JP2002249338A - Ultraviolet ray absorbing colorless and transparent soda lime silica-base glass, method for manufacturing the same, and glass container formed from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet ray absorbing, colorless, and transparent soda lime silica-base glass which absorbs ultraviolet ray while keeping high light transmittance in visible area, a method for manufacturing the glass, and the glass container in which the content is clearly shown, which prevents the content from coloring, discoloration, fading, degradation of flavors, etc., caused by ultraviolet ray, and is commonly reused as cullets of flint glass. SOLUTION: The ultraviolet ray absorbing, colorless, and transparent soda lime silica glass contains 0.04-0.10 wt.% of vanadium oxide interms of V2 O5 and 0.04-0.13 wt.% of manganese oxide interms of MnO and has 0.6-1.7 weight ratio of V2 O5 /MnO. In the manufacturing method, a batch composition comprising the glass, silica sand, soda ach, limestone, carbon, and mirabilite is melted and added with coloring flits or coloring pellets containing vanadium oxide and coloring flits or coloring pellets containing manganese oxide in a feeder. The glass container is formed of the glass.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colorless and transparent ultraviolet-absorbing soda-lime-silica glass, a method for producing the same, and a glass container obtained by molding the glass. More specifically, the present invention prevents the contents of soft drinks, alcoholic beverages, and the like filled in a glass container from being colored, discolored, and discolored by ultraviolet rays, preventing deterioration of flavor, etc. The present invention relates to a UV-absorbing colorless and transparent soda-lime-silica-based glass that does not have a beautiful color such as beverages of contents, a method for producing the same, and a glass container formed by molding the glass.

[0002]

2. Description of the Related Art Conventionally, brown bottles, green bottles, blue bottles and the like have been used for sake and beer in order to suppress coloring, discoloration, fading and deterioration of flavor of contents such as beverages due to light. Glass containers are widely used. All of these glass containers were dark colored glass bottles, and could not be used for products that wanted to show the color of the contents. Since the color of the contents of the glass container enhances the commercial value and is closely related to the consumer's willingness to purchase, a transparent and colorless glass container with high brightness is required so that the contents look beautiful. However, many transparent and colorless glass containers having high lightness have high transmittance of ultraviolet rays at the same time. When ultraviolet rays pass through the glass container, the contents of the glass container are colored,
Discoloration and fading are apt to occur, and in particular, when the content contains a blue-based, red-based, or yellow-based pigment, discoloration due to photolysis of the pigment is a problem. As the content fades, the color eventually becomes almost colorless, and the commercial value is significantly impaired. In the field of architectural and vehicular sheet glass, glass that absorbs ultraviolet rays is manufactured for the purpose of preventing sunburn and the like.However, these ultraviolet absorbing glasses are colored so that the visibility becomes slightly darker. There's a problem. As a method for solving the above problem, the present inventors have disclosed a method disclosed in
Japanese Patent No. 16270 proposes an ultraviolet-absorbing colorless and transparent soda-lime-silica glass containing V ₂ O ₅ and Se. The soda-lime-silica glass obtained by containing V ₂ O ₅ and Se at a specific ratio can solve the above-mentioned problems. However, when this glass is recycled and used as a cullet of ordinary flint glass, , Se
However, there is a problem from the viewpoint of environmental compatibility, since the resin is colored pink by the reduction coloration. The glass was changed to Se in Mn, there are ultraviolet absorbing colorless soda-lime glass containing V ₂ O ₅ and MnO ₂ as disclosed in JP-A-52-47811. However, this glass
Very small amounts of MnO ₂ relative to the amount of V ₂ O _5, V ₂ O
It is difficult to completely decolor the coloring by ₅ with MnO ₂ . For this reason, the transmittance is high in the visible range, the contents look beautiful at the storefront, the exposure of the contents to ultraviolet rays can be avoided in the distribution process and at the store, and it can be reused as cullet of flint glass in general. There has been a demand for a colorless and transparent ultraviolet-absorbing glass container and a method for easily producing the same.

[0003]

