Glass articles

Abstract

The present invention provides a novel article having excellent brilliance and having a bright neon blue or neon green color.　This glass article is characterized by containing, on a molar basis: more than 0% to 70% of La2O3; 0-80% of B2O3; 0-40% of SiO2; 0-80% of B2O3 + Al2O3 + SiO2; 0-85% of Gd2O3 + Ga2O3 + Y2O3 + Yb2O3 + ZrO2 + TiO2 + Nb2O5 + Ta2O5 + WO3; 0-15% of MgO + CaO + SrO + BaO; 0-35% of ZnO; and more than 0% to 5% of CuO.

Description

[Technical Field]

[0001] The present invention relates to a glass article suitable for use as an ornament such as a ring, pendant, earring, or bracelet. [Background technology]

[0002] Paraiba tourmaline is known as a gemstone with vivid neon blue and neon green colors (see, for example, Non-Patent Document 1). The neon blue and neon green colors of Paraiba tourmaline are caused by copper ions and manganese ions, and the color tone changes depending on the content ratio of these ions. Currently, no other gemstones with similar colors are known. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Gems & Gemology, Fall 1990, Vol. 26, No. 3, 189-204 Summary of the Invention [Problem to be solved by the invention]

[0004] The vivid neon blue and neon green Paraiba tourmaline is produced in very small quantities, and has many inclusions and cracks, making it prone to breaking.Tourmaline, another mineral, also has a color tone similar to Paraiba tourmaline, but its refractive index is low at 1.62 to 1.64, so it does not have enough sparkle when used as jewelry.

[0005] In view of the above, an object of the present invention is to provide a novel article that has excellent brightness and a vivid neon blue or neon green color tone. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by a glass article having a composition in which CuO is added to a base glass containing La2O3 as an essential component.

[0007] That is, the glass article of the present invention is characterized by containing, in mole percent, more than 0 to 70% La2O3, 0 to 80% B2O3, 0 to 40% SiO2, 0 to 80% B2O3 + Al2O3 + SiO2, 0 to 85% Gd2O3 + Ga2O3 + Y2O3 + Yb2O3 + ZrO2 + TiO2 + Nb2O5 + Ta2O5 + WO3, 0 to 15% MgO + CaO + SrO + BaO, 0 to 35% ZnO, and more than 0 to 5% CuO. In this specification, "x + y +..." means the total amount of each component.

[0008] The glass article of the present invention preferably contains, in mole percent, more than 80% of B2O3+Al2O3+SiO20.

[0009] The glass article of the present invention preferably contains, in mole percent, more than 85% of Gd2O3+Ga2O3+Y2O3+Yb2O3+ZrO2+TiO2+Nb2O5+Ta2O5+WO3.

[0010] The glass article of the present invention may contain 0 to 20% by mole of a coloring component made of an oxide of V, Cr, Mn, Fe, Co, Ni, Mo, Ru, Ce, Pr, or Er, which allows the color tone of the glass article to be varied in a variety of ways.

[0011] The glass article of the present invention preferably has a refractive index of 1.7 or more. By increasing the refractive index of the glass article, the difference in refractive index between the inside and outside (atmosphere) of the glass article increases, making it easier for light to be reflected inside the glass article. As a result, it becomes easier to obtain a sufficient brightness as a glass article.

[0012] The glass article of the present invention preferably has an Abbe number of not more than 50. By reducing the Abbe number of the glass article, high dispersion is achieved, and the rainbow-colored sparkle known as fire is more likely to appear.

[0013] The glass article of the present invention is preferably chamfered, which makes it easier for light to be reflected inside the glass article, thereby enhancing brightness.

[0014] The glass article of the present invention is preferably for decorative purposes.

[0015] The glass article of the present invention is preferably a pseudo-gemstone.

