JP7181841B2 - 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 the step of cooling the glass plate, the glass plate is strengthened by heating the glass plate and then rapidly cooling it. However, since the ceramic collar and the glass plate generally have different coefficients of thermal expansion, the ceramic collar applies tensile stress to the surface of the glass plate 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.

As a method for improving the strength of a region (portion) with a ceramic collar, a method of lowering the coefficient of thermal expansion of the ceramic collar is known. For example, Japanese Patent Application Laid-Open No. 8-34640 (Patent Document 1) describes that the inorganic components include 5 to 35% by weight of colored heat-resistant pigment powder, 65 to 95% by weight of bismuth-based glass powder, and 0 to 10% by weight of refractory filler powder. % and 0.1 to 20% by weight of an additive consisting of at least one selected from the group consisting of silicon, borides and silicides. It is stated that the breaking load of the baked glass plate is improved.

In addition, JP-A-2000-154038 (Patent Document 2) describes 5 to 40% 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 filler. A ceramic color composition characterized by comprising 0.1 to 40% by weight is disclosed, and it is stated that the thermal expansion coefficient of a glass plate baked with the ceramic color composition is reduced and the strength of the glass plate is improved. It is

However, even in Patent Documents 1 and 2, the reduction in the coefficient of thermal expansion of the ceramic color composition was insufficient, and the strength of the glass plate on which the ceramic color composition was baked was insufficient.

In Japanese Patent Application Laid-Open No. 2017-88106 (Patent Document 3), the difference between the linear expansion coefficient of a shielding film laminated on a glass plate at 500 ° C. and the linear expansion coefficient of the glass plate is the linear expansion of the glass plate. It is described that a decrease in the strength of the glass plate due to the shielding film can be suppressed by setting the coefficient within ±5%.

However, since the linear expansion coefficient of the shielding film in Patent Document 3 is affected by all the compositions contained in the shielding film, the shielding film having a linear expansion coefficient within ±5% of the linear expansion coefficient of the glass plate In order to obtain the above, it was necessary to appropriately adjust the composition of the shielding film depending on the type of glass plate on which the shielding film is laminated.

Since the ceramic color is baked by heating the glass plate, it is preferably made of a material that can be baked at about 600 to 700.degree. Furthermore, the performance requirements for ceramic colors include high strength of the baked glass, high acid resistance and acid rain resistance, appearance such as color tone and transmittance, and mold release during molding. is also good. Further, bismuth-based glass is known as a low-melting-point glass with excellent acid resistance, but it is difficult to release from the mold, and when it becomes crystalline, the coefficient of thermal expansion increases and the strength of the glass decreases. Furthermore, bismuth-based glass has a problem that acid resistance decreases as the bismuth content increases.

JP-A-8-34640 JP-A-2000-154038 JP 2017-88106 A

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a ceramic color paste capable of simply and efficiently improving the strength of ceramic colored glass, a method for producing the same, and a method for improving the strength of ceramic colored glass.

Another object of the present invention is to provide a ceramic color paste and a method for producing the same that can obtain ceramic-colored glass with high strength while maintaining the performance, color tone, transmittance, and other appearance properties of the ceramic color. be.

Still another object of the present invention is to provide a ceramic color paste which is excellent in acid resistance such as acid rain resistance and which exhibits good mold releasability during molding, and a method for producing the same.

The inventors of the present invention have made intensive studies to achieve the above object, and found that when a silicone-based resin is further added to a ceramic color paste containing a glass frit and a heat-resistant pigment, a glass substrate (with a ceramic color) on which the ceramic color paste is baked is obtained. The inventors have found that the strength of glass) is improved, and completed the present invention.

That is, the ceramic color paste of the present invention is a ceramic color paste containing a glass frit and a heat-resistant pigment, and further contains a silicone resin. 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 frit may contain a bismuth-based glass frit. The ceramic color paste of the present invention may further contain a plate-like inorganic compound. 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, 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 may be mixed with the glass frit and the heat-resistant pigment after dissolving the silicone resin in the dispersion medium.

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

The present invention provides a ceramic colored glass comprising a glass substrate and a ceramic color film, wherein the ceramic color film is formed on at least a partial region of at least one surface of the glass substrate. Also included is ceramic colored glass laminated with .

The present invention also includes a method of manufacturing a ceramic-colored glass by laminating a ceramic-colored film formed of the ceramic color on at least a part of a glass substrate on at least one surface.

The present invention also includes a method for improving the strength of glass with a ceramic color, comprising laminating a ceramic color film formed with the ceramic color on a glass substrate.

