JP2000154037A - Ceramic color composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a ceramic color layer having excellent acid resistance by compounding specified proportions of glass powder, pigment powder, silica powder and refractory filler powder to prepare a compsn. containing neither lead nor cadmium. SOLUTION: The ceramic color compsn. prepared contains, by wt.%, 55 to 94.9 of glass powder, 5 to 40 of pigment powder, 0.1 to 20 of silica powder, and 0 to 10 of refractory filler powder and contains neither lead nor cadmium. The glass powder substantially consists of 30 to 60 of SiO2, 8 to 60 of ZnO, 0 to 40 of Bi2O3, 0 to 25 of B2O3, 0 to 10 of Li2O, 0 to 15 of Na2O, 0 to 10 of K2O, 0.1 to 20 of LiO+Na2O+K2I, 0 to 20 of MgO+CaO+SrO+BaO, 0 to 10 of TiO2, 0 to 10 of P2O5 and 0 to 5 of F. As for the pigment powder, black heat-resistant pigment powder such as Fe-Mn-O is used, and as for the silica powder, for example, an amorphous silicon dioxide powder prepared by melting quartz at a high temp. is used. As for the refractory filler powder, α-alumina or the like is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a lead and cadmium-free ceramic color composition.

[0002]

BACKGROUND OF THE INVENTION A typical use of ceramic color compositions is in coatings on automotive glazings. The coating is performed by screen-printing a paste of a ceramic color composition on the periphery of an automobile window glass and the like, drying the ceramic color composition, and then baking in a glass plate heating step for bending. By baking the paste-colored ceramic color composition on the periphery of an automotive window glass to form a colored opaque layer (ceramic color layer), it is possible to prevent the urethane sealant from being deteriorated by ultraviolet rays, and the heating wire terminal is not visible from outside the vehicle. And the like are obtained.

[0003] As a ceramic color composition, a composition in which various heat-resistant coloring pigments are mixed with powder of a low-melting glass is known. Conventionally, low melting glass containing lead or cadmium is used.
And so on.

[0004] However, in recent years, ceramic color compositions that do not contain lead and cadmium have been desired. A bismuth-based ceramic color composition that does not contain lead and cadmium and that can be baked on a glass plate at the same time that the glass plate is bent by press molding and that has excellent mold release properties and does not adhere to the press mold One containing glass powder has been proposed (JP-A-6-234).
547, JP-A-7-144933).

Further, glass powders containing zinc as a flux without containing lead and cadmium are disclosed in JP-A-5-339029, JP-A-6-191884, and US Pat. No. 5,252,521.

[0006] These materials are excellent in nature, but suffer from problems such as a change in the color tone of the ceramic color layer and a peeling of the ceramic color layer when exposed to acid rain for a long time. there were. In addition, depending on the type and model of the automobile, a bus bar made of silver formed on the ceramic color layer is immersed in a strongly acidic plating solution for the purpose of improving antenna characteristics. There was also a problem that the busbar portion was peeled off.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a ceramic color composition which can form a ceramic color layer having excellent acid resistance on a glass plate and does not contain lead and cadmium.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a lead-free and cadmium-free glass powder of 55 to 94.9% by weight, a pigment powder of 5 to 40% by weight, a silica powder of 0.1 to 20% by weight.
And a ceramic color composition comprising 0 to 10% by weight of a refractory filler powder.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The ceramic color composition of the present invention is used to form a colored opaque layer, that is, a ceramic color layer by baking on the surface of a glass plate, particularly a soda lime silica glass plate. The ceramic color composition of the present invention is suitable for simultaneously baking a glass sheet by press molding and baking the glass sheet.

The components and compositions of the ceramic color composition of the present invention are described below. The glass powder is preferably a low-melting glass powder having a softening point of 650 ° C. or less.

When the glass powder content is less than 55% by weight, it is difficult to bake the ceramic color composition on the glass plate at a temperature at which the glass plate is bent. Preferably 6
0% by weight or more. If it exceeds 94.9% by weight, the content of the pigment powder becomes relatively small, and the opacity of the ceramic color layer is impaired. It is preferably at most 90% by weight, more preferably at most 85% by weight.

[0012] The glass powder is preferably a crystalline glass powder that precipitates crystals at 500 to 700 ° C. When baking the ceramic color composition on an automotive glass plate, crystals are precipitated during bending performed at 500 to 700 ° C. and apparently the glass viscosity is increased,
This is because the adhesion of the ceramic color composition to the press mold can be prevented. The crystalline glass referred to here is a glass that is in a glass state at normal temperature, but that precipitates crystals when subjected to heat treatment under appropriate conditions. Preferably, the crystals are lithium zinc silicate crystals. This is expected to further improve the acid resistance of the ceramic color layer.

