JP2007210812A - Porcelain paint and method for producing porcelain paint - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a porcelain paint which is free from lead components, is coping with various legal regulations, and has durability high enough not to cause faults such as peeling upon being thickly applied. <P>SOLUTION: The porcelain paint is produced by a method comprising a weighing and mixing step of weighing respective oxide components and mixing them, a melting step of melting the mixture of the raw materials at a melting temperature of 1,300°C, a quenching step of quenching the molten glass molten in a furnace, a powdering step of grinding the cooled glass frit into a powder, and a drying step of drying the powder to remove moisture therefrom. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a ceramic paint and a method for producing a ceramic paint, and in particular, a ceramic paint that does not contain a lead component in the composition and does not have a risk of peeling off when it is thickened. The present invention relates to a method for manufacturing a paint.

  Conventionally, when coloring ceramics, a so-called “Japanese paint” frit containing pigment for ceramics has been used. This porcelain frit-containing pigment (hereinafter simply referred to as “ceramic paint”) is composed of various metal oxide components, particularly in the frits of high content lead oxide components. It is generally known that a transition metal oxide such as copper or cobalt for imparting color developability is added.

  However, ceramic paints containing a large amount of these lead components have been exposed to problems such as environmental pollution and pollution caused by the lead components, and their usage and usage are limited by various laws and regulations. For this reason, development of lead-free ceramic paints that do not contain a lead component is underway (see, for example, Patent Document 1 or Patent Document 2).

Japanese Patent Publication No. 63-51984 Japanese Patent Publication No. 63-51985

  However, ceramic paints that do not contain these lead components may cause the following problems. That is, ceramic paints that do not contain a lead component tend to have a high coefficient of thermal expansion, and may have poor compatibility with glazes during firing, which may limit the usable range. . Furthermore, there are cases where the color developability is inferior to that of a ceramic paint containing a lead component or a higher baking temperature is required.

  Here, the ceramic paint which does not contain a lead component has a high ratio of the alkali oxide component in the glass component. As a result, the alkali oxide component, which has the property of easily melting at low temperatures, has the effect of increasing luster and gloss on the surface of the ceramic after coloring, but it tends to increase the expansion coefficient and generally reduce chemical durability. Was strong.

  Furthermore, if the ratio of oxide components such as aluminum oxide and silicon oxide is increased in order to compensate for the above problems, firing at a higher temperature is required, and the firing conditions may become more severe. In addition, it is conceivable to contain a large amount of boron oxide in order to suppress the influence of expansion due to heat, but problems such as chemical durability or surface smoothness or gloss reduction due to the separation layer arise. There was a thing.

  Therefore, in view of the above circumstances, the present invention is capable of complying with various laws and regulations without containing a lead component, and has durability that does not cause problems such as peeling when thickened. It is an object of the present invention to provide a ceramic paint excellent in quality and a method for producing a ceramic paint.

  In order to solve the above-described problems, the ceramic paint of the present invention has a "silicon oxide component of 40.0 parts by weight or more and 70.0 parts by weight or less, and 12.0 parts by weight or more and 30.0 parts by weight or less. Comprising a boron oxide component, an alkali metal oxide component of 3.0 to 15.0 parts by weight, and an aluminum oxide component of 3.0 to 11.0 parts by weight " It is mainly composed.

  Here, the characteristics of each metal oxide in the ceramic paint are shown. The silicon oxide component and the aluminum oxide component mainly have a function of improving the chemical durability of the ceramic paint, while the firing temperature. Has a high property. Further, the boron oxide component has a function of keeping the expansion coefficient due to heat low, while having a property of reducing chemical durability and impairing surface smoothness. In addition, alkali metal oxide components (for example, sodium oxide, potassium oxide, or lithium oxide) have a low-temperature melting property and a function to give gloss to the surface after color addition, while having a high expansion coefficient. It has the property to become.

  Therefore, according to the ceramic paint of the present invention, the silicon oxide component, the boron oxide component, the alkali metal oxide component, and the aluminum oxide component are mixed at the above blending ratio. That is, it is possible to construct a ceramic paint that does not contain a lead component and that uses the properties of each oxide component, suppresses the thermal expansion coefficient, and is excellent in chemical durability.

