JP2020138897A - Ceramic color paste, ceramic color, glass with ceramic color and manufacturing method thereof - Google Patents

Abstract

To provide a ceramic color paste capable of improving die releasability in forming while maintaining sinterability and appearance such as color tone and transmittance.SOLUTION: A ceramic color paste is prepared which contains a glass frit having a softening point lower than a forming temperature, a heat-resistant pigment, a glass filler having a softening point higher than the forming temperature, and a silicone-based resin. The forming temperature may be a temperature of press forming. The silicone-based resin may contain a silicone-based resin having a thermal decomposition finish temperature of 550°C or higher when a decomposition temperature is measured using a thermogravimetric differential thermal analyzer(TG-DTA) under a condition that a temperature is raised from 40°C to 750°C at a heating rate of 20°C/min in an air atmosphere. The glass filler may be glass beads having a particle size range of 2 to 30 μm and/or glass fibers having a fiber diameter range of 10 to 30 μm and a fiber length range of 10 to 50 μm.SELECTED DRAWING: None

Description

The present invention relates to various types of glass, for example, a ceramic color paste for baking and coloring or molding on a glass plate which is a substrate for automobile glass, a ceramic color, and a glass with a ceramic color to which the ceramic color is applied, and manufacturing thereof. Regarding the method (molding method).

Among automobile glass, fixed window glass such as windshield, side glass, rear glass and sunroof glass is attached to the vehicle body using an organic adhesive. The peripheral part of each glass attached to the car body is a door glass to prevent deterioration of the organic adhesive due to sunlight, conceal excess adhesive (extruded adhesive) at the adhesive part, improve the design of the glass, etc. In order to reduce the sliding resistance and improve the design, the sliding window glass such as the above is colored black or dark gray. In such automobile glass, generally, a ceramic color (black ceramic) paste formed of a meltable glass frit containing a black pigment is screen-printed on the periphery of a flat glass plate cut into a predetermined shape. After that, the glass plate is bent and molded by heating, and at the same time, the ceramic color paste is baked on the glass plate and then cooled.

In recent years, as a production form of a bending molding method for window glass for automobiles, a method in which a press machine is provided in a heating furnace or the like to perform bending molding has been used in order to improve productivity and bending molding accuracy. In press molding, the problem is the separation of the press mold and the ceramic collar. Specifically, the mold release property in press molding is reduced when the heated and melted ceramic color adheres to the heat-resistant cloth (stainless steel cloth, glass cloth, etc.) used for the surface of the press mold. In particular, as automobile designs have diversified in recent years, demands for deep bending of glass and molding into complex shapes have increased, and mold release has become an important issue.

WO2013 / 146264 (Patent Document 1) includes glass frit, vehicle, heat-resistant pigment, and heat-resistant large-diameter particles, and the heat-resistant large-diameter particles form an average thickness of a dry coating film for forming a ceramic color. Ceramic color pastes with a larger particle size are disclosed.

However, since this ceramic color paste contains heat-resistant large-diameter particles having a particle size larger than the thickness of the dry coating film, although the mold release property is excellent, the coating film surface has an uneven shape, and the particles become uneven when the glass is passed through. It is transparent, has high transmittance, and has low concealment.

Further, in the cooling step of the glass plate, the glass plate is strengthened by heating the glass plate and then rapidly cooling the glass plate. However, in general, since the coefficient of thermal expansion differs between the ceramic collar and the glass plate, tensile stress acts on the surface of the glass plate from the ceramic collar in the cooling step, 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 where the ceramic color is attached. However, the ceramic color paste of Patent Document 1 has low strength.

According to JP-A-6-234547 (Patent Document 2), the inorganic components are 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. The ceramic color composition is disclosed, and Japanese Patent Application Laid-Open No. 6-256039 (Patent Document 3) contains 20 to 68 parts by weight of crystalline glass frit and 2 to 30 parts by weight of amorphous glass frit. A ceramic color composition comprising 20 to 40 parts by weight of a heat-resistant coloring pigment and 0 to 10 parts by weight of a refractory filler is disclosed.

However, when crystallized glass is blended, a part of the crystallized glass is crystallized by heating and baked on the glass, so that the mold release property is improved, but the crystallized glass has a high coefficient of thermal expansion, so that the glass strength is high. descend. Further, in the composition containing crystallized glass, bismuth-based glass is often used as a glass frit that is low-melting glass and does not contain lead, but in the case of the crystallization type, Bi ₂ SiO _{5 and the} like are precipitated by crystallization. When the amount of Bi is increased and the crystallization component is increased, the acid resistance is lowered.

According to JP-A-6-239647 (Patent Document 4), the glass plate is applied to a predetermined portion of the glass plate, fired, fused onto the glass plate, crystallized, and then the glass plate is formed by a press device provided in the furnace. A ceramic color composition suitable for bending, the inorganic components thereof are 5 to 30% by weight of colored heat-resistant pigment powder, 70 to 95% by weight of crystallized glass powder, and 1.5 to 2.5% by weight of alumina powder. A ceramic color composition consisting of% is disclosed. Further, Japanese Patent Application Laid-Open No. 2000-154038 (Patent Document 5) describes colored heat-resistant pigment powder 5 to 40.5% by weight, glass powder 50 to 94% by weight, refractory filler 0 to 25% by weight, whisker-like fire resistance. A ceramic color composition comprising 0.1 to 40% by weight of a material filler is disclosed. Further, in Japanese Patent Application Laid-Open No. 2002-362940 (Patent Document 6), lead-free glass powder: 63 to 78.99% by mass, heat-resistant whiskers: 5 to 12% by mass, dibismuth trioxide powder: 0.01 to 1% by mass. %, Heat Resistant Pigment Powder: A ceramic color composition comprising 16 to 26% by mass is disclosed. Further, Japanese Patent Application Laid-Open No. 2016-79084 (Patent Document 7) describes a particle size having a glass powder and a particle shape having an average aspect ratio of less than 8 and showing a volume-based frequency distribution measured by a laser diffraction / scattering method. A ceramic color composition containing a refractory filler having a peak between 0.1 and 8.4 μm and a peak between 8.5 and 30 μm in the distribution curve and a heat-resistant pigment powder is disclosed.