The pigment powder is preferably a black heat-resistant pigment powder which normally does not contain lead and cadmium and which exhibits a stable black color from room temperature to 700 ° C. Black heat-resistant pigments include Fe-Mn-O-based pigments, Cu-Cr-
O-based, Co-Cr-O-based and the like are exemplified.

If the pigment powder content is less than 5% by weight, the opacity of the ceramic color layer is impaired. It is preferably at least 7% by weight, more preferably at least 10% by weight. 40
If the content is more than 10% by weight, the content of the glass powder becomes relatively small, and it becomes difficult to bake the ceramic color composition on the glass plate at a temperature at which the glass plate is bent. It is preferably at most 37% by weight, more preferably at most 35% by weight.

The weight average diameter of the glass powder and the pigment powder is preferably from 0.1 to 10 μm. 0.1μ
If it is less than m, the productivity may be reduced. More preferably, it is 1 μm or more. If it exceeds 10 μm, the screen printability of the paste-formed ceramic color composition may be reduced. More preferably, it is 6 μm or less.

The silica powder referred to in the present invention is 1) an amorphous silicon dioxide powder (hereinafter referred to as a fused silica powder) prepared by dissolving quartz at a high temperature of about 2000 ° C.
2) a gel-like silicon dioxide powder prepared by hydrolyzing an alkoxide of silicon (Si) and subjecting it to polycondensation; and 3) an amorphous silicon dioxide prepared by heating and calcining the gel-like silicon dioxide powder. At least one selected from the group consisting of silicon powder, which is an essential component for improving the acid resistance of the ceramic color layer.

If the silica powder content is less than 0.1% by weight, there is no effect of improving the acid resistance of the ceramic color layer. It is preferably at least 1% by weight. If it exceeds 20% by weight, the content of the glass powder becomes relatively small, and it becomes difficult to bake the ceramic color composition on the glass plate at a temperature at which the glass plate is bent. It is preferably at most 15% by weight.

The shape of the silica powder is not particularly limited, but the weight average diameter is preferably 0.1 to 10 μm. If it is less than 0.1 μm, the productivity may be reduced. Preferably it is 0.5 μm or more. If it exceeds 10 μm, there is a possibility that the surface roughness of the glass plate on which the ceramic color layer is formed becomes large, and the screen printability of the ceramic color composition that has been made into paste is reduced.
Preferably it is 6 μm or less.

The refractory filler powder is not essential, but may be contained up to 10% by weight for controlling the thermal expansion coefficient, controlling the fluidity, improving the mold releasability, and the like. If it exceeds 10% by weight, the content of the glass powder becomes relatively small, and it may be difficult to bake the ceramic color composition on the glass plate at the temperature at which the glass plate is bent. It is preferably at most 8% by weight.

The refractory filler is preferably a ceramic which does not usually contain lead and cadmium and does not react with the glass powder when fired at 500 to 700 ° C.
When the purpose is to control the coefficient of thermal expansion or to control the fluidity, α-alumina, α-quartz, zircon, cordierite, forsterite, bismuth titanate, etc. are exemplified. When the purpose is to improve mold release properties, metal silicide powder, metal boride powder, and the like are exemplified. Examples of the metal constituting the metal silicide or metal boride include Ti, C
r, Mn, Fe, Co, Ni, Cu, Zr, Mo, A
g, Sn, La, Ce, etc. are illustrated.

The weight average diameter of the refractory filler powder is 0.1
It is preferably from 10 to 10 μm. If it is less than 0.1 μm, the productivity may be reduced. More preferably 0.5 μm
That is all. If it exceeds 10 μm, the screen printability of the paste-formed ceramic color composition may be reduced. More preferably, it is 6 μm or less.

The metal powder is not essential, but may be contained up to 5% by weight for coloring purposes. As the metal powder, Ti, Cr, Mn, Fe, Co, Ni, Cu, Z
Examples thereof include powders of metals such as r, Mo, Ag, Sn, La, and Ce, and usually do not include powders of lead and cadmium.

In a preferred embodiment of the present invention is a glass powder substantially wt% _{display, SiO 2 30~60, ZnO 8~60,} Bi 2 O 3 0~40, B 2 O 3 0~ 5, Li _{2 O 0~10, Na 2 O 0~15} , K 2 O 0~10, Li 2 O + Na 2 O + K 2 O 0.1~20, MgO + CaO + SrO + BaO 0~20, TiO 2 0~10, P 2 O 5 0~ 10, F0-5.

