JP7157029B2 - CERAMIC COLOR PASTE, CERAMIC COLOR AND GLASS WITH CERAMIC COLOR, AND METHOD OF MANUFACTURING SAME - Google Patents

Description

The present invention provides a ceramic color paste, a ceramic color, a glass with a ceramic color to which the ceramic color is applied, and the production thereof, for coloring and molding by baking on a glass plate serving as a substrate for various types of glass, for example, glass for automobiles. It relates to a method (molding method).

Among automotive glasses, fixed panes such as windshields, side glasses, rear glasses and sunroof glasses are attached to the vehicle body using organic adhesives. The peripheries of each glass attached to the vehicle body are coated with door glass in order to prevent organic adhesives from deteriorating due to sunlight, to hide surplus adhesives (adhesives that protrude) from the adhesive areas, and to improve the design of the glass. Such sliding window glass is colored black or dark gray in order to reduce sliding resistance and improve design. Such automotive glass is generally produced by screen-printing a ceramic color (black ceramic) paste formed of fusible glass frit containing a black pigment on the periphery of a flat glass plate cut into a predetermined shape. After that, the glass plate is bent by heating, and at the same time, the ceramic color paste is baked on the glass plate, followed by cooling.

In recent years, in order to improve productivity and bending accuracy, a bending forming method for automobile window glass has been performed by installing a press machine in a heating furnace or the like. A problem in press molding is the release of the press die from the ceramic collar. More specifically, mold releasability in press molding is reduced when the heated and melted ceramic collar adheres to the heat-resistant cloth (stainless cloth, glass cloth, etc.) used on the surface of the press mold. In particular, with the diversification of automobile designs in recent years, demands for deep bending of glass and molding into complex shapes have increased, making mold separation an important issue.

WO2013/146264 (Patent Literature 1) discloses a composition comprising a glass frit, a vehicle, a heat-resistant pigment, and heat-resistant large-diameter particles, and wherein the heat-resistant large-diameter particles provide an average thickness of a dry coating film for forming a ceramic color. Ceramic color pastes are disclosed having particle sizes larger than .

However, since this ceramic color paste contains heat-resistant large-diameter particles that are larger in diameter than the thickness of the dry coating film, although it is excellent in releasability, the coating film surface becomes uneven, and the particles can be seen through glass. Transparent, high transmittance and low concealability.

Further, in the step of cooling the glass plate, the glass plate is strengthened by rapidly cooling after heating the glass plate. However, since the ceramic collar and the glass plate generally have different coefficients of thermal expansion, a tensile stress acts on the surface of the glass plate from the ceramic collar in the cooling process, and the surface compressive stress of the glass plate decreases. Therefore, in general, there is a problem that the strength of the glass plate is lowered in the region with the ceramic color. However, the ceramic color paste of Patent Document 1 also has low strength.

Japanese Patent Application Laid-Open No. 6-234547 (Patent Document 2) discloses that the inorganic component contains 5 to 35% by weight of colored heat-resistant pigment powder, 65 to 95% by weight of crystallized glass powder, and 0 to 10% by weight of refractory filler powder. Japanese Patent Application Laid-Open No. 6-256039 (Patent Document 3) discloses that the inorganic component is 20 to 68 parts by weight of crystalline glass frit and 2 to 30 parts by weight of amorphous glass frit. , 20 to 40 parts by weight of a heat-resistant color pigment, and 0 to 10 parts by weight of a refractory filler.

However, when crystallized glass is blended, part of the crystallized glass is crystallized by heating and baked into the glass. descend. _In addition, in compositions containing crystallized glass, bismuth _- based glass is often used as glass frit that is low-melting glass and does not contain lead. When the amount of Bi is increased and the amount of crystallized components is increased, the acid resistance is lowered.

Japanese Patent Application Laid-Open No. 6-239647 (Patent Document 4) discloses that the composition is applied to a predetermined portion of a glass plate, sintered, fused and crystallized on the glass plate, and then the glass plate is pressed by a pressing device provided in a furnace. A ceramic color composition suitable for bending, the inorganic components of which are 5-30% by weight of colored heat-resistant pigment powder, 70-95% by weight of crystallized glass powder, and 1.5-2.5% by weight of alumina powder. %. In addition, JP-A-2000-154038 (Patent Document 5) describes 5 to 40.5% by weight of colored heat-resistant pigment powder, 50 to 94% by weight of glass powder, 0 to 25% by weight of refractory filler, and whisker-like refractory powder. A ceramic color composition is disclosed characterized by comprising 0.1 to 40% by weight of a monofilament filler. In addition, Japanese Patent Application Laid-Open No. 2002-362940 (Patent Document 6) describes lead-free glass powder: 63 to 78.99% by mass, heat-resistant whiskers: 5 to 12% by mass, and dibismuth trioxide powder: 0.01 to 1% by mass. %, heat-resistant pigment powder: 16-26 mass %. Furthermore, Japanese Patent Application Laid-Open No. 2016-79084 (Patent Document 7) has a glass powder and a particle shape having an average aspect ratio of less than 8, and a particle size showing a volume-based frequency distribution measured by a laser diffraction scattering method. A ceramic color composition is disclosed that contains a refractory filler and a refractory pigment powder having peaks in the distribution curve between 0.1 and 8.4 μm and between 8.5 and 30 μm, respectively.

However, even if the whisker-like refractory is blended, the releasability is improved, but the distribution volume of the whisker-like refractory has been decreasing in recent years because the evaluation of the effects on the human body is unclear. Furthermore, whisker-like refractories include, for example, aluminum borate, alumina, potassium titanate, and zircon. Performance such as durability is reduced.

WO2013/146264 (Claim 1) Japanese Patent Application Laid-Open No. 6-234547 (Claim 1) Japanese Patent Application Laid-Open No. 6-256039 (Claim 1) Japanese Patent Application Laid-Open No. 6-239647 (Claim 1) Japanese Patent Application Laid-Open No. 2000-154038 (Claim 1) Japanese Patent Application Laid-Open No. 2002-362940 (Claim 1) JP 2016-79084 A (Claim 1)

Accordingly, an object of the present invention is to provide a ceramic color paste, a ceramic color, a glass with a ceramic color, and a method for producing the same, which can improve mold release properties during molding while maintaining sinterability and appearance such as color tone and transmittance. to provide.

Another object of the present invention is to provide a ceramic color paste, a ceramic color, a ceramic color glass, and a method for producing the same, which are excellent in acid resistance such as acid rain resistance and which can improve the strength of the ceramic color glass. .

Still another object of the present invention is to provide a ceramic color paste, a ceramic color, a glass with a ceramic color, which can suppress adhesion of the ceramic color to the press mold and can be easily separated from the press mold after firing, and a method for producing the same. to do.

The present inventors have made intensive studies to achieve the above object, and found that a glass frit having a softening point lower than the molding temperature, a heat-resistant pigment, and a glass filler of a specific size having a softening point higher than the molding temperature. The inventors have found that when a ceramic color paste is prepared in combination with a silicone-based resin, it is possible to improve mold release during molding while maintaining sinterability and appearance such as color tone and transmittance, and completed the present invention.

