when the raw material of the glaze-forming component is crushed by a ball mill consisting of alumina balls and a container whose inner lining is made of alumina, particles having a large particle size generated by grinding by the ball mill during crushing are mixed. It is possible to more reliably prevent this, and to form a glaze layer having excellent antifouling properties.

A glaze layer is formed on the surface of the ceramic body by forming a layer of the above glaze composition on the surface of the ceramic body and firing the layer of the glaze composition at a maximum temperature of 1150 to 1250 ° C. for 8 hours or more. By forming the, it is difficult for dirt to adhere to the surface and is excellent in removing dirt that has adhered, and also has a good opacification degree and a reduced amount of bubbles, and a good glaze layer-formed antifouling ceramic is obtained. Is something that can be done.

At this time, if a glaze layer was formed in which the ZrSiO ₄ crystal was not present and the SnO ₂ crystal and the Ca ₃ (PO ₄ ) ₂ crystal were present, the SnO ₂ crystal and the Ca ₃ (PO ₄ ) ₂ crystal were excellent. It is possible to obtain an antifouling ceramics having a milky degree and a smooth surface and a glaze layer having a high antifouling property formed.

Further, since ZrSiO ₄ crystal does not exist, Ca
When a glaze layer containing SnSiO ₅ crystals and Ca ₃ (PO ₄ ) ₂ crystals is formed, CaSnSiO ₅ crystals and Ca ₃ (PO ₄ ) _{2 are formed.}
It is possible to obtain an antifouling porcelain having a smooth surface and a glaze layer having a high antifouling property formed thereon, which has an excellent opacification degree.

Also, ZrSiO_FourNo crystals exist, Ca
SnSiO_FiveCrystal and SnO₂Crystal and Ca₃(PO_Four)₂crystal
When a glaze layer containing CaSnSiO is formed,_Fivecrystal
And Ca ₃(PO_Four)₂It has excellent opalescence and
Anti-fouling ceramics with a smooth surface and a glaze layer with high anti-fouling properties formed
Is what you can get.

The thickness of the glaze layer is 0.2 to 1.2 mm.
When formed into, with the glaze layer has a good appearance that the substrate surface is sufficiently concealed, it is possible to prevent the occurrence of cracks in the glaze layer, it is possible to prevent the occurrence of so-called dragging failure. is there.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuhiro Matsuura             1-7-27 Yokoe-cho, Sabae City, Fukui Prefecture Hokuriku Kiln             Business

Claims (40)

