WO2014148616A1 - Pigments comprising glass containing colored components, paints, resin compositions, and exterior members - Google Patents

Abstract

Provided are: pigments capable of imparting, on resin compositions, change characteristics for desired apparent color tones; paints and resin compositions containing said pigments; and exterior members comprising glass and resin compositions coated with said paints. The pigments comprise glass containing colored components. When the chromaticity of the main surface of the glass is measured, with the glass being a glass plate having a thickness of 0.8 mm or less, the absolute value of the difference (Δa* (D65 - F2)) between the chromaticity (a*) of reflected light from a D65 light source and the chromaticity (a*) of reflected light from an F2 light source of the L*a*b* color space, represented by formula (1), and/or the absolute value of the difference (Δa* (A - F2)) between the chromaticity (a*) of reflected light from an A light source and the chromaticity (a*) of reflected light from an F2 light source of the L*a*b* color space, represented by formula (2), is at least 0.2. Δa^* (D65 - F2) = a^* value (D65 light source) - a^* value (F2 light source) (1) Δa^* (A - F2) = a^* value (A light source) - a^* value (F2 light source) (2)

Description

Pigments, paints, resin compositions, exterior members made of glass containing coloring components

The present invention uses a resin composition used for an exterior member of an electronic device, for example, a communication device that can be carried and used for an exterior member of an information device, a pigment added to a paint applied to glass, and the pigment. It is related with a coating material, a resin composition, and the exterior member obtained using these.

Appropriate materials such as resin and metal are selected and used for exterior members and ornaments of electronic devices such as mobile phones in consideration of various factors such as decoration, scratch resistance, workability, and cost. Yes.
In recent years, an attempt has been made to use glass that has not been conventionally used as a material for an exterior member (Patent Document 1). According to Patent Document 1, in an electronic device such as a mobile phone, a unique decorative effect with a transparent feeling can be exhibited by forming the exterior member itself with glass.

JP 2009-61730 A

¡Exterior materials and decorations for electronic devices are required to express various designs that reflect the diversity of consumer preferences. The color tone is one of the most important designs. The glass used for the exterior member of the electronic device is required to faithfully reproduce the color tone based on the data obtained through marketing activities and the color tone determined by the designer.

For example, a glass colored with a resin composition or paint used for an exterior member is visible when the lightness L ^* (L ^* a ^* b ^* color system standardized by the International Commission on Illumination (CIE)) is 20 or more. Since a certain amount of light having a wavelength in the visible region is transmitted without completely blocking light having a wavelength in the region, it is important to set the color tone in consideration of the apparent color tone.

However, the present inventor has found that there is a difference in appearance color tone between outdoors and indoors depending on the coloring components contained in the exterior member. When the exterior member has a surface made of a different material, the change in the apparent color tone when the light source is different is different depending on the different material, so that the change in the apparent color tone is recognized more remarkably. .
The present invention aims to provide a pigment capable of imparting a desired change in color tone to a resin composition, a paint or resin composition containing these pigments, and an exterior member made of glass or resin composition coated with these paints. And

As a result of various investigations, the present inventor has paid attention to color appearance conditions such as color tone (hereinafter sometimes referred to as metamerism) when the light sources of the colorant and pigment contained in the resin composition are different. . And it discovered that a desired metamerism was obtained as a resin composition by containing in a resin composition the pigment provided with the metamerism different from the metamerism of a coloring agent with respect to the metamerism of a coloring agent.

That is, the pigment of the present invention is a pigment made of glass containing a coloring component, and the glass has the following (1) when the chromaticity of the main surface is measured in the state of a glass plate having a thickness of 0.8 mm or less. ), The difference (Δa ^* (D65−F2)) between the chromaticity a ^* of the reflected light from the D65 light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light from the F2 light source The absolute value and the difference (Δa ^*) between the chromaticity a ^* of the reflected light by the A light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light by the F2 light source expressed by the following equation (2) It has a characteristic that at least one of the absolute values of (A−F2)) is 0.2 or more.
Δa ^* (D65−F2) = a ^* value (D65 light source) −a ^* value (F2 light source) (1)
Δa ^* (A−F2) = a ^* value (A light source) −a ^* value (F2 light source) (2).

The pigment of the present invention is a pigment made of glass containing a coloring component, and the pigment is added to the resin composition together with a colorant other than the pigment, and the glass has a thickness of 0. When the chromaticity of the main surface is measured in the state of a glass plate of .8 mm or less, the chromaticity a ^* and F2 of the reflected light from the D65 light source of the L ^* a ^* b ^* color system shown by the following formula (1) The difference from the chromaticity a ^* of the reflected light from the light source is (Δa ^* (D65-F2)), and the color of the reflected light from the A light source of the L ^* a ^* b ^* color system expressed by the following equation (2) When the difference between the degree a ^* and the chromaticity a ^* of the reflected light from the F2 light source is (Δa ^* (A−F2)), (Δa ^* (D65−F2)) of the glass and (Δa of the colorant ^* Absolute value of difference from (D65-F2)), (Δa ^* (A-F2)) of the glass and the colorant It is characterized in that at least one of the absolute values of the difference from (Δa ^* (A−F2)) has a characteristic of 0.2 or more.
Δa ^* (D65−F2) = a ^* value (D65 light source) −a ^* value (F2 light source) (1)
Δa ^* (A−F2) = a ^* value (A light source) −a ^* value (F2 light source) (2)

According to the present invention, it is possible to obtain a pigment capable of imparting a desired color tone condition and the like to the resin composition. Further, by containing these pigments, it is possible to obtain a paint or a resin composition having a desired appearance color tone or the like. Further, by using a paint or a resin composition containing the pigment, an exterior member having a desired color tone condition and the like can be obtained.