SUMMARY OF THE INVENTION The present invention absorbs ultraviolet rays while maintaining a high light transmittance in the visible region, makes the contents look beautiful, and causes the contents to be colored, discolored, faded, and flavored by the ultraviolet rays. UV-absorbing colorless and transparent soda-lime-silica glass, which can prevent the deterioration of
An object of the present invention is to provide a method for producing the glass and a glass container obtained by molding the glass.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have controlled the contents of sodium sulfate and carbon in the usual basic constituent materials of soda-lime-silica glass. By controlling the oxidation-reduction property, and adding a vanadium oxide-containing colored frit or colored pellet and a manganese oxide-containing colored frit or colored pellet in a feeder, and further adding a cobalt-containing colored frit or colored pellet as needed. It has been found that UV-absorbing colorless and transparent soda-lime-silica glass suitable for recycling can be stably produced, which has a large UV-absorbing rate and a large visible-light transmittance, and based on this finding, completes the present invention. Reached.
That is, according to the present invention, (1) the content of vanadium oxide is V
0.04 to 0.10% by weight in terms of ₂ O ₅ , the content of manganese oxide is 0.04 to 0.13% by weight in terms of MnO, and the weight ratio of vanadium oxide to manganese oxide is V ₂ O ₅ / A UV-absorbing, colorless, transparent soda-lime-silica-based glass characterized by being in the range of 0.6 to 1.7 in terms of MnO, (2) the first in which the content of SO ₃ is 0.15 to 0.30% by weight; Item 3. The ultraviolet-absorbing colorless and transparent soda-lime-silica glass according to item 3,
3. The ultraviolet-absorbing colorless and transparent soda-lime-silica glass according to item 1 or 2, wherein the content of cobalt oxide is 0.0005% by weight or less in terms of CoO, (4) transmission of the sample measured at a thickness of 3.5 mm. In the rate curve, the wavelength 330n
m is 7% or less, and the wavelength is 430 to 430.
There is no absorption in the specific wavelength range in the visible range of 780 nm,
Item 4. An ultraviolet-absorbing colorless and transparent soda-lime-silica glass according to any one of Items 1 to 3 having a transmittance of 88% or more, (5) 100 parts by weight of silica sand, 25 parts of soda ash
~ 36 parts by weight, 23 ~ 33 parts by weight of limestone, carbon 0.
A batch composition containing each material is melted at a ratio of 026 to 0.13 parts by weight and 1.0 to 3.0 parts by weight of sodium sulfate, and in a feeder, a colored frit or a colored pellet containing vanadium oxide is mixed with manganese oxide. A method for producing a colorless frit or a colored pellet containing manganese oxide, comprising: adding a colored frit or a colored pellet containing No. 5 which is produced from a batch composition containing at least 1.5 parts by weight of nitrate ion in 100 parts by weight of the raw material mixture for production.
Item 7. The method for producing a colorless and transparent soda lime silica glass according to item 7, wherein the colored frit added in the feeder contains ₅ to 15% by weight of vanadium oxide in terms of V ₂ O _{5 based on} 100 parts by weight of the molten glass. 0.27 to 2.0 parts by weight of a colored frit contained, 0.25 to 2.0 parts by weight of a colored frit containing manganese oxide in an amount of 5 to 15% by weight in terms of MnO
7. The method for producing a UV-absorbing colorless and transparent soda-lime-silica glass according to item 5 or 6, wherein the colored frit contains 2.7 parts by weight and 0.1 to 1% by weight of cobalt and is 0 to 0.4 parts by weight. (8) 0.13 to 1.0 parts by weight of colored pellets containing 10 to 30% by weight of vanadium oxide in terms of V ₂ O _{5 based on} 100 parts by weight of molten glass, 10-30 in conversion
Colored pellets containing 0.1% by weight of manganese oxide 0.13
Item 5 or Item 6 which is 0 to 0.4 parts by weight of colored pellets containing 0.1 to 1.3 parts by weight and 0.1 to 1% by weight of cobalt.
Item 9. A method for producing a UV-absorbing colorless and transparent soda-lime-silica glass according to item 9, a glass container formed by molding the UV-absorbing colorless and transparent soda-lime-silica glass according to any one of items 1 to 4, and (10) The glass container according to (9), wherein the inner surface is subjected to a dealkalization treatment. Here, vanadium oxide is V ₂ O ₃ , V
Both O ₂ and V ₂ O ₅ are referred to, and the percentage by weight is represented by a value when all the contained vanadium oxide is replaced with V ₂ O ₅ . Manganese oxide refers to both MnO and Mn ₂ O ₃ , and the weight% display indicates that all contained manganese oxide is MnO.
It is represented by a value when it is replaced with O. Furthermore, the value of cobalt oxide is also expressed by a value when all of the contained cobalt oxide is replaced with CoO.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION
Diet of blue, red and yellow pigments contained in the contents
Coloring agents (for example, Food Red No. 104, Food Red 105
No., Food Red No. 106, Food Yellow No. 4, Food Yellow No. 5,
Food Blue No. 1, Food Blue No. 2, β-carotene, hibis
Cass pigments, grape skin pigments and the like are known. ) Characteristics
Investigation revealed that the decomposition of these dyes
Not only the light at the wavelength where the extinction coefficient of the
Energy is small, but energy in the short wavelength region from near ultraviolet to visible
High energy light, that is, 450 nm or less, especially 300 to 40
It is revealed that light with a wavelength of 0 nm also has a significant effect
And the results indicate that all beverages and beer
Relationship between degradation of cole beverages and the wavelength of light that causes them
This was consistent with the study results. That is, visible short to near ultraviolet region
Glass that has excellent absorption in the wavelength range
Suppresses photodeterioration, high glass brightness,
The colorless glass container makes the contents look beautiful
It became clear. The colorless transparent UV-absorbing solution of the present invention
The soda lime silica-based glass converts vanadium oxide to V_TwoO_Five
0.04 to 0.10% by weight of manganese oxide and MnO
0.04 to 0.13% by weight in conversion, and vanadium oxide
The weight ratio of chromium to manganese oxide is V_TwoO _Five/ MnO conversion
0.6 to 1.7.

[0006] Vanadium oxide acts as an ultraviolet absorber and is contained mainly in the form of V ₂ O ₅ in the glass of the present invention, but does not prevent the presence of V ₂ O ₃ and VO _2. . The content ratio of V ₂ O ₃ and VO ₂ to V ₂ O ₅ is as follows:
Although it is not clear that it changes depending on the content of SO ₃ , V ₂
When O ₃ and VO ₂ increase, the glass is colored green and it becomes difficult to erase the color with manganese. Therefore, it is preferable that these are not present. If the content of vanadium oxide is less than 0.04% by weight in terms of V ₂ O ₅ , the ultraviolet absorbing effect may be insufficient. On the other hand, if it exceeds 0.10% by weight, it becomes difficult to erase the color. In consideration of the ultraviolet absorption effect, decoloration, and the like of the glass, the content of vanadium oxide is more preferably 0.05 to 0.09% by weight in terms of V ₂ O ₅ . Manganese oxide contains vanadium oxide contained as an ultraviolet absorber and F which is inevitably introduced from a raw material.
According to e ₂ O _3, an essential component for decolorizing a yellow-green coloration of the glass, SO _3, vanadium oxide, depending on the content of iron oxide, 0.04 to 0.13 wt% in terms of MnO Is contained. Manganese oxide exists in glass as MnO and Mn ₂ O ₃ , and the ratio is not clear, but Mn ³⁺ ions have a decolorizing effect. When the content of manganese oxide is less than 0.04% by weight in terms of MnO,
The effect of the decoloring may be insufficient. Also, 0.1
If it exceeds 3% by weight, reddish purple coloring of excess Mn ³⁺ ion cannot be sufficiently eliminated even if cobalt oxide described below for eliminating the color is contained, or even if the color can be eliminated. The brightness of the glass may be reduced, and the transparency may be impaired. In consideration of the decoloring effect and the like, the content of manganese oxide is more preferably 0.05 to 0.10% by weight in terms of MnO.

