JPH11116270A - Ultraviolet-ray absorbing colorless transparent soda lime-silica glass, its production and glass bottle obtained by molding same - Google Patents
Ultraviolet-ray absorbing colorless transparent soda lime-silica glass, its production and glass bottle obtained by molding sameInfo
- Publication number
- JPH11116270A JPH11116270A JP27600897A JP27600897A JPH11116270A JP H11116270 A JPH11116270 A JP H11116270A JP 27600897 A JP27600897 A JP 27600897A JP 27600897 A JP27600897 A JP 27600897A JP H11116270 A JPH11116270 A JP H11116270A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- glass
- colored
- colorless
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 107
- 239000005361 soda-lime glass Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000465 moulding Methods 0.000 title claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004576 sand Substances 0.000 claims abstract description 11
- 235000019738 Limestone Nutrition 0.000 claims abstract description 8
- 239000006028 limestone Substances 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 8
- 238000002834 transmittance Methods 0.000 claims description 43
- 239000006060 molten glass Substances 0.000 claims description 26
- 238000004040 coloring Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 230000006866 deterioration Effects 0.000 abstract description 11
- 239000000796 flavoring agent Substances 0.000 abstract description 10
- 235000019634 flavors Nutrition 0.000 abstract description 8
- 238000005562 fading Methods 0.000 abstract description 3
- 239000011669 selenium Substances 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 16
- 235000013334 alcoholic beverage Nutrition 0.000 description 15
- 230000001186 cumulative effect Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 229910052711 selenium Inorganic materials 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 5
- 235000013361 beverage Nutrition 0.000 description 5
- 235000009508 confectionery Nutrition 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006103 coloring component Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- SXQCTESRRZBPHJ-UHFFFAOYSA-M lissamine rhodamine Chemical compound [Na+].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O SXQCTESRRZBPHJ-UHFFFAOYSA-M 0.000 description 4
- 206010042496 Sunburn Diseases 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000001055 blue pigment Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000002864 food coloring agent Nutrition 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 241000257161 Calliphoridae Species 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000005308 flint glass Substances 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 235000019990 fruit wine Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 235000014214 soft drink Nutrition 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000001052 yellow pigment Substances 0.000 description 2
- 235000005940 Centaurea cyanus Nutrition 0.000 description 1
- 235000005206 Hibiscus Nutrition 0.000 description 1
- 235000007185 Hibiscus lunariifolius Nutrition 0.000 description 1
- 244000284380 Hibiscus rosa sinensis Species 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000013734 beta-carotene Nutrition 0.000 description 1
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 description 1
- 239000011648 beta-carotene Substances 0.000 description 1
- 229960002747 betacarotene Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- VQHHOXOLUXRQFQ-UHFFFAOYSA-L dipotassium;4,5,6,7-tetrachloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [K+].[K+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 VQHHOXOLUXRQFQ-UHFFFAOYSA-L 0.000 description 1
- JFVXEJADITYJHK-UHFFFAOYSA-L disodium 2-(3-hydroxy-5-sulfonato-1H-indol-2-yl)-3-oxoindole-5-sulfonate Chemical compound [Na+].[Na+].Oc1c([nH]c2ccc(cc12)S([O-])(=O)=O)C1=Nc2ccc(cc2C1=O)S([O-])(=O)=O JFVXEJADITYJHK-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003280 down draw process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000576 food coloring agent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/10—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce uniformly-coloured transparent products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/08—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths
- C03C4/085—Compositions for glass with special properties for glass selectively absorbing radiation of specified wave lengths for ultraviolet absorbing glass
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、紫外線吸収無色透
明ソーダライムシリカ系ガラス、その製造方法及び該ガ
ラスを成形してなるガラス瓶に関する。さらに詳しく
は、本発明は、ガラス瓶内に詰められる清涼飲料、アル
コール飲料等の内容物の紫外線による変色或いは褪色や
香味等の劣化を防止し、かつ内容物の飲料の色がより美
しく見える紫外線吸収無色透明ソーダライムシリカ系ガ
ラス、その製造方法及び該ガラスを成形してなるガラス
瓶に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-absorbing colorless and transparent soda-lime-silica glass, a method for producing the same, and a glass bottle obtained by molding the glass. More specifically, the present invention prevents the discoloration or discoloration or deterioration of flavors and the like of contents such as soft drinks and alcoholic beverages packed in a glass bottle due to ultraviolet rays, and absorbs ultraviolet rays so that the beverage of the contents looks more beautiful. The present invention relates to a colorless and transparent soda lime silica glass, a method for producing the same, and a glass bottle obtained by molding the glass.
【０００２】[0002]
【従来の技術】従来、光による飲料等の内容物の褪色或
いは劣化を抑制するために、清酒用やビール用には、茶
色瓶、緑色瓶、或いは青色瓶が広く用いられている。こ
れらの瓶は、いずれも濃色に着色されたガラス瓶であ
り、瓶内の内容物の色を見せようとする商品には使用す
ることができなかった。ガラス瓶の内容物の色は、商品
価値を高め、消費者の購買意欲をそそるため、内容物が
より美しく見えるように、明度の高い透明で無色のガラ
ス瓶が求められている。しかし、明度が高く透明で無色
のガラスは、同時に紫外線の透過率が高いものが多い。
ガラス瓶が紫外線を透過すると、ガラス瓶の内容物が褪
色しやすく、特に青色系、赤色系及び黄色系の色素が光
分解によって褪色しやすい。内容物の褪色が進むと、つ
いには無色に近い色となってしまい、商品価値が著しく
損なわれ、消費者の苦情の対象ともなってしまう。ま
た、建築用や車両用板ガラスの分野では、日焼け防止等
の目的で紫外線を吸収するガラスが製造されているが、
これらの紫外線吸収ガラスは着色しており、またそのた
めに視界がやや暗くなる等の問題がある。上記の課題を
解決する手段として、特公昭４４−１４８２４号公報に
は、Ｖ2Ｏ5とＳｅを共に含有する紫外線遮断無色中空容
器ガラス用フリットが開示されている。しかし、このフ
リットは、バナジウムとセレンが同一フリット中に分散
されているため、１,２５０〜１,３３０℃のフィーダー
に添加した際に、バナジウムが５価から４価若しくは３
価へ還元され、セレンが０価から２価へ酸化される酸化
還元反応が起こり易く、その結果、ガラスが緑色乃至深
緑色に着色する傾向がある。また、特開昭５２−４７８
１１号公報には、Ｖ2Ｏ5とＳｅを共に含有する紫外線吸
収無色ソーダ石灰ガラスが開示されている。しかし、こ
のガラスは、Ｖ2Ｏ5の量に対してＳｅの量が極めて少な
く、Ｖ2Ｏ5による着色をＳｅで完全に消色することは困
難である。また、Ｖ2Ｏ5とＳｅを共に含む原料バッチ
を、通常の方法で溶融してガラス製品を得るためには、
経済性に大きな問題がある。このため、可視域において
は透過率が高く、店頭において内容物が美しく見え、流
通過程や店頭においては内容物への紫外線の露光を避け
ることができる無色透明の紫外線吸収性ガラス瓶及びそ
の容易な製造方法が求められていた。2. Description of the Related Art Conventionally, brown bottles, green bottles, and blue bottles have been widely used for sake and beer in order to suppress fading or deterioration of contents such as beverages due to light. These bottles are all glass bottles that are colored dark and cannot be used for products that attempt to show the color of the contents in the bottle. The color of the contents of the glass bottle increases the value of the product and invites consumers to purchase. In order to make the contents look more beautiful, a transparent and colorless glass bottle with high brightness is required. However, many transparent and colorless glasses with high brightness have high transmittance of ultraviolet rays at the same time.
When the glass bottle transmits ultraviolet light, the contents of the glass bottle are easily discolored, and in particular, blue, red and yellow pigments are easily discolored by photolysis. As the content fades, it eventually becomes a colorless color, and the commercial value is significantly impaired, and it becomes a subject of consumer complaints. In the field of architectural and vehicular sheet glass, glass that absorbs ultraviolet rays for the purpose of preventing sunburn is manufactured.
These ultraviolet absorbing glasses are colored, and therefore have a problem that the field of view becomes slightly dark. As a means for solving the above-mentioned problems, Japanese Patent Publication No. 44-14824 discloses a frit for a glass for a colorless hollow container for ultraviolet shielding which contains both V 2 O 5 and Se. However, since vanadium and selenium are dispersed in the same frit, vanadium becomes pentavalent to tetravalent or trivalent when added to a feeder at 1,250 to 1,330 ° C.