That is, the ceramic color paste of the present invention contains a glass frit having a softening point lower than the molding temperature, a heat-resistant pigment, a glass filler having a softening point higher than the molding temperature, and a silicone resin. The molding temperature may be the press temperature. The decomposition temperature of the silicone-based resin was measured using a thermogravimetric differential thermal analyzer (TG-DTA) under the condition that the temperature was raised from 40° C. to 750° C. at a heating rate of 20° C./min in an air atmosphere. In some cases, a silicone-based resin having a thermal decomposition finish temperature of 550° C. or higher may be included. A silicone-based resin having a thermal decomposition end temperature of 550° C. or higher may have a residue of about 40 to 70% by mass at the thermal decomposition end temperature. The silicone resin may contain a silicone resin soluble in an organic solvent such as butyl carbitol acetate. The silicone resin may include a C _1-4 alkyl C _6-10 aryl silicone resin. The ratio of the silicone-based resin may be about 0.1 to 50 parts by mass with respect to 100 parts by mass as the total amount of the glass frit and the heat-resistant pigment. The glass filler may be glass beads with a particle size range of 2-30 μm (especially 2-20 μm) and/or glass fibers with a fiber diameter range of 10-30 μm and a fiber length range of 10-50 μm. The proportion of the glass filler may be 12 to 26 parts by mass (particularly 20 to 25 parts by mass) with respect to 100 parts by mass as the total amount of the glass frit and the heat-resistant pigment. The glass frit may contain at least one selected from the group consisting of bismuth-based glass frit, silica-based glass frit, zinc-based glass frit, and lead-based glass frit. The ceramic color paste of the present invention may further contain a vehicle.

The present invention also includes a method of producing the ceramic color paste by mixing a glass frit, a heat-resistant pigment, a glass filler, and a silicone-based resin. In this method, the silicone-based resin is decomposed under the condition that the temperature is raised from 40° C. to 750° C. at a heating rate of 20° C./min in an air atmosphere using a thermogravimetric differential thermal analyzer (TG-DTA). It may contain a silicone resin having a thermal decomposition completion temperature of 550° C. or higher when the temperature is measured, and the silicone resin may be dissolved in a dispersion medium and then mixed with a glass frit, a heat-resistant pigment, and a glass filler.

The present invention also includes a ceramic color formed by firing the ceramic color paste.

The present invention provides a glass with a ceramic color, comprising a glass substrate and a ceramic color paste film, wherein the ceramic color is formed in at least a part of a region of at least one surface of the glass substrate. Also included are glass with ceramic colors that are laminated with membranes.

The present invention includes a lamination step of laminating a ceramic color film formed of the ceramic color on at least a part of a region of at least one surface of a glass substrate, and Also included is a method for producing ceramic-colored glass, which includes a bending-forming step of heating and bending at the above temperature and simultaneously firing the ceramic color paste. The bending step may include press forming.

The ceramic color paste of the present invention combines a glass frit having a softening point lower than the molding temperature, a heat-resistant pigment, a glass filler having a softening point higher than the molding temperature, and a silicone resin. It is possible to improve the releasability from the mold during molding while maintaining appearance properties such as binding properties, color tone and transmittance. In addition, it is excellent in acid resistance such as acid rain resistance, and can improve the strength of the ceramic-colored glass. Furthermore, it is possible to prevent the ceramic collar from adhering to the press mold and to easily separate it from the press mold after firing.

FIG. 1 is a schematic diagram for explaining a method for measuring the strength of a glass plate with a ceramic collar obtained in Examples.

[Ceramic color paste]
The ceramic color paste (or ceramic color composition) of the present invention contains a glass frit having a softening point lower than the molding temperature, a heat-resistant pigment, a glass filler having a softening point higher than the molding temperature, and a silicone resin.

(glass frit)
The glass frit (fusible glass powder or particles) is blended to form a ceramic color film and fixed to the glass plate, and may be any glass frit that softens at the molding temperature.

As the glass frit, a customary glass frit used in ceramic collars can be used. Common glass frits include, for example, bismuth-based glass frit, silica-based glass frit, zinc-based glass frit, borosilicate-based glass frit, zinc borosilicate-based glass frit, and lead-based glass frit. These glass frits can be used alone or in combination of two or more.

Among these, bismuth-based glass frit, silica-based glass frit, zinc-based glass frit, lead-based glass frit, and the like are widely used. , preferably at least a bismuth-based glass frit.

The bismuth-based glass frit only needs to contain bismuth oxide (Bi ₂ O ₃ ), and may contain other oxides in addition to bismuth oxide. Other oxides include, for example, other metal oxides (for example, alkali metal oxides such as lithium oxide, sodium oxide and potassium oxide; alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide and barium oxide; periodic table group 4A metal oxides such as titanium oxide and zirconium oxide; periodic table group 6A metal oxides such as chromium oxide; periodic table group 8 metal oxides such as iron oxide; periodic table such as zinc oxide Group 2B metal oxides; Group 3B metal oxides of the periodic table such as aluminum oxide; Group 4B metal oxides of the periodic table such as tin oxide and lead oxide), silicon oxide, boron oxide and the like. These other oxides can be used alone or in combination of two or more. Among these other oxides, they often contain lithium oxide, sodium oxide, barium oxide, zinc oxide, lead oxide, silicon oxide, boron oxide, and the like. The proportion of bismuth oxide is, for example, 10% by mass or more, preferably 15% by mass or more (eg, 15 to 95% by mass), more preferably 20 to 90% by mass (especially 30 to 80% by mass), relative to the entire bismuth-based glass frit. % by mass).

When the glass frit contains the bismuth-based glass frit, the ratio of the bismuth-based glass frit in the glass frit may be 10% by mass or more, preferably 50% by mass or more, more preferably 80% by mass or more (especially 90% by mass). % or more), and may be 100% by mass.

The softening point (or melting point) of the glass frit should be lower than the forming temperature (heating temperature for bending, especially pressing temperature), for example, it can be selected from a range of about 350 to 700 ° C., which is lower than the pressing temperature for press forming. For example, it may be 360 to 650°C, preferably 400 to 600°C, more preferably 450 to 580°C (especially 500 to 550°C). If the softening point is too low, the strength of the glass may be lowered.

The average particle size of the glass frit may be, for example, about 0.1 to 10 μm, preferably 0.3 to 8 μm, more preferably 0.5 to 5 μm (especially 1 to 4 μm). If the particle size of the glass frit is too large, the printability and the uniformity of the fired film are deteriorated, and clogging is likely to occur in screen printing or the like. On the other hand, if the particle size is too small, the dispersibility of the glass frit is lowered, so that the printability of the ceramic color paste may be lowered and the economic efficiency may be lowered.

