JPS598638A - Glaze composition - Google Patents

Abstract

PURPOSE:To improve the anticorrosion of the titled composition, by incorporating SiO2, BaO and Al2O3 as main components, SrO, B2O3, CaO or MgO as the first accessory component, Y2O3, La2O3, ZrO2, TiO2 or ZnO as the second accessory component in the glaze. CONSTITUTION:The titled glaze composition used on the surface of a ceramic has the following composition: 83-99.8mol% main component consisting of 56-71mol% SiO2, 15.5-28mol% BaO and 6-16mol% Al2O3, 0.1-10mol% sum of the first accessory component, and 0.1-7mol% sum of the second accessory component. The total amount is 100mol%. The first accessory component consist of one or more of <=10mol% SrO, <=8mol% B2O3, <=10mol% CaO and <=3mol% MgO. The second accessory component consists of one or more of <=4mol% Y2P2O3, <=4mol% La2O3, <=6mol% ZrO2, <=6mol% TiO2 and <=3mol% ZnO. The composition has smoothness, heat resistance, and low thermal conductivity and further improved anticorrosion against a mixture of HF with HNO3.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is particularly suited to alumina or berrier porcelain-based materials used as electronic components such as thin-walled or thick-film resistive elements, integrated circuits utilizing high-precision film circuits, or thermal heads of thermosensitive recording devices. The present invention relates to a glaze composition for glazed ceramics.

Glazed ceramics for these electronic components, particularly glazes used for thermal heads, are required to be free of PbO and alkali components, and to have surface smoothness, heat resistance, and low thermal conductivity to function as a heat storage layer.

The applicant has succeeded in developing a glaze that meets these demands, and has previously proposed it as a glazed ceramic substrate (
(Japanese Patent Application No. 114710), however, the glaze surface is exposed to HF + )iNO3 during wiring mounting.
It was found that there was dissatisfaction with the corrosion resistance against.

The present invention provides the above-mentioned 1) bO, does not contain alkali components, maintains smoothness, heat resistance, and low thermal conductivity, and in addition, HF +
This provides a glaze composition with markedly improved corrosion resistance to HNO3, 5tozz+-7/%, B
aO/, tJ-, 2i%, AlaOs A~/4%
Karanashi main component and SrOr less than /Q 1% or less (
f) Bz, Os r 70% or less (D CaO * 3
In contrast to the glaze composition of the glazed ceramic substrate of the above Japanese Patent Application No. Sho J-J-/1t710, which consists of one or more selected from Mgo and its subcomponents, the above Sing + BaO+ AI! The main components consisting of 03 are combined as
3r CaOI A subcomponent selected from MgO is set as the first subcomponent and its total amount is set to 0.1 to 10%, and the second subcomponent is Y2O3 below Dachi, La2O5+ Achi below ≠ Chi. The following ZnO, also selected from 4% or less Ti0a, 3% or less ZrOx/
Select i or more so that the total composition is ioo%
, i to 7 h.

In the glaze composition of the present invention, StO is used as the main component.
□+ The reason for choosing BaO and Altos is that
This is mainly to obtain low thermal conductivity, high heat resistance, and surface smoothness, but if 5i (h is less than 56%), the coefficient of thermal expansion will become high and the adhesion to the substrate made of alumina porcelain etc. will be poor. If it exceeds 7%, it becomes difficult to melt, and if BaO is less than /rj4, low thermal conductivity and surface smoothness cannot be obtained, and if it is more than cot%, the coefficient of thermal expansion becomes large and the adhesion to the substrate becomes difficult. Sexuality worsens and AlaO
If s is less than 6 inches, a stable glass cannot be obtained, and if it is more than 1z, the melting point will rise and it will be difficult to melt. In order to obtain this, a large amount of BaO is contained together with Altos to prevent crystallization and improve heat resistance, but as for the content! 3-5! Set it to the word.

Next, B2O3, selected as the first subcomponent, promotes vitrification, promotes melting, and improves the smoothness of the glaze, but it is 1%
Exceeding this will seriously reduce heat resistance, and
Similarly, MgO promotes vitrification, but if it exceeds 10%, devitrification tends to occur.Also, MgO easily removes bubbles and is effective when added in a small amount, but if added in a large amount, the tendency to devitrify increases, so 3% At most, these first subcomponents can be effective by combining any of seven types, and even if two or more types are used together, one
The upper limit is 0%, and devitrification resistance becomes stronger when two or more types are used together.

Additionally, Y2O3 is blended as a second subcomponent.

LazOs r ZnO+ Ti()+ and Zr0z
As with the first subcomponent, any one of them has the uniform effect of increasing the corrosion resistance against HF + HNOa, simultaneously further improving the heat resistance, and increasing the hardness when mixed in a small amount. However, if Y2O3 and LaaOa exceed 44%, they tend to devitrify.
When ZnO exceeds 6%, the corrosion resistance against HF-HNO3 is reduced, and when TiOz exceeds the same <j%, it tends to devitrify and also reduces heat resistance.
When z exceeds 3%, air bubbles tend to remain and it becomes difficult to obtain a flat surface. Therefore, each of these subcomponents is limited within the above range, and even when two or more types are used together, 7% is the lower limit. be.

