JP2011105587A - Flaky glass and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a new flaky glass having coloring. <P>SOLUTION: The flaky glass comprises components of 60≤SiO<SB>2</SB>≤80, 1≤(Li<SB>2</SB>O+Na<SB>2</SB>O+K<SB>2</SB>O)≤20, and 5≤CuO≤20, whose amount is calculated from the content of CuO obtained from the total amount of Cu, in terms of mass%. The flaky glass may include a crystal such as Cu, Cu<SB>2</SB>O, or CuO whose constituent atom is Cu. The flake glass exhibits a blue-green color, a reddish black color, a yellow color and the like depending on the state of copper which is included in the flaky glass. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a glass flake that can be blended and used in resin compositions, paints, inks (inks), cosmetics, etc., and can exhibit excellent color tone and gloss, and a method for producing the same.

  When the glass flakes are dispersed in a resin composition (resin matrix), the strength and dimensional accuracy of a resin molded product obtained from the resin composition can be improved. Moreover, scaly glass is mix | blended with a coating material as a lining material, and is apply | coated to a metal or concrete surface. The glass flakes exhibit a metallic color when the surface is coated with a metal, and exhibit an interference color due to interference of reflected light when the surface is coated with a metal oxide. The glass flakes coated with a film made of metal or metal oxide is suitably used as a luster pigment. Bright pigments using such glass flakes are preferably used in applications where color tone and gloss are important, such as paints and cosmetics.

  As a composition suitable for scaly glass, Patent Document 1 describes C glass, E glass, and plate glass composition. Patent Documents 2 and 3 describe scaly glass having high ultraviolet absorption performance.

  As one of flaky glasses whose surface is coated with a metal or metal oxide and improved in colorability, light reflectivity and hiding property, Patent Document 4 discloses flaky glass with rutile titanium dioxide deposited on the surface. Is described.

  Patent Document 5 describes scaly glass whose visible light transmittance is kept low by iron oxide.

JP 63-201041 A JP-A-63-307142 JP-A-3-40938 JP 2001-31421 A International Publication No. 2004/076372

  The glass flakes described in Patent Literature 1 and Patent Literature 4 contain almost no component that absorbs visible light, and the coloring of the glass flake itself is not considered. Moreover, also in the scale-like glass of patent document 2 and patent document 3, there is little quantity of the component which absorbs visible light, and the coloring of scale-like glass itself is not considered.

  The scaly glass described in Patent Document 5 has a reddish brown color or black brown color derived from iron oxide. However, the color derived from iron oxide has a limited color type and does not match a desirable color depending on the application.

  An object of the present invention is to provide a scaly glass exhibiting new coloring.

The present invention is expressed in mass%,
60 ≦ SiO ₂ ≦ 80,
1 ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 20,
5 ≦ CuO ≦ 20,
A scaly glass containing the following components is provided. However, the value of the CuO indicates a value obtained by converting all Cu atoms contained in the glass flakes to CuO.

In the present invention, the content of copper (Cu) is set to 5 to 20% by mass in terms of CuO. For this reason, scaly glass exhibits sufficient coloring derived from copper. If it is simply desired to reduce the visible light transmittance, it is sufficient to add iron oxide to the glass flakes. However, addition of copper is effective for preferable coloring. Moreover, since the content of silicon dioxide (SiO ₂ ) is sufficiently secured in the present invention, silicon dioxide, which is a component that forms the skeleton of the glass network, effectively exhibits its function. Moreover, in this invention, since the total content of lithium oxide, sodium oxide, and potassium oxide is set to the suitable range, scaly glass can be obtained using the conventional manufacturing method.

(A) is a perspective view which shows an example of the scale-like glass of this invention, (b) is a top view of this scale-like glass. It is sectional drawing which shows an example of the scale-like glass containing the crystal | crystallization which makes Cu a constituent atom. It is sectional drawing which shows an example of the scale-like glass with a film. It is sectional drawing which shows an example of the base material with which the coating film containing scale-like glass or scale-like glass with a film was formed in the surface. It is a figure showing the cross-section of the apparatus which manufactures scale-like glass. It is a figure showing the cross-section of another apparatus which manufactures scale-like glass.

[Ingredients of scale glass]
The scaly glass of the present invention contains the following components expressed in mass%.
60 ≦ SiO ₂ ≦ 80,
1 ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 20,
5 ≦ CuO (CuO converted from total Cu) ≦ 20.

The scaly glass of the present invention contains copper (Cu) as an essential component, but the valence of Cu is not limited. That is, Cu may be contained in the scaly glass in any form of copper metal, cuprous oxide (Cu ₂ O), and cupric oxide (CuO).

  Hereafter, the said each component and the arbitrary component which may be contained in scale-like glass are demonstrated. In the following, all percentages indicating the content of components are mass%.

(SiO ₂ )
Silicon dioxide (SiO ₂ ) is a component that forms the skeleton of the glass composition or glass matrix constituting the scaly glass. SiO ₂ is a component that adjusts the devitrification temperature and viscosity during glass production while maintaining the heat resistance of the glass, and is also a component that improves acid resistance. When the content of SiO ₂ is less than 60%, the devitrification temperature is excessively increased and it becomes difficult to form the glass flakes, and the acid resistance of the glass flakes is lowered. If the content of SiO ₂ exceeds 80%, the melting point of the glass becomes too high, and it becomes difficult to melt the raw material uniformly. Accordingly, the content of SiO ₂ is 60% or more, preferably 63% or more, and more preferably greater than 65%. The content of SiO ₂ is 80% or less, preferably 75% or less, more preferably 72% or less, and most preferably less than 70%.

(B ₂ O ₃ )
Diboron trioxide (B ₂ O ₃ ) is an optional component that forms a glass skeleton together with SiO ₂ , and is also a component that adjusts the devitrification temperature and viscosity during glass production. When the content of B ₂ O ₃ exceeds 10%, the furnace walls of the melting kiln and the heat storage kiln are eroded when the glass is melted, and the life of the kiln is significantly reduced. Therefore, the content of B ₂ O ₃ is preferably 10% or less, more preferably 5% or less, particularly preferably 2% or less, and most preferably not substantially contained.

(Al ₂ O ₃ )
Aluminum oxide (Al ₂ O ₃ ) is an optional component that forms a glass skeleton together with SiO ₂ , and is also a component that adjusts the devitrification temperature and viscosity during glass production while maintaining the heat resistance of the glass. Al ₂ O ₃ is a component that improves water resistance, but is also a component that reduces acid resistance. If the content of Al ₂ O ₃ exceeds 10%, the melting point of the glass becomes too high and it becomes difficult to uniformly melt the raw material, and the acid resistance is also deteriorated. Therefore, the content of Al ₂ O ₃ is preferably greater than 0% and more preferably 0.1% or more. The content of Al ₂ O ₃ is preferably 10% or less, more preferably 8% or less, and further preferably 5% or less.