The proportion of the glass frit in the ceramic color paste can be selected from the range of about 30 to 95% by mass, for example 40 to 95% by mass, preferably 45 to 80% by mass, more preferably 50 to 75% by mass (especially 50 to 70% by mass). % by mass). If the proportion of the glass frit is too high, the color tone of the ceramic color may be lowered, and if it is too low, the adhesion to the glass substrate may be reduced.

(Heat resistant pigment)
A heat-resistant pigment is blended to impart a desired color to the ceramic color. As the heat-resistant pigment, a commonly used heat-resistant pigment can be used as long as it can withstand the firing temperature of the ceramic color paste.

Examples of heat-resistant pigments include black pigments (copper-chromium composite oxide, iron-manganese composite oxide, copper-chromium-manganese composite oxide, cobalt-iron-chromium composite oxide, magnetite, etc.), and brown pigments. (zinc-iron composite oxide, zinc-iron-chromium composite oxide), blue pigment (cobalt blue, etc.), green pigment (chromium green, cobalt-zinc-nickel-titanium composite oxide, cobalt-aluminum-chromium) composite oxides, etc.), red pigments (red iron oxide, etc.), yellow pigments (titanium yellow, titanium-barium-nickel composite oxides, titanium-antimony-nickel composite oxides, titanium-antimony-chromium composite oxides, etc.), white pigments (titanium white, zinc oxide, etc.). These heat-resistant pigments can be used alone or in combination of two or more.

These heat-resistant pigments are selected according to the desired color, and black heat-resistant pigments (for example, composite oxide black such as copper-chromium-manganese composite oxide) are commonly used.

Examples of the shape of the heat-resistant pigment include substantially spherical, ellipsoidal, polygonal (polypyramidal, cubic, cuboid, etc.), plate-like, rod-like, and irregular shapes. Among these shapes, an isotropic shape (substantially spherical shape, etc.) is preferable in terms of dispersibility, color tone, and the like.

The average particle size of the heat-resistant pigment is, for example, about 0.1 to 10 μm, preferably 0.2 to 5 μm, more preferably 0.3 to 4 μm (especially 0.5 to 3 μm). If the particle size of the heat-resistant pigment is too small, it may become difficult to disperse it evenly, resulting in deterioration of the color developability.

The proportion of the heat-resistant pigment in the ceramic color paste is, for example, about 5 to 50% by mass, preferably 10 to 40% by mass, more preferably 15 to 30% by mass (especially 18 to 25% by mass). The proportion of the heat-resistant pigment is, for example, 1 to 100 parts by weight, preferably 10 to 60 parts by weight, more preferably 20 to 50 parts by weight (especially 30 to 45 parts by weight) with respect to 100 parts by weight of the glass frit. . If the proportion of the heat-resistant pigment is too large, the strength of the ceramic color film may be reduced, and if it is too small, the color developability may be reduced.

(glass filler)
The glass filler (heat-resistant glass powder or particles) is added to form a ceramic-colored film and to improve the releasability during molding, and any glass filler that does not soften at the molding temperature may be used. In the present invention, by blending as a filler a glass filler that does not soften (melt) at the molding temperature (heating temperature for bending), particularly at the press temperature for press molding, it is possible to suppress the flow of the molten ceramic color, and during pressing, It is presumed that the contact area between the surface fibers of the press mold (forming die) and the molten ceramic color is reduced, and the mold separation is improved.

Furthermore, in the present invention, by adjusting the particle diameter of the glass filler within the range described later, the release property in press molding can be further improved. On the other hand, in Patent Document 1, by making the heat-resistant large-diameter particles larger than the thickness of the dry coating film, the mold release property during molding is improved. It is especially effective in glass. In other words, in the case of bending laminated glass, the surface in contact with the ceramic collar is a flat surface (glass surface). When the color is not touched, the releasability is exhibited. In the case of particles smaller than the film thickness, the particles are pushed by the laminated glass and enter the inside of the film, and the ceramic color on the surface and the glass come into contact with each other. Therefore, in the bending of laminated glass, it is necessary that the large-diameter particles protrude from the film in the state of a dry film because the ceramic color-printed glass and the facing glass are placed in a heating furnace.

In contrast, the present invention is particularly suitable for release from press molding rather than laminated glass. In the case of press molding, since the glass on which the ceramic color is printed is heated and held and then pressed, there is little need for the glass filler to protrude from the film in the state of a dry film as in laminated glass. Furthermore, in press molding, the press surface that comes into contact with the ceramic collar is covered with a heat-resistant cloth such as stainless steel cloth. If the particles are incompletely large, the fibers will enter the gaps between the particles and adhere to the ceramic collar. Therefore, in press molding, the greater the number of contact surfaces between the particles and the press mold, the more the releasability can be improved. . The reason for this is that the number of small glass filler particles present in the film is large, so the distance between the particles becomes short, and it acts as a filler that is uniformly present throughout the film (the surface area of the glass filler increases). It can be presumed that this is because the contact surface with the glass beads increases.

Examples of the shape of the glass filler include substantially spherical, ellipsoidal, polygonal (polypyramidal, cubic, cuboid, etc.), plate-like, rod-like, fibrous, and irregular shapes. Of these shapes, isotropic (substantially spherical, cubic, etc.) granular and fibrous shapes are commonly used, and substantially spherical shapes are particularly preferred because they have a small contact area with the surface of the press mold (press surface). The glass filler is preferably primary particles (independent integral particles or monolayer particles), but may be secondary particles in which small particles are agglomerated as long as they can exist stably.

As described above, the glass filler preferably has a predetermined size in order to improve the release property during molding.

When the glass filler is granular (glass beads), the particle size range (range from minimum particle size to maximum particle size) may be about 1 to 50 μm, for example, 2 to 30 μm, preferably 2 to 20 μm, and further It is preferably about 2 to 10 μm. In particular, when the particle diameter range of the granular glass filler is 30 μm or less (especially 15 μm or less), it is possible to achieve both mold releasability during molding and strength of the ceramic-colored glass by combining with the silicone resin. The volume average particle size of the particulate glass filler is, for example, about 3 to 20 μm, preferably 3 to 15 μm, more preferably about 4 to 10 μm. If the particle size of the granular glass filler is too small, uniform dispersion may become difficult, and there is a risk that the release from the mold during molding may deteriorate. There is a possibility that the releasability may be deteriorated due to close contact with the ceramic collar.

In the present specification and claims, the method for measuring the particle size range and the volume average particle size of particles is not particularly limited. Available.

When the glass filler is fibrous (glass fiber), the fiber diameter range (range from minimum fiber diameter to maximum fiber diameter) may be about 5 to 30 μm, for example, 10 to 30 μm, preferably 10 to 25 μm, and further It is preferably about 10 to 20 μm. The average fiber diameter of the fibrous glass filler is, for example, about 5-20 μm, preferably about 8-18 μm, more preferably about 10-15 μm. If the fiber diameter of the fibrous glass filler is too small, it will be difficult to disperse it evenly, and there is a risk that the release from the mold during molding will decrease. There is a possibility that the releasability of the mold may be deteriorated by entering the gap and coming into close contact with the ceramic collar.

