JP2016079084A - Ceramic color composition, glass sheet with ceramic color and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ceramic color composition capable of having both of low temperature sinterability and high sheet strength.SOLUTION: There is provided a ceramic color composition comprising a glass powder which is a glass composition containing 40 to 55% of SiO, 5 to 15% of BO, 5 to 30% of ZnO, 10 to 25% of at least one selected from a group consisting of LiO, NaO and KO, 0 to 3% of AlO, 5 to 25% of BiO, 0.1 to 8% of CuO, 0 to 3% of MnO, 0 to 5% of MgO, 0 to 5% of CaO, 0 to 5% of BaO and 0 to 5% of SrO with SiO/BOof 3.5 to 6.5 and practically free of F, PbO and CdO, a refractory filler having a particle shape with an average aspect ratio of less than 8 and peaks between 0.1 to 8.4 μm and 8.5 to 30 μm respectively in a particle size distribution curve and a heat resistant pigment powder.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a ceramic color composition, a glass plate with a ceramic color layer, and a method for producing the same.

  Conventionally, pasted ceramic color composition (ceramic color paste) is screen-printed on the periphery of window glass such as windshield, side glass, rear glass or roof glass of automobile, dried, heated and baked on a glass plate ( Sintered glass plates with colored opaque layers (ceramic color layers) for automobiles are in widespread use.

  As this paste-like ceramic color composition, a colored opaque layer is formed by baking on the peripheral edge of the glass plate, and the purpose of preventing deterioration of the urethane sealant holding the window glass at the peripheral edge by ultraviolet rays, or of the glass plate It is used for the purpose of preventing the terminal of the heating wire attached around from seeing from the outside of the vehicle. In addition, recently, there is also the meaning of improving the appearance design of the window glass, such as forming a fine dot pattern in gradation from the periphery of the glass plate to the center by baking ceramic color paste.

  Ceramic color compositions for such applications are based on non-crystalline glass powder that is not crystallized during glass baking, or based on crystalline glass powder that crystallizes during glass baking. A mixture of various heat-resistant pigments is known.

  Here, with the recent reduction in weight of automobile parts, there is a demand for thinner window glass for automobiles, and the strength of window glass for automobiles may be weakened. In general, it is known that a glass plate with a ceramic color layer is inferior in strength to a glass plate without it. Therefore, in order to improve the strength of the glass plate with a ceramic color layer, a technique for reducing the thermal expansion coefficient of the ceramic color composition is known.

  Furthermore, as the glass plate is made thinner, the bending temperature in bending by heating the glass plate is also being lowered as compared with the conventional case. Since the ceramic color composition is baked onto a glass plate simultaneously with bending, the glass powder used for the ceramic color composition is also required to be sintered at a lower temperature. However, in general, since the thermal expansion coefficient of the glass powder sintered at a lower temperature becomes larger, the low thermal expansion coefficient is lowered to increase the plate strength of the glass plate with the ceramic color layer, while lowering the low temperature sinterability. It was difficult to obtain a ceramic color composition provided.

  Therefore, as a method to achieve both the low-temperature sinterability of the ceramic color composition and the high strength of the glass plate with the ceramic color layer, the ceramic color composition includes a whisker-like refractory, and the glass plate with the ceramic color layer has toughness. There is known a method of providing the same (for example, see Patent Document 1). However, whisker-like refractories have become difficult to obtain in recent years due to a decrease in the amount of circulation because there are those whose human body effect assessment is unknown or uncertain.

  In addition to the method using whisker-like refractories, as a method for achieving both low-temperature sinterability and high plate strength, a method of matching the thermal expansion coefficient of the ceramic color composition with a glass plate (for example, see Patent Document 2) is also known. It has been. However, in this method, it has been difficult to achieve both low-temperature sinterability and high plate strength as compared with the case of using whisker-like refractories.

JP 2000-154038 A Japanese Patent Laid-Open No. 11-157873

The present invention has been made to solve the above-described problems, and is a ceramic color composition that can achieve both low-temperature sinterability of a ceramic color composition and high plate strength of a glass plate with a ceramic color layer. The purpose is to provide goods.
Another object of the present invention is to provide a glass plate with a ceramic color layer that can achieve both low-temperature sinterability of the ceramic color composition and high plate strength of the glass plate with the ceramic color layer, and a method for producing the same. To do.

The ceramic color composition of the present invention is a ceramic color composition containing glass powder, a refractory filler, and a heat resistant pigment powder, wherein the refractory filler has a particle shape with an average aspect ratio of less than 8. The glass powder having a peak between 0.1 to 8.4 μm and 8.5 to 30 μm in a particle size distribution curve showing a volume-based frequency distribution measured by a laser diffraction scattering method, Is expressed in mol% in terms of oxide,
40-55% of _SiO 2,
5-15% B ₂ O ₃ ,
5-30% ZnO,
At least one selected from the group consisting of 10 to 25% Li ₂ O, Na ₂ O and K ₂ O;
0 to 3% _Al 2 _O 3,
5-25% Bi ₂ O ₃ ,
0.1-8% CuO,
0-3% of _MnO 2,
0-5% MgO,
0-5% CaO,
0-5% BaO and 0-5% SrO
SiO ₂ / B ₂ O ₃ is 3.5 to 6.5, and the glass composition is substantially free of F, PbO and CdO (hereinafter referred to as “ceramic color composition A”). Also called.).

The ceramic color composition of the present invention is a ceramic color composition containing a glass powder, a refractory filler, and a heat resistant pigment powder, wherein the refractory filler has particles having an average aspect ratio of less than 8. Having a shape, the glass powder is expressed in mol% in terms of oxide,
40-55% of _SiO 2,
5-15% B ₂ O ₃ ,
5-30% ZnO,
At least one selected from the group consisting of 10 to 25% Li ₂ O, Na ₂ O and K ₂ O;
0 to 3% _Al 2 _O 3,
5-25% Bi ₂ O ₃ ,
0.1-8% CuO,
0-5% MgO,
0-5% CaO,
0-5% BaO,
A glass composition containing 0 to 5% SrO and 0 to 3% MnO ₂ , SiO ₂ / B ₂ O ₃ being 3.5 to 6.5 and substantially free of F, PbO and CdO. A low softening point glass powder which is the glass composition having a softening point of 490 ° C. to 530 ° C. and a thermal expansion coefficient of 89 × 10 ⁻⁷ / ° C. to 97 × 10 ⁻⁷ / ° C., and a softening point of 530 ° C. One or two or more kinds of high softening point glass powders, each of which is the glass composition having a thermal expansion coefficient of 79 × 10 ⁻⁷ / ° C. to 87 × 10 ⁻⁷ / ° C. The content ratio of the point glass powder and the high softening point glass powder is 10: 1 to 1:10 in a volume ratio indicated by the low softening point glass powder: the high softening point glass powder ( Hereinafter also referred to as “ceramic color composition B”).

The ceramic color composition of the present invention is a ceramic color composition containing a glass powder, a refractory filler, and a heat resistant pigment powder, wherein the refractory filler has particles having an average aspect ratio of less than 8. Having a shape, the glass powder is expressed in mol% in terms of oxide,
45-60% of _SiO 2,
1-5% B ₂ O ₃ ,
5-15% ZnO,
At least one selected from the group consisting of 5 to 15% Li ₂ O, Na ₂ O and K ₂ O;
0 to 3% _Al 2 _O 3,
15-35% Bi ₂ O ₃ ,
0.1-8% CuO,
0-3% of _MnO 2,
0-5% MgO,
0-5% CaO,
0-5% BaO and 0-5% SrO
And a glass composition substantially free of F, PbO and CdO (hereinafter also referred to as “ceramic color composition C”).

  The glass plate with a ceramic color layer of the present invention has a glass plate and a ceramic color layer in which any one of the ceramic color compositions A to C is baked in at least a part of the main surface of the glass plate. It is characterized by that.

  The method for producing a glass plate with a ceramic color layer of the present invention comprises a step of preparing a ceramic color paste containing an organic vehicle and any one of the ceramic color compositions A to C, and the ceramic color paste on the main surface of the glass plate. Applying the ceramic color paste to the glass plate by heating the glass plate to which the ceramic color paste has been applied, and applying the ceramic color paste to the glass plate.

According to the ceramic color composition of the present invention, both the low temperature sinterability of the ceramic color composition and the high plate strength of the glass plate with a ceramic color layer can be achieved.
According to the glass plate with a ceramic color layer and the method for producing the same according to the present invention, whisker-like refractories are not used, and the low-temperature sinterability of the ceramic color composition and the high plate strength of the glass plate with the ceramic color layer are compatible. be able to.