  Furthermore, the ceramic paint according to the present invention has, in addition to the above configuration, “the alkali metal oxide component is 1.0 part by weight or more and 2.0 parts by weight or less of lithium oxide component, 1.0 part by weight or more, 6 0.01 part by weight or less of the potassium oxide component or 1.0 part by weight or more and 10.0 parts by weight or less of the sodium oxide component may be selected ".

  Therefore, according to the ceramic paint of the present invention, any one of a lithium oxide component, a potassium oxide component, and a sodium oxide component is selected and used as the alkali metal oxide component. Here, as a feature of each alkali metal oxide component, the potassium oxide component has a higher firing temperature than the sodium oxide component and further has an action of promoting thermal expansion. On the other hand, lithium oxide has a lower firing temperature than a sodium oxide component, and further has an action of promoting thermal expansion. Therefore, one of these alkali metal oxide components can be selected and added to the ceramic paint according to the composition of each oxide component other than the alkali metal oxide component. That is, the properties of the ceramic paint can be adjusted by changing the type of the alkali metal oxide component.

  Furthermore, the ceramic paint according to the present invention has, in addition to the above-described structure, “1.0 parts by weight or more and 7.0 parts by weight or less of calcium oxide component, 1.0 part by weight or more and 3.0 parts by weight or less of zinc oxide. Ingredient, 1.0 parts by weight or more and 2.0 parts by weight or less of magnesium oxide component, 1.0 part by weight or more and 2.0 parts by weight or less of strontium oxide component, 0.1 part by weight or more, 2.0 parts by weight Any one of the following zirconium oxide components, 1.0 part by weight or more and 30.0 parts by weight or less bismuth oxide component, or 1.0 part by weight or more and 3.0 parts by weight or less barium oxide component ” Furthermore, you may comprise.

  Therefore, according to the ceramic paint of the present invention, in the ceramic paint, calcium oxide component, zinc oxide component, magnesium oxide component, strontium oxide component, zirconium oxide component, cobalt oxide component, manganese oxide component, copper oxide component, And at least one of a bismuth oxide component and a barium oxide component. Here, the calcium oxide component and the zinc oxide component increase the firing temperature, decrease the coefficient of expansion due to heat, and further improve the chemical resistance. Furthermore, the magnesium oxide component, the strontium oxide component, and the zirconium oxide component have properties that increase the firing temperature and suppress thermal expansion, and at the same time, can improve chemical resistance. On the other hand, barium oxide has the property of raising the firing temperature and lowering the thermal expansion, and bismuth oxide has the property of being able to obtain a highly refractive glassy material by firing and lowering the firing temperature. Yes. Therefore, when the thermal expansion coefficient is high, a barium oxide component can be added to suppress the thermal expansion coefficient, while when the firing temperature is high, a bismuth oxide component can be added to suppress an increase in the firing temperature. It becomes.

  Furthermore, the ceramic paint according to the present invention has, in addition to the above-described configuration, “a cobalt oxide component of 1.0 part by weight or more and 8.0 parts by weight or less, a manganese oxide of 1.0 part by weight or more and 8.0 parts by weight or less. A component, at least one of 1.0 parts by weight or more and 8.0 parts by weight or less of a copper oxide component, or 1.0 part by weight or more and 5.0 parts by weight or less of an iron oxide component ”. It does not matter.

  Therefore, according to the ceramic paint of the present invention, the cobalt oxide component, the manganese oxide component, the copper oxide component, and the iron oxide component are elementary components for coloring the ceramic paint in various colors. The blending is 0 part by weight or less. Thereby, vivid colors such as red and blue can be obtained.

