Black resin composition

Abstract

To provide a glass-reinforced black resin composition which easily adjusts light transmittance in a visible light region to a desired hue, has high dispersion stability, and is excellent in adhesion to a glass substrate.SOLUTION: A black resin composition contains a coloring agent (A) and a resin (B). A siloxane resin (C) is contained as the resin (B), and a content of the siloxane resin (C) is 35 mass% or more to the total solid content in the black resin composition. A film is formed on a transparent glass substrate from the black resin composition with film thickness of 2 μm, total light transmittance at a wavelength of 400 nm to 700 nm when light rays are emitted and transmitted to the film from a D65 standard light source is 20% or more at minimum and 80% or less at maximum, and chromaticities a* and b* are within the range of -3 to +3.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a black resin composition containing a colorant (A) and a resin (B), wherein the resin (B) contains a siloxane resin (C), and to a black coating and a black resin-coated glass substrate using the black resin composition. [Background technology]

[0002] Conventionally, the back housings of various display devices such as wearable devices, smartphones, and tablet PCs (personal computers) have adopted a laminated structure of a transparent glass layer, a colorless and transparent glass reinforced transparent coating film layer, and a decorative layer to improve design.

[0003] On the other hand, as an invention of a colored resin composition that can form a colored coating film with excellent adhesion to a glass substrate and excellent film thickness uniformity, for example, Patent Document 1 proposes an invention in which a gradation film is formed by inkjet-coating a 6.0 μm-thick coating film made of a red, green, blue, purple, or yellow pigment or dye.

[0004] The invention of Patent Document 1 relates to a colored resin composition having a surface tension of 26 mN or more and 28 mN or less at 25°C, comprising (A) a siloxane resin having a methyl group and a phenyl group, and (B) a colorant, in which the content of the siloxane resin (A) is 30% by weight or more based on 100% by weight of the solid content, and the film shrinkage rate upon thermal curing is 10% or less. When inkjet coated onto a glass substrate, the colored resin composition has the effect of forming a colored coating with a good appearance without repellency or unevenness. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-63144 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, there has been a demand for further improvements in the design of the rear housings of various display devices, and studies have begun on laminated rear glass housings in which the above-mentioned glass substrate is replaced with translucent color glass tinted pale black (see Figure 2). However, there are issues with the workability of black-tinted translucent color glass, which can lead to uneven printing.

[0007] Therefore, the inventors mixed the colored resin compositions containing the red, green, blue, purple, or yellow (B) colorants described in Patent Document 1 to create a pseudo-black resin composition, which was then coated on a conventional transparent glass substrate to study a new laminated structure of a transparent glass substrate / glass-reinforced black resin composition layer / decorative layer for a glass-backed housing. That is, the laminated structure has a glass-reinforced black resin composition layer as a dimming layer that adjusts the brightness of the decorative layer (see Figure 1).

[0008] However, when attempting to prepare a black resin composition having a pseudo-black color by mixing colored resin compositions containing red, green, blue, purple, or yellow (B) colorants, it is difficult to adjust the color to the desired hue, and since the transmittance of each wavelength in the visible light range differs for each (B) colorant, there is a problem in that it is difficult to adjust the light transmittance of the entire black resin composition to the desired value.

[0009] Furthermore, when these red, green, blue, purple, or yellow colored resin compositions are mixed and used, the compatibility between the siloxane resin and each (B) colorant differs for each (B) colorant, and therefore the appropriate dispersant also differs somewhat for each (B) colorant, which presents a problem that the dispersion stability of the entire black resin composition consisting of a pseudo-black color tends to decrease.

[0010] The present invention has been made in view of the above-mentioned problems, and has an object to provide a glass-reinforced black resin composition which allows for easy adjustment of light transmittance in the visible light region to a desired hue, has high dispersion stability, and exhibits excellent adhesion to glass substrates; and to provide tempered glass which is more processable than a laminated structure of translucent colored glass colored pale black, and which can reduce the occurrence of uneven firing marks. [Means for solving the problem]

[0011] The present invention is achieved by the following configuration. (1) A black resin composition containing a colorant (A) and a resin (B), wherein the resin (B) is a siloxane resin (C), and the content of the siloxane resin (C) is 35 mass% or more relative to the total solid content in the black composition; the black resin composition is formed into a film having a thickness of 2 μm on a transparent glass substrate; and when light is irradiated onto the film from a D65 standard light source and transmitted through the film, the total light transmittance at wavelengths of 400 nm to 700 nm is a minimum of 20% or more and a maximum of 80% or less; and the chromaticity a* and b* of the film are both in the range of -3 to +3. (2) The black resin composition according to (1), wherein the haze value of the film is less than 3%. (3) The black resin composition according to (1) or (2), wherein the content of the coloring material (A) is 1 to 6% by mass based on the total solid content in the black composition. (4) The black resin composition according to (1) or (2), wherein the colorant (A) contains carbon black (A-1) and titanium nitride (A-2), and the total amount of the two is 50 mass% or more based on the total amount of the colorant (A). (5) The black resin composition according to (4), wherein the coloring material (A) comprises carbon black (A-1) and titanium nitride (A-2). (6) The black resin composition according to (5), wherein the content of the carbon black (A-1) in the colorant (A) is 25 to 50 mass % based on the total amount of the colorant (A), and the content of the titanium nitride (A-2) is 50 to 75 mass % based on the total amount of the colorant (A). (7) The black resin composition according to (1) or (2), wherein the colorant (A) contains at least carbon black (A-1) and zirconium nitride (A-3), and the total amount of the two is 50% by mass or more based on the total amount of the colorant (A). (8) The black resin composition according to (7), wherein the coloring material (A) contains only carbon black (A-1) and zirconium nitride (A-3). (9) The black resin composition according to (7), wherein the content of the carbon black (A-1) in the colorant (A) is 30 to 70 mass% based on the total amount of the colorant (A), and the content of the zirconium nitride (A-3) is 30 to 70 mass% based on the total amount of the colorant (A). (10) The black resin composition according to (1) or (2), which contains a dispersant (D) having an amine value of 30 mgKOH / g or less. (11) The black resin composition according to (10), wherein the content of the dispersant (D) is 0.1 to 10% by mass based on the total solid content in the black resin composition. (12) The black resin composition according to (1) or (2), further comprising inorganic particles (E), the content of which is 10% by mass or more relative to the total solid content of the black composition; the inorganic particles (E) including silica particles, the content of which is 60% by mass or more relative to the inorganic particles (E). (13) The black resin composition according to (12), wherein the inorganic particles (E) contain only silica particles. (14) A glass-reinforced black resin layer comprising a film of the black resin composition according to (1) or (2). (15) A tempered glass comprising a glass substrate on which the glass-reinforcing black resin layer according to (14) above is formed. (13) Decorative glass comprising a glass substrate on which the glass-reinforced black resin layer according to (14) above is formed. [Effects of the Invention]

[0012] The black resin composition of the present invention can be easily adjusted to a predetermined light transmittance in the visible light region and to a pale, translucent, neutral black hue, which, in combination with the hue of the decorative layer behind it, can improve the design to have a deep, profound feel. Furthermore, the inclusion of a predetermined amount of siloxane resin (C) provides excellent adhesion to the glass substrate and enhances the strength of the glass substrate.

[0013] Furthermore, by adjusting the chromaticity a* and b* of the film to be within the range of -3 to +3, the black resin composition of the present invention can prevent the color tone from changing even when light is reflected from the surface of the decorative layer at the back and passes through the film twice. Furthermore, by adjusting the haze value of the film to be less than 3%, light scattering within the film can be reduced. As a result, a more profound, jet-black design can be achieved.

[0014] Furthermore, by incorporating a predetermined amount of carbon black (A-1) and titanium nitride (A-2) or carbon black (A-1) and zirconium nitride (A-3) as the coloring material (A), it is possible to easily adjust the light transmittance to a desired level. Furthermore, by incorporating a dispersant (D) having an amine value of 30 mgKOH / g or less, it is possible to improve the dispersion stability of the black resin composition as a whole.

[0015] Furthermore, by coating a glass substrate with the black resin composition of the present invention to form a glass-reinforced black resin layer, tempered glass that is easier to process than black colored glass can be obtained, and this has the effect of making it applicable to decorative glass as a curved back glass housing. [Brief explanation of the drawings]

[0016] [Figure 1] 1 is a diagram showing an example of decorative glass coated with the black resin composition of the present invention to form a glass-reinforced black resin layer. FIG. [Figure 2] FIG. 1 is a diagram showing an example of a glass-backed housing having a laminated structure using a translucent colored glass layer, which has recently begun to be considered. [Figure 3] 1 is an example of a spectrum showing the total light transmittance when the black resin composition of the present invention is formed into a film having a thickness of 2 μm, and the spectrum shows the total light transmittance when carbon black (CB), titanium nitride (TiN), and a mixture thereof (CB / TiN=40 / 60) are used as the colorant (A), each at a concentration of 6 wt % (total solid content ratio). [Figure 4]1 is an example of a spectrum showing the total light transmittance when the black resin composition of the present invention is formed into a film having a thickness of 2 μm, and when a mixture of carbon black (CB) and titanium nitride (TiN) (CB / TiN=40 / 60) is used as the colorant (A) at a concentration of 1 wt % to 6 wt % (total solid content ratio). [Figure 5] 1 is an example of a spectrum showing the total light transmittance when the black resin composition of the present invention is formed into a film having a thickness of 2 μm, and when carbon black (CB), zirconium nitride (ZrN), and a mixture thereof (CB / ZrN=50 / 50) are used as the colorant (A), each at a concentration of 2 wt % (total solids content). [Figure 6] 1 is an example of a spectrum showing the total light transmittance when the black resin composition of the present invention is formed into a film having a thickness of 2 μm, and when a mixture of carbon black (CB) and zirconium nitride (ZrN) (CB / ZrN=50 / 50) is used as the colorant (A) at a concentration of 2 wt % to 4 wt % (total solids content). DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention will be described in detail below. The black resin composition of the present invention is a black resin composition containing a colorant (A) and a resin (B), wherein the resin (B) contains a siloxane resin (C), the content of the siloxane resin (C) being 35 mass% or more relative to the total solid content in the black composition, and wherein the black resin composition is formed into a film having a thickness of 2 μm on a transparent glass substrate, and when light is irradiated from a D65 standard light source onto the film and transmitted through it, the total light transmittance at wavelengths of 400 nm to 700 nm is at least 20% and at most 80%.

[0018] The reason for the phrase "when a film is formed with a thickness of 2 μm" is that this is the optimum thickness when a film is formed by coating a transparent glass substrate with the black resin composition of the present invention. That is, the film thickness is preferably 0.5 μm or more because of the need to strengthen the transparent glass substrate, and is preferably 5 μm or less because of the need to adjust the film to a pale translucent black hue, and 2 μm is an intermediate thickness that strikes a good balance between these two.

[0019] The reason for using the "D65 standard light source" is that it is a standard light source defined by the CIE (International Commission on Illumination) and JIS, and is a daylight light source consisting of average noon light (a combination of direct sunlight and diffused light from a clear sky) intended to reproduce an outdoor lighting environment, and is close to the lighting environment in which various display terminals to which the black resin composition of the present invention is applied are used.