When the ceramic color paste of the present invention is baked on a glass substrate, porosity occurs in the ceramic color film because it contains a silicone-based resin. Therefore, in the present invention, it is not necessary to adjust the composition of the ceramic color paste according to the composition of the glass substrate, and the decrease in glass strength due to the ceramic color can be suppressed, so that the strength of the glass with a ceramic color can be improved simply and efficiently. can. In addition, by selecting a specific silicone resin, warpage can be suppressed, sinterability can be improved, ceramic color performance can be improved, and strength can be maintained while maintaining appearance such as color tone and transmittance. can improve. Furthermore, when the plate-like inorganic compound is included, the mold release property during molding is good even if the bismuth-based glass is included, and the acid resistance, acid rain resistance, and appearance characteristics are excellent, and the mold release property during molding is good. A ceramic color paste can be obtained.

FIG. 1 is a schematic diagram for explaining a method for measuring the strength of ceramic-colored glass obtained in Examples.

[Ceramic color paste]
The ceramic color paste (or ceramic color composition) of the present invention is characterized by containing a silicone-based resin in addition to conventionally blended glass frit and heat-resistant pigment.

(silicone resin)
In the present invention, by combining the glass frit and the heat-resistant pigment with a silicone-based resin (silicone-based resin), it is possible 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.

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 alkyl 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. Of these, C _1-2 alkyl C _6-8 aryl silicone resins such as methylphenyl silicone resins are preferred. As described above, the C _1-2 alkyl C _6-8 aryl silicone resin can improve the strength, appearance and mold releasability. Salt) can greatly improve strength.

In alkylaryl silicone resins, the number of aryl groups (especially _C6-8 aryl groups such as phenyl groups) in the molecule and the number of alkyl groups (especially _C1-3 alkyl groups such as methyl groups and propyl groups) The ratio of the number of aryl groups/number of alkyl groups can be selected from a range of about 100/1 to 1/100 (eg, 50/1 to 1/10), for example, 50/1 to 1/3, preferably 10/1. to 1/2, more preferably 5/1 to 1/1, more preferably 3/1 to 1.5/1, most preferably 2.5/1 to 1.7/1. When the ratio of the aryl group and the alkyl group is within such a range, the strength, appearance and releasability can be improved in a well-balanced manner.

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 ~3000).

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 650 to 750, in order to achieve both glass strength and appearance properties. ° C., and most preferably the silicone resin having a decomposition temperature of 700 to 730° C. and a residue of 45 to 55% by weight. 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). 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.

(glass frit)
Glass frit (fusible glass powder or particles) is incorporated to form a ceramic color film and to adhere to the glass plate. 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, and the like are widely used, and from the viewpoint that the remarkable effects of the present invention, such as compatibility between acid resistance and glass strength, are likely to be exhibited, at least bismuth-based glass It preferably contains a 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 of the glass frit may be lower than the firing temperature of the ceramic color paste, and can be selected from the range of about 350 to 600°C, for example, 360 to 580°C, preferably 380 to 580°C, more preferably 400 to 580°C. (particularly 410 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 95% by mass). 70% 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 40 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.

(Plate-like inorganic compound)
Since the ceramic color paste of the present invention can improve the appearance characteristics such as color tone and the release property during molding, in addition to silicone resin, glass frit and heat-resistant pigment, plate-like (scale-like or layer-like) inorganic compound preferably further comprises

Plate-like inorganic compounds include, for example, graphite, silicon carbide, silica, silicon nitride, boron nitride, quartz powder, hydrotalcite, glasses (glass flakes, glass beads, glass powder, milled glass fiber, etc.), carbonates ( calcium carbonate, magnesium carbonate, etc.), silicates (calcium silicate, aluminum silicate, talc, mica, kaolin, clay, etc.), metal oxides (iron oxide, titanium oxide, zinc oxide, alumina, etc.), sulfates ( calcium sulfate, barium sulfate, etc.), various metal powders and metal foils. These plate-like inorganic compounds can be used alone or in combination of two or more. Among these, silicates such as talc and mica are preferable because they have a high affinity with glass frit and can improve glass strength and releasability.

The average diameter of the plate surface of the plate-like inorganic compound (in the case of an anisotropic shape, the average diameter of the major axis and the minor axis is regarded as the plate surface diameter of each compound) is, for example, 0.5 to 30 μm, preferably 1 to 20 μm, More preferably, it is about 2 to 10 μm (especially 3 to 5 μm). The average thickness of the plate-like inorganic compound is, for example, about 10 to 300 nm, preferably 30 to 200 nm, more preferably 50 to 150 nm (especially 100 to 130 nm).