Oxidation-reduction reaction in which selenium is reduced to zero and selenium is oxidized from zero to two is likely to occur, and as a result, the glass tends to be colored from green to dark green. Further, Japanese Patent Application Laid-Open No. 52-478
No. 11 discloses an ultraviolet-absorbing colorless soda-lime glass containing both V 2 O 5 and Se. However, this glass is very small amount of Se relative to the amount of V 2 O 5, it is difficult to completely decolorized coloration due V 2 O 5 in Se. Further, in order to obtain a glass product by melting a raw material batch containing both V 2 O 5 and Se by an ordinary method,
There is a big problem in economics. For this reason, the transmittance is high in the visible region, the contents look beautiful at the storefront, and the colorless and transparent UV-absorbing glass bottle capable of avoiding the exposure of the contents to ultraviolet light during the distribution process and the storefront, and its easy production. A way was sought.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、可視域にお
いて高い光線透過率を保ちながら、紫外線を吸収し、内
容物が美しく見えるとともに、内容物の紫外線による褪
色や香味等の劣化を防止することができる紫外線吸収無
色透明ソーダライムシリカ系ガラス、その製造方法及び
該ガラスを成形してなるガラス瓶を提供することを目的
としてなされたものである。SUMMARY OF THE INVENTION The present invention absorbs ultraviolet rays while maintaining a high light transmittance in the visible range, makes the contents look beautiful, and prevents the contents from deteriorating due to the ultraviolet rays and deterioration of flavor and the like. An object of the present invention is to provide an ultraviolet-absorbing colorless and transparent soda-lime-silica glass, a method for producing the same, and a glass bottle obtained by molding the glass.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意研究を重ねた結果、ソーダライムシ
リカ系ガラスの通常の基本構成原料において、芒硝の含
有量を厳密にコントロールしてレドックスナンバー（バ
ッチの酸化還元の程度を示す指数）を制御し、かつフィ
ーダーにおいてＶ2Ｏ5含有着色フリット、Ｓｅ含有着色
フリット、及び必要に応じてＣｏ含有着色フリットを添
加することにより、紫外線の吸収率と可視光線の透過率
の大きい紫外線吸収無色透明ソーダライムシリカ系ガラ
スを安定して製造し得ることを見出し、この知見に基づ
いて本発明を完成するに至った。即ち、本発明は、
（１）試料の厚み３.５mmで測定した透過率曲線におい
て、波長３１５ｎｍにおける透過率が１.５％以下であ
り、かつ４３０〜７８０ｎｍの可視域において特定波長
域の吸収がなく、透過率が８８％以上であることを特徴
とする紫外線吸収無色透明ソーダライムシリカ系ガラ
ス、（２）Ｖ2Ｏ5及びＳｅが、Ｖ2Ｏ5／Ｓｅ＝２〜７の
重量比で含有される第(１)項に記載の紫外線吸収無色透
明ソーダライムシリカ系ガラス、（３）Ｃｏが、Ｖ2Ｏ5
／Ｃｏ＝３００〜８５０、Ｓｅ／Ｃｏ＝６５〜３００の
重量比で含有される第(２)項に記載の紫外線吸収無色透
明ソーダライムシリカ系ガラス、（４）珪砂１００重量
部に対して、ソーダ灰２６〜３６重量部、石灰石２３〜
３３重量部、カーボン０.０１７〜０.０７重量部、芒硝
１.０〜２.０重量部の比率で各原料が含まれるバッチ組
成物を溶融し、フィーダーにおいて、Ｖ2Ｏ5を含有する
着色フリットとＳｅを含有する着色フリットを添加して
撹拌した後、成形することを特徴とする紫外線吸収無色
透明ソーダライムシリカ系ガラスの製造方法、（５）フ
ィーダーにおいて添加する着色フリットが、溶融ガラス
１００重量部に対し、５〜１５重量％のＶ2Ｏ5を含有す
る着色フリット０.４〜１.７重量部、１.０〜１.３重量
％のＳｅを含有する着色フリット１.０〜３.１重量部及
び０.１〜０.５重量％のＣｏを含有する着色フリット０
〜０.２重量部である第(４)項に記載の紫外線吸収無色
透明ソーダライムシリカ系ガラスの製造方法、（６）フ
ィーダーにおいて添加する着色フリットが、溶融ガラス
１００重量部に対し、５〜１５重量％のＶ2Ｏ5と０.０
０６〜０.０５重量％のＣｏを含有する着色フリット０.
４〜１.７重量部及び１.０〜１.３重量％のＳｅを含有
する着色フリット１.０〜３.１重量部である第(４)項に
記載の紫外線吸収無色透明ソーダライムシリカ系ガラス
の製造方法、（７）フィーダーにおいて添加する着色フ
リットが、溶融ガラス１００重量部に対し、５〜１５重
量％のＶ2Ｏ5を含有する着色フリット０.４〜１.７重量
部及び１.０〜１.３重量％のＳｅと０.００３３〜０.０
２重量％のＣｏを含有する着色フリット１.０〜３.１重
量部である第(４)項に記載の紫外線吸収無色透明ソーダ
ライムシリカ系ガラスの製造方法、及び、（８）第(１)
項乃至第(３)項のいずれかに記載の紫外線吸収無色透明
ソーダライムシリカ系ガラスを成形してなるガラス瓶、
を提供するものである。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, strictly controlled the content of sodium sulfate in the ordinary basic constituent material of soda-lime silica glass. To control the redox number (an index indicative of the degree of redox of the batch) and to add a V 2 O 5 -containing colored frit, a Se-containing colored frit and, if necessary, a Co-containing colored frit in a feeder, The present inventors have found that it is possible to stably produce an ultraviolet-absorbing colorless and transparent soda-lime-silica glass having a large ultraviolet ray absorption rate and visible light transmittance, and have completed the present invention based on this finding. That is, the present invention
(1) In a transmittance curve measured at a sample thickness of 3.5 mm, the transmittance at a wavelength of 315 nm is 1.5% or less, and there is no absorption in a specific wavelength range in the visible range of 430 to 780 nm, and the transmittance is ultraviolet absorbing colorless and transparent soda-lime-silica glass, characterized in that at least 88%, first is contained in (2) V 2 O 5 and Se is the weight ratio of V 2 O 5 / Se = 2~7 ( (1) UV-absorbing colorless and transparent soda lime silica glass according to (1), (3) Co is V 2 O 5
/ Co = 300-850, Se / Co = 65-300 in weight ratio, UV-absorbing colorless transparent soda lime silica glass according to item (2), (4) 100 parts by weight of silica sand, 26-36 parts by weight of soda ash, limestone 23-
33 parts by weight, 0.017 to 0.07 parts by weight of carbon, and 1.0 to 2.0 parts by weight of sodium sulfate are melted in a batch composition containing each raw material, and the feeder contains V 2 O 5 . A method for producing a UV-absorbing, colorless, transparent soda-lime-silica-based glass, comprising adding a colored frit and a colored frit containing Se, followed by shaping, and (5) a colored frit added in a feeder is a molten glass. relative to 100 parts by weight, the colored frit 0.4 to 1.7 parts by weight containing V 2 O 5 of 5 to 15 wt%, colored frits 1.0 containing 1.0-1.3 wt% of Se Color frit containing 0.1 to 3.1 parts by weight and 0.1 to 0.5% by weight of Co
(4) The method for producing a colorless transparent soda lime silica-based glass according to the above item (4), wherein the colored frit to be added in the feeder is 5 to 100 parts by weight of the molten glass. 15% by weight of V 2 O 5 and 0.0
Colored frit containing 0.6-0.05% by weight of Co.
The ultraviolet absorbing colorless transparent soda lime silica according to item (4), which is 1.0 to 3.1 parts by weight of a colored frit containing 4 to 1.7 parts by weight and 1.0 to 1.3 parts by weight of Se. (7) The colored frit added in the feeder is 0.4 to 1.7 parts by weight of a colored frit containing 5 to 15% by weight of V 2 O 5 based on 100 parts by weight of the molten glass; 1.0 to 1.3% by weight of Se and 0.0033 to 0.0
(4) The method for producing a UV-absorbing colorless and transparent soda-lime-silica glass according to item (4), wherein 1.0 to 3.1 parts by weight of a colored frit containing 2% by weight of Co; )
A glass bottle formed by molding the ultraviolet-absorbing colorless and transparent soda lime silica-based glass according to any one of items to (3),
Is provided.