However, although the mold release property is improved even if a whisker-like refractory is blended, the distribution amount of the whisker-like refractory has been decreasing in recent years because the evaluation of the effect on the human body is unclear. Further, examples of the whisker-like refractory include aluminum borate, alumina, potassium titanate, zircon, etc. When a large amount of these whisker-like refractories are added to the ceramic color, color tone, acid resistance, and sintering are performed. Performance such as sex deteriorates.

WO2013 / 146264 (Claim 1) JP-A-6-234547 (Claim 1) JP-A-6-256039 (Claim 1) JP-A-6-239647 (Claim 1) JP-A-2000-154038 (Claim 1) JP-A-2002-362940 (Claim 1) JP-A-2016-79084 (Claim 1)

Therefore, 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 the mold release property at the time of molding while maintaining the sinterability and the appearance such as the color tone and the transmittance. To provide.

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

Still another 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 suppress the adhesion of the ceramic color to the press mold and can be easily separated from the press mold after firing. To do.

As a result of diligent studies to achieve the above problems, the present inventors have found 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 present invention has been completed by finding that when a ceramic color paste is prepared in combination with a silicone-based resin, it is possible to improve mold releasability during molding while maintaining appearance such as sinterability and color tone and transmittance.

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-based 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. At this time, a silicone-based resin having a thermal decomposition end temperature of 550 ° C. or higher may be contained. Silicone-based resins 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-based resin may contain a silicone-based resin that is soluble in an organic solvent, for example, butyl carbitol acetate. The silicone-based resin may contain a C _1-4 alkyl C _6-10 aryl-based 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 of the total amount of the glass frit and the heat-resistant pigment. The glass filler may be glass beads having a particle size range of 2 to 30 μm (particularly 2 to 20 μm) and / or glass fibers having a fiber diameter range of 10 to 30 μm and a fiber length range of 10 to 50 μm. The ratio 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 of 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 using a thermogravimetric differential thermal analyzer (TG-DTA) 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. When the temperature is measured, a silicone-based resin having a thermal decomposition end temperature of 550 ° C. or higher may be contained, and the silicone-based 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 is a glass with a ceramic color provided with a glass substrate and a ceramic color paste film, wherein the ceramic color is formed in at least a part of a region on at least one surface of the glass substrate. Also included is ceramic colored glass with laminated membranes.

In the present invention, a laminating step of laminating a ceramic color film formed of the ceramic color on at least a part of a glass substrate on at least one surface, and a laminating body obtained by laminating the obtained laminate to a softening point of the glass plate. It also includes a method for producing a glass with a ceramic color, which includes a bending molding step of firing the ceramic color paste at the same time as bending and molding by heating at the above temperature. The bending molding step may include press molding.

The ceramic color paste of the present invention is a combination of 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-based resin. It is possible to improve mold release during molding while maintaining appearance such as bondability, color tone and transparency. In addition, it has excellent acid resistance such as acid rain resistance and can improve the strength of glass with a ceramic color. Further, it is possible to prevent the ceramic color from adhering to the press mold, and it can be easily separated from the press mold after firing.

FIG. 1 is a schematic view for explaining a method of measuring the strength of the ceramic colored glass plate obtained in the examples.

[Ceramic color paste]
The ceramic color paste (or ceramic color composition) of the present invention includes 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-based resin.

(Glass frit)
The glass frit (meltable glass powder or particles) may be any glass frit that is blended to form a ceramic-colored film and fix to a glass plate and softens at a molding temperature.

As the glass frit, a conventional glass frit used in a ceramic color can be used. Examples of conventional glass frit include 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.

Of these, bismuth-based glass frit, silica-based glass frit, zinc-based glass frit, lead-based glass frit, etc. are widely used, and the remarkable effects of the present invention such as both acid resistance and glass strength are likely to be exhibited. , At least preferably contains bismuth-based glass frit.

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

When the glass frit contains a 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, and more preferably 80% by mass or more (particularly 90% by mass). % Or more), and may be 100% by mass.

The softening point (or melting point) of the glass frit may be lower than the molding temperature (heating temperature of bending molding, particularly press temperature), for example, it can be selected from the range of about 350 to 700 ° C., and is lower than the press temperature of press molding. It may be, for example, 360 to 650 ° C., preferably 400 to 600 ° C., more preferably 450 to 580 ° C. (particularly 500 to 550 ° C.). If the softening point is too low, the glass strength may decrease, and conversely, if it is too high, the melt fluidity decreases, so that the adhesion to the glass substrate may decrease.

The average particle size of the glass frit may be, for example, 0.1 to 10 μm, preferably 0.3 to 8 μm, and more preferably 0.5 to 5 μm (particularly 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 is lowered and the economy may be lowered.

The proportion of 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, and more preferably 50 to 75% by mass (particularly 50 to 70%). Mass%). If the proportion of the glass frit is too large, the color tone of the ceramic color may be deteriorated, and if it is too small, the adhesion to the glass substrate may be deteriorated.

(Heat-resistant pigment)
The heat-resistant pigment is blended to give the ceramic color a desired color. As the heat-resistant pigment, it suffices as long as it can withstand the firing temperature of the ceramic color paste, and a conventional heat-resistant pigment can be used.

Examples of the heat-resistant pigment 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 pigments (cobalt blue, etc.), green pigments (chrome green, cobalt-zinc-nickel-titanium composite oxide, cobalt-aluminum-chromium) Composite oxides, etc.), red pigments (Bengala, etc.), yellows (titanium yellow, titanium-valium-nickel composite oxides, titanium-antimon-nickel composite oxides, titanium-antimon-chromium composite oxides, etc.), white Examples include system 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, but black heat-resistant pigments (for example, composite oxide black such as copper-chromium-manganese composite oxide) are widely used.