[0020] The reason for the requirement that "the total light transmittance in the wavelength range of 400nm to 700nm must be a minimum of 20% or more and a maximum of 80% or less" is that by setting the light transmittance within this range, a pale translucent film will form, which will act as a dimming layer that adjusts the brightness of the decorative layer, and in combination with the hue of the decorative layer, it will be possible to create a design with a sense of depth and dignity that could not be achieved with the conventional laminated structure of transparent glass layer / colorless transparent glass reinforced transparent coating film layer / decorative layer.

[0021] The total light transmittance at each wavelength of this black resin composition film is a value obtained using a spectrophotometer (UV-2500PC, manufactured by Shimadzu Corporation). After zero-base correction is performed using only the transparent glass substrate as a reference, the two-layer glass consisting of the transparent glass substrate and the black resin composition film is measured and used as the light transmittance of the black resin composition film (see Examples below). Furthermore, in embodiments in which other layers are also formed, similar measurements are made using the substrate and other layers as references, and the light transmittance of the black resin composition film is used. Note that "total light transmittance is at least 20% and at most 80%" means that the minimum total light transmittance measured by this measurement method is at least 20% and the maximum total light transmittance is at most 80%.

[0022] The total light transmittance can be appropriately adjusted by adjusting the content of the color material (A) described below. The greater the content of the color material (A), the lower the total light transmittance.

[0023] The black resin composition of the present invention is a black resin composition in which the chromaticity a* and b* of the film are both in the range of -3 to +3, preferably -2.0 to +2.0. When the chromaticity of the film is in this range, the color tone does not change much even when light is reflected from the surface of the decorative layer and transmitted through the film twice, making it possible to achieve a design with a jet-black, luxurious color.

[0024] The chromaticity a* and b* of the film are chromaticity (a*, b*) values ​​obtained by the so-called transmitted light measurement method, in which the wavelength distribution of light transmitted through the film is detected from the light spectrum of light transmittance obtained using the spectrophotometer (UV-2500PC, manufactured by Shimadzu Corporation), and color information is obtained from the wavelength distribution.

[0025] The chromaticity a* can be adjusted to a range of -3 to +3, preferably -2.0 to +2.0, by, for example, adjusting the content of carbon black (A-1) in the colorant (A) to 25 to 50 mass% and the content of titanium nitride (A-2) to 50 to 75 mass% based on the total amount of colorant (A). Alternatively, the content of carbon black (A-1) can be adjusted to 30 to 70 mass% and the content of zirconium nitride (A-3) to 30 to 70 mass% based on the total amount of colorant (A). However, the above chromaticity can also be achieved by combining multiple pigments in other ways, so this is not limiting.

[0026] Furthermore, the chromaticity b* can be adjusted to a range of -3 to +3, preferably -2.0 to +2.0, by, for example, adjusting the content of carbon black (A-1) in the colorant (A) to 25 to 50 mass% and the content of titanium nitride (A-2) to 50 to 75 mass% based on the total amount of colorant (A). Alternatively, the content of carbon black (A-1) can be adjusted to 30 to 70 mass% and the content of zirconium nitride (A-3) to 30 to 70 mass% based on the total amount of colorant (A). However, the above chromaticity can also be achieved by combining multiple pigments in other ways, so this is not limiting.

[0027] Furthermore, the black resin composition of the present invention is a black resin composition that provides a film with a haze value of less than 3%. The haze value is preferably less than 2.5%, and more preferably less than 1.5%. A low haze value of the film reduces light scattering within the film, making it possible to create a design with a jet-black, luxurious luster.

[0028] The haze value of the film is a numerical value calculated by the formula Haze (%) = [(T4 / T2) - (T3 / T1)] × 100, as defined in JIS K 7136. Here, T1 is the diffuse transmittance when no sample is placed, T2 is the diffuse transmittance when a sample is placed, T3 is the total light transmittance when no sample is placed, and T4 is the total light transmittance when a sample is placed.

[0029] The haze value can be set to less than 3%, preferably less than 2.5%, and more preferably less than 1.5%, by improving dispersibility by increasing the rotation speed during dispersion or reducing the bead diameter, or by improving the compatibility between the resin (B), dispersant (D), and solvent.

[0030] As the colorant (A), pigments, dyes, etc. generally used in display devices can be used. It is preferable to use a pigment to improve the heat resistance, reliability, and light resistance of the coating film. There are no particular restrictions on the pigment, but black pigments such as carbon black, titanium black (titanium nitride or titanium oxynitride), perylene black, acetylene black, aniline black, zirconium nitride, and bisbenzofuranone are preferred. These colorants may be used alone or in combination of two or more.

[0031] The content of colorant (A) is preferably 1% by mass or more and 10% by mass or less, and more preferably 2% by mass or more and 6% by mass or less, based on 100% by mass of the total solid content contained in the black resin composition. If the content of colorant (A) is too low, it becomes difficult to form a film with a maximum total light transmittance of 80% or less at wavelengths of 400 nm to 700 nm, and the resulting film will not differ much from the structure of a conventional colorless, transparent, glass-reinforced transparent coating film layer and will not exhibit sufficient design properties. On the other hand, if the content of colorant (A) is too high, the total light transmittance at wavelengths of 400 nm to 700 nm will tend to be less than 20% at minimum, which will hide the decorative layer and result in a dull, monotonous design.

[0032] Among the black pigments, a combination of carbon black (A-1) and titanium black (A-2) or carbon black (A-1) and zirconium nitride (A-3) is preferred, and the total amount of these is preferably 50% by mass or more, more preferably 90% by weight or more, of the total colorant (A). This combination results in a nearly constant, flat spectrum of total light transmittance in the visible light range (see Figures 4 and 6), and has the effect of easily adjusting the total light transmittance to a minimum of 20% or more and a maximum of 80% or less.

[0033] That is, the total light transmittance in the visible light region of carbon black (A-1) gradually decreases from its peak around 400 nm toward longer wavelengths around 680 nm, while the total light transmittance in the visible light region of titanium nitride (A-2) and zirconium nitride (A-3) tends to gradually increase from around 400 nm toward longer wavelengths around 680 nm (see Figures 3 and 5). Therefore, the spectrum of carbon black (A-1) and the spectrum of titanium nitride (A-2) or zirconium nitride (A-3) cancel each other out, resulting in a nearly constant, flat spectrum of total light transmittance in the visible light region (see Figures 3, 4, 5, and 6).

[0034] When the coloring agent (A) contains carbon black (A-1) and titanium nitride (A-2), the content of carbon black (A-1) is preferably 25 to 50 mass% of the total amount of the coloring agent (A) and the content of titanium nitride (A-2) is preferably 50 to 75 mass% of the total amount of the coloring agent (A). Furthermore, the content of carbon black (A-1) is more preferably 35 to 45 mass% of the total amount of the coloring agent (A) and the content of titanium nitride (A-2) is more preferably 55 to 65 mass% of the total amount of the coloring agent (A). Furthermore, when the coloring agent (A-1) contains carbon black (A-1) and zirconium nitride (A-3), the content of carbon black (A-1) is preferably 30 to 70 mass% of the total amount of the coloring agent (A) and the content of zirconium nitride (A-3) is more preferably 30 to 70 mass% of the total amount of the coloring agent (A). Furthermore, it is more preferable that the content of carbon black (A-1) is 40 to 60 mass % based on the total amount of the coloring material (A), and the content of zirconium nitride (A-3) is 40 to 60 mass % based on the total amount of the coloring material (A).

[0035] If the total light transmittance of the colorant (A) in the visible light region becomes a nearly constant, flat spectrum, the range of the content of the colorant (A) in which the total light transmittance in the wavelength range of 400 nm to 700 nm is 20% or more at minimum and 80% or less at maximum is expanded, making it easier to adjust the total light transmittance within that range. Furthermore, because the total light transmittance can be easily adjusted to a desired value by changing the concentration of the colorant (A), black resin composition films of various translucent densities can be obtained (see Figures 4 and 6), which also has the effect of enabling a variety of designs that are difficult to achieve with colored glass.

[0036] The carbon black (A-1) is preferably a weakly acidic carbon black dispersion having, for example, an average primary particle size of 10 to 40 nm, a dibutyl phthalate absorption of 20 to 50 cm3 / 100 g, and a pH of 2.5 to 5.0. By controlling the average primary particle size and acidity of the carbon black (A-1) within the above ranges, a jet black hue can be easily achieved, and compatibility with the inorganic particles (E) described below can be improved, resulting in a lower diffuse reflectance value. Furthermore, by controlling the dibutyl phthalate absorption within the above range, aggregation can be suppressed. The dibutyl phthalate absorption can be measured according to JIS K6221 (1982).

[0037] Titanium nitride (A-2) may have, for example, an oxygen content of 3 to 10%, a nitrogen content of 15 to 25%, and the remainder titanium, and has an average primary particle size of 10 to 80 nm, a specific gravity of 5.0 to 5.4, and a specific surface area of ​​25 to 100 m 2 It is preferable to use a weakly acidic titanium nitride dispersion in which the pH of the aqueous dispersion is 4.0 to 6.5 and the specific surface area is large, so that the titanium nitride particles in the dispersion are less likely to settle, and long-term changes in the jet-black hue when a black resin composition is prepared can be reduced. Furthermore, by keeping the acidity within the above range, affinity with the dispersant is improved, and dispersion stability in the dispersion is improved despite the large specific surface area. Examples of zirconium nitride (A-3) include those with a composition of 83 to 90% zirconium, 7 to 12% nitrogen, and about 2% other components such as hafnium, and are spherical particles with an average primary particle size of 10 to 300 nm, a specific gravity of 6.8 to 7.3, and a specific surface area of ​​20 to 100 m.2 It is preferable to use a weakly acidic zirconium nitride dispersion in which the pH of the aqueous dispersion is 4.0 to 6.5 at 1000 kJ / g. Because the specific surface area is large, the zirconium nitride particles in the dispersion are less likely to settle, and long-term changes in the jet-black hue of the prepared black resin composition can be minimized. Furthermore, by keeping the acidity within the above range, affinity with the dispersant is improved, and dispersion stability in the dispersion is improved despite the large specific surface area.

[0038] The average primary particle diameter of the colorant (A) can be determined by the following method. First, the colorant (A) is ultrasonically dispersed in chloroform, dropped onto a mesh with a collodion film attached, and dried. A primary particle image of the colorant (A) is obtained by observation with a transmission electron microscope (TEM). Next, the primary particle diameter of each colorant (A) particle is converted into the diameter of a circle with the same area as the primary particle diameter of the individual colorant (A) particles, and the particle diameter of each of multiple particles (usually about 200 to 300 particles) of colorant (A) is determined. The obtained primary particle diameter values ​​are used to calculate the number average value, and the average primary particle diameter is determined.