【０００５】[0005]
【発明の実施の形態】ガラス瓶に詰められる飲料等の内
容物に含まれる青色系、赤色系及び黄色系の色素の食用
着色料（例えば、食用赤色１０４号、食用赤色１０５
号、食用赤色１０６号、食用黄色４号、食用黄色５号、
食用青色１号、食用青色２号、β−カロチン、ハイビス
カス色素、ブドウ果皮色素等が知られている。）の特性
を調べたところ、これらの色素の分解には、色素の可視
部の吸光係数が最大になる波長の光ばかりではなく、吸
光係数は小さいが近紫外乃至可視部の短波長領域のエネ
ルギーの高い光、即ち４５０ｎｍ以下、特に３００〜４
００ｎｍの波長の光も大きく影響していることが解明さ
れ、またその結果は、各種清涼飲料、ビールを除くアル
コール飲料の劣化とその原因となる光の波長との関係の
研究結果とも一致した。即ち、近紫外領域から可視短波
長域の吸収に優れるガラスは、ガラス瓶の内容物の光劣
化を抑制し、ガラスの明度が高く、ガラス自身がほぼ無
色であるガラス瓶は、内容物の色をより美しく見せるこ
とができることが明らかになった。本発明の紫外線吸収
無色透明ソーダライムシリカ系ガラスは、試料の厚み
３.５mmで測定した透過率曲線において、波長３１５ｎ
ｍにおける透過率が１.５％以下、より好ましくは０.５
％以下であり、かつ４３０〜７８０ｎｍの可視域におい
て特定波長域の吸収がなく、透過率が８８％以上であ
る。図１(ａ)は、本発明のガラスの透過率曲線の一例で
ある。本図に見られるように、３１５ｎｍにおける透過
率が１.５％以下であると、通常は２５０〜３１５ｎｍ
の波長域においては光の透過はほとんど認められず、ガ
ラス瓶として用いた場合、瓶内の飲料等の内容物へ影響
を与える紫外線の侵入を実質的に遮断することができ、
内容物の色素の分解や香味等の劣化を十分に抑制するこ
とができる。また、４３０〜７８０ｎｍの可視域におい
て特定波長域の吸収がなく、透過率が８８％以上である
ために、ガラス瓶として用いた場合、内容物を美しく見
せることができる。４３０〜７８０ｎｍの可視域におい
て、透過率が８８％未満の領域があると、ガラス瓶の透
明感が損なわれたり、薄く着色する場合がある。さら
に、本発明のガラスを建築用、車両用板ガラスとして使
用した場合、日焼け防止等の紫外線遮断効果を十分に発
揮することができる。図１(ｂ)は、通常のフリントガラ
スの透過率曲線の一例である。このガラスのように、紫
外線吸収端が３１５ｎｍよりも短波長側にあると、ガラ
ス瓶として用いた場合、瓶内の内容物の色素の分解を抑
制することができない。BEST MODE FOR CARRYING OUT THE INVENTION Food colorants of blue, red and yellow pigments contained in the contents of beverages and the like packed in glass bottles (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, hibiscus pigment, grape skin pigment and the like are known. According to the investigation of the characteristics of (1) and (2), the decomposition of these dyes is not only at the wavelength where the extinction coefficient in the visible part of the dye is maximized, but also at the energy in the short wavelength region from the near ultraviolet to the visible part where the extinction coefficient is small High light, ie, 450 nm or less, especially 300 to 4
It was clarified that light having a wavelength of 00 nm also had a significant effect, and the results were in agreement with the results of research on the relationship between the deterioration of various soft drinks and alcoholic beverages other than beer and the wavelength of the light that causes the deterioration. That is, glass excellent in the absorption from the near ultraviolet region to the visible short wavelength region suppresses light deterioration of the contents of the glass bottle, the brightness of the glass is high, and the glass bottle in which the glass itself is almost colorless, the color of the contents is more. It became clear that it could look beautiful. The UV-absorbing colorless and transparent soda-lime-silica glass of the present invention has a wavelength of 315 n in a transmittance curve measured at a sample thickness of 3.5 mm.
m is not more than 1.5%, more preferably 0.5%.
% Or less, and there is no absorption in a specific wavelength range in the visible range of 430 to 780 nm, and the transmittance is 88% or more. FIG. 1A is an example of a transmittance curve of the glass of the present invention. As can be seen from the figure, when the transmittance at 315 nm is 1.5% or less, it is usually from 250 to 315 nm.
In the wavelength range of light, light transmission is hardly recognized, and when used as a glass bottle, it is possible to substantially block the penetration of ultraviolet rays that affect the contents such as beverages in the bottle,
It is possible to sufficiently suppress the decomposition of the coloring matter in the contents and the deterioration of the flavor and the like. In addition, since there is no absorption in a specific wavelength range in the visible range of 430 to 780 nm and the transmittance is 88% or more, when used as a glass bottle, the contents can be seen beautifully. In the visible region of 430 to 780 nm, if there is a region having a transmittance of less than 88%, the transparency of the glass bottle may be impaired or the glass bottle may be lightly colored. Further, when the glass of the present invention is used as an architectural or vehicular plate glass, it is possible to sufficiently exhibit an ultraviolet blocking effect such as sunburn prevention. FIG. 1B is an example of a transmittance curve of ordinary flint glass. If the UV absorption edge is on the shorter wavelength side than 315 nm like this glass, when used as a glass bottle, the decomposition of the pigment in the contents in the bottle cannot be suppressed.
【０００６】本発明のガラスは、Ｖ2Ｏ5及びＳｅを含有
し、Ｖ2Ｏ5／Ｓｅの重量比が２〜７であることが好まし
く、３〜５であることがより好ましい。Ｖ2Ｏ5／Ｓｅの
重量比が２未満であると、ガラスがピンク色に着色する
場合がある。Ｖ2Ｏ5／Ｓｅの重量比が７を超えると、ガ
ラスが緑黄色に着色する場合がある。Ｖ2Ｏ5／Ｓｅの重
量比を２〜７とすることにより、試料厚み３.５mmで得
たデータから１０mmにおける値に換算した値として、明
度（Ｙ）８０％以上、主波長（λd）５６２〜５８５ｎ
ｍ、刺激純度（Ｐe）２.５％以下の紫外線吸収無色透明
ソーダライムシリカ系ガラスを得ることができる。さら
に、Ｖ2Ｏ5／Ｓｅの重量比を３〜５とすることにより、
試料厚み３.５mmで得たデータから１０mmにおける値に
換算した値として、明度（Ｙ）８３％以上、主波長（λ
d）５６５〜５８０ｎｍの一層無色感の強い紫外線吸収
無色透明ソーダライムシリカ系ガラスを得ることができ
る。本発明のガラスは、さらにＣｏを含有せしめること
ができる。Ｃｏを含有せしめる場合は、Ｖ2Ｏ5／Ｃｏの
重量比が３００〜８５０であることが好ましく、４００
〜７００であることがより好ましい。また、Ｓｅ／Ｃｏ
の重量比が６５〜３００であることが好ましく、９０〜
２００であることがより好ましい。Ｖ2Ｏ5／Ｃｏの重量
比を３００〜８５０とし、Ｓｅ／Ｃｏの重量比を６５〜
３００とすることにより、刺激純度（Ｐe）を２.０％以
下とすることができ、より一層無色感の強い紫外線吸収
無色透明ソーダライムシリカ系ガラスを得ることができ
る。The glass of the present invention contains V 2 O 5 and Se, and the weight ratio of V 2 O 5 / Se is preferably from 2 to 7, more preferably from 3 to 5. When the weight ratio of V 2 O 5 / Se is less than 2, the glass may be colored pink. If the weight ratio of V 2 O 5 / Se exceeds 7, the glass may be colored green-yellow. By setting the weight ratio of V 2 O 5 / Se to 2 to 7, a value obtained by converting the data obtained at a sample thickness of 3.5 mm to a value at 10 mm is 80% or more of lightness (Y) and the main wavelength (λd). 562-585n
m, a UV-absorbing colorless and transparent soda lime silica glass having a stimulating purity (Pe) of 2.5% or less can be obtained. Further, by setting the weight ratio of V 2 O 5 / Se to 3 to 5,
The value obtained by converting the data obtained at a sample thickness of 3.5 mm to a value at 10 mm is as follows: lightness (Y) 83% or more;
d) A colorless and transparent soda lime silica-based glass having a more colorless feeling of 565 to 580 nm can be obtained. The glass of the present invention can further contain Co. When Co is contained, the weight ratio of V 2 O 5 / Co is preferably 300 to 850,
It is more preferable that the number is from 700 to 700. Also, Se / Co
Is preferably 65 to 300, and 90 to 300.
More preferably, it is 200. The weight ratio of V 2 O 5 / Co is 300 to 850, and the weight ratio of Se / Co is 65 to 850.
By setting it to 300, the stimulus purity (Pe) can be made 2.0% or less, and a more colorless, ultraviolet-absorbing, colorless, transparent soda-lime-silica glass can be obtained.
【０００７】本発明の紫外線吸収無色透明ソーダライム
シリカ系ガラスの製造方法は、珪砂１００重量部に対し
て、ソーダ灰２６〜３６重量部、石灰石２３〜３３重量
部、カーボン０.０１７〜０.０７重量部、芒硝１.０〜
２.０重量部の比率で各原料が含まれるバッチ組成物を
溶融し、フィーダーにおいて、Ｖ2Ｏ5を含有する着色フ
リットとＳｅを含有する着色フリットを添加して撹拌し
た後、成形するものである。本発明方法においては、珪
砂１００重量部に対する芒硝の重量（以下、砂比とい
う。）を１.０〜２.０重量部、より好ましくは１.２〜
１.８重量部とすることにより、引上量１３０〜１８０
トン／日の連続溶解窯での紫外線吸収無色透明ソーダラ
イムシリカ系ガラスの生産において、所望の透過率曲線
を有するガラスを得るためのレドックスナンバーを達成
することができる。引上量を少なくする場合には、バー
ナーの燃焼の程度を下げるので、窯内の雰囲気が酸化性
側に寄ることから、酸化剤として使用する芒硝の量を前
述の範囲内で少な目に設定することが好ましい。逆に、
引上量を多くする場合には、バーナーの燃焼の程度を上
げるので、窯内の雰囲気が還元性側に寄ることから、酸
化剤として使用する芒硝の量を前述の範囲内で多目に設
定することが好ましい。芒硝の砂比が１.０重量部未満
又は２.０重量部を超えると、所望の紫外線吸収無色透
明ソーダライムシリカ系ガラスの生産の安定性が低下す
る。なお、上記のソーダ灰、石灰石、カーボンの比率は
通常のフリント（無色透明）ガラスを製造する場合の比
率と同じである。また、ここで示したカーボンの比率は
カーボン純度１００％の場合の数値であり、使用するカ
ーボンの純度が異なる場合には、それに応じて比率を変
更する。The method for producing a colorless and transparent soda lime silica glass of the present invention absorbs 26 to 36 parts by weight of soda ash, 23 to 33 parts by weight of limestone, and 0.017 to 0.1 parts of carbon per 100 parts by weight of silica sand. 07 parts by weight, sodium sulfate 1.0-1.0
Melting a batch composition containing each raw material at a ratio of 2.0 parts by weight, adding a colored frit containing V 2 O 5 and a colored frit containing Se in a feeder, stirring, and then molding. It is. In the method of the present invention, the weight of Glauber's salt relative to 100 parts by weight of silica sand (hereinafter, referred to as a sand ratio) is 1.0 to 2.0 parts by weight, more preferably 1.2 to 2.0 parts by weight.
