阅读说明：本技术 装饰用玻璃物品 (Glass article for decoration ) 是由 藤田直树 西田晋作 榎本朋子 于 2020-03-18 设计创作，主要内容包括：本发明提供一种亮光和火彩优异的装饰用玻璃物品。该装饰用玻璃物品的特征在于,实质上不含有氧化铅,折射率为1.9以上,且阿贝数为42以下。(The invention provides a decorative glass article having excellent brilliance and fire. The decorative glass article is characterized by containing substantially no lead oxide, having a refractive index of 1.9 or more and an Abbe number of 42 or less.)

1. A glass article for decoration, characterized in that,

substantially contains no lead oxide, has a refractive index of 1.9 or more and an Abbe number of 42 or less.

2. The ornamental glass article according to claim 1,

degree of coloration lambda₅Is 395 or less.

3. The ornamental glass article according to claim 1 or 2,

the content of bismuth oxide is 30% or less in mol%.

4. A decorative glass article according to any one of claims 1 to 3,

contains, in mole%: 0-63% of La₂O₃0 to 40% of B₂O₃0 to 50% of Al₂O₃0 to 40% of ZrO₂0 to 80% of Nb₂O₅0 to 60 of Gd₂O₃0 to 60% of Ta₂O₅0.1 to 100% of La₂O₃+Nb₂O₅+Ta₂O₅+Gd₂O₃。

5. The ornamental glass article according to claim 4,

in mol percent, 0 to 85 percent of TiO₂。

6. The decorative glass article according to any one of claims 1 to 5,

the decorative glass article is subjected to chamfering.

7. The decorative glass article according to any one of claims 1 to 6,

the decorative glass article is a simulated gemstone.

8. An ornament which is characterized in that the ornament is provided with a base,

a decorative glass article according to any one of claims 1 to 7.

Technical Field

The present invention relates to a decorative glass article suitable for decorative use in rings, pendants, earrings, bracelets and the like.

Background

According to the definition of japan niter industrial association, crystal glass is "glass containing lead oxide as a main component and glass containing potassium oxide, barium oxide, titanium oxide, and the like as main components, has high transparency and a refractive index nd of 1.52 or more, and is characterized by glossy and beautiful brilliance and clear and crisp timbre". These crystal glasses are excellent in brightness, transparency, echo, thickness, processability, etc., and are useful for ornaments (jewels, artworks, tableware, etc.).

However, since lead-containing crystal glasses are harmful to the human body and are easily damaged, crystal glasses substantially free of lead have been developed (patent documents 1 and 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 2588468

Patent document 2: japanese patent No. 4950876

Disclosure of Invention

Technical problem to be solved by the invention

The lead-free crystal glass described in patent document 2 cannot provide sufficient brightness as a decorative article. In addition, the bright light of iridescence called "fire" also tends to be weak.

In view of the above circumstances, an object of the present invention is to provide a decorative glass article excellent in gloss and fire.

Means for solving the problems

The decorative glass article of the present invention is characterized by containing substantially no lead oxide, having a refractive index of 1.9 or more and an Abbe number of 40 or less. Since the glass article of the present invention has a high refractive index, the difference in refractive index between the inside and the outside (atmosphere) of the glass article becomes large, and light is easily reflected inside the glass article. As a result, a sufficient gloss as a decorative glass article can be easily obtained. In addition, the glass article of the present invention has a small abbe number and a high dispersion, and therefore, it is easy to develop a sparkle. In the present specification, "substantially not contained" means that the glass composition is not intentionally contained, and the incorporation of inevitable impurities is not excluded. Objectively, this means that the content is less than 0.1% in mol%.

Coloring degree lambda of the glass article for decoration of the present invention₅Preferably 395 or less. Thus, visible light is easily transmitted, and thus, colorless and transparent are easily obtained. Note that the "degree of coloration λ₅"represents the shortest wavelength (nm) at which the light transmittance is 5% in a transmittance curve at a thickness of 10 mm.

In the decorative glass article of the present invention, the content of bismuth oxide is preferably 30% or less in mol%. When bismuth oxide is contained, the glass article tends to be excessively colored and the fire color tends to be deteriorated. Therefore, by reducing the content of bismuth oxide, a glass article excellent in fire color can be easily produced.