(B ₂ O ₃ + Al ₂ O ₃ )
B ₂ O, which is an optional component that forms a glass skeleton together with SiO ₂ , and also adjusts the devitrification temperature and viscosity during glass production while maintaining the heat resistance of the glass when emphasizing the moldability of the glass flakes The sum of the contents of ₃ and Al ₂ O ₃ (B ₂ O ₃ + Al ₂ O ₃ ) is important. If the total content of (B ₂ O ₃ + Al ₂ O ₃ ) exceeds 15%, the melting point of the glass becomes too high and it becomes difficult to uniformly melt the raw material, and the devitrification temperature also rises. Therefore, the total content of (B ₂ O ₃ + Al ₂ O ₃ ) is preferably greater than 0%, more preferably 0.1% or more. The total content of (B ₂ O ₃ + Al ₂ O ₃ ) is preferably 15% or less, more preferably 10% or less, and even more preferably 5% or less.

(MgO)
Magnesium oxide (MgO) is an optional component that adjusts the devitrification temperature and viscosity during glass production while maintaining the heat resistance of the glass. If the MgO content exceeds 10%, the devitrification temperature rises too much, making it difficult to form a glass flake. Therefore, the MgO content is preferably greater than 0%, more preferably 0.1% or more. The content of MgO is preferably 10% or less, more preferably 8% or less, further preferably 5% or less, and most preferably less than 2%.

(CaO)
Calcium oxide (CaO) is an optional component for adjusting the devitrification temperature and viscosity during glass production while maintaining the heat resistance of the glass. If the content of CaO exceeds 15%, the devitrification temperature rises too much and it becomes difficult to form a glass flake. Therefore, the CaO content is preferably greater than 0%, more preferably 0.1% or more. The CaO content is preferably 15% or less, more preferably 10% or less, further preferably 8% or less, and most preferably less than 5%.

(SrO)
Strontium oxide (SrO) is an optional component that adjusts the devitrification temperature and viscosity during glass production while maintaining the heat resistance of the glass, but is also a component that lowers the acid resistance of the glass. If the SrO content exceeds 10%, the acid resistance decreases. Therefore, the content of SrO is preferably 10% or less, more preferably 5% or less, further preferably 2% or less, and most preferably not substantially contained.

(BaO)
Barium oxide (BaO) is an optional component that adjusts the devitrification temperature and viscosity during glass production while maintaining the heat resistance of the glass, but is also a component that lowers the acid resistance of the glass. If the BaO content exceeds 10%, the acid resistance decreases. Therefore, the content of BaO is preferably 10% or less, more preferably 5% or less, still more preferably 2% or less, and most preferably not substantially contained.

(MgO + CaO + SrO + BaO)
When emphasizing the moldability of glass flakes, the total content of MgO, CaO, SrO and BaO (MgO + CaO + SrO + BaO), which are components for adjusting the devitrification temperature and viscosity during glass production while maintaining the heat resistance of the glass, is important It is. When the total content of (MgO + CaO + SrO + BaO) exceeds 20%, the devitrification temperature rises too much, and it becomes difficult to form scale glass. Therefore, the total content of (MgO + CaO + SrO + BaO) is preferably greater than 0% and more preferably 0.1% or more. The total content of (MgO + CaO + SrO + BaO) is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less.

(ZnO)
Zinc oxide (ZnO) is an optional component that adjusts the devitrification temperature and viscosity during glass production. However, since ZnO is volatile, it may be scattered during melting. If the ZnO content exceeds 10%, the volatilization rate increases, and it becomes difficult to manage the ZnO content in the glass. Therefore, the content of ZnO is preferably 10% or less, more preferably 5% or less, further preferably 2% or less, and most preferably not substantially contained.

(Li ₂ O, Na ₂ O, K ₂ O)
Alkali metal oxides (Li ₂ O, Na ₂ O, K ₂ O) are components that adjust the devitrification temperature and viscosity during glass production. Li ₂ O, Na ₂ O, and K ₂ O are individually optional components, but any of them must be contained in the glass flake. If the total content of (Li ₂ O + Na ₂ O + K ₂ O) is less than 1%, the melting point of the glass becomes too high, making it difficult to uniformly melt the raw material, and the devitrification temperature is too high. This makes it difficult to form scaly glass. When the total content of (Li ₂ O + Na ₂ O + K ₂ O) exceeds 20%, the glass transition temperature is lowered, the heat resistance of the glass is lowered, and the chemical durability is lowered. Therefore, the total content of (Li ₂ O + Na ₂ O + K ₂ O) is 1% or more, preferably 5% or more, more preferably 8% or more, and most preferably 10% or more. The total content of (Li ₂ O + Na ₂ O + K ₂ O) is 20% or less, preferably 18% or less, more preferably 16% or less, and most preferably 15% or less.

Lithium oxide (Li ₂ O) is a component for adjusting the devitrification temperature and viscosity during glass production. Li ₂ O has an effect of lowering the melting point of the glass, and makes it easy to melt the glass raw material uniformly. In addition, Li ₂ O has an effect of lowering the working temperature and facilitates the formation of scale-like glass. However, if the content of Li ₂ O exceeds 9%, the glass transition temperature is lowered, and the heat resistance of the glass is deteriorated. Therefore, the content of Li ₂ O is preferably greater than 0%, and more preferably 0.1% or more. The content of Li ₂ O is preferably 9% or less, more preferably 5% or less, further preferably 2% or less, and most preferably 1% or less.

Sodium oxide (Na ₂ O) is a component that adjusts the devitrification temperature and viscosity during glass production. When the content of Na ₂ O exceeds 20%, the glass transition temperature is lowered and the heat resistance of the glass is lowered. Therefore, the content of Na ₂ O is preferably greater than 0%, more preferably 1% or more, further preferably 5% or more, and most preferably 8% or more. The content of Na ₂ O is preferably 20% or less, more preferably 17% or less, further preferably 15% or less, and most preferably 14% or less.

Potassium oxide (K ₂ O) is a component for adjusting the devitrification temperature and viscosity during glass production. When the content of K ₂ O exceeds 5%, the glass transition temperature is lowered, and the heat resistance of the glass is lowered. Therefore, the content of K ₂ O is preferably greater than 0%, more preferably 0.1% or more. The content of K ₂ O is preferably 5% or less, more preferably 3% or less, further preferably 2% or less, and most preferably 1% or less.