[0016] The decorative article of the present invention is characterized by comprising the glass article described above. [Effects of the Invention]

[0017] According to the present invention, a glass article can be provided which has excellent brightness and fire and a vivid neon blue or neon green color tone. [Brief explanation of the drawings]

[0018] [Figure 1] 1 is a plan photograph showing samples Nos. 8, 9, and 39 in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0019] The glass article of the present invention is characterized by containing, in mole percent, more than 0 to 70% La2O3, 0 to 80% B2O3, 0 to 40% SiO2, 0 to 80% B2O3 + Al2O3 + SiO2, 0 to 85% Gd2O3 + Ga2O3 + Y2O3 + Yb2O3 + ZrO2 + TiO2 + Nb2O5 + Ta2O5 + WO3, 0 to 15% MgO + CaO + SrO + BaO, 0 to 35% ZnO, and more than 0 to 5% CuO. The reasons for limiting the glass composition in this way are explained below. In the following explanation of the content of each component, "%" means "mol %" unless otherwise specified.

[0020] La2O3 is a component that forms the glass skeleton and increases the refractive index without reducing the transmittance. It also has the effect of improving weather resistance. The La2O3 content is more than 0 to 70%, and preferably 5 to 68%, 8 to 65%, 14 to 63%, and particularly preferably 20 to 63%. If the La2O3 content is too low, it becomes difficult to obtain the above effects. On the other hand, if the La2O3 content is too high, it becomes difficult to vitrify.

[0021] B2O3 is a component that forms the glass skeleton and expands the vitrification range. The B2O3 content is preferably 0 to 80%, 3 to 70%, 5 to 50%, and particularly preferably 10 to 40%. If the B2O3 content is too high, the refractive index decreases, making it difficult to obtain the desired optical properties.

[0022] SiO2 is a component that forms the glass skeleton and expands the vitrification range. The SiO2 content is preferably 0 to 40%, 1 to 30%, and particularly preferably 3 to 20%. If the SiO2 content is too high, the refractive index decreases, making it difficult to obtain the desired optical properties.

[0023] To facilitate vitrification, it is preferable to adjust the content of B2O3 + Al2O3 + SiO2. The content of B2O3 + Al2O3 + SiO2 is preferably 0% or more, more than 0%, 0.1% or more, 3% or more, and particularly 5% or more. However, if the content of B2O3 + Al2O3 + SiO2 is too high, the refractive index decreases, making it difficult to obtain the desired optical properties, so it is preferable that the content be 80% or less, 75% or less, and particularly 70% or less.

[0024] Al2O3 is a component that forms the glass skeleton and expands the vitrification range. However, if the Al2O3 content is too high, the refractive index decreases, making it difficult to obtain the desired optical properties. Therefore, the Al2O3 content is preferably 0 to 80%, 1 to 75%, and particularly 3 to 70%.

[0025] Gd2O3, Ga2O3, Y2O3, Yb2O3, ZrO2, TiO2, Nb2O5, Ta2O5, and WO3 are components that increase the refractive index, decrease the Abbe number to achieve high dispersion, and expand the vitrification range. The content of Gd2O3+Ga2O3+Y2O3+Yb2O3+ZrO2+TiO2+Nb2O5+Ta2O5+WO3 is 0 to 85%, preferably greater than 0 to 85%, 1 to 80%, 5 to 75%, and particularly preferably 10 to 70%. If the content of Gd2O3+Ga2O3+Y2O3+Yb2O3+ZrO2+TiO2+Nb2O5+Ta2O5+WO3 is too high, vitrification becomes difficult. When two or more selected from Gd2O3, Ga2O3, Y2O3, Yb2O3, ZrO2, TiO2, Nb2O5, Ta2O5 and WO3 are contained, the total amount thereof is preferably within the above range.

[0026] Each of the components Gd2O3, Ga2O3, Y2O3, Yb2O3, ZrO2, TiO2, Nb2O5, Ta2O5 and WO3 will be described in detail below.

[0027] Gd2O3 is a component that increases the refractive index. It also has the effect of improving weather resistance. However, if the Gd2O3 content is too high, vitrification becomes difficult. Therefore, the Gd2O3 content is preferably 0 to 45%, 0.1 to 40%, 1 to 35%, 3 to 30%, and particularly preferably 5 to 20%.

[0028] Ga2O3 is a component that increases the refractive index. It also forms a glass skeleton as an intermediate oxide, which has the effect of widening the vitrification range. However, if the Ga2O3 content is too high, vitrification becomes difficult and raw material costs tend to increase. Therefore, the Ga2O3 content is preferably 0 to 50%, 5 to 40%, 10 to 35%, and particularly 15 to 30%. If raw material costs are prioritized, the Ga2O3 content is preferably 0 to 30%, 0 to 20%, and particularly 0 to 10%.