Examples In order to obtain a glass having the morti composition shown in Table 1,
g r AI (OH)3+ BaC0a * HsB
Oa * CaC0a +5rCOa + MgCO5
r Y2O5+ LaaOa l ZnO+ TiOx
and ZrO2 are weighed, mixed in a Raikai machine according to the conventional method, melted at the optimum temperature in an alumina crucible, poured into water and rapidly cooled, and then finely ground in an alumina ball mill to form a frit. The mixture was added and kneaded to obtain 7 pieces of paste.

The same table shows the results of various measurements of the glaze substrate and other objects obtained by coating and baking this paste-like 7-lit on an alumina substrate. However, (1) HF + HNOa alumina content is 7chi! The above paste-like frit was applied by screen printing to an alumina porcelain substrate with a diameter of Oxjθ between X/mt, and after drying, it was fired using the glazing shown in the table to make a glazed substrate with a glaze thickness of 30±ioμ.'HF: The eroded thickness of the glazed surface was measured by a surface roughness meter after being immersed in a solution of HNOs = / : / for 11 seconds.

(2) A cylindrical glaze with a yield point of jaφ x 20 t was manufactured at the same glazing temperature as in (1), and the thermal expansion was measured to measure the peak of the expansion curve.

(3) Measurement using a glazed substrate with Vickers hardness/) and a load coefficient.

C) A disk-shaped glaze with a thermal conductivity distribution of φ×l■t was manufactured in the same manner as in 0) and measured using the laser pulse method.

In general, the molar ratio as revealed by Table 1 is SiO!
J-j~7/%, BaO/JJ-,21%,
Main component ♂3~tab consisting of AlaOij-04? %and,
B2O5I/'% less than lrs, CaOe also less than 70%, SrO+ less than 3%, MgOo/m or more, 0.1 to 70%, and Y2O2° less than 4Ichi, same <4'%. The following La*Os + t
% or less ZnO*Also 4% or less Tl (h
The glaze composition of the present invention in which the total amount of these components is 100%, that is, (1) small cod as the main component [and the constituent components are all fixed at approximately intermediate values, and the first and Sample A/-J in which the subtotal of the first subcomponent and the constituent components were also set to approximately intermediate values.

(2) Samples A7 to 3 in which the main component's small needle was set to approximately the intermediate value, each of the constituent components was set at the upper and lower limits, and the first and first subcomponents were increased or decreased according to the sample mura.

(3) The components of the main component are set near the lower limit, their sum is set as the lower limit, the subtotal of the first and first subcomponents are both set as the upper limit, and the first subcomponent corresponds to sample AI, Sample JI61 which is increased and fixed and also uses two or more types of first subcomponent in combination
θ~ノj0C) Samples AI6~ko00, in which the constituent components of the main component are fixed around the intermediate value, their subtotals are fixed at the upper limit, and the remainder is equally divided into the first and first subcomponents, are all (I) The seventh and first subcomponents are not included, and only the main component is used, and the constituent components are approximately the middle 5insj7%, Ba
Sample A with O-2j% + AlzOa' 7%
2/.

(2) Compared to sample I6.23°, which did not include the second subcomponent and had only the main component and the first subcomponent together with their subtotals and constituent components near the median value, it was worse for other properties. We succeeded in significantly improving the IF' + HNOs properties without any negative effects.

In summary, the present invention achieves remarkable effects by combining the first and first subcomponents with the main component (10).
Contrary to the above samples A and 2J, sample I6 did not contain the first subcomponent and contained only the main component and the first subcomponent. Any sample layer containing too many subcomponents will cause devitrification, and the sample A,
Contrary to 2j, even if the first subcomponent is at an intermediate value, sample 2j, which has an excessive amount of the first subcomponent, does not cause devitrification and is HF+HNO resistant.
s, but there are dissatisfaction with other properties.

The conventional lead borosilicate glass containing alkali, which was cited as a reference, shows high values for HF + HNOj resistance, but has major dissatisfaction with various properties such as the underlying yield point, thermal conductivity, and surface resistance. be.

Patent applicant: Nippon Tokushu Tokugyo Co., Ltd. Agent Takashi Imai (/l) Handbook continuation supplementary text (self-published) Showa! 7th year IO month 2? Day ♂ Mr. Kazuo Wakasugi, Commissioner of the Patent Office Displaying the incident Showa, t7 patent application No. 1/7//j 2 Name of invention glaze composition 3. Person who makes corrections Representative Shuji Ogawa

Claims (1)

[Claims] (1) Molar ratio testo, j t ~7/%
+ BaO/J: j ~ cot%. Consists of A1*Os Otsu~/j Chi, total amount 13~ri51! The main components of
A seventh subcomponent consisting of one or more selected from MgO, whose total amount is o, 1-io, and Y2O2, which is less than Hirochi, and LazOs, which is also less than IIl. A first subcomponent consisting of one or more selected from Zr0m below S + Ti (h*' below 6) and ZnO with a total amount of 0./~7 A glaze composition for a ceramic surface, characterized in that the entire amount is tooth.Q) A glaze composition, characterized in that the ceramic according to claim 1 is alumina or Beriria porcelain.