Fig.1 (a) is a front view which represents typically one Embodiment of the glass plate with a ceramic color layer, FIG.1 (b) is CC of the glass plate with a ceramic color layer of Fig.1 (a). It is sectional drawing.

Hereinafter, embodiments of the present invention will be described in detail.
(First Embodiment (Ceramic Color Composition A))
Embodiment which concerns on the ceramic color composition A contains glass powder, a refractory filler, and a heat resistant pigment powder. The refractory filler has a particle shape with an average aspect ratio of less than 8, and has a particle size distribution curve showing a volume-based frequency distribution measured by a laser diffraction scattering method between 0.1 and 8.4 μm and 8 Each has a peak between 5 and 30 μm.

Moreover, the glass powder in the ceramic color composition according to the present embodiment is expressed in mol% in terms of oxide,
40-55% of _SiO 2,
5-15% B ₂ O ₃ ,
5-30% ZnO,
At least one selected from the group consisting of 10 to 25% Li ₂ O, Na ₂ O and K ₂ O;
0 to 3% _Al 2 _O 3,
5-25% Bi ₂ O ₃ ,
0.1-8% CuO,
0-3% of _MnO 2,
0-5% MgO,
0-5% CaO,
0-5% BaO and 0-5% SrO
SiO ₂ / B ₂ O ₃ is 3.5 to 6.5 and is a glass composition substantially free of F, PbO and CdO (hereinafter, the above glass composition is referred to as “glass composition A”). Also called.).
Hereinafter, each component contained in the ceramic color composition according to the first embodiment will be described.

[Glass powder]
The glass powder used in the present embodiment is a powder of the glass composition A. The reasons for limiting the composition of the glass composition A are as follows. In the glass composition A, “%” represents the mol% in terms of oxide unless otherwise specified.

In the glass composition A, SiO ₂ is an essential component. SiO ₂ is a component that forms a network of glass, and is a component that improves the material strength of the glass and improves acid resistance. In the glass composition A, when the content of SiO ₂ is increased, the softening point is increased and the sinterability may be deteriorated. For this reason, in the glass composition A, the content of SiO ₂ is preferably 53% or less, more preferably 51% or less, and further preferably 49% or less. When the content of SiO ₂ is reduced, the softening point of the glass is lowered, but the acid resistance is deteriorated. For this reason, the content of SiO ₂ is preferably 41% or more, more preferably 45% or more, and further preferably 47% or more in the glass composition A.

In the glass composition A, B ₂ O ₃ is an essential component and a component that facilitates vitrification. Acid resistance is deteriorated when the content of B ₂ O ₃ is too large. Therefore, the content of B ₂ O ₃ is preferably 14% or less, more preferably 12% or less, and still more preferably 10% or less in the glass composition A. Further, the content of B ₂ O _{3 in} the glass composition A is preferably 6% or more, more preferably 7% or more, and further preferably 8% or more.

In the glass composition A, the softening point can be lowered by optimizing the content ratio of SiO ₂ and B ₂ O ₃ . In the glass composition A, the content ratio of SiO ₂ and B ₂ O ₃ is preferably such that SiO ₂ / B ₂ O ₃ is 3.5 to 6.5, and preferably 4.5 to 6.0. More preferably, it is 5.0 to 5.7.

  In the glass composition A, ZnO is an essential component and a component that decreases the thermal expansion coefficient. When the ZnO content is increased, the stability of the glass is lowered, and the glass tends to be devitrified at the time of molding, or crystallized at the time of firing. For this reason, in the glass composition A, the content of ZnO is preferably 28% or less, more preferably 20% or less, and further preferably 15% or less. Further, the content of ZnO in the glass composition A is preferably 7% or more, more preferably 10% or more, and further preferably 12% or more.

In the glass composition A, Li ₂ O, Na ₂ O and K ₂ O (alkali metal oxide) are effective as a low softening component. The glass composition A contains at least one selected from the group consisting of Li ₂ O, Na ₂ O and K ₂ O. When these total contents increase, there exists a possibility of devitrification of glass, phase separation, and excessive crystallization. Moreover, when these total content increases, there exists a tendency for the water resistance and acid resistance of glass to deteriorate, and the thermal expansion coefficient of glass becomes high.

  Here, in recent years, for example, when a glass plate with a ceramic color layer is used as a windshield of a car, a sintered layer of a ceramic color composition (hereinafter referred to as “ceramic color layer”) is used to impart an antenna function to the windshield. An Ag layer is formed thereon as an electrode. In this case, a ceramic color paste is applied on the main surface of the glass plate, dried, and further an Ag paste is applied thereon, followed by firing to form an Ag layer. When firing a glass plate further coated with an Ag paste on this ceramic color paste, Ag is incorporated into the glass composition, and when the alkali metal oxide component is contained in the glass composition, the alkali metal oxide A redox potential difference is generated between the component and Ag, and this facilitates the phenomenon that Ag is converted into a metal colloid in the glass composition. When Ag is converted into a metal colloid, the thermal expansion coefficient of the ceramic color layer containing the glass composition is remarkably increased, the difference in thermal expansion coefficient between the ceramic color layer and the glass plate is increased, and the strength of the glass plate with the ceramic color layer is increased. May be weakened. Therefore, the total content of alkali metal oxides in glass composition A is preferably 23% or less, more preferably 20% or less, and even more preferably 19% or less. Further, the total content thereof is preferably 11% or more, more preferably 13% or more, and further preferably 17% or more in the glass composition A.

In the glass composition A, the alkali metal oxide has a property of increasing the thermal expansion coefficient of the glass in the order of Li ₂ O <Na ₂ O <K ₂ O. Therefore, it is preferable that the glass composition A contains at least Li ₂ O. However, in the case where the glass composition A contains Na ₂ O and / or K ₂ O in a predetermined ratio in addition to Li ₂ O, a mixed alkali effect is produced, and thus when Li ₂ O is contained alone. The crystallization potential can be suppressed compared to. Therefore, the glass composition A in the present embodiment, it is more preferable to include two or more containing Li 2 _O. At this time, considering the effect of increasing the thermal expansion coefficient, it is preferable to increase the content of Li ₂ O compared to Na ₂ O and K ₂ O, and the content ratio in mol% in terms of oxide Is preferably in the order of Li ₂ O ≧ Na ₂ O ≧ K ₂ O. The content ratio of Li ₂ O, Na ₂ O, and K ₂ O in the glass composition A is preferably 3: 1: 0 to 4: 1: 0, and more preferably 3: 1: 0.

In the glass composition A, Al ₂ O ₃ is an optional component. Al ₂ O ₃ is a component that facilitates vitrification and is a component that suppresses crystallization. When the content of Al ₂ O ₃ increases, the softening point of the glass becomes too high, so that sintering at a low temperature becomes difficult, and there is a possibility that it will not vitrify. Therefore, if the glass composition A contains _Al 2 _{O 3, Al} 2 _{O 3} content in a glass composition A, the following is preferably from 2.5%, more preferably at most 2%, 1% or less Is more preferable. Further, the content of Al ₂ O ₃ in glass composition A is preferably 0% or more, more preferably 0.1% or more, further preferably 0.2 or more, and particularly preferably 0.3% or more.

In the glass composition A, Bi ₂ O ₃ is effective as a low softening component. Bi ₂ O ₃ has a lower thermal expansion coefficient than Na ₂ O and K ₂ O, which are low softening components, like Bi ₂ O ₃ . If the content of Bi ₂ O ₃ is too large, the acid resistance and solder wettability of glass at room temperature may be deteriorated. Further, when the Ag layer is formed on the ceramic color layer, since the oxidation-reduction potential is close to Ag as compared with the alkali metal oxide which is a low softening component like Bi ₂ O ₃ , the above-mentioned Ag metal colloid Can be suppressed. Therefore, in the glass composition A, Bi ₂ O ₃ is an essential component. In the glass composition A, the content of Bi ₂ O ₃ is preferably 25% or less, more preferably 20% or less, and still more preferably 10% or less. Further, the content of Bi ₂ O _{3 in} the glass composition A is preferably 6% or more, more preferably 6.3% or more, and further preferably 6.6% or more.