Metamerism (conditional color, etc.) is an index that indicates the degree of color change of the color tone or appearance color due to the color of external light. The L ^* a ^* b ^* color system standardized by the CIE (International Lighting Commission) is used. Can be defined using The lower the metamerism, the smaller the degree of color change or color change due to external light color. When the metamerism of the exterior member is high, the appearance color tone of the exterior member is greatly different if the type of the light source is different. For example, the color tone of the exterior member indoors is greatly different from the color tone of the exterior members outdoor.
Further, when a surface made of a different material exists in the exterior member or the like, the change in the apparent color tone is recognized more remarkably because the metamerism differs depending on the different material.

The pigment of the present invention is a pigment made of glass containing a coloring component, and the glass has the following formula (1) when the chromaticity of the main surface is measured in a state of a glass plate having a thickness of 0.8 mm or less. The absolute value of the difference (Δa ^* (D65−F2)) between the chromaticity a ^* of the reflected light from the D65 light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light from the F2 light source And the difference between the chromaticity a ^* of the reflected light from the A light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light from the F2 light source (Δa ^* (A At least one of the absolute values of -F2)) has a characteristic of 0.2 or more.
That is, Δa ^* (D65−F2) is the difference between the chromaticity a ^* of the reflected light from the D65 light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light from the F2 light source.
Δa ^* (A−F2) is the difference between the chromaticity a ^* of the reflected light from the A ^* light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light from the F2 light source.
Δa ^* (D65−F2) = a ^* value (D65 light source) −a ^* value (F2 light source) (1)
Δa ^* (A−F2) = a ^* value (A light source) −a ^* value (F2 light source) (2)
As Δa ^* (D65-F2) defined by the above equation (1) and Δa ^* (A−F2) defined by the above equation (2) are smaller, the light source is different. The change in the characteristic of the apparent color tone due to this can be reduced.
Therefore, the pigment of the present invention has a greater effect of correcting the metamerism of the resin composition as the amount different from Δa ^* (D65-F2) and Δa ^* (A-F2) of the colorant is larger.
As a result, the pigment made of glass has a color having a certain color tone or the like. Therefore, a paint or resin composition containing a pigment made of these glass can provide a paint or resin composition having a desired metamerism. In the pigment, at least one of an absolute value of (Δa ^* (D65-F2)) and an absolute value of (Δa ^* (A−F2)) is 0.2 or more, preferably 0.4 or more, and 6 or more is more preferable.
If the absolute value of (Δa ^* (D65-F2)) and the absolute value of (Δa ^* (A-F2)) are both less than 0.2, the pigment and the appearance of the paint composition There is a possibility that the effect of correcting the color tone may not be sufficiently obtained.

The pigment of the present invention is a pigment made of glass containing a coloring component, and the pigment is added to the resin composition together with a colorant other than the pigment, and the glass has a thickness of 0. When the chromaticity of the main surface is measured in a state of a glass plate of .8 mm or less, the chromaticity a ^* and F2 of the reflected light from the D65 light source of the L ^* a ^* b ^* color system shown by the above equation (1) The difference from the chromaticity a ^* of the reflected light by the light source is (Δa ^* (D65-F2)), and the color of the reflected light by the A light source of the L ^* a ^* b ^* color system represented by the above equation (2) When the difference between the degree a ^* and the chromaticity a ^* of the reflected light from the F2 light source is (Δa ^* (A−F2)), (Δa ^* (D65−F2)) of the glass and (Δa of the colorant ^* Absolute value of difference from (D65-F2)), (Δa ^* (A-F2)) of the glass and the colorant It is characterized in that at least one of the absolute values of the difference from (Δa ^* (A−F2)) has a characteristic of 0.2 or more.

Thereby, the pigment made of the glass is different from the colorant other than the pigment by a certain amount or more in the color tone condition. Therefore, a paint or a resin composition containing both the pigment and the colorant can correct a metamerism caused by the colorant by the pigment and obtain a paint or resin composition having a desired metamerism. The pigment includes an absolute value of a difference between (Δa ^* (D65-F2)) of the glass and (Δa ^* (D65-F2)) of the colorant, and (Δa ^* (A−F2)) of the glass. At least one of the absolute values of the difference from (Δa ^* (A−F2)) of the colorant is 0.2 or more, preferably 0.4 or more, and more preferably 0.6 or more.
The pigment includes an absolute value of a difference between (Δa ^* (D65-F2)) of the glass and (Δa ^* (D65-F2)) of the colorant, and (Δa ^* (A−F2)) of the glass. If the absolute value of the difference between (Δa ^* (A−F2)) of the colorant is less than 0.2, the effect of correcting the apparent color tone of the paint or resin composition may not be sufficiently obtained. There is.

The metamerism of the resin composition has the following two correction directions.
The first is that the resin composition contains the pigment of the present invention so that Δa ^* (D65-F2) and Δa ^* (A-F2) of the resin composition is different from the resin composition used for the exterior member. This is to make Δa ^* (D65-F2) and Δa ^* (A-F2) of (for example, a metal material) similar. Thereby, even if a resin composition and a material different from the resin composition are used for the same exterior member, the degree of metamerism is similar as described above, and thus there is no sense of incongruity in the change in the apparent color tone due to the difference in the light source.
Second, by including the pigment of the present invention in the resin composition, Δa ^* (D65-F2) and Δa ^* (A-F2) are made as close to zero as possible, that is, the indoor color tone and the outdoor This is to reduce the difference from the apparent color tone. The larger the color, such as the apparent color condition, of the pigment and the colorant other than the pigment is, the greater the effect of correcting the apparent color condition, etc., of the resin composition. Therefore, Δa ^* (D65-F2) and Δa ^* (A-F2) of the pigment should be selected in consideration of Δa ^* (D65-F2) and Δa ^* (A-F2) of the colorant other than the pigment. Thus, the apparent color tone of the resin composition containing the pigment and the colorant other than the pigment can be made as close to zero as possible.