(TiO ₂ )
Titanium dioxide (TiO ₂ ) is an optional component that improves the meltability, the chemical durability of the glass, and the ultraviolet absorption characteristics. When the content of TiO ₂ exceeds 5%, the devitrification temperature of the glass is excessively increased, and it becomes difficult to form a glass flake. Therefore, the content of TiO ₂ is preferably 5% or less, more preferably 2% or less, still more preferably 1% or less, and most preferably not substantially contained.

(ZrO ₂ )
Zirconium oxide (ZrO ₂ ) is an optional component that adjusts the devitrification temperature and viscosity during glass production, and has a function of accelerating the devitrification growth of the glass. When the content of ZrO ₂ exceeds 5%, the devitrification temperature of the glass is excessively increased, and it becomes difficult to form a glass flake. Therefore, the content of ZrO ₂ is preferably 5% or less, more preferably 2% or less, further preferably 1% or less, and most preferably not substantially contained.

(Fe)
Iron (Fe) in glass usually exists in the state of Fe ²⁺ or Fe ³⁺ . Fe ³⁺ is a component that improves the ultraviolet absorption property of the glass flakes, and Fe ²⁺ is a component that ^improves the heat ray absorption property. Iron oxide (Fe ₂ O ₃ , FeO) may be used as an optional component for adjusting the optical properties of the glass flakes. Even if iron oxide is not intentionally included, iron oxide may inevitably be mixed with industrial raw materials. However, as the iron oxide content increases, the glass flakes become more noticeable. Coloring with iron should be avoided in applications of glass flakes where color tone and gloss are important. Therefore, the content of iron oxide is preferably 5% or less, more preferably 2% or less, further preferably 1% or less, and most preferably substantially not contained in terms of Fe ₂ O ₃ .

(Cu)
In the glass composition, copper (Cu) is in a state where an equilibrium relationship is established between Cu ⁺ and Cu ^2+, and exhibits a blue-green color derived from Cu ²⁺ (Cu ⁺ is colorless). . However, in scaly glass, Cu may be present in a colloidal or crystalline state. Cu causes different coloring depending on the state. Cu is also a component that improves water resistance. If the copper content in the glass flakes exceeds 20% in terms of CuO, the devitrification temperature rises too much, making it difficult to form the glass flakes. On the other hand, when the copper content is less than 5% in terms of CuO, the color derived from copper cannot be obtained sufficiently. Therefore, the CuO content is 5% or more, preferably 8% or more, and more preferably 10% or more in terms of CuO. The CuO content is preferably 20% or less, more preferably 18% or less, still more preferably 16% or less, and most preferably 15% or less in terms of CuO.

(SO ₃ )
Sulfur trioxide (SO ₃ ) is not an essential component, but may be used as a fining agent. When a sulfate raw material is used, SO ₃ may be mixed at a content of 0.5% or less.

(F)
Since fluorine (F) is easily volatilized, it may be scattered during melting, making it difficult to manage the content of F in the glass. Therefore, it is preferable that F is not substantially contained.

  In addition, in this invention, that it does not contain substantially means not including intentionally except the case where it mixes unavoidably from an industrial raw material. The phrase “substantially not containing” specifically means that the content is less than 0.1%, preferably 0.05% or less, more preferably 0.03% or less.

From the above description, it can be understood that the glass flakes of the present invention may contain the following components expressed in mass%.
60 ≦ SiO ₂ ≦ 80,
1 ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 20,
5 ≦ CuO (CuO converted from total Cu) ≦ 20,
0 ≦ (B ₂ O ₃ + Al ₂ O ₃ ) ≦ 15, preferably 0.1 ≦ (B ₂ O ₃ + Al ₂ O ₃ ) ≦ 15,
0 ≦ (MgO + CaO + SrO + BaO) ≦ 20, preferably 0.1 ≦ (MgO + CaO + SrO + BaO) ≦ 20,
0 ≦ ZnO ≦ 10,
0 ≦ TiO ₂ ≦ 5,
0 ≦ ZrO ₂ ≦ 5,
_{0 ≦ Fe 2 O 3 (Fe} 2 O 3 was converted from the total Fe) ≦ 5
0 ≦ SO ₃ ≦ 0.5.

[Shape-like glass shape]
In this specification, the glass flakes are flakes having an average thickness t of 0.1 μm or more and less than 100 μm, preferably 0.1 to 15 μm, and an aspect ratio (average particle diameter a / average thickness t) of 2 to 1000. This refers to the particle 10 (see FIG. 1A). Here, the average particle diameter a is defined as the square root of the area S when the scaly glass 10 is viewed in plan (see FIG. 1B; a = S ^1/2 ). The average thickness t is preferably 0.1 to 15 μm, but may be adjusted to 0.5 to 5 μm, and further to 0.5 to 1 μm depending on the application.

[Crystal with Cu as a constituent atom]
The scaly glass of the present invention may be composed of a glass composition containing the above-described components, but may be in a state where fine crystals having Cu as a constituent atom are dispersed. When the glass composition containing the above-described components is used, the scaly glass is entirely amorphous (glass composition). However, when the scaly glass includes a minute crystal, the scaly glass includes the minute crystal and the crystal. It consists of the remaining amorphous part (glass matrix). In the latter case, as shown in FIG. 2, the scaly glass 10 is composed of a glass matrix 2 including a crystal 3 having Cu as a constituent atom. As will be described later, the crystal 3 containing Cu as a constituent atom can be precipitated by heat-treating a glass flake made of a previously formed glass composition. The visible light transmittance and color tone of the glass flakes can be easily adjusted by controlling the amount of crystals deposited, the crystal grain size and the type thereof. The crystal 3 having Cu as a constituent atom is usually at least one selected from Cu, Cu ₂ O and CuO. Cu deposition results in red-black coloration, Cu ₂ O deposition results in yellow color, and CuO deposition results in gray-black color. A crystal having Cu as a constituent atom precipitated in a glass flake can be detected by an X-ray diffraction method, but may be observed using an electron microscope. Moreover, the phase separation structure generated in the glass flakes may be observed with an electron microscope.

[Method for producing scaly glass]
The scaly glass of the present invention can be obtained by a conventionally known method. The glass flakes of the present invention can be manufactured, for example, using the manufacturing apparatus shown in FIG. As shown in FIG. 5, the glass substrate 21 melted in the refractory kiln 20 is swelled in a balloon shape by the gas 23 fed into the blow nozzle 22 to become a hollow glass film 24. The glass flakes 10 are obtained by pulverizing the hollow glass membrane 24 with a pair of pressing rolls 25.

  The glass flakes of the present invention can also be produced using, for example, the production apparatus shown in FIG. As shown in FIG. 6, the molten glass substrate 21 poured into the rotating cup 26 flows out radially from the upper edge of the rotating cup 26 due to centrifugal force, and the annular plate disposed above and below the upper edge. 27 is sucked by the air flow through 27 and introduced into the annular cyclone collector 28. The glass substrate 21 is cooled and solidified in the form of a thin film while passing between the upper and lower annular plates 27 and is further crushed into fine pieces in the process of being introduced into the collector 28. As a result, scaly glass 10 is obtained.