  On the other hand, the method for producing a ceramic paint according to the present invention includes a "40.0 parts by weight or more and 70.0 parts by weight or less silicon oxide component, 12.0 parts by weight or more and 30.0 parts by weight or less boron oxide component, A metering and mixing step of weighing 3.0 parts by weight or more and 15.0 parts by weight or less of an alkali metal oxide component, 3.0 parts by weight or more and 11.0 parts by weight or less of an aluminum oxide component by a predetermined amount and mixing them; A melting step of melting the mixed raw material mixture at a melting temperature of 1200 ° C. or higher and 1400 ° C. or lower, a quenching step of quenching the melt melted by the melting step, and a rapidly cooled melt cooled by the quenching step It mainly comprises a pulverization step for pulverizing an object to form a powder and a drying step for drying the powdered powder body to remove moisture.

  Therefore, according to the method for manufacturing a ceramic paint of the present invention, it is possible to manufacture a lead-free ceramic paint through the above steps.

  As an effect of the present invention, it is possible to provide a good ceramic paint that does not contain a lead component, can be thickened with respect to ceramics, and does not cause problems such as surface smoothness and loss of gloss. it can. In particular, by blending individual metal oxide components, it is possible to make ceramic paints with good firing conditions and quality by utilizing properties such as suppression / increase of thermal expansion or increase / decrease of firing temperature.

  Hereinafter, a ceramic paint that is an embodiment of the present invention and a method for producing the ceramic paint will be described.

  As shown in Table 1, the ceramic paint of the present embodiment is configured by mixing various oxide components such as a silicon oxide component according to a specified ratio. In Table 1, formulation examples 1 to 9 are shown as examples, and formulation examples 10 to 13 are shown as comparative examples.

Table 1 above shows the chemical composition of ceramic paints in parts by weight. Specifically, for example, in the case of Formulation Example 1, a silicon oxide component (silica: SiO ₂ ) / boron oxide Ingredient (B ₂ O ₃ ), sodium oxide component (Na ₂ O), calcium oxide component (CaO), aluminum oxide component (Al ₂ O ₃ ), color developing component (copper oxide component (CuO), cobalt oxide component (CoO) , Iron oxide component (Fe ₂ O ₃ ), manganese oxide component (MnO)) are mixed in a predetermined amount. Formulation Example 2 is obtained by adding a barium oxide component (BaO) in addition to the component configuration of Formulation Example 1, and Formulation Example 3 is a bismuth oxide component (Bi ₂ O) in addition to the component configuration of Formulation Example 1. ₃ ) is added. In addition, Formulation Example 4 is obtained by adding a zinc oxide component (ZnO) to the component configuration of Formulation Example 2. On the other hand, Formulation Example 5 is obtained by adding a strontium oxide component (SrO) to the component configuration of Formulation Example 2. Further, Formulation Example 6 is obtained by adding a magnesium oxide component (MgO) to the component configuration of Formulation Example 4. In addition, Formulation Example 7 is obtained by adding a zirconium oxide component (ZrO ₂ ) to the component configuration of Formulation Example 4. Although the compounding example 8 is the same component structure as the compounding example 1, the compounding ratio of the sodium oxide component which is an alkali metal oxide component and a calcium oxide component is raised as a whole, while the compounding example 9 is compounded. Although the composition is the same as that of Example 1, the boron oxide component blending ratio is increased as a whole and the alkali metal oxide component blending ratio is decreased as a whole.

  On the other hand, the blending example 10 shown as a comparative example has a component composition substantially the same as the blending example 2, but the blending ratio of the barium oxide component is increased, while the blending example 11 is a blending ratio of the sodium oxide component. Is higher than that of Formulation Example 1, and Formulation Example 12 is a component structure having a strontium oxide component and a zirconium oxide component, and the respective blending ratios are increased. Formulation Example 13 is an example in which the blending ratio of the copper oxide component, the cobalt oxide component, the iron oxide component, and the manganese oxide component added as the color forming component is increased.

  First, according to the blending ratio shown in Table 1, each oxide component is weighed and mixed (metering and mixing step). Here, the measurement (weighing) and mixing (preparation) are performed by converting to oxides, carbonate raw materials and the like generally used in the ceramic industry by using a conventionally known method, and measuring and mixing.