[0039] The dibutyl phthalate absorption of the colorant (A) can be measured in accordance with JIS K 6221. The pH value of the colorant (A) can be measured in accordance with ASTM D1512. A resin-coated colorant (A) may also be used as the colorant (A). The resin-coated colorant (A) can be obtained by treating a known colorant (A) using the method described in, for example, JP-A Nos. 9-26571, 9-71733, 9-95625, 9-238863, or 11-60989.

[0040] In this case, it is preferable to include a colorant with a small crystallite size, since this can reduce deterioration due to scattering. The secondary particle diameter of the colorant (A) is preferably 30 nm to 100 nm. When the secondary particle diameter is 30 nm or more, the storage stability after dispersion is excellent. On the other hand, when the secondary particle diameter is 100 nm or less, the diffuse reflection value when formed into a film is low, and a vivid color can be achieved.

[0041] The secondary particle diameter of the colorant (A) is determined as the particle diameter (D50) at 50% cumulative frequency from the particle size distribution measured by dynamic light scattering (DLS). The secondary particle diameter is measured at 25°C for a sufficiently diluted black resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass; however, if a concentration recommended by the measuring instrument is available, that concentration should be followed).

[0042] Resin (B) is a material that is the main element in film formation, dissolving in a solvent to envelop particles of colorant (A), giving it the appropriate viscosity, and quickly forming a solid film that adheres to the glass substrate. Examples of resins that can be used include synthetic resins such as siloxane, polyimide, acrylic, polyester, and cardo, as well as natural resins such as cellulose.

[0043] However, in order to adhere to the glass substrate and strengthen the glass substrate, and particularly to achieve stable adhesion and glass substrate strengthening, the resin (B) must contain at least a siloxane resin (C), and the content of the siloxane resin (C) must be at least 35% by mass relative to the total solid content of the black composition. The solid content refers to non-volatile components other than the solvent in the black resin composition. The content of the siloxane resin (C) relative to the total resin (B) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass (total amount being siloxane resin).

[0044] A preferred siloxane resin (C) is represented by the following general formula:

[0045] [ka]

[0046] In the above formula, X and Y represent hydrogen atoms, halogen atoms, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups, phenyl groups, aryl groups, hydroxyl groups, amino groups, amido groups, alkoxy groups, or alkyl groups having 1 to 20 carbon atoms in which one or more hydrogen atoms have been substituted with carboxyl groups, carbonyl groups, epoxy groups, epoxycycloalkyl groups, methacrylic groups, acrylic groups, or succinic anhydride, and X and Y may be the same or different. One siloxane resin (C) may contain two or more different repeating units or functional groups. In the above formula, n represents an integer of 1 or more, preferably an integer of 10-500.

[0047] Among these, siloxane resins (C) represented by the following general formula, for example, in which the side chain is an alkyl group having 1 to 5 carbon atoms and one or more hydrogen atoms thereof are substituted with a highly reactive radical polymerizable group, are more preferred.

[0048] [ka]

[0049] In the above formula, R is a hydrocarbon group having 1 to 5 carbon atoms, and Z is a radically polymerizable group. In the above formula, n represents an integer of 1 or more, preferably an integer of 10-500.

[0050] Siloxane resin (C) is an intermediate substance between inorganic silica and organic silicone, synthesized by the hydrolysis and dehydration condensation of alkoxysilane compounds, and is characterized by its excellent adhesion to glass substrates and its ability to form three-dimensional structures such as random structures and cage structures through siloxane bonds, thereby forming a strong, high-molecular-weight resin film. The main chain of siloxane resin (C) preferably contains three or four repeating siloxane bond units, due to the need to improve the hardness of the film and strengthen the glass.

[0051] The functional groups on the side chains of the siloxane resin (C) may be partially substituted with radically polymerizable groups. In this case, the radically polymerizable groups may be radically polymerized in the cured product of the resin composition. The inclusion of radically polymerizable groups has the effect of forming a stronger film through a crosslinking reaction with additives, etc.

[0052] Examples of the radically polymerizable group include unsaturated organic groups such as a vinyl group, an α-methylvinyl group, an acryloyl group, a methacryloyl group, an alkenyl group, a styryl group, etc. Among these radically polymerizable organic groups, those having an acryloyl group or a methacryloyl group are preferred because they allow the curing reaction in the film to proceed smoothly and provide good crack resistance.

[0053] The method for producing the siloxane resin (C) is not particularly limited, but for example, an alkoxysilane compound is hydrolyzed to convert the alkoxide into a hydroxyl group to form a silanol group, and then the silanolized hydroxyl group is polymerized by a dehydration condensation reaction and distilled off to obtain the resin. Examples of the alkoxysilane compound include alkoxysilane compounds having a phenyl group or an aryl group in the molecule, such as diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methyltrimethoxysilane, and phenyltrimethoxysilane.

[0054] The alkoxysilane compound having a phenyl group or an aryl group in the molecule preferably accounts for 20 to 60 mol % of the total alkoxysilane compounds. When the phenyl group or aryl group is within this range, the viscosity of the resulting siloxane resin composition is stable. More preferably, the alkoxysilane compound accounts for 33 to 48 mol % of the total alkoxysilane compounds. Within this range, the viscosity of the siloxane resin composition is more stable, and the optical properties of the resulting cured film are improved.

[0055] Also preferred alkoxysilane compounds having an unsaturated organic group in the molecule include γ-acryloylpropyltrimethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-acryloxypropyltrimethoxysilane. The alkoxysilane compound having an unsaturated organic group in the molecule preferably accounts for 10 to 30 mol % of the total alkoxysilane compounds.

[0056] Alternatively, an alkoxysilane compound having a succinic acid group in the molecule, which is a carbonyl group of a cyclic anhydride, may be used. The succinic acid group has the function of improving adhesion to glass substrates. Examples of alkoxysilane compounds having a succinic acid group in the molecule include 3-dimethylmethoxysilylpropyl succinic anhydride, 3-dimethylethoxysilylpropyl succinic anhydride, and trimethoxysilylpropyl succinic anhydride. The alkoxysilane compound having a succinic acid group preferably accounts for 5 to 20 mol % of the silicon atoms in the entire siloxane resin.

[0057] Other examples that may be used include epoxy group- or oxetane group-containing alkoxysilane compounds such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-ethyl-3-{[3-(trimethoxysilyl)propoxy]methyl}oxetane; carboxyl group-containing alkoxysilane compounds such as 3-trimethoxysilylpropionic acid; and fluorine group-containing alkoxysilane compounds such as trifluoropropyltrimethoxysilane.

[0058] The hydrolysis and dehydration condensation reaction of the alkoxysilane compound are preferably carried out in a solvent. The solvent can be appropriately selected taking into consideration the stability, wettability, volatility, etc. of the resin composition. Furthermore, if a solvent is produced by the hydrolysis reaction, it is also possible to carry out the hydrolysis without a solvent. When used in a resin composition, it is also preferable to adjust the resin composition to an appropriate concentration by adding a solvent after the hydrolysis reaction is completed. Furthermore, after the hydrolysis, it is also possible to distill and remove all or part of the produced alcohol, etc. by heating and / or under reduced pressure, and then add a suitable solvent.

[0059] When a solvent is used in the hydrolysis reaction, the amount of the solvent added is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, per 100 parts by mass of the total alkoxysilane compounds, from the viewpoint of suppressing gel formation due to overreaction, while the amount of the solvent added is preferably 500 parts by mass or less, more preferably 200 parts by mass or less, per 100 parts by mass of the total alkoxysilane compounds, from the viewpoint of promoting hydrolysis more rapidly.

[0060] Examples of methods for the dehydration condensation reaction include heating the silanol compound solution obtained by the hydrolysis reaction of the alkoxysilane compound as is. The heating temperature is preferably 50°C or higher and the boiling point of the solvent or lower, and the heating time is preferably 1 to 100 hours. Depending on the purpose, after the dehydration condensation reaction, an appropriate amount of the produced alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.

[0061] From the viewpoint of coatability, the mass average molecular weight (Mw) of the siloxane resin (C) is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000. The mass average molecular weight (Mw) refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0062] The photosensitive resin composition of the present invention preferably contains a dispersant (D). The dispersant (D) is coated on the surface of the colorant (A) or resin (B) to promote wetting and humidification of the surface. In particular, colorants (A) and some resins (B) that have large surface areas and oil absorptions and low surface energies, such as carbon black, do not wet well, and are prone to significant thickening and re-aggregation, resulting in decreased dispersion stability. However, the inclusion of a dispersant (D) improves dispersion stability, thereby improving the smoothness, gloss, and clarity of the film surface.

[0063] Since the photosensitive resin composition of the present invention contains a siloxane resin (C) in the resin (B), a dispersant (D) having an amine value of 30 mgKOH / g or less and compatible with the siloxane resin (C) is preferred. The amine value here refers to the weight of potassium hydroxide equivalent to the acid that reacts with 1 g of sample, and can be determined by neutralizing 1 g of sample with acid and then titrating it with an aqueous potassium hydroxide solution.

[0064] Conventionally, dispersants commonly used to disperse difficult-to-disperse pigments such as carbon black and phthalocyanine pigments have been alkylammonium salt dispersants with a high amine value, emphasizing improved adsorption performance. However, the presence of siloxane resin (C) increases viscosity, making aggregation and gel formation more likely. Dispersant (D) with an amine value of 30 mgKOH / g or less alleviates this problem. Furthermore, dispersants with an amine value of 30 mgKOH / g or less and containing one or more polymer chains selected from acrylic resins, polyoxyalkylene ethers, polycaprolactones, polyesters, polyurethanes, polyols, polyethyleneimines, polyallylamines, and the like are preferred. The inclusion of such polymer chains facilitates adsorption to the colorant surface, improving the ability to prevent reagglomeration of colorant particles and improving storage stability. Furthermore, the interfacial tension can be reduced, thereby reducing viscosity, improving colorant wettability and increasing the solids concentration of the dispersion.

[0065] Various dispersants (D) are commercially available, and commercially available products can be preferably used. Commercially available dispersants (D) having an amine value of 30 mgKOH / g or less include, for example, DISPERBYK-161 (amine value 11), 163 (amine value 18), 2000 (amine value 4), 2001 (amine value 29), 2163 (amine value 10), 2164 (amine value 14), and 2200 (amine value 0) (all manufactured by BYK-Chemie), EFKA4330 (amine value 28), and 4340 (amine value 4) (all manufactured by BASF), and AJISPER PB821 (amine value 10), and PB822 (amine value 17) (all manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0066] Among these, dispersants (D) produced by controlled radical polymerization are more preferred. Dispersants (D) produced by this polymerization method have a high local concentration of adsorbing groups in the dispersant (D) molecule, resulting in excellent adsorption ability even with a low amine value. They can strongly adsorb to the surface of colorant (A) and form a thick protective layer. Therefore, they are less likely to adsorb to the surface of other nearby colorants (A) or to attract other dispersants, resulting in an increase in viscosity. This allows for a Newtonian dispersion, resulting in higher dispersion stability.