[0029] Y2O3 is a component that increases the refractive index. It also forms a glass skeleton as an intermediate oxide, which has the effect of widening the vitrification range. However, if the Y2O3 content is too high, vitrification becomes difficult. Therefore, the Y2O3 content is preferably 0 to 50%, 0 to 30%, 0 to 20%, and particularly preferably 0 to 10%.

[0030] Yb2O3 is a component that increases the refractive index. However, if the Yb2O3 content is too high, vitrification becomes difficult. Therefore, the Yb2O3 content is preferably 0 to 50%, 0 to 30%, 0 to 20%, and particularly preferably 0 to 10%.

[0031] ZrO2 is a component that increases the refractive index. It also forms a glass skeleton as an intermediate oxide, which has the effect of widening the vitrification range. However, if the ZrO2 content is too high, vitrification becomes difficult and the melting temperature becomes too high. Therefore, the ZrO2 content is preferably 0 to 40%, 0.1 to 35%, 1 to 30%, 3 to 25%, and particularly preferably 5 to 20%.

[0032] TiO2 is a component that is highly effective in increasing the refractive index and also in enhancing chemical durability. It also has the effect of lowering the Abbe number and achieving high dispersion. The TiO2 content is preferably 0 to 85%, 0.1 to 83%, 5 to 80%, and particularly 10 to 75%. If the TiO2 content is too high, the absorption edge shifts to the long wavelength side, which tends to reduce the transmittance of visible light (especially visible light in the short wavelength range). It also becomes difficult to vitrify.

[0033] Nb2O5 is a component that has a significant effect of increasing the refractive index, lowering the Abbe number and achieving high dispersion. It also has the effect of widening the vitrification range. The Nb2O5 content is preferably 0 to 85%, 0.5 to 75%, 1 to 73%, and particularly preferably 2 to 70%. If the Nb2O5 content is too high, vitrification becomes difficult.

[0034] Ta2O5 is a component that is highly effective in increasing the refractive index. However, if the Ta2O5 content is too high, vitrification becomes difficult and the raw material cost tends to increase. Therefore, the Ta2O5 content is preferably 0 to 60%, 0 to 50%, 0 to 45%, and particularly preferably 0.1 to 40%.

[0035] WO3 is a component that increases the refractive index. It also forms a glass skeleton as an intermediate oxide, which has the effect of widening the vitrification range. However, if the WO3 content is too high, vitrification becomes difficult. Therefore, the WO3 content is preferably 0 to 50%, 0 to 30%, 0 to 20%, and particularly preferably 0 to 10%.

[0036] MgO, CaO, SrO, and BaO are components that broaden the vitrification range. The content of MgO+CaO+SrO+BaO is 0 to 15%, preferably 0 to 10%. If the content of MgO+CaO+SrO+BaO is too high, the refractive index decreases, making it difficult to obtain the desired optical properties.

[0037] ZnO is a component that widens the vitrification range and also has the effect of increasing the thermal stability of the glass. The ZnO content is 0 to 35%, preferably 0 to 30%. If the ZnO content is too high, the refractive index decreases, making it difficult to obtain the desired optical properties.

[0038] CuO is a blue coloring component, and by including it in glass, a vivid neon blue or neon green color tone can be obtained. The CuO content is more than 0 to 5%, preferably 0.01 to 3%, 0.05 to 2%, and particularly preferably 0.1 to 1%. If the CuO content is too high, the coloring becomes too dark. In the present invention, the CuO content indicates all Cu components contained in the glass converted into CuO. Cu in the glass is hexacoordinated Cu. 2+ In the glass, Cu is preferably in the state + The blue color becomes lighter as the number of Cu atoms increases. 2+ If the amount of Cu becomes too large, the glass turns brown, making it difficult to obtain neon blue glass. In particular, in glasses containing large amounts of high refractive index components such as TiO2 and Nb2O5, tetrahedral Cu 2+Therefore, the proportion of 6-coordinated Cu relative to the total Cu in the glass is 2+ The proportion is preferably 80 mol % or more, and particularly preferably 90 mol % or more.