[0024] More _{preferably, SiO 2 31~50, ZnO 15~50,} Bi 2 O 3 0~30, B 2 O 3 0~ 5, Li 2 O 0.3~ 5, Na 2 O 0~15, _{K 2 O 0~10, Li 2 O} + Na 2 O + K 2 O 5~15, MgO + CaO + SrO + BaO 0~10, TiO 2 0~ 7, P 2 O 5 0~ 7, F 0~ 3, made of.

Particularly preferred are SiO ₂ 31 to 45, ZnO 25 to 45, Bi ₂ O _{30 to} 25, B ₂ O _{30 to} 5, Li ₂ O 0.3 to 5, Na ₂ O 0 to 8, _{K 2 O 0~ 8, Li 2} O + Na 2 O + K 2 O 5~13, MgO + CaO + SrO + BaO 0~ 7, TiO 2 0~ 6, P 2 O 5 0~ 5, F 0~ 2, consisting. The reasons for limiting the composition of the above glass powder will be described below by simply expressing weight% as%.

SiO ₂ is a glass network former, is a component for improving chemical resistance and heat resistance, and is essential. If the content is less than 30%, vitrification may not be achieved. It is preferably at least 31%. If it exceeds 60%, the softening point becomes too high, and for example, it may be difficult to simultaneously bake the ceramic color composition at the time of bending an automotive glass plate.
Preferably it is 50% or less, more preferably 45% or less.

ZnO is a flux and a component for improving the melting property of glass, and is essential. If the content is less than 8%, the fluidity of the glass at the time of baking decreases, and it may be difficult to simultaneously bake the ceramic color composition at the time of, for example, bending an automotive glass plate. Preferably at least 15%, more preferably 2%
5% or more. If it exceeds 60%, vitrification may not be achieved. Preferably not more than 50%, more preferably 45%
It is as follows.

Bi ₂ O ₃ is not essential, but as a flux and in order to improve the melting property of the glass, the fluidity of the glass at the time of baking is further improved to improve the adhesion between the ceramic color composition and the glass plate. 4 to improve
It may be contained up to 0%. If it exceeds 40%, the precipitation amount of lithium zinc silicate crystals will be small, and the mold releasability at the time of press molding may be deteriorated. Preferably not more than 30%,
It is more preferably at most 25%.

B ₂ O ₃ is not essential, but may be contained up to 5% as a flux and to improve the melting property of the glass. If it exceeds 5%, the acid resistance is significantly reduced.

Li ₂ O, Na ₂ O and K ₂ O are fluxes, which are contained in a total amount of 0.1 to 20%. If it is less than 0.1%, the effect as a flux is small. It is preferably at least 5%. If the total amount exceeds 20%, the acid resistance may decrease. Preferably not more than 15%, more preferably 13%
% Or less.

Although Li ₂ O is not essential, it is also a component that strongly influences the crystallization behavior and thus the acid resistance. That is,
Li ₂ O is a component to promote the precipitation of lithium zinc silicate crystal at the time of baking, the it is possible to improve the acid resistance by precipitation of crystals, also the precipitation temperature of the crystal and by containing Li ₂ O The amount of precipitation can be controlled.
It may be contained up to 0%. The preferred content is 0.1 to 1
0%. If the content is less than 0.1%, the above effect may be small. It is preferably at least 0.3%. 10
%, Li ₂ present in the residual glass phase after crystallization
Since the ratio of the O amount is increased, the acid resistance is reduced, and the thermal expansion coefficient is increased, so that the strength of the glass plate on which the ceramic color layer is formed may be reduced. Preferably 5
% Or less.

Na_TwoO content greater than 15% or K_TwoO
When the content exceeds 10%, the coefficient of thermal expansion increases,
The strength of the glass plate on which the lamic color layer is formed decreases
May be lost. Each content is preferably
8% or less. Na _TwoO, K_TwoO at least
It is preferable to contain at least one of them.

Alkaline earth oxides, ie, MgO, Ca
O, SrO and BaO are not essential, but may be contained up to a total amount of 20% in order to improve acid resistance or adjust the softening point and the coefficient of thermal expansion. If it exceeds 20%, the softening point and the coefficient of thermal expansion become too high, which may cause a decrease in fluidity and a decrease in the strength of the glass plate on which the ceramic color layer is formed. It is preferably at most 10%, more preferably at most 7%. In particular, by reducing the difference in the coefficient of thermal expansion between the ceramic color layer and the glass plate on which the ceramic color composition is baked, the strength of the glass plate baked with the ceramic color composition can be increased. Therefore, it is preferable to appropriately select the type and amount of the alkaline earth oxide depending on the type of the glass plate on which the ceramic color composition is to be baked. For example, when the glass plate is soda lime silica glass, it is effective to contain MgO.