By using 1.8 parts by weight, the lifting amount is 130 to 180.
In the production of UV-absorbing colorless and transparent soda-lime silica-based glass in a continuous melting furnace in tons / day, a redox number for obtaining a glass having a desired transmittance curve can be achieved. When the pulling amount is reduced, since the degree of combustion of the burner is reduced, the atmosphere in the kiln is shifted toward the oxidizing side, so the amount of sodium sulfate used as the oxidizing agent is set to a smaller value within the above range. Is preferred. vice versa,
If the pulling amount is increased, the degree of combustion of the burner will be increased, so the atmosphere in the kiln will be closer to the reducing side, so the amount of sodium sulfate used as the oxidizing agent should be set to a large value within the above range. Is preferred. When the sand ratio of the sodium sulfate is less than 1.0 part by weight or more than 2.0 parts by weight, the stability of production of a desired ultraviolet-absorbing colorless and transparent soda lime silica-based glass decreases. In addition, the ratio of the above-mentioned soda ash, limestone, and carbon is the same as that in the case of producing ordinary flint (colorless and transparent) glass. The carbon ratio shown here is a numerical value when the carbon purity is 100%, and when the carbon used has a different purity, the ratio is changed accordingly.
【０００８】本発明方法においては、フィーダーにおい
て、Ｖ2Ｏ5を含有する着色フリットとＳｅを含有する着
色フリットを、溶融ガラスに添加して撹拌する。Ｖ2Ｏ5
を含有する着色フリットは、Ｓｅを含有しないものであ
り、Ｓｅを含有する着色フリットは、Ｖ2Ｏ5を含有しな
いものである。フィーダーにおいて添加する着色フリッ
トは、それぞれの着色成分を含有する硼珪酸塩系等の低
融点ガラスのものを使用することができる。Ｖ2Ｏ5とＳ
ｅを共に含有するフリットを用いず、Ｖ2Ｏ5を含有する
着色フリットとＳｅを含有する着色フリットをそれぞれ
添加することにより、１,２５０〜１,３３０℃のフィー
ダーに添加した際に、溶融ガラス中でバナジウムが５価
から４価若しくは３価へ還元され、セレンが０価から２
価へ酸化される酸化還元反応が起こり難く、ガラスが緑
色乃至深緑色に着色することを防止することができる。
本発明方法において、フィーダーにおいて溶融ガラスに
添加するＶ2Ｏ5を含有する着色フリットのＶ2Ｏ5濃度
は、５〜１５重量％であることが好ましい。また、Ｖ2
Ｏ5を含有する着色フリットの添加量は、溶融ガラス１
００重量部に対して０.４〜１.７重量部であることが好
ましく、０.４３〜１.６重量部であることがより好まし
い。Ｖ2Ｏ5を含有する着色フリット中のＶ2Ｏ5の濃度が
５重量％未満であると、着色フリットの添加量を多くす
る必要があり、溶融ガラスの温度が下がり泡切れが悪く
なる傾向となる。Ｖ2Ｏ5の濃度が１５重量％を超える着
色フリットは、製造が困難であると共に、添加量を少な
くする必要があり、ガラス中のＶ2Ｏ5の分散が均一にな
りにくい。Ｖ2Ｏ5を含有する着色フリットの添加量が溶
融ガラス１００重量部に対して０.４重量部未満である
と、３１５ｎｍ以下の波長の紫外線吸収が不十分となる
場合がある。Ｖ2Ｏ5を含有する着色フリットの添加量が
溶融ガラス１００重量部に対して１.７重量部を超える
と、Ｓｅによる消色が十分に行われず、黄緑色に着色す
る場合がある。Ｖ2Ｏ5を含有する着色フリットを添加す
ることにより、紫外線吸収性に優れ、可視域の透過率の
大きいガラスを得ることができる。In the method of the present invention, a colored frit containing V 2 O 5 and a colored frit containing Se are added to a molten glass and stirred in a feeder. V 2 O 5
Is a color frit that does not contain Se, and a color frit that contains Se does not contain V 2 O 5 . 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. V 2 O 5 and S
The frit containing both V 2 O 5 and the frit containing Se is added without using a frit containing both e and e. Vanadium is reduced from pentavalent to tetravalent or trivalent in glass, and selenium is reduced from zero to two
The oxidation-reduction reaction, which is oxidized to a valence, is unlikely to occur, and it is possible to prevent the glass from being colored green to dark green.
In the method of the present invention, V 2 O 5 concentration of the colored frit containing V 2 O 5 added to the molten glass in the feeder is preferably 5 to 15 wt%. Also, V 2
The added amount of the colored frit containing O 5 is as follows.
The amount is preferably from 0.4 to 1.7 parts by weight, more preferably from 0.43 to 1.6 parts by weight, per 100 parts by weight. If the concentration of V 2 O 5 in the coloring frit containing V 2 O 5 is less than 5% by weight, the amount of the coloring frit needs to be increased, and the temperature of the molten glass tends to decrease, and the bubble removal tends to be poor. Becomes A colored frit having a V 2 O 5 concentration of more than 15% by weight is difficult to produce, and needs to be added in a small amount, so that the dispersion of V 2 O 5 in glass is difficult to be uniform. If the added amount of the coloring frit containing V 2 O 5 is less than 0.4 parts by weight based on 100 parts by weight of the molten glass, the absorption of ultraviolet rays having a wavelength of 315 nm or less may be insufficient. If the added amount of the coloring frit containing V 2 O 5 exceeds 1.7 parts by weight with respect to 100 parts by weight of the molten glass, the color may not be sufficiently erased by Se and may be colored yellow-green. By adding a colored frit containing V 2 O 5 , it is possible to obtain a glass having excellent ultraviolet absorption and a high transmittance in the visible region.
【０００９】本発明方法において、フィーダーにおいて
溶融ガラスに添加するＳｅを含有する着色フリットのＳ
ｅ濃度は、１.０〜１.３重量％であることが好ましい。
また、Ｓｅを含有する着色フリットの添加量は、溶融ガ
ラス１００重量部に対して１.０〜３.１重量部であるこ
とが好ましく、１.２〜２.６重量部であることがより好
ましい。Ｓｅを含有する着色フリット中のＳｅの濃度が
１.０重量％未満であると、着色フリットの添加量を多
くする必要があり、溶融ガラスの温度が下がり泡切れが
悪くなる傾向となる。Ｓｅの濃度が１.３重量％を超え
るフリットは、フリット製造過程におけるＳｅの揮発が
激しいために、製造そのものが困難である。Ｓｅを含有
する着色フリットの添加量が溶融ガラス１００重量部に
対し１.０重量部未満であると、Ｖ2Ｏ5による着色を十
分に消色しきれない場合がある。Ｓｅを含有する着色フ
リットの添加量が溶融ガラス１００重量部に対し３.１
重量部を超えると、ピンク色に着色する場合がある。Ｓ
ｅを含有する着色フリットを添加することにより、優れ
た消色能を発揮して、可視域における吸収の少ないガラ
スを得ることができる。本発明方法において、紫外線吸
収無色透明ソーダライムシリカ系ガラスを製造するため
に添加されるＳｅの量は、従来用いられてきた量よりも
はるかに多く、これによってＶ2Ｏ5による着色を完全に
消色することができる。還元発色性のＳｅの量を多くす
るには、雰囲気が酸化性に寄りすぎないように、酸化剤
である芒硝の量を少なくする必要があると考えられた
が、芒硝の量を減らすと所望のガラスは得られず、逆に
芒硝の量を増やすことにより、消色が完全で可視域に吸
収のない、品質が安定した紫外線吸収無色透明ソーダラ
イムシリカ系ガラスの製造が初めて可能になった。即
ち、芒硝、Ｖ2Ｏ5及びＳｅの比率が極めて重要であるこ
とを見出して本発明を完成した。In the method of the present invention, the colored frit containing Se to be added to the molten glass in the feeder may have an S content.
The e concentration is preferably 1.0 to 1.3% by weight.
Further, the addition amount of the colored frit containing Se is preferably 1.0 to 3.1 parts by weight, more preferably 1.2 to 2.6 parts by weight, based on 100 parts by weight of the molten glass. preferable. If the concentration of Se in the colored frit containing Se is less than 1.0% by weight, it is necessary to increase the amount of the colored frit to be added, and the temperature of the molten glass tends to decrease, and the bubble removal tends to be poor. A frit having a Se concentration of more than 1.3% by weight is difficult to produce itself because the volatilization of Se in the frit production process is severe. If the addition amount of the coloring frit containing Se is less than 1.0 part by weight based on 100 parts by weight of the molten glass, the coloring due to V 2 O 5 may not be sufficiently eliminated. The addition amount of the coloring frit containing Se is 3.1 with respect to 100 parts by weight of the molten glass.