The proportion of the plate-like inorganic compound can be selected from the range of about 0.1 to 30 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 1 to 10 parts by mass, preferably 1.5 to 7 parts by mass. Parts by mass, more preferably about 2 to 6 parts by mass (especially 3 to 5 parts by mass). If the proportion of the plate-like inorganic compound is too low, the effect of improving the appearance characteristics and mold releasing property may be reduced. be.

(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 boiling point of the dispersion medium is low as long as it is low in volatility at room temperature and can be easily volatilized without melting the glass frit. °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 may contain customary additives such as hue modifiers, brighteners, metal corrosion inhibitors, stabilizers (antioxidants, UV absorbers, etc.), surfactants or dispersants. (anionic surfactant, cationic surfactant, nonionic surfactant, amphoteric surfactant, etc.), dispersion stabilizer, thickener or viscosity modifier, moisturizing agent, thixotropic imparting agent, leveling agent, Defoamers, 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 a ceramic color of the present invention is obtained by laminating the ceramic color paste on at least a part of at least one surface of a glass plate, and applying the obtained laminate to the glass frit contained in the ceramic color paste. It is obtained by a manufacturing method including a firing step of heating and firing at a temperature equal to or higher than the softening point of .

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.

Since the dispersion medium evaporates from the obtained dry coating film, there are portions where the silicone resin exists on the coating film surface. Therefore, even if the glass frit is melted by baking the dry coating film in the next step, the release from the mold during molding can be improved. In particular, when the coating film contains a plate-like inorganic compound such as talc or mica, the contact between the molten glass frit contained in the ceramic color film and a molding die such as a press mold is suppressed. Effectively improve sexuality.

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

In the firing step, depending on the application, the laminate may be bent and formed together with the firing of the ceramic color paste. Bending may be performed after baking the ceramic color paste, but from the point of view of productivity and the like, the laminate is usually bent and baked by heating at the same time.

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. Examples of the bending method include 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), etc. In the baking process, heating for baking The temperature may be any temperature above the softening point of the glass frit, but in the case where the laminated body is also bent at the same time in the firing process, it is necessary to heat at a temperature above the softening point of the glass substrate. It is about 750°C, preferably 570 to 700°C, more preferably about 580 to 680°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.

Reference Examples 1-2, Examples 1-22 and Comparative Examples 1-9
[Materials used]
Table 1 shows the details and characteristics of the materials used.

The methods for measuring the thermal decomposition completion temperature and residue, which are the characteristics of the silicone resin and silicone oil 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.

The phenyl/alkyl ratio in Table 1 is the ratio of the number of phenyl groups to the number of alkyl groups (methyl groups or propyl groups) in the silicone resin.

[Preparation of ceramic color paste]
After mixing the materials shown in Tables 2 to 4 with a stirring mixer, they were homogenously dispersed with three rolls to prepare a ceramic color paste. The silicone resins other than Silicone Resin X-52-854 were dissolved in the dispersion medium in advance and then added to the agitating and mixing device. In addition, the silicone resin 9, silica 2, silica 3, glass beads and glass fibers were homogenously dispersed by three rolls, added to the obtained paste, and thoroughly mixed and dispersed by a mixer to prepare the final ceramic color paste. did.

[Preparation of glass with ceramic color]
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 15 to 20 μm. After drying, it was placed in a furnace at 640° C. and heated and baked in the atmosphere for 5 minutes. When the average thickness of the fired film (ceramic color film) was measured using a stylus type film thickness meter, it was 10 to 15 μm. The obtained glass with ceramic color was evaluated as follows.

[Volume ratio of silicone residue (or additive)]
The volume ratio of silicone residue (or additive) means the volume ratio of residue (or additive) derived from silicone resin or silicone oil in the ceramic color film (fired film). agent) was converted based on the amount of residue in the thermal decomposition test. In addition, the said additive means an additive (residual additive) other than a silicone residue.

[Strength]
A ring-on-ring bending test was performed using an autograph ("AGX-5kN" manufactured by Shimadzu Corporation) from the glass surface side of the obtained glass with ceramic color (sample), and the strength at the time of glass breakage was measured. It was measured. 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 having a tip with a curvature radius of R3.2 mm, and the glass is broken. Strength 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.

[Warp (mm)]
For the sample, the amount of warpage from a horizontal desk was measured with a metal rule.