The fiber length range of the fibrous glass filler (range from minimum fiber length to maximum fiber length) may be about 10 to 100 μm, for example, 10 to 50 μm, preferably 15 to 45 μm, more preferably about 20 to 40 μm. . The average fiber length of the fibrous glass filler is, for example, about 10-50 μm, preferably about 15-45 μm, more preferably about 20-40 μm. If the fiber length of the fibrous glass filler is out of this range, uniform dispersion may be difficult, and there is a risk that the release from the mold during molding may deteriorate.

In the present specification and claims, the method for measuring the fiber diameter or fiber length range and the average fiber diameter or fiber length of the fiber is not particularly limited. A known measurement method such as a method of observing a cross section or fiber length can be used.

The softening point (or melting point) of the glass filler may be higher than the molding temperature (the heating temperature for bending, particularly the pressing temperature), and can be selected from a range of, for example, 600° C. or higher (eg, about 600 to 2000° C.). For example, 650 to 1800°C, preferably 700 to 1500°C, more preferably 750 to 1200°C (especially 800 to 1000°C). If the softening point is too low, the releasability may deteriorate.

Examples of glass constituting the glass filler include soda glass (soda lime glass or soda lime silica glass), borosilicate glass, crown glass, barium-containing glass, strontium-containing glass, boron-containing glass, low-alkali glass, and alkali-free glass. , silica glass, quartz glass, and heat-resistant glass. These glasses can be used alone or in combination of two or more. Among these, soda glass, borosilicate glass, quartz glass, heat-resistant glass, and the like are preferable.

The proportion of the glass filler is, for example, 10 to 30 parts by mass, preferably 12 to 26 parts by mass, more preferably 15 to 25 parts by mass (especially 20 to 24 parts by mass). In particular, when the ratio of the glass filler is adjusted to about 20 to 25 parts by mass with respect to the total amount of 100 parts by mass and the size is adjusted to the above range, various properties can be improved in a well-balanced manner. If the proportion of the glass filler is too small, there is a risk that the release property during molding will be reduced, and if it is too high, there is a risk that the appearance such as transmittance and sinterability will be reduced.

(silicone resin)
In the present invention, the glass frit, the heat-resistant pigment, and the glass filler are combined with a silicone-based resin (silicone-based resin) to suppress the decrease in glass strength due to the ceramic color. The details of the mechanism that can suppress the decrease in glass strength are unknown, but compared to other organic compounds, silicone is heat resistant and has a high thermal decomposition temperature. However, since it is still in the process of being decomposed, it is presumed that when it is added to the ceramic color, porosity is generated in the film, the surface compressive stress is relieved, and the strength of the glass is improved.

The silicone-based resin may be a thermoplastic resin, a curable resin (uncrosslinked resin), or a curable resin (crosslinked resin) having a polyorganosiloxane skeleton. The polyorganosiloxane skeleton is a linear, branched or network compound having a Si—O bond (siloxane bond) and has the formula: R _a SiO _(4-a)/2 (wherein R is represents a substituent, and the coefficient a is a number from 0 to 3). Examples of silicone resins include monofunctional M units (generally represented by R ₃ SiO _1/2 ) and bifunctional D units (generally R ₂ SiO _2/2 ), trifunctional T units (commonly represented by RSiO _3/2 ), tetrafunctional Q units (commonly represented by SiO _4/2 ). of the units), polyorganosiloxanes containing T units as main units are usually used.

In the above formula, the substituent R includes, for example, a C _1-10 alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group and the like. C _2-10 alkenyl groups such as halogenated C _1-10 alkyl groups, vinyl groups, allyl groups and butenyl groups, C _6-20 aryl groups such as phenyl groups, tolyl groups and naphthyl groups, cyclopentyl groups and cyclohexyl groups and C _6-12 aryl-C _1-4 alkyl groups such as a C _3-10 cycloalkyl group, a benzyl group and a phenethyl group. These substituents can be used alone or in combination of two or more.

Among these, R is preferably a C _1-4 alkyl group such as a methyl group or a propyl group, a C _6-10 aryl group such as a phenyl group or a naphthyl group, a C _1-3 alkyl group, or a C _6-8 aryl group. group is more preferred, and methyl group and phenyl group are most preferred. Furthermore, as R, it is preferable to use two or more in combination from the viewpoint that the strength of the _ceramic colored glass, the appearance such as color tone, and the mold release property can be improved at the same time, rather than being used alone. A combination of a ₄ alkyl group and a C _6-10 aryl group is preferred, a combination of a C _1-3 alkyl group and a C _6-8 aryl group is more preferred, and a combination of a methyl group and a phenyl group is most preferred.

When a C _1-4 alkyl group and a C _6-10 aryl group are combined, the molar ratio of the two is selected from the range of about C _1-4 alkyl group/C _6-10 aryl group = 10/1 to 1/30. For example, 5/1 to 1/20, preferably 1/1 to 1/10, more preferably 1/1.5 to 1/5, more preferably 1/2 to 1/3.

The silicone resin may be a straight silicone resin or a modified silicone resin. Modified silicone resins include, for example, silicone resins modified with other resins such as alkyd resins, phenol resins, urea resins, melamine resins, and epoxy resins.

Specifically preferred silicone-based resins include C _1-4 alkyl-based silicone resins in which the substituent R is a C _1-4 alkyl group such as a methyl group (for example, C _1-3 alkyl-based silicone resins such as methyl-based silicone resins). resins), _6-10 aryl silicone resins in which the substituent R is a C _6-10 aryl group such as a phenyl group (e.g., C _6-8 aryl silicone resins such as a phenyl silicone resin), C _1-4 alkyl C _6-10 aryl silicone resins that are a combination of a C _1-4 alkyl group and a C _6-10 aryl group (for example, C _{1- 3} alkyl C _6-8 aryl silicone resins, etc.). These silicone resins can be used alone or in combination of two or more. Among these, alkylaryl-based silicone resins such as C _1-4 alkyl C _6-10 aryl-based silicone resins are preferable because they can improve appearance such as color tone, and because they can achieve both the above-mentioned appearance and glass strength. C _1-2 alkyl C _6-8 aryl-based silicone resins such as , methylphenyl-based silicone resins are particularly preferred.

The molecular weight of the silicone resin is not particularly limited, but the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography is, for example, 500 to 5000, preferably 1000 to 4000, more preferably 1500 to 3500 (particularly 2000 to 3000), more preferably about 1500 to 2500.

When the decomposition temperature of the silicone-based resin is measured using a thermogravimetric differential thermal analyzer (TG-DTA) under the condition that the temperature is raised from 40 ° C. to 750 ° C. at a temperature increase rate of 20 ° C./min in an air atmosphere. can be selected from a range of, for example, about 450 to 800°C (especially 550 to 800°C), for example, 500 to 780°C, preferably 550 to 760°C (for example, 600 to 750°C), more preferably 650 ~740°C (especially 700-730°C). If the pyrolysis finish temperature is too low, the strength of the glass may decrease, probably because the porosity effect is reduced. There is fear.