Examples of the shape of the heat-resistant pigment include substantially spherical shape, ellipsoidal shape, polygonal shape (polygonal pyramid shape, rectangular parallelepiped shape, rectangular parallelepiped shape, etc.), plate shape, rod shape, and irregular shape. Of these shapes, an isotropic shape (substantially spherical or the like) is preferable from the viewpoint of dispersibility and color tone.

The average particle size of the heat-resistant pigment is, for example, 0.1 to 10 μm, preferably 0.2 to 5 μm, and more preferably 0.3 to 4 μm (particularly 0.5 to 3 μm). If the particle size of the heat-resistant pigment is too small, uniform dispersion becomes difficult and the color-developing property may be lowered. On the contrary, if the particle size is too large, the coatability may be lowered or the color-developing property may be lowered.

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, and more preferably about 15 to 30% by mass (particularly 18 to 25% by mass). The ratio of the heat-resistant pigment is, for example, 1 to 100 parts by mass, preferably 10 to 60 parts by mass, and more preferably 20 to 50 parts by mass (particularly 30 to 45 parts by mass) with respect to 100 parts by mass of the glass frit. .. If the proportion of the heat-resistant pigment is too large, the strength of the ceramic color film may decrease, and if it is too small, the color development property may decrease.

(Glass filler)
The glass filler (heat-resistant glass powder or particles) may be any glass filler that is blended to form a ceramic-colored film and improve mold release during molding, and does not soften at the molding temperature. In the present invention, by blending a glass filler that does not soften (melt) at the molding temperature (heating temperature of bending molding), particularly the press temperature of press molding, as a filler, the flow of the molten ceramic color can be suppressed, and during pressing. It can be estimated that the contact area between the surface fibers of the press die (molding die) and the molten ceramic collar is reduced, and the mold release property is improved.

Further, in the present invention, by adjusting the particle size of the glass filler to the range described later, it is possible to further improve the mold release property in press molding. On the other hand, in Patent Document 1, the heat-resistant large-diameter particles are made larger than the thickness of the dry coating film to improve the mold release property at the time of molding, but the large-diameter particles in Patent Document 1 are combined. Especially effective in glass. That is, in the case of bending and molding of laminated glass, the surface in contact with the ceramic collar is a flat surface (glass surface), so when large-diameter particles protrude from the film larger than the film thickness, the particles act as spacers and the glass surface and ceramic. When the color does not touch, the mold release property develops. In the case of particles smaller than the film thickness, the particles are pushed by the stacked glass and the particles enter the inside of the film, and the ceramic color on the surface comes into contact with the glass, so that the mold release property is lowered. Therefore, in the bending molding of laminated glass, since the facing glass is put into the heating furnace in a state of being superposed on the glass on which the ceramic color is printed, it is necessary that the large-diameter particles protrude from the film in the state of a dry film.

On the other hand, in the present invention, it is particularly suitable for mold release in 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, it is less necessary for the glass filler to protrude from the film in the state of a dry film like laminated glass. Further, 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. For example, in knit knitting of stainless steel cloth, cushioning properties and texture irregularities are provided in the thickness direction. If the particles are halfway large, the fibers will enter the gaps between the particles and adhere to the ceramic collar. Therefore, in press molding, it is possible to improve the mold release property when there are many contact surfaces between the particles and the press mold, and even if the glass filler has a smaller particle size than the large diameter particles of Patent Document 1, the mold release property can be improved. .. The reason is that since the number of small-particle glass fillers present in the film is large, the distance between the particles is short, and it acts as a filler that is uniformly present throughout (the surface area of the glass filler is large), and the fibers 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 shape, ellipsoidal shape, polygonal shape (polygonal pyramid shape, rectangular parallelepiped shape, rectangular parallelepiped shape, etc.), plate shape, rod shape, fibrous shape, and indefinite shape. Of these shapes, isotropic (substantially spherical, rectangular parallelepiped, etc.) granular and fibrous shapes are widely used, and substantially spherical shapes are particularly preferable because they have a small contact area with the surface (pressed surface) of the press mold. The glass filler is preferably primary particles (independent integrated particles or single-layer particles), but may be secondary particles in which small particles are aggregated as long as they can exist stably.

As described above, the glass filler preferably has a predetermined size from the viewpoint of improving mold releasability during molding.

When the glass filler is granular (glass beads), the particle size range (range from the minimum particle size to the 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 size range of the granular glass filler is 30 μm or less (particularly 15 μm or less), the mold release property at the time of molding and the strength of the ceramic colored glass can be compatible with each other in combination with the silicone resin. The volume average particle size of the granular glass filler is, for example, 3 to 20 μm, preferably 3 to 15 μm, and more preferably about 4 to 10 μm. If the particle size of the granular glass filler is too small, uniform dispersion becomes difficult and the mold release property during molding may decrease. On the contrary, if it is too large, the fibers enter the gaps between the particles in press molding. There is a risk that the mold release property will decrease due to the 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 the particles is not particularly limited, and for example, a known measuring method using a laser diffraction type particle size distribution measuring device or the like is used. Can be used.

When the glass filler is fibrous (glass fiber), the fiber diameter range (range from the minimum fiber diameter to the 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, 5 to 20 μm, preferably 8 to 18 μm, and more preferably about 10 to 15 μm. If the fiber diameter of the fibrous glass filler is too small, uniform dispersion becomes difficult and the mold release property during molding may decrease. On the contrary, if it is too large, the press mold fibers are separated between the fillers in press molding. If it enters the gap and adheres to the ceramic collar, the mold release property may decrease.

The fiber length range (range from the minimum fiber length to the maximum fiber length) of the fibrous glass filler may be about 10 to 100 μm, for example, 10 to 50 μm, preferably 15 to 45 μm, and more preferably about 20 to 40 μm. .. The average fiber length of the fibrous glass filler is, for example, 10 to 50 μm, preferably 15 to 45 μm, and more preferably about 20 to 40 μm. If the fiber length of the fibrous glass filler is not within this range, uniform dispersion becomes difficult, and the mold release property during molding may decrease.

