JPS6320777B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a paint binder glass suitable for applying a precious metal color to the surface of ceramic products such as ceramics, glass, and enamel.

Conventionally, paste gold, paste silver, liquid gold, liquid silver, etc. have been used to decorate the surfaces of ceramics, glass products, etc. with precious metal colors. These are colloidal compounds of gold, silver, platinum, etc., and can be made by adjusting the viscosity, applying it to ceramic products, and baking them, depending on the purpose.
It gives the color of a precious metal such as gold or platinum itself. Therefore, since precious metals themselves are used, they are expensive, and as a result of the recent rise in the prices of precious metals, ceramic products decorated with these materials are becoming increasingly difficult to commercialize. In addition, in gold printing that uses conventional gold liquid, cracks and cracks may occur with one coat, and this cannot be prevented unless the concentration is 20% or more. This prevented the occurrence of cracks.

In order to solve these problems, one of the inventors of the present invention first invented a method for painting ceramic products that does not use precious metals such as gold or platinum, and can be painted with almost the same color and luster as these metals. , which was proposed in patent application No. 1983-92822.

In this method, glass paint is printed in a desired pattern on the surface of a ceramic product, and while the paint is sticky, mica powder with a coating layer such as titanium oxide is sprinkled on it and adhered to the printed area.
After that, it is baked.

According to this method, it is possible to form a beautiful precious metal color pattern at a low cost, but since it involves handling fine mica powder, there is a problem that the work environment is deteriorated due to the scattering of the fine mica powder. It required two steps, and had the disadvantage of poor work efficiency. In particular, the process of removing mica powder sprinkled on areas other than the printed surface is difficult to automate, and thus has to be done manually.

Therefore, there is a strong desire to develop a method that can simplify the process and print directly onto the surface of ceramic products, and some methods have been proposed to meet this demand, but mica powder cannot be held firmly enough to the surface of ceramic products. A new problem has come to the fore, and no satisfactory solution has yet been found. Therefore, the development of a binder glass that can be directly printed, increases the bonding strength of mica powder, and sufficiently supports the precious metal coloring effect of the mica powder has been awaited.

The present invention was made in response to the above-mentioned needs, and its gist is a binder glass for adhering mica powder having a coating layer of titanium oxide or the like on the surface of a ceramic product, and , a binder glass in which the ratio of mica powder/binder glass to the mica powder is adjusted within the range of 1/6 to 5, wherein PbO13 to 60
Weight% (same below), SiO ₂ 15-65%, B ₂ O ₃ 1-
14%, R ₂ O 0.5-15%, (R represents an alkali metal such as Li, Na, K, etc.) However, B ₂ O ₃ + R ₂ O 5-25% is the main component, ZnO 0-5%, CdO0 ~5%, ZrO ₂ 0
~5%, Al ₂ O ₃ 0~4%, and Tl ₂ O 0~3% as subcomponents, and the surface tension at the melting point is 280dyne/
It consists of a glass body with a diameter of less than cm.

The fine mica powder that is used in the present invention and has a coating layer of titanium oxide or the like on its surface is a transparent material and has a different refractive index. is reflected and refracted at the interface between the two, and the incident white light is split into a selectively reflected light of a specific wavelength and a transmitted light of its complementary wavelength, resulting in a deep metallic color resembling a pearl. . Furthermore, by changing the thickness of the coating layer such as titanium oxide, light interference can be caused and various interference colors can be obtained. For example, if the optical thickness of titanium oxide is approximately 140 mμ, the reflected light will be silver-colored and approximately
In the case of 210 mμ, reflected light appears gold and transmitted light appears purple. Furthermore, the thickness of titanium oxide has increased to approximately
At 270 mμ, the reflected light is red and the transmitted light is its complementary color, green; at 330 mμ, the reflected light is blue,
The transmitted light is orange. The optical thickness used here means the value obtained by multiplying the actual thickness (geometric thickness) by the refractive index. As described above, mica powder having a coating layer of titanium oxide exhibits a noble metal color including gold, silver, and other metal colors, but it may be coated with iron oxide, chromium oxide, carbon black, etc. instead of titanium oxide, or When titanium oxide is coated with iron oxide, chromium oxide, carbon black, etc., interference colors of each coating layer or interference colors of these overlapping layers are obtained, and different color tones are obtained. In addition, the particle size of the mica powder also affects the color tone, with smaller particles producing a silky luster and larger ones producing a metallic luster. If the particle size is less than 5μ, the luster will be lost, and if it exceeds 150μ, the adhesion rate of titanium oxide, etc. will decrease, and there will be clogging when screen printing is performed.Therefore, the particle size of mica should be between 5 and 150μ. It is appropriate to set it within the range of .