When the amount is more than the weight part, it may be colored pink. S
By adding a colored frit containing e, a glass exhibiting excellent decoloring ability and having low absorption in the visible region can be obtained. In the method of the present invention, the amount of Se added to produce a UV-absorbing, colorless, transparent soda-lime-silica-based glass is much larger than that conventionally used, thereby completely preventing coloring by V 2 O 5. Can be erased. It was thought that in order to increase the amount of reduced coloring Se, it was necessary to reduce the amount of sodium sulfate, which is an oxidizing agent, so that the atmosphere would not be too oxidative. No glass was obtained, and conversely, by increasing the amount of sodium sulfate, it became possible for the first time to produce a stable UV-absorbing, colorless, transparent soda-lime-silica glass with complete decoloration and no absorption in the visible range. . That is, they found that the ratio of sodium sulfate, V 2 O 5 and Se was extremely important, and completed the present invention.
【００１０】本発明方法において、フィーダーにおいて
溶融ガラスに添加するＣｏを含有する着色フリットのＣ
ｏ濃度は、０.１〜０.５重量％であることが好ましい。
また、Ｃｏを含有する着色フリットの添加量は、溶融ガ
ラス１００重量部に対して０.２重量部以下であること
が好ましく、０.０２〜０.１８重量部であることがより
好ましい。Ｃｏを含有する着色フリット中のＣｏ濃度が
０.１重量％未満であると、着色フリットの添加量を多
くする必要があり、溶融ガラスの温度が下がり泡切れが
悪くなる傾向となる。Ｃｏを含有する着色フリット中の
Ｃｏ濃度が０.５重量％を超えると、着色フリットの添
加量を少なくする必要があり、溶融ガラス中の分散が均
一になりにくい。Ｃｏを含有する着色フリットの添加量
が溶融ガラス１００重量部に対して０.２重量部を超え
ると、青色に着色する場合がある。Ｃｏを含有する着色
フリットを添加することにより、清涼感があり、かつ可
視域の吸収の少ないガラスを得ることができる。本発明
方法において、Ｖ2Ｏ5とＳｅの両者を含有する着色フリ
ットを用いることはできないが、Ｖ2Ｏ5とＣｏを含有す
る着色フリット及びＳｅとＣｏを含有する着色フリット
を用いることは可能である。Ｖ2Ｏ5とＣｏを含有する着
色フリットを用いる場合は、フィーダーにおいて添加す
る着色フリットが、溶融ガラス１００重量部に対し、５
〜１５重量％のＶ2Ｏ5と０.００６〜０.０５重量％のＣ
ｏを含有する着色フリット０.４〜１.７重量部及び１.
０〜１.３重量％のＳｅを含有する着色フリット１.０〜
３.１重量部であることが好ましい。着色フリットをこ
のように添加することにより、可視域において高い光線
透過率を有し優れた透明感を保ちながら、紫外線吸収性
の良好な紫外線吸収無色透明ソーダライムシリカ系ガラ
スを得ることができる。ＳｅとＣｏを含有する着色フリ
ットを用いる場合は、フィーダーにおいて添加する着色
フリットが、溶融ガラス１００重量部に対し、５〜１５
重量％のＶ2Ｏ5を含有する着色フリット０.４〜１.７重
量部及び１.０〜１.３重量％のＳｅと０.００３３〜０.
０２重量％のＣｏを含有する着色フリット１.０〜３.１
重量部であることが好ましい。着色フリットをこのよう
に添加することにより、可視域において高い光線透過率
を有し優れた透明感を保ちながら、紫外線吸収性の良好
な紫外線吸収無色透明ソーダライムシリカ系ガラスを得
ることができる。しかし、通常は、Ｖ2Ｏ5、Ｓｅ及びＣ
ｏをそれぞれ単独に含有する着色フリットを用いること
が、工程管理の上からも好ましい。In the method of the present invention, the colored frit containing Co added to the molten glass in the feeder is C
The o concentration is preferably 0.1 to 0.5% by weight.
Further, the addition amount of the colored frit containing Co is preferably 0.2 parts by weight or less, more preferably 0.02 to 0.18 parts by weight, based on 100 parts by weight of the molten glass. If the Co concentration in the colored frit containing Co is less than 0.1% by weight, it is necessary to increase the amount of the colored frit to be added, and the temperature of the molten glass tends to decrease, and the bubble removal tends to deteriorate. If the Co concentration in the colored frit containing Co exceeds 0.5% by weight, it is necessary to reduce the amount of the colored frit to be added, and it is difficult for the dispersion in the molten glass to be uniform. If the added amount of the coloring frit containing Co exceeds 0.2 parts by weight with respect to 100 parts by weight of the molten glass, it may be colored blue. By adding a coloring frit containing Co, a glass having a refreshing feeling and little absorption in the visible region can be obtained. In the method of the present invention, a colored frit containing both V 2 O 5 and Se cannot be used, but a colored frit containing V 2 O 5 and Co and a colored frit containing Se and Co can be used. It is. In the case where a colored frit containing V 2 O 5 and Co is used, the colored frit added in the feeder is 5 parts per 100 parts by weight of the molten glass.
15 wt% V 2 O 5 and from 0.006 to 0.05 wt% of C
0.4 to 1.7 parts by weight of a colored frit containing o and 1.
Colored frit containing 0-1.3% by weight of Se
Preferably it is 3.1 parts by weight. By adding the colored frit in this way, it is possible to obtain a UV-absorbing colorless transparent soda-lime-silica glass having a good UV-absorbing property while maintaining a high light transmittance in the visible region and excellent transparency. When using a colored frit containing Se and Co, the colored frit added in the feeder is 5 to 15 parts by weight based on 100 parts by weight of the molten glass.
Colored frit 0.4 to 1.7 parts by weight and 1.0-1.3% by weight of Se and 0.0033 to 0 containing V 2 O 5 weight%.
Colored frit 1.0 to 3.1 containing 02% by weight of Co
It is preferably in parts by weight. By adding the colored frit in this way, it is possible to obtain a UV-absorbing colorless transparent soda-lime-silica glass having a good UV-absorbing property while maintaining a high light transmittance in the visible region and excellent transparency. However, usually, V 2 O 5 , Se and C
It is preferable from the viewpoint of process control to use colored frits each containing o alone.
【００１１】ソーダライムシリカ系ガラスには、通常１
〜５重量％程度のアルミナ成分が含まれているが、珪砂
中にアルミナ成分が存在しない場合には、上記の原料の
他に、さらにアルミナ、水酸化アルミニウム、長石類等
の原料を用いて組成を調整することができる。本発明の
ガラス瓶を製造するには、十分に溶融された本発明のガ
ラスを作業室で１,２００〜１,３００℃に調整し、フィ
ーダーにおいてＶ2Ｏ5を含有する着色フリット、Ｓｅを
含有する着色フリット、さらに必要に応じてＣｏを含有
する着色フリットを添加して撹拌した後、成形機に入
れ、７００〜１,０００℃の間で瓶の形状に成形するこ
とができる。成形されたガラス瓶は、５００〜６００℃
で歪みを取り除くために徐冷炉に導入され、１〜２時間
で常温まで冷却され製品となる。本発明のガラスから板
ガラスを成形する場合には、キャスティング−プレス
法、フロート法、ダウンドロー法、引上法等の常法を用
いることができる。本発明においては、着色剤としてガ
ラス化している着色フリットを用いるが、着色成分を含
まない低融点ガラスフリットと着色剤粉末を混合、造粒
して得た着色ペレットを用いることも可能である。この
場合は、フリットよりも着色成分の濃度を高めることが
できるが、バインダー等の影響により泡切れが劣るとい
うデメリットも生ずる。高濃度の着色成分を含むペレッ
トを用いる場合には、添加量をそれに見合った量に減じ
て添加すればよい。Soda-lime silica glass usually contains 1
Alumina component of about 5% by weight is contained, but when the alumina component is not present in the silica sand, in addition to the above-mentioned raw materials, the raw materials such as alumina, aluminum hydroxide, feldspars and the like are used. Can be adjusted. In order to manufacture the glass bottle of the present invention, the sufficiently melted glass of the present invention is adjusted to 1,200 to 1,300 ° C. in a working room, and a coloring frit containing V 2 O 5 and containing Se in a feeder. After adding a colored frit and, if necessary, a colored frit containing Co and stirring the mixture, the mixture is placed in a molding machine and molded into a bottle at a temperature of 700 to 1,000 ° C. The molded glass bottle is 500-600 ° C
In order to remove the strain, it is introduced into a lehr, and cooled to room temperature in 1-2 hours to obtain a product. When a plate glass is formed from the glass of the present invention, a conventional method such as a casting-press method, a float method, a down-draw method, or a pull-up method can be used. In the present invention, a vitrified colored frit is used as a colorant, but a colored pellet obtained by mixing and granulating a low-melting glass frit containing no coloring component and a colorant powder can also be used. In this case, the concentration of the coloring component can be higher than that of the frit, but there is a demerit that the bubble removal is inferior due to the influence of the binder and the like. When pellets containing a high concentration of a coloring component are used, the amount of addition may be reduced to an amount corresponding to the addition.
【００１２】[0012]
【実施例】以下に、実施例を挙げて本発明をさらに詳細
に説明するが、本発明はこれらの実施例によりなんら限
定されるものではない。実施例及び比較例において、明
度（Ｙ）、主波長（λd）、刺激純度（Ｐe）は、３.５m
m厚に鏡面研磨したサンプルを分光光度計［(株)日立製
作所製、Ｕ−３４１０］で測定して得た透過率曲線か
ら、ＪＩＳ Ｚ ８７０１に記載のＣＩＥ法に基づいて計
算し、１０mmにおける値に換算した。また、アルコール
飲料の吸光度は、分光光度計［(株)島津製作所製、ＵＶ
−１６０］を用いて測定した。 実施例１（ガラス瓶の製造） 珪砂１００重量部、ソーダ灰２８重量部、石灰石２７重
量部、セレン０.００１重量部、カーボン（純度８５重
量％）０.０５重量部及び芒硝１.５５重量部を秤し、混
合してバッチ組成物を調製した。このバッチ組成物を、
溶解能力１８０トン／日の連続溶解窯に導入し、ガラス
溶融温度１,４００℃で２４時間溶融し、さらに１,２７
０℃のフィーダーにおいて溶融ガラス１００重量部に対
し、１０重量％のＶ2Ｏ5を含有する着色フリットを０.