[0067] More preferred examples of the dispersant (D) having an amine value of 30 mgKOH / g or less, containing one or more polymer chains selected from acrylic resin, polycaprolactone, polyurethane, polyol, polyethyleneimine, polyallylamine, etc., and produced by controlled radical polymerization include DISPERBYK-2000, 2001, and 2200. Controlled radical polymerization is a polymerization method in which growing radicals are reversibly protected with protecting groups, and the deprotection (activation), addition of monomers (growth), and protection (inactivation) are repeated to grow molecular chains little by little and almost uniformly, and is characterized by the fact that no chain transfer reaction occurs and polymers with a narrow molecular weight distribution can be obtained.

[0068] The content of the dispersant (D) is preferably 0.1 to 10 mass% based on the total solid content in the black resin composition. By setting the content of the dispersant (D) within this range, it is possible to suppress aggregation of colorant (A) particles and polymer chains of the siloxane resin (C), thereby improving dispersion stability. Furthermore, the content of the dispersant (D) is more preferably 1 to 6 mass% based on the total solid content in the black resin composition, so that the dispersant is rapidly adsorbed to the surface of one colorant (A) particle but is more likely to suppress subsequent adsorption to the surface of another colorant (A) particle.

[0069] The black resin composition of the present invention may also contain inorganic particles (E). Silica particles are preferred as the inorganic particles (E) from the viewpoints of improving film strength and viscosity, as well as accelerating the progress of the hydrolysis reaction and dehydration condensation reaction of the siloxane resin. Silica particles can be obtained by a method such as hydrolysis and polycondensation of one or more alkoxysilane compounds in the presence of water, an organic solvent, and a base (preferably ammonia). The composition may also contain inorganic particles other than silica particles. Examples of such inorganic particles include magnesium fluoride particles, titania particles, and zirconia particles. The content of silica particles in the inorganic particles is preferably 60% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass (all silica particles).

[0070] Specific examples of silica particles include IPA-ST, which uses isopropanol as a dispersion medium and has an average particle diameter of 12 nm; MIBK-ST, which uses methyl isobutyl ketone as a dispersion medium and has an average particle diameter of 12 nm; PGM-AC-3140Y, which uses propylene glycol monomethyl ether as a dispersion medium and has an average particle diameter of 22 nm; PMA-ST, which uses propylene glycol monomethyl ether acetate as a dispersion medium and has an average particle diameter of 12 nm; IPA-ST-L, which uses isopropanol as a dispersion medium and has an average particle diameter of 45 nm; and IPA-ST-ZL, which uses isopropanol as a dispersion medium and has an average particle diameter of 80 nm (all trade names, manufactured by Nissan Chemical Industries, Ltd.).

[0071] Other examples include OSCAR 101, which uses gamma-butyrolactone as a dispersion medium and has an average particle size of 12 nm; OSCAR 105, which uses gamma-butyrolactone as a dispersion medium and has an average particle size of 60 nm; OSCAR 106, which uses diacetone alcohol as a dispersion medium and has an average particle size of 120 nm; and CATALOID-S, which uses water as a dispersion medium and has an average particle size of 5 to 80 nm (all trade names, manufactured by Catalysts and Chemical Industries Co., Ltd.); QUATRONE PL-2L-PGME, which uses propylene glycol monomethyl ether as a dispersion medium and has an average particle size of 16 nm; QUATRONE PL-1-PGME, which uses propylene glycol monomethyl ether as a dispersion medium and has an average particle size of 12 nm; and γ Examples of such dispersion media include Quatrone PL-2L-BL and Quatrone PL-1-BL, each with an average particle size of 17 nm, and Quatrone PL-2L-DAA and Quatrone PL-1-DAA, each with an average particle size of 17 nm and 13 nm, respectively, which use diacetone alcohol as the dispersion medium; Quatrone PL-2L, GP-2L, and Quatrone PL-1, each with an average particle size of 18 to 20 nm, which use water as the dispersion medium (all trade names manufactured by Fuso Chemical Co., Ltd.); silica (SiO2) SG-SO100, each with an average particle size of 100 nm (trade name manufactured by Kyoritsu Material Co., Ltd.); and Reolosil, each with an average particle size of 5 to 50 nm (trade name manufactured by Tokuyama Corporation).

[0072] These silica particles may be used alone or in combination of two or more. In addition, if the surface of the silica particles used has a reactive group, it is preferable because it facilitates bonding between the siloxane resin (C) and the silica particles and increases the strength of the film. Examples of the reactive group include hydroxyl groups such as silanol, alcohol, and phenol, vinyl groups, acrylic groups, ethynyl groups, epoxy groups, and amino groups.

[0073] The content of silica particles is preferably 10% by weight or more, more preferably 20% by weight or more, of the solid content from the viewpoint of further improving the film strength, while the content of silica particles is preferably 50% by weight or less, more preferably 40% by weight or less, of the solid content from the viewpoint of improving the light transmittance of the cured film and the adhesion to the substrate.

[0074] It is also preferable that the silica particles are chemically bonded to a portion of the siloxane resin (C) to form a homogenized silica particle. When the silica particles are homogenized, the hardness of the cured film is improved and it is possible to prevent the silica particles from precipitating from the cured film. Here, "homogenized" refers to the reaction between the silica component of the silica particles and a portion of the siloxane resin (C) and the silica particles being incorporated into the siloxane resin (C) at a constant density.

[0075] This state can be confirmed by observing the boundary between the silica particles and the siloxane resin (C) using a transmission electron microscope (hereinafter referred to as TEM). When homogenized, the boundary between the silica particles and the siloxane resin (C) is not observed in TEM observation. Homogenization is also preferred because a homogenized system has higher adhesion than a system in which the same amount of silica particles is added to the siloxane resin (C).

[0076] A method for producing the siloxane resin (C) of the present invention containing silica particles chemically bonded to at least a portion thereof includes adding a solvent, water, and optionally a catalyst to an alkoxysilane compound to hydrolyze the alkoxysilane compound, and then partially condensing the silica particles with the hydrolyzed alkoxysilane compound.

[0077] The silica particles may be added together with the alkoxysilane compound from the beginning, or may be added after the hydrolysis and condensation polymerization of the alkoxysilane compound is completed to form the siloxane resin (C), or may be added during the hydrolysis and condensation polymerization of the alkoxysilane compound.

[0078] The average particle size of the silica particles is preferably 1 to 80 nm. If the average particle size is smaller than 1 nm, the particles will be prone to aggregation even with the catalyst specifications of the present invention. If the average particle size is larger than 80 nm, the particles will deteriorate over time and be prone to peeling off from the cured film. A more preferred size is 10 nm to 45 nm. A size of 10 nm or more will fully demonstrate performance and effects such as improved film strength, while a size of 45 nm or less will suppress light scattering and improve the optical properties of the cured film.

[0079] The average particle size of silica particles can be determined by dynamic light scattering. Specifically, a dispersion liquid with a silica particle concentration of 10 to 30% by weight is irradiated with light of 780 nm wavelength from a semiconductor laser, the scattered light is measured, and then frequency analysis is performed using the FFT-heterodyne method to determine the average particle size.

[0080] The black resin composition of the present invention may contain a solvent to adjust the viscosity to a range suitable for application and to improve application uniformity. Examples of solvents include alcohols such as water, ethanol, propanol, diacetone alcohol, and methoxymethylbutanol; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether and propylene glycol monoethyl ether; ketones such as methyl ethyl ketone and cyclopentanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethylene glycol monoethyl ether acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxy-3-methyl-1-butyl acetate; aromatic or aliphatic hydrocarbons such as toluene, xylene, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. The black resin composition may contain two or more of these solvents.

[0081] From the viewpoint of coatability, it is preferable to combine a solvent having a boiling point of 150° C. or higher and 250° C. or lower under atmospheric pressure with a solvent having a boiling point of 150° C. or lower. For example, diacetone alcohol can be combined as a solvent having a boiling point of 150° C. or higher and 250° C. or lower under atmospheric pressure with propylene glycol monomethyl ether as a solvent having a boiling point of 150° C. or lower.

[0082] The content of the solvent may be set arbitrarily depending on the application method, etc. For example, when forming a film by spin coating, the content of the solvent in the composition of the present invention is generally 50% by mass or more and 95% by mass or less.

[0083] The black resin composition of the present invention may also contain a photopolymerizable compound. The photopolymerizable compound refers to a compound having two or more ethylenically unsaturated double bonds in the molecule. Examples of the photopolymerizable compound include glycol acrylates, glycol methacrylates, methylol acrylates, methylol methacrylates, butanediol acrylates, diol methacrylates, diol diacrylates, isocyanuric acid diacrylates, and isocyanuric acid triacrylates. Two or more of these may be contained. The content of the photopolymerizable compound is preferably 1% by mass or more and 50% by mass or less of the solid content.

[0084] Furthermore, the black resin composition of the present invention may contain a photosensitizer to impart photosensitivity. When negative photosensitivity is imparted, it is preferable to contain a photopolymerization initiator as the photosensitizer. When positive photosensitivity is imparted, it is preferable to contain a quinone diazide compound as the photosensitizer.

[0085] Examples of the photopolymerization initiator include an α-aminoalkylphenone compound, an acylphosphine oxide compound, an oxime ester compound, an α-hydroxyketone compound, a benzophenone compound, an acetophenone compound, a benzoic acid ester compound, etc. The content of the photopolymerization initiator is preferably 0.01% by mass or more and 10% by mass or less of the solid content.

[0086] The quinone diazide compound may be a compound in which a sulfonic acid of naphthoquinone diazide is bonded to a compound having a phenolic hydroxyl group via an ester bond. The content of the quinone diazide compound is preferably 0.5% by mass or more and 20% by mass or less of the solid content. Two or more of these may be contained.

[0087] Furthermore, the black resin composition of the present invention may contain, as necessary, an ultraviolet absorber, a polymerization inhibitor, a surfactant, an adhesion improver, a colorant other than the colorant (A), particles other than the inorganic particles (E), etc. Two or more of these may be contained. The content of these is preferably 0.1 mass % or more and 50 mass % or less of the solid content.

[0088] Examples of ultraviolet absorbers include benzotriazole-based, benzophenone-based, and triazine-based compounds. Examples of polymerization inhibitors include 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. Examples of surfactants include fluorine-based, silicone-based, polyalkylene oxide-based, and poly(meth)acrylate-based surfactants. Examples of adhesion improvers include alicyclic epoxy compounds and silane coupling agents.

[0089] Examples of colorants other than the colorant (A) include white pigments such as titanium dioxide, zirconium oxide, zinc oxide, and barium sulfate, and color pigments such as red, blue, black, green, yellow, purple, brown, orange, magenta, and cyan. Examples of particles other than the inorganic particles (E) include magnesium fluoride particles, titania particles, and zirconia particles.

[0090] Examples of glass substrates to which the black resin composition is applied include quartz glass, soda-lime glass, borosilicate glass, crystal glass, crystallized glass, thermally strengthened glass, and chemically strengthened glass. Chemically strengthened glass such as aluminosilicate glass and zirconia glass, and borosilicate glass are particularly preferred. The thickness is preferably about 0.1 mm to 5 mm.