  If the conventional manufacturing apparatus as shown to FIG. 5, FIG. 6 is used, the scale-like glass which consists of a predetermined | prescribed glass composition can be obtained.

  By heat-treating the flaky glass thus produced, it is possible to obtain flaky glass on which crystals having Cu as a constituent atom are deposited. The heat treatment is preferably performed by holding the glass flakes for a certain period of time at a temperature not lower than the glass transition temperature of the glass used and not higher than the softening point. In addition, it is possible to obtain the scaly glass in which crystals having Cu as a constituent atom are deposited by appropriately adjusting the holding temperature of the molten glass before forming the scaly glass.

  By performing heat treatment in an atmosphere in which the Cu in the glass flakes is oxidized or in an atmosphere in which Cu is reduced, the type of crystals having Cu as a constituent atom is controlled, and the visible light transmittance and color tone of the glass flakes are controlled. Can be adjusted.

  The atmosphere in which Cu in the glass flakes is oxidized is an oxidizing atmosphere. As the oxidizing atmosphere, an oxidizing gas such as air or oxygen gas may be used. CuO can be deposited on the glass flakes by heat treatment in an oxidizing atmosphere.

The atmosphere in which Cu in the glass flakes is reduced may be a reducing atmosphere or an inert atmosphere. As the reducing atmosphere, a reducing gas such as a mixed gas containing hydrogen may be used. As the inert atmosphere, an inert gas such as nitrogen gas, helium gas, or argon gas may be used. Cu can be deposited on the glass flakes by heat treatment in a reducing atmosphere. Cu ₂ O can be deposited on the glass flakes by heat treatment in an inert atmosphere.

  The heat treatment may be performed a plurality of times, and the oxidation / reduction atmosphere may be changed in each heat treatment. Further, the oxidizing / reducing atmosphere may be changed during one heat treatment.

As is clear from the above, the present invention provides another aspect thereof.
Display in mass%,
60 ≦ SiO ₂ ≦ 80,
1 ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 20,
5 ≦ CuO ≦ 20,
A scaly glass made of a glass composition containing the components of
By heat-treating the scaly glass, crystals containing Cu as a constituent atom are precipitated in the scaly glass,
Provided is a method for producing scaly glass, which obtains scaly glass in which crystals containing Cu as a constituent atom are dispersed in a glass matrix. Again, the value of CuO indicates a value obtained by converting all Cu atoms contained in the glass flakes made of the glass composition to CuO.

[Temperature characteristics / Working temperature]
The temperature at which the viscosity of the molten glass is 100 Pa · s (1000 P) is called the working temperature. The working temperature is an indicator of the ease with which the glass flakes are formed. When the working temperature is lower than 1000 ° C., it becomes difficult to form the hollow glass film 24 with a uniform film thickness when producing the glass flakes using the production apparatus shown in FIG. It becomes difficult to obtain the scaly glass 10. On the other hand, when the working temperature exceeds 1300 ° C., the glass manufacturing apparatus becomes susceptible to corrosion due to heat, and the life of the apparatus is shortened. Therefore, the working temperature is preferably 1000 ° C. or higher, and more preferably 1050 ° C. or higher. The working temperature is preferably 1300 ° C. or lower, more preferably 1250 ° C. or lower, and further preferably 1200 ° C. or lower.

[Chemical durability / water resistance, acid resistance]
It is desirable that the glass flakes used for applications such as resin moldings, paints, cosmetics, and inks have excellent chemical durability such as water resistance and acid resistance.

  As an index of water resistance, the alkali elution amount described later is adopted, and the smaller the alkali elution amount, the higher the water resistance. When the glass flakes are dispersed in the resin composition (resin matrix), when the amount of alkali elution of the glass exceeds 0.4 mg, the strength of the resin composition is reduced. Therefore, the alkali elution amount is preferably 0.4 mg or less, more preferably 0.3 mg or less, and further preferably 0.2 mg or less.

  As an index of acid resistance, a mass reduction rate ΔW described later is adopted, and the smaller the mass reduction rate ΔW, the higher the acid resistance. When using paint containing scale glass as an anticorrosion lining material in an acidic environment, or when using glass scale as a substrate for forming a film by a liquid phase method using an acidic solution, an index of acid resistance The mass reduction rate ΔW is preferably a small value. When the mass reduction rate ΔW of the glass exceeds 1.5% by mass, the anticorrosion property of the anticorrosion lining material in an acidic environment is lowered, and as a base material for forming a film by a liquid phase method using an acidic solution It cannot be used. Accordingly, the mass reduction rate ΔW is preferably 1.5% by mass or less, more preferably 0.8% by mass or less, further preferably 0.4% by mass or less, and most preferably 0.3% by mass or less.

[Film with glass]
As schematically shown in FIG. 3, a scale-like glass 12 with a coating is produced by forming a coating 11 mainly composed of a metal or a metal oxide on the surface of the glass-like glass 10 as a base material. Can do. The coating 11 is preferably formed substantially from at least one of a metal and a metal oxide. The form of the film 11 may be any of a single layer, a mixed layer, or a multilayer.

  Specifically, the coating 11 is at least one metal selected from silver, gold, platinum, palladium, and nickel, or titanium oxide, aluminum oxide, iron oxide, cobalt oxide, zirconium oxide, zinc oxide, tin oxide. And at least one metal oxide selected from silicon dioxide. Among these, it is preferable that the film 11 is formed of titanium dioxide having a high refractive index and transparency and good interference color development, and iron oxide capable of developing a characteristic interference color.

  The coating film 11 may be a laminated film including a first film mainly containing a metal and a second film mainly containing a metal oxide. Further, the coating film 11 does not have to be formed on the entire surface of the glass flake 10 serving as the substrate, and the coating film 11 may be formed on a part of the surface of the glass flake 10.

  The thickness of the film 11 can be appropriately set depending on the purpose. Examples of the method for forming the film 11 on the surface of the glass flake 10 include a sputtering method, a sol-gel method, a CVD method (chemical vapor deposition method), a liquid phase deposition method for depositing a metal oxide from a metal salt on the surface of a substrate, etc. Any method can be adopted including known methods. Here, the liquid phase deposition method (LPD method) is a method in which a metal oxide is deposited as a coating from the reaction solution onto the surface of a substrate or the like.

[Uses (resin compositions, paints, ink compositions and cosmetics)]
The scaly glass of the present invention is suitably used for applications such as resin molded products, paints, cosmetics, and inks due to the above-described properties.

