Colored glass material, method for manufacturing the same, and pigments

Abstract

To provide a novel colored glass material.SOLUTION: A colored glass material is represented by a general formula (1): yRO-(100-y)(Al(2-x)MnxO3), where 0.001≤x≤1 and 40≤y≤95 are satisfied and RO is at least one kind selected from among CaO, SrO and BaO.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to colored glass materials, methods for producing the same, and pigments. [Background technology]

[0002] Techniques for imparting various colors to glass by adding colorants are known. For example, colored glass materials using colored ions or colloidal particles as coloring factors have been produced for a long time, and a wide range of colors have been achieved.

[0003] For example, colored glass materials exhibiting green to blue-green hues are known to be colored by colored ions such as Cr, Fe, Cu, and Co (see, for example, Patent Documents 1-3). Also, colored glass materials exhibiting red hues are known to be colored by Au colloids and Cu colloids. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Unexamined Patent Publication No. 1-108134 [Patent Document 2] Patent No. 4440729 [Patent Document 3] Japanese Patent Publication No. 2019-94244 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, design has become increasingly diverse, and there is a demand for materials with new colors to broaden the range of expression.

[0006] In view of the above, the present invention aims to provide a novel colored glass material, a method for manufacturing the same, and a pigment. [Means for solving the problem]

[0007] Hereinafter, each aspect of the colored glass material that solves the above problems, its manufacturing method, and the pigment will be described.

[0008] That is, the colored glass material of Aspect 1 is characterized in that in the following general formula (1), 0.001 ≦ x ≦ 1 and 40 ≦ y ≦ 95, and RO is at least one selected from CaO, SrO, and BaO. yRO-(100-y)(Al (2-x) Mn x O3)···Formula (1)

[0009] The colored glass material of Aspect 2 preferably contains at least one selected from SrO and BaO among the RO in Aspect 1.

[0010] The colored glass material of Aspect 3 is characterized in that in the following general formula (2), 0.001 ≦ x ≦ 1, 40 ≦ y ≦ 95, and 0 < z < 1, and R 1 and R 2 are preferably two selected from Ca, Sr, and Ba. y(R 1 (1-z) R 2 z O)-(100-y)(Al (2-x) Mn x O3)···Formula (2)

[0011] The colored glass material of Aspect 4 is preferably such that R 1 is Sr, and R 2 is any one selected from Ca and Ba in Aspect 3.

[0012] The colored glass material of Aspect 5 is preferably such that 0 < z ≦ 0.5 in Aspect 3 or Aspect 4.

[0013] The pigment of Aspect 6 is characterized by being composed of the colored glass material described in any one of Aspects 1 to 5.

[0014] The pigment of Aspect 7 is preferably a blue pigment in Aspect 6.

[0015] The method for manufacturing a colored glass material according to Embodiment 8 is a method for manufacturing a colored glass material according to any one embodiment of Embodiments 1 to 5, characterized by comprising the steps of: heating and melting glass raw materials while the glass raw materials are suspended and held in the air to obtain molten glass; and cooling the molten glass after obtaining the molten glass. [Effects of the Invention]

[0016] According to the present invention, it is possible to provide a novel colored glass material, a method for manufacturing the same, and a pigment. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 is a schematic cross-sectional view of a manufacturing apparatus for colored glass material according to the first embodiment of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view of a manufacturing apparatus for colored glass material according to a second embodiment of the present invention. [Modes for carrying out the invention]

[0018] <Colored glass material> The colored glass material of the present invention is characterized in that, in the following general formula (1), 0.001 ≤ x ≤ 1 and 40 ≤ y ≤ 95, and RO is at least one selected from CaO, SrO, and BaO. yRO-(100-y)(Al (2-x) Mn x O3)...Equation (1)

[0019] In general formula (1), RO is at least one selected from CaO, SrO, and BaO. In other words, RO may be any one selected from CaO, SrO, and BaO. Also, RO may be two or more selected from CaO, SrO, and BaO. Furthermore, RO may contain all of CaO, SrO, and BaO. RO has the effect of broadening the vitrification range and improving the stability of vitrification. It is also a component that forms the glass skeleton in this invention. Also, Al (2-x) Mn x O3 is a component that forms the glass skeleton.

[0020] It is preferable that the RO contains at least one selected from SrO and BaO. Including these components makes it easier to obtain a variety of colored glass materials.

[0021] The reason for defining the range of each coefficient in general formula (1) as described above is explained below.