In addition, it is preferable that at least one of the directivity of Δa ^* (D65-F2) and the directivity of Δa ^* (A−F2) is different between the pigment and the colorant other than the pigment. The “directionality” in the directionality of Δa ^* (D65-F2) and the directionality of Δa ^* (A−F2) means that these values are on the plus side (0 or more) and minus side (less than 0). Then, it means that the "direction are different", for example, in the case of pigment Δa ^* (D65-F2) were positive, .DELTA.a colorant ^* (D65-F2) is negative .
As described above, the pigment according to the present invention is different from the colorant in both or either of the directivity of Δa ^* (D65-F2) and the directivity of Δa ^* (A-F2). The effect of correcting the metamerism can be increased. Thereby, desired metamerism can be provided in a resin composition by containing the pigment of this invention in a resin composition.

In the pigment of the present invention, the reason why the apparent color tone of glass is measured in a state of a glass plate having a thickness of 0.8 mm or less is as follows. This is because the pigment is used in a powder state, but in the powder state, the smoothness of the surface to be measured is low, and incident light and reflected light are scattered on the surface, which hinders accurate measurement. Further, since the apparent color tone of the glass plate changes depending on the plate thickness, it was specified that the plate thickness was 0.8 mm or less. When measuring the apparent color tone of the glass plate, the measurement is performed after placing a white resin plate on the back surface of the glass plate (the surface opposite to the surface on which the light source is incident). In addition, it is preferable that the plate | board thickness of glass at the time of measuring the color tone of the appearance of a glass plate is 0.1 mm or more. This is because if the glass plate thickness is less than 0.1 mm, it takes time and effort to process the glass plate for measurement. More preferably, it is 0.4 mm or more, More preferably, it is 0.5 mm or more.

In the L ^* a ^* b ^* color system, a ^* represents a change in color tone from red to green, and b ^* represents a change in color tone from yellow to blue. It is the color change from red to green that makes people feel color change more sensitively. Therefore, the pigment of the present invention has a difference (Δa ^* (D65−F2)) between the chromaticity a ^* of the reflected light from the D65 light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light from the F2 light source. ) And L ^* a ^* b ^* , the difference (Δa ^* (A−F2)) between the chromaticity a ^* of the reflected light from the A light source of the color system and the chromaticity a ^* of the reflected light from the F2 light source.

The pigment of the present invention preferably has a lightness L ^* (F2 light source) defined using the L ^* a ^* b ^* color system in the range of 20 to 90. That is, when L ^* is within the above range, the lightness of the pigment is an intermediate region between “bright” and “dark”, and thus it is in a range where it is easy to recognize a change in color tone, and it is more effective to use the present invention. Is. If the L ^* is less than 20, the pigment exhibits a dark color, so it is difficult to recognize the color tone change of the pigment. Further, when L ^* exceeds 90, the pigment exhibits a light color, and thus it is difficult to recognize the color tone change of the pigment. L ^* is more preferably 22 to 85, still more preferably 23 to 80, and particularly preferably 24 to 75. The lightness L ^* is the reflected light when a white resin plate is installed on the back side of the glass plate when the chromaticity of the main surface is measured in the state of a 0.8 mm thick glass plate using an F2 light source. Based on measured data.

The pigment of the present invention is made of glass containing a coloring component. Therefore, the apparent color tone of the pigment described above depends on the apparent color tone of the glass containing the coloring component.
The pigment of the present invention contains MpOq as a coloring component in glass (where M is Fe, Cu, V, Se, Co, Ti, Cr, Pr, Ce, Bi, Eu, Mn, Er, Ni, Nd, Containing at least one selected from the group consisting of W, Rb, and Ag, and p and q are atomic ratios of M and O) in an amount of 0.001 to 10% in terms of mole percentage based on oxide It is preferable to do. These coloring components are components for coloring the glass in a desired color and adjusting metamerism, and by appropriately selecting the coloring components, for example, blue, green, yellow, purple, pink, Colored glass such as red and achromatic can be obtained.

When the content of the coloring component is less than 0.001%, the coloring of the glass becomes extremely thin. Therefore, when such a glass is used as a pigment, it is difficult to adjust the apparent color tone of the resin composition. Therefore, it is preferable to contain 0.001% or more. More preferably, it is 0.005% or more, More preferably, it is 0.01% or more. On the other hand, if the content exceeds 10%, the glass becomes unstable and devitrification may occur. Therefore, the content is preferably 10% or less. More preferably, it is 8% or less, More preferably, it is 5% or less.

Further, the coloring components are, for example, at least one use selected from the group consisting of Co ₃ O ₄ and CuO, can be obtained colored glass of blue. By using at least one selected from the group consisting of V ₂ O ₅ , Cr ₂ O ₃ , CuO and Pr ₆ O ₁₁ , a green colored glass can be obtained. By using at least one selected from the group consisting of CeO ₂ , V ₂ O ₅ , Bi ₂ O ₃ and Eu ₂ O ₃ , a yellow colored glass can be obtained. By using at least one selected from the group consisting of MnO ₂ , Er ₂ O ₃ , NiO, Nd ₂ O ₃ and WO ₃ , a purple to pink colored glass can be obtained. By using at least one selected from the group consisting of Cu ₂ O and Ag ₂ O, a red colored glass can be obtained. By using at least one selected from the group consisting of Fe ₂ O ₃ , V ₂ O ₅ , Cr ₂ O ₃ , NiO and Se, a gray to black (achromatic) colored glass can be obtained.