  The glass flakes 10 and the glass flakes 12 with a film are blended in a resin composition, a paint, an ink composition, a cosmetic, or the like as a pigment or a reinforcing filler by a known method. In particular, the scale-like glass 12 with a coating exhibits a color such as a metal color or an interference color due to the coating 11, and therefore can be suitably used as a bright pigment.

  Specifically, a resin molded body having improved physical properties such as strength and dimensional accuracy can be obtained by blending the glass flakes 10 and 12 into the resin composition, and the coating film can be made into a metal by blending in the paint. Color and gloss can be imparted, and by blending with an ink composition, a metal color or gloss can be imparted to characters and figures formed by this composition, and by blending in cosmetics, the face, etc. Good color tone and gloss can be imparted to the cosmetics applied to.

  FIG. 4 is a schematic cross-sectional view for explaining an example in which the flaky glass 10 or the coated flaky glass 12 is blended in a paint and applied to the surface of the substrate 13. As shown in FIG. 4, the glass flakes 10 or the glass flakes 12 with a film are dispersed in a resin matrix 15 of the coating film 14.

  As a resin composition, a paint, an ink composition, and a cosmetic, known ones can be appropriately selected and used according to the purpose. The mixing ratio between the glass flakes (or the glass flakes with coating) and these materials can also be set as appropriate, and a known method can be adopted as this mixing method.

  When scale-like glass (or scale-like glass with a film) is blended in the resin composition, a thermosetting resin or a thermoplastic resin can be appropriately selected and blended with the base material resin.

  The thermosetting resin is not particularly limited, and acrylic resin, polyester resin, epoxy resin, phenol resin, urea resin, fluororesin, polyester-urethane curing resin, epoxy-polyester curing resin, acrylic-polyester resin, acrylic -Urethane curable resin, acrylic-melamine curable resin, polyester-melamine curable resin, and the like.

  The thermoplastic resin is not particularly limited. Polyvinyl chloride, polypropylene, polyethylene, polystyrene, polyester, polyamide, polycarbonate, polybutylene, polybutylene terephthalate, a copolymer obtained by copolymerizing these monomers, polyphenylene Examples thereof include sulfides, polyphenylene ethers, polyether ether ketones, liquid crystal polymers (type I, type II, or type III), thermoplastic fluororesins, and the like.

  When scale-like glass (or coated glass-like glass) is blended in the paint, the above-described various thermosetting resins, thermoplastic resins, or curing agents can be appropriately selected and blended into the base resin. .

  The curing agent is not particularly limited, and examples thereof include polyisocyanate, amine, polyamide, polybasic acid, acid anhydride, polysulfide, boron trifluoride, acid dihydrazide, and imidazole.

  When scale-like glass (or scale-like glass with a coating) is blended in an ink composition, examples of the ink composition include ink for writing instruments such as various ballpoint pens and felt pens, and printing ink such as gravure ink and offset ink. It is done. The vehicle constituting the ink composition is made of resins, oils, solvents, etc., and functions to disperse the pigment and fix the ink to the paper.

  Resins in the ink vehicle for writing instruments include acrylic resins, styrene-acrylic copolymers, polyvinyl alcohol, polyacrylic acid salts, acrylic monomer-vinyl acetate copolymers, microorganism-produced polysaccharides such as xanthan gum, guar gum And water-soluble vegetable polysaccharides such as water, alcohols, hydrocarbons, esters and the like.

  The resins for gravure ink vehicles include gum rosin, wood rosin, tall oil rosin, lime rosin, rosin sell, maleic resin, polyamide resin, vinyl resin, nitrocellulose, cellulose acetate, ethyl cellulose, chlorinated rubber, cyclized rubber, ethylene -Vinyl acetate copolymer resin, urethane resin, polyester resin, alkyd resin, gilsonite, dammar, shellac, etc., and mixtures thereof, and water-soluble resins or aqueous emulsion resins obtained by water-solubilizing these resins. Examples of the solvent include hydrocarbons, alcohols, ethers, esters, water, and the like.

  Examples of resins in the offset ink vehicle include rosin-modified phenolic resins, petroleum resins, alkyd resins, and dry-modified resins thereof. Oils include vegetable oils such as linseed oil, tung oil, and soybean oil. Furthermore, examples of the solvent include n-paraffin, isoparaffin, aromatech, naphthene, α-olefin, water and the like.

  In addition, conventional additives such as dyes, pigments, surfactants, lubricants, antifoaming agents, and leveling agents may be appropriately selected and blended with each vehicle.

  When scaly glass (or scaly glass with a film) is blended in a cosmetic, examples of the cosmetic include a wide range of cosmetics such as facial cosmetics, makeup cosmetics, and hair cosmetics. Among these, it is particularly preferable to add scaly glass (or scaly glass with a coating) to foundation, powdered white powder, eye shadow, blusher, makeup base, nail enamel, eyeliner, mascara, lipstick, fancy powder, etc. It is.

  Depending on the purpose of the cosmetic, the glass flakes can be appropriately subjected to a hydrophobic treatment. The following five methods can be mentioned as the method of hydrophobizing treatment.

(1) A treatment method using a silicone compound such as methyl hydrogen polysiloxane, high-viscosity silicone oil, or silicone resin.
(2) A treatment method with a surfactant such as an anionic surfactant or a cationic surfactant.
(3) Nylon, polymethyl methacrylate, polyethylene, various fluororesins [polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer ( FEP), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), etc.], a treatment method with a polymer compound such as polyamino acid.
(4) A treatment method using a perfluoro group-containing compound, lecithin, collagen, metal soap, lipophilic wax, polyhydric alcohol partial ester or complete ester.
(5) A processing method combining these.

  In addition, as long as it is a general method applicable to the hydrophobic treatment of powder, methods other than the above can also be used.

  In addition, other materials usually used as cosmetics can be blended with the cosmetics as necessary. Examples of this material include inorganic powders, organic powders, pigments and dyes, hydrocarbons, esters, oil components, organic solvents, resins, plasticizers, ultraviolet absorbers, antioxidants, preservatives, surfactants, and moisturizing agents. Agents, fragrances, water, alcohol, thickeners and the like.

  Examples of inorganic powders include talc, kaolin, sericite, muscovite, phlogopite, saucite, biotite, lithia mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, magnesium silicate, calcium silicate, aluminum silicate, Examples thereof include barium sulfate, metal tungstate, silica, hydroxyapatite, zeolite, boron nitride, and ceramic powder.

  Examples of the organic powder include nylon powder, polyethylene powder, polystyrene powder, benzoguanamine powder, polytetrafluoroethylene powder, (distyrenebenzene polymer powder), epoxy resin powder, acrylic resin powder, and microcrystalline cellulose.