７５重量部、１.３重量％のＳｅを含有する着色フリッ
トを１.５重量部、０.４重量％のＣｏを含有する着色フ
リットを０.０４重量部添加し、撹拌して均一にした後
成形し、通常の徐冷窯設備を有するラインで内容積２１
０mlのＶ2Ｏ5を０.０７５重量％、Ｓｅを０.０２重量
％、Ｃｏを０.０００１６重量％含有するガラス瓶を製
造した。得られたガラス瓶から測定用サンプルを切り出
して研磨し、分光光度計を用いて透過率曲線を求めた。
得られた透過率曲線を、図１(ａ)に示す。このガラス瓶
は、試料厚さ１０mm換算で、明度（Ｙ）８３.２％、主
波長（λd）５７２.６ｎｍ、刺激純度（Ｐe）が１.６％
であった。また、３３０ｎｍにおける透過率は１.５％
であり、３１５ｎｍにおける透過率は０.４％であっ
た。さらに、４３０〜７８０ｎｍの可視域において、透
過率は８８.２％以上であり、特定波長域の吸収は認め
られなかった。 実施例２〜１３ 芒硝の配合量及び着色フリットの種類と添加量を変更す
る以外は、実施例１と同様の条件でガラス瓶を生産し、
色調と透過率の測定を行った。 比較例１ 珪砂１００重量部、ソーダ灰２８重量部、石灰石２７重
量部、セレン０.００１重量部、カーボン（純度８５重
量％）０.０５重量部及び芒硝１.１重量部を秤し、混合
してバッチ組成物を調製した。このバッチ組成物から、
着色フリットを添加することなく、内容積２１０mlの通
常フリント瓶を製造した。実施例１と同様にして、分光
光度計を用いて透過率曲線を求めた。得られた透過率曲
線を、図１(ｂ)に示す。このガラス瓶は、試料厚さ１０
mm換算で、明度（Ｙ）８７.８％、主波長（λd）５７
３.４ｎｍ、刺激純度（Ｐe）が１.０％であった。ま
た、３３０ｎｍにおける透過率は５６.１％であり、３
１５ｎｍにおける透過率は２１.５％であった。さら
に、４３０〜７８０ｎｍの可視域において、透過率は８
８.３％以上であり、特定波長域の吸収は認められなか
った。 比較例２ 珪砂１００重量部、ソーダ灰２８重量部、石灰石２７重
量部、セレン０.００１重量部、カーボン（純度８５重
量％）０.０５重量部及び芒硝１.１重量部を秤し、混合
してバッチ組成物を調製した。このバッチ組成物を、実
施例１と同様にして連続溶解窯に導入して溶融した後、
さらにフィーダーにおいて溶融ガラス１００重量部に対
し、１０重量％のＶ2Ｏ5を含有する着色フリットを０.
７５重量部添加し、撹拌して均一にした後成形し、徐冷
して内容積２１０mlのＶ2Ｏ5を０.０７５重量％含有す
るガラス瓶を製造した。実施例１と同様にして、分光光
度計を用いて透過率曲線を求めた。このガラス瓶は、試
料厚さ１０mm換算で、明度（Ｙ）８６.６％、主波長
（λd）５５７.９ｎｍ、刺激純度（Ｐe）が２.２％であ
った。また、３３０ｎｍにおける透過率は１.１％であ
り、３１５ｎｍにおける透過率は０.４％であった。さ
らに、４３０〜７８０ｎｍの可視域において、透過率は
８８.２％以上であったが、４４０〜５７０ｎｍの透過
率が他の波長域より高く、淡緑黄色に着色していた。実
施例１〜１３及び比較例１〜２のガラスの組成と、色調
及び透過率を第１表に示す。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 (λd), and stimulus purity (Pe) were 3.5 m.
Calculated based on the CIE method described in JIS Z 8701 from a transmittance curve obtained by measuring a sample mirror-polished to a thickness of m with a spectrophotometer [U-3410, manufactured by Hitachi, Ltd.] It was converted to a value. The absorbance of alcoholic beverages was measured using a spectrophotometer [Shimadzu Corporation, UV
-160]. Example 1 (Manufacture of glass bottle) 100 parts by weight of silica sand, 28 parts by weight of soda ash, 27 parts by weight of limestone, 0.001 parts by weight of selenium, 0.05 parts by weight of carbon (purity 85% by weight) and 1.55 parts by weight of sodium sulfate Were weighed and mixed to prepare a batch composition. This batch composition is
Introduced into a continuous melting furnace with a melting capacity of 180 tons / day, melted at a glass melting temperature of 1,400 ° C for 24 hours, and
In a feeder at 0 ° C., a colored frit containing 10% by weight of V 2 O 5 is added to 100 parts by weight of the molten glass.
75 parts by weight, 1.5 parts by weight of a colored frit containing 1.3% by weight of Se, and 0.04 parts by weight of a colored frit containing 0.4% by weight of Co were added, and the mixture was stirred to be uniform. After molding, the internal capacity is 21
A glass bottle containing 0.075% by weight of V 2 O 5 , 0.02% by weight of Se, and 0.0016% by weight of Co was prepared. A measurement sample was cut out from the obtained glass bottle, polished, and a transmittance curve was obtained using a spectrophotometer.
The obtained transmittance curve is shown in FIG. This glass bottle has a lightness (Y) of 83.2%, a dominant wavelength (λd) of 572.6 nm, and a stimulus purity (Pe) of 1.6% in terms of a sample thickness of 10 mm.
Met. The transmittance at 330 nm is 1.5%.
And the transmittance at 315 nm was 0.4%. Furthermore, in the visible region of 430 to 780 nm, the transmittance was 88.2% or more, and no absorption in a specific wavelength region was observed. Examples 2 to 13 Glass bottles were produced under the same conditions as in Example 1 except that the blending amount of sodium sulfate and the type and amount of the colored frit were changed.
The color tone and transmittance were measured. Comparative Example 1 100 parts by weight of silica sand, 28 parts by weight of soda ash, 27 parts by weight of limestone, 0.001 parts by weight of selenium, 0.05 parts by weight of carbon (purity 85% by weight) and 1.1 parts by weight of sodium sulfate were weighed and mixed. To prepare a batch composition. From this batch composition,
A normal flint bottle with an internal volume of 210 ml was produced without adding a colored frit. In the same manner as in Example 1, a transmittance curve was obtained using a spectrophotometer. The obtained transmittance curve is shown in FIG. This glass bottle has a sample thickness of 10
When converted to mm, the lightness (Y) is 87.8% and the dominant wavelength (λd) is 57.
3.4 nm, stimulus purity (Pe) was 1.0%. The transmittance at 330 nm is 56.1%, and 3
The transmittance at 15 nm was 21.5%. Further, in the visible region of 430 to 780 nm, the transmittance is 8%.
Above 8.3%, no absorption in a specific wavelength range was observed. Comparative Example 2 100 parts by weight of silica sand, 28 parts by weight of soda ash, 27 parts by weight of limestone, 0.001 parts by weight of selenium, 0.05 parts by weight of carbon (85% by weight), and 1.1 parts by weight of sodium sulfate were weighed and mixed. To prepare a batch composition. After introducing this batch composition into a continuous melting furnace and melting it in the same manner as in Example 1,
Further, in the feeder, a colored frit containing 10% by weight of V 2 O 5 with respect to 100 parts by weight of the molten glass was added in an amount of 0.1%.