The ultraviolet-absorbing, colorless, transparent soda-lime-silica glass of the present invention must further contain vanadium oxide and manganese oxide in a weight ratio of 0.6 to 1.7 in terms of V ₂ O ₅ / MnO. is there. If V ₂ O ₅ / MnO is less than 0.6, the main wavelength (λ _d ) of the glass shifts to the longer wavelength side, and the glass may be colored light pink. Conversely, when V ₂ O ₅ / MnO exceeds 1.7, the main wavelength (λ _d )
May shift to the short wavelength side, and the glass may be colored light yellow green. In order to more reliably obtain the colorless feeling of glass, vanadium oxide and manganese oxide are converted to V ₂ O ₅ / Mn.
More preferably, it is contained in a weight ratio of 0.8 to 1.5 in terms of O. Ultraviolet absorbing colorless and transparent soda-lime-silica glass of the present invention preferably contains a SO ₃ 0.15 to 0.30 wt%. SO ₃ may be a residue in the glass of the fining agent added to the raw material batch in the combination of sodium sulfate and carbon, such that the amount is 0.15 to 0.30% by weight, and The amounts of the oxidizing agent and the reducing agent that govern the redox properties of other raw material batches, frit or pellets can be determined, and the atmosphere of a furnace such as a continuous melting furnace can be adjusted. When SO ₃ content in the glass is less than 0.15 wt%, the glass is biased to a reducing side, V ₂ O ₃ with respect to V ₂ O _5, the ratio of VO ₂ and Fe ₂ O
_As the ratio of FeO to ₃ increases and the ratio of Mn ₂ O _{3 to} MnO decreases, the glass may have a green or blue tint. Conversely, SO ₃ in glass
If the content exceeds 0.30% by weight, seeds may remain in the glass. Considering the prevention of the light green to light blue coloration of the glass and the seeds in the glass, the S in the glass
O ₃ content is more preferably controlled to 0.20 to 0.28 wt%.

[0008] Cobalt oxide is Mn³⁺Red purple by ion
It has the effect of decoloring the color. Contains cobalt oxide
Is not essential, but Mn³⁺If the ions are excessive,
In order to decolor the reddish purple due to
It can be contained in an amount of 0.0005% by weight or less in conversion.
it can. The amount of cobalt oxide exceeds 0.0005% by weight
If this occurs, the brightness will decrease and the transparency of the glass will be impaired.
There is. Considering the transparency of glass, etc.
Content is 0.0004% by weight or less in terms of CoO
More preferably, there is. UV-absorbing colorless and transparent of the present invention
The composition of soda lime silica glass has excellent chemical resistance
There is no danger of devitrification.
Considering easiness, etc., SiO_Two65-75% by weight, A
l_TwoO_Three0-5% by weight, 6-15% by weight of CaO, MgO0
~ 4% by weight, Na_TwoO10-17% by weight, K_TwoO0-4 layers
%, Fe _TwoO_Three0-0.08% by weight, FeO 0-0.01
Wt%, SO_Three0.15 to 0.30% by weight, vanadium oxide
(V_TwoO_Five0.04 to 0.10% by weight, manganese oxide
0.04 to 0.13% by weight (in terms of MnO)
0 to 0.0005% by weight (in terms of CoO)
Is preferred. SiO_TwoIs a glass forming oxide, 65
Preferably, it is contained in an amount of about 75% by weight. SiO_TwoIncluding
If the content is less than 65% by weight, the chemical durability of the glass
May decrease. Conversely, if it exceeds 75% by weight,
There is a tendency for devitrification to occur. Glass chemical durability,
Considering devitrification, etc., SiO 2_TwoContains 68 to 74% by weight
It is more preferred to have.

Al ₂ O ₃ is a glass intermediate oxide, and has an effect of improving the chemical durability of glass. Al ₂ O ₃
Is not essential, but when it is contained, it is preferably at most 5% by weight. Al ₂ O ₃ content of 5% by weight
If it exceeds, melting may be difficult. Considering the chemical durability and melting property of glass, Al ₂ O ₃
More preferably, the content is 4% by weight. CaO is a glass-modified oxide, has the effect of improving the chemical durability of glass, and improves the meltability. CaO is
It is preferable to contain 6 to 15% by weight. When the content of CaO is less than 6% by weight, the chemical durability may be insufficient. On the contrary, when the content exceeds 15% by weight, devitrification tends to occur. Glass chemical durability, meltability,
In consideration of devitrification and the like, CaO is more preferably contained in an amount of 8 to 13% by weight. MgO is a glass-modified oxide and, like CaO, has the effect of improving the chemical durability of glass and also improves the meltability. The content of MgO is not essential, but when it is contained, it is preferably at most 4% by weight. When the content of MgO exceeds 4% by weight, the glass tends to be easily devitrified. Considering the chemical durability, melting property, devitrification property, etc. of glass, MgO is 0.1
More preferably, it is contained in an amount of about 3% by weight. Na ₂ O is a glass-modified oxide and has an effect of promoting the dissolution of the raw material. Preferably, Na ₂ O is contained in an amount of 10 to 17% by weight. If the content of Na ₂ O is less than 10% by weight, it becomes difficult to melt the glass, and if it exceeds 17% by weight, the chemical durability of the glass may be reduced.
Considering the melting property and chemical durability of glass, Na ₂
O is more preferably contained in an amount of 11 to 15% by weight.