  Pigments are roughly classified into inorganic pigments and organic pigments.

  Examples of inorganic pigments include various types according to color tone. Inorganic white pigments: titanium oxide, zinc oxide and the like. Inorganic red pigments: iron oxide (Bengara), iron titanate, etc. Inorganic brown pigment: γ iron oxide and the like. Inorganic yellow pigments: yellow iron oxide, ocher, etc. Inorganic black pigments: black iron oxide, carbon black, etc. Inorganic purple pigments: mango violet, cobalt violet, etc. Inorganic green pigments: cobalt titanate and the like. Inorganic blue pigments: ultramarine blue, bitumen and the like. Pearl-like pigments: titanium oxide coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide coated talc, fish scale foil, colored titanium oxide coated mica, etc. Metal powder pigments: aluminum powder, copper powder, etc.

  As organic pigments, red 201, red 202, red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow No. 401 and blue No. 404 are listed. In addition to these, organic pigments in which dyes are raked into extender pigments such as talc, calcium carbonate, barium sulfate, zirconium oxide, and aluminum white are used. As this dye, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1 and the like.

  Examples of the pigment include natural pigments such as chlorophyll and β-carotene.

  As hydrocarbons, squalane, liquid paraffin, petrolatum, microcrystalline wax, okezolite, ceresin, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, hexadecyl alcohol, oleyl alcohol, 2-ethylhexanoic acid Cetyl, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, neopentyl glycol di-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, -2-octyldodecyl oleate, isopropyl myristate, triisostearic acid Examples include glycerol, tricoconut oil fatty acid glycerol, olive oil, avocado oil, beeswax, myristyl myristate, mink oil, lanolin and the like.

  Examples of the oil component include esters such as silicone oil, higher fatty acids and oils, higher alcohols, waxes and the like. Examples of the organic solvent include acetone, toluene, butyl acetate, acetate ester and the like. Examples of the plasticizer include resins such as alkyd resins and urea resins, camphor, and acetyltributyl citrate.

  The shape of the cosmetic is not particularly limited, and examples thereof include powder, cake, pencil, stick, ointment, liquid, emulsion, and cream.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and embodiment of this invention is described more concretely, this invention is not limited to this.

(Examples 1-24, Comparative Examples 1-4)
The raw materials of the respective components were prepared so as to have the compositions shown in Tables 1 to 3 and 5, and glass batches were produced. Using an electric furnace, each batch was heated to 1400-1600 ° C. to melt and held at this temperature for about 4 hours until the composition was uniform. Thereafter, the molten glass was formed into pellets while being cooled. The pellets were put into the manufacturing apparatus shown in FIG. 5, and the manufacturing conditions such as the temperature of the glass substrate were appropriately adjusted so that the average thickness of the glass flakes was 0.7 μm, 1 μm, and 15 μm. Thereby, for each composition, scale-like glass with good uniformity having an average thickness of 0.7 μm, 1 μm, and 15 μm was produced.

(Examples 25 to 28)
The scale-like glass having an average thickness of 0.7 μm, 1 μm, and 15 μm produced in Examples 1, 3, 6, and 13 was mixed with a 3% hydrogen and 97% nitrogen mixed gas atmosphere that is a reducing atmosphere in which Cu is reduced. Then, it was kept in a heating furnace at 500 ° C. or 550 ° C. for 2 hours (Table 4). As a result, a scaly glass having crystals (Cu) with Cu as constituent atoms deposited therein was produced.

(Examples 29 to 32)
The glass flakes having an average thickness of 0.7 μm, 1 μm, and 15 μm prepared in Examples 1, 3, 6, and 13 were placed in a heating furnace at 550 ° C. in an air atmosphere that is an oxidizing atmosphere in which Cu is oxidized. Hold for 2 hours (Table 4). As a result, a scaly glass in which crystals containing Cu as a constituent atom (CuO) were deposited was produced.

(Example 33)
The glass flakes having an average thickness of 0.7 μm, 1 μm, and 15 μm prepared in Example 3 were held in a heating furnace at 500 ° C. for 2 hours under a nitrogen gas atmosphere that is an inert atmosphere (Table 4). As a result, a scaly glass was produced in which crystals (Cu ₂ O) having Cu as a constituent atom were deposited.

  For the glasses of Examples 1 to 24 and Comparative Example 1, the working temperature, alkali elution amount, and ΔW were measured. In addition, among the glass flakes prepared in Examples 1 to 33 and Comparative Examples 1 to 4, the glass flakes having an average thickness of 15 μm were observed for color tone and measured for visible light transmittance. The presence or absence of precipitation was determined and the composition of this crystal was identified. These measurement / evaluation methods will be described below.

[Visible light transmittance]
The visible light transmittance was determined from the transmittance spectrum obtained by measuring the transmittance using a commercially available spectrophotometer [Shimadzu Corporation, spectrophotometer, UV3100PC]. Visible light transmittance can be used as an index of the degree of coloring. In this specification, the visible light transmittance in terms of a thickness of 15 μm measured using an A light source based on JIS R3106 was obtained and used as the index.

  Here, the explanation is supplemented about the measuring method of the visible light transmittance of glass flakes.

  When the particle size of the glass flake is sufficiently large and the thickness is more than 15 μm, it is preferable to adjust the thickness of the glass flake to 15 μm by polishing or etching and measure the visible light transmittance using an A light source.

  When the particle size of the glass flakes is small and it is difficult to directly measure the visible light transmittance, a glass flake with the same composition as the glass flakes, an average thickness of 15 μm and a sufficiently large particle size is produced. The visible light transmittance is measured using an A light source. Alternatively, the visible light transmittance may be calculated from an approximate expression as follows.

First, A light source is irradiated perpendicularly with respect to the main surface (surface perpendicular to the thickness direction) of scaly glass. Next, a photograph in which the glass flakes are viewed in plan from the direction opposite to the A light source with the glass flakes sandwiched is taken using an optical microscope. From this photograph, the lightness L ^* of the glass flake is read with the lightness of the photo when no light source is present as 0 and the lightness of the photo when only the light source is placed without placing the glass flakes as 100. The lightness L ^* can be read by, for example, converting these photographs into an image file of a personal computer and using an image editing application or the like. The lightness L ^* of the glass flakes can be converted into Y / Y _n based on JIS Z 8729, and this Y / Y _n is approximately set as the visible light transmittance. Here, Y is a value of tristimulus values in the XYZ system, and Y _n is a value of Y by standard light on the complete diffuse reflection surface. This operation is performed on two glass flakes having different thicknesses close to 15 μm, and an approximate expression based on Lambert-Beer's law is created for the relationship between the thickness and the visible light transmittance, and visible light converted to a thickness of 15 μm. Calculate the transmittance.