The decorative glass article of the present invention preferably contains, in mol%: 0-63% of La₂O₃0 to 40% of B₂O₃0 to 50% of Al₂O₃0 to 40% of ZrO₂0 to 80% of Nb₂O₅0 to 60 of Gd₂O₃0 to 60% of Ta₂O₅And 0.1 to 100% of La₂O₃+Nb₂O₅+Ta₂O₅+Gd₂O₃. By defining the glass composition in this way, a glass article having desired optical constants can be easily obtainedAnd (5) preparing the product.

The decorative glass article of the present invention preferably further contains, in mol%: 0-85% of TiO₂。

The decorative glass article of the present invention is preferably subjected to chamfering. Thus, light is easily reflected inside the glass article, and the brightness can be improved.

The glass article for decoration of the present invention is suitable as a simulated gem.

The decoration of the present invention is characterized by comprising the decorative glass article.

Effects of the invention

According to the present invention, a decorative glass article having excellent brilliance and fire can be provided.

Drawings

FIG. 1 is a plan view of samples No.8, 34 and 35 in the examples.

Detailed Description

The decorative glass article of the present invention has a refractive index (nd) of 1.9 or more, preferably 2.0 or more, 2.1 or more, 2.2 or more, and particularly preferably 2.25 or more. Thus, the difference in refractive index between the inside and the outside (atmosphere) of the glass article becomes large, and light is easily reflected inside the glass article. As a result, a sufficient gloss as a decorative glass article can be easily obtained. The upper limit of the refractive index is not particularly limited, but if it is too large, the vitrification becomes unstable, and therefore, it is preferably 2.6 or less, 2.5 or less, and particularly preferably 2.4 or less.

The abbe number (ν d) of the glass article for decoration of the present invention is preferably 42 or less, 40 or less, 35 or less, 30 or less, and particularly preferably 25 or less. Thus, the glass article becomes highly dispersed and easily exhibits a sparkle. The lower limit of the abbe number is not particularly limited, but if it is too small, the vitrification becomes unstable, and therefore, it is preferably 10 or more, and particularly preferably 15 or more.

The composition of the decorative glass article of the present invention is not particularly limited as long as it has the above optical properties, and examples thereof include, in mol%: 0-63% of La₂O₃0 to 40% of B₂O₃0 to 50% of Al₂O₃0 to 40% of ZrO₂0 to 80% of Nb₂O₅0 to 60 of Gd₂O₃0 to 60% of Ta₂O₅0.1 to 100% of La₂O₃+Nb₂O₅+Ta₂O₅+Gd₂O₃. The reason why the glass composition is limited in this manner will be described below. In the following description of the content of each component, "%" means "% by mole" unless otherwise specified.

La₂O₃The glass skeleton is a component that forms a glass skeleton and increases the refractive index without decreasing the transmittance. In addition, the weather resistance is also improved. La₂O₃The content of (B) is preferably 0 to 63%, 0 to 60%, and particularly preferably 1 to 55%. If La is present₂O₃If the content of (b) is too small, the above-mentioned effects are hardly obtained. On the other hand, if La₂O₃When the content of (B) is too large, vitrification becomes difficult.

Nb₂O₅The component is a component having a large effect of increasing the refractive index, and is a component having a high dispersion by decreasing the Abbe number. In addition, the glass transition temperature is increased. Nb₂O₅The content of (B) is 0 to 80%, 1 to 78%, 5 to 75%, 10 to 73%, particularly preferably 20 to 70%. If Nb₂O₅When the content of (B) is too large, vitrification becomes difficult.

Gd₂O₃Is a component for increasing the refractive index. In addition, the weather resistance is also improved. However, if Gd₂O₃When the content of (B) is too large, vitrification becomes difficult. Thus, Gd₂O₃The content of (b) is preferably 0 to 60%, 0.1 to 60%, 1 to 50%, 2 to 45%, and particularly preferably 3 to 40%.

Ta₂O₅Is a component having a large effect of increasing the refractive index. However, if Ta₂O₅When the content of (b) is too large, vitrification becomes difficult and the raw material cost tends to be high. Thus, Ta₂O₅The content of (b) is preferably 0 to 60%, 0.1 to 60%, 1 to 50%, 2 to 45%, particularly preferably 0 to 60%, particularly preferably 2 to 45%3 to 40 percent.