  Then, the mixed raw material mixture is put into a glass melting furnace set at a furnace temperature of 1200 to 1400 ° C. or higher (here, 1300 ° C.) to melt the raw material mixture (melting step). Thereby, a raw material mixture is converted into a molten glass. Thereafter, the molten glass taken out from the furnace (corresponding to a melt) is poured into water or passed through a water-cooled roll machine to be cooled at once and vitrified (rapid cooling step). Thereby, a glass frit (corresponding to a rapidly cooled melt) is formed. Thereafter, the glass frit is pulverized to a desired particle size using a pulverizing device such as a ball mill to form a powder (powdering step). And the water | moisture content used in the rapid cooling process is removed from a powder body (equivalent to the ceramic paint) by heat drying (drying process). Thereby, the ceramic paint which does not contain a lead component is manufactured.

  By performing the above-described processing on each of Formulation Examples 1 to 13, 13 types of ceramic paints including the Examples and Comparative Examples are manufactured.

  Next, in order to confirm the properties of the ceramic paint of the present embodiment, 1) presence or absence of peeling from the ceramic surface and occurrence of cracks, 2) acid resistance test with a 4% aqueous solution of special grade acetic acid, 3) cargonite detergent An alkali resistance test with a 0.5% aqueous solution was performed. In addition, for these confirmations, an appropriate amount of water and an adhesive material having adhesive properties such as glue, paraffin, and acrylic resin are added to the powdery ceramic paint produced by the above process, and the paste is added. Form.

  After that, this paste is applied to the surface of the ceramic that has not been glazed with well-known coloring means (for example, hand-painting with a brush, spraying using a spray, transfer using a screen printing technique, or dipping). The test piece with the ceramic paint added is put into an electric furnace set at a firing temperature of 830 ° C. Then, after a predetermined firing time, the specimen is taken out from the furnace.

Here, the test according to 1) was performed by slowly cooling the specimen taken out from the furnace to room temperature and then visually checking the surface state. On the other hand, the test according to 2) was performed by depositing the test body in a 4% aqueous solution of acetic acid, taking it out after 24 hours, and visually checking the surface state. Further, in the test according to 3), a 0.5% aqueous solution of a cargonite detergent was heated to 90 ° C., and a test specimen was deposited therein, taken out after 16 hours, 24 hours, and 48 hours, respectively, and the surface condition was determined. This was done by visual confirmation. This evaluation method using a cargoite detergent is mainly used for evaluating the performance of a dishwasher. Generally, a 0.5% aqueous solution of a cargoite detergent is heated to 77 ° C. and deposited for 16 hours. Thus, the washing by the dishwasher corresponds to 250 cycles. That is, in the test for confirming the properties of the ceramic paint of the present embodiment, with the recent performance improvement of the dishwasher, the test specimen is placed under conditions more severe than the above standards, and the surface condition is visually confirmed. ing. The evaluation results are shown in Table 2. Here, the evaluation results are performed based on the following evaluation criteria. That is, in the evaluation criteria related to the surface appearance, if it is a and b, it can be thickened against the ceramic surface and can withstand use, whereas the evaluation criteria related to chemical resistance, If it is A, it has the property which can be used.
<Surface appearance evaluation criteria>
a: No surface crack-No surface peeling-No b: No surface crack-No surface peeling-C: No surface crack-No surface peeling-<Chemical resistance evaluation criteria>
A: With surface gloss B: Without surface gloss C: Fading discoloration, no gloss

As shown in Table 2 above, the ceramic paints of Formulation Example 1 to Formulation Example 9 are sufficiently resistant to practical use in any of the evaluation items of 1) surface appearance and 2), 3) acid resistance and alkali resistance. The possible properties were shown. In particular, Formulation Example 2, Formulation Example 6, and Formulation Example 9 were evaluated as a or A (A ⁻ ) in any of the evaluation items 1) to 3).

  That is, it is possible to manufacture ceramic paint of sufficient quality by interpolating the action of the lead component with the barium oxide component, the sodium oxide component, etc. without using the lead component.