[0022] x is 0.001 ≤ x ≤ 1, preferably 0.001 ≤ x ≤ 0.5, and particularly preferably 0.001 ≤ x ≤ 0.1. If x is too small, the glass coloring tends to become too light. If x is too large, the glass coloring tends to become too dark.

[0023] The value of y is 40 ≤ y ≤ 95, preferably 50 ≤ y ≤ 85, more preferably 55 ≤ y ≤ 85, and particularly preferably 60 ≤ y ≤ 80. If y is too small, glass formation tends to be difficult. If y is too large, glass formation also tends to be difficult.

[0024] Furthermore, if RO is two types selected from CaO, SrO, and BaO, it is preferable that the following general formula (2) is satisfied. That is, the colored glass material of the present invention satisfies the following general formula (2): 0.001≦x≦1, 40≦y≦95, 0 <z<1であり、R 1 and R 2 It is preferable that y(R) be two selected from Ca, Sr, and Ba. 1(1-z) R 2 z O) is y(1-z)R 1 O-yzR 2 It is sometimes written as O. y(R 1 (1-z) R 2 z O)-(100-y)(Al (2-x) Mn x O3)...Equation (2)

[0025] In general formula (2), R 1 and R 2 These are different components. In other words, among Ca, Sr, and Ba, R 1 From the components that were not selected, R 2 For example, R is selected. 1 If Sr, then R 2 It is preferable that it is one of Ca and Ba selected.

[0026] In general formula (2), R 1 is Sr, and R 2 It is preferable that is one selected from Ca and Ba. In other words, it is preferable that the colored glass material of the present invention contains SrO and one selected from CaO and BaO. 1 and R 2 Even when the settings are configured as described above, it becomes easier to obtain a wide variety of colored glass materials.

[0027] The reason for defining the range of each coefficient in general formula (2) as described above is explained below.

[0028] x is 0.001 ≤ x ≤ 1, preferably 0.001 ≤ x ≤ 0.5, and particularly preferably 0.001 ≤ x ≤ 0.1. If x is too small, the glass coloring tends to become too light. If x is too large, the glass coloring tends to become too dark.

[0029] y satisfies 40 ≤ y ≤ 95, preferably 50 ≤ y ≤ 85, more preferably 55 ≤ y ≤ 85, and particularly preferably 60 ≤ y ≤ 80. If y is too small, glass formation tends to be difficult. If y is too large, glass formation also tends to be difficult.

[0030] z satisfies 0 < z < 1, preferably 0 < z ≤ 0.5, and particularly preferably 0 < z ≤ 0.4. By satisfying the above values, it becomes easier to change the color tone of the colored glass material. Although the lower limit of z only needs to be more than 0, for example, it may be 0.001 or more.

[0031] Thus, in the general formula (2), the ratio of R 1 and R 2 (that is, the value of the parameter z) is defined as a new variable. By adjusting the values of various parameters including the parameter z, it becomes easier to change the color tone of the colored glass material.

[0032] For example, when R 1 is Sr and R 2 is Ca, blue, green, and yellow colored glass materials are easily obtained. In this case, from the viewpoint of obtaining a blue colored glass material, the product yz of the parameters y and z is preferably more than 0 to 10, and particularly preferably more than 0 to 8. Also, from the viewpoint of obtaining a green colored glass material, the product yz of the parameters y and z is preferably more than 10 to 30 or less. Further, from the viewpoint of obtaining a yellow colored glass material, the product yz of the parameters y and z is preferably more than 30.

[0033] For example, when R 1 is Sr and R 2 is Ba, blue and light blue colored glass materials are easily obtained. In this case, from the viewpoint of obtaining a blue colored glass material, the product yz of the parameters y and z is preferably more than 6 to 40, and particularly preferably 6.5 to 35. Also, from the viewpoint of obtaining a light blue colored glass material, the product yz of the parameters y and z is preferably more than 0 to 6.

[0034] Thus, our research has revealed that novel colored glass materials can be formed by adding a small amount of Mn to RO-Al2O3-based glass materials. In particular, colored glass materials containing at least one selected from SrO and BaO among RO exhibit colors (blue, light blue, green, yellow) not normally observed with Mn ions, making them useful as materials with new colors. In other words, it becomes easier to obtain a variety of colored glass materials. Blue colored glass materials are especially preferred as blue pigments. The reason for the above-mentioned coloration is unknown, but our inventors estimate that it is due to the valence and coordination number of Mn in the colored glass material.