[0091] The glass substrate means a transparent glass substrate that does not contain the colorant (A) to an extent that would impair processability, and a glass substrate that contains a very small amount of the colorant (A) to an extent that does not impair processability is included in the glass substrate of the present invention. Also, a glass substrate whose surface has been made semi-transparent by sandblasting, such as frosted glass, is included in the glass substrate of the present invention as long as the decorative layer at the back can be seen when it is formed into the laminated structure shown in Figure 1.

[0092] The method for applying the black resin composition to the glass substrate is not particularly limited, and examples thereof include spin coating, gravure coating, die coating, roll coating, slit coating, dip coating, lip coating, spray coating, and inkjet coating.

[0093] Drying methods include vacuum drying and heat drying. Both vacuum drying and heat drying may be performed, or only one of them may be used. Heat drying may be performed using a hot plate, oven, infrared rays, etc. The heating temperature varies depending on the type and purpose of the coating film, and is preferably in the range of 50°C to 280°C for 1 minute to several hours. Volatile components such as solvents are removed during the drying process.

[0094] The decorative layer formed on the film of the black resin composition is not particularly limited, and may be any layer having design properties, such as a thick colored screen printing ink layer of about 10 to 30 μm, or an extremely thin decorative layer such as a metal film layer or an inorganic oxide film layer. The decorative layer may be formed in one layer or in multiple layers. [Example]

[0095] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0096] [Measurement and evaluation methods] (1) Thickness of the black resin composition film The black resin compositions obtained in each of the Examples and Comparative Examples were spin-coated onto a 1 mm-thick transparent glass substrate made of borosilicate glass to form a coating film, which was then placed in an oven and dried at 100°C for 2 minutes to evaporate the solvent, and heated to 200°C for 60 minutes to cure the black resin composition film.The film thickness of the cured black resin composition film was measured using a stylus profiling system, "Dektak XT Stylus Profiler," manufactured by Bruker.

[0097] (2) Total Light Transmittance of Black Resin Composition Film The black resin composition was spin-coated onto the transparent glass substrate to form a coating film with a dry thickness of 2 μm, and then placed in an oven and heated at 200°C for 1 hour for drying and heat treatment. The total light transmittance of the resulting test piece in the wavelength range of 400 nm to 700 nm was measured using a spectrophotometer (UV-2500PC, 0.1 nm resolution, double-beam photometry, manufactured by Shimadzu Corporation). The scan speed was set to low-speed mode, the slit width was set to 2.5 nm, and zero-base correction was performed in advance. The values ​​are shown in Tables 1 to 4.

[0098] (3) Color of the black resin composition film The total light transmittance of the black resin composition film in wavelengths of 380 nm to 780 nm was measured using the spectrophotometer (UV-2500PC, manufactured by Shimadzu Corporation). From the transmission spectrum, the XYZxy values ​​were calculated assuming a D65 light source, and the a* and b* values ​​were calculated from the XYZxy values. The evaluation results are shown in Tables 1 to 4. A was the best rating, and A to C were acceptable ratings.

[0099] A: Both a* and b* values ​​are -2.0 to +2.0 B: Either the a* or b* value is -2.0 to +2.0 The other one is -3.0 to -2.0 or +2.0 to +3.0 C: Both a* and b* values ​​are -3.0 to -2.0 or +2.0 to +3.0 D: Either the a* or b* value is less than -3.0 or exceeds +3.0

[0100] (4) Haze value of black resin composition film The black resin composition was spin-coated onto the transparent glass substrate to form a coating film with a dry thickness of 2 μm, and then placed in an oven and heated at 200°C for 1 hour for drying and heat treatment. The total light transmittance and diffuse transmittance of the resulting test specimen were measured using a spectrophotometer (UV-2500PC, Shimadzu Corporation) and an integrating sphere accessory (ISR-2200, Shimadzu Corporation), and the haze value of the black resin composition film was calculated using the formula: haze (%) = [(T4 / T2) - (T3 / T1)] x 100. The evaluation results are shown in Tables 1 to 4. A is the best rating, and A to C are acceptable ratings.

[0101] A: Haze value is less than 1.5% B: Haze value is 1.5% or more and less than 2.5% C: Haze value is 2.5% or more and 3.0% or less D: Haze value exceeds 3.0 (%)

[0102] (5) Adhesion of the black resin composition film The black resin composition was spin-coated onto the transparent glass substrate to form a coating film with a dry thickness of 2 μm, which was then placed in an oven and heated to 200° C. for 1 hour for drying and heat treatment. The resulting test piece was immersed in boiling pure water for 60 minutes, dried, and then evaluated for adhesion between the transparent glass substrate and the black resin composition film according to the JIS K5400 8.5.2 (1990) cross-cut tape method, based on the following criteria:

[0103] For the evaluation, 11 parallel lines, each perpendicular to the other, were drawn at 1 mm intervals on the black resin composition film on the transparent glass substrate with a cutter knife, reaching the base of the transparent glass substrate, to create 100 1 mm x 1 mm grids. Cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) was attached to the cut film surface and rubbed with an eraser (JIS S6050 compliant) to adhere it. One end of the tape was held perpendicular to the transparent glass substrate and instantly peeled off. The number of remaining grids was visually counted and the peeled area of ​​the grids was evaluated. The evaluation results are shown in Tables 1 to 4. A was the best rating, and A to C were acceptable ratings.

[0104] A: Peeling area less than 5% B: Peeling area 5% or more but less than 10% C: Peeling area 10% or more but less than 20% D: Peeled area 20% or more

[0105] (6) Glass reinforcement of black resin composition film The flexural strength and flexural modulus of elasticity were measured for each of a test piece of the glass substrate alone and a test piece obtained by spin-coating the black resin composition onto the glass substrate to form a coating film with a thickness of 2 μm after drying, and then heating the composition in an oven at 200° C. for 1 hour to dry and heat-treat the composition. The glass strengthening ability of the black resin composition film was evaluated according to the following criteria.

[0106] Two test pieces were prepared for measuring the bending strength and bending modulus. One test piece was subjected to the bending strength measurement in accordance with ISO 178. The other test piece was subjected to moist heat treatment by leaving it in an environment of 60°C and 95% RH for 700 hours, and the bending strength (bending strength after moist heat treatment) was measured in the same manner as in ISO 178. The bending strength retention rate was calculated using the following formula. The evaluation results are shown in Tables 1 to 4. A is the best rating, and A and B are acceptable ratings.

[0107] (Bending strength retention rate) (unit: %) = (Bending strength after moist heat treatment) / (Bending strength before moist heat treatment) × 100 A: Bending strength and bending strength retention rate are improved by more than 5% compared to the transparent glass substrate alone. B: Either the bending strength or the bending strength retention rate is improved by 5% or more compared to the transparent glass substrate alone, and the other is improved by less than 5% compared to the transparent glass substrate alone. C: The bending strength and bending strength retention rate are improved by less than 5% compared to the transparent glass substrate alone.

[0108] (7) Storage stability of black resin composition The viscosity of the black resin compositions obtained in each example was measured immediately after preparation and after leaving the black resin compositions at room temperature (30°C) for one week using a viscometer (RE105L manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25.0±0.2°C and a rotation speed of 50 rpm, and the viscosity change rate was calculated. The evaluation results are shown in Tables 1 to 4. A is the best rating, and A and B are acceptable ratings.

[0109] A: Viscosity change rate is less than 15% B: Viscosity change rate is 15% or more and less than 20% C: Viscosity change rate is 20% or more

[0110] (8) Amine value of dispersant (D) 1 g of dispersant was weighed into a 100 mL beaker and dissolved in 50 mL of acetic acid. Using an automatic titrator (AT-510; Kyoto Electronics Manufacturing Co., Ltd.), this solution was neutralized with a 0.1 mol / L HClO4 acetic acid solution. The inflection point of the titration pH curve was taken as the titration endpoint. The amine value was calculated using the formula: amine value [mgKOH / g] = (561 × V) / (W × S). The values ​​are shown in Tables 1 to 4. W is the weight of the dispersant sample [g], V is the titration volume [mL] at the titration endpoint, and S is the solids concentration [wt%] of the dispersant sample.

[0111] (7) Designability due to the film of the black resin composition A 0.5 mm thick transparent aluminosilicate glass was sandblasted to form a frosted glass substrate. The black resin composition was spin-coated onto the glass substrate to form a coating with a dry thickness of 2 μm. The substrate was then placed in an oven for 1 hour at 200°C for drying and heat treatment. A layer of colored screen printing ink (VAC Color Ink 690 Black; manufactured by Jujo Chemical Co., Ltd.) was then applied to the substrate to form a dry thickness of 10 μm. The substrate was then placed in an oven for 30 minutes at 160°C for drying and heat treatment, yielding a decorative glass. The decorative glass was evaluated for design from the glass substrate side. The evaluation results are shown in Tables 1 to 4. A was the best rating, and A to C were acceptable ratings.

[0112] A: A design with depth and a profound feeling B: A design with a certain depth and a profound feel C: A design that gives off a sense of depth and weight. D: A design that lacks depth and dignity

[0113] (10) Weight-average molecular weight of siloxane resin The weight average molecular weight of the siloxane resin in the synthesis examples described below was determined in terms of polystyrene using the following apparatus and conditions.

[0114] Apparatus: Waters GPC measurement device with RI detector (2695) Column: PLgelMIXED-C column (Polymer Laboratories, 300 mm) x 2 (connected in series) Measurement temperature: 40℃ Flow rate: 1mL / min Solvent: tetrahydrofuran (THF) 0.5% by mass solution Standard material: polystyrene Detection mode: RI

[0115] [Synthesis of Siloxane Resin Solution (C-1)] A 1000 ml three-neck flask was charged with 81.7 g of methyltrimethoxysilane, 148 g of phenyltrimethoxysilane, 37.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 201 g of propylene glycol monomethyl ether acetate, and an aqueous catalyst solution prepared by dissolving 0.8 g (0.3% by mass based on the total amount of charged monomers) of p-toluenesulfonic acid pyridine salt in 81 g of water was added over 30 minutes with stirring at 40°C.

[0116] The flask was then immersed in a 70°C oil bath and stirred for 60 minutes. The oil bath was then heated to 115°C over 30 minutes, and the mixture was then heated and stirred for 3 hours (internal temperature: 100-110°C), yielding a siloxane resin solution. During the temperature increase and heating and stirring, a gas mixture of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 185 g of by-products, methanol and water, was distilled during the reaction.

[0117] Propylene glycol monomethyl ether acetate was added to the obtained siloxane resin solution so that the solids concentration was 45% by mass, and siloxane resin solution (C-1) was obtained without removing the catalyst. The weight average molecular weight of the siloxane resin in the obtained siloxane resin solution (C-1) was 9,500.

[0118] [Synthesis of Siloxane Resin Solution (C-2)] A 1000 ml three-neck flask was charged with 10.2 g of methyltrimethoxysilane, 148 g of phenyltrimethoxysilane, 158 g of 3-acryloxypropyltrimethoxysilane, 0.79 g of dibutylhydroxytoluene, and 92.1 g of propylene glycol monomethyl ether acetate, and an aqueous catalyst solution prepared by dissolving 1.6 g (0.5% by mass based on the total amount of charged monomers) of p-toluenesulfonic acid pyridine salt in 81 g of water was added over 30 minutes with stirring at 40°C.