The reason why metamerism occurs in glass is considered as follows.
The apparent color tone of the glass is a superposition of the spectral distribution of the light source and the spectral reflectance of the glass. The spectral distribution of the light source differs depending on the type of light source. The D65 light source is a light source for measuring the object color illuminated by daylight including the ultraviolet region, and shows a broad spectral distribution in the visible wavelength region. The F2 light source is white light of a typical fluorescent lamp, and shows a spectral distribution having a peak at a specific wavelength in the visible wavelength range. The A light source is light emitted from a tungsten light bulb, corresponds to light of a general household light bulb, and exhibits a spectral distribution that monotonously increases at a wavelength of about 400 nm to 800 nm. On the other hand, the color components contained in the glass have different wavelengths to be absorbed depending on the respective components.
Therefore, it is considered that metamerism occurs in the spectral reflectance of the glass containing the coloring component due to the difference in the absorption characteristics of the wavelength due to the type of the light source depending on the type and content of the coloring component to be contained.

Next, the glass composition of the glass of the present invention (excluding the coloring components of the colorant other than the pigment of the present invention described above) will be described.
As the glass of the present invention, SiO ₂ is 55 to 80%, Al ₂ O ₃ is 0.05 to 16%, B ₂ O ₃ is 0 to 12%, Na ₂ O in terms of mole percentage based on the following oxides. 0-20%, K ₂ O 0-15%, MgO 0-15%, CaO 0-15%, ΣRO (R is Mg, Ca, Sr, Ba, Zn) 0-30%, MpOq (where M is at least selected from the group consisting of Fe, Cu, V, Se, Co, Ti, Cr, Pr, Ce, Bi, Eu, Mn, Er, Ni, Nd, W, Rb, and Ag) And a compound containing 0.001 to 10% of p and q is an atomic ratio of M and O).

Hereinafter, the composition of the glass of the present invention will be described using the oxide-based molar percentage display content unless otherwise specified.
In addition, in this specification, content of each component of a glass and a coloring component shows conversion content when each component which exists in glass shall exist as a displayed oxide.
For example, “containing 0.001 to 5% of Fe ₂ O ₃ ” means that the Fe content in the case where all the Fe present in the glass is present in the form of Fe ₂ O ₃ , that is, Fe of Fe _This means that the content in terms of ₂ O ₃ is 0.001 to 5%.

SiO ₂ is a component constituting the skeleton of the glass and is essential. If it is less than 55%, the stability as glass may be lowered, or the weather resistance may be lowered. Preferably it is 60% or more. More preferably, it is 65% or more. If the SiO ₂ content exceeds 80%, the viscosity of the glass increases and the meltability may be significantly reduced. Preferably it is 75% or less, More preferably, it is 70% or less.

Al ₂ O ₃ is a component that improves the weather resistance of glass and is essential. If it is less than 0.05%, the weather resistance may be lowered. Preferably it is 0.25% or more, more preferably 0.5% or more, and still more preferably 1% or more.
If Al ₂ O ₃ exceeds 16%, the viscosity of the glass becomes high and there is a possibility that homogeneous melting becomes difficult. Preferably it is 14% or less, More preferably, it is 12% or less.

B ₂ O ₃ is a component that improves the weather resistance of the glass, but is not essential and can be contained as necessary. When B ₂ O ₃ is contained, if it is less than 4%, a significant effect may not be obtained for improving weather resistance. Preferably it is 5% or more, more preferably 6% or more.
If B ₂ O ₃ exceeds 12%, striae due to volatilization may occur and the yield may decrease. Preferably it is 11% or less, More preferably, it is 10% or less.

Na ₂ O is a component that improves the meltability of the glass, but is not essential, and a component that is preferably contained as necessary. When Na ₂ O is contained, if it is less than 3%, the meltability may deteriorate. Preferably it is 5% or more, More preferably, it is 6% or more, More preferably, it is 7% or more.
If Na ₂ O exceeds 20%, the weather resistance may be lowered. Preferably it is 18% or less, More preferably, it is 16% or less, More preferably, it is 10% or less.

K ₂ O is a component that improves the meltability of the glass, but is not essential and is a component that is preferably contained. When it contains K ₂ O, if it is less than 0.01%, there is a possibility that a significant effect cannot be obtained for improving the meltability. Preferably it is 0.15% or more, more preferably 0.3% or more. If K ₂ O exceeds 15%, the weather resistance decreases. Preferably it is 13% or less, More preferably, it is 10% or less.

RO (R represents Mg, Ca, Sr, Ba, Zn) is a component that improves the meltability of the glass, but is not essential, and may contain one or more as required. . In that case, if the total RO content ΣRO (ΣRO represents MgO + CaO + SrO + BaO + ZnO) is less than 1%, the meltability may decrease. Preferably it is 3% or more, More preferably, it is 5% or more. If ΣRO exceeds 30%, the weather resistance may decrease. It is preferably 27% or less, more preferably 25% or less, still more preferably 20% or less, still more preferably 18% or less, and particularly preferably 15% or less.

MgO is a component that improves the meltability of the glass, but is not essential and can be contained as necessary. When it contains MgO, if it is less than 3%, there is a possibility that a significant effect cannot be obtained for improving the meltability. Preferably it is 4% or more. If MgO exceeds 15%, the weather resistance may decrease. Preferably it is 13% or less, More preferably, it is 12% or less.

CaO is a component that improves the meltability of the glass, but is not essential and can be contained as necessary. When CaO is contained, if it is less than 0.01%, there is a possibility that a significant effect cannot be obtained for improving the meltability. Preferably it is 0.1% or more. If CaO exceeds 15%, the chemical strengthening properties may be deteriorated. Preferably it is 12% or less, More preferably, it is 10% or less.

SrO is a component for improving the meltability, but is not essential and can be contained as necessary. When it contains SrO, if it is less than 1%, there is a possibility that a significant effect cannot be obtained for improving the meltability. Preferably it is 3% or more, More preferably, it is 6% or more. If SrO exceeds 15%, the weather resistance may be lowered. Preferably it is 12% or less, More preferably, it is 9% or less.

BaO is a component for improving the meltability, but is not essential and can be contained as necessary. When it contains BaO, if it is less than 1%, there is a possibility that a significant effect cannot be obtained with respect to improvement in meltability. Preferably it is 3% or more, More preferably, it is 6% or more. If BaO exceeds 15%, the weather resistance may decrease. Preferably it is 12% or less, More preferably, it is 9% or less.