B₂O₃Is a glass skeleton and is a component for widening the vitrification range. However, if B₂O₃When the content of (b) is too large, the refractive index decreases, and it becomes difficult to obtain desired optical characteristics. Thus, B₂O₃The content is preferably 0 to 40%, 0.1 to 40%, 1 to 30%, 2 to 25%, and particularly preferably 3 to 20%.

Al₂O₃Is a component which forms a glass skeleton and expands the vitrification range. However, if Al₂O₃When the content of (b) is too large, the refractive index decreases, and it becomes difficult to obtain desired optical characteristics. Thus, Al₂O₃The content is preferably 0 to 50%, 0.1 to 40%, 1 to 30%, 2 to 25%, and particularly preferably 3 to 20%.

ZrO₂Is a component for increasing the refractive index. In addition, since the glass skeleton is formed as an intermediate oxide, the vitrification range is widened. However, if ZrO₂When the content (c) is too large, vitrification becomes difficult and the melting temperature becomes too high. Thus, ZrO₂The content of (b) is preferably 0 to 40%, 0.1 to 40%, 1 to 30%, 2 to 25%, and particularly preferably 3 to 20%.

La₂O₃+Nb₂O₅+Ta₂O₅+Gd₂O₃The content of (b) is preferably 0.1 to 100%, more preferably 10 to 95%, and particularly preferably 20 to 90%. If La is present₂O₃+Nb₂O₅+Ta₂O₅+Gd₂O₃If the amount is too small, it becomes difficult to obtain a desired refractive index and Abbe number.

The decorative glass article of the present invention may contain the following components in addition to the above components.

TiO₂Is a component having a large effect of increasing the refractive index, and also has an effect of improving chemical durability. In addition, the Abbe number is reduced to achieve high dispersion. TiO 2₂The content of (b) is preferably 0 to 85%, 0.1 to 83%, 5 to 80%, 10 to 80%, 30 to 77%, and particularly preferably 50 to 75%. If TiO is present₂When the content of (B) is too large, thenSince the absorption edge shifts to the longer wavelength side, the transmittance of visible light (particularly visible light in the short wavelength region) tends to decrease. In addition, vitrification is difficult.

The glass used for the decorative glass article of the present invention may contain a coloring component other than the above-described coloring components such as transition metal oxides and rare earth oxides in order to impart a desired color tone to the glass. Specifically, the transition metal oxide includes Cr₂O₃、Mn₂O₃、Fe₂O₃、CoO、NiO、CuO、V₂O₅、MoO₃、RuO₂And the like. Examples of the rare earth oxide include CeO₂、Nd₂O₃、Eu₂O₃、Tb₂O₃、Dy₂O₃、Er₂O₃And the like. These transition metal oxides and rare earth oxides may be contained alone or in an amount of 2 or more. The content (total amount when 2 or more of these transition metal oxides and rare earth oxides are contained) of these transition metal oxides and rare earth oxides is preferably 0 to 5%, 0.001 to 3%, 0.01 to 2%, and particularly preferably 0.02 to 1%. Depending on the components contained in the composition, the coloring may become too strong, and the visible light transmittance may be lowered, so that desired bright light or sparkle cannot be obtained. In this case, the content of the transition metal oxide and the rare earth oxide may be set to less than 1%, 0.5% or less, and further 0.1% or less.

The glass used for the decorative glass article of the present invention may contain SiO in an amount of 10% or less, respectively, in addition to the above components, in order to widen the vitrification range₂ZnO, MgO, CaO, SrO, BaO, etc.

When bismuth oxide (Bi) is contained₂O₃) In the case of glass, the glass article tends to be excessively colored and the fire color tends to be deteriorated. Therefore, the content of bismuth oxide in the decorative glass article of the present invention is preferably 30% or less, 20% or less, 10% or less, particularly preferably 1% or less, and most preferably substantially none, in mol%.

The glass article for decoration of the present invention does not substantially contain lead oxide harmful to the human body.