K ₂ O is a glass-modified oxide, and Na ₂ O
Similarly to the above, it has the effect of promoting the dissolution of the raw material. K ₂ O
Is not essential, but when it is contained, it is preferably at most 4% by weight. When the content of K ₂ O exceeds 4% by weight, there is a tendency that devitrification tends to occur. Considering the solubility and devitrification of the glass, it is more preferable that K ₂ O is contained in an amount of 0.1 to 3% by weight. Fe ₂ O ₃ is a component inevitably generated from iron contained as an impurity in the silica sand of the raw material batch of glass. The ultraviolet-absorbing colorless and transparent soda lime silica-based glass of the present invention does not need to be contained in the glass, and it is preferable that it is not contained at all. The content of Fe ₂ O ₃ is usually 0.08% by weight or less when silica sand sold as a raw material for glass is used. When the content of Fe ₂ O ₃ exceeds 0.08% by weight, it becomes difficult to eliminate yellowish green coloring by Fe ³⁺ ions with Mn ³⁺ ions. Considering prevention of coloring of glass, etc., Fe ₂ O ₃ is 0.1%.
The content is more preferably not more than 06% by weight, and further preferably not more than 0.04% by weight. FeO is derived from iron contained as an impurity in quartz sand of glass raw material batch,
It is a component that is inevitably generated during the glass melting process. It is an unnecessary component for obtaining the ultraviolet-absorbing colorless and transparent soda lime silica glass of the present invention, and its content is preferably 0.01% by weight or less. FeO content is 0.
If it exceeds 01% by weight, the glass may be bluish. To ensure that the glass is colorless and transparent, FeO
Is more preferably 0.006% by weight or less, and even more preferably 0.004% by weight or less.

By setting the above composition range, the transmittance curve measured at a sample thickness of 3.5 mm has a wavelength of 33
The transmittance at 0 nm is 7% or less, and the wavelength 43
An ultraviolet-absorbing colorless and transparent soda-lime-silica glass having no absorption in a specific wavelength region in the visible region of 0 to 780 nm and having a transmittance of 88% or more can be obtained. Wavelength 3
When the transmittance at 30 nm is 7% or less, when used as a glass container, it is possible to substantially block intrusion of ultraviolet rays that affect contents such as beverages in the container, and color the contents with ultraviolet rays. , Discoloration, discoloration due to decomposition of pigment, deterioration of flavor, and the like can be prevented. Wavelength 330
The transmittance in nm is more preferably 5% or less, further preferably 3% or less. In addition, when there is no absorption in a specific wavelength range in the visible range of wavelengths of 430 to 780 nm and the transmittance is 88% or more, the contents can be seen beautifully when used as a glass container.
The transmittance is 88 in the visible range of wavelength 430 to 780 nm.
%, The transparency of the glass container may be impaired or the glass container may be lightly colored. Further, when the glass of the present invention is used as an architectural or vehicular sheet glass, it is possible to sufficiently exhibit an ultraviolet shielding effect such as sunburn prevention. The colorless transparent soda lime silica glass of the present invention absorbs lightness (Y) as a value obtained by converting data obtained at a thickness of 3.5 mm into a value at a thickness of 10 mm.
It is preferable that it is 80% or more, the main wavelength (λ _d ) is 560 to 585 nm, and the stimulus purity (Pe) is 2.5% or less. In this type of glass having no specific wavelength absorption in the visible region, if the main wavelength (λ _d ) is less than 560 nm, the glass may become bluish, and if it exceeds 585 nm, the glass may become reddish. is there. Further, by controlling the contents and ratios of vanadium oxide and manganese oxide in the glass and the content of cobalt oxide, the value obtained by converting the data obtained at a thickness of 3.5 mm of the sample to a value at a thickness of 10 mm was used as the lightness. (Y) 82% or more, dominant wavelength (λ _d ) 565 to 5
It is possible to obtain a UV-absorbing, colorless, transparent soda-lime-silica glass with a stronger colorlessness having a wavelength of 75 nm and a stimulating purity (Pe) of 2% or less.

One embodiment of the method for producing the ultraviolet-absorbing colorless and transparent soda-lime-silica glass and the glass container of the present invention is as follows. That is, based on 100 parts by weight of silica sand, 25 to 36 parts by weight of soda ash, 23 to 33 parts by weight of limestone, 0.026 to 0.13 parts by weight of carbon (as purity 100% by weight), 1.0 to 3.0 parts of sodium sulfate. A batch composition containing each raw material at a ratio of 0 parts by weight was melted at 1,400 to 1,500 ° C., adjusted to 1,200 to 1,350 ° C. in a working chamber, and 1,270 to 1,350 ° C.
In a feeder at 1,330 ° C., add a colored frit or colored pellet containing vanadium oxide, a colored frit or colored pellet containing manganese oxide, and if necessary, add a colored frit or colored pellet containing cobalt and stir. After that, put the gob into the molding machine,
It is formed into a container at a temperature of 700 to 1,000 ° C. The formed glass container is introduced into an annealing furnace at 500 to 600 ° C. in order to remove strain, and cooled to room temperature in 30 minutes to 2 hours to obtain a product. When forming a sheet glass from the glass of the present invention, casting-press method, float method,
Conventional methods such as a down-draw method and a pull-up method can be used. Incidentally, the ratio of carbon in the above batch composition,
This is a numerical value when the carbon purity is 100% by weight. If the purity of the carbon used is different, the ratio is changed accordingly. The amounts of carbon (purity 100% by weight) and sodium sulfate are 100 parts by weight of silica sand, respectively.
More preferably, the amount is 3 to 0.07 parts by weight, and 1.2 to 2.0 parts by weight. The soda-lime silica glass, contains Al ₂ O ₃ component in the order of typically several wt%, when Al ₂ O ₃ component is contained as an impurity is small in silica sand, the raw materials In addition, the composition can be adjusted by further adding raw materials such as alumina, aluminum hydroxide, and feldspar. When using cullet, adjust the blending ratio of the batch and the amount of colored frit and colored pellets according to the content of SO ₃ , vanadium oxide, manganese oxide, iron oxide, cobalt oxide, etc. in the cullet. Can be. When cobalt oxide is contained in the batch, the amount of the colored frit or colored pellet containing cobalt can be adjusted.