In the glass composition A, CuO is a glass softening component and a coloring component. Similar to Bi ₂ O ₃ , the oxidation-reduction potential is close to Ag. Therefore, when the Ag layer is formed, the above-described colloidalization of Ag can be suppressed. Therefore, CuO is an essential component. When the firing furnace used when forming the ceramic color layer on the glass plate is a far infrared heating furnace (hereinafter also referred to as “IR furnace”) or the like, CuO uses far infrared radiation (hereinafter also referred to as “IR”). Absorbing has an effect that the glass is easily softened. Further, CuO also has an effect of improving the binder removal property in the process of sintering the ceramic color paste coating layer. However, when there is too much content of CuO, stability of glass will fall, it will become easy to devitrify, or it will become easy to crystallize. For this reason, the content of CuO in the glass composition A is preferably 7% or less, more preferably 6% or less, and still more preferably 5% or less. Further, the content of CuO in the glass composition A is preferably 0.3% or more, more preferably 1% or more, and further preferably 3% or more.

In the glass composition A, TiO ₂ is a component that improves acid resistance and is an optional component. When the content of TiO ₂ is too large, the sinterability deteriorates. Therefore, if the glass composition A contains TiO _2, the content thereof in the glass composition A, preferably 2.5% or less, more preferably 2% or less, more preferably 1% or less. Further, the content of TiO _2, the glass composition A, preferably at least 0.01%, more preferably at least 0.5%.

In the glass composition A, MnO ₂ is a coloring component and an optional component. When the firing furnace for sintering the coating layer of the ceramic color paste is an IR furnace or the like, since MnO ₂ absorbs IR, there is an effect of easily softening the glass. When melting the raw material of the glass composition with a platinum (Pt) crucible or the like, there is a possibility that the metal Bi generated by the reduction of the Bi ₂ O ₃ raw material and Pt will be alloyed and the Pt crucible may be damaged. . Here, when the glass composition contains MnO ₂ , since MnO ₂ releases oxygen at around 600 ° C., the atmosphere when melting the raw material of the glass composition can be an oxidizing atmosphere. Therefore, reduction of Bi ₂ O ₃ in the glass composition can be suppressed and generation of metal Bi can be suppressed. When the content of MnO ₂ is too large, deteriorates the sintering property of the glass, there is a risk of or devitrification. When the glass composition A contains MnO ₂ , the content is preferably 2.5% or less, more preferably 2% or less, and further preferably 1% or less in the glass composition A. Further, the content of MnO ₂ is in the glass composition A, preferably at least 0.01%, more preferably at least 0.3%.

Since F, PbO, and CdO are all environmental pollutants, the glass composition A does not substantially contain them. In this specification, PbO represents an oxide of Pb and includes all oxides of Pb such as PbO and Pb ₃ O ₄ . Further, in the present specification, “substantially not containing” does not exclude contamination by impurities. When specifically shown by a numerical value, it is less than 0.01% in the glass composition A.

In the glass composition A, Ag ₂ O is an optional component. Ag ₂ O is very expensive as a raw material, but the color tone of the ceramic color layer can be adjusted by utilizing the above-described colloidalization of Ag. Therefore, when the color tone of the ceramic color layer needs to be adjusted, the glass composition A can contain Ag ₂ O. In this case, the content of Ag ₂ O is preferably 1% or less, more preferably 0.5% or less, and further preferably 0.1% or less. The content of Ag ₂ O is in the glass composition A, preferably at least 0.01%, more preferably at least 0.02%.

  In the glass composition A, MgO, CaO, BaO, and SrO are all optional components. These are components that facilitate vitrification, but as the content increases, the stability of the glass decreases and the glass tends to devitrify. For this reason, when the glass composition A contains MgO, CaO, BaO, SrO, the total content thereof is preferably 0 to 20%, more preferably 0 to 10% in the glass composition A, and 0 to 5% is more preferable.

In addition to the above components, the glass composition A is Fe ₂ O ₃ , CoO, CeO ₂ , Nb ₂ O ₃ , Ta ₂ O ₅ , Sb ₂ O ₃ , Cs ₂ O, P ₂ O ₅ , ZrO ₂ , La _2. O ₃ , SnO _X (x is 1 or 2) and the like can be contained as optional components. However, if the content of the optional component increases, the glass becomes unstable and devitrification may occur. Moreover, there exists a possibility that the transition point and softening point of glass may rise. Therefore, when the glass composition A contains these, the total content is preferably 10% or less in the glass composition A.

The glass powder has a softening point of 490 ° C. to 530 ° C. and a thermal expansion coefficient of 89 × 10 ⁻⁷ / ° C. to 97 × 10 ⁻⁷ / ° C. Expansion) glass powder (hereinafter referred to as “low softening point glass powder”), a softening point of 530 ° C. to 570 ° C., and a thermal expansion coefficient of 79 × 10 ⁻⁷ / ° C. to 87 × 10 ⁻⁷ / ° C. It preferably contains a glass powder having a high softening point (low expansion) (hereinafter referred to as “high softening point glass powder”). By combining the low softening point glass powder and the high softening point glass powder, it becomes easier to achieve high strength while maintaining the low temperature sinterability as compared with the case of using any one kind of glass powder. Further, when the glass powder is melted during firing, the adhesiveness between the ceramic color layer and the glass plate is increased, so that the gap is filled and light scattering between the glass plate and the ceramic color layer is suppressed. Therefore, the color tone of the glass plate with the ceramic color layer becomes closer to the color tone of the ceramic color layer. Also, when two types of low softening point glass powder and high softening point glass powder are used, the low softening point glass powder sinters first, compared to the case of using the high softening point glass powder alone. Since the glass powder fills the gap between the glass plate and the ceramic color layer, the thermal expansion coefficients of the glass plate and the ceramic color layer can be matched. Therefore, the low-temperature sinterability can be improved while maintaining the plate strength of the obtained glass plate with a ceramic color layer. In addition, low softening point glass powder and high softening point glass powder may be used individually by 1 type, respectively, and may use 2 or more types together, respectively.

The softening point of the low softening point glass powder is preferably in the range of 500 ° C. to 525 ° C., and the thermal expansion coefficient is preferably in the range of 91 × 10 ⁻⁷ / ° C. to 95 × 10 ⁻⁷ / ° C. . The softening point of the high softening point glass powder is preferably in the range of 540 ° C. to 560 ° C., and the thermal expansion coefficient is preferably in the range of 81 × 10 ⁻⁷ / ° C. to 86 × 10 ⁻⁷ / ° C.
In this specification, the softening point of glass powder (including low softening point glass powder and high softening point glass powder) is a value obtained by differential thermal analysis (DTA), and the thermal expansion coefficient is DTA. It is the value which computed the average linear expansion coefficient of the range of 50-300 degreeC measured by (1).

  When the low softening point glass powder and the high softening point glass powder are used in combination as the glass powder, the content ratio thereof is a volume ratio indicated by the low softening point glass powder: the high softening point glass powder, and 10: 1 to 1: The range is preferably 10, and more preferably 5: 1 to 1: 5.

The particle diameter of the glass powder is preferably as small as possible from the viewpoint of sinterability of the ceramic color composition. However, when the glass composition A has a high crystallization potential, if it is too fine, crystallization is promoted when the glass powder is melted by heating, the fluidity is hindered and the sinterability deteriorates. . For this reason, the particle diameter of the glass powder is preferably 3 μm or less, more preferably 2 μm or less, and further preferably 1.5 μm or less in terms of the cumulative median diameter D ₅₀ of the volume-based particle size distribution. Further, D ₅₀ of the glass powder is preferably 0.02 μm or more, more preferably 0.1 μm or more, and further preferably 0.3 μm or more. In addition, the maximum particle diameter _Dmax of the glass powder is preferably 100 μm or less, more preferably 80 μm or less, and preferably 30 μm or less from the viewpoint of suppressing the occurrence of screen clogging during printing. Further preferred. In addition, the particle diameter and particle size distribution described in this specification are measured by a laser diffraction scattering method. In the present specification, D ₅₀ represents a cumulative median diameter in a volume-based particle size distribution.

  When there is too little content of the glass powder in the ceramic color composition of this embodiment, the sinterability of a ceramic color composition will deteriorate. On the other hand, if the content of the glass powder is too large, the thermal expansion coefficient of the ceramic color composition increases, and as a result, the difference in thermal expansion coefficient between the glass plate and the ceramic color layer increases, and the glass with the ceramic color layer The strength of the plate may be reduced. In particular, when an Ag layer is formed on the surface of the ceramic color layer, the Ag component is taken into the glass composition during firing as described above, and the thermal expansion coefficient of the ceramic color composition in the vicinity of the portion where the Ag paste is applied and in the vicinity thereof. It may be different from other parts, and it may be difficult to adjust the thermal expansion coefficient of the ceramic color layer.