75 parts by weight were added, the mixture was stirred to make it uniform, then molded and gradually cooled to produce a glass bottle containing 210 ml of V 2 O 5 having a content of 0.075% by weight. In the same manner as in Example 1, a transmittance curve was obtained using a spectrophotometer. This glass bottle had a lightness (Y) of 86.6%, a dominant wavelength (λd) of 557.9 nm, and a stimulus purity (Pe) of 2.2% in terms of a sample thickness of 10 mm. The transmittance at 330 nm was 1.1%, and the transmittance at 315 nm was 0.4%. Further, in the visible range of 430 to 780 nm, the transmittance was 88.2% or more, but the transmittance in the range of 440 to 570 nm was higher than in other wavelength ranges, and it was colored pale green yellow. Table 1 shows the composition, color tone, and transmittance of the glasses of Examples 1 to 13 and Comparative Examples 1 and 2.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【表２】 [Table 2]
【００１５】[0015]
【表３】 [Table 3]
【００１６】［注］ １）カーボンの純度８５重量％。 ２）溶融ガラス１００重量部に対する添加量。 ３）１０重量％のＶ2Ｏ5を含有する着色フリット。 ４）１５重量％のＶ2Ｏ5を含有する着色フリット。 ５）１.３重量％のＳｅを含有する着色フリット。 ６）１.０重量％のＳｅを含有する着色フリット。 ７）０.４重量％のＣｏを含有する着色フリット。 ８）１０重量％のＶ2Ｏ5と０.０２重量％のＣｏを含有
する着色フリット。 ９）１.３重量％のＳｅと０.０１重量％のＣｏを含有す
る着色フリット。 第１表に見られるように、実施例１〜１３の本発明のガ
ラスは、色調が良好で無色透明感に優れ、かつ３１５ｎ
ｍにおける透過率が０.９％以下で紫外線遮蔽性にも優
れている。これに対して、比較例１の通常のフリントガ
ラスは、透明感は良好であるが、紫外線透過性が大き
い。また、Ｖ2Ｏ5のみを含有し、ＳｅもＣｏも含有しな
い比較例２のガラスは、紫外線遮蔽性は良好であるが、
４４０〜５７０ｎｍの透過率が他の波長域より高く、無
色感が不足している。 実験例１（光による褪色の抑制効果） 食品添加物である食用青色１号（以下、青色１号と略
す。）と食用赤色１０６号（以下、赤色１０６号と略
す。）の色素を含むアルコール飲料（アルコール度数６
％）を、実施例１及び実施例３において製造したガラス
瓶並びに比較例１において製造した通常フリント瓶各２
０本に、２００mlずつ充填し、キャップで封をした。ア
ルコール飲料を充填したガラス瓶を、５本ずつ４グルー
プに分け、そのうち３グループは屋外の影のない場所に
放置して日光に暴露させ、残り１グループは冷暗所で保
存した。日光に暴露した３グループはそれぞれ、日光暴
露中の紫外線照射量をＡ領域紫外線計［英弘精機社製］
にて測定し、累積照射量が５.４２Ｊ／ｍ2、６.６４Ｊ
／ｍ2及び８.６３Ｊ／ｍ2に達した時点で、１グループ
ずつ暴露を中止し回収した。暴露終了後、４グループの
ガラス瓶中のアルコール飲料を、０.４５μｍメンブレ
ンでろ過後、６３０ｎｍ及び５６５ｎｍにおける吸光度
を測定した。色素残存率は、各グループの吸光度の平均
値を使用して、照射量ｔにおける色素の極大吸収波長に
おける吸光度Ａ（ｔ）を、日光に暴露していない冷暗所
保存ガラス瓶中のアルコール飲料の吸光度Ａ（０）で除
した商で表した。 色素残存率＝｛Ａ（ｔ）／Ａ（０）｝×１００（％） 実験例１の結果を、第２表に示す。[Note] 1) Purity of carbon is 85% by weight. 2) The amount added to 100 parts by weight of the molten glass. 3) 10 wt% V 2 O 5 colored frit containing. 4) 15 wt% V 2 O 5 colored frit containing. 5) A colored frit containing 1.3% by weight of Se. 6) A colored frit containing 1.0% by weight of Se. 7) Colored frit containing 0.4% by weight Co. 8) A colored frit containing 10% by weight of V 2 O 5 and 0.02% by weight of Co. 9) A colored frit containing 1.3% by weight of Se and 0.01% by weight of Co. As can be seen in Table 1, the glasses of Examples 1 to 13 of the present invention had good color tone, excellent colorless transparency, and 315 n
The transmittance at 0.9 m is 0.9% or less, which is excellent in ultraviolet ray shielding properties. On the other hand, the ordinary flint glass of Comparative Example 1 has good transparency but has high ultraviolet transmittance. Further, the glass of Comparative Example 2 containing only V 2 O 5 and containing neither Se nor Co has a good ultraviolet shielding property,
The transmittance at 440 to 570 nm is higher than other wavelength ranges, and the colorless feeling is insufficient. Experimental Example 1 (Effect of Suppressing Discoloration due to Light) Alcohol containing food additives, Food Color No. 1 (hereinafter abbreviated as Blue No. 1) and Food Color No. 106 (hereinafter abbreviated as Red No. 106) Beverages (alcohol 6
%) Is 2% for each of the glass bottles manufactured in Examples 1 and 3 and the normal flint bottles manufactured in Comparative Example 1.
Zero bottles were filled with 200 ml each and sealed with a cap. The glass bottles filled with alcoholic beverages were divided into four groups of five bottles, three of which were left outdoors in an unshaded area and exposed to sunlight, and the other group was stored in a cool and dark place. For each of the three groups exposed to sunlight, the UV irradiation dose during sunlight exposure was measured using an A-area UV meter [manufactured by Eiko Seiki Co., Ltd.].
And the cumulative irradiation dose is 5.42 J / m 2 , 6.64 J
/ M 2 and 8.63 J / m 2 , the exposure was stopped and collected one group at a time. After the exposure, the alcoholic beverages in the glass bottles of the four groups were filtered through a 0.45 μm membrane, and the absorbance at 630 nm and 565 nm was measured. Using the average value of the absorbance of each group, the absorbance A (t) of the dye at the maximum absorption wavelength of the dye at the irradiation amount t was calculated as the absorbance A of the alcoholic beverage in a glass bottle kept in a cool and dark place not exposed to sunlight. Expressed as the quotient divided by (0). Dye residual ratio = {A (t) / A (0)} × 100 (%) The results of Experimental Example 1 are shown in Table 2.
【００１７】[0017]
【表４】 [Table 4]
【００１８】６３０ｎｍ吸光度から求めたアルコール飲
料中の青色１号の残存率は、８.６３Ｊ／ｍ2の累積照射
量において、比較例１において製造した通常フリント瓶
では５２.１％であったのに対して、実施例１において
製造したガラス瓶では８９.９％、実施例３において製
造したガラス瓶では９１.５％といずれも９０％前後の
高い残存率であった。また、５６５ｎｍ吸光度から求め
たアルコール飲料中の赤色１０６号の残存率は、８.６
３Ｊ／ｍ2の累積照射量において、比較例１において製
造した通常フリント瓶では２８.６％であったのに対し
て、実施例１において製造したガラス瓶では５２.９
％、実施例３において製造したガラス瓶では６１.０％
であり、いずれも５０％以上の残存率であった。比較例
１において製造した通常フリント瓶では５.４２Ｊ／ｍ2
の累積照射量で残存率が６４.１％であるのに対して、
実施例１又は実施例３において製造したガラス瓶では
６.６４Ｊ／ｍ2の累積照射量で６３.３％、６３.２％の
残存率とほぼ同等の残存率を示した。このことから、実
施例１又は実施例３において製造したガラス瓶中の内容
物への赤色１０６号での比較による遮蔽効果は、比較例
１において製造した通常フリント瓶の約１.６５倍であ
ることが判った。 実験例２ 食品添加物である食用青色１号の色素を含むアルコール
飲料（アルコール度数６％）を、実施例１において製造
したガラス瓶及び比較例１において製造した通常フリン
ト瓶各１５本に、工場で、通常通り２００mlずつ瓶詰め
してキャップをした。アルコール飲料を充填したガラス
瓶を、５本ずつ３グループに分け、そのうち２グループ
は屋外の影のない場所に放置し日光に暴露させ、残り１
グループは冷暗所で保存した。暴露させた２グループ
は、１グループずつ時間を変えて暴露を中止させて回収
した。実験例１と同様に、暴露中、併せて紫外線照射量
をＡ領域紫外線計にて測定したところ、累積照射量はそ
れぞれ１４.４Ｊ／ｍ2と２７.９Ｊ／ｍ2であった。暴露
終了後、３グループのガラス瓶中のアルコール飲料を
０.４５μｍメンブレンで濾過後に６３０ｎｍにおける
吸光度を測定して、アルコール飲料中の青色色素残存率
を、実験例１と同様にして求めた。実験例２の結果を、
第３表に示す。The residual ratio of Blue No. 1 in the alcoholic beverage determined from the absorbance at 630 nm was 52.1% in the ordinary flint bottle manufactured in Comparative Example 1 at the cumulative irradiation dose of 8.63 J / m 2 . On the other hand, the glass bottle manufactured in Example 1 had a high residual rate of 89.9%, and the glass bottle manufactured in Example 3 had a high residual rate of about 90%, which was 91.5%. The residual ratio of Red No. 106 in alcoholic beverages determined from 565 nm absorbance was 8.6.
At a cumulative irradiation dose of 3 J / m 2 , it was 28.6% for the normal flint bottle manufactured in Comparative Example 1 and 52.9 in the glass bottle manufactured in Example 1.
%, 61.0% in the glass bottle manufactured in Example 3.
In each case, the residual ratio was 50% or more. The normal flint bottle manufactured in Comparative Example 1 had 5.42 J / m 2.
The residual rate is 64.1% at the cumulative irradiation amount of
The glass bottle manufactured in Example 1 or Example 3 showed a residual rate of 63.3% and a residual rate of almost 63.2% at a cumulative irradiation dose of 6.64 J / m 2 . From this, the shielding effect on the contents in the glass bottle manufactured in Example 1 or Example 3 by the comparison with Red No. 106 is about 1.65 times that of the normal flint bottle manufactured in Comparative Example 1. I understood. Experimental Example 2 Alcoholic beverages (alcohol content 6%) containing food color No. 1 as food additive were added to 15 glass bottles manufactured in Example 1 and 15 normal flint bottles manufactured in Comparative Example 1 at a factory. As usual, bottled 200 ml each and capped. The glass bottles filled with alcoholic beverages were divided into three groups of five bottles, two of which were left outdoors in an unshaded area and exposed to sunlight, and the remaining one was exposed to sunlight.