It is preferable that the inner surface of the glass container of the present invention is subjected to a dealkalization treatment. By subjecting the inner surface of the glass container to a dealkalization treatment, the amount of ultraviolet light incident on the contents can be reduced. The mechanism by which this effect appears is not clear, but the effect increases as the light incident angle increases. When a product is displayed, the light incidence angle is relatively large, so that the effect of the dealkalization treatment works advantageously.
Examples of the dealkalization treatment include a treatment using a compound having a fluorinated hydrocarbon group, sulfur dioxide, ammonium sulfate, or the like. Among these, in consideration of handling and the like, a treatment using a compound having a fluorohydrocarbon group and being a gas at normal temperature is preferable. Examples of the compound having a fluorinated hydrocarbon group and having a gaseous state at room temperature include 1,1,
Examples thereof include 1-difluoroethane, 1,1,1,2-tetrafluoroethane, difluoromethane and the like. The temperature of the inner surface of the glass container during the dealkalization treatment is 500
~ 730 ° C. If the temperature of the inner surface of the glass container is less than 500 ° C., the effect of the alkali removal treatment may be insufficient, and if it exceeds 730 ° C., the glass container may be deformed. The temperature of the inner surface of the glass container during the dealkalization treatment is more preferably 580 to 700C.

In the method of the present invention, in the feeder, a colored frit or colored pellet containing vanadium oxide, a colored frit or colored pellet containing manganese oxide, and if necessary, a colored frit or colored pellet containing cobalt. Is added to the molten glass and stirred. The colored frit or colored pellet may contain each coloring component alone or may contain two or more kinds in combination. As the coloring frit to be added in the feeder, a low melting point glass such as a borosilicate glass containing each coloring component can be used. As the colored pellets, those obtained by mixing and granulating each colorant powder and a low melting point glass frit containing no coloring component can be used. These colored frits or colored pellets can be used in any combination. The colored frit or colored pellet containing manganese oxide may be produced from a batch composition containing at least 1.5 parts by weight of nitrate ions (NO ₃ ⁻ ) in 100 parts by weight of the raw material mixture for production. preferable. When the content of nitrate ions in 100 parts by weight of the raw material mixture for producing colored frit or colored pellets is less than 1.5 parts by weight, M with respect to MnO in the obtained glass.
There is a possibility that the ratio of n ₂ O ₃ decreases and a sufficient decoloring effect cannot be obtained. Considering the decoloring effect of Mn ³⁺ ions, the nitrate ion content in 100 parts by weight of the raw material mixture for producing colored frit or colored pellets is more preferably 2.0 parts by weight or more, and the glass is more than necessary. Nitrate ions can be contained in an amount that does not cause oxidization.

In the method of the present invention, the concentration of vanadium oxide in the colored frit containing vanadium oxide added to the molten glass in the feeder is ₅ to 15 in terms of V ₂ O 5.
% By weight. Further, the addition amount of the colored frit containing vanadium oxide is preferably 0.27 to 2.0 parts by weight, and more preferably 0.33 to 1.8 parts by weight based on 100 parts by weight of the molten glass. More preferred.
If the concentration of vanadium oxide in the colored frit containing vanadium oxide is less than 5% by weight in terms of V ₂ O ₅ , it is necessary to increase the amount of the colored frit to be added, the temperature of the molten glass is lowered, and the bubbles are poor. It tends to be. Conversely, a colored frit having a vanadium oxide concentration of more than 15% by weight in terms of V ₂ O ₅ is difficult to produce and needs to be added in a small amount, so that the vanadium oxide in the molten glass can be uniformly dispersed. It is hard to be. If the amount of the colored frit containing vanadium oxide is less than 0.27 parts by weight based on 100 parts by weight of the molten glass, the ultraviolet absorbing effect may be insufficient. The amount of the colored frit containing vanadium oxide was 2.
If the amount exceeds 0 parts by weight, decoloring becomes difficult, and there is a possibility that yellowish green coloration occurs.

In the method of the present invention, the manganese oxide concentration of the colored frit containing manganese oxide to be added to the molten glass in the feeder is preferably 5 to 15% by weight in terms of MnO. Further, the addition amount of the coloring frit containing manganese oxide is preferably 0.27 to 2.7 parts by weight based on 100 parts by weight of the molten glass,
It is more preferable that the amount be 0.33 to 2.0 parts by weight. When the manganese oxide concentration of the colored frit containing manganese oxide is less than 5% by weight in terms of MnO, it is necessary to increase the amount of the colored frit to be added, and the temperature of the molten glass is lowered, and the bubbles tend to be poor. Become. Conversely, a colored frit having a manganese oxide concentration of more than 15% by weight in terms of MnO is difficult to produce and needs to be added in a small amount, so that the dispersion of manganese oxide in the molten glass is difficult to be uniform. If the amount of the colored frit containing manganese oxide is less than 0.27 parts by weight based on 100 parts by weight of the molten glass, the effect of decoloring may be insufficient. When the addition amount of the coloring frit containing manganese oxide exceeds 2.7 parts by weight with respect to 100 parts by weight of the molten glass, the reddish purple coloring of the excess Mn ³⁺ ion is described later for decolorizing the Mn ³⁺ ion. Even if cobalt oxide is contained, the color cannot be sufficiently erased, or even if the color can be erased, the brightness of the glass may be reduced and the transparency may be impaired.