  From the above, the content of the glass powder in the ceramic color composition is preferably 57% by volume or more, more preferably 60% by volume or more, and still more preferably 62% by volume or more. Moreover, 75 volume% or less is preferable, as for content of glass powder, 70 volume% or less is more preferable, and 65 volume% or less is further more preferable.

[Refractory filler]
In general, glass powder and heat-resistant pigment have a higher thermal expansion coefficient than a glass plate (eg, soda lime glass plate). Therefore, the ceramic color composition contains a refractory filler as a component for adjusting the thermal expansion coefficient. The refractory filler used in the shellac color composition of the present embodiment has a particle shape with an average aspect ratio of less than 8. In the present specification, the average aspect ratio of the refractory filler particles is the length of the longest portion (L ₁ ) of the refractory filler particles observed with a scanning electron microscope (SEM) and the longest portion of the particles. 5 is a value calculated by L ₁ / L ₂ using the length (L ₂ ) of the shortest part orthogonal to the thickness, and is randomly selected among the refractory filler particles contained in the ceramic color composition 5 It is an average value of L ₁ / L ₂ of individual refractory filler particles.

  The shape of the refractory filler is preferably crushed or spherical. Since the spherical refractory filler has a small specific surface area, the ceramic color composition has excellent fluidity during firing and good sinterability, so the content in the ceramic color composition can be relatively large. . On the other hand, crushed refractory fillers are slightly inferior in sinterability compared to spherical shapes, but are easily available because they can be mass-produced by a low-cost process such as pulverization with a ball mill.

The ceramic color composition is prepared on a glass plate with a # 150 to # 250 mesh screen after preparing a ceramic color paste as described later. In order to suppress clogging of the screen during printing of the ceramic color paste, the maximum particle diameter _Dmax of the refractory filler is preferably 100 μm or less, and more preferably 80 μm or less.

  In addition, the refractory filler has a peak in each of a particle size distribution curve showing a volume-based frequency distribution measured by a laser diffraction scattering method between 0.1 to 8.4 μm and 8.5 to 30 μm. Have. By doing so, the distribution becomes close to the closest packing, and the ceramic color composition has more refractories while maintaining the sinterability of the ceramic color composition and the plate strength of the glass plate with the ceramic color layer high. A filler can be contained.

  In addition, the maximum value of the part which shows a mountain shape in a particle size distribution curve is called a peak. For example, “having a peak between 0.1 and 8.4 μm” means that the peak of the mountain shape of the curve exists between 0.1 and 8.4 μm.

  If the ratio of particles having a particle diameter of 8.5 μm or more is too small in the refractory filler used in the present embodiment, the fluidity at the time of firing the ceramic color composition is deteriorated. Therefore, the ratio of particles of 8.5 μm or more is preferably a volume-based particle size distribution of 25 cumulative% or more, more preferably 30 cumulative% or more with respect to the total amount of the refractory filler. If the proportion of particles of 8.5 μm or more is too large, the dispersibility of the refractory filler in the ceramic color composition tends to be poor, and this tends to cause variation in plate strength. For this reason, it is preferable that the ratio of 8.5 micrometers or more of particle | grains is 55 cumulative% or less with respect to the total amount of a refractory filler, and it is more preferable that it is 50 cumulative% or less.

  The higher the dispersibility of the refractory filler in the ceramic color composition (the more uniformly it is dispersed), the more uniform the plate strength of the glass plate with the ceramic color layer can be suppressed from partially varying the plate strength. Therefore, it is preferable that the ceramic color composition contains a refractory filler having a small particle diameter in a predetermined ratio. From this point, in the refractory filler, the ratio of the particles having a particle size of 3 μm or less is preferably 15 cumulative% or more, and 20 cumulative% or more with respect to the total amount of the refractory filler in the volume-based particle size distribution. It is more preferable. If the proportion of particles of 3 μm or less is too large, the fluidity at the time of firing the ceramic color composition is deteriorated. Therefore, the proportion of particles of 3 μm or less is preferably 40 cumulative% or less with respect to the total amount of the refractory filler. 35% or less is more preferable.

  In the refractory filler, in order to obtain the above preferable particle size distribution, a method of pulverizing the refractory filler with a ball mill, a jet mill or the like can be used. For example, when pulverizing with a ball mill, a desired particle size distribution can be obtained by adjusting conditions such as ball size and pulverization time. Moreover, it can classify | categorize into 2 or more types of refractory fillers of a particle size distribution by airflow classification etc., and mix them, and can also adjust to the said preferable particle size distribution.

  As the content of the refractory filler in the ceramic color composition increases, the thermal expansion coefficient of the ceramic color composition decreases and the difference in thermal expansion from the glass plate decreases, so the plate strength of the glass plate with the ceramic color layer increases. Become. On the other hand, when there is too much content, the sinterability of a ceramic color composition will worsen. For this reason, the content of the refractory filler is preferably 35% by volume or less, more preferably 30% or less, and even more preferably 28% volume or less in the ceramic color composition. Further, the content of the refractory filler in the ceramic color composition is preferably 5% by volume or more, more preferably 15% by volume or more, and further preferably 24% by volume or more.

  As the refractory filler, cordierite, alumina, titania, zircon, zirconium phosphate, silica or the like is preferably used.

[Heat-resistant pigment powder]
In the ceramic color composition of the present embodiment, the heat-resistant pigment powder is a component that is usually blended so that the ceramic color layer obtained by sintering the ceramic color composition exhibits a black color tone. Examples of the heat-resistant pigment powder include heat-resistant pigment powders mainly composed of iron-manganese oxides, those composed mainly of copper-chromium oxides, and heat-resistant that do not change at the firing temperature mainly composed of cobalt-chromium oxides. It can be used.

  In general, since the heat-resistant pigment powder has a high coefficient of thermal expansion, if the content is too large, the coefficient of thermal expansion of the ceramic color composition increases and the strength of the glass plate with the ceramic color layer decreases. Moreover, when there is too much content of a heat resistant pigment powder, the sinterability of a ceramic color composition will also deteriorate. On the other hand, when there is too little content of heat resistant pigment powder, there exists a possibility that sufficient color tone (blackness) may not be obtained. From these points, the content of the heat-resistant pigment powder is preferably in the range of 8 to 30% by volume with respect to the total amount of the ceramic color composition. The content of the heat resistant pigment powder is more preferably 10% by volume or more. Moreover, 20 volume% or less is more preferable, and 12 volume% or less is further more preferable.

If the particle diameter of the heat-resistant pigment powder is too small, the fluidity of the ceramic color composition during firing deteriorates. On the other hand, if it is too large, the transmittance of the ceramic color layer is increased. Therefore, the cumulative median diameter _{D 50} of the heat-resistant pigment powder is preferably at least 0.02 [mu] m, more preferably not less than 0.1 [mu] m. Further, D ₅₀ of the heat resistant pigment powder is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 4 μm or less. Similar to the above-described refractory filler, in order to obtain a distribution close to the closest packing, the heat-resistant pigment powder is 0.02 to 0.02 in a particle size distribution curve showing a volume-based frequency distribution measured by a laser diffraction scattering method. It is more preferable to have peaks between 1 μm and 1.1 to 5 μm.

[Optional additives]
In the ceramic color composition of the present embodiment, as an optional additive, a metal oxide or boride may be added for the purpose of a colorant or a release agent within a range of 15% by mass or less in the total amount. . Moreover, you may add a metallic silicon for the purpose of a reducing agent, a color tone regulator, and a thermal expansion coefficient regulator. When the amount of these optional additives exceeds 15% by mass, the amount of glass powder in the ceramic color composition is relatively insufficient, and the ceramic color composition can be baked on the glass plate at the bending temperature. It can be difficult. Examples of the metal oxide or boride include oxides or borides such as Ni, Sn, Ti, Mn, Fe, Cu, Ag, La, Zr, Co, Mo, Cr, and Ce.

  As described above, the ceramic color composition according to the present embodiment includes a glass powder having a predetermined glass composition and a refractory filler having a specific particle size distribution, so that a whisker-like refractory is not used and the ceramic color composition is It is possible to achieve both low-temperature sinterability and high plate strength of the glass plate with a ceramic color layer.