Although TiO ₂ is not essential, it may be contained up to 10% as a nucleating agent for controlling crystallization. 10
%, The fluidity and acid resistance may be reduced. It is preferably at most 7%, more preferably at most 6%.

P ₂ O ₅ is not essential, but may be contained up to 10% for improving the fluidity. If it exceeds 10%, the acid resistance may decrease. It is preferably at most 7%, more preferably at most 5%.

F is not essential, but may be contained up to 5% in order to lower the softening point and improve the fluidity. 5%
If it is more than 1, the acid resistance may decrease. Preferably 3
% Or less, more preferably 2% or less.

The glass powder according to the present invention is substantially composed of the above-mentioned components. In addition, Al ₂ O ₃ , La ₂ O ₃ , Zr
O ₂ , SnO ₂ , CeO ₂ , etc. are converted to a softening point, a coefficient of thermal expansion,
In order to adjust the glass composition and the like, the glass may be appropriately contained up to a total amount of 5% as long as the homogeneity of the glass is not impaired.

Next, a method for forming a ceramic color layer on the surface of a glass plate using the ceramic color composition of the present invention will be described. First, the ceramic color composition of the present invention is made into a paste by containing an organic vehicle. As the organic vehicle, a polymer obtained by dissolving a commonly used polymer such as ethyl cellulose, acrylic resin, styrene resin, phenol resin, and butyral resin in a solvent such as α-terpineol, butyl carbitol acetate, phthalate, or the like is used. Is done.

Next, the paste-formed ceramic color composition is applied to a desired portion of the surface of the glass plate by an application means such as screen printing. For example, in the case of a glass plate for an automobile, the portion to be applied is a peripheral portion of a front glass, a side glass, and a rear glass.

The glass plate coated with the paste of the ceramic color composition is dried, carried into a heating furnace and heated. The heating temperature is 500 to 620 ° C, and the heating causes the ceramic color composition to fuse to the glass plate.

The glass plate on which the ceramic color composition has been fused is further heated and maintained at 600 to 700 ° C., whereby the ceramic color composition is baked on the glass plate. At this time, it is preferable that the glass in the ceramic color composition is crystallized.

Next, in the case of a glass plate for an automobile, the glass plate on which the ceramic color composition has been baked is bent by a molding device such as a press device or a vacuum suction molding device provided in a furnace by a conventional method. At this time, stainless steel covered with a glass fiber cloth is usually used for a mold such as a press apparatus or a vacuum suction molding apparatus, and the glass plate is pressed through the cloth. The bending may be performed by a weight-weight bending method. The bent glass sheet is subjected to slow cooling or rapid cooling for strengthening, and becomes a window glass for automobiles.

The ceramic color composition of the present invention can be used not only for glass plates for automobiles but also for various glass or ceramic articles. For example, the present invention can be applied to a building glass plate and the like.

[0044]

EXAMPLES Raw materials were prepared and mixed so as to have a glass composition (unit:% by weight) shown in the column of SiO _{2 to} F in the table, and the mixture was mixed with a mixture of 120%.
It melted and vitrified at a temperature of 0 ° C. to 1500 ° C. to obtain a crystalline glass. This crystalline glass was pulverized with a ball mill to obtain a crystalline glass powder having a weight average diameter of 2.5 μm.
This crystalline glass powder and a fused silica powder having a weight average diameter of 2.5 μm (Fuselex X, manufactured by Tatsumori Co., Ltd.)
And a Cu—Cr—O-based black heat-resistant pigment powder having a weight average diameter of 2.5 μm (manufactured by Nippon Fellow Co., Ltd., product number 30
2A) and a refractory filler powder having a weight average diameter of 3 μm were blended and mixed at a ratio shown by weight% in the table. Next, 20 parts by weight of an α-terpineol solution in which 10% by weight of ethyl cellulose was dissolved was added to 80 parts by weight of this mixed powder, kneaded, and homogenized by passing through a three-roll mill three times to obtain a desired dispersion. The paste viscosity was adjusted to obtain a paste-like ceramic color composition (Examples 1 to 10).

The paste-like ceramic color composition thus obtained is screen-printed on the entire surface of a soda lime silica glass plate (thickness: 3.5 mm, 10 cm square), dried, and then silver The paste (712B, manufactured by Murata Manufacturing Co., Ltd.) was screen-printed in a pattern simulating the busbar portion. After drying it again, 6
Baking was performed at 70 ° C. to obtain a glass plate with a ceramic color layer. The glass plate with a ceramic color layer is a glass plate in which a silver layer is formed in a bus bar pattern on a ceramic color layer formed on the surface of the glass plate.