Groups were stored in a cool, dark place. The two exposed groups were collected by stopping the exposure for one group at different times. Similarly to Experimental Example 1, during the exposure, when the ultraviolet irradiation amount was measured by an ultraviolet ray meter in the A region, the cumulative irradiation amounts were 14.4 J / m 2 and 27.9 J / m 2 , respectively. After the exposure was completed, the alcoholic beverages in the three groups of glass bottles were filtered through a 0.45 μm membrane, and the absorbance at 630 nm was measured. The residual ratio of the blue pigment in the alcoholic beverages was determined in the same manner as in Experimental Example 1. The results of Experimental Example 2
It is shown in Table 3.
【００１９】[0019]
【表５】 [Table 5]
【００２０】累積照射量１４.４Ｊ／ｍ2の６３０ｎｍ吸
光度から求めたアルコール飲料中の青色１号の残存率
は、実施例１において製造したガラス瓶では１００％で
あったのに対して、比較例１において製造した通常フリ
ント瓶では２３％であった。また、更に累積照射量がそ
の１.９倍の２７.９Ｊ／ｍ2における実施例１において
製造したガラス瓶での色素の残存率は、２３％よりも遥
かに高く、８０％であり、比較例１において製造した通
常フリント瓶では０％であった。従って、同一累積照射
量の場合、実施例１において製造したガラス瓶中の内容
物への青色１号での比較による遮蔽効果は、比較例１に
おいて製造した通常フリント瓶と比べると１.９倍又は
それ以上であった。実験例３（アルコール飲料での光に
よる香味劣化の抑制効果）甘味果実酒を紫外線吸収無色
透明ガラス瓶に詰め、光を照射し、アルコール飲料の香
味の劣化抑制を評価した。甘味果実酒（アルコール度数
１４.５％）を、実施例１において製造したガラス瓶及
び比較例１において製造した通常フリント瓶各３０本に
２００mlずつ充填し、キャップで封をした。甘味果実酒
を充填したガラス瓶のうち１５本を５本ずつ３グループ
に分け、いずれも屋外の影のない場所に放置し日光に暴
露させ、残り１５本は冷暗所で保存した。日光に暴露し
た３グループは、実験例１と同様にそれぞれ日光暴露中
の紫外線照射量をＡ領域紫外線計にて測定し、累積照射
量が１０.３１、２４.５１及び３８.７２Ｊ／ｍ2に達し
た時点で、１グループずつ暴露を中止し回収した。各グ
ループ暴露を終了した時点で、日光に暴露したガラス瓶
中の甘味果実酒と、同数本の日光に暴露していない冷暗
所保存のガラス瓶中の甘味果実酒とを、訓練された醸造
技術者５名により官能評価で比較した。累積照射量が１
０.３１Ｊ／ｍ2においては、いずれも官能的な変化は見
られなかったが、２４.５１Ｊ／ｍ2においては比較例１
において製造した通常フリント瓶に詰められた甘味果実
酒に、火薬臭のような異臭が明らかに認められ、３８.
７２Ｊ／ｍ2においては更にその異臭が強くなった。実
施例１において製造したガラス瓶に詰められた甘味果実
酒には、いずれの累積照射量においても、香味、外観、
色に変化は認められなかった。The residual ratio of Blue No. 1 in the alcoholic beverage determined from the absorbance at 630 nm at a cumulative irradiation dose of 14.4 J / m 2 was 100% in the glass bottle manufactured in Example 1, whereas it was in Comparative Example. The ratio was 23% for the normal flint bottle manufactured in 1. Further, the residual ratio of the dye in the glass bottle manufactured in Example 1 at a cumulative irradiation dose of 1.9 times that of 27.9 J / m 2 was much higher than 23%, and was 80%. It was 0% for the normal flint bottle manufactured in 1. Therefore, in the case of the same cumulative irradiation amount, the shielding effect of the content of the glass bottle manufactured in Example 1 by comparison with Blue No. 1 is 1.9 times or more than that of the normal flint bottle manufactured in Comparative Example 1. It was more. Experimental Example 3 (Effect of Suppression of Flavor Deterioration by Light in Alcoholic Beverage) Sweet fruit liquor was packed in a UV-absorbing colorless and transparent glass bottle, irradiated with light, and evaluated for the suppression of deterioration in flavor of the alcoholic beverage. 200 ml of sweet fruit liquor (alcohol content: 14.5%) was filled into each of the glass bottles manufactured in Example 1 and the normal flint bottles manufactured in Comparative Example 1 by 200 ml and sealed with a cap. Of the glass bottles filled with sweet fruit liquor, 15 bottles were divided into three groups of 5 bottles, all of which were left outdoors in an unshaded place and exposed to sunlight, and the remaining 15 bottles were stored in a cool dark place. In the three groups exposed to sunlight, the amount of ultraviolet irradiation during sunlight exposure was measured with an A region UV meter in the same manner as in Experimental Example 1, and the cumulative irradiation amounts were 10.31, 24.51, and 38.72 J / m 2. At that time, the exposure was stopped and collected one group at a time. At the end of each group exposure, five trained brewers trained the sweetened fruit wine in a glass bottle exposed to sunlight and the same number of sweetened fruit wine in a glass bottle kept in a cool, dark place not exposed to sunlight. And sensory evaluation. Cumulative irradiation amount is 1
At 0.31 J / m 2 , no sensory change was observed, but at 24.51 J / m 2 , Comparative Example 1
In the sweet fruit liquor usually packed in a flint bottle manufactured in the above, an off-flavor such as explosive odor was clearly recognized, and 38.
At 72 J / m 2 , the off-flavor became even stronger. In the sweet fruit liquor packed in the glass bottle manufactured in Example 1, the flavor, appearance,
No change in color was observed.
【００２１】[0021]
【発明の効果】本発明の紫外線吸収無色透明ソーダライ
ムシリカ系ガラスは、紫外線吸収作用、特に近紫外領域
から可視短波長域の吸収に優れ、ガラス瓶に成形して用
いる場合には、その内容物の光による変色や褪色或いは
香味等の劣化を防止し、なおかつガラス瓶内の内容物の
色が従来の紫外線吸収着色ガラス瓶に比べ、一層美しく
見える無色透明ガラス瓶とすることができる。また、建
築用、車両用等の板ガラスとした場合には、日焼け防止
用等の紫外線遮断効果が得られると共に、視界の明るい
無色透明な板ガラスとすることができる。The ultraviolet absorbing colorless and transparent soda lime silica glass of the present invention is excellent in ultraviolet absorbing function, especially in the near-ultraviolet region to the visible short-wavelength region, and when used in a glass bottle, its contents. A colorless and transparent glass bottle can be provided that prevents discoloration, fading or deterioration of flavor due to the light, and the color of the contents in the glass bottle looks more beautiful than a conventional ultraviolet absorption colored glass bottle. Further, when the glass sheet is used for architectural purposes, vehicles, and the like, it is possible to obtain a colorless and transparent sheet glass with a bright view while having an ultraviolet blocking effect for preventing sunburn and the like.
【図１】図１は、２５０〜７８０ｎｍの波長域における
透過率曲線である。FIG. 1 is a transmittance curve in a wavelength range of 250 to 780 nm.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大橋 一郎 東京都港区元赤坂１丁目２番３号 サント リー株式会社東京支社内 (72)発明者 北山 正男 兵庫県西宮市浜松原町２番21号 山村硝子 株式会社内 (72)発明者 阿部 善弘 兵庫県西宮市浜松原町２番21号 山村硝子 株式会社内 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Ichiro Ohashi 1-3-2 Moto-Akasaka, Minato-ku, Tokyo Suntory Co., Ltd., Tokyo branch office (72) Inventor Masao Kitayama 2-21, Hamamatsubara-cho, Nishinomiya-shi, Hyogo Prefecture Yamamura Glass Co., Ltd. (72) Inventor Yoshihiro Abe 2-21 Hamamatsubara-cho, Nishinomiya City, Hyogo Prefecture
Claims (8)
において、波長３１５ｎｍにおける透過率が１.５％以
下であり、かつ４３０〜７８０ｎｍの可視域において特
定波長域の吸収がなく、透過率が８８％以上であること
を特徴とする紫外線吸収無色透明ソーダライムシリカ系
ガラス。1. In a transmittance curve measured at a sample thickness of 3.5 mm, the transmittance at a wavelength of 315 nm is 1.5% or less, and there is no absorption in a specific wavelength range in the visible range of 430 to 780 nm, and the transmittance is higher. An ultraviolet-absorbing, colorless, transparent soda-lime-silica glass having a ratio of 88% or more.
の重量比で含有される請求項１に記載の紫外線吸収無色
透明ソーダライムシリカ系ガラス。2. V 2 O 5 and Se are V 2 O 5 / Se = 2 to 7
The colorless transparent soda lime silica glass according to claim 1, which is contained in a weight ratio of:
Ｓｅ／Ｃｏ＝６５〜３００の重量比で含有される請求項
２に記載の紫外線吸収無色透明ソーダライムシリカ系ガ
ラス。3. Co is V 2 O 5 / Co = 300-850,
The ultraviolet-absorbing colorless and transparent soda-lime-silica-based glass according to claim 2, which is contained in a weight ratio of Se / Co = 65 to 300.
〜３６重量部、石灰石２３〜３３重量部、カーボン０.
０１７〜０.０７重量部、芒硝１.０〜２.０重量部の比
率で各原料が含まれるバッチ組成物を溶融し、フィーダ
ーにおいて、Ｖ2Ｏ5を含有する着色フリットとＳｅを含
有する着色フリットを添加して撹拌