(Second Embodiment (Ceramic Color Composition B))
The embodiment according to the ceramic color composition B includes glass powder, a refractory filler, and a heat-resistant pigment powder. The glass powder used in this embodiment is a glass composition A of the above low softening point glass powder and the above high softening point glass powder in a volume ratio of 10: 1 by the low softening point glass powder: high softening point glass powder. ˜1: 10. Thereby, the ceramic color composition of this embodiment is the same as the ceramic color composition according to the first embodiment, regardless of the peak position of the particle size distribution curve indicating the volume-based frequency distribution of the refractory filler. A whisker-like refractory is not used, and the low-temperature sinterability of the ceramic color composition and the high plate strength of the glass plate with the ceramic color layer are both achieved. Hereinafter, although the ceramic color composition according to the present embodiment will be described, description overlapping with the first embodiment will be omitted.

[Glass powder]
In the ceramic color composition according to the present embodiment, a preferable aspect of the content ratio of each component in the glass powder is the same as that of the glass composition A. Further, the softening point and the thermal expansion coefficient of the low softening point glass powder and the high softening point glass powder are the same as those of the first embodiment, respectively, and the preferred mode is also the same as that of the first embodiment.

The content ratio of the low softening point glass powder and the high softening point glass powder is preferably in the range of 5: 1 to 1: 5 as a volume ratio represented by the low softening point glass powder: the high softening point glass powder. The softening point of the low softening point glass powder is preferably in the range of 500 ° C. to 525 ° C., and the thermal expansion coefficient is preferably in the range of 91 × 10 ⁻⁷ / ° C. to 95 × 10 ⁻⁷ / ° C. . The softening point of the high softening point glass powder is preferably in the range of 540 ° C. to 560 ° C., and the thermal expansion coefficient is preferably in the range of 81 × 10 ⁻⁷ / ° C. to 86 × 10 ⁻⁷ / ° C. Each of the low softening point glass powder and the high softening point glass powder may be used alone or in combination of two or more.

  Moreover, the preferable aspect about the particle diameter and particle size distribution of the glass powder in this embodiment, and content of the glass powder in a ceramic color composition is the same as that of 1st Embodiment.

[Refractory filler]
The refractory filler in the ceramic color composition according to the present embodiment is not particularly limited as long as it has a particle shape with an average aspect ratio of less than 8. The refractory filler in the present embodiment has peaks in the particle size distribution curve showing the volume-based frequency distribution measured by the laser diffraction scattering method between 0.1 to 8.4 μm and 8.5 to 30 μm, respectively. It is preferable to have.

  Preferred aspects of the shape, particle diameter, particle size distribution other than the peak position of the particle size distribution curve, content, and the like in the present embodiment are the same as those in the first embodiment.

[Heat-resistant pigment powder and optional additives]
In the ceramic color composition of the present embodiment, the preferred aspect of the heat resistant pigment powder is the same as that of the first embodiment. Moreover, also about arbitrary additives, the preferable aspect is the same as that of 1st Embodiment.

(Third embodiment (ceramic color composition C))
The embodiment according to the ceramic color composition C contains glass powder, a refractory filler having a particle shape with an average aspect ratio of less than 8, and a heat-resistant pigment powder. And glass powder is the mol% display of oxide conversion,
45-60% of _SiO 2,
1-5% B ₂ O ₃ ,
5-15% ZnO,
At least one selected from the group consisting of 5 to 15% Li ₂ O, Na ₂ O and K ₂ O;
0 to 3% _Al 2 _O 3,
15-35% Bi ₂ O ₃ ,
0.1-8% CuO,
0-3% of _MnO 2,
0-5% MgO,
0-5% CaO,
0-5% BaO and 0-5% SrO
The glass composition is substantially free of F, PbO and CdO (hereinafter, the glass composition is also referred to as “glass composition B”).

  As described above, in recent years, an Ag layer is formed on a ceramic color layer in order to impart an antenna function to a windshield or the like of an automobile. In the conventional glass plate with a ceramic color layer, when the Ag layer is formed on the ceramic color layer, the plate strength may be lowered. The ceramic color composition of the present embodiment makes it possible to maintain the high plate strength of the glass plate with the ceramic color layer even when the Ag layer is formed in the ceramic color composition according to the first embodiment. The composition is adjusted. Hereinafter, although each component which the ceramic color composition of this embodiment contains is demonstrated, the description which overlaps with 1st Embodiment is abbreviate | omitted.

[Glass powder]
The glass powder used in the present embodiment is a powder of the glass composition B. Compared with the glass composition A, the glass composition B reduces the amount of alkali (Li ₂ O, Na ₂ O, K ₂ O), which is a low softening component, and increases the Bi ₂ O ₃ content instead. Thus, the low temperature sinterability can be maintained while suppressing the color development due to the colloidal formation of Ag. Hereinafter, the reasons for limiting the glass composition in the glass composition B will be described. In the glass composition B, unless otherwise specified, “%” represents mol% in terms of oxide.

In the glass composition B, SiO ₂ is an essential component. SiO ₂ is a component that forms a network of glass, and is a component that improves the material strength of the glass and improves acid resistance. However, when the content of SiO ₂ increases, the softening point of the glass increases and the sinterability deteriorates. For this reason, the content of SiO ₂ is preferably 58% or less, more preferably 54% or less, and further preferably 53% or less in the glass composition B. When the content of SiO ₂ decreases, the softening point of the glass decreases, but the acid resistance deteriorates. For this reason, the content of SiO ₂ is preferably 46% or more, more preferably 48% or more, and still more preferably 50% or more in the glass composition B.

In the glass composition B, B ₂ O ₃ is an essential component, a component that forms a glass network, and a component that facilitates vitrification. Acid resistance is deteriorated when the content of B ₂ O ₃ is too large. For this reason, the content of B ₂ O ₃ is preferably 4% or less, more preferably 3.5% or less, and still more preferably 3% or less in the glass composition B. Further, the content of B ₂ O ₃ is preferably 1.2% or more, more preferably 1.5% or more, and further preferably 2% or more in the glass composition B.

  In the glass composition B, ZnO is an essential component and a component that lowers the thermal expansion coefficient. When the content of ZnO increases, the stability of the glass decreases and the glass becomes easily devitrified or crystallized easily. For this reason, the content of ZnO in the glass composition B is preferably 14% or less, more preferably 13% or less, and further preferably 12.5% or less. Further, the content of ZnO in the glass composition B is preferably 6% or more, more preferably 9% or more, and further preferably 11% or more.

In the glass composition B, Li ₂ O, Na ₂ O and K ₂ O (alkali metal oxide) are effective as a low softening component. The glass composition B contains at least one selected from the group consisting of Li ₂ O, Na ₂ O, and K ₂ O. When these total contents increase, there exists a possibility of devitrification of glass, phase separation, and excessive crystallization. Moreover, when these total content increases, there exists a tendency for the water resistance and acid resistance of glass to deteriorate, and the thermal expansion coefficient of glass becomes high.

  Further, as described above, when an Ag layer is further formed on the ceramic color layer, Ag is taken into the glass composition during firing, and oxidized between Ag and the alkali metal oxide in the glass composition. A reduction potential difference is generated, and a phenomenon that Ag is converted into a metal colloid in the glass composition easily occurs. When Ag is converted into a metal colloid, the thermal expansion coefficient of the ceramic color layer containing the glass composition is remarkably increased, and the plate strength is decreased. Therefore, the total content thereof is preferably 14% or less, more preferably 10% or less, and further preferably 4% or less in the glass composition B. Further, the total content thereof is preferably 1% or more, more preferably 1.5% or more, and further preferably 2% or more in the glass composition B.

In the glass composition B, Li ₂ O, Na ₂ O, and K ₂ O have the property of increasing the thermal expansion coefficient in the order of Li ₂ O <Na ₂ O <K ₂ O. Therefore, the glass composition B used in the present _{embodiment, Li 2 O, Na 2 O} , of _{K 2} O, preferably contains at least Li ₂ O. However, when glass composition B contains Na ₂ O and / or K ₂ O in a predetermined ratio in addition to Li ₂ O, a mixed alkali effect occurs, and thus when Li ₂ O is contained alone. In comparison with the glass, the crystallization potential of the glass can be suppressed. Therefore, glass composition B in the present _embodiment, Li 2 _O, Na 2 O, and more preferably contains two or more containing at least Li ₂ O of _{K 2} O. At this time, it is preferable to increase the Li ₂ O content as compared with Na ₂ O and K ₂ O in consideration of the effect of increasing the thermal expansion coefficient, and the content ratio is Li ₂ O ≧ Na. ₂ O ≧ K ₂ O is preferable. The content ratio of Li ₂ O, Na ₂ O, and K ₂ O in the glass composition B is preferably 3: 1: 0 to 4: 1: 0, and more preferably 3: 1: 0. .