In the present specification and the scope of patent 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, and the fiber is, for example, using a scanning electron microscope (SEM). Known measuring methods such as a method of observing the cross section and the fiber length can be used.

The softening point (or melting point) of the glass filler may be higher than the molding temperature (heating temperature of bending molding, particularly press temperature), and can be selected from the range of, for example, 600 ° C. or higher (for example, about 600 to 2000 ° C.), and press molding. It is preferably higher than the press temperature of, for example, 650 to 1800 ° C., preferably 700 to 1500 ° C., and more preferably 750 to 1200 ° C. (particularly 800 to 1000 ° C.). If the softening point is too low, the mold release property may decrease.

Examples of the 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 non-alkali glass. , Silica glass, quartz glass, heat-resistant glass and the like. These glasses can be used alone or in combination of two or more. Of these, soda glass, borosilicate glass, quartz glass, heat-resistant glass and the like are preferable.

The ratio of the glass filler is, for example, 10 to 30 parts by mass, preferably 12 to 26 parts by mass, and more preferably 15 to 25 parts by mass (particularly 20 to 20 to 20 parts by mass) with respect to 100 parts by mass of the total amount of the glass frit and the heat-resistant pigment. It is about 24 parts by mass). In particular, if the ratio of the glass filler is adjusted to about 20 to 25 parts by mass with respect to 100 parts by mass of the total amount and the size is adjusted within the above range, various characteristics can be improved in a well-balanced manner. If the proportion of the glass filler is too small, the mold releasability at the time of molding may be deteriorated, and if it is too large, the appearance such as transmittance and the sinterability may be deteriorated.

(Silicone resin)
In the present invention, by combining a silicone-based resin (silicone-based resin) with a glass frit, a heat-resistant pigment, and a glass filler, it is possible to suppress a decrease in glass strength due to a ceramic color. The details of the mechanism that can suppress the decrease in glass strength are unknown, but silicone has heat resistance compared to other organic compounds, has a high thermal decomposition temperature, and is near the baking temperature of ceramic colors such as black ceramics and the molding temperature of glass. However, it can be presumed that when the glass is mixed with the ceramic color, porous is generated in the film, the surface compressive stress is relaxed, and the glass strength is improved.

The silicone-based resin may be a thermoplastic resin having a polyorganosiloxane skeleton, a curable resin (uncrosslinked resin), or a cured resin (crosslinked resin). The polyorganosiloxane skeleton is a linear, branched chain or network compound having a Si—O bond (siloxane bond), and the formula: _Ra SiO _{(4-a) / 2} (in the formula, R is It indicates a substituent, and the coefficient a is a number from 0 to 3). As the silicone-based resin, a monofunctional M unit (generally represented by R ₃ SiO _1/2 ) and a bifunctional D unit (generally R), which are units represented by the above formulas, are used. ₂ SiO _2/2 unit), trifunctional T unit (generally represented by RSiO _3/2 ), tetrafunctional Q unit (generally represented by SiO _4/2) Of the units), polyorganosiloxane containing the T unit as the main unit is 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 group such as halogenated C _1-10 alkyl group, vinyl group, allyl group, butenyl group, C _6-20 aryl group such as phenyl group, tolyl group, naphthyl group, cyclopentyl group, cyclohexyl group and the like. Examples thereof include C _6-12 aryl-C _1-4 alkyl groups such as C _3-10 cycloalkyl group, benzyl group and phenethyl group. These substituents can be used alone or in combination of two or more.

Of these, as R, 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 is preferable, and a C _1-3 alkyl group or a C _6-8 aryl group is preferable. The group is more preferable, and the methyl group and the phenyl group are most preferable. Further, as R, it is preferable to use two or more types in combination because it is possible to simultaneously improve the appearance such as strength and color tone of the ceramic colored glass and the mold release property, rather than using it alone. C _{1- A 4-} alkyl group and a C _6-10 aryl group are preferable, a combination of a C _1-3 alkyl group and a C _6-8 aryl group is more preferable, and a combination of a methyl group and a phenyl group is most preferable.

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

The silicone-based resin may be a straight silicone-based resin or a modified silicone-based resin. Examples of the modified silicone-based resin include silicone-based resins modified with other resins such as alkyd resin, phenol resin, urea resin, melamine resin, and epoxy resin.

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 silicones such as methyl silicone resins). Resin etc.), _6-10 aryl silicone resin whose substituent R is a C _6-10 aryl group such as a phenyl group (for example, C _6-8 aryl silicone resin such as phenyl silicone resin), and substituent R C _{1-4 C 1-4} alkyl _{C 6-10} aryl silicone resin is a combination of an alkyl group and the _{C 6-10} aryl group (e.g., methyl phenyl silicone resins, such as propyl phenyl silicone resin _{C 1- 3} Alkyl C _6-8 aryl silicone resin, etc.) and the like. These silicone-based resins can be used alone or in combination of two or more. Of these, alkylaryl silicone resins such as C _1-4 alkyl C _6-10 aryl silicone resins are preferable from the viewpoint of improving the appearance such as color tone, and the appearance and glass strength can be compatible with each other. , C _1-2 alkyl C _6-8 aryl silicone resin such as methylphenyl silicone resin is particularly preferable.

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

When the decomposition temperature of a 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 heating rate of 20 ° C / min in an air atmosphere. The thermal decomposition end temperature of the above can be selected from the range of, for example, about 450 to 800 ° C. (particularly 550 to 800 ° C.), for example, 500 to 780 ° C., preferably 550 to 760 ° C. (for example, 600 to 750 ° C.), and more preferably 650. It is about ~ 740 ° C. (particularly 700 to 730 ° C.). If the pyrolysis end temperature is too low, the porous effect may be reduced, and the glass strength may decrease. If the pyrolysis end temperature is too high, the silicone resin remains and the performance of the ceramic color film deteriorates. There is a risk.