[0119] The flask was then immersed in a 70°C oil bath and stirred for 60 minutes. The oil bath was then heated to 115°C over 30 minutes, and the mixture was then heated and stirred for 3 hours (internal temperature: 100-110°C), yielding a siloxane resin solution. During the temperature increase and heating and stirring, a gas mixture of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 185 g of by-products, methanol and water, was distilled during the reaction.

[0120] Propylene glycol monomethyl ether acetate was added to the obtained siloxane resin solution so that the solids concentration was 70% by mass, and siloxane resin solution (C-2) was obtained without removing the catalyst. The weight average molecular weight of the siloxane resin in the obtained siloxane resin solution (C-2) was 2,500.

[0121] [Preparation example of colorant dispersion A-1] 402.0 g of sulfonic acid group-surface-modified carbon black particles (CB-Bk1, manufactured by Cabot Corporation), 451.7 g of a 45 wt% solution of the siloxane resin (C-1) in propylene glycol monomethyl ether acetate, 120.0 g of DISPERBYK-2200 (manufactured by BYK-Chemie) as a dispersant, and 3045.7 g of propylene glycol monoethyl ether acetate were charged into a tank and stirred with a homomixer (manufactured by Primix) for 20 minutes to obtain a preliminary dispersion. The preliminary dispersion was then fed into an Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) equipped with a centrifugal separator filled to 75% with 0.10 mm diameter zirconia beads (manufactured by Netsuren, YTZ balls), and dispersed at a rotation speed of 9 m / s for 4 hours to obtain a carbon black dispersion A-1 with a colorant concentration (colorant / total weight ratio) of 10 wt%.

[0122] [Preparation example of colorant dispersion A-2] 402.0 g of titanium nitride particles (Ti-Bk1, manufactured by Nisshin Engineering Co., Ltd.) produced by thermal plasma processing, 632.4 g of a 45 wt% solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate, 120.6 g of DISPERBYK-2000 (manufactured by BYK-Chemie Co., Ltd.) as a dispersant, and 2865.0 g of propylene glycol monoethyl ether acetate were charged into a tank and stirred with a homomixer (manufactured by Primix) for 20 minutes to obtain a preliminary dispersion. The preliminary dispersion was then fed into an Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) equipped with a centrifugal separator filled 75% with 0.10 mm diameter zirconia beads (manufactured by Netsuren, YTZ balls), and dispersed at a rotation speed of 12 m / s for 4 hours to obtain titanium black dispersion A-2 with a colorant concentration (colorant / total weight ratio) of 10 wt%.

[0123] [Preparation of Colorant Dispersions A-3 to A-14] Carbon black dispersions A-3 to A-14 were obtained in the same manner as in preparation of colorant dispersion A-1, except that the dispersants were changed to those shown in Table 4, respectively.

[0124] [Preparation of Colorant Dispersions A-23 to A-34] Titanium black dispersions A-23 to A-34 were obtained in the same manner as in the preparation of colorant dispersion A-2, except that the dispersants were changed to those shown in Table 4, respectively.

[0125] [Preparation example of colorant dispersion A-35] 402.0 g of zirconium nitride powder (Zr-Bk1, manufactured by Kojundo Chemical Laboratory Co., Ltd.), 632.4 g of a 45 wt% solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate, 120.6 g of DISPERBYK-2000 (manufactured by BYK-Chemie Co., Ltd.) as a dispersant, and 2865.0 g of propylene glycol monoethyl ether acetate were charged into a tank and stirred with a homomixer (manufactured by Primix Co., Ltd.) for 20 minutes to obtain a preliminary dispersion. The preliminary dispersion was then fed into an Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) equipped with a centrifugal separator filled 75% with 0.10 mm diameter zirconia beads (manufactured by Netsuren, YTZ balls), and dispersed at a rotation speed of 12 m / s for 4 hours to obtain zirconium nitride dispersion A-35 with a colorant concentration (colorant / total weight ratio) of 10 wt%.

[0126] [Preparation of Colorant Dispersions A-36 to A-47] Zirconium nitride dispersions A-36 to A-45 were obtained in the same manner as in preparation of colorant dispersion A-35, except that the dispersants were changed to those shown in Table 9, respectively.

[0127] Example 1 Carbon black dispersion A-1 and titanium black dispersion A-2 were mixed, and the mixture was mixed with a 45 wt% solution (31.8 g) of siloxane resin (C-1) in propylene glycol monomethyl ether acetate, a 30 wt% solution (21.2 g) of silica particles in propylene glycol monomethyl ether acetate manufactured by Nissan Chemical Industries, Ltd. as inorganic particles (E), KBM9659 (0.4 g) manufactured by Shin-Etsu Chemical Co., Ltd. and OXT manufactured by Toagosei Co., Ltd. as adhesion improvers. Black resin composition 1 was obtained by adding 1.0 g of POLYMER-191, 1.3 g of ZC-150 (manufactured by Matsumoto Fine Chemical Co., Ltd.), 0.2 g of a 10 wt% solution of silicone surfactant propylene glycol monomethyl ether acetate, and 0.4 g of a 5.2 wt% solution of acrylic surfactant propylene glycol monomethyl ether acetate to 30.7 g of propylene glycol monomethyl ether acetate. The siloxane resin content of the resulting black resin composition 1 was 58.1 wt% based on 100 wt% of the total solids. The carbon black particle content was 2.0 wt% based on 100 wt% of the total solids, and the titanium nitride particle content was 3.0 wt% based on 100 wt% of the total solids. The storage stability of the resulting black resin composition 1 was evaluated. The results are shown in Table 1.

[0128] Next, this black resin composition 1 was applied to an alkali-free glass AN100 substrate using a spinner 1H-DS manufactured by Mikasa Co., Ltd., and prebaked at 100°C for 2 minutes to produce a coating film. Further, it was cured at 200°C for 60 minutes to form a 2 μm-thick translucent glass-reinforced black resin layer (black resin composition film), producing tempered glass. The total light transmittance, chromaticity, haze value, adhesion, and glass temperability of the black resin composition film were evaluated based on the resulting tempered glass. Furthermore, the above-mentioned decorative glass was produced and its design was evaluated. The results are shown in Table 1.

[0129] Example 2 Black resin composition 2 was prepared in the same manner as in Example 1, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.6% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 2.4% by mass relative to 100% by mass of the total solid content. Using the obtained black resin composition 2, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0130] Example 3 Black resin composition 3 was prepared in the same manner as in Example 1, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.2% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 1.8% by mass relative to 100% by mass of the total solid content. Using the obtained black resin composition 3, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0131] Example 4 Black resin composition 4 was prepared in the same manner as in Example 1, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.8% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 1.2% by mass relative to 100% by mass of the total solid content. Using the obtained black resin composition 4, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0132] Example 5 Black resin composition 5 was prepared in the same manner as in Example 1, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.4% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.6% by mass relative to 100% by mass of the total solid content. Using the obtained black resin composition 5, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0133] Example 6 A black resin composition 6 was prepared in the same manner as in Example 1, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 49.4% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 6 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0134] Example 7 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 50.2% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.5% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 2.3% by weight based on 100% by weight of the total solid content. A black resin composition 7 was prepared in the same manner as in Example 1. The obtained black resin composition 7 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0135] Example 8 A black resin composition 8 was prepared in the same manner as in Example 3, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 50.7% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 8 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0136] Example 9 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 51.1% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.0% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 1.5% by weight based on 100% by weight of the total solid content. A black resin composition 9 was prepared in the same manner as in Example 1. The obtained black resin composition 9 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0137] Example 10 A black resin composition 10 was prepared in the same manner as in Example 4, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 51.4% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 10 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0138] Example 11 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 51.9% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.5% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.8% by weight based on 100% by weight of the total solid content. A black resin composition 11 was prepared in the same manner as in Example 1. The obtained black resin composition 11 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0139] Example 12 A black resin composition 12 was prepared in the same manner as in Example 5, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 52.1% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 12 was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0140] [Table 1]

[0141] Example 13 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 39.5% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.4% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 2.1% by weight based on 100% by weight of the total solid content. A black resin composition 13 was prepared in the same manner as in Example 1. The obtained black resin composition 13 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0142] Example 14 A black resin composition 14 was prepared in the same manner as in Example 3, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 39.8% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 14 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0143] Example 15 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 40.4% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.7% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 1.1% by weight based on 100% by weight of the total solid content. A black resin composition 15 was prepared in the same manner as in Example 1. The obtained black resin composition 15 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0144] Example 16 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 40.6% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.6% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.9% by weight based on 100% by weight of the total solid content. A black resin composition 16 was prepared in the same manner as in Example 1. The obtained black resin composition 16 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0145] Example 17 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 40.8% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.5% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.6% by weight based on 100% by weight of the total solid content. A black resin composition 17 was prepared in the same manner as in Example 1. The obtained black resin composition 17 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0146] [Examples 18 to 24] Black resin compositions 18 to 24 were prepared in the same manner as in Examples 1 to 5, 8, and 14, except that the 45 wt% solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was replaced with a 70 wt% solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate. The obtained black resin compositions 18 to 24 were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0147] [Table 2]

[0148] [Examples 25 to 36] Black resin compositions 25 to 36 were prepared in the same manner as in Example 3, except that the colorant dispersion and dispersant (D) were changed as shown in Table 3. The obtained black resin compositions 25 to 36 were evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0149] [Table 3]

[0150] Example 37 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 58.5% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 2.7% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 1.8% by weight based on 100% by weight of the total solid content. A black resin composition 37 was prepared in the same manner as in Example 1. The obtained black resin composition 37 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0151] Example 38 A black resin composition 38 was prepared in the same manner as in Example 3, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.8% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 1.2% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 38 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0152] Example 39 A black resin composition 39 was prepared in the same manner as in Example 5, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.6% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.4% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 39 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0153] Example 40 A black resin composition 40 was prepared in the same manner as in Example 37, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 2.3 mass% relative to 100 mass% of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 2.3 mass% relative to 100 mass% of the total solid content. The obtained black resin composition 40 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0154] Example 41 A black resin composition 41 was prepared in the same manner as in Example 3, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.5% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 1.5% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 41 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0155] Example 42 A black resin composition 42 was prepared in the same manner as in Example 5, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.5% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.5% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 42 was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0156] [Table 4]

[0157] Example 43 3.6 g of carbon black dispersion A-1 and 3.6 g of zirconium nitride dispersion A-35 were mixed, and the mixture was diluted with 33.8 g of a 45 wt % solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate, 21.8 g of a 30 wt % solution of silica particles in propylene glycol monomethyl ether acetate manufactured by Nissan Chemical Industries, Ltd. (PMA-ST) as inorganic particles (E), 0.4 g of KBM9659 manufactured by Shin-Etsu Chemical Co., Ltd. and 0.4 g of Toagosei Co., Ltd. ( OXT-191 (1.0 g) manufactured by Nippon Chemi-Con Corp., ZC-150 (1.3 g) manufactured by Matsumoto Fine Chemical Co., Ltd., 0.4 g of a 10 wt% solution of a silicone surfactant in propylene glycol monomethyl ether acetate, and 0.4 g of a 5.2 wt% solution of an acrylic surfactant in propylene glycol monomethyl ether acetate were dissolved in 33.6 g of propylene glycol monomethyl ether acetate to obtain black resin composition 43. The siloxane resin content of the obtained black resin composition 43 was 59.8 wt% based on 100 wt% of the total solids. The carbon black particle content was 1.4 wt% based on 100 wt% of the total solids, and the zirconium nitride dispersion A-3 particle content was 1.4 wt% based on 100 wt% of the total solids. The storage stability of the obtained black resin composition 43 was evaluated. The results are shown in Table 5.

