JPS6055454B2 - Colored ceramic color frit composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION A colored opaque ceramic color composition (in the form of a strip or in various shapes) is applied to the periphery along the window frame of an automobile window glass plate.
By baking a coating layer of frit, heating wires, terminals, or gaskets around the glass panel inside the car cannot be seen from outside the car (Utility Model Publication No. 50-38895, Utility Model Application No. 38895). 49-95624).

This ceramic color frit coating layer usually has 10 to 3
It consists of 0% heat-resistant colored (usually black) pigment and 70-90% low melting point binder glass.

In its formation, the powder mixture vehicle is kneaded and made into a paste, and then applied to the periphery of a glass plate by a screen printing method, etc. After the vehicle is dried, the glass plate is strengthened or bent. While heating to its softening point, a coating of ceramic color frit is simultaneously baked onto the surface of the glass plate. However, in the case of current products, the mechanical strength of the glass plate after baking is such that it is fused to the glass surface.

The disadvantage is that the strength of the ceramic layer is low. The present invention has been made to solve the above-mentioned difficulties, and provides a ceramic color frit composition with almost no decrease in strength.

The ceramic color composition according to the present invention is characterized by comprising a colored heat-resistant pigment powder and a low melting point binder glass powder, and the glass powder has the following composition/range.

si025-20wt% A12030.5-10 zno52-65 average 0a0.5-15 0.5-15 MgO] One or more of zircon, cordierite, or alumina is added as a filler to the composition, for example, by weight ratio of glass By containing the powder in a ratio of 85 to 1 (1) parts and the filler powder in a ratio of 15 to 0 parts, it is possible to measure a decrease in the coefficient of thermal expansion of the baked frit.

The reason for limiting the composition of the low melting point binder glass is as follows: If BiO2 is less than 5%, devitrification will form during melting.
Even if formation of devitrification occurs or no devitrification occurs,
The resulting glass is undesirable because it has low fluidity and crystallizes quickly.

If it exceeds 20%, the softening point of the glass becomes too high, while the crystallization temperature also becomes higher than the prescribed baking conditions, which is preferable, and the range is preferably 7 to 17 wt%.

Al2O3: Used as a crystallization control agent.

If it is less than 0.5%, crystallization becomes ShOrt.
This is unfavorable in terms of decreased fluidity. If it is more than 10%, the crystallization will be 1d, and therefore low expansion cannot be expected.

It is preferably 1 to 7 wt%. ZnO: A crystal precipitation component and also a fluxing agent.

If it is less than 55%, sufficient crystallization will not occur, and therefore low expansion cannot be expected.

On the other hand, if it exceeds 65%, the crystallization will be too much.
t becomes too high, resulting in poor fluidity and adhesion. It is preferably in the range of 56 to 64 wt%. B. O3: Used as a fluxing agent.

If it is less than 15%, the softening temperature will be high and it cannot be used under the specified baking conditions.

On the other hand, if it exceeds 30%, the softening point of the glass becomes too low and the crystallization properties also deteriorate. Desirable 4
The content ranges from 17 to 27 wt%. R2O(Na
2O, K2O and/or Li2O): Used as a fluxing agent.

If it is less than 0.1%, no effect can be expected.

If it exceeds 10%, the coefficient of thermal expansion increases and the desired strength cannot be achieved.

The content is preferably 0.5 to 7 Wt%. RO(MgO,C
aO and/or BaO): Used for the purpose of improving glass meltability.

There is no effect if it is less than 0.5%. 15%.
If the number is too large, the coefficient of thermal expansion will become too large.

It is preferably in the range of 1 to 13 wt%. RO2
(TiO2 and/or SnO2): Although not an essential component, the introduction of this component has the effect of improving chemical durability (water resistance, etc.).

No effect can be expected if the amount exceeds 5%, so it is preferable to keep the amount within 3%.

F: Low melting component, used as a fluxing agent
Also used.

It is also effective as a crystallization promoter. However, 2%
Introducing an amount exceeding It is preferably 1.5% or less. By introducing a filler that is a low expansion material and has excellent heat resistance properties into the frit as a refractory filler, the coefficient of thermal expansion of the ceramic color frit during baking can be lowered. Zircon, cordierite, or alumina fine powder is mixed in an amount of 1 to 15 wt% with respect to the above-mentioned glass composition. If it exceeds 15%, the fluidity of the entire frit will decrease and the adhesion will be insufficient, which is not preferable.

The range is desirably 10% or less. As colored heat-resistant pigments, known black pigments such as MnO2, CaO, C
dS, Cr2O3 powder is used and usually contains 10 to 30 wt% of the total composition.

After thoroughly mixing these three powders, they are kneaded in an appropriate vehicle to form a paste, which is applied to a predetermined location on a glass plate. After drying, it is baked during heat treatment for strengthening and/or bending the glass plate. wear. Example (1) Method for Preparing Ceramic Color Frit Six types of low melting point binder glasses shown in the attached table are melted by a conventional method, and the melted glass is pulverized.

The obtained glass particles and a commercially available black heat-resistant pigment (main component: Fe,
Mix 20 wt% (added) of Mn-based spinel, and place in a pot.
Wet-grind by adding an appropriate amount of water in a mill. Furthermore, NO. In the case of sample 4, which of the glass powder? ■Replace % with cordierite powder, NO. 6, 5Wt. % with zircon, NO. In the case of No. 6, 7 wt% was replaced with zircon powder.

The pulverization is carried out until the average particle size becomes 2 μm or less, and the obtained pulverized product is dried to prepare a powdery mixture. Mix this powder with a viscosity-adjusted vehicle (normally ethyl cellulose is added to TVneol to adjust the viscosity) in a ratio of 4:1.
Thoroughly knead with a kneader to form a paste. (2) Glass Reinforcement Baking Treatment A plate glass of 30 x 30 cm and 5Tn1n in thickness is prepared, and the above-mentioned ceramic color paste is screen printed on the center of the glass in a size of about 10 cm x 10 cm.

The screen was made of 150rT1eSh, and the thickness of the ceramic color layer after baking was adjusted to 20 to 30μ. The plate glass after printing is dried in a dryer at about 200° C. for about 10 minutes to volatilize the vehicle component. Next, these plate glasses are subjected to air-cooling strengthening treatment by a conventional method. Strengthening is 70
After heating at 0° C. for 3 minutes, a method of rapidly cooling with a wind pressure of 400° C.-H, O was used. Through this strengthening treatment, the applied ceramic color frit is firmly baked onto the surface of the glass plate. 3) Measurement of strength The strength was compared using normal falling ball strength.

In the falling ball strength test, a 227g steel ball was dropped from a height of 50C71, and if it did not break, it would be 10C! The height was increased by n increments, and the height at which the ball broke was taken as the falling strength. Note that the data are shown as the average value of each 5 sheets. 4) The results are as shown in the table below.The table also shows the soft transition point of the binder glass by DTA,
Measurement results of softening point and crystallization peak temperature, and thermal expansion coefficient (50~
350°C) is shown.

Claims (1)

[Scope of Claims] 1. Consisting of a colored heat-resistant pigment powder and a low melting point glass powder, the glass powder having the following composition range:
O_25-20wt% Al_2O_30.5-10 ZnO52-65 B_2O_315-30 ▲There are mathematical formulas, chemical formulas, tables, etc.▼0.1-10▲There are mathematical formulas, chemical formulas, tables, etc.▼0.5-15▲Mathematical formulas, chemical formulas, A colored ceramic color frit composition suitable for baking onto automobile window glass plates characterized by ▼0~5F0~2.