The decorative glass article of the present invention comprises La actively₂O₃、Nb₂O₅、B₂O₃And the like, thereby suppressing the occurrence of unreasonable crystallization during glass production and facilitating the increase in the size (for example, 2mm or more, 3mm or more, 4mm or more, and particularly 5mm or more) of the glass article.

The coloring degree lambda of the glass used for the decorative glass article of the present invention₅Preferably 395, 390, 380 or less, and particularly preferably 370 or less. Thus, since visible light is easily transmitted, colorless and transparent glass can be easily obtained. In addition, the brightness and the fire color are easy to improve.

The higher the density of the glass used for the decorative glass article of the present invention is, the more the sense of thickness of the appearance is increased, and the higher the sense of quality as a decorative glass article (particularly, a glass article for jewelry) is improved, and therefore, this is preferable. The density of the glass is preferably 3g/cm, for example³Above, 4g/cm³Above, particularly preferably 5g/cm³The above.

The glass article for decoration of the present invention can be used for ornaments such as jewel ornaments, artworks, tableware, etc. For example, a simulated gem can be attached to a decorative article (gem ornament) such as a ring, a pendant, an earring, or a bracelet. The shape of the decorative glass article is not particularly limited, and examples thereof include a spherical shape, an ellipsoidal shape, and a polyhedral shape.

The decorative glass article of the present invention is preferably subjected to chamfering such as so-called brightening. Thus, the light is easily reflected inside the glass article, and the brilliance can be improved, and the artificial gem is particularly suitable.

Examples

Hereinafter, the decorative glass article of the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

Tables 1 to 4 show examples (Nos. 1 to 33) and comparative examples (Nos. 34 to 35) of the present invention.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

First, raw materials were prepared into glass compositions shown in the table, and raw material batches were prepared. The resulting batch of raw materials was melted to homogeneity and quenched to provide glass samples. The melting temperature is 1500-2000 ℃ for sample No. 1-33 and 1400-1500 ℃ for sample No. 34-35. The obtained glass sample was annealed at a temperature near the glass transition temperature (450 to 700 ℃ C.), and then subjected to refractive index (nd), Abbe number (. nu.d) and coloring degree (. lamda.) by the following methods₅) Measurement of (1) and appearance evaluation (lightness, fire, hue).

The glass sample was subjected to right angle polishing for refractive index (nd) and Abbe number (. nu.d), and measured using KPR-2000 (manufactured by Shimadzu corporation). The refractive index (nd) was evaluated by a measurement value with respect to a helium lamp d line (587.6 nm). The abbe number (ν d) is calculated from the formula { (nd-1)/(nF-nC) } of the abbe number (ν d) using the values of the refractive index of the d line and the refractive indices of the F line (486.1nm) and C line (656.3nm) of the hydrogen lamp.

With respect to the degree of coloration (. lamda.)₅) The spectral transmittance was measured for a glass sample ground to a thickness of 10. + -. 0.1mm, and a wavelength showing a transmittance of 5% in the obtained transmittance curve was used. The spectral transmittance is expressed in the followingV-670 manufactured by Spectroscopy Ltd.

The appearance evaluation was performed as follows. First, each sample was brightly processed so that the planar shape thereof became about 5 to 7mm phi. Next, the glass sample after processing was evaluated for brightness and fire by visual observation under a fluorescent lamp light source. Evaluation was performed according to 4 grades shown below. Further, the color tone was evaluated by visual observation. Further, fig. 1 shows planar photographs of samples nos. 8, 34 and 35.

[ Brightness ]

Very good: the bright light can be seen and is very strong.

O: bright light can be seen.

And (delta): a faint bright light can be seen.

X: little brilliance (to the same extent as a glazing) was seen.

[ fire-coloured glaze ]

Very good: iridescent (various colors) bright light can be seen.

O: iridescent bright light can be seen, but the number of colors is small.

And (delta): a faint iridescent glow can be seen.

X: little iridescent bright light is visible.

As is clear from tables 1 to 4, the samples Nos. 1 to 33 of the examples had a refractive index of 1.90 or more and an Abbe number of 41.4 or less, and were excellent in the brilliance and the sparkle. On the other hand, comparative example samples No.34 to 35 had a refractive index as low as 1.56 or less and an Abbe number as high as 45 or more, and thus were inferior in lightness and color.