  In addition, when it is difficult to directly measure the thickness of the glass flakes, it is preferable to take a cross-sectional photograph of the glass flakes with an electron microscope or the like and read the thickness of the glass flakes.

[Working temperature]
The viscosity was measured by an ordinary platinum ball pulling method, and the temperature at which the viscosity of the molten glass reached 100 Pa · s was determined from the relationship between the obtained viscosity and temperature, and was taken as the working temperature. Here, the platinum ball pulling method is the relationship between the speed, the gravity acting on the platinum ball, the resistance, the pulling force, and the viscosity of the molten glass when pulling the platinum ball immersed in the molten glass at a constant speed. This is a method of measuring the viscosity according to the Stokes law shown.

[Alkali elution amount]
The glass powder obtained by pulverizing the glass sample is passed through a standard mesh sieve specified in JIS Z 8801, passed through a standard mesh sieve with an opening of 420 μm, and the glass powder remaining in the standard mesh sieve with an opening of 250 μm is the specific gravity of the glass. Weighed the same gram quantity. After this glass powder was immersed in 50 mL of distilled water at 100 ° C. for 1 hour, the alkaline component in this aqueous solution was titrated with 0.01 N sulfuric acid. By multiplying the number of milliliters of 0.01 N sulfuric acid required for titration by 0.31, the number of milligrams of the alkali component converted to Na ₂ O was obtained, and this milligram number was defined as the amount of alkali elution. It shows that water resistance is so high that this alkali elution amount is small. This measuring method is based on “Japanese Industrial Standards (JIS)“ Testing Method for Glassware for Chemical Analysis R 3502-1995 ”.

[Mass reduction rate (ΔW)]
The glass powder obtained by pulverizing the glass sample is passed through a standard mesh sieve specified in JIS Z 8801, passed through a standard mesh sieve having an opening of 710 μm and a standard mesh sieve having an opening of 590 μm, and remains in a standard mesh sieve having an opening of 420 μm. The glass powder was weighed in the same gram quantity as the specific gravity of the glass. This glass powder was immersed in 100 mL of a 10% by mass sulfuric acid aqueous solution at 80 ° C. for 72 hours, and then the mass reduction rate of this glass was determined to be the mass reduction rate ΔW. It shows that acid resistance is so high that this mass reduction rate (DELTA) W is small. This measurement method is based on “Optical Glass Chemical Durability Measurement Method (Powder Method) 06-1975” of the Japan Optical Glass Industry Association Standard (JOGIS). However, 10 mass% sulfuric acid aqueous solution is used instead of 0.01 N (mol / L) nitric acid aqueous solution used in the measuring method of JOGIS. Moreover, the temperature of sulfuric acid aqueous solution shall be 80 degreeC, and the liquid quantity is 100 mL instead of 80 mL in the measuring method of JOGIS. Further, the processing time is 72 hours instead of 60 minutes in the measuring method of JOGIS.

[Presence and absence of crystals and composition]
Determination of the presence or absence of precipitation of crystals containing Cu as a constituent atom in the glass flakes and identification of the type of the crystals were performed by measurement by X-ray diffraction. The presence or absence of crystal precipitation was determined based on the presence or absence of a crystal diffraction peak in the obtained X-ray diffraction pattern. However, when the amount of crystals precipitated inside the glass flakes is very small, bulk glass having the same composition as the glass flakes is prepared, and glass fragments obtained by pulverizing the glass glass are obtained by the X-ray diffraction method. Measurements were made to identify the type.

  These measurement results are shown in Tables 1 to 5.

  The working temperatures of the glasses of Examples 1 to 24 are 1031 to 1270 ° C., and are within a range suitable for the production of scaly glass. Moreover, as for the glass of Examples 1-24, the amount of alkali elution is 0.001-0.4 mg, More specifically, 0.06-0.37 mg, In Examples 1-19 and 21-24, 0.3 mg Hereinafter, in Examples 1-19, 21, 23, and 24, it is 0.2 mg or less, which indicates that the glass flakes of the present invention have excellent water resistance.

  The visible light transmittance of the glass flakes of Examples 1 to 33 is 90% or less, more specifically 89.4% or less. In Examples 1 to 15, 17 to 19, 21, 24, 25 to 33, 85% or less, 80% or less in Examples 4 to 7, 21, 25 to 33, and 30% or less in Examples 25 to 33. This indicates that these glass flakes are sufficiently colored. In the scale-like glass (Examples 1 to 24) made of the glass composition, the visible light transmittance was in the range of 75 to 90%.

  In Examples 25 to 33, the glass flakes are heat-treated, and crystals having Cu as a constituent atom are precipitated in the glass flakes, whereby the visible light transmittance is reduced and the glass flakes exhibit more sufficient coloration. Glass was obtained.

  On the other hand, since the scaly glass of Comparative Example 1 did not contain CuO, coloring was not visually recognized, and the visible light transmittance exceeded 90%. Further, the glass of Comparative Example 1 had an alkali elution amount of more than 0.4 mg and insufficient water resistance.

In Comparative Example 2, since alkali metal oxide (Li ₂ O + Na ₂ O + K ₂ O) was not included, devitrification occurred, and scaly glass was not obtained.

  In Comparative Example 3, since the CuO content was too high, devitrification occurred, and no scaly glass was obtained.

In Comparative Example 4, since the content of SiO ₂ was too low, devitrification occurred, and no scaly glass was obtained.

(Examples 34 to 57)
The glass flakes having an average thickness of 0.7 μm and 1 μm prepared in Examples 1 to 24 were further pulverized and passed through a standard mesh sieve defined in JIS Z8801. The surface of the glass flakes that passed through the standard mesh sieve having an aperture of 212 μm and remained in the standard mesh sieve having an aperture of 45 μm was coated with titanium oxide by a liquid phase method. The liquid phase method is a method in which titanium dioxide is deposited on the surface of a glass flake from a metal salt. That is, stannous chloride dihydrate as a metal salt was dissolved in ion-exchanged water, and diluted hydrochloric acid was added to adjust the pH to 2.0 to 2.5. The glass flakes were added while stirring the solution, and the solution was filtered after 10 minutes while adjusting the pH by adding dilute hydrochloric acid. Subsequently, hexachloroplatinic acid hexahydrate was dissolved in ion-exchanged water, and the glass flakes after filtration were added with stirring, followed by filtration after 10 minutes. Next, a hydrochloric acid solution (35% by mass) was added to ion-exchanged water to obtain a hydrochloric acid acidic solution having a pH of 0.5 to 1.0. While stirring the acidic solution, the glass flakes were added, and the temperature of the solution was raised to 75 ° C.