In the silicone-based resin, the residue (residue at the end temperature of thermal decomposition) when the decomposition temperature is measured under the above conditions can be selected from the 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 (for example, 40 to 70% by mass), more preferably about 45 to 60% by mass (particularly 46 to 55% by mass). If there is too much residue, the performance of the ceramic color film may deteriorate, and if there is too little residue, the effect of the silicone resin may be low and the glass strength may decrease.

In the present specification and claims, the thermal decomposition end temperature and the residue can be measured from 40 ° C. at a heating rate of 20 ° C./min under 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., and in detail, it can be measured by the method described in Examples described later.

In the present invention, the silicone-based resin preferably contains the silicone-based resin having a thermal decomposition end temperature of 550 ° C. or higher (for example, 550 to 800 ° C.), and the decomposition temperature is 600 to 775, from the viewpoint of achieving both glass strength and appearance characteristics. It is more preferable to contain a silicone-based resin at ° C. (for example, 650 to 750 ° C.), and it is particularly preferable to include a silicone-based resin having a decomposition temperature of 675 to 740 ° C. Further, 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-based resin preferably contains a silicone-based resin that is soluble in an organic solvent such as butyl carbitol acetate. Further, for the same reason, the silicone-based resin preferably contains a thermoplastic resin or an uncrosslinked resin (curable resin). Therefore, the silicone-based resin having a thermal decomposition end 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.

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

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

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

The ratio of the silicone-based resin can be selected from the range of about 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the glass frit and the heat-resistant pigment, for example, 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass. Parts (for example, 2 to 15 parts by mass), more preferably 3 to 10 parts by mass (particularly 5 to 8 parts by mass). In particular, the proportion of silicone-based resin is glass frit and heat resistance because it can improve mold release during molding and glass strength while maintaining appearance such as sinterability and color tone and transmittance. 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, and more preferably 4.5 to 8 parts by mass. It is preferably about 5 to 7 parts by mass (particularly 5.5 to 6.5 parts by mass). If the proportion of silicone resin is too small, the effect of improving the glass strength will be reduced, and if it is too large, the performance of the ceramic color will be reduced, such as warpage and sinterability, and the color tone. There is a risk that the appearance will deteriorate.

(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 used as a vehicle for a ceramic color paste, such as a dispersion medium and / or a binder. The vehicle may be either a dispersion medium or a binder, but if the silicone-based resin contains a thermoplastic or uncrosslinked silicone resin, the thermoplastic or uncrosslinked silicone resin is previously dissolved in the paste. It is preferable to contain at least a dispersion medium from the viewpoint of easy uniform dispersion, and usually, it is a combination of a dispersion medium and a binder.

Examples of the dispersion medium include aliphatic alcohols (for example, saturated or unsaturated C _6-30 aliphatic alcohols such as 2-ethyl-1-hexanol, octanol, and decanol), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.). 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 (methylcarbitol, ethylcarbitol, propylcarbitol, etc.) C _1-4 alkyl carbitols such as butyl carbitol), carbitol acetates (C _1-4 alkyl cellosolve acetates such as ethyl carbitol acetate and butyl carbitol acetate), aliphatic polyhydric alcohols (eg) , Ethyl glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, triethylene glycol, glycerin, etc.), alicyclic alcohols [for example, cycloalkanols such as cyclohexanol; terpine alcohols such as terpineol, dihydroterpineol (e.g., monoterpene alcohols, etc.), etc.], an aromatic carboxylic acid esters (dibutyl phthalate, di C _1-10 alkyl ester such as dioctyl phthalate, di-C _1-10 alkyl aralkyl esters 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 may have low volatility at room temperature and can be easily volatilized without melting the glass frit, and the boiling point of the dispersion medium is, for example, 50 to 250 ° C., preferably 70 to 220 ° C., more preferably. 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, and the like, because they have an appropriate boiling point and can improve the fluidity and printability of the paste. Phthalate diC _1-10 alkyl esters such as dibutyl phthalate are particularly preferred.

Binders include organic binders and inorganic binders.

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

Examples of the inorganic binder include silica sol, alumina sol, titania sol, and zirconia sol. Inorganic binders can be used alone or in combination of two or more.

Among these binders, organic binders (for example, acrylic resins, styrene resins, alkyl celluloses, phenol resins, etc.) are widely used, and C _1-3 alkyl celluloses such as ethyl cellulose are preferable from the viewpoint of thermal decomposability.

The thermal decomposition temperature of the binder is, for example, 200 to 550 ° C, preferably 220 to 500 ° C, and more preferably 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 (coatability). For example, it is about 5 to 80 parts by mass, preferably 10 to 50 parts by mass, and more preferably about 20 to 40 parts by mass (particularly 25 to 35 parts by mass). If the proportion of the vehicle is too large, it becomes difficult to prepare a coating film having a predetermined thickness, and if it is too small, the improvement effect of the vehicle may decrease.

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

(Other additives)
Depending on the application, the ceramic color paste may contain conventional additives such as inorganic fillers (graphite, silicon carbide, silica, silicon nitride, boron nitride, quartz powder, hydrotalcite, carbonate, silicate, metal oxidation. Materials, sulfates, various metal powders, metal foils, etc.), hue improvers, gloss enhancers, metal corrosion inhibitors, stabilizers (antioxidants, UV absorbers, etc.), surfactants or dispersants (phosphate esters) Anionic surfactants such as system surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc.), dispersion stabilizers, thickeners or viscosity modifiers, moisturizers, and thixotropic properties. Agents, leveling agents, antifoaming agents, bactericides, fillers and the like may be included. These additives can be used alone or in combination of two or more. The ratio of these additives can be selected from a 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, and can be appropriately selected depending on the type. It is about 10 parts by mass, preferably 0.3 to 5 parts by mass, and more preferably about 0.5 to 3 parts by mass.