  On the other hand, in the blending examples 10 to 13 shown as comparative examples, when the barium oxide component is excessive (blending example 10 and blending example 12), when the blending ratio of the sodium oxide component is excessive (blending example 11), oxidation is performed. When the blending ratio of the zirconium component and the strontium oxide component is excessive (Formulation Example 12), when the blending ratio of the coloring component that causes color development is excessive (Formulation Example 13), the surface appearance corresponds to c, and the acid resistance and alkali resistance Most of them were B or C, and they did not have good surface quality and excellent chemical resistance, and were not practical. That is, it was difficult to apply and use in actual ceramics.

  As described above, the ceramic paint and the method for producing the ceramic paint of the present invention have been described with reference to preferred embodiments and examples. However, the present invention is not limited to these embodiments, and is as follows. In addition, various improvements and design changes can be made without departing from the scope of the present invention.

  That is, in order to evaluate the performance of the ceramic paint of the present embodiment, the ceramic paint is applied to the surface of the ceramic that has not been glazed. However, the present invention is not limited to this. Of course, it is possible to add color to the surface of the glaze that has already been applied with a glaze or the like that is used in general.

  In addition, the composition ratio of each oxide component in Formulation Examples 1 to 9 shown in the present embodiment is not particularly limited as long as the ratio of each oxide component is within a specified range. In addition to the above configuration, the color of the ceramic paint according to the present invention can be further diversified by adding a pigment made of an existing metal oxide.

Claims (5)

40.0 parts by weight or more and 70.0 parts by weight or less of a silicon oxide component;
12.0 parts by weight or more and 30.0 parts by weight or less of a boron oxide component;
3.0 parts by weight or more and 15.0 parts by weight or less of an alkali metal oxide component;
A ceramic paint comprising 3.0 to 11.0 parts by weight of an aluminum oxide component. The alkali metal oxide component is
1.0 part by weight or more and 2.0 parts by weight or less of lithium oxide component,
1.0 parts by weight or more and 6.0 parts by weight or less of a potassium oxide component, or
The ceramic paint according to claim 1, wherein any one of 1.0 parts by weight or more and 10.0 parts by weight or less of a sodium oxide component is selected. 1.0 part by weight or more and 7.0 parts by weight or less of calcium oxide component,
1.0 parts by weight or more and 3.0 parts by weight or less of zinc oxide component,
1.0 parts by weight or more and 2.0 parts by weight or less of magnesium oxide component,
1.0 part by weight or more and 2.0 parts by weight or less of a strontium oxide component,
0.1 parts by weight or more and 2.0 parts by weight or less of zirconium oxide component,
1.0 parts by weight or more and 30.0 parts by weight or less of a bismuth oxide component, or
The ceramic paint according to claim 1 or 2, further comprising any one of 1.0 parts by weight or more and 3.0 parts by weight or less of a barium oxide component. 1.0 parts by weight or more and 8.0 parts by weight or less of cobalt oxide component,
1.0 part by weight or more and 8.0 parts by weight or less of manganese oxide component,
1.0 parts by weight or more and 8.0 parts by weight or less of a copper oxide component, or
The ceramic paint according to any one of claims 1 to 3, further comprising at least one of iron oxide components in an amount of 1.0 to 5.0 parts by weight. . A method for producing a ceramic paint for producing the ceramic paint according to any one of claims 1 to 4,
40.0 parts by weight or more and 70.0 parts by weight or less of silicon oxide component,
12.0 parts by weight or more and 30.0 parts by weight or less of boron oxide component,
3.0 parts by weight or more and 15.0 parts by weight or less of an alkali metal oxide component,
A weighing and mixing step of weighing and mixing 3.0 parts by weight or more and 11.0 parts by weight or less of an aluminum oxide component by a predetermined amount; and
A melting step of melting the mixed raw material mixture at a melting temperature of 1200 ° C. or higher and 1400 ° C. or lower;
A quenching step of quenching the melt melted by the melting step;
Pulverizing the rapidly cooled melt cooled by the rapid cooling step into a powder,
A method for producing a ceramic paint, comprising: drying a powdered powder body to remove moisture.