In the glass composition B, Al ₂ O ₃ is an optional component. Al ₂ O ₃ is a component that facilitates vitrification and is a component that suppresses crystallization of glass. When the content of Al ₂ O ₃ increases, the softening point of the glass becomes too high, so that sintering at a low temperature becomes difficult, and there is a possibility that it will not vitrify. Therefore, if the glass composition B contains _Al 2 _{O 3,} the content thereof in the glass composition B, preferably 2.5% or less, more preferably 2% or less, more preferably 1% or less. Further, the content of Al ₂ O ₃ is preferably 0.05% or more, more preferably 0.1% or more, and further preferably 0.3% or more in the glass composition B.

In the glass composition B, Bi ₂ O ₃ is a component that forms a glass forming network and is effective as a low softening component. Similarly, Bi ₂ O ₃ has a lower thermal expansion coefficient than Na ₂ O and K ₂ O, which are low softening components. Further, when an Ag layer is formed on the ceramic color layer, the oxidation-reduction potential is close to Ag as compared with Li ₂ O, Na ₂ O, and K ₂ O, which are low softening components, similarly to Bi ₂ O _3. From the above, it is possible to suppress the above-described colloidal formation of Ag. Therefore, Bi ₂ O ₃ is an essential component. Since Bi ₂ O ₃ is expensive, if the content of Bi ₂ O ₃ is too high, the cost of the ceramic color composition is also increased, but the glass composition B has a content of Bi ₂ O ₃ . A large composition is preferred. The content of Bi ₂ O ₃ is preferably larger than the total content of Li ₂ O, Na ₂ O and K ₂ O, in glass composition B, preferably 16% or more, more preferably 20% or more, 25% or more is more preferable. In addition, the Bi ₂ O ₃ content in the glass composition B is preferably 34% or less, more preferably 30% or less, and even more preferably 26% or less.

In the glass composition B, CuO is both a low softening component and a coloring component. Similar to Bi ₂ O ₃ , since the oxidation-reduction potential is close to Ag, when the Ag layer is formed on the ceramic color layer, the above-described colloidalization of Ag can be suppressed to some extent. Therefore, in the glass composition B, CuO is an essential component. When the firing furnace used when the ceramic color paste coating layer is sintered is an IR furnace, CuO absorbs IR, and thus the glass is easily softened. In addition, CuO also has an effect of improving the binder removal property in the step of sintering the ceramic color paste coating layer. When the content of CuO is too large, the stability of the glass is lowered and the glass tends to be devitrified or crystallized easily. For this reason, the content of CuO in the glass composition B is preferably 7% or less, more preferably 6% or less, and still more preferably 5% or less. Further, the content of CuO in glass composition B is preferably 0.5% or more, more preferably 1% or more, and further preferably 3% or more.

In the glass composition B, TiO ₂ is a component that improves acid resistance and is an optional component. When the content of TiO ₂ is too large, the sinterability deteriorates. Therefore, if the glass composition B contains TiO _2, the content thereof in the glass composition B, preferably 3% or less, more preferably 2% or less, more preferably 1% or less. Further, the content of TiO _2, the glass composition B, preferably at least 0.01%, more preferably at least 0.5%.

In the glass composition B, MnO ₂ is a coloring component and an optional component. When the firing furnace for sintering the coating layer of the ceramic color paste is an IR furnace or the like, since MnO ₂ absorbs IR, there is an effect of easily softening the glass. When the raw material of the glass composition is melted with a Pt crucible or the like, the metal Bi generated during melting and Pt may be alloyed and the crucible may be damaged, but MnO ₂ contains oxygen at around 600 ° C. Since it discharges, the oxidation-reduction atmosphere during melting can be adjusted to the oxidation side. Therefore, reduction of Bi ₂ O ₃ in the glass composition can be suppressed and generation of metal Bi can be suppressed. If too much MnO _{2 is} contained, the sinterability may be deteriorated or the glass may be devitrified. When the glass composition B contains MnO ₂ , the content thereof is preferably 2.5% or less, more preferably 2% or less, and further preferably 1% or less in the glass composition B. Further, the content of MnO ₂ is in the glass composition B, preferably at least 0.01%, more preferably at least 0.3%.

  In the glass composition B, F, PbO, and CdO are all environmental pollutants, and thus are not substantially contained.

In the glass composition B, Ag ₂ O is an optional component. Ag ₂ O is very expensive as a raw material, but the color tone of the ceramic color layer can be adjusted by utilizing the above-described colloidalization of Ag. Therefore, when it is necessary to adjust the color tone of the ceramic color layer, the glass composition B can contain Ag ₂ O. In this case, the content of Ag ₂ O is preferably 1% or less, more preferably 0.5% or less, and further preferably 0.1% or less in the glass composition B. The content of Ag ₂ O is in the glass composition B, preferably at least 0.001%, more preferably at least 0.02%.

  In the glass composition B, MgO, CaO, BaO, and SrO are all optional components. These are components that facilitate vitrification, but as the content increases, the stability of the glass decreases and the glass tends to devitrify. For this reason, when the glass composition B contains MgO, CaO, BaO, and SrO, the total content thereof is preferably 0 to 20%, more preferably 0 to 10%, and more preferably 0 to 5 in the glass composition B. % Is more preferable.

In addition to the above components, the glass composition B is Fe ₂ O ₃ , CoO, CeO ₂ , Nb ₂ O ₃ , Ta ₂ O ₅ , Sb ₂ O ₃ , Cs ₂ O, P ₂ O ₅ , TiO ₂ , ZrO _2. , La ₂ O ₂ , SnO _X (x is 1 or 2) and the like can be contained as optional components. However, if the content of the optional component increases, the glass becomes unstable and devitrification may occur. Moreover, there exists a possibility that a glass transition point and a softening point may rise. Therefore, the total content of these optional components is preferably 10% or less in the glass composition B.

  It is preferable that the glass powder used in this embodiment contains the low softening point glass powder and the high softening point glass powder from said glass composition B. In this case, the softening point and the thermal expansion coefficient of the low softening point glass powder and the high softening point glass powder are the same as those of the first embodiment, and preferred aspects are also the same as those of the first embodiment. In this embodiment, the content ratio of the low softening point glass powder and the high softening point glass powder is a volume ratio indicated by the low softening point glass powder: the high softening point glass powder and is in the range of 10: 1 to 1:10. Preferably, it is in the range of 5: 1 to 1: 5.

Further, preferred embodiments of the content of the glass powder of the glass particle size of the powder (D _50, D _max etc.) and size distribution, the ceramic color composition to be used in the present embodiment, similar to the first embodiment is there.

[Refractory filler]
The refractory filler in the ceramic color composition according to the present embodiment is not particularly limited as long as it has a particle shape with an average aspect ratio of less than 8. The refractory filler in the present embodiment has peaks in the particle size distribution curve showing the volume-based frequency distribution measured by the laser diffraction scattering method between 0.1 to 8.4 μm and 8.5 to 30 μm, respectively. It is preferable to have.

  Preferred aspects of the shape, particle diameter, particle size distribution other than the particle size distribution curve, content, and the like of the refractory filler in the present embodiment are the same as those in the first embodiment.

[Heat-resistant pigment powder and optional additives]
In the ceramic color composition of the present embodiment, preferred aspects of the heat-resistant pigment powder and optional additives are the same as in the first embodiment.

[Ceramic color paste]
The ceramic color compositions of the first to third embodiments are, for example, a paste containing a vehicle containing an organic binder (hereinafter also referred to as “organic vehicle”) for application to the main surface of a glass plate. Used in the form. Examples of the organic vehicle include those obtained by dissolving a polymer material such as ethyl cellulose, acrylic resin, styrene resin, phenol resin or butyral resin in a solvent such as α-terpineol, butyl carbitol acetate, or phthalate ester as a binder. Preferably used. The concentration of the organic binder in such an organic vehicle is usually 3 to 15% by mass, and the organic binder as a solid content is 0.5 to 20 parts by mass per 100 parts by mass of the inorganic component in the ceramic color composition. Is preferably used in the range of 3 to 20 parts by mass.