(How to prepare 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 crushing function (for example, three rolls, a mortar, a mill, etc.) May be used. When a thermoplastic or uncrosslinked silicone resin is used as the silicone resin, the silicone resin may be previously dissolved in a dispersion medium and then mixed with other components in order to improve dispersibility in the paste. ..

[Ceramic colored glass and its manufacturing method]
The glass with a ceramic color of the present invention includes a glass substrate and a ceramic color film laminated on at least a part of the area on at least one surface of the glass substrate and formed of the ceramic color.

Examples of the glass constituting the glass substrate include soda glass, borosilicate glass, crown glass, barium-containing glass, strontium-containing glass, boron-containing glass, low-alkali glass, non-alkali glass, crystallized transparent glass, silica glass, and quartz. Examples include glass, heat-resistant glass, and tempered glass. Among these glasses, alkaline 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, for example, discharge treatment (corona discharge treatment, glow discharge, etc.), acid treatment (chromic acid treatment, etc.), ultraviolet irradiation treatment, flame treatment, etc.], surface unevenness treatment (solvent). Surface treatment such as treatment, sandblasting, etc.) may be performed.

The thickness of the glass substrate may be appropriately selected depending on the intended use, and may be, for example, 0.01 to 50 mm, preferably 0.1 to 30 mm, and more preferably 0.5 to 10 mm (particularly 1 to 5 mm). 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 (particularly 3 to 7% by volume). If the proportion of the silicone-based resin residue is too small, the glass strength may decrease, and if it is too large, warpage may occur, and the color tone and sinterability may decrease.

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

The ceramic-colored glass of the present invention has a laminating step of laminating the ceramic color paste on at least a part of a region on at least one surface of the glass plate, and the temperature of the obtained laminate is equal to or higher than the softening point of the glass plate. It is obtained by a manufacturing method including a bending molding step of firing the ceramic color paste at the same time as bending and molding by heating with.

In the laminating step, the ceramic color paste may be laminated over the entire surface on at least one surface of the glass substrate, but may be laminated on a part of the region. For example, in automobile glass, it is usually usual. It is laminated on the peripheral edge (near the edges of the four circumferences).

As a method for laminating the ceramic color paste, a laminating method by coating is usually used. Examples of the coating method (or printing method) of the ceramic color paste include a flow coating method, a spin coating method, a spray coating method, a screen printing method, a flexographic printing method, a casting method, a bar coating method, a curtain coating method, and a roll coating method. , Gravure coating method, slit method, photolithography method, inkjet method and the like. Of these, the screen printing method is preferable. Further, the printing may be single-layer printing or multi-layer printing.

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

The average thickness of the dry coating film (on the surface of the coating film, the average thickness in the region excluding the convex portion formed by the glass filler) can be selected depending on the application, and is, for example, 1 to 100 μm, preferably 5 to 50 μm, and further. It is preferably about 10 to 30 μm (particularly 12 to 20 μm).

In the bending molding step, the laminate is usually bent and fired at the same time by heating from the viewpoint of productivity and the like, but depending on the bending molding conditions, the ceramic color paste may be pre-baked.

As a bending molding method for the laminate, a conventional bending molding method can be used, and in the molding method using a press mold, a cloth formed of heat-resistant fibers (for example, metal fibers, glass fibers, etc.) is usually used as a press surface. It is bent and molded using a press mold covered with (contact surface).

In bending molding, a predetermined curvature is imparted to the glass substrate by using a bending molding method involving conventional heat treatment. Examples of the bending forming method include a self-weight bending method and a pressing method using a press die (for example, a metal press die whose contact surface is covered with the cloth).

In the firing step, the heating temperature for firing may be a temperature equal to or higher than the softening point of the glass frit, but when bending and molding the laminate is also performed at the same time in the firing step, the temperature is higher than the softening point of the glass substrate. It needs to be heated, for example, about 580 to 780 ° C., preferably 600 to 750 ° C., more preferably 620 to 720 ° C. (particularly 640 to 700 ° C.).

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

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

The method for measuring the thermal decomposition end temperature and the residue, which are the characteristics of the silicone resin in Table 1, is as follows.

The thermal decomposition completion temperature and residue of the silicone resin were determined by using a thermogravimetric differential thermal analyzer (“TG / DTA6200” manufactured by SII Nanotechnology Co., Ltd.) in an air atmosphere at a heating rate of 20 ° C./min. The temperature was raised from 1 to 750 ° C., and the temperature at which the thermal decomposition was completed 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 and mixing device, and then 3 Uniform dispersion was carried out with this roll to prepare a base ceramic color paste (ceramic color paste of Reference Example 1). The silicone resin was dissolved in a dispersion medium in advance so that it could be easily dispersed, and then added to the stirring and mixing device. Further, in Comparative Examples 2 to 7, the same components as in Examples 1 to 32 were uniformly dispersed without blending a silicone resin to prepare a base ceramic color paste (ceramic color paste of Comparative Example 1). ..

To the obtained ceramic color paste (ceramic color paste of Reference Example 1 or Comparative Example 1), particles or silica shown in Tables 2 to 4 and 2 parts by mass of a phosphate ester dispersant are added, and the mixture is stirred and mixed. The ceramic color pastes of Examples 1 to 32, Reference Examples 2 to 4 and Comparative Examples 2 to 7 containing particles and silica were obtained by sufficiently mixing and dispersing.

[Lamination of ceramic color paste]
The obtained ceramic color paste is solidly printed on a 90 mm × 90 mm portion on a 100 mm × 100 mm × 2 mm thick glass plate (soda glass) using a polyester screen plate (180 mesh) at 150 ° C. It was 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 mold release in press molding]
A ceramic color is printed and a dried glass plate is placed under the press mold that is placed in the heating furnace and whose mold surface is covered with stainless cloth ("KN / C1 (316L)" manufactured by Bekarto). After holding the glass plate at 700 ° C. for 4 minutes, the glass plate was pressed into a curved shape. The average thickness of the fired film (ceramic color film) was measured using a stylus type film thickness meter and found to be 15 μm. The degree of force when the glass plate was peeled off from the press mold (covered surface formed of the stainless steel cloth) of the curved glass plate was evaluated according to the following four criteria, and ⊚ and ◯ were evaluated as acceptable.