To this solution, 16.5% by mass of titanium tetrachloride (TiCl ₄ ) aqueous solution in terms of Ti was added at a rate of 4.5 g per hour per liter of the solution, and 10% by mass of sodium hydroxide aqueous solution was added. At a rate of 22.5 mL per hour per liter of solution. By this reaction, titanium tetrachloride was produced as titanium dioxide (TiO ₂ ) or its hydrate, and deposited on the glass flake surface. This treatment was carried out while visually checking the color tone of the glass flakes until the glass flakes reached the target color tone product. Thereafter, the glass flakes having a film formed on the surface were filtered and dried at 180 ° C., thereby producing glass flakes with a film. When this scaly glass with a film was observed with an electron microscope, it was confirmed that a film of titanium oxide was formed on the surface of the scaly glass.

  This scaly glass with a coating exhibited a thin pearly tone with a brilliant sensation, in which the interference color of the titanium dioxide coating was added to the color tone of the substrate based on light blue-green. Of particular note is the color tone that develops after the glass flakes with a coating are heat-treated in a heating furnace at 600 ° C. in an air atmosphere. The scaly glass with a film after being treated under these conditions exhibited not only a colored metallic luster color tone but also a polychromaticity in which the color tone changed depending on the viewing angle. This is because, under the above conditions, Cu in the glass is oxidized and discolored to the same color tone as that of the glass of Examples 29 to 32. This is because the color tone of the base material appears to be dominant at a viewing angle at which the interference color of the titanium dioxide coating is not sufficiently visually recognized.

  The average particle size of the glass flakes of Example 3 having an average thickness of 0.7 μm and the glass flakes of Example 36 having an average thickness of 0.7 μm using the glass flakes of Example 3 Diameter, brightness and saturation were measured. These measurement methods will be described below.

[Average particle size]
The median diameter D50 obtained by measuring the particle size distribution using a commercially available laser diffraction particle size distribution measuring device (Nikkiso Co., Ltd., particle size analyzer, Microtrac HRA) was defined as the average particle size.

[Brightness and saturation]
A mixed solution obtained by mixing scaly glass provided with a titanium dioxide film and an acrylic resin (manufactured by Nippon Paint Co., Ltd., Acrylic Auto Clear Super) was applied onto concealment measurement paper to form a coating film. Specifically, it is mixed in a ratio of 1 g of glass flakes with a coating to 30 g of acrylic resin (solid content weight) and sufficiently stirred and mixed to obtain a mixed solution. This mixed solution is subjected to the concealment using a 9 mil applicator. It apply | coated on the measurement paper. The lightness (L ^* ) and chroma (a ^* , b ^* ) of the obtained coating film were measured using a color difference meter (manufactured by Minolta, CR-400). The measurement results are shown in Tables 6 and 7. The yellow to green data in Table 7 are the chromaticity coordinates when the color appears most clearly in the chromaticity coordinates when measured by changing the angle of the light receiving portion of the apparatus with respect to the sample.

(Examples 58 to 66)
As the flaky glass to be crushed, the flaky glass with a coating film was prepared in the same manner as in Examples 34 to 57 except that the flaky glass having an average thickness of 0.7 μm and 1 μm prepared in Examples 25 to 33 was used. Was made. When this scaly glass with a film was observed with an electron microscope, it was confirmed that a film of titanium oxide was formed on the surface of the scaly glass.

(Examples 67 to 99)
The glass flakes having an average thickness of 1 μm produced in Examples 1 to 33 were further pulverized to obtain glass flakes having an appropriate particle size. The surface of the flaky glass was coated with silver by a normal electroless plating method. This electroless plating method will be described. First, in the same manner as in Examples 34 to 66, scaly glass was pretreated with stannous chloride and hexachloroplatinic acid hexahydrate. Subsequently, 200 g of silver nitrate and an appropriate amount of ammonia water were added to 10 L of ion-exchanged water to obtain a silver liquid. While stirring this silver solution, 1 kg of pretreated glass flakes was added, and a glucose solution was added as a reducing solution to coat the surface of the glass flakes with silver. Thereafter, the scaly glass was filtered and dried at 400 ° C. to produce a scaly glass with a coating having a silver coating on the surface.

  When this scaly glass with a film was observed with an electron microscope, it was confirmed that a silver film was formed on the surface of the scaly glass.

  As described above, according to the present invention, scale-like glass having an unprecedented color tone is provided.

DESCRIPTION OF SYMBOLS 2 Glass matrix 3 Crystal 10 Scale-like glass 11 Coating 12 Coated scale-like glass 13 Base material 14 Coating film 15 Resin matrix 20 Refractory kiln tank 21 Glass substrate 22 Blow nozzle 23 Gas 24 Hollow glass membrane 25 Press roll 26 Rotary cup 27 Annular plate 28 collector

Claims (10)

Expressed in mass%,
60 ≦ SiO ₂ ≦ 80,
1 ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 20,
5 ≦ CuO ≦ 20,
A glass flake containing the above ingredients.
However, the value of the CuO indicates a value obtained by converting all Cu atoms contained in the glass flakes to CuO.   The scale-like glass according to claim 1, further comprising 0.1 ≦ (MgO + CaO + SrO + BaO) ≦ 20 in terms of mass%. The scale-like glass according to claim 1 or 2, further comprising 0.1 ≦ (B ₂ O ₃ + Al ₂ O ₃ ) ≦ 15 in terms of mass%.   The glass flakes according to any one of claims 1 to 3, comprising a glass composition containing the component.   The scale-like glass according to any one of claims 1 to 4, wherein an alkali elution amount by a measuring method based on JIS R 3502-1995 is 0.001 to 0.4 mg.   The glass flakes according to any one of claims 1 to 3, comprising a glass matrix containing a crystal having Cu as a constituent atom. The glass flakes according to claim 6, wherein the crystal contains at least one selected from Cu, Cu ₂ O and CuO.   The scaly glass according to any one of claims 1 to 7, which has a visible light transmittance of 90% or less when converted to a thickness of 15 µm.   A scaly glass with a coating comprising the scaly glass according to any one of claims 1 to 8 and a coating formed on a surface of the scaly glass, wherein the coating is made of a metal or a metal oxide. Display in mass%,
60 ≦ SiO ₂ ≦ 80,
1 ≦ (Li ₂ O + Na ₂ O + K ₂ O) ≦ 20,
5 ≦ CuO ≦ 20,
A scaly glass made of a glass composition containing the components of
By heat-treating the scaly glass, crystals containing Cu as a constituent atom are precipitated in the scaly glass,
A method for producing flaky glass, which obtains flaky glass in which crystals containing Cu as a constituent atom are dispersed in a glass matrix.
However, the value of said CuO shows the value obtained by converting all the Cu atoms contained in the glass flakes which consist of the said glass composition into CuO.

Images