In the method of the present invention, the concentration of vanadium oxide in the colored pellets containing vanadium oxide added to the molten glass in the feeder is 10 to _{3 in} terms of V ₂ O _5.
It is preferably 0% by weight. The amount of the colored pellets containing vanadium oxide was 100
It is preferably from 0.13 to 1.0 part by weight, more preferably from 0.17 to 0.91 part by weight, based on part by weight. When the concentration of vanadium oxide in the colored pellets containing vanadium oxide is less than 10% by weight in terms of V ₂ O ₅ ,
It is necessary to increase the amount of the colored pellets to be added, and the temperature of the molten glass is lowered, and the bubble removal tends to be poor. Conversely, in the case of colored pellets having a vanadium oxide concentration exceeding 30% by weight in terms of V ₂ O ₅ , the ratio of the low melting point glass frit containing no coloring component to the coloring agent powder is reduced, so that the melting property in the feeder is deteriorated. And the dispersion of vanadium oxide in the molten glass is difficult to be uniform. If the added amount of the colored pellets containing vanadium oxide is less than 0.13 parts by weight with respect to 100 parts by weight of the molten glass, the ultraviolet absorbing effect may be insufficient. If the amount of the added colored pellets containing vanadium oxide exceeds 1.0 part by weight with respect to 100 parts by weight of the molten glass, the decoloring becomes difficult, and there is a possibility of yellowish green coloring.

In the method of the present invention, the concentration of manganese oxide in the colored pellets containing manganese oxide added to the molten glass in the feeder is preferably 10 to 30% by weight in terms of MnO. Further, the addition amount of the colored pellets containing manganese oxide is preferably 0.13 to 1.3 parts by weight based on 100 parts by weight of the molten glass,
More preferably, it is 0.17 to 1.0 part by weight. When the manganese oxide concentration of the colored pellets containing manganese oxide is less than 10% by weight in terms of MnO, it is necessary to increase the amount of the colored pellets to be added, and the temperature of the molten glass is lowered, and the bubble removal tends to be poor. Become. Conversely, in the case of colored pellets having a manganese oxide concentration exceeding 30% by weight in terms of MnO, the ratio of the low-melting glass frit containing no coloring component to the coloring agent powder is reduced, so that the meltability in the feeder may be deteriorated. In addition, the dispersion of manganese oxide in the molten glass is difficult to be uniform. If the amount of the colored pellets containing manganese oxide is less than 0.13 parts by weight based on 100 parts by weight of the molten glass, the effect of decoloring may be insufficient. The amount of the colored pellets containing manganese oxide was 10
If the amount exceeds 1.3 parts by weight with respect to 0 parts by weight, excessive Mn
Red-violet coloring of ³⁺ ion, can not be sufficiently decolored even if it contains cobalt oxide described below to decolor this,
Alternatively, even if the color can be erased, the brightness of the glass may be reduced, and the transparency may be impaired.