The feature of the present invention is that the above-mentioned mica powder can be mixed with a viscosity-adjusting kneading agent together with the above-specified glass powder, and can be applied directly to the ceramic surface by screen printing or the like.
When baked, when the glass body melts into a molten body, the mica powder can be reliably held with good wettability based on its surface tension. For this purpose, the present invention provides a binder glass for adhering mica powder having a coating layer of titanium oxide or the like on the surface of a ceramic product, the ratio of mica powder/binder glass to the mica powder being The binder glass should be adjusted within the range of 1/6 to 5, and the composition should be PbO 13 to 60% by weight, SiO ₂ 15 to 65%, B ₂ O ₃ 1 to 60% by weight.
14%, R ₂ O 0.5 to 15%, with B ₂ O ₃ + R ₂ O 5 to 25% as the main component, and ZnO 0 to 5%, CdO0 as subcomponents.
~5%, ZrO2 ₀ ~5%, _{Al2O3 0} ~4%, _Tl2O0 ~
3%, and the surface tension at the melting point is limited to 280 dyne/cm or less in view of wettability with mica powder.

Since mica powder is a material with poor adhesive properties, the surface tension of the binder for mica powder at the melting point of the glass must be 280 dyne/cm or less due to the interfacial properties between the mica powder and the binder glass. Surface tension greatly affects the wettability of the material in relation to the other material, and the lower the surface tension, the more securely the material can be retained as a binder and the bonding strength can be increased. Therefore, when the surface tension in relation to the other substance exceeds a certain standard, the holding power of that substance becomes weaker and detachment becomes more likely to occur. In the present invention, the limit for the glass body relative to the mica powder is 280 dyne/cm due to its practicality. or,
A glass body with a surface tension exceeding 280 dyne/cm acts as a binder and causes wrinkles, cracks, etc. on the decorative surface, making it impractical. The limitations on the surface tension of the binder glass of the present invention are based on a collection of numerous experimental examples.

In the binder glass of the present invention, the amount of mica powder added to the amount of binder can be controlled as desired, there is no need to particularly consider bonding strength, and pattern color tone etc. can be easily controlled. Extremely advantageous effects can be obtained in the decorative field. In addition, when the ratio of mica powder and binder glass is approximately 1:1 (weight ratio),
This ratio will give the most favorable effect, but this ratio will be adjusted appropriately depending on the substrate type and decorative preference. However, if the amount of binder glass is too large, the amount of light reflected by the mica powder itself will decrease, so the mica powder/binder glass ratio will eventually be 1/6 to 5.
It is appropriate to adjust within the range of .

The melting point of the binder glass can be freely set within a fairly wide range by adjusting the composition within the above glass composition range, especially from around 450°C to around 800°C.
can be controlled within a range, especially glass products,
Suitable for decoration of ceramic products. Of course, it is not limited to these.

As the kneading agent for viscosity adjustment, a mixture of camphor oil, turpentine oil, lavender oil, etc. in an appropriate ratio is used. Alternatively, a mixture of an acrylic ester and a petroleum solvent in an appropriate ratio may be used. The amount of kneading agent is determined so that the viscosity of the paint becomes a value suitable for screen printing, etc. In addition, mica powder,
Slide transfer paper can also be produced using a paint prepared with a binder glass and a kneading agent. This is produced by printing the above-mentioned paint using a screen on the surface of a water-absorbent mount on which a water-soluble adhesive layer such as dextrin has been formed, and then forming a cover coat layer on the top surface. By applying such a transfer paper to a ceramic product and baking it, a noble metal color pattern can be applied to the surface of the product. Furthermore, the present invention can also be applied to heated transfer paper.

Next, examples of the present invention will be described.

<Example 1> 5 parts (parts by weight, hereinafter the same) of mica powder with a particle size of about 30μ and having a coating layer of titanium oxide with an optical thickness of about 210μ are mixed with 16.5% PbO, 57.8% SiO ₂ ,
Na ₂ O 10.4%, B ₂ O ₃ 9.6% and ZnO 1.2%, Al ₂ O ₃ 3.5
%, Tl ₂ O 1.0%, and 5 parts of powder of binder glass (melting point: 762°C, surface tension: 243 dyne/cm), and this was mixed with 6 parts of an organic kneading agent containing acrylic ester. The mixture was kneaded to create paste paint. Using this paint, they screen-printed a suitable pattern directly onto the surface of a ceramic plate and baked it at approximately 800 degrees Celsius, creating a beautiful golden pattern on the surface of the plate. The surface of the pattern is covered with glass, so the color is matte gold, but the bonding strength is so strong that even when the surface of the pattern was rubbed against other ceramic pieces, there was no change.