  The ceramic color composition (ceramic color paste) formed into a paste in this way is used, for example, in the production of a glass plate with a ceramic color layer described below.

[Glass plate with ceramic color layer and manufacturing method thereof]
Next, a glass plate with a ceramic color layer using the ceramic color composition of the present embodiment and a manufacturing method thereof will be described. The glass plate with a ceramic color layer of the present embodiment is a ceramic color in which the glass plate and the first to third ceramic color compositions described above are baked onto at least a part of the main surface of the glass plate. And having a layer. In the ceramic color layer, one of the first to third ceramic color compositions may be used alone, or two or more may be used in combination.

  In the glass plate with a ceramic color layer of the present embodiment, as the glass plate, for example, soda lime glass is used as an automotive window glass. The ceramic color layer is provided, for example, on the peripheral edge of the glass plate. If this peripheral part is a glass plate for motor vehicles, for example, it will be peripheral parts, such as a windshield, a side glass, a rear glass, and a roof glass.

  The glass plate with a ceramic color layer which has a ceramic color layer in the peripheral part of a glass plate is demonstrated with reference to FIG. Fig.1 (a) is a top view which shows typically an example of the glass plate with a ceramic color layer which has a ceramic color layer in the peripheral part of a glass plate. FIG.1 (b) is CC sectional drawing of the glass plate with a ceramic color layer of Fig.1 (a). In the glass plate 1 with a ceramic color layer of this embodiment shown in FIGS. 1A and 1B, the ceramic color composition of the above embodiment is formed in at least a part of the main surface of the glass plate 2. A baked ceramic color layer 3 is provided.

  A glass plate 1 with a ceramic color layer shown in FIG. 1 includes a step of preparing a ceramic color paste containing an organic vehicle and the ceramic color composition of the above embodiment, and at least a part of the ceramic color paste on the main surface of the glass plate. And the step of heating the glass plate coated with the ceramic color paste to sinter the ceramic color composition into the glass plate.

  In the step of preparing the ceramic color paste, the ceramic color paste as described above is prepared using the ceramic color composition of the above embodiment as described above. Next, the ceramic color paste is applied to a desired region of the main surface of the glass plate 2. As a method for applying the ceramic color paste, a screen printing method, an ink jet method, or the like can be used. For example, it is preferable to print on a screen of # 150 to # 250 mesh.

  Next, the glass plate 2 on which the ceramic color paste is printed is dried. In the step of baking the ceramic color composition on the glass plate 2 (hereinafter also referred to as “baking step”), the dried glass plate 2 is heated using a baking furnace such as an IR furnace. The heating temperature is preferably 580 to 640 ° C. Thereby, the ceramic color composition applied to the glass plate 2 is baked on the glass plate 1 to form the ceramic color layer 3. Further, in the firing step, the glass plate 2 on which the ceramic color paste is printed may be subjected to self-weight bending molding or press bending molding in a state where the glass plate 2 is maintained at the above temperature. In press bending, for example, a glass plate is bent by a press device (heating press device) according to a desired shape of a window glass for an automobile. In self-weight bending, a glass plate can be bent by a self-weight bending apparatus. Furthermore, wind cooling strengthening or the like may be performed according to safety standards required for automobile window glass.

  Since the glass plate with the ceramic color layer obtained in this way is manufactured using the ceramic color composition of the above embodiment, the whisker-like refractory is not used, and the low temperature sinterability of the ceramic color composition, The high plate | board strength of the glass plate with a ceramic color layer can be made compatible.

Next, examples will be described.
The raw materials were prepared and mixed so as to have the compositions represented by mol% in Tables 2 to 4, melted at 1150 to 1350 ° C., and then rapidly cooled to obtain a flaky glass composition. Then, the flake-shaped glass was pulverized by a ball mill, D ₅₀ was obtained glass powder 3 to 5 [mu] m. The particle size distribution and the particle size were measured with Microtrac MT3300EXII (manufactured by Nikkiso Co., Ltd.). The solvent was water, and the measurement was carried out after dispersing with ultrasonic waves. With respect to the heat resistant pigment powder and the refractory filler, the particle size distribution and the particle diameter were measured in the same manner as the glass powder.
In addition, in the glass compositions of Tables 2 to 4, a blank means that the content ratio is less than 0.01%.

  The glass powder thus obtained was classified with an airflow classifier to obtain glass powder having a particle size distribution shown in Tables 2 to 4.

The obtained glass powder is subjected to differential thermal analysis in which the temperature is raised to 700 ° C. at 10 ° C./min, and the transition point (first inflection point), softening point (fourth inflection point) (unit: ° C.) and crystal Measure peak temperature (unit: ° C) and measure thermal expansion coefficient α (average linear expansion coefficient in the range of 50 to 300 ° C, unit: 10 ^-7 / ° C) using differential thermal dilatometer did.

  Next, the glass powder obtained above and the refractory filler and heat resistant pigment powder shown in Table 1 below were mixed at the ratios shown in Tables 2 to 4 to obtain ceramic color compositions. About the obtained ceramic color composition, the thermal expansion coefficient was measured similarly to the above.

In Table 1, the following were used as the refractory filler.
"Cordierite": AGC Ceramics Rotec M (specific gravity: 2.7, average aspect ratio: 1.5)
“Silica”: spherical silica FUSELX X (manufactured by Tatsumori Co., Ltd.) (specific gravity: 2.2, average aspect ratio: 1)
The refractory filler was pulverized by a ball mill, classified by airflow, and mixed with the classified refractory filler of each particle distribution to obtain a refractory filler having a particle size distribution shown in Table 1.
Moreover, as a whisker-like refractory filler, Arbolex Y (Shikoku Kasei Kogyo Co., Ltd., aluminum borate whisker) was used.

In Tables 2-4, the following were used as the heat resistant pigment powder.
“42-302A”: manufactured by Nippon Fellow, chromium-copper-manganese complex oxide black heat-resistant pigment powder, 42-302A (specific gravity: 5.3, D ₅₀ : 2.0 μm, D _max : 4.6 μm, volume) Standard particle size distribution (frequency distribution) peak: 2.1 μm)
“3300”: manufactured by Asahi Sangyo Co., Ltd., copper-iron-manganese complex oxide black heat resistant pigment powder, black 3300 (specific gravity: 4.8, D ₅₀ : 1.0 μm, D _max : 3.3 μm, particle size based on volume) Distribution (frequency distribution) peak: 1.0 μm)
“Black No. 1”: manufactured by The Shepherd Color, copper-chromium double oxide black heat resistant pigment powder, Black No. 1 (specific gravity: 5.5, D ₅₀ : 3.2 μm, D _max : 13.0 μm, Volume-based particle size distribution Particle size distribution (frequency distribution) peak: 3.3 μm)

  Next, to 80 parts by mass of the ceramic color composition, 20 parts by mass of an α-terpineol solution in which 10% of ethyl cellulose is dissolved in terms of mass percentage is added and kneaded, and homogeneously dispersed by a three-roll mill. Simply referred to as “paste”). The paste thus obtained was screen-printed in a size of 9 × 9 cm with a # 180 mesh on the main surface of a soda-lime glass plate having a thickness of 3.5 mm and a size of 10 cm × 10 cm, and dried.

  The following evaluation was performed about the glass plate which printed the ceramic color paste above. The results are shown in Tables 2 to 4 together with the characteristics and blending amounts of each component of the ceramic color composition.

[Printability evaluation]
When the ceramic color paste was printed, “X” indicates that many pinholes were confirmed on the printed surface, and “◯” indicates that no pinholes were confirmed.

[Low-temperature sintering evaluation]
The glass plate coated with the ceramic color paste was baked by holding at 580 ° C. for 4 minutes, and then cooled to room temperature to obtain a glass plate with a ceramic color layer. About this glass plate with a ceramic color layer, color difference (DELTA) E was measured. The color difference ΔE is the color difference between the reference colored glass plate (L * = 21, a * = 0.7, b * = − 0.3) and the non-printed surface of the sample, and a color difference meter (CR-manufactured by Minolta Co., Ltd.). 400). The color difference ΔE is preferably 1.0 or less. If it exceeds 1.0, the sinterability of the ceramic color composition is insufficient, and the ceramic color layer may appear whitish when viewed from the non-printed side. The color difference ΔE is more preferably 0.7 or less.