[0158] Next, this black resin composition 1 was applied to an alkali-free glass AN100 substrate using a spinner 1H-DS manufactured by Mikasa Co., Ltd., and prebaked at 100°C for 2 minutes to produce a coating film. This was then cured at 200°C for 60 minutes to form a 2 μm-thick translucent glass-reinforced black resin layer (film of the black resin composition), producing tempered glass. The total light transmittance, chromaticity, haze value, and adhesion of the black resin composition film were evaluated based on the resulting tempered glass. Furthermore, the above-mentioned decorative glass was produced and its design was evaluated. The results are shown in Table 5.

[0159] Example 44 A black resin composition 44 was prepared in the same manner as in Example 43, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.3% by mass relative to 100% by mass of the total solid content, and zirconium nitride dispersion (A-35) was added so that the content of zirconium nitride particles in the colored resin composition was 1.3% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 44 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0160] Example 45 A black resin composition 45 was prepared in the same manner as in Example 43, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.2% by mass relative to 100% by mass of the total solid content, and zirconium nitride dispersion (A-35) was added so that the content of zirconium nitride particles in the colored resin composition was 1.2% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 45 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0161] Example 46 A black resin composition 46 was prepared in the same manner as in Example 43, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.1% by mass relative to 100% by mass of the total solid content, and zirconium nitride dispersion (A-35) was added so that the content of zirconium nitride particles in the colored resin composition was 1.1% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 46 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0162] Example 47 A black resin composition 47 was prepared in the same manner as in Example 43, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.9% by mass relative to 100% by mass of the total solid content, and zirconium nitride dispersion (A-35) was added so that the content of zirconium nitride particles in the colored resin composition was 0.9% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 47 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0163] Example 48 A black resin composition 48 was prepared in the same manner as in Example 43, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.8% by mass relative to 100% by mass of the total solid content, and zirconium nitride dispersion (A-35) was added so that the content of zirconium nitride particles in the colored resin composition was 0.8% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 48 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0164] Example 49 A black resin composition 49 was prepared in the same manner as in Example 43, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 50.9% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 49 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0165] Example 50 A black resin composition 50 was prepared in the same manner as in Example 44, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 51.1% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 50 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0166] Example 51 A black resin composition 51 was prepared in the same manner as in Example 46, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 51.4% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 51 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0167] Example 52 A black resin composition 52 was prepared in the same manner as in Example 47, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 51.7% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 52 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0168] Example 53 A black resin composition 53 was prepared in the same manner as in Example 48, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 51.9% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 53 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0169] Example 54 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 52.1% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.7% by weight based on 100% by weight of the total solid content, and zirconium nitride dispersion (A-35) was added so that the content of zirconium nitride particles in the colored resin composition was 0.7% by weight based on 100% by weight of the total solid content. A black resin composition 54 was prepared in the same manner as in Example 43. The obtained black resin composition 54 was evaluated in the same manner as in Example 43. The results are shown in Table 5.

[0170] [Table 5]

[0171] Example 55 A black resin composition 55 was prepared in the same manner as in Example 43, except that a propylene glycol monomethyl ether acetate solution of siloxane resin (C-1) was added so that the content of siloxane resin (C-1) in the colored resin composition was 41.3 mass% relative to 100 mass% of the total solid content. The obtained black resin composition 55 was evaluated in the same manner as in Example 43. The results are shown in Table 6.

[0172] Example 56 A black resin composition 56 was prepared in the same manner as in Example 44, except that a propylene glycol monomethyl ether acetate solution of the siloxane resin (C-1) was added so that the content of the siloxane resin (C-1) in the colored resin composition was 43.3% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 56 was evaluated in the same manner as in Example 43. The results are shown in Table 6.

[0173] Example 57 A black resin composition 57 was prepared in the same manner as in Example 46, except that a propylene glycol monomethyl ether acetate solution of siloxane resin (C-1) was added so that the content of siloxane resin (C-1) in the colored resin composition was 45.9% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 57 was evaluated in the same manner as in Example 43. The results are shown in Table 6.

[0174] Example 58 A black resin composition 58 was prepared in the same manner as in Example 47, except that a propylene glycol monomethyl ether acetate solution of siloxane resin (C-1) was added so that the content of siloxane resin (C-1) in the colored resin composition was 47.9% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 58 was evaluated in the same manner as in Example 43. The results are shown in Table 6.

[0175] Example 59 A black resin composition 59 was prepared in the same manner as in Example 48, except that a propylene glycol monomethyl ether acetate solution of siloxane resin (C-1) was added so that the content of siloxane resin (C-1) in the colored resin composition was 49.9% by mass relative to 100% by mass of the total solid content. The obtained black resin composition 59 was evaluated in the same manner as in Example 43. The results are shown in Table 6.

[0176] [Examples 60 to 63] Black resin compositions 60 to 63 were prepared in the same manner as in Examples 43, 44, and 46, except that the propylene glycol monomethyl ether acetate solution of siloxane resin (C-1) was changed to a propylene glycol monomethyl ether acetate solution of siloxane resin (C-2). The obtained black resin compositions 60 to 63 were evaluated in the same manner as in Example 43. The results are shown in Table 6.

[0177] Example 64 Black resin compositions 60 to 64 were prepared in the same manner as in Example 54, except that the propylene glycol monomethyl ether acetate solution of siloxane resin (C-1) was changed to a propylene glycol monomethyl ether acetate solution of siloxane resin (C-2) 61.1 wt %. The obtained black resin composition 64 was evaluated in the same manner as in Example 43. The results are shown in Table 6.

[0178] [Examples 65 and 66] Black resin compositions 65 to 66 were prepared in the same manner as in Example 61, except that the 45 wt% solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was replaced with 51.1 wt% and 43.3 wt% solutions of siloxane resin (C-2) in propylene glycol monomethyl ether acetate. The resulting black resin compositions 65 to 66 were evaluated in the same manner as in Example 43. The results are shown in Table 6.

[0179] [Table 6]

[0180] [Examples 67 to 78] A propylene glycol monomethyl ether acetate solution of siloxane resin (C-1) was added so that the content of siloxane resin (C-1) in the colored resin composition was 60.1% by mass relative to 100% by mass of the total solid content, and black resin compositions 67 to 78 were prepared in the same manner as in Examples 25 to 36, except that the colorant dispersion and dispersant (D) were changed as shown in Table 7. The obtained black resin compositions 67 to 78 were evaluated in the same manner as in Example 43. The results are shown in Table 7.

[0181] [Table 7]

[0182] [Examples 79 to 84] A propylene glycol monomethyl ether acetate solution of siloxane resin (C-1) was added so that the content of siloxane resin (C-1) in the colored resin composition was the mass% shown in Table 8 relative to 100% by mass of the total solid content, and carbon black dispersion (A-1) and zirconium nitride dispersion (A-35) were added so that the content of carbon black particles and zirconium nitride particles in the colored resin composition was the mass% shown in Table 8 relative to 100% by mass of the total solid content. Black resin compositions 79 to 84 were prepared in the same manner as in Example 37, except that they were added so that the content of carbon black particles and zirconium nitride particles in the colored resin composition was the mass% shown in Table 8 relative to 100% by mass of the total solid content. The obtained black resin compositions 79 to 84 were evaluated in the same manner as in Example 43. The results are shown in Table 8.

[0183] [Table 8]

[0184] Comparative Example 1 Comparative black resin composition 1 was prepared in the same manner as in Example 1, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 2.4% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 3.5% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 1, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 9.

[0185] Comparative Example 2 Comparative black resin composition 2 was prepared in the same manner as in Example 1, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.2% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.3% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 2, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 9.

[0186] Comparative Example 3 A 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 49.0% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 2.2% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 3.3% by weight based on 100% by weight of the total solid content. Comparative black resin composition 3 was prepared in the same manner as in Example 1. Evaluations were performed using the obtained comparative black resin composition 3 in the same manner as in Example 1. The results are shown in Table 9.

[0187] Comparative Example 4 Comparative black resin composition 4 was prepared in the same manner as in Comparative Example 2, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 52.5% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 4, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 9.

[0188] Comparative Example 5 Comparative black resin composition 5 was prepared in the same manner as in Comparative Example 3, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 38.4% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 5, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 9.

[0189] Comparative Example 6 Comparative black resin composition 6 was prepared in the same manner as in Comparative Example 2, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 41.1% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 6, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 9.

[0190] Comparative Example 7 Comparative black resin composition 7 was prepared in the same manner as in Example 1, except that the 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was replaced with a 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate, and the 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-2) in the colored resin composition was 57.7% by weight based on 100% by weight of the total solid content. Carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 2.2% by weight based on 100% by weight of the total solid content. Titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 3.3% by weight based on 100% by weight of the total solid content. Comparative black resin composition 7 was prepared in the same manner as in Example 1, except that the obtained comparative black resin composition 7 was evaluated in the same manner as in Example 1. The results are shown in Table 9.

[0191] Comparative Example 8 A 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-2) in the colored resin composition was 61.7% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.2% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.3% by weight based on 100% by weight of the total solid content. Comparative black resin composition 8 was prepared in the same manner as in Comparative Example 7. Evaluations were performed in the same manner as in Example 1 using the obtained comparative black resin composition 8. The results are shown in Table 9.

[0192] Comparative Example 9 A 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-2) in the colored resin composition was 49.4% by weight based on 100% by weight of the total solid content, carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 2.0% by weight based on 100% by weight of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 3.0% by weight based on 100% by weight of the total solid content. Comparative black resin composition 9 was prepared in the same manner as in Comparative Example 7. Evaluations were performed in the same manner as in Example 1 using the obtained comparative black resin composition 9. The results are shown in Table 9.

[0193] Comparative Example 10 A comparative black resin composition 10 was prepared in the same manner as in Comparative Example 8, except that a 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-2) in the colored resin composition was 52.5% by mass relative to 100% by mass of the total solid content. The obtained comparative black resin composition 10 was evaluated in the same manner as in Example 1. The results are shown in Table 9.

[0194] Comparative Example 11 Comparative black resin composition 11 was prepared in the same manner as in Comparative Example 9, except that a 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-2) in the colored resin composition was 38.7% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 11, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 9.