[Claims] 1. A glaze composition containing a glaze-forming component that forms a glaze layer upon firing, which does not contain a zirconium component and is 55.0 to 6 in terms of oxide when fired.
7.0 wt% SiO ₂ , 7.0-15.0 wt% Al ₂ O ₃ , 0.5-8.0 wt% SnO ₂ ,
₅ to 10.0% by weight of P ₂ O ₅ , 10.0 to 20.0% by weight of any divalent metal oxide, and 2.0 to 10.0% by weight of any monovalent metal. A glaze composition comprising a glaze-forming component whose composition is determined so as to form a sintered body composed of an oxide. 2. A silicon component in an amount of 55.0 to 67.0 wt% in terms of SiO ₂ and an aluminum component in an amount of 7.0 to 1 in terms of Al ₂ O ₃ with respect to the total amount of glaze-forming components in terms of oxide.
5.0 wt%, tin component converted to SnO ₂ 0.5-8.
0 wt%, 0.5 to 10.0 wt% of phosphorus component in terms _of P ₂ O _5, in terms of oxide of any divalent metal component 10.0
The glaze composition according to claim 1, wherein the glaze composition comprises 20.0% by weight and 2.0 to 10.0% by weight of an arbitrary monovalent metal component in terms of oxide. 3. A silicon component in an amount of 55.0 to 67.0 wt% in terms of SiO ₂ and an aluminum component in an amount of 7.0 to 1 in terms of Al ₂ O ₃ with respect to the total amount of glaze-forming components in terms of oxide.
5.0 wt%, tin component in terms of SnO ₂ 3.0-6.
0 wt%, phosphorus component is 0.5 to 5.0 wt% in terms of P ₂ O ₅ , and arbitrary divalent metal component is 15.0 to 2 in terms of oxide.
The glaze composition according to claim 1 or 2, comprising 0.0 wt% and 2.0 to 5.0 wt% of an arbitrary monovalent metal component in terms of oxide. 4. The calcium component is 7.0 in terms of CaO with respect to the total amount of glaze-forming components in terms of oxide, containing a calcium component and a zinc component as arbitrary divalent metal components.
~ 15.0% by weight, zinc component is 2.0 in terms of ZnO
The glaze composition according to any one of claims 1 to 3, wherein the glaze composition contains 7.0% by weight. 5. The calcium component and the zinc component are contained as arbitrary divalent metal components, and the calcium component is calculated as CaO in terms of CaO with respect to the total amount of the glaze-forming components in terms of oxide.
0 to 15.0% by weight, zinc component 2.0 to 2.0 in terms of ZnO
The glaze composition according to any one of claims 1 to 4, wherein the glaze composition contains 7.0% by weight. 6. A magnesium component as an optional divalent metal component is contained in an amount of 0.1 to 2.0 wt% in terms of MgO, based on the total weight of glaze-forming components in terms of oxide. The glaze composition according to claim 4 or 5. 7. Sodium as an optional monovalent metal component
A glaze form containing oxide and potassium components, converted to oxides
Sodium component is Na ₂O conversion
0.1-5.0% by weight, potassium component K₂O conversion
A contract characterized by containing 1.0 to 5.0% by weight
The glaze composition according to any one of claims 1 to 6. 8. A lithium component as an arbitrary monovalent metal component, based on the total amount of glaze-forming components in terms of oxide, Li
The glaze composition according to claim 7, wherein the glaze composition contains 0.1 to 5.0% by weight in terms of O ₂ . 9. The glaze composition according to any one of claims 1 to 8, wherein calcium hydrogen phosphate is used as a raw material containing a phosphorus component for preparing the glaze composition. 10. The glaze composition according to claim 1, wherein bone ash is used as a raw material containing a phosphorus component for preparing the glaze composition. 11. The glaze composition according to claim 1, wherein hydroxyapatite is used as a raw material containing a phosphorus component for preparing the glaze composition. 12. The glaze composition according to claim 1, wherein calcium metaphosphate is used as a raw material containing a phosphorus component for preparing the glaze composition. 13. The glaze composition according to claim 1, wherein tricalcium phosphate is used as a raw material containing a phosphorus component for preparing the glaze composition. 14. The emulsifier raw material contains 0.1 to 8% by weight in terms of TiO _{2 of} titanium component based on the total amount of glaze-forming components in terms of oxide. The glaze composition according to any one of 1 to 13. 15. The emulsifier raw material contains 0.1 to 8% by weight of CeO _{2 in} terms of CeO _{2 of a} cerium component which does not form a frit, based on the total amount of glaze-forming components in terms of oxide. The glaze composition according to any one of claims 1 to 14. 16. The glaze composition according to claim 1, wherein the colorant contains a pigment in an amount of 0.1 to 8% by weight based on the total amount of the glaze-forming components. . 17. The glaze composition according to any one of claims 1 to 16, which comprises a tin-based pigment. 18. The colorant is selected from cobalt compounds, manganese compounds, nickel compounds, uranium compounds, chromium compounds, iron compounds, copper compounds, gold compounds, antimony compounds, arsenic acid compounds, molybdenum compounds, tungsten compounds and vanadium compounds. Any one of claims 1 to 17 containing at least one of the above, and the total content is 0.1 to 5% by weight based on the total amount of glaze-forming components in terms of oxide. The glaze composition according to claim 1. 19. As a part or all of the glaze-forming component,
The glaze composition according to any one of claims 1 to 18, characterized in that it contains a frit obtained by previously vitrifying the raw material constituting the glaze-forming component and then pulverizing the material. 20. A raw material containing a silicon component for preparing a glaze composition, which is finely powdered and does not contain particles having a particle size of 30 μm or more.