In the method of the present invention, the cobalt concentration of the colored frit or the colored pellet containing cobalt, which is added to the molten glass in a feeder as required, is 0.1%.
It is preferably from 1 to 1% by weight. The amount of the colored frit or colored pellet containing cobalt is preferably at most 0.4 part by weight, more preferably at most 0.32 part by weight, based on 100 parts by weight of the molten glass. If the cobalt concentration of the colored frit or colored pellet containing cobalt is less than 0.1% by weight,
It is necessary to increase the amount of the colored frit or the colored pellet, and the temperature of the molten glass is lowered, and the bubble removal tends to be poor. Conversely, a colored frit or a colored pellet having a cobalt concentration of more than 1% by weight makes it difficult for cobalt to be uniformly dispersed in the molten glass. The amount of the colored frit or the colored pellet containing cobalt is 10
If the amount exceeds 0.4 part by weight with respect to 0 part by weight, there is a possibility that the color is colored blue. By adding a colored frit or a colored pellet containing cobalt, an ultraviolet-absorbing, colorless, transparent soda-lime-silica glass having a refreshing feeling can be produced.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples and comparative examples, the brightness (Y), dominant wavelength (λ _d ), and stimulus purity (Pe) were 3.5 m.
From a transmittance curve obtained by measuring a mirror-polished sample having a thickness of m with a spectrophotometer [U-3410, Hitachi, Ltd.]
It was calculated based on the CIE method described in JIS Z8701 and converted to a value at 10 mm. The analysis of the glass composition was performed using a fluorescent X-ray analyzer [Rigaku Corporation, 3070]. The ratio between Fe ₂ O ₃ and FeO was calculated from the absorbance at a wavelength of 1,000 nm using a spectrophotometer.
The absorbance of the alcoholic beverage was measured using a spectrophotometer [Shimadzu Corporation, UV-1600]. Example 1 (Manufacture of glass container) 100 parts by weight of Kemerton silica sand, 27.5 parts by weight of soda ash, 27.5 parts by weight of limestone, 0.002 parts by weight of selenium, 0.06 parts by weight of carbon (purity 85% by weight), 1.5 parts by weight of sodium sulfate and 0.00015 parts by weight of cobalt oxide (Co ₃ O ₄ ) were weighed and mixed to prepare a batch composition. This batch composition was introduced into a continuous melting furnace having a melting capacity of 180 tons / day, and was melted at a glass melting temperature of 1,400 ° C. for 24 hours,
Further, in a feeder at 1,270 ° C., 0.4 part by weight of a colored frit containing 10% by weight (in terms of V ₂ O ₅ ) vanadium oxide and 100 parts by weight of molten glass, and 9.
Add 0.5 parts by weight of a colored frit containing 8% by weight (in terms of MnO) of manganese oxide (using sodium nitrate as one component of the raw material for producing the frit), stir to homogenize, then mold, and form an annealing furnace In a line having a volume of 210 mL, vanadium oxide of 0.040 in terms of V ₂ O ₅
% By weight, manganese oxide is 0.049% by weight in terms of MnO, and cobalt oxide is 0.00012% by weight in terms of CoO.
A glass container containing was produced. A measurement sample was cut out from the obtained glass container and polished, and a transmittance curve was obtained with a spectrophotometer. This glass container has a sample thickness of 10 mm
In conversion, the brightness (Y) is 85.2%, and the dominant wavelength (λ _d ) is 56
0.2 nm, stimulus purity (Pe) was 1.2%. 33
At 0 nm, the transmittance was 6.9%. 430-
In the visible region of 780 nm, the transmittance was 88% or more, and no absorption in a specific wavelength region was observed. Examples 2 to 15 and Comparative Examples 1 and 2 Glass containers were manufactured under the same conditions as in Example 1 except that the mixing ratio of the batches and the type and amount of the colored frit were changed, and the physical properties were measured. Comparative Example 3 Physical properties of a normal flint glass container were measured. Table 1 shows the results of Examples 1 to 15 and Comparative Examples 1 to 3. 1 and 2 show transmittance curves of the glasses of Example 10, Comparative Example 2 and Comparative Example 3. FIG.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[Note] Batch composition: Kemerton silica sand 100 parts by weight Soda ash 27.5 parts by weight Limestone 27.5 parts by weight Selenium 0.002 parts by weight Glauberite 1.5 parts by weight Carbon (85% by weight) 0.06 parts by weight Part 0.0015 parts by weight of Co ₃ O ₄ Color frit: contains 10% by weight of vanadium oxide in terms of V ₂ O ₅ contains 8.2% by weight or 9.8% by weight of manganese oxide in terms of MnO contains 0.4% by weight of cobalt selenium Colored pellets containing 1.3% by weight: 20% by weight of vanadium oxide in terms of V ₂ O ₅ 16.4% by weight of manganese oxide in terms of MnO 0.4% by weight of cobalt Other than vanadium oxide, manganese oxide, cobalt oxide and selenium Glass composition of SiO ₂ 71 wt% Al ₂ O ₃ 2 wt% CaO 11.3 wt% MgO 0.15 wt% Na ₂ O 12.5 wt% K ₂ O 1.4 wt% SO ₃ 0.22 weight% Fe ₂ O ₃ 0.024 wt% FeO 0.008 wt% tonal value: 10 mm thickness corresponding value transmittance: 3.5 mm thickness Found Table 1, seen in Figures 1 and 2 As described above, the UV-absorbing colorless and transparent soda lime silica-based glass of the present invention has a transmittance of 330 n in a transmittance curve measured at a sample thickness of 3.5 mm.
m is 7% or less, and 430 to 780 n
In the visible region of m, there is no absorption in a specific wavelength region, the transmittance is 88% or more, and it has the same performance as the glass of Comparative Example 2 containing vanadium oxide and selenium. The glass of Comparative Example 1 having a low content of manganese oxide has a dominant wavelength (λ _d ).
Is 554.7 nm and has a bluish tint. The ordinary flint glass of Comparative Example 3 has a high transmittance of ultraviolet rays. Experimental Example 1 (Dealkaline Treatment of Glass Container) After the glass container of Example 10 was molded and subjected to hot end coating, the temperature of the inner surface of the container was about 630 ° C. Then, a mixed gas of 1,1-difluoroethane and air at a volume ratio of 1: 1 was introduced into the mixture to carry out a dealkalization treatment. Next, annealing was performed in an annealing furnace.
A 30 mm x 20 mm x 5 mm piece of glass is cut out from the center of the bottle bottom of the alkali-treated glass container, and the outer surface side of the glass container is mirror-polished using cerium oxide abrasive having an average particle size of 0.5 m. And the thickness was adjusted to 4.89 mm.
In addition, a similar sample was prepared for a glass container having the same composition but not subjected to the alkali removal treatment. The measurement cell shown in FIG. 3 was manufactured using a quartz glass plate 1, an acrylic resin plate 2, a rubber plate 3, and an epoxy adhesive. The sample 4 subjected to the dealkalization treatment was arranged such that the dealkalized surface, which is the inner surface of the glass container, was the surface that came into contact with water. In addition, the samples that had not been subjected to the alkali removal treatment were also arranged such that the inner surface of the glass container was in contact with water. Spectrophotometer [U-341, Hitachi, Ltd.
0], an integrating sphere was attached to the detector opening, and the light incident angle with respect to the measuring cell filled with distilled water was 0 °, 10 °, 23 °.
The measurement cell was set at angles of 30 °, 30 °, and 40 °, and the transmittance was measured for ultraviolet light having a wavelength of 350 nm, and the results shown in FIG. 4 were obtained. As shown in FIG. 4, the ultraviolet transmittance of the glass of the present invention subjected to the dealkalization treatment is lower than that of the glass of the present invention not subjected to the dealkalization treatment. Experimental Example 2 (Effect of Suppressing Discoloration due to Light) An alcoholic beverage (education 6% by volume) containing food blue No. 1 pigment, which is a food additive, was prepared by the glass bottle manufactured in Example 10 and dealkalized in Experimental Example 1. Each of the treated glass bottle, the glass bottle manufactured in Comparative Example 2, and the normal flint bottle of Comparative Example 3 was filled with 200 mL each, and sealed with a cap. Glass bottles filled with alcoholic beverages,
Each group was divided into three groups, three of which were left outdoors in an unshaded area and exposed to sunlight, and the other group was stored in a cool, dark place. The two groups exposed to sunlight
The amount of ultraviolet irradiation during each exposure to sunlight was measured using an A region ultraviolet meter [Eiko Seiki Co., Ltd.], and the cumulative irradiation amount was 4.8.
Upon reaching MJ / m ² and 11.0MJ / m ^2, were then one group discontinued exposure recovery. After the exposure is completed, the alcoholic beverage in the glass bottle is filtered through a membrane filter having a pore size of 0.45 μm, and the dye has a maximum absorption wavelength of 630 nm.
Was measured. The dye residual ratio is calculated by dividing the absorbance A (t) at the irradiation dose t by the absorbance A (0) of the alcoholic beverage in a cool and dark storage glass bottle not exposed to sunlight, using the average value of the absorbance of each group. Quotient. Dye residual ratio = {A (t) / A (0)} × 100 (%) The results are shown in Table 2.

