JPS6144735A - Method of decorating crystallized glass having low expansion - Google Patents

Abstract

PURPOSE:To reduce cracks, and to improve functional characteristics and decorative effect, by coloring glass with paint consisting of glass fine powder comprising SiO2, Al2O3, BaO+CaO, Li2O, and P2O5 in a given ratio and pigment for high-temperature pottery. CONSTITUTION:Glass comprising 50-75wt% SiO2, 5-25wt% Al2O3, 5-30wt% BaO+CaO, 1-8wt% Li2O, and 0-10wt% P2O5 is pulverized. Paint obtained by blending flux prepared from fine powder of the glass with pigment for high- temperature pottery is prepared. The paint is applied to crystalline glass having low expansion, the glass is crystallized, heat-treated, and colored. Consequently, coefficient of expansion of the paint approaches that of the crystallized glass having low expansion and cracks and peeling are reduced.

Description

[Detailed Description of the Invention] L! 1. Field of the Invention The present invention relates to a method for decorating low-expansion crystallized glass used for kitchen utensils, tableware, etc.

BACKGROUND OF THE INVENTION Generally, in crystallized glass having a low coefficient of thermal expansion,
There are two methods for performing heat treatment for glass crystallization and decoration at the same time. The first method is to diffuse iron, cobalt, nickel, or a metal compound thereof into crystallized glass as a coloring agent. (Unexamined Japanese Patent Publication No. 51-89519
No. etc.). The second method is to apply a mixture of glass flux and high-temperature ceramic pigment to crystallized glass and then bake it (Japanese Patent Application Laid-Open No. 17484/1984, etc.).
As an improved method (Japanese Unexamined Patent Publication No. 57-145052), a low expansion flux and pigment mixture is applied to the lower layer, and a low melting point flux is applied to the upper layer to improve the gloss and abrasion resistance of the decorative part. There is a way.

Problems to be Solved by the Invention In the first method, the types of metals are limited, and the coloring results are limited to yellow, green, blue, etc., and cannot cope with the diversification of modern colors. The second method is good for decoration, but its application to functional materials is difficult because of problems such as cracks and stress concentration. In addition, in the second improved method, the manufacturing process is complicated, and the difference in thermal expansion coefficient between the crystallized glass and the low-expansion flux is still large, so the influence of the decorative part on the crystallized glass is completely (no). It can not be said.

The present invention solves various conventional drawbacks such as cracks, peeling due to cracks, and reduced strength, and
It is intended to be both decorative and functional.

Means for solving the problem The present invention is 5iOz 50-75% by weight A+2O3
5-25% by weight BaO+CaO5~
30% by weight LizQ i~8% by weight-P'2O5
A glass raw material having a composition containing 0 to 10% by weight is melted, pulverized to form a flux, mixed with a pigment for high-temperature ceramics to make a paint, and this paint is applied to a low expansion crystalline glass, This is a method for decorating low-expansion crystallized glass, which is characterized by heat-treating the glass-ceramic and coloring it at the same time.

The flux having the above composition was selected for the following reasons.

If Si 02 is less than 50% by weight, chemical resistance and abrasion resistance will deteriorate. Moreover, if it exceeds 75% by weight, the melting temperature becomes high, and at a heat treatment temperature of crystallized glass, there is no gloss (and fusion does not proceed).

Al2O3 helps in the production of beta-spodumene, and when its amount is less than 5% by weight, the amount of beta-spodumene solid solution in the flux is not sufficient and the thermal expansion coefficient of the flux increases. Moreover, if it exceeds 25% by weight, the melting temperature will be high and fusion with crystallized glass will not proceed.

3a O+Ca 2 O cooperates to promote fusion with the substrate. The amount may be either one, but if it is less than 5% by weight, the fusion with the crystallized glass will not proceed, and if the amount is less than 5% by weight,
If the value exceeds 1, crystallization of the beta spodumene solid solution is hindered, and the coefficient of thermal expansion increases.