When the decomposition temperature of the silicone resin is measured under the above conditions, the residue (residue at the thermal decomposition end temperature) can be selected from a range of, for example, about 30 to 90% by mass, for example, 35 to 85% by mass, preferably 38%. It may be about 80% by mass (eg, 40 to 70% by mass), more preferably about 45 to 60% by mass (especially 46 to 55% by mass). If the residue is too much, the performance of the ceramic color film may be deteriorated, and if the residue is too small, the effect of the silicone-based resin may be low and the strength of the glass may be lowered.

In the present specification and claims, the thermal decomposition end temperature and residue are measured from 40 ° C. at a temperature increase rate of 20 ° C./min in an air atmosphere using a thermogravimetric differential thermal analyzer (TG-DTA). It can be measured by thermal decomposition under the condition that the temperature is raised to 750° C. Specifically, it can be measured by the method described in Examples below.

In the present invention, the silicone resin preferably contains a silicone resin having a thermal decomposition end temperature of 550° C. or higher (for example, 550 to 800° C.), and the decomposition temperature of 600 to 775. °C (for example, 650 to 750°C), and particularly preferably a silicone resin with a decomposition temperature of 675 to 740°C. Moreover, it is most preferable to contain a silicone-based resin having a decomposition temperature of 700 to 730° C. and a residue of 45 to 55% by mass. For the same reason, the silicone resin preferably contains a silicone resin soluble in an organic solvent such as butyl carbitol acetate. Furthermore, for the same reason, the silicone resin preferably contains a thermoplastic resin or an uncrosslinked resin (curable resin). Therefore, the silicone-based resin having a thermal decomposition finish temperature of 550° C. or higher may be a thermoplastic resin or an uncrosslinked resin that is soluble in an organic solvent such as butyl carbitol acetate.

A silicone resin having a thermal decomposition finish temperature of 550° C. or higher and a silicone resin having a thermal decomposition finish temperature of lower than 550° C. (for example, 450 to 530° C.) may be combined. The silicone-based resin having a thermal decomposition finish temperature of less than 550° C. may be a crosslinked resin that is insoluble in butyl carbitol acetate. The ratio of the silicone-based resin having a thermal decomposition finish temperature of less than 550°C may be 100 parts by mass or less, preferably 1 to 50 parts by mass, with respect to 100 parts by mass of the silicone-based resin having a thermal decomposition finish temperature of 550°C or higher. is about 3 to 30 parts by mass, more preferably about 5 to 20 parts by mass.

The ratio of the silicone-based resin having a thermal decomposition end temperature of 550° C. or higher may be 50% by mass or higher, preferably 80% by mass or higher, more preferably 90% by mass or higher, with respect to the entire silicone-based resin, and 100% by mass. %. If the proportion of the silicone-based resin having a thermal decomposition finish temperature of 550° C. or higher is too small, it may be difficult to achieve both glass strength and appearance properties.

The state of the silicone-based resin is not particularly limited, but it may be solid at room temperature. The form of the solid silicone-based resin is not particularly limited either, and may be powder, flake, spherical, fibrous, amorphous, or the like.

The ratio of the silicone-based resin can be selected from a range of about 0.1 to 50 parts by weight, for example, 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, with respect to 100 parts by weight as the total amount of the glass frit and the heat-resistant pigment. parts (for example, 2 to 15 parts by mass), more preferably about 3 to 10 parts by mass (especially 5 to 8 parts by mass). In particular, while maintaining sinterability and external appearance such as color tone and transmittance, the mold release property during molding can be improved, and the glass strength can be improved. It may be 3.5 parts by mass or more with respect to 100 parts by mass of the total amount of the pigment, for example, 3.5 to 10 parts by mass, preferably 4 to 9 parts by mass, more preferably 4.5 to 8 parts by mass, and more It is preferably about 5 to 7 parts by mass (especially 5.5 to 6.5 parts by mass). If the proportion of the silicone resin is too small, the effect of improving the strength of the glass will be reduced. There is a possibility that the appearance such as is deteriorated.

(vehicle)
The ceramic color paste of the present invention may further contain a vehicle in order to paste the ceramic color composition and facilitate application to a coating process such as screen printing.

The vehicle may be a conventional vehicle utilized as a vehicle for ceramic color pastes, such as dispersion media and/or binders. The vehicle can be either a dispersion medium or a binder. It preferably contains at least a dispersion medium from the viewpoint of facilitating uniform dispersion, and is usually a combination of a dispersion medium and a binder.

Dispersion media include, for example, aliphatic alcohols (e.g. saturated or unsaturated _C6-30 aliphatic alcohols such as 2-ethyl-1-hexanol, octanol and decanol), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve C _1-4 alkyl cellosolves such as ), cellosolve acetates (C _1-4 alkyl cellosolve acetates such as ethyl cellosolve acetate and butyl cellosolve acetate), carbitols (methyl carbitol, ethyl carbitol, propyl carbitol, C _1-4 alkyl carbitols such as butyl carbitol, etc.), carbitol acetates (C _1-4 alkyl cellosolve acetates such as ethyl carbitol acetate and butyl carbitol acetate), aliphatic polyhydric alcohols (e.g. , ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, triethylene glycol, glycerin, etc.), alicyclic alcohols [e.g., cycloalkanols such as cyclohexanol; terpene alcohols such as terpineol and dihydroterpineol (e.g., monoterpene alcohol, etc.)], aromatic carboxylic acid esters (di-C _1-10 alkyl phthalates such as dibutyl phthalate and dioctyl phthalate, di-C _1-10 alkyl phthalates such as dibutyl benzyl phthalate) etc.) are commonly used. These dispersion media can be used alone or in combination of two or more.

The dispersion medium has low volatility at room temperature and can be easily volatilized without melting the glass frit. is about 80 to 200°C.

Among these dispersion media, alicyclic alcohols such as terpineol, C _1-4 alkyl cellosolve acetates such as butyl carbitol acetate, Particularly preferred are phthalic acid di-C _1-10 alkyl esters such as dibutyl phthalate.

Binders include organic binders and inorganic binders.

Examples of organic binders include thermoplastic resins (olefin resins, vinyl resins, acrylic resins, styrene resins, polyester resins, polyamide resins, cellulose derivatives, etc.), thermosetting resins (thermosetting acrylic resins, epoxy resins, phenol resins, unsaturated polyester resins, polyurethane resins, etc.). These organic binders can be used alone or in combination of two or more.

Examples of inorganic binders include silica sol, alumina sol, titania sol, and zirconia sol. An inorganic binder can be used individually or in combination of 2 or more types.

Among these binders, organic binders (eg, acrylic resins, styrene resins, alkylcelluloses, phenolic resins, etc.) are widely used, and C _1-3 alkylcelluloses such as ethylcellulose are preferred from the viewpoint of thermal decomposition.

The thermal decomposition temperature of the binder is, for example, about 200 to 550°C, preferably about 220 to 500°C, more preferably about 250 to 480°C.