ZnO is a component for improving the meltability and water resistance, but is not essential and can be contained as necessary. When it contains ZnO, if it is less than 1%, there is a possibility that a significant effect cannot be obtained with respect to improvement in meltability. Preferably it is 3% or more, More preferably, it is 5% or more. If ZnO exceeds 15%, the glass may become unstable or the weather resistance may decrease. Preferably it is 13% or less, More preferably, it is 12% or less, More preferably, it is 9% or less. (Both water resistance and weather resistance are acceptable.)

In addition to the above components, the following components may be introduced into the glass composition.

ZrO ₂ is a component for improving the meltability and water resistance, but is not essential and may be contained in a range of 1% or less. If the ZrO ₂ content exceeds 1%, the meltability may be deteriorated and remain in the glass as an unmelted product. Preferably it is 0.5% or less, more preferably 0.4% or less, and even more preferably ZrO ₂ is not contained.
SO ₃ is a component that acts as a fining agent, but is not essential and can be contained as necessary. When containing SO _3, can not be obtained refining effect expected is less than 0.005%. Preferably it is 0.01% or more, More preferably, it is 0.02% or more. More preferably, it is 0.03% or more. On the other hand, if it exceeds 0.5%, it becomes a generation source of bubbles, and there is a possibility that the glass melts slowly or the number of bubbles increases. Preferably it is 0.3% or less, More preferably, it is 0.2% or less, More preferably, it is 0.1% or less.

SnO ₂ is a component that acts as a fining agent, but is not essential and can be contained as necessary. When SnO ₂ is contained, if it is less than 0.005%, the expected clarification action may not be obtained. Preferably it is 0.01% or more, More preferably, it is 0.05% or more. On the other hand, if it exceeds 1%, it becomes a generation source of bubbles, and there is a possibility that the glass melts slowly or the number of bubbles increases. Preferably it is 0.8% or less, More preferably, it is 0.5% or less, More preferably, it is 0.3% or less.

In addition to the SO ₃ and SnO ₂ described above, chloride or fluoride may be appropriately contained as a fining agent when the glass is melted.

Li ₂ O is a component for improving the meltability, but is not essential and can be contained as necessary. When Li ₂ O is contained, if it is less than 1%, there is a possibility that a significant effect cannot be obtained for improving the meltability. Preferably it is 3% or more, More preferably, it is 6% or more. If Li ₂ O exceeds 15%, the weather resistance may decrease. Preferably it is 10% or less, More preferably, it is 5% or less.

The alkali elution amount of the glass is preferably 0 to 2.4 ppm. If it is greater than 2.4 ppm, the adhesion to the substrate may be reduced due to the influence of the eluted alkali on the resin component, or the desired characteristics may not be exhibited due to the influence on other pigments. More preferably, it is 1.5 ppm or less, More preferably, it is 1.0 ppm or less, More preferably, it is 0.5 ppm or less. The measuring method of the alkali elution amount here is mentioned later.

The glass containing the coloring component used in the pigment of the present invention may be so-called phase-separated glass or crystallized glass in which phase separation or crystal is generated in the glass. When glass coated with a paint containing a pigment is used as an exterior member, a so-called shielding property (opacity) in which the back side is not transparent from the front side may be required. As a means for imparting shielding properties to such glass, there is a method of applying a paint containing a dark pigment to the glass to reduce the visible light reflection transmittance. Further, there is a method in which phase separation or crystals are generated in the glass in the pigment to diffuse the light transmitted through the paint applied to the glass by the phase separation or crystal fine structure, thereby reducing the reflection transmittance. Since the pigment of the present invention is made of phase-separated glass or crystallized glass containing a coloring component, a pigment having a desired color tone with high shielding properties can be obtained. Further, by containing such a pigment, a paint or resin composition having a desired color tone and high shielding properties can be obtained.

In crystallized glass, a crystal phase of several nm to several μm in size is distributed in the glass matrix, and by selecting the composition of the base glass and controlling the manufacturing conditions and heat treatment conditions, By changing the size, a desired shielding glass can be obtained.
In the phase-separated glass, two or more glass phases having different compositions are distributed. There are spinodal in which two phases are continuously distributed and binodal in which one phase is distributed in the form of particles in a matrix, and each phase has a size of 1 μm or less. As for the phase-separated glass, a desired shielding glass can be obtained under the heat treatment conditions for performing composition control and phase-separation treatment for obtaining an appropriate phase-separation region.

The method for producing the pigment of the present invention is not particularly limited. The glass contained in the pigment can be produced by an ordinary method, for example, a melting method. Specifically, it can be produced by mixing and mixing glass raw materials so as to have the composition as described above, melting at about 1300 to 1600 ° C., and then cooling and solidifying. The glass obtained above is crushed and used as a glass powder. The pulverization can be performed using a pulverizer such as a roll mill, a ball mill, or a jet mill. If the coarsely pulverized product is appropriately finely pulverized with a ball mill or the like, and after removing coarse particles with a sieve or the like, if necessary, the fine particles are removed with a wind separator or the like to adjust to a predetermined particle size and average particle size. Good. Various mechanisms for the apparatus for preparing the powder have been proposed, but the present invention has no particular limitation and should be selected from an industrial and economical viewpoint.
The glass contained in the pigment of the present invention is used in a powder state, and its 50% particle size (D ₅₀ ) is preferably 0.1 to 50 μm. If D ₅₀ of the glass is less than 0.1 [mu] m, industrially and difficult manufacture and made for easily aggregate, it is difficult to handle. The D ₅₀ of the glass is more preferably 1 μm or more, further preferably 2 μm or more, and even more preferably 3 μm or more. On the other hand, when D50 exceeds ₅₀ μm, the smoothness of the resin composition or the coating film surface may be deteriorated when it is contained with a resin composition or a paint. Therefore, D ₅₀ of the glass powder is more preferably 30 μm or less, further preferably 15 μm or less, and still more preferably 10 μm or less. The particle size can be adjusted, for example, by classification as necessary after pulverization. In addition, the 50% particle size (D ₅₀ ) in the present specification is a value measured by a laser diffraction scattering method.