◎: Glass can be removed with just a little force (good)
◯: Glass can be removed with a little force (good)
Δ: Requires force ×: Requires considerable force (extremely low mold release).

[Evaluation of fired glass plate]
1. 1. From the glass surface side of the glass plate (sample) with ceramic color obtained by printing and drying the strength ceramic color in the same way as the evaluation of mold release, and firing at 640 ° C, Autograph Co., Ltd. A ring-on-ring bending test was carried out using "AGX-5kN"), and the strength at the time of glass breaking was measured. Specifically, as shown in FIG. 1, when a load is applied to the non-printed surface (glass surface) of sample 1 at a speed of 0.5 mm / min with a jig 2 having a tip having a radius of curvature R3.2 mm and the glass is broken. The strength of the glass was measured. The ring (upper ring) 3 on which the load is applied has an outer diameter of φ12 mm, and the ring (lower ring) 4 that supports the glass substrate has an inner diameter of φ76 mm. The number of evaluations was n = 10, and the average value was calculated. The strength is shown by the strength ratio when the strength of Comparative Example 1 is 1.00.

2. 2. Sinterability The ceramic color is printed and dried in the same way as the evaluation of mold release, and a line is drawn with oil-based ink (magic ink) on the film of the fired film (thickness 15 μm) fired at 640 ° C. It was visually confirmed from the non-printed surface) whether or not the marker ink was impregnated, and evaluated according to the following criteria.

◯: Magic ink is not impregnated ×: Magic ink is impregnated.

3. 3. Color tone evaluation method A fired film (thickness 15 μm) obtained by printing and drying a ceramic color in the same manner as the evaluation of mold releasability and firing at a setting of 640 ° C. is measured from the glass surface side (non-printing surface). Lab was measured from the glass surface side using "ZE-2000" manufactured by Kogyo Co., Ltd., and the L values were compared. The smaller the L value, the blacker and better the color tone, and the larger the L value, the grayer the color.

4. Transmittance evaluation method A fired film (thickness 15 μm) obtained by printing and drying a ceramic color in the same manner as the evaluation of mold releasability and firing at a setting of 640 ° C. is measured from the glass surface side (non-printing surface). The transmittance was measured with "ZE-2000" manufactured by Color Industry Co., Ltd.

5. Dry hardness The scratch hardness (pencil method) of the dry film (ceramic color film) of the sample dried at 150 ° C. was measured 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) was added to a total of 100 parts by mass of the glass frit and the heat-resistant pigment. In this case, the mold release property was improved (Example 3), and when 15 parts by mass or more was added, the mold release property was particularly excellent. Addition of up to 23 parts by mass satisfied other performances (Examples 4 and 5), but when the amount was 27 parts by mass or more, the sinterability and concealing property (transmittance) decreased (Example 6). Similar results were obtained when particles 2 (particle size range 10 to 20 μm, glass beads) were added, but the transmittance was higher than that of particles 1. When particle 3 (particle size range 20 to 30 μm, glass beads) was added, the mold release property was improved at 10 parts by mass or more as in particles 1 and 2, but there was no change when 15 parts by mass was added, and 23 mass was added. When partially added, the mold releasability was further improved. When 15 parts by mass of particles 4 (43 to 53 μm, glass beads) were added, the mold release property was not improved and the transmittance was increased. The strength (strength ratio) improved as the amount of glass beads added increased, but the strength tended to decrease as the particle size increased.

When particles 5 (particle size range 53 to 63 μm, glass beads) considerably larger than the film thickness were added (Example 19), it is considered that the mold release effect appeared even with the addition amount of 7 parts by mass due to the spacer effect. The glass beads could be seen through, and the appearance became abnormal.

From these results, the strength and mold release effect were higher when the particle size of the glass beads was smaller, and the sinterability, color tone, and hiding property were lowered when the amount of the glass beads added was large. Further, when the particle size is increased, although the mold release effect is obtained, the strength is decreased and the transmittance is increased, and when glass beads considerably larger than the film thickness are added, the glass beads are visually transparent. Agglomeration was confirmed, and the appearance was poor.

The glass fibers of the particles 6 used in Examples 21 to 27 are milled fibers obtained by crushing long glass fibers having a fiber diameter of 10 μm to a length of 10 to 50 μm, and the total amount of glass frit and heat-resistant pigment is 100 parts by mass. On the other hand, when 3 to 15 parts by mass was added, the mold release property was the same as that of the particle 1, but the hiding property (permeability) and the color tone of the glass beads were slightly superior. When 27 parts by mass of the particles 6 were added (Example 26), the sinterability was superior to that of the particles 1, but the transmittance was increased. As with the glass beads, the strength improved 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 and the amount of the silicone resin was varied with respect to 100 parts by mass of the total of the glass frit and the heat-resistant pigment, the silicone resin was added. The ratio of the above was good in the range of 3 to 12 parts by mass with respect to 100 parts by mass of the total of the glass frit and the heat-resistant pigment, and Example 4 was the most excellent in the balance of various properties. Specifically, compared with the case where the silicone resin was not contained (Comparative Example 2), when 3 parts by mass of the silicone resin was added, almost no change was observed in the physical properties (Example 28), but 6 parts by mass of the silicone resin was added. When added, the mold releasability and strength were improved (Example 4). When 12 parts by mass of the silicone resin was added, the strength was further improved, but the sinterability and the color tone were lowered (Example 29).

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

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 ink thickened and printing became impossible. In addition, silica did not have the effect of improving mold release property and strength regardless of whether it was powder or spherical (Reference Examples 2 to 4).