The ratio of the vehicle can be selected from the range of about 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the glass frit and the heat-resistant pigment, from the viewpoint of obtaining the desired viscosity and improving the printability (applicability). For example, it is about 5 to 80 parts by mass, preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass (especially 25 to 35 parts by mass). If the proportion of the vehicle is too large, it will be difficult to prepare a coating film having a desired thickness.

When the vehicle is formed by a combination of a dispersion medium and a binder, the ratio of the dispersion medium is, for example, 100 to 10000 parts by weight, preferably 200 to 5000 parts by weight, more preferably 300 to 10000 parts by weight, with respect to 100 parts by weight of the binder. It is about 2000 parts by mass (especially 500 to 1500 parts by mass).

(other additives)
Depending on the application, the ceramic color paste contains conventional additives such as inorganic fillers (graphite, silicon carbide, silica, silicon nitride, boron nitride, quartz powder, hydrotalcite, carbonate, silicate, metal oxide substances, sulfates, various metal powders and metal foils, etc.), hue modifiers, gloss imparting agents, metal corrosion inhibitors, stabilizers (antioxidants, UV absorbers, etc.), surfactants or dispersants (phosphate esters anionic surfactants such as surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc.), dispersion stabilizers, thickeners or viscosity modifiers, moisturizing agents, thixotropic imparting agents Agents, leveling agents, antifoaming agents, bactericides, fillers and the like may also be included. These additives can be used alone or in combination of two or more. The proportion of these additives can be selected from a range of about 1 to 100 parts by mass for each of 100 parts by mass of the total amount of the glass frit and the heat-resistant pigment, and can be appropriately selected depending on the type. 10 parts by mass, preferably 0.3 to 5 parts by mass, more preferably about 0.5 to 3 parts by mass.

(Method for preparing ceramic color paste)
As a method for preparing the ceramic color paste, in order to uniformly disperse each component, a method of mixing using a conventional mixer can be used, and an apparatus having a grinding function (e.g., three rolls, mortar, mill, etc.) can be used. may be used. When a thermoplastic or uncrosslinked silicone resin is used as the silicone resin, in order to improve the dispersibility in the paste, the silicone resin may be dissolved in a dispersion medium in advance and then mixed with other components. .

[Glass with ceramic color and its manufacturing method]
The ceramic-colored glass of the present invention comprises a glass substrate and a ceramic-colored film laminated on at least a partial region of at least one surface of the glass substrate and formed of the ceramic color.

Examples of glass constituting the glass substrate include soda glass, borosilicate glass, crown glass, barium-containing glass, strontium-containing glass, boron-containing glass, low-alkali glass, alkali-free glass, crystallized transparent glass, silica glass, and quartz. Examples include glass, heat-resistant glass, and tempered glass. Among these glasses, alkali glass such as soda glass and tempered glass are widely used.

The surface of the glass substrate is subjected to oxidation treatment [surface oxidation treatment, e.g. discharge treatment (corona discharge treatment, glow discharge treatment, etc.), acid treatment (chromic acid treatment, etc.), ultraviolet irradiation treatment, flame treatment, etc.], surface unevenness treatment (solvent treatment, sandblasting, etc.) may be applied.

The thickness of the glass substrate may be appropriately selected depending on the application. good.

The volume ratio of the silicone-based resin residue (component derived from the silicone-based resin) in the ceramic color may be 50% by volume or less, for example, 0.1 to 30% by volume, preferably 0.5 to 20% by volume (for example, 1 to 10% by volume), more preferably about 2 to 8% by volume (especially 3 to 7% by volume). If the ratio of the silicone-based resin residue is too small, the strength of the glass may be lowered.

The average thickness of the ceramic color film (fired film) can be selected depending on the application, but is, for example, about 1 to 80 μm, preferably 5 to 40 μm, more preferably 8 to 25 μm (especially 10 to 18 μm).

The glass with ceramic color of the present invention is prepared by laminating the ceramic color paste on at least a part of at least one surface of a glass plate, and heating the resulting laminate at a temperature equal to or higher than the softening point of the glass plate. It is obtained by a manufacturing method including a bending step of heating and bending with and simultaneously baking the ceramic color paste.

In the lamination step, the ceramic color paste may be laminated over the entire surface of at least one surface of the glass substrate, but may be laminated on a partial area. Laminated on the periphery (near the ends of the four circumferences).

As a lamination method of the ceramic color paste, a lamination method by coating is usually used. The application method (or printing method) of the ceramic color paste includes, for example, flow coating method, spin coating method, spray coating method, screen printing method, flexographic printing method, casting method, bar coating method, curtain coating method, and roll coating method. , gravure coating method, slit method, photolithography method, inkjet method, and the like. Of these, the screen printing method is preferred. Moreover, the printing may be single-layer printing or multi-layer printing.

In the lamination process, when the ceramic color paste contains a dispersion medium, the applied ceramic color paste is dried to form a dry coating film. Drying may be natural drying, but drying by heating is preferred. The heating temperature can be selected according to the type of dispersion medium, and is, for example, about 50 to 250°C, preferably 80 to 200°C, more preferably about 100 to 180°C (especially 120 to 160°C). The heating time is, for example, 1 minute to 3 hours, preferably 3 minutes to 1 hour, more preferably 5 to 30 minutes.

The average thickness of the dry coating film (the average thickness of the area on the surface of the coating film excluding the protrusions formed of the glass filler) can be selected depending on the application, and is, for example, 1 to 100 μm, preferably 5 to 50 μm, and more preferably 5 to 50 μm. It is preferably about 10 to 30 μm (especially 12 to 20 μm).

In the bending process, from the viewpoint of productivity, the laminated body is usually bent and fired by heating, but depending on the bending conditions, the ceramic color paste may be pre-fired.

As the method for bending and forming the laminate, a conventional bending and forming method can be used. In the forming method using a press mold, a fabric made of heat-resistant fibers (for example, metal fibers, glass fibers, etc.) is usually used to form the pressing surface. The (contact surface) is bent using a coated press die.

In bending, a predetermined curvature is imparted to the glass substrate using a conventional bending method involving heat treatment. The bending method includes, for example, a self-weight bending method, a press method using a press mold (for example, a metal press mold whose contact surface is covered with the fabric), and the like.

In the firing process, the heating temperature for firing may be a temperature equal to or higher than the softening point of the glass frit. It is necessary to heat, for example, 580 to 780°C, preferably 600 to 750°C, more preferably 620 to 720°C (especially 640 to 700°C).

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited by these examples.

Examples 1-32, Comparative Examples 1-7 and Reference Examples 1-4
[Materials used]
Table 1 shows the details and characteristics of the materials used.

The thermal decomposition completion temperature and residue measurement method, which are the characteristics of the silicone resin in Table 1, are as follows.

The thermal decomposition completion temperature and residue of the silicone resin were measured using a thermogravimetric differential thermal analyzer ("TG/DTA6200" manufactured by SII Nanotechnology Co., Ltd.) in an air atmosphere at a temperature increase rate of 20°C/min to 40°C. to 750° C., and the temperature at which thermal decomposition ends and the amount of residue (% by mass) at that time were measured.