[0039] The glass article of the present invention is made of La2O3, Nb2O 5、 By actively incorporating components such as B2O3 that expand the vitrification range, undesired crystallization during glass production can be suppressed, making it easier to increase the size of the glass article (for example, diameters of 2 mm or more, 3 mm or more, 4 mm or more, 5 mm or more, and particularly 6 mm or more).

[0040] The glass article of the present invention may contain the following components in addition to those described above.

[0041] P2O5 is a component that forms a glass skeleton and expands the vitrification range. However, if the P2O5 content is too high, the refractive index decreases, making it difficult to obtain the desired optical properties. Therefore, the P2O5 content is preferably 0 to 20%, 0 to 15%, and particularly preferably 0 to 10%.

[0042] Li2O, Na2O, and K2O are components that broaden the vitrification range. However, if the content of Li2O + Na2O + K2O is too high, the refractive index decreases, making it difficult to obtain the desired optical properties. Furthermore, weather resistance decreases. Therefore, the content of Li2O + Na2O + K2O is preferably 0 to 20%, 0 to 15%, and particularly preferably 0 to 10%. It is also preferable that the contents of each of the Li2O, Na2O, and K2O components are within the above ranges.

[0043] Bi2O3 is a component that increases the refractive index. However, if the Bi2O3 content is too high, the glass will turn yellow or red, making it difficult to obtain a glass with the desired color tone. Therefore, the Bi2O3 content is preferably 0-20%, 0-15%, 0-10%, 0-5%, or 0-1%, and most preferably, it is substantially free of Bi2O3. Here, "substantially free of Bi2O3" means that it is not intentionally added to the raw materials, and does not exclude the inclusion of unavoidable impurities. Objectively, it means that the content is less than 0.1%.

[0044] By adding a coloring component consisting of an oxide of V, Cr, Mn, Fe, Co, Ni, Mo, Ru, Ce, Pr, or Er, the glass article can be adjusted to a desired color tone. These coloring components may be added alone or in combination of two or more. The content of these oxides (total amount when two or more are added) is preferably 0 to 20%, 0.001 to 10%, 0.005 to 5%, and particularly 0.01 to 1%. However, depending on the component added, the color may be too strong, reducing visible transmittance and preventing the desired brilliance and fire from being achieved. In such cases, the content of the above oxides may be less than 1%, 0.5% or less, or even 0.1% or less.

[0045] The glass article of the present invention preferably has a refractive index (nd) of 1.7 or more, 1.8 or more, 1.9 or more, 1.95 or more, particularly 2.0 or more. This increases the difference in refractive index between the inside and outside (atmosphere) of the glass article, making it easier for light to be reflected inside the glass article. As a result, it becomes easier to obtain sufficient brightness as a decorative glass article. There is no particular upper limit to the refractive index, but if it is too high, vitrification becomes unstable, so it is preferably 2.6 or less, 2.5 or less, particularly 2.4 or less.

[0046] The Abbe number (νd) of the glass article of the present invention is preferably 50 or less, 45 or less, and particularly preferably 43 or less. This makes the glass article highly dispersible and facilitates the occurrence of fire. There is no particular lower limit to the Abbe number, but if it is too small, vitrification becomes unstable, so it is preferably 10 or more, and particularly preferably 15 or more.

[0047] The glass article of the present invention can be used for decorative purposes such as jewelry, artwork, and tableware. For example, it can be attached to decorative items (jewelry) such as rings, pendants, earrings, and bracelets as a pseudo-gemstone. The shape of the decorative glass article is not particularly limited, and examples include spherical, ellipsoidal, and polyhedral shapes.

[0048] The glass article of the present invention is preferably subjected to chamfering such as brilliant cut, step cut, or mixed cut, which makes it easier for light to be reflected inside the glass article, enhancing its brilliance and making it particularly suitable as a pseudo-gemstone. [Example]

[0049] The glass article of the present invention will be described in detail below using examples, but the present invention is not limited to the following examples.