The above glass plate with a ceramic color layer was
After dipping in a plating solution (CuSO ₄ —H ₂ SO ₄ ) at 0 ° C. for 6 minutes, the glass plate was taken out, and the surface properties of the glass plate with the ceramic color layer were visually observed to evaluate acid resistance. The evaluation results are shown in the table. ◎ indicates the case where the color tone of the surface of the glass plate with the ceramic color layer was not changed before and after the test and the silver layer was firmly adhered to the ceramic color layer. No change was observed in the color tone of the glass plate surface, but when the silver layer was peeling off from the ceramic color layer, the x mark indicates that the color tone of the glass plate surface with the ceramic color layer changed drastically before and after the test. Are completely separated from the ceramic color layer.

Further, the ceramic color composition may be used in an amount of 500 to
By maintaining the temperature at 700 ° C. for 3 minutes, it was examined by an X-ray diffraction method whether or not lithium zinc silicate crystals were precipitated. Those in which precipitation of crystals was strongly recognized are shown in the table as ○.

Examples 1 to 8 are Examples and Examples 9 and 10 are Comparative Examples. As is clear from the table, the glass plate with the ceramic color layer using the ceramic color composition of the present invention has excellent acid resistance.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

By using the ceramic color composition of the present invention, a ceramic color layer having excellent acid resistance can be obtained. Further, by using the ceramic color composition of the present invention containing a crystalline glass powder in which crystals precipitate at 500 to 700 ° C., crystallization can be performed at a bending temperature of a glass plate.

Since the ceramic color layer is excellent in acid resistance, a glass plate on which the ceramic color composition of the present invention is baked can be plated. Further, since the ceramic color composition of the present invention crystallizes at the bending temperature of the glass plate and has an apparent viscosity, it does not fuse with the press mold in the press bending process of the glass plate, and thus, for example, window glass for automobiles. Can be manufactured at low cost. Furthermore, it does not contain lead or cadmium, which is an environmental pollutant, and has the advantage that it does not burden the environment.

Continued on the front page F-term (reference) 2K009 AA12 BB02 CC03 DD01 EE01 FF01 4G062 AA08 AA09 AA11 AA15 BB01 DA05 DA06 DB01 DC01 DC02 DC03 DD01 DD02 DD03 DE03 DE04 DE05 DE06 DF01 EA01 EA02 EA03 EA01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 EB01 ED04 EE01 EE02 EE03 EE04 EF01 EF02 EF03 EF04 EG01 EG02 EG03 EG04 FA01 FA10 FB01 FB02 FB03 FC01 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA02 GA03 GA04 GA05 GA10 H01 GE01H01 H01 GE01H01 H01 GE01H03H JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM07 NN05 PP01 PP02 PP03 PP05 PP09 PP10 QQ08

Claims (6)

[Claims] 1. Lead and cadmium-free glass powder 55 to 94.9% by weight, pigment powder 5 to 40% by weight, silica powder 0.1 to 20% by weight and refractory filler powder 0
A ceramic color composition comprising from 10 to 10% by weight. 2. The ceramic color composition according to claim 1, wherein the glass powder is a crystalline glass powder that precipitates crystals at 500 to 700 ° C. 3. A glass powder is substantially wt% _{display, SiO 2 30~60, ZnO 8~60,} Bi 2 O 3 0~40, B 2 O 3 0~ 5, Li 2 O 0~10, _{Na 2 O 0~15, K 2 O} 0~10, Li 2 O + Na 2 O + K 2 O 0.1~20, MgO + CaO + SrO + BaO 0~20, TiO 2 0~10, P 2 O 5 0~10, F 0~ 5 The ceramic color composition according to claim 1, comprising: 4. The glass powder has a Li ₂ O content of 0.1.
The ceramic color composition according to claim 3, wherein the content is from 10 to 10% by weight. In 5. glass powder substantially wt% _{display, SiO 2 31~50, ZnO 15~50,} Bi 2 O 3 0~30, B 2 O 3 0~ 5, Li 2 O 0.3~ _{5, Na 2 O 0~15, K} 2 O 0~10, Li 2 O + Na 2 O + K 2 O 5~15, MgO + CaO + SrO + BaO 0~10, TiO 2 0~ 7, P 2 O 5 0~ 7, F 0~ 3 The ceramic color composition according to claim 1, comprising: 6. The ceramic color composition according to claim 3, wherein the crystals precipitated at 500 to 700 ° C. are lithium zinc silicate.