[0026]

[Table 5]

As can be seen from Table 2, the residual ratio of Food Blue No. 1 in alcoholic beverages determined from the absorbance at 630 nm was the alkalinization treatment of Comparative Example 3 at a cumulative irradiation dose of 11.0 MJ / m ^2. 1% for normal flint bottles without
The glass bottle containing vanadium oxide, cobalt oxide, and selenium of Comparative Example 2 without the alkali removal treatment was 18%, whereas Example 1 without the alkali removal treatment of the present invention was used.
The glass bottle of No. 0 was 65%, and the glass bottle of Experimental Example 1 subjected to the dealkalization treatment of the present invention was 73%. In particular, it can be seen that the glass bottle of the present invention that has been subjected to the dealkalization treatment has a higher dye remaining rate.

[0028]

The ultraviolet-absorbing colorless and transparent soda-lime-silica glass of the present invention has an excellent ultraviolet-absorbing effect, especially in the near-ultraviolet region to the visible short-wavelength region. Coloring, discoloration,
A colorless and transparent glass container that prevents fading, deterioration of flavor, and the like, and makes the color of the contents in the glass container look more beautiful than conventional UV-absorbing colored glass containers can be obtained. Further, when the glass sheet is used for architectural purposes, vehicles, and the like, it is possible to obtain a colorless and transparent glass sheet having a bright field of view while providing an ultraviolet shielding effect for preventing sunburn.

[Brief description of the drawings]

FIG. 1 is a transmittance curve in a wavelength range of 250 to 780 nm.

FIG. 2 is a transmittance curve in a wavelength range of 250 to 500 nm.

FIG. 3 is an explanatory diagram showing the shape of a measuring cell and a measuring method used in an experimental example.

FIG. 4 is a graph showing a relationship between a light incident angle and a transmittance.

[Explanation of symbols]

 1 Quartz glass plate 2 Acrylic resin plate 3 Rubber plate 4 Sample

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C03C 4/08 B65D 1/00 A (72) Inventor Kazuhito Ikusei 2-chome Dojima, Kita-ku, Osaka-shi, Osaka No. 1-5 Suntory Co., Ltd. (72) Masao Kitayama 2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Japan Yamamura Glass Co., Ltd. (72) Hidekazu Sakae 2-21 Hamamatsubara-cho, Nishinomiya-shi, Hyogo Japan F-term (reference) in Yamamura Glass Co., Ltd. ED03 EE03 EE04 EF01 EG01 FA01 FB01 FC01 FD01 FE01 FF02 FG01 FH01 FJ01 FK01 FL01 GA01 GB02 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH10 HH11 HH12 HH13 HH15 HH17 JJ 01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM01 NN13

Claims (10)

[Claims] 1. The content of vanadium oxide is 0.04 to 0.10% by weight in terms of V ₂ O ₅ , and the content of manganese oxide is M
0.04 to 0.13% by weight in terms of nO, and the weight ratio of vanadium oxide to manganese oxide is 0.6 in terms of V ₂ O ₅ / MnO.
A UV-absorbing, colorless, transparent soda-lime-silica-based glass, characterized in that 2. The ultraviolet-absorbing colorless and transparent soda lime silica glass according to claim 1, wherein the content of SO ₃ is 0.15 to 0.30% by weight. 3. The colorless transparent soda-lime silica glass according to claim 1, wherein the content of cobalt oxide is 0.0005% by weight or less in terms of CoO. 4. In a transmittance curve measured at a sample thickness of 3.5 mm, the transmittance at a wavelength of 330 nm is 7% or less, and there is no absorption in a specific wavelength range in a visible wavelength range of 430 to 780 nm, and 88%. The ultraviolet-absorbing colorless and transparent soda-lime-silica glass according to any one of claims 1 to 3, which has the above transmittance. 5. A soda ash 25 based on 100 parts by weight of silica sand.
~ 36 parts by weight, 23 ~ 33 parts by weight of limestone, carbon 0.
A batch composition containing each material is melted at a ratio of 026 to 0.13 parts by weight and 1.0 to 3.0 parts by weight of sodium sulfate, and in a feeder, a colored frit or a colored pellet containing vanadium oxide is mixed with manganese oxide. A method for producing an ultraviolet-absorbing, colorless, transparent soda-lime-silica-based glass, comprising adding a colored frit or a colored pellet containing, stirring, and then molding. 6. The colored frit or colored pellet containing manganese oxide is produced from a batch composition containing at least 1.5 parts by weight of nitrate ions in 100 parts by weight of the raw material mixture for production. 6. The method for producing a colorless transparent soda lime silica-based glass according to 5 above. 7. The coloring frit added in the feeder is ₅ to 5 parts in terms of V ₂ O _{5 based on} 100 parts by weight of the molten glass.
0.27 to 2.0 parts by weight of a colored frit containing 15% by weight of vanadium oxide, 0.27 to 2.7 parts by weight of a colored frit containing 5 to 15% by weight of manganese oxide in terms of MnO, and 0.1. The method for producing a UV-absorbing colorless and transparent soda lime silica glass according to claim 5 or 6, wherein the colored frit contains 0 to 0.4 parts by weight of cobalt containing 1 to 1% by weight of cobalt. 8. The coloring pellets added in the feeder are 10 parts by weight based on 100 parts by weight of molten glass in terms of V ₂ O _5.
0.13 to 1.0 parts by weight of colored pellets containing up to 30% by weight of vanadium oxide, 10 to 30% by weight in terms of MnO
0.13 to 1.3 colored pellets containing manganese oxide
7. A colored pellet containing 0.1 to 1% by weight of cobalt and 0.1 to 1% by weight of 0 to 0.4% by weight.
The method for producing the ultraviolet-absorbing colorless and transparent soda-lime-silica glass according to the above. 9. A glass container formed by molding the ultraviolet-absorbing colorless and transparent soda-lime-silica glass according to any one of claims 1 to 4. 10. The glass container according to claim 9, wherein the inner surface is subjected to a dealkalization treatment.