[Preparation of ceramic color paste]
In Examples 1 to 32, 70 parts by mass of glass frit, 30 parts by mass of heat-resistant pigment, 20 parts by mass of vehicle, 3 to 12 parts by mass of silicone resin, and 5 parts by mass of butyl carbitol acetate were mixed by a stirring mixer, and then 3 Uniform dispersion was carried out by this roll to prepare a base ceramic color paste (ceramic color paste of Reference Example 1). In order to facilitate dispersion, the silicone resin was dissolved in a dispersion medium in advance and then added to the agitating and mixing device. In Comparative Examples 2 to 7, a base ceramic color paste (ceramic color paste of Comparative Example 1) was prepared by uniformly dispersing the same components as in Examples 1 to 32 without blending a silicone resin. .

The obtained ceramic color paste (the ceramic color paste of Reference Example 1 or Comparative Example 1) was added with particles or silica shown in Tables 2 to 4 and 2 parts by mass of a phosphoric acid ester-based dispersant, and stirred and mixed by a mixing device. After thorough mixing and dispersion, ceramic color pastes of Examples 1-32, Reference Examples 2-4 and Comparative Examples 2-7 containing particles and silica were obtained.

[Lamination of ceramic color paste]
The resulting ceramic color paste was printed solidly on a 90 mm x 90 mm portion of a 100 mm x 100 mm x 2 mm thick glass plate (soda glass) using a polyester screen plate (180 mesh) and printed at 150°C. Dried for 10 minutes. When the average thickness of the dry film was measured using a stylus type film thickness meter, it was 20 μm.

[Evaluation of releasability in press molding]
A ceramic color is printed and a dried glass plate is placed under a press mold which is placed in a heating furnace and whose mold surface is covered with a stainless steel cloth (“KN/C1 (316L)” manufactured by Bekaert). After being held at 700° C. for 4 minutes, the glass plate was pressed into a curved shape. When the average thickness of the fired film (ceramic color film) was measured using a stylus type film thickness meter, it was 15 μm. The degree of force when the curved glass plate was peeled off from the press mold (coated surface formed of the stainless steel cloth) was evaluated according to the following four-grade criteria, and ⊚ and ◯ were regarded as acceptable.

◎: Glass can be removed with a little force (good)
○: The glass can be removed with a little force (good)
Δ: Force required ×: Considerable force required (extremely low releasability).

[Evaluation of fired glass plate]
1. Strength From the glass surface side of a glass plate with a ceramic color (sample) obtained by printing, drying, and firing at a setting of 640 ° C. "AGX-5kN"), a ring-on-ring bending test was performed to measure the strength when the glass was broken. Specifically, as shown in FIG. 1, a load is applied to the non-printing surface (glass surface) of sample 1 at a speed of 0.5 mm/min with a jig 2 whose tip has a curvature radius of R3.2 mm, and when the glass breaks was measured. A ring (upper ring) 3 to which a load is applied has an outer diameter of φ12 mm, and a ring (lower ring) 4 that supports the glass substrate has an inner diameter of φ76 mm. As for the number of evaluations, an average value was obtained with n=10. The strength is shown as a strength ratio when the strength of Comparative Example 1 is set to 1.00.

2. Sinterability A ceramic color was printed in the same manner as in the evaluation of releasability, dried, and fired at 640 ° C. A line was drawn on the fired film (thickness 15 μm) with an oil-based ink (magic ink), and the glass surface side ( It was visually confirmed whether or not the marker ink had penetrated from the non-printed surface), and evaluation was made according to the following criteria.

○: Magic ink is not soaked ×: Magic ink is soaked.

3. Color tone evaluation method A ceramic color is printed in the same manner as the evaluation of releasability, dried, and fired at 640 ° C. A fired film (thickness 15 μm) is measured from the glass surface side (non-printed surface) with a colorimetric color difference meter (Nippon Denshoku Using "ZE-2000" manufactured by Kogyo Co., Ltd., Lab was measured from the glass surface side, and the L values were compared. The smaller the L value, the darker and better the color tone, and the larger the L value, the grayer.

4. Transmittance evaluation method A ceramic color is printed and dried in the same manner as in the evaluation of releasability, and the fired film (thickness 15 μm) fired at 640 ° C is measured from the glass side (non-printed side) with a colorimetric color difference meter (Nippon Electric The transmittance was measured with "ZE-2000" manufactured by Shiki Kogyo Co., Ltd.).

5. Dry Hardness A sample dry film (ceramic color film) dried at 150° C. was measured for scratch hardness (pencil method) based on JIS K5600-5-4.

The evaluation results are shown in Tables 2-4.

As is clear from the results of Examples 1 to 20 in Tables 2 to 4, 10 parts by mass of particles 1 (particle size range 2 to 10 μm, glass beads) is added to a total of 100 parts by mass of the glass frit and heat-resistant pigment. When 15 parts by mass or more was added, the mold releasing properties were particularly excellent (Example 3). When added up to 23 parts by mass, other properties were satisfied (Examples 4 and 5), but when the amount was 27 parts by mass or more, the sinterability and hiding power (transmittance) decreased (Example 6). Similar results were obtained when Particle 2 (size range 10-20 μm, glass beads) was added, but the transmittance was higher than for Particle 1. When Particles 3 (particle size range 20 to 30 μm, glass beads) were added, the release property was improved at 10 parts by mass or more as with Particles 1 and 2, but there was no change with the addition of 15 parts by mass, and 23 parts by mass. The release property was further improved when the addition of When 15 parts by mass of particles 4 (43 to 53 μm, glass beads) were added, the releasability was not improved and the transmittance was increased. The strength (strength ratio) increased as the amount of glass beads added increased, but there was a tendency for the strength to decrease as the particle size increased.

When particles 5 (particle diameter range: 53 to 63 μm, glass beads) considerably larger than the film thickness were added (Example 19), it is thought that the release property effect appeared even at an addition amount of 7 parts by mass due to the spacer effect. The glass beads were seen through, and the appearance was abnormal.

From these results, the smaller the particle size of the glass beads, the higher the strength and releasability effect. In addition, when the particle size is large, even if the mold separation effect is obtained, the strength decreases and the transmittance increases. Also, aggregation was confirmed, and the appearance was poor.

The glass fiber of Particle 6 used in Examples 21 to 27 is a milled fiber obtained by pulverizing a long glass fiber with a fiber diameter of 10 μm into a length of 10 to 50 μm. On the other hand, when 3 to 15 parts by mass were added, the release property was equivalent to that of Particle 1, but the glass beads were slightly superior in hiding property (transmittance) and color tone. When 27 parts by mass of Particle 6 was added (Example 26), the sinterability was superior to that of Particle 1, but the transmittance increased. As with the glass beads, the strength increased as the amount of glass fiber added increased.