[12O helps in the formation of beta spodumene, and if its amount is less than 1% by weight, the amount of beta spodumene is insufficient and the coefficient of thermal expansion increases. Also 8%
Adding more than 100% of the amount will increase the skin's appearance, causing the product to lose its luster and reduce its adhesive strength.

P2O5 acts as a nucleation component.

However, P2O5 may not be included.

Moreover, if it exceeds 10%, human skin will rise, the product will lose its luster, and the fusion strength will decrease.

In addition to the above-mentioned components, the present invention may contain up to 5% of MQ O and up to 2% of each of Na2O°K2OSTi02. These lower the melting temperature of the flux and give the decorative parts a glossy appearance. However, if each limit is exceeded, it becomes an obstacle to achieving low expansion.

Function The present invention lowers the expansion coefficient of the paint by generating beta spodumene in the paint through heat treatment, bringing it closer to that of low expansion crystallized glass, thereby eliminating cracks and peeling due to cracks. be.

Additional Examples Various mixtures having the compositions shown in Table 1 were mixed at 1,400 to 150
After melting at 0°C, it is poured into water, rapidly cooled, and pulverized using a ball mill.

Table 1 10 parts of a well-known high-temperature ceramic pigment, such as No. 3312 Leave Chocolate manufactured by Yomura Kagaku ■, is thoroughly wet-mixed with 90 parts of the flux in a ball mill, and then thoroughly mixed with the finely ground flux. After drying, create decorative paints.

This paint was applied to a crystallized glass molded body having the composition shown in Table 2 using a commonly used ceramic transfer method such as screen printing transfer method, and then subjected to a known heat treatment, for example, held at about 700°C for 2 hours. Thereafter, by holding at 1150° C. or higher for about 1 hour, the crystallized glass is microcrystallized and turned into porcelain, and at the same time, it is possible to obtain a glossy olive-chocolate decorative part.

Table 2 Crystalline Glass Component Composition Next, in order to confirm that these decorative parts do not affect the crystallized glass by cracking or peeling, it was tested using the commonly used rapid heating and cooling method and steel ball drop impact test method. I conducted a test.

The common use temperature of the material in the present invention is 350°C,
Further, the thermal shock fracture temperature difference of the materials themselves is 600°C. Therefore, in order to prove that the present invention is not only decorative but also functional, the temperature difference in the rapid heating and cooling test was set to 600"C compared to the conventional 400°C. The results of this test are shown in Table 3. Shown below.

The steel ball drop impact test tests how stress concentration due to the difference in thermal expansion coefficient between the decorative part and the crystallized glass affects the strength of the crystallized glass. The method is to place the decorated side at the bottom and apply more impact to the undecorated side. Steel ball weight 84Q1 test product size 110 x 110 x 3.8111 m, distance between fulcrums s
I did it with omm. The test results are shown in Table 4.

Table 4 Steel ball drop impact test results As shown in Table 1, the flux of the present invention did not exhibit a coefficient of thermal expansion comparable to that of low-expansion crystallized glass. In addition, from Table 3, it was confirmed that the flux did not have any effect on crystallized glass such as cracking or peeling, and was also able to withstand a thermal shock fracture temperature of 600°C, indicating that the flux had no effect on crystallized glass. It was confirmed that there was no effect. Further, from Table 4, it was found that there was no problem in the strength of the crystallized glass even with the decoration of the present invention, compared to the test specimen without decoration.

Therefore, it is extremely useful when applied to the decoration of kitchen utensils, tableware, etc.

Claims (1)

[Claims] A glass raw material having a composition containing 50 to 75% by weight of SiO_2, 5 to 25% by weight of Al_2O_3, 5 to 3% by weight of BaO+CaO, 1 to 8% by weight of Li_2O, and 0 to 10% by weight of P_2O_5 is melted and pulverized. A method of producing low-expansion crystallized glass, which is characterized in that it is made into a flux and mixed with a pigment for high-temperature ceramics to make a paint, and this paint is applied to low-expansion crystalline glass and colored at the same time as the glass-ceramic heat treatment. Decoration method.