The glaze composition according to any one of 1 to 19. 21. The fine powdery material having a median diameter of 0.2 to 4.0 μm is used as a raw material containing a tin component for preparing a glaze composition. The glaze composition according to claim 1. 22. A fine powder having a median diameter of 1.0 to 5.0 μm is used as a raw material containing a phosphorus component for preparing a glaze composition. The glaze composition according to claim 1. 23. An emulsion material raw material containing at least one of a titanium component and a cerium component is mixed, and a fine powder having a median diameter of 0.1 to 2.0 μm is used as the emulsion material raw material. The glaze composition according to any one of claims 1 to 22, wherein the glaze composition comprises: 24. The glaze-forming component as a whole has a median diameter of 3 to 5 μm.
The glaze composition according to any one of 3 above. 25. At least one raw material selected from raw materials containing a silicon component, raw materials containing a tin component and a raw material containing a phosphorus component among raw materials of a glaze forming component is pulverized to a predetermined particle size in advance, and then the remaining glaze forming component. 25. The glaze composition according to any one of claims 1 to 24, wherein the glaze-forming component is added to the above ingredients and ground until the entire glaze-forming component has a predetermined particle size. 26. Of the raw materials for the glaze-forming component, a raw material containing a silicon component is pulverized in advance to a median diameter of 5 μm or less, and then the remaining raw materials for the glaze-forming component are added so that the entire glaze-forming component has a predetermined particle size. 26. The glaze composition according to claim 25, wherein the glaze composition is obtained by pulverizing the glazing. 27. Of the raw materials for the glaze-forming component, a raw material containing a tin component is pulverized in advance to a median diameter of 1.5 to 2 μm, and the rest of the raw materials for the glaze-forming component are added to make the entire glaze-forming component. 26. The glaze composition according to claim 25, which is obtained by pulverizing to a predetermined particle size. 28. Of the raw materials for the glaze-forming component, a raw material containing a phosphorus component is crushed in advance to a median diameter of 3 to 5 μm, and the remaining raw materials for the glaze-forming component are added to the whole glaze-forming component to have a predetermined particle size. 26. The glaze composition according to claim 25, characterized in that it is pulverized until 29. Of the raw materials for the glaze-forming component, a raw material containing a silicon component, a raw material containing a tin component and a raw material containing a phosphorus component are pulverized in advance until the total median diameter becomes 5 μm or less, and then the remaining glaze-forming component is formed. 26. The glaze composition according to claim 25, which is obtained by adding raw materials of the components and pulverizing the entire glaze-forming component to a predetermined particle size. 30. A raw material containing a silicon component among raw materials for the glaze-forming component is pulverized in advance to a median diameter of 5 μm or less, and then the rest of the raw materials for the glaze-forming component are added so that the median diameter of the entire glaze-forming component is 26. The glaze composition according to claim 25, which is obtained by pulverizing to a size of 3 to 5 μm. 31. Of the raw materials for the glaze-forming component, a raw material containing a tin component is pulverized in advance to a median diameter of 1.5 to 2 μm, and the remaining raw material for the glaze-forming component is added to the whole glaze-forming component. 26. The glaze composition according to claim 25, wherein the glaze composition is obtained by pulverizing to a median diameter of 3 to 5 μm. 32. Of the raw materials for the glaze-forming component, a raw material containing a phosphorus component is pulverized in advance to a median diameter of 3 to 5 μm, and then the remaining raw materials for the glaze-forming component are added to obtain a median diameter of the entire glaze-forming component. 26. The glaze composition according to claim 25, wherein the glaze composition is pulverized to a particle size of 3 to 5 μm. 33. Among the raw materials of the glaze-forming component, the raw material containing the silicon component, the raw material containing the tin component and the raw material containing the phosphorus component are pulverized in advance until the total median diameter becomes 5 μm or less, and then the remaining glaze-forming component. 26. The glaze composition according to claim 25, characterized in that the glaze-forming component is pulverized until the median diameter of the entire glaze-forming component becomes 3 to 5 μm. 34. The glaze composition according to any one of claims 1 to 33, wherein the raw material of the glaze-forming component is pulverized using a ball mill made of alumina balls. 35. The raw material of the glaze-forming component is pulverized by a ball mill consisting of alumina balls and a container whose inner lining is made of alumina.
The glaze composition according to any one of 4 above. 36. The surface of a ceramic body according to claim 1.
Forming a layer comprising the glaze composition according to any one of 1. to 8 at a maximum temperature of 1150 to 1250 ° C.
An antifouling ceramics characterized by being formed by forming a glaze layer on the surface of a base material by firing for a time or more. 37. SnO ₂ free from ZrSiO ₄ crystals
37. The antifouling ceramic according to claim 36, which is formed by forming a glaze layer in which crystals and Ca ₃ (PO ₄ ) ₂ crystals are present. 38. ZrSiO_FourNo crystals, CaS
nSiO_FiveCrystal and Ca ₃(PO_Four)₂Glaze layer with crystals
37. The protection according to claim 36, characterized in that
Dirty pottery. 39. ZrSiO ₄ crystals are not present and CaS
37. The antifouling ceramics according to claim 36, which is formed by forming a glaze layer containing nSiO ₅ crystals, SnO ₂ crystals and Ca ₃ (PO ₄ ) ₂ crystals. 40. The antifouling ceramics according to claim 36, wherein the glaze layer has a thickness of 0.2 to 1.2 mm.