[Color (L value)]
For the samples, using a color difference meter (Nippon Denshoku Industries Co., Ltd., "colorimetric color difference meter ZE-2000"), Lab was measured from the glass surface side, and L values were compared. The smaller the L value, the darker and better the color tone, and the larger the L value, the grayer.

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

[Sinterability]
A line was drawn on the ceramic color layer with an oil-based ink (magic ink) on the sample, and it was confirmed whether or not the marker ink had permeated when viewed from the non-printed surface side, and evaluation was made according to the following criteria.

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

[Mold separation evaluation 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 [Bekaert "KN/C1 (316L)"]. After being held at 700° C. for 4 minutes, the glass plate was pressed into a curved shape. The degree of force when the curved glass plate was peeled off from the press mold (coated surface formed of the stainless cloth) was evaluated according to the following four-grade criteria. However, △ or more is a practical level.
◎: 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).

The evaluation results are shown in Tables 2-5.

As is clear from Tables 2 and 3, the ceramic-colored glasses obtained in Examples had high strength, and were excellent in color tone and releasability. In particular, the ceramic-colored glasses obtained in Examples 1 to 3, 7 and 9 to 15 had no warpage and were excellent in dry film hardness and sinterability. As for the silicone resins, when silicone resins 1 to 8, which are soluble in solvents, were used, the silicone resins formed a film in the state of a dry film, so that the dry film hardness was improved. On the other hand, silicone resin 9, which has no solvent solubility, did not form a film in the dry film state, so the dry film hardness was lowered.

On the other hand, as is clear from Table 4, the ceramic-colored glasses obtained in Comparative Examples 1 to 6 had low strength. In Comparative Example 7 using silicone oil, the glass was not cured, and the glass with ceramic color obtained in Comparative Example 8 using zirconia had a low color tone, low dry film hardness, and low sinterability.

Moreover, as is clear from the results in Table 5, by changing the type of glass frit for the ceramic colors in Tables 2 and 3, the effect was slightly reduced, but the strength ratio was improved. Further, from the comparison between Example 18 and Example 20, and between Example 21 and Example 22, Examples 18 and 21, in which methylphenyl-based silicone was blended as the silicone resin, blended phenyl-based silicone. The strength ratio was higher than those of Examples 20 and 22, and the color tone and dry film hardness were also excellent. Furthermore, as is clear from the results of Examples 21 and 22, when the silicone resin and mica are combined, the strength ratio is further improved. The color tone and dry film hardness were also excellent. In addition, when the silicone resin and mica are combined, the releasability is improved.

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 (15)

A ceramic color paste for reinforcing glass, comprising a glass frit and a heat-resistant pigment, and further comprising a silicone resin. 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 for reinforcing glass according to claim 1, comprising a silicone-based resin having a thermal decomposition finish temperature of 550[deg.] C. or higher. The ceramic color paste for reinforcing glass 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. The ceramic color paste for reinforcing glass 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 for glass reinforcement 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. The ceramic color paste for reinforcing glass according to any one of claims 1 to 5, wherein the proportion of the silicone resin is 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 ceramic color paste for reinforcing glass according to any one of claims 1 to 6, wherein the glass frit contains a bismuth-based glass frit. The ceramic color paste for reinforcing glass according to any one of claims 1 to 7, further comprising a plate-like inorganic compound. The ceramic color paste for reinforcing glass according to any one of claims 1 to 8, further comprising a vehicle. A method for producing the ceramic color paste for reinforcing glass according to any one of claims 1 to 9 by mixing glass frit, a heat-resistant pigment and a silicone resin. 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. 11. The production method according to claim 10, which comprises a silicone resin having a thermal decomposition completion temperature of 550° C. or higher, and the silicone resin is dissolved in the dispersion medium and then mixed with the glass frit and the heat-resistant pigment. A ceramic color formed by firing the ceramic color paste for reinforcing glass according to any one of claims 1 to 9. A ceramic colored glass comprising a glass substrate and a ceramic color film, wherein the ceramic color film formed with the ceramic color according to claim 12 is formed on at least a part of at least one surface of the glass substrate. Laminated ceramic colored glass. A method for producing a ceramic-colored glass by laminating a ceramic-colored film formed with the ceramic-colored according to claim 12 on at least a part of a region of at least one surface of a glass substrate. 13. A method for improving the strength of glass with a ceramic color, comprising laminating a ceramic color film formed with the ceramic color according to claim 12 on a glass substrate.

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