[0035] <Manufacturing method for colored glass materials> The colored glass material of the present invention is preferably manufactured by a containerless flotation method in which the glass raw material is melted and cooled while suspended in the air. RO-Al2O3 glass material has a strong tendency to crystallize and is prone to devitrification. Therefore, when the glass raw material is melted in a molten container such as a crucible, crystal precipitation tends to progress starting from the contact interface between the molten glass and the molten container. On the other hand, by using a containerless flotation method, interfacial contact between the molten glass and the molten container can be eliminated, and devitrification can be suppressed.

[0036] Figure 1 is a schematic cross-sectional view of a manufacturing apparatus for colored glass material according to the first embodiment of the present invention. The method for manufacturing colored glass material according to the present invention will be described below with reference to Figure 1.

[0037] The colored glass material manufacturing apparatus 1 has a mold 10. The mold 10 has a molding surface 10a and a gas ejection hole 10b opening in the molding surface 10a. The gas ejection hole 10b consists of at least one opening. In this embodiment, the molding surface 10a is tapered, narrowing downwards, and one gas ejection hole 10b opens in the center of the molding surface 10a.

[0038] The gas outlet 10b is connected to a gas supply mechanism 11, such as a gas cylinder. Gas is supplied from this gas supply mechanism 11 to the molded surface 10a via the gas outlet 10b. The type of gas is not particularly limited and may be air or oxygen, or a reducing gas containing nitrogen gas, argon gas, helium gas, carbon monoxide gas, carbon dioxide gas, or hydrogen.

[0039] First, the glass raw material block 12 is placed on the molding surface 10a. The glass raw material block 12 can be made, for example, by molding glass material raw material powder (raw material batch) into pellets. However, the glass raw material block 12 is not limited to the above, and may be made by integrating the raw material batch by press molding or the like. Alternatively, the glass raw material block 12 may be made by molding the raw material batch into pellets and then heat-treating it. Furthermore, the glass raw material block 12 may be, for example, an aggregate of crystals having a composition equivalent to the target glass composition.

[0040] Next, the glass raw material mass 12 is suspended on the molding surface 10a by ejecting gas from the gas ejection hole 10b. That is, the glass raw material mass 12 is held in a state where it is not in contact with the molding surface 10a. In this state, laser light is irradiated onto the glass raw material mass 12 from the laser light irradiation device 13. This heats and melts the glass raw material mass 12, causing it to vitrify and obtain molten glass. Note that the method of heating the glass raw material mass 12 is not particularly limited to the method of irradiating with laser light. For example, the glass raw material mass 12 may be heated by radiation.

[0041] Subsequently, the molten glass can be cooled to obtain a colored glass material. At this time, it is preferable to continue ejecting gas until the temperature of the molten glass falls below its softening point to suppress contact between the molten glass or colored glass material and the molded surface 10a. Furthermore, the obtained colored glass material may be processed into a desired shape by cutting, polishing, pressing, etc., as needed.

[0042] Figure 2 is a schematic cross-sectional view of a colored glass material manufacturing apparatus according to a second embodiment of the present invention. In the colored glass material manufacturing apparatus 2 according to this embodiment, a plurality of gas ejection holes 10b are opened in the molding surface 10a. For example, the plurality of gas ejection holes 10b are arranged radially from the center of the molding surface 10a. In this embodiment as well, colored glass material can be suitably manufactured, similar to the first embodiment.

[0043] <Pigments> The colored glass material of the present invention can be suitably used as a pigment. In particular, a colored glass material containing at least one selected from SrO and BaO is preferred as a material having new colors. That is, in the following general formula (1), it is preferable that 0.001 ≤ x ≤ 1, 40 ≤ y ≤ 95, and RO is at least one selected from SrO and BaO. yRO-(100-y)(Al (2-x) Mn x O3)...Equation (1)

[0044] The pigment of the present invention consists of the colored glass material of the present invention described above. More specifically, the pigment of the present invention consists of powder of the colored glass material described above. For example, a pigment consisting of powder of the colored glass material can be obtained by crushing the colored glass material and then adjusting the particle size. The pigment of the present invention is preferably a blue pigment.

[0045] Since the pigment of the present invention does not contain toxic elements, it can be applied to coloring various materials such as plastics, ceramics, glass, and paper. It can also be used in paints, glazes, printing inks, dyes, etc. Furthermore, when using the pigment as a paint, it may be used as a slurry by appropriately blending it with resin materials, solvents, dispersants, auxiliary agents, drying accelerators, surfactants, etc.

[0046] The pigment of the present invention can be used in combination with, for example, a resin material.