[Plate strength evaluation]
The glass plate coated with the paste was fired by holding at 640 ° C. for 4 minutes, and then cooled to room temperature to obtain a glass plate with a ceramic color layer. About this glass plate with a ceramic color layer, plate | board strength was evaluated as follows. The glass plate with the ceramic color layer was placed on a ring having a diameter of 10 cm so that the ceramic color layer was below, and the glass plate with the ceramic color layer was pressed from above with a 5 mm diameter ball at a rate of 1 mm / min. The position where the ball is pressed is the center of the ring. Thus, the strength [kgf] when the glass plate with the ceramic color layer was broken was measured. Thus, the board strength was measured 10 times and the average value was calculated.

[Acid resistance evaluation]
The glass plate coated with the paste was fired by holding at 600 ° C. for 4 minutes, and then cooled to room temperature to obtain a glass plate with a ceramic color layer. This glass plate with a ceramic color layer was immersed in a 0.1 N sulfuric acid aqueous solution at 80 ° C. for 4 hours, and visually confirmed from the side of the soda lime glass plate was x. "

[Strength evaluation after formation of Ag layer]
The Ag paste was printed in the center with a size of 3 × 3 cm on the glass plate coated with the paste, and dried. The glass plate coated with this Ag paste was fired by holding at 600 ° C. for 4 minutes, and then cooled to room temperature to obtain a glass plate with a ceramic color layer with an Ag layer.

  This glass plate with a ceramic color layer with Ag is placed on a ring with a diameter of 10 cm so that the ceramic color layer is below, and a glass with a ceramic color layer with Ag at a speed of 5 mm / min using a 10 mm diameter ball. The plate was pressurized from above. The position where the ball is pressed is the center of the ring. Thus, strength [kgf] when the glass plate with the ceramic color layer with the Ag layer was broken was measured. In this way, the plate strength after the formation of the Ag layer was measured 10 times, and the average value and (average value −3σ) were calculated (“σ” represents the standard deviation of 10 times measurement).

[Solder adhesion evaluation]
Sn—Pb solder was soldered at 400 ° C. to the Ag layer surface of the glass plate with the ceramic color layer with Ag layer. The case where the Sn—Pb solder was easily peeled from the Ag layer surface by hand was indicated as x, and the case where the Sn—Pb solder was not peeled off was indicated as ◯.

  From Tables 2-4, according to the ceramic color composition of Examples 1-31, the glass plate with a ceramic color layer of the board strength equivalent or more than the comparative example 1 using the whisker-like refractory filler was obtained. I understand that. Moreover, it turns out that the ceramic color composition of Examples 1-31 is excellent in low-temperature sintering property, and can acquire sufficient printability, the acid resistance of a glass plate with a ceramic color layer, and solder wettability. On the other hand, in Comparative Example 2, the printability is inferior, and in Comparative Examples 3 and 5, the low-temperature sinterability is not sufficient. Moreover, in the comparative example 4, it turns out that the board strength at the time of forming an Ag layer is low.

DESCRIPTION OF SYMBOLS 1 ... Glass plate with a ceramic color layer, 2 ... Glass plate, 3 ... Ceramic color layer

Claims (9)

A ceramic color composition containing glass powder, a refractory filler, and a heat-resistant pigment powder,
The refractory filler has a particle shape with an average aspect ratio of less than 8, and has a particle size distribution curve showing a volume-based frequency distribution measured by a laser diffraction scattering method between 0.1-8.4 μm and 8. Each having a peak between 5 and 30 μm,
The glass powder is expressed in mol% in terms of oxide,
40-55% of _SiO 2,
5-15% B ₂ O ₃ ,
5-30% ZnO,
At least one selected from the group consisting of 10 to 25% Li ₂ O, Na ₂ O and K ₂ O;
0 to 3% _Al 2 _O 3,
5-25% Bi ₂ O ₃ ,
0.1-8% CuO,
0-3% of _MnO 2,
0-5% MgO,
0-5% CaO,
0-5% BaO and 0-5% SrO
A ceramic color composition comprising SiO ₂ / B ₂ O ₃ of 3.5 to 6.5 and substantially free of F, PbO and CdO. The glass powder is
A low softening point glass powder which is the glass composition having a softening point of 490 ° C. to 530 ° C. and a thermal expansion coefficient of 89 × 10 ⁻⁷ / ° C. to 97 × 10 ⁻⁷ / ° C .;
One or two or more kinds of high softening point glass powders each having a softening point of 530 ° C. to 570 ° C. and a thermal expansion coefficient of 79 × 10 ⁻⁷ / ° C. to 87 × 10 ⁻⁷ / ° C. Including
The content ratio of the low softening point glass powder and the high softening point glass powder is 10: 1 to 1:10 in a volume ratio indicated by the low softening point glass powder: the high softening point glass powder. The ceramic color composition as described. A ceramic color composition containing glass powder, a refractory filler, and a heat-resistant pigment powder,
The refractory filler has a particle shape with an average aspect ratio of less than 8;
The glass powder is expressed in mol% in terms of oxide,
40-55% of _SiO 2,
5-15% B ₂ O ₃ ,
5-30% ZnO,
At least one selected from the group consisting of 10 to 25% Li ₂ O, Na ₂ O and K ₂ O;
0 to 3% _Al 2 _O 3,
5-25% Bi ₂ O ₃ ,
0.1-8% CuO,
0-5% MgO,
0-5% CaO,
0-5% BaO,
A glass composition containing 0 to 5% SrO and 0 to 3% MnO ₂ , SiO ₂ / B ₂ O ₃ being 3.5 to 6.5 and substantially free of F, PbO and CdO. Yes,
A low softening point glass powder which is the glass composition having a softening point of 490 ° C. to 530 ° C. and a thermal expansion coefficient of 89 × 10 ⁻⁷ / ° C. to 97 × 10 ⁻⁷ / ° C .;
One or two or more kinds of high softening point glass powders each having a softening point of 530 ° C. to 570 ° C. and a thermal expansion coefficient of 79 × 10 ⁻⁷ / ° C. to 87 × 10 ⁻⁷ / ° C. Including
The content ratio of the low softening point glass powder and the high softening point glass powder is 10: 1 to 1:10 in a volume ratio indicated by the low softening point glass powder: the high softening point glass powder. A ceramic color composition. A ceramic color composition containing glass powder, a refractory filler, and a heat-resistant pigment powder,
The refractory filler has a particle shape with an average aspect ratio of less than 8;
The glass powder is expressed in mol% in terms of oxide,
45-60% of _SiO 2,
1-5% B ₂ O ₃ ,
5-15% ZnO,
At least one selected from the group consisting of 5 to 15% Li ₂ O, Na ₂ O and K ₂ O;
0 to 3% _Al 2 _O 3,
15-35% Bi ₂ O ₃ ,
0.1-8% CuO,
0-3% of _MnO 2,
0-5% MgO,
0-5% CaO,
0-5% BaO and 0-5% SrO
And a glass composition substantially free of F, PbO and CdO.   The refractory filler has a peak between 0.1 to 8.4 μm and 8.5 to 30 μm, respectively, in a particle size distribution curve showing a volume-based frequency distribution measured by a laser diffraction scattering method. Item 5. The ceramic color composition according to Item 4. The glass powder is
A low softening point glass powder which is the glass composition having a softening point of 490 ° C. to 530 ° C. and a thermal expansion coefficient of 89 × 10 ⁻⁷ / ° C. to 97 × 10 ⁻⁷ / ° C .;
One or two or more kinds of high softening point glass powders each having a softening point of 530 ° C. to 570 ° C. and a thermal expansion coefficient of 79 × 10 ⁻⁷ / ° C. to 87 × 10 ⁻⁷ / ° C. Including
The content ratio of the low softening point glass powder and the high softening point glass powder is 10: 1 to 1:10 in a volume ratio indicated by the low softening point glass powder: the high softening point glass powder. Or the ceramic color composition of 5.   The ceramic color composition according to any one of claims 1 to 6, wherein the refractory filler is at least one selected from the group consisting of cordierite, alumina, zircon, and silica.   It has a glass plate and the ceramic color layer by which the ceramic color composition of any one of Claims 1-7 was baked in the at least one part area | region on the main surface of the said glass plate. Glass plate with ceramic color layer. Preparing a ceramic color paste comprising an organic vehicle and the ceramic color composition of any one of claims 1-7;
Applying the ceramic color paste to at least a portion of the main surface of the glass plate;
Heating the glass plate coated with the ceramic color paste and baking the ceramic color composition onto the glass plate. A method for producing a glass plate with a ceramic color layer.

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