As is clear from the results of Examples 4, 28 to 29, and Comparative Example 2 in which 15 parts by mass of Particle 1 was added to a total of 100 parts by weight of the glass frit and the heat-resistant pigment, and the silicone resin was varied, the silicone resin is in the range of 3 to 12 parts by weight per 100 parts by weight of the glass frit and the heat-resistant pigment in total, and Example 4 has the best balance of properties. Specifically, compared to the case without silicone resin (Comparative Example 2), almost no change in physical properties was observed when 3 parts by mass of silicone resin was added (Example 28), but 6 parts by mass of silicone resin was added. When added, mold releasability and strength were improved (Example 4). When 12 parts by mass of silicone resin was added, the strength was further improved, but the sinterability and color tone were lowered (Example 29).

15 parts by mass of Particle 1 was added to a total of 100 parts by weight of glass frit and heat-resistant pigment so that the amount of silicone residue in the fired film was the same as that of silicone resin 1 (methylphenyl-based) of Example 4. As is clear from the results of Examples 30 to 32 in which silicone resins 2 (methyl-based), 3 (phenyl-based), and 4 (propylphenyl-based) were added to the above, mold releasability and sinterability depend on the type of silicone. No difference was seen. However, when methyl-based and phenyl-based silicone resins were added, the color tone was lower than that of alkylphenyl-based silicone resins. In terms of strength ratio, the methylphenyl-based silicone resin was superior, and the methylphenyl-based silicone resin was overall superior.

In Reference Example 2, when 15 parts by mass of silica having an average particle size of 1.4 μm was added to a total of 100 parts by mass of the glass frit and the heat-resistant pigment, the viscosity of the ink increased and printing became impossible. It should be noted that regardless of whether the silica was powdery or spherical, it was not possible to obtain mold releasability and strength improvement effects (Reference Examples 2 to 4).

From the dry hardness of Reference Example 1 and Comparative Example 1, it can be seen that the addition of the silicone resin increases the dry hardness. The dry hardness of the glass-filled film cannot be measured because the unevenness of the glass filler on the surface of the glass-filled film is caught by a pencil. Therefore, it is possible to prevent the glass filler from moving and scratching the glass when the glass is handled, resulting in a defective product. Therefore, in Comparative Examples 2 to 7, which do not contain a silicone resin, the strength of the dry film is insufficient, so defective products are likely to occur.

Regarding the strength, as is clear from the results of the comparative examples, when the glass filler is contained and the silicone resin is not contained, particles 1, 2, and 3 (particle diameter 30 μm When 15 parts by mass of particles 6 (φ10 μm glass fiber) and 15 parts by mass of particles 6 (φ10 μm glass fiber) were added, the strength was slightly improved (Comparative Examples 2 to 4 and 7). In this case, the strength decreased (Comparative Examples 5 and 6). Further, as in Examples 1 to 20, the smaller the particle size of the glass beads, the higher the strength. When the glass filler was not contained and the silicone resin was contained, the mold releasability was not obtained, but the strength and dry film hardness were improved (Reference Example 1).

That is, when the glass filler and the silicone resin were used in combination (Examples 1 to 32), particles 1, 2, 3 (glass beads with a particle size of 30 µm or less) and particle 6 (φ10 μm glass fiber) increased the strength, and when particles 4 and 5 (glass beads with a diameter of 45 μm or more) were added, the strength decreased. improved (comparison of Examples 4, 9, 14, 18, 24 with Comparative Examples 2-5 and 7). In addition, the releasability of particles 1 and 2 (glass beads with a particle size of 20 μm or less) and particle 6 (glass fiber of φ10 μm) was improved by the addition of the silicone resin. From these results, it was found that the combined use of glass beads or glass fibers having a particle size of 30 μm or less and a silicone resin can simultaneously improve the releasability and the strength ratio.

Summarizing these results, it was found that the greater the amount of glass filler added, the more the releasability and strength tended to improve. It can be said that Example 5 is the best mode because it has an excellent balance of these properties.

INDUSTRIAL APPLICABILITY The present invention can be used as a paste for forming ceramic collars on various glass substrates, and can also be used for glass with ceramic collars having a curved shape. Ceramic colored glass can be used, for example, as window glass for vehicles such as trains, cars, airplanes, airships, and ships, or as security glass for buildings. , side glass, etc.).

1...Sample 2...Jig 3...Upper ring 4...Lower ring

Claims (10)

A ceramic color paste containing a glass frit having a softening point of 360 to 650°C , a heat-resistant pigment, a glass filler having a softening point of 650 to 1800°C, and a silicone resin ,
The softening point of the glass filler is higher than that of the glass frit,
The glass filler is glass beads with a particle diameter range of 2 to 30 μm and/or glass fibers with a fiber diameter range of 10 to 30 μm and a fiber length range of 10 to 50 μm,
The ratio of the glass beads is 10 to 23 parts by mass with respect to 100 parts by mass of the total amount of the glass frit and the heat-resistant pigment, and the ratio of the glass fiber is 100 parts by mass of the total amount of the glass frit and the heat-resistant pigment 10 to 27 parts by mass,
A ceramic color paste in which the proportion of silicone resin is 3 to 10 parts by mass with respect to 100 parts by mass of the total amount of glass frit and heat-resistant pigment . When the decomposition temperature of the silicone-based resin is measured using a thermogravimetric differential thermal analyzer (TG-DTA) under the condition that the temperature is raised from 40°C to 750°C at a temperature elevation rate of 20°C/min in an air atmosphere. 2. The ceramic color paste according to claim 1 , comprising a silicone resin having a thermal decomposition finish temperature of 550[deg.] C. or higher. 3. The ceramic color paste according to claim 2 , wherein the silicone resin having a thermal decomposition finish temperature of 550° C. or higher has a residue of 40 to 70% by mass at the thermal decomposition finish temperature. 4. The ceramic color paste according to any one of claims 1 to 3 , wherein the silicone resin contains a silicone resin soluble in an organic solvent. The ceramic color paste according to any one of claims 1 to 4 , wherein the silicone resin comprises a C _1-4 alkyl C _6-10 aryl silicone resin. 6. The ceramic color paste according to any one of claims 1 to 5 , wherein the proportion of the silicone resin is 4 to 10 parts by weight per 100 parts by weight of the total amount of the glass frit and the heat-resistant pigment. The ceramic color paste according to any one of claims 1 to 6 , wherein the proportion of the glass filler is 10 to 23 parts by weight per 100 parts by weight of the total amount of the glass frit and the heat-resistant pigment. Claims 1 to 7 , wherein the glass filler is glass beads having a particle size range of 2 to 20 µm, and the ratio of the glass filler is 20 to 23 parts by mass with respect to the total amount of 100 parts by mass of the glass frit and the heat-resistant pigment. A ceramic color paste according to any one of . The ceramic color paste according to any one of claims 1 to 8 , wherein the glass frit contains at least one selected from the group consisting of bismuth-based glass frit, silica-based glass frit, zinc-based glass frit and lead-based glass frit. A ceramic color paste according to any one of claims 1 to 9 , further comprising a vehicle.

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