The pigment made of glass containing the coloring component described above is different in metamerism from other colorants contained in the resin composition or paint. Therefore, the metamerism in a resin composition and a coating material can be adjusted to a desired characteristic by mix | blending this pigment with a resin composition or a coating material.
The resin composition and paint can be appropriately selected and used according to the purpose as long as they are generally known. Further, the mixing ratio of the pigment and the component other than the pigment can be selected as appropriate.

When a pigment is blended in the paint, it is prepared by mixing other colorant, resin, additive and solvent in addition to the pigment of the present invention.
Other colorants can be optionally contained for the purpose of obtaining a desired color tone. As other pigments, known organic pigments and inorganic pigments can be used.
The resin is a component that causes the coating film to harden, and the characteristics of the resin determine the coating film performance such as weather resistance, flexibility, and water resistance. As the resin, in addition to synthetic resins such as alkyd resin, acrylic resin, epoxy resin, polyurethane resin, vinyl chloride resin, silicone resin, and fluorine resin, oils and fats, natural resins, processed resins, rubber derivatives, cellulose derivatives, and the like can be used.

The additive is an auxiliary chemical that improves the performance of the paint, and is not contained in all paints, but is appropriately added depending on the intended function and application of the paint. For example, plasticizers, dispersants, antisettling agents, emulsifiers, thickeners, antifoaming agents, antifungal agents, antiseptics, antiskinning agents, desiccants, antisagging agents, matting agents, antistatic agents, conductive agents And flame retardants can be used.
The solvent is used for dissolution (dilution) of resins, and it itself does not evaporate into a coating film. In the painting work, it is used to adjust the paint to an appropriate viscosity or to improve the finish of the coated surface. For example, oil, water, thinner, alcohol or the like can be used.

When a pigment is blended in the resin composition, in addition to the pigment of the present invention, a thermosetting resin or a thermoplastic resin can be used as the other colorant and base material resin.
As the thermosetting resin, known resins can be used in addition to phenol resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins, and silicon resins.
As the thermoplastic resin, known resins can be used in addition to polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, fluororesin, polycarbonate, polyester resin.
These resin compositions can be molded into a desired shape and used.

The pigment of the present invention can be used by being contained in a paint or a resin composition as described above. And these coating materials and resin compositions can also be used for an exterior member. Since the metamerism of the pigment of the present invention is adjusted to a desired characteristic, an apparatus using an exterior member can give a high aesthetic appearance with little change in appearance color characteristic due to a difference in light source. The exterior member is, for example, provided on the outer surface of the electronic device, but is not limited to the electronic device, and may be provided on the outer surface of an ornament, a building material, furniture, an operation panel / interior of an automobile. The shape of the exterior member is not limited to a flat plate shape, and may have a shape other than the flat plate shape.

In the case of using a coating material for the exterior member, there are a method of applying to the surface or back surface of the glass serving as the base material, and a method of applying to the surface of the metal or resin molded product serving as the base material.
When using a resin composition for an exterior member, there exists the method of using what shape | molded the resin composition in the desired shape of the exterior member.

Although it does not specifically limit as an exterior member, For example, it can use suitably for the portable electronic device assumed to be used indoors and outdoors. The portable electronic device is a concept that includes communication devices and information devices that can be carried around. For example, as communication devices, communication terminals include mobile phones, PHS (Personal Handy-phone System), smartphones, PDAs (Personal Data Assistance), PNDs (Portable Navigation Devices, portable car navigation systems), and broadcast receivers. Mobile radio, mobile TV, one-seg receiver and the like. Information devices include digital cameras, video cameras, portable music players, sound recorders, portable DVD players, portable game machines, notebook computers, tablet PCs, electronic dictionaries, electronic notebooks, electronic book readers, portable printers, portable scanners, etc. Can be mentioned. It can also be used for stationary electronic devices and electronic devices installed in automobiles. Note that the present invention is not limited to these examples.

As described above, the pigment, paint, resin composition, and exterior member of the present invention have been described by way of examples. However, the configuration can be appropriately changed as necessary without departing from the spirit of the present invention.

Hereinafter, although it demonstrates in detail based on the Example of this invention, this invention is not limited only to these Examples.

For Examples 1 to 43 in Tables 1 to 6 (Examples 1 to 23, Examples 25 to 43 are Examples, and Example 24 is Comparative Example), oxides, hydroxides are prepared so as to have compositions represented by mole percentages in the tables. Commonly used glass materials such as products, carbonates and nitrates were appropriately selected, and weighed to 100 ml as glass. Note that the SO ₃ in Table, was added to bow the glass raw material nitric _(Na 2 SO _4), a residual SO ₃ remaining in glass after Glauber's salt decomposition, is a calculated value.

Next, this raw material mixture was put in a platinum crucible, placed in a resistance heating type electric furnace at 1500 to 1600 ° C., heated for about 0.5 hours, and then the raw materials were melted, and then melted and degassed for 1 hour. Then, it was poured into a mold having a length of about 50 mm × width of about 100 mm × height of about 20 mm preheated to about 300 ° C., and slowly cooled at a rate of about 1 ° C./min to obtain a glass block. The glass block was cut to cut out the glass so that the size was 40 mm × 40 mm and the thickness was 0.8 mm or less, followed by grinding. Finally, both surfaces were polished to a mirror surface to obtain a glass plate. Here, Examples 1 to 37 and Example 42 have a thickness of 0.8 mm, and Examples 38 to 41 and Example 43 have a thickness of 0.5 mm.