[0195] Comparative Example 12 Black resin composition 54 was prepared in the same manner as comparative black resin composition 12, except that a 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-2) in the colored resin composition was 41.1% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 12, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 9.

[0196] [Table 9]

[0197] Comparative Example 13 Comparative black resin composition 13 was prepared in the same manner as in Comparative Example 1, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 5.9% by mass, based on 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.0% by mass, based on 100% by mass of the total solid content. Using the obtained comparative black resin composition 13, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 10.

[0198] Comparative Example 14 Comparative black resin composition 14 was prepared in the same manner as in Comparative Example 13, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 3.0% by mass, relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 14, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 10.

[0199] Comparative Example 15 Comparative black resin composition 15 was prepared in the same manner as in Comparative Example 13, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 1.0 mass% relative to 100 mass% of the total solid content. Using the obtained comparative black resin composition 15, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 10.

[0200] Comparative Example 16 Comparative black resin composition 16 was prepared in the same manner as in Comparative Example 13, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 45.9% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 16, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 10.

[0201] Comparative Example 17 Comparative black resin composition 17 was prepared in the same manner as in Comparative Example 14, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 47.8% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 17, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 10.

[0202] Comparative Example 18 Comparative black resin composition 18 was prepared in the same manner as in Comparative Example 15, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 49.1% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 18, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 10.

[0203] Comparative Example 19 Comparative black resin composition 19 was prepared in the same manner as in Comparative Example 13, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 38.2% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 19, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 10.

[0204] Comparative Example 20 A comparative black resin composition 20 was prepared in the same manner as in Comparative Example 14, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 39.8% by mass relative to 100% by mass of the total solid content. The obtained comparative black resin composition 20 was evaluated in the same manner as in Example 1. The results are shown in Table 10.

[0205] Comparative Example 21 Comparative black resin composition 21 was prepared in the same manner as in Comparative Example 15, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 40.9% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 21, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 10.

[0206] [Comparative Examples 22 to 24] Comparative black resin compositions 22 to 24 were prepared in the same manner as in Comparative Examples 13 to 15, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was replaced with a 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate. The obtained comparative black resin compositions 22 to 24 were evaluated in the same manner as in Example 1. The results are shown in Table 10.

[0207] [Table 10]

[0208] Comparative Example 25 Comparative black resin composition 25 was prepared in the same manner as in Comparative Example 1, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.0% by mass, relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 5.9% by mass, relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 25, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 11.

[0209] Comparative Example 26 Comparative black resin composition 26 was prepared in the same manner as in Comparative Example 25, except that titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 3.0 mass% relative to 100 mass% of the total solid content. Using the obtained comparative black resin composition 26, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 11.

[0210] Comparative Example 27 Comparative black resin composition 27 was prepared in the same manner as in Comparative Example 25, except that titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 1.0 mass% relative to 100 mass% of the total solid content. Using the obtained comparative black resin composition 27, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 11.

[0211] Comparative Example 28 Comparative black resin composition 28 was prepared in the same manner as in Comparative Example 25, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 45.9% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 28, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 11.

[0212] Comparative Example 29 Comparative black resin composition 29 was prepared in the same manner as in Comparative Example 26, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 47.8% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 29, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 11.

[0213] Comparative Example 30 A comparative black resin composition 30 was prepared in the same manner as in Comparative Example 27, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 49.1% by mass relative to 100% by mass of the total solid content. The obtained comparative black resin composition 30 was evaluated in the same manner as in Example 1. The results are shown in Table 11.

[0214] Comparative Example 31 Comparative black resin composition 31 was prepared in the same manner as in Comparative Example 25, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 38.2% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 31, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 11.

[0215] Comparative Example 32 Comparative black resin composition 32 was prepared in the same manner as in Comparative Example 26, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 39.8% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 32, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 11.

[0216] Comparative Example 33 Comparative black resin composition 33 was prepared in the same manner as in Comparative Example 27, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was added so that the content of siloxane resin (C-1) in the colored resin composition was 40.9% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 33, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 11.

[0217] [Comparative Examples 34 to 36] Comparative black resin compositions 34 to 36 were prepared in the same manner as in Comparative Examples 25 to 27, except that a 45% by weight solution of siloxane resin (C-1) in propylene glycol monomethyl ether acetate was replaced with a 70% by weight solution of siloxane resin (C-2) in propylene glycol monomethyl ether acetate. The obtained comparative black resin compositions 34 to 36 were evaluated in the same manner as in Example 1. The results are shown in Table 11.

[0218] [Table 11]

[0219] Comparative Example 37 Comparative black resin composition 37 was prepared in the same manner as in Example 37, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 3.6% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.9% by mass relative to 100% by mass of the total solid content. The obtained comparative black resin composition 37 was evaluated in the same manner as in Example 1. The results are shown in Table 12.

[0220] Comparative Example 38 Comparative black resin composition 38 was prepared in the same manner as in Example 3, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 2.4% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.6% by mass relative to 100% by mass of the total solid content. The obtained comparative black resin composition 38 was evaluated in the same manner as in Example 1. The results are shown in Table 12.

[0221] Comparative Example 39 Comparative black resin composition 39 was prepared in the same manner as in Example 5, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.8% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.2% by mass relative to 100% by mass of the total solid content. The obtained comparative black resin composition 39 was evaluated in the same manner as in Example 1. The results are shown in Table 12.

[0222] Comparative Example 40 Comparative black resin composition 40 was prepared in the same manner as in Example 37, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.9% by mass, based on 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 3.6% by mass, based on 100% by mass of the total solid content. Using the obtained comparative black resin composition 40, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 12.

[0223] Comparative Example 41 Comparative black resin composition 41 was prepared in the same manner as in Example 3, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.6% by mass relative to 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 2.4% by mass relative to 100% by mass of the total solid content. Using the obtained comparative black resin composition 41, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 12.

[0224] Comparative Example 42 Black resin composition 8 and comparative black resin composition 42 were prepared in the same manner as in Example 5, except that carbon black dispersion (A-1) was added so that the content of carbon black particles in the colored resin composition was 0.2% by mass based on 100% by mass of the total solid content, and titanium black dispersion (A-2) was added so that the content of titanium nitride particles in the colored resin composition was 0.8% by mass based on 100% by mass of the total solid content. Using the obtained comparative black resin composition 42, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 12.

[0225] [Table 12]

[0226] [Comparative Examples 43 to 54] Comparative black resin compositions 43 to 54 were prepared in the same manner as in Comparative Examples 13 to 24, except that titanium black dispersion (A-2) was changed to zirconium nitride dispersion (A-35), carbon black dispersion (A-1) and zirconium nitride dispersion (A-35) were added so that the content of carbon black particles and zirconium nitride particles in the colored resin composition was the mass% shown in Table 13, relative to 100% by mass of the total solid content, and dispersant (D) was changed to BYK-2000 and added in the amount shown in Table 13. Comparative black resin compositions 43 to 54 were evaluated in the same manner as in Example 1 using the obtained comparative black resin compositions 43 to 54. The results are shown in Table 13.

[0227] [Table 13]

[0228] [Comparative Examples 55 to 60] Comparative black resin compositions 55 to 60 were prepared in the same manner as in Comparative Examples 55 to 60, except that titanium black dispersion (A-2) was changed to zirconium nitride dispersion (A-35), carbon black dispersion (A-1) and zirconium nitride dispersion (A-35) were added so that the content of carbon black particles and zirconium nitride particles in the colored resin composition was the mass% shown in Table 14, relative to 100% by mass of the total solid content, and dispersant (D) was changed to BYK-2000 and added in the amount shown in Table 13. Comparative black resin compositions 55 to 60 were evaluated in the same manner as in Example 1, using the obtained comparative black resin compositions 55 to 60. The results are shown in Table 14.

[0229] [Table 14] [Explanation of symbols]

[0230] 1. Glass-reinforced black resin layer (film of black resin composition) 2 Decorative layer 3. Glass substrate 4 Coloring material (A) 5. Colorless and transparent glass reinforced transparent coating film layer 6. Translucent colored glass 10. Tempered glass 100 Decorative Glass

Claims

1. A black resin composition comprising a colorant (A) and a resin (B), wherein the resin (B) is a siloxane resin (C), and the content of the siloxane resin (C) is 35% by mass or more relative to the total solid content in the black composition; the black resin composition is formed into a film having a thickness of 2 μm on a transparent glass substrate, and when the film is irradiated with light from a D65 standard light source and transmitted through, the total light transmittance in the wavelength range of 400 nm to 700 nm is 20% or more at minimum and 80% or less at maximum; and the chromaticities a* and b* of the film are both in the range of −3 to +3.

2. 2. The black resin composition according to claim 1, wherein the haze value of the film is less than 3%.

3. 3. The black resin composition according to claim 1, wherein the content of the colorant (A) is 1 to 6 mass% based on the total solid content of the black composition.

4. 3. The black resin composition according to claim 1, wherein the colorant (A) contains at least carbon black (A-1) and titanium nitride (A-2), and the total amount of the two is 50% by mass or more based on the total amount of the colorant (A).

5. 5. The black resin composition according to claim 4, wherein the coloring material (A) contains only carbon black (A-1) and titanium nitride (A-2).

6. 6. The black resin composition according to claim 5, wherein the content of the carbon black (A-1) in the colorant (A) is 25 to 50 mass% based on the total amount of the colorant (A), and the content of the titanium nitride (A-2) is 50 to 75 mass% based on the total amount of the colorant (A).

7. 3. The black resin composition according to claim 1, wherein the colorant (A) contains at least carbon black (A-1) and zirconium nitride (A-3), and the total amount of the two is 50% by mass or more based on the total amount of the colorant (A).

8. The black resin composition according to claim 7, wherein the colorant (A) contains only carbon black (A-1) and zirconium nitride (A-3).

9. 8. The black resin composition according to claim 7, wherein the content of the carbon black (A-1) in the colorant (A) is 30 to 70 mass% based on the total amount of the colorant (A), and the content of the zirconium nitride (A-3) is 30 to 70 mass% based on the total amount of the colorant (A).

10. 3. The black resin composition according to claim 1, further comprising a dispersant (D) having an amine value of 30 mgKOH / g or less.

11. 11. The black resin composition according to claim 10, wherein the content of the dispersant (D) is 0.1 to 10 mass % based on the total solid content in the black resin composition.

12. 3. The black resin composition according to claim 1, further comprising inorganic particles (E), the content of the inorganic particles (E) being 10% by mass or more relative to the total solid content in the black composition; and the inorganic particles (E) including at least silica particles, the content of the silica particles being 60% by mass or more relative to the inorganic particles (E).

13. The black resin composition according to claim 12, wherein the inorganic particles (E) are silica particles only.

14. A glass-reinforced black resin layer comprising a film of the black resin composition according to claim 1 or 2.

15. Tempered glass comprising a glass substrate and the glass-reinforcing black resin layer according to claim 14 formed on the glass substrate.

16. A decorative glass comprising a glass substrate and the glass-reinforced black resin layer according to claim 14 formed on the glass substrate.

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