[0047] Examples of resin materials include polyamide resins, polyacetal resins, acrylic resins, melamine resins, acrylonitrile-butadiene-styrene resins, polycarbonate resins, polystyrene resins, polyvinyl chloride resins, silicone resins, fluororesins, polyester resins, epoxy resins, thermosetting modified polyphenylene ether resins, polyimide resins, urea resins, unsaturated polyester resins, alkyd resins, furan resins, polyurethane resins, polyethylene resins, and polypropylene resins. These resin materials may be used individually or in combination of multiple types.

[0048] The average particle size of the pigment is preferably 0.01 μm to 10 μm, 0.05 μm to 5 μm, 0.1 μm to 3 μm, and particularly preferably 0.1 μm to 2 μm. If the average particle size of the pigment is too small, the pigment powder tends to aggregate, making it difficult to handle. If the average particle size of the pigment is too large, the dispersibility tends to decrease. The average particle size is the median diameter derived from the volume distribution measured by laser diffraction scattering.

[0049] When adding the pigment of the present invention to a resin material, the amount is preferably 30% or less, 20% or less, 15% or less, 10% or less, and particularly 5% or less by weight, and preferably 0.01% or more, 0.1% or more, 0.5% or more, and particularly 1% or more. If the amount of pigment added is too little, it will be difficult to obtain the desired coloring. If the amount of pigment added is too much, the flexibility of the resin material may be impaired. [Examples]

[0050] The present invention will be described below based on examples, but the present invention is not limited to these examples.

[0051] Tables 1 and 2 show Examples 1 to 27 and Comparative Examples 1 to 5 of the present invention.

[0052] [Table 1]

[0053] [Table 2]

[0054] The samples were prepared as follows. First, raw material powders were mixed to obtain the glass composition shown in Tables 1 and 2, and a raw material batch was prepared. Next, the raw material batch was formed into pellets, and a target was prepared by heat treatment at 1000°C for 12 hours. A glass raw material mass was prepared by crushing the obtained target.

[0055] Next, using a glass raw material block, glass material (approximately 1.5 mm in diameter) was fabricated using a containerless levitation method with an apparatus similar to that shown in Figure 1. A 100 W CO2 laser oscillator was used as the heat source. O2 gas was used to levitate the glass raw material block in the air, with a supply flow rate of 0.1 L / min to 30 L / min. After melting, the molten glass was cooled to obtain the glass material.

[0056] The color tone of the obtained glass material was checked. The results are shown in Tables 1 and 2. The color tone of the glass material was evaluated by visual observation under a fluorescent light source and by analyzing the diffuse reflectance spectrum.

[0057] As shown in Tables 1 and 2, the colored glass materials of the examples exhibited brown, light brown, blue, light blue, green, or yellow hues. In particular, samples containing SrO or BrO as RO yielded glass materials exhibiting a wide range of hues not typically observed with Mn ions. On the other hand, Comparative Examples 1 to 5, which did not contain Mn, yielded colorless and transparent glass materials. [Industrial applicability]

[0058] The colored glass material of the present invention can be suitably used as a novel colored glass material and a pigment using the same. [Explanation of Symbols]

[0059] 1,2 Manufacturing equipment for colored glass materials 10 mold 10a Molding surface 10b Gas outlet 11. Gas supply mechanism 12 Glass raw material ingots 13. Laser light irradiation device

Claims

1. A colored glass material in the following general formula (1), where 0.001 ≤ x ≤ 1, 40 ≤ y ≤ 95, and RO is at least one selected from CaO, SrO, and BaO. yRO-(100 - y)(Al （２－ｘ） Mn ｘ O ３ )... Formula (1)

2. The colored glass material according to claim 1, wherein the RO contains at least one selected from SrO and BaO.

3. In the following general formula (2), 0.001 ≤ x ≤ 1, 40 ≤ y ≤ 95, 0 < z < 1, and R １ and R ２ The colored glass material according to claim 1, wherein is two selected from Ca, Sr, and Ba. y(R １ （１－ｚ） R ２ ｚ O)-(100 - y)(Al （２－ｘ） Mn ｘ O ３ )... Equation (2)

4. R １ is Sr, R ２ The colored glass material according to claim 3, wherein is one selected from Ca and Ba.

5. A colored glass material according to claim 3 or 4, wherein 0 < z ≤ 0.

5.

6. A pigment comprising the colored glass material described in claim 1 or 3.

7. The pigment according to claim 6, which is a blue pigment.

8. A method for producing a colored glass material according to claim 1 or 3, A method for manufacturing a colored glass material, comprising the steps of: heating and melting glass raw materials while they are suspended and held in the air to obtain molten glass; and cooling the molten glass after it has been obtained.

Images