The color tone was measured about the obtained glass plate. The color tone of each glass was measured by the chromaticity of reflected light of the L ^* a ^* b ^* color system standardized by CIE. The F2 light source, D65 light source, and A light source were used as the light sources, and the chromaticity of reflected light was measured for each. The chromaticity of the reflected light of the L ^* a ^* b ^* color system was measured using a spectrocolorimeter (X-Rite, Color 7). The measurement was performed by placing a white resin plate on the back side of the glass (the back side of the surface irradiated with light from the light source).

The alkali elution amount was measured for the obtained glass. First, the glass was pulverized in an agate mortar, and a glass powder that passed through a # 590 sieve but did not pass through a # 420 sieve was prepared. Next, the glass powder was fractionated so as to have a specific gravity and impregnated with 100 ml of 80 ml of distilled water for 60 minutes for an elution test. The amount of alkali eluted from this solution was measured using an ICP analyzer (ICPS-7500, manufactured by Shimadzu Corporation).

The above evaluation results are shown in Tables 1 to 6.

As shown in Tables 1 to 6, the glasses of the examples (Examples 1 to 23, Examples 25 to 43) have an absolute value of Δa ^* (D65-F2)) and (Δa ^* (A-F2)). At least one of the absolute values is 0.2 or more. When this glass is used as a pigment, metamerism caused by other pigments or resin components can be corrected. Thereby, the resin composition and coating material containing the pigment which consists of glass of an Example can be made into a desired metamerism. In contrast, the glass of the comparative example (Example 24) has an absolute value of Δa ^* (D65−F2)) and an absolute value of (Δa ^* (A−F2)) both less than 0.2. When glass is used as a pigment, the metamerism of the resin composition or paint cannot be corrected. Thereby, it is difficult to make the resin composition and paint containing the pigment made of the glass of the comparative example into a desired metamerism. Next, the alkali elution amounts of the glasses of the examples (Examples 25 to 43) are all 2.4 ppm or less, and when this glass is used as a pigment, the adhesion to the substrate is impaired, and other pigments It can be seen that it can be used without degrading the characteristics.

Next, the effect of correcting metamerism when the glass of the example was contained in the paint as a pigment was confirmed.
First, a commercially available acrylic paint (Tamiya Co., Ltd., Tamiya Color XF-56) was applied to a transparent glass plate (Shot Co., D263) having a thickness of 0.1 mm with a flat brush. On the other hand, the glass of Example (Example 2) in powder form (center particle size: about 20 μm) was mixed with the acrylic paint described above as follows. That is, in the glass of this example, 30% of the glass powder by mass was added to the paint, and the paint and the glass powder of the example were stirred to uniformly disperse the glass powder in the paint. And the coating material containing glass powder was apply | coated to the above-mentioned transparent glass plate with the flat brush.
After the paint was dried, the color tone of the glass coated with the paint (L ^* a ^* b ^* chromaticity of reflected light of the color system standardized by CIE) was measured. The color tone was measured by entering light from the side of the glass plate opposite to the coating surface. This is to eliminate the influence of the application surface because of the influence of the application state. Table 7 shows the measurement results.

As shown in Table 7, when the glass of the example is contained in the paint as a pigment, Δa ^* (D65-F2)) and (Δa ^* (A-F2)) are “paint only” and “paint + glass powder”. It was confirmed that it changed with. In addition, the amount of change (Δa ^* (D65-F2)) and (Δa ^* (A-F2) (value of “paint + glass powder”-“paint only”) agrees with the metamerism of glass powder. It is a result which shows the correction effect of the metamerism of the paint in the glass of an Example.

The pigment of the present invention is disposed around the operation panel of AV equipment / OA equipment, the door of the product, the operation button / knob, or the rectangular display surface of an image display panel such as a digital photo frame or TV. It can be used for paints and resin compositions such as decorative items such as decorative panels and exterior members for electronic devices. Moreover, it can utilize also for coating materials and resin compositions, such as interior materials for motor vehicles, members, such as furniture, and building materials used outdoors or indoors.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-060799 filed on March 22, 2013 are incorporated herein by reference.

Claims (17)