<Example 2> 3 parts of mica powder with a particle size of 50μ having a coating layer of titanium oxide with an optical thickness of about 140μ,
PbO51.5%, _SiO2 28.1%, _Na2O3.4 %, _{B2O3 9.5} %
and ZrO ₂ 2.6%, CdO 2.1%, Tl ₂ O 1.0%, MgO 1.8
Binder glass (melting point: 565℃,
along with 7 parts of powder with surface tension: 197 dyne/cm).
A paste paint was prepared by thoroughly kneading with 8 parts of an acrylic acid ester/petroleum-based mixed organic kneading agent. After using this paint to screen print the outer surface of a glass pot, we baked it at approximately 580℃.
A beautiful pine-like silver pattern was formed on the surface of the tip. Even when the patterned surface was rubbed against another patterned surface, no change occurred, indicating that the bonding strength was high.

<Example 3> 7 parts of mica powder with a particle size of 100μ, which has a titanium oxide coating layer with an optical thickness of about 210μ and an iron oxide coating layer thereon,
PbO45.6%, _SiO2 34.8%, _Na2O12.4 %, _{B2O3 3.6}
%, and a binder glass with a composition of 2.6% Al ₂ O ₃ and 1.0% Tl ₂ O (melting point: 787°C, surface tension:
A paste-like paint was prepared by thoroughly kneading 3 parts of powder (188 dyne/cm) and 5 parts of a kneading agent made by mixing an acrylic acid ester and a petroleum-based organic solvent at a ratio of 1:1. This paint was screen printed using a 150 mesh nylon screen onto a water-absorbent mount on which a water-soluble adhesive layer of dextrin had been formed, and a cover coat layer was further formed thereon to produce a slide transfer paper. When this transfer paper was attached to the surface of the enamel product and fired at approximately 830°C, a bright golden pattern was formed on the surface of the enamel product. The pattern surface of this example is similar to <Example 2>,
Even when rubbed against other patterned surfaces, no surface changes were observed, indicating that the bonding strength was high.

The binder glass of the present invention described above has the following advantages.

The binder glass of the present invention uses special mica without using precious metals such as gold or silver, making it possible to paint with a beautiful precious metal color that is almost the same as when using precious metals.

The binder glass of the present invention conveniently acts as a binder for mica powder exhibiting a precious metal color, and by kneading it with a suitable organic kneading agent, it is possible to prepare a paste-like paint that can be applied directly to ceramic surfaces. This eliminates the need for the traditional two-step process of printing glass paint and sprinkling mica powder. As a result, the manufacturing process has become easier to simplify, automate, and increase production speed, making it possible to lower product costs.

When the binder glass of the present invention becomes a molten body by baking, it has a characteristic of exhibiting preferable wettability for mica powder with poor adhesion, so that the mica powder is reliably retained and the decorative surface has high bonding strength. is obtained. In addition, the wear resistance properties are far superior to those using noble metals.

Since the binder glass of the present invention has a composition that can be easily adjusted, it can be used for ceramics, glass, enamel, etc. as required. It is also possible to add a small amount of pigment to the glass body, thereby making the color of the mica appear even more vivid.

The binder glass of the present invention has a relatively high melting point, excellent chemical resistance, and extremely little elution of lead, for example, and is very advantageous for use in utensils such as dishes and pots.

When using the binder glass of the present invention to decorate enamel products with a precious metal color, it can be done with one printing without causing cracks or cracks on the decorative surface, and the decoration can be done with multicolor printing. It became possible.

As described in detail above, the binder glass of the present invention sufficiently eliminates the drawbacks of the prior art, and makes a great contribution to the ceramics, glass, enamel, and other industries.

Claims (1)

[Claims] 1 A binder glass for adhering mica powder having a coating layer of titanium oxide or the like on the surface of a ceramic product, and the ratio of mica powder/binder glass to the mica powder is 1/1.
Binder glass adjusted within the range of 6 to 5, PbO 13 to 60% by weight (the same applies hereinafter),
_{SiO2 15-65} %, _B2O3 1-14%, _R2O0.5-15 %,
(R represents an alkali metal such as Li, Na, K, etc.) However, the main component is B ₂ O ₃ + B ₂ O 5 to 25%, and ZnO 0 to 5%.
%, CdO 0-5%, ZrO ₂ 0-5%, Al ₂ O ₃ 0-4%,
A binder glass for precious metal color paints containing 0 to 3% Tl ₂ O as a subcomponent and having a surface tension at the melting point of 280 dyne/cm or less.