[0050] Tables 1 to 4 show examples (Nos. 1 to 36) of the present invention and comparative examples (Nos. 37 to 39).

[0051] [Table 1]

[0052] [Table 2]

[0053] [Table 3]

[0054] [Table 4]

[0055] First, raw materials were mixed to prepare raw material batches to obtain the glass compositions shown in the table. The obtained raw material batches were melted until homogeneous and then rapidly cooled to obtain glass samples. The obtained glass samples were homogeneous and showed no defects such as cracks on the surface. The melting temperature was 1400-1700°C. The obtained glass samples were annealed near the glass transition temperature (650-850°C), and then the refractive index (nd) and Abbe number (νd) were measured and the appearance (color change, brilliance, and fire) were evaluated using the methods described below.

[0056] The refractive index and Abbe number were measured using a precision refractometer (Shimadzu KPR-2000) after polishing the glass sample at a right angle. The refractive index was evaluated using the measurement value for the d-line (587.6 nm) of a helium lamp. The Abbe number was calculated using the refractive index for the d-line and the refractive index for the F-line (486.1 nm) and C-line (656.3 nm) of a hydrogen lamp, using the formula: Abbe number (νd) = {(nd-1) / (nF-nC)}.

[0057] Appearance evaluation was performed as follows. First, each sample was subjected to a brilliant finish so that the planar shape was approximately 5 to 7 mm in diameter. The processed glass samples were visually evaluated for brilliance and fire under a fluorescent light source. Evaluation was performed on a four-point scale as shown below. Planar photographs of samples No. 8, 9, and 39 are shown in Figure 1.

[0058] [Shine] ◎: Looks shiny and has a strong shine. ○: Looks shiny. ×: Does not appear shiny (similar to a glass window).

[0059] [fire] ◎: Rainbow-colored (various colors) sparkle. ○: Iridescent sparkle is visible, but the number of colors is limited. ×: The rainbow color is barely visible.

[0060] As is clear from Table 1, samples Nos. 1 to 36, which are examples, exhibited vivid neon blue or neon green color tones, and were good, with brilliance rated as ⊚ and fire rated as ◯ to ⊚. On the other hand, sample No. 37, a comparative example, contained too much SiO2 and MgO+CaO+SrO+BaO, resulting in a low refractive index of 1.61, a large Abbe number of 55.6, and poor brilliance and fire. Sample No. 38 was colorless because it did not contain CuO. Sample No. 39, on the other hand, contained too much CuO, resulting in a dark, black color.

Claims

1. In mol%, La ２ O ３ 5-70%, B ２ O ３ 0-80%, SiO ２ 0-40%, B ２ O ３ +Al ２ O ３ +SiO ２ 0-80%, Gd ２ O ３ +Ga ２ O ３ +Y ２ O ３ +Yb ２ O ３ + ZrO ２ + TiO ２ +Nb ２ O ５ +Ta ２ O ５ +WO ３ 0 to 85% of MgO+CaO+SrO+BaO, 0 to 15% of MgO+CaO+SrO+BaO, 0 to 35% of ZnO, and 0.01 to 5% of CuO, and having a refractive index nd of 1.81 or more.

2. In mole percent, B ２ O ３ +Al ２ O ３ +SiO ２ 2. The glass article according to claim 1, wherein the glass article contains more than 0 to 80%.

3. In mole percent, Gd ２ O ３ +Ga ２ O ３ +Y ２ O ３ +Yb ２ O ３ + ZrO ２ + TiO ２ +Nb ２ O ５ +Ta ２ O ５ +WO ３ 3. The glass article according to claim 1, wherein the glass article contains more than 0 to 85%.

4. 4. The glass article according to claim 1, further comprising a coloring component comprising an oxide of V, Cr, Mn, Fe, Co, Ni, Mo, Ru, Ce, Pr, or Er in an amount of 0 to 20% by mole.

5. 5. The glass article according to claim 1, wherein the Abbe number νd is 50 or less.

6. 6. The glass article according to claim 1, which has been subjected to chamfering.

7. 7. The glass article according to claim 1, which is for decorative purposes.

8. 8. The glass article according to claim 7, which is a pseudo-gemstone.

9. A decorative article comprising the glass article according to claim 7 or 8.

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