From the dry hardness of Reference Example 1 and Comparative Example 1, it can be seen that the dry hardness is increased by adding the silicone resin. The dry hardness of the film containing the glass filler cannot be measured because the pencil is caught on the unevenness of the glass filler on the surface. However, the harder the dry hardness of the base ceramic paste, the stronger the glass filler is fixed in the dry film. Therefore, it is possible to prevent the glass filler from moving and being scratched when handling the glass, resulting in a defective product. Therefore, in Comparative Examples 2 to 7 which do not contain the silicone resin, the strength of the dry film is insufficient, so that defective products are likely to occur.

As for 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, the particles 1, 2, 3 (particle size 30 μm) are 1, 2, 3 (particle size 30 μm) with respect to 100 parts by mass of the total of the glass frit and the heat-resistant pigment. Although the strength was slightly improved when 15 parts by mass of the following glass beads) and particles 6 (φ10 μm glass fiber) were added (Comparative Examples 2 to 4 and 7), particles 4 and 5 (glass beads having a particle size of 45 μm or more) were included. In the 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 release property was not obtained, but the strength and the dry film hardness were improved (Reference Example 1).

That is, when the glass filler and the silicone resin are used in combination (Examples 1 to 32), the particles 1, 2, 3 (glass beads having a particle size of 30 μm or less) and the particles 6 are the same as in the case where the silicone resin of the comparative example is not contained. When (φ10 μm glass fiber) was added, the strength was improved, and when particles 4 and 5 (glass beads having a particle size of 45 μm or more) were added, the strength was decreased, but the strength was higher than when no silicone resin was contained. It was improved (comparison between Examples 4, 9, 14, 18, 24 and Comparative Examples 2-5 and 7). Further, in the particles 1 and 2 (glass beads having a particle size of 20 μm or less) and the particles 6 (φ10 μm glass fiber), the mold release property was also improved by adding the silicone resin. From these results, it was found that the mold release property and the strength ratio can be improved at the same time by using the glass beads or glass fibers having a particle size of 30 μm or less and the silicone resin in combination.

Taken together, these results tended to improve mold release and strength as the amount of glass filler added increased, but when it exceeded 27 parts by mass, sinterability, color tone, and concealment tended to decrease. It can be said that the fifth embodiment is the best mode from the viewpoint of excellent balance of these various characteristics.

The present invention can be used as a paste for forming ceramic colors of various glass substrates, and can also be used for glass with a ceramic color having a bent shape. As the glass with ceramic color, for example, it can be used for window glass of vehicles or transport machines such as trains, cars, airplanes, airships, ships, security glass of buildings, etc., and in particular, window glass for automobiles (windshield, rear glass). , Side glass, etc.).

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

Claims (18)

A ceramic color paste containing 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-based resin. The ceramic color paste according to claim 1, wherein the molding temperature is the press temperature. When the decomposition temperature of a silicone-based resin is measured using a thermogravimetric differential thermal analyzer (TG-DTA) under the condition that the temperature rises from 40 ° C to 750 ° C at a heating rate of 20 ° C / min in an air atmosphere. The ceramic color paste according to claim 1 or 2, which comprises a silicone-based resin having a thermal decomposition end temperature of 550 ° C. or higher. The ceramic color paste according to claim 3, wherein the silicone-based resin having a thermal decomposition end temperature of 550 ° C. or higher has a residue of 40 to 70% by mass at the thermal decomposition end temperature. The ceramic color paste according to any one of claims 1 to 4, wherein the silicone-based resin contains a silicone-based resin that is soluble in an organic solvent. The ceramic color paste according to any one of claims 1 to 5, wherein the silicone-based resin contains a C _1-4 alkyl C _6-10 aryl-based silicone resin. The ceramic color paste according to any one of claims 1 to 6, wherein the ratio of the silicone-based resin is 0.1 to 50 parts by mass with respect to 100 parts by mass 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 7, wherein the glass filler is glass beads having a particle size range of 2 to 30 μm and / or glass fibers having a fiber diameter range of 10 to 30 μm and a fiber length range of 10 to 50 μm. The ceramic color paste according to any one of claims 1 to 8, wherein the ratio of the glass filler is 12 to 26 parts by mass with respect to 100 parts by mass of the total amount of the glass frit and the heat-resistant pigment. Claims 1 to 9 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 25 parts by mass with respect to 100 parts by mass of the total amount of the glass frit and the heat-resistant pigment. The ceramic color paste described in any of. The ceramic color paste according to any one of claims 1 to 10, wherein the glass frit comprises 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 according to any one of claims 1 to 11, further comprising a vehicle. The method for producing a ceramic color paste according to any one of claims 1 to 12, wherein a glass frit, a heat-resistant pigment, a glass filler, and a silicone-based resin are mixed. When the decomposition temperature of a silicone-based resin is measured using a thermogravimetric differential thermal analyzer (TG-DTA) under the condition that the temperature rises from 40 ° C to 750 ° C at a heating rate of 20 ° C / min in an air atmosphere. The production method according to claim 13, wherein the silicone-based resin having a thermal decomposition end temperature of 550 ° C. or higher is contained, and the silicone-based resin is dissolved in a dispersion medium and then mixed with a glass frit, a heat-resistant pigment, and a glass filler. A ceramic color formed by firing the ceramic color paste according to any one of claims 1 to 12. A ceramic-colored glass provided with a glass substrate and a ceramic color paste film, wherein the ceramic color film formed in at least a part of at least one surface of the glass substrate with the ceramic color according to claim 15. Ceramic colored glass with laminated layers. A laminating step of laminating a ceramic color film formed of the ceramic color according to claim 15 on at least a part of a glass substrate on at least one surface, and the obtained laminate having a softening point or more of the glass plate. A method for producing a glass with a ceramic color, which comprises a bending molding step of firing the ceramic color paste at the same time as bending and molding by heating at the temperature of. The manufacturing method according to claim 17, wherein the bending molding step includes press molding.

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