1. A pigment made of glass containing a coloring component,
   When the glass measures the chromaticity of the main surface in the state of a glass plate having a thickness of 0.8 mm or less,
   The difference (Δa ^* (D65−F2) between the chromaticity a ^* of the reflected light by the D65 light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light by the F2 light source represented by the following formula (1) )) Absolute value,
   And the difference between the chromaticity a ^* of the reflected light from the A light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light from the F2 light source (Δa ^* (A− A pigment made of glass containing a coloring component, wherein at least one of the absolute values of F2)) has a characteristic of 0.2 or more.
   Δa ^* (D65−F2) = a ^* value (D65 light source) −a ^* value (F2 light source) (1)
   Δa ^* (A−F2) = a ^* value (A light source) −a ^* value (F2 light source) (2)
2. A pigment made of glass containing a coloring component,
   When the glass measures the chromaticity of the main surface in the state of a glass plate having a thickness of 0.8 mm,
   The difference (Δa ^* (D65−F2) between the chromaticity a ^* of the reflected light by the D65 light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light by the F2 light source represented by the following formula (1) )) Absolute value,
   And the difference between the chromaticity a ^* of the reflected light from the A light source of the L ^* a ^* b ^* color system and the chromaticity a ^* of the reflected light from the F2 light source (Δa ^* (A− The pigment made of glass containing a coloring component according to claim 1, wherein at least one of the absolute values of F2)) is 0.2 or more.
   Δa ^* (D65−F2) = a ^* value (D65 light source) −a ^* value (F2 light source) (1)
   Δa ^* (A−F2) = a ^* value (A light source) −a ^* value (F2 light source) (2)
3. A pigment made of glass containing a coloring component,
   The said pigment is added to a resin composition with coloring agents other than the said pigment, The pigment which consists of glass containing the coloring component of Claim 1 or 2 characterized by the above-mentioned.
4. The coloring according to any one of claims 1 to 3, wherein the glass has a lightness L ^* (F2 light source) in an L ^* a ^* b ^* color system in a range of 20 to 90. A pigment made of glass containing components.
5. The glass is expressed in terms of mole percentage based on the following oxides: SiO ₂ 55 to 80%, Al ₂ O ₃ 0.05 to 16%, B ₂ O ₃ 0 to 12%, Na ₂ O 0 to 20%, K ₂ O 0-15%, MgO 0-15%, CaO 0-15%, ΣRO (R is Mg, Ca, Sr, Ba, Zn) 0-30%, MpOq (however, , M is at least one selected from the group consisting of Fe, Cu, V, Se, Co, Ti, Cr, Pr, Ce, Bi, Eu, Mn, Er, Ni, Nd, W, Rb, and Ag. 5. The glass containing a coloring component according to any one of claims 1 to 4, wherein 0.001 to 10% is contained (wherein p and q are atomic ratios of M and O). Pigments.
6. The glass is expressed in terms of mole percentages based on the following oxides: SiO ₂ 55 to 80%, Al ₂ O ₃ 0.25 to 16%, B ₂ O ₃ 0 to 12%, Na ₂ O 5 to 5%. 20%, K ₂ O 0-15%, MgO 0-15%, CaO 0-15%, ΣRO (R is Mg, Ca, Sr, Ba, Zn) 0-25%, MpOq (however, , M is at least one selected from the group consisting of Fe, Cu, V, Se, Co, Ti, Cr, Pr, Ce, Bi, Eu, Mn, Er, Ni, Nd, W, Rb, and Ag. The glass containing a coloring component according to any one of claims 1 to 5, wherein 0.001 to 10% is contained (wherein p and q are atomic ratios of M and O) Pigments.
7. The coloring component is MpOq (where M is Fe, Cu, V, Se, Co, Ti, Cr, Pr, Ce, Bi, Eu, Mn, Er, Ni, Nd, W, Rb, and Ag) The glass containing a coloring component according to any one of claims 1 to 6, wherein at least one selected from the group consisting of p and q is an atomic ratio of M and O). Pigments.
8. The pigment made of glass containing a coloring component according to any one of claims 1 to 7, wherein the glass has an alkali elution amount of 0 to 2.4 ppm.
9. The pigment made of glass containing a coloring component according to any one of claims 1 to 8, wherein the resin composition is a paint.
10. A resin composition to which a pigment made of glass containing the coloring component according to any one of claims 1 to 8 and a colorant other than the pigment are added,
    The glass is reflected by a D65 light source of the L ^* a ^* b ^* color system represented by the following formula (1) when the chromaticity of the main surface is measured in a state of a glass plate having a thickness of 0.8 mm or less. of the difference between the chromaticity ^{a *} of the reflected light by the chromaticity ^{a *} and F2 light source and (.DELTA.a ^* (D65-F2)), represented by the following formula ^(2), L ^* a * ^{b *} color system the difference between the chromaticity ^{a *} of the reflected light by the chromaticity ^{a *} and F2 light source of the reflected light by the light source a case of ^{(Δa * (a-F2)} ) and the glass ^{(Δa * (D65-F2)} ) the difference between the said colorant ^{(Δa * (D65-F2)} ) the absolute value of the difference between the glass ^{(Δa * (a-F2)} ) and the colorant ^{(Δa * (a-F2)} ) A resin composition having a characteristic that at least one of the absolute values thereof is 0.2 or more.
    Δa ^* (D65−F2) = a ^* value (D65 light source) −a ^* value (F2 light source) (1)
    Δa ^* (A−F2) = a ^* value (A light source) −a ^* value (F2 light source) (2)
11. 11. The resin composition according to claim 10, wherein at least one of the directivity of Δa ^* (D65-F2) and the directivity of Δa ^* (A-F2) is different between the pigment and the colorant other than the pigment. A resin composition characterized by comprising:
12. A paint to which a pigment made of glass containing the coloring component according to any one of claims 1 to 9 and a colorant other than the pigment are added,
    The glass is reflected by a D65 light source of the L ^* a ^* b ^* color system represented by the following formula (1) when the chromaticity of the main surface is measured in a state of a glass plate having a thickness of 0.8 mm or less. of the difference between the chromaticity ^{a *} of the reflected light by the chromaticity ^{a *} and F2 light source and (.DELTA.a ^* (D65-F2)), represented by the following formula ^(2), L ^* a * ^{b *} color system the difference between the chromaticity ^{a *} of the reflected light by the chromaticity ^{a *} and F2 light source of the reflected light by the light source a case of ^{(Δa * (a-F2)} ) and the glass ^{(Δa * (D65-F2)} ) the difference between the said colorant ^{(Δa * (D65-F2)} ) the absolute value of the difference between the glass ^{(Δa * (a-F2)} ) and the colorant ^{(Δa * (a-F2)} ) A paint having a characteristic that at least one of its absolute values is 0.2 or more.
    Δa ^* (D65−F2) = a ^* value (D65 light source) −a ^* value (F2 light source) (1)
    Δa ^* (A−F2) = a ^* value (A light source) −a ^* value (F2 light source) (2)
13. 13. The paint according to claim 12, wherein at least one of the directivity of Δa ^* (D65-F2) and the directivity of Δa ^* (A-F2) is different between the pigment and the colorant other than the pigment. Paint characterized by.
14. An exterior member comprising the resin composition according to claim 10 or 11.
15. An exterior member made of glass coated with the paint according to claim 12 or 13.
16. The exterior member according to claim 14 or 15, wherein the exterior member is exteriorized on an electronic device.
17. An electronic device having the exterior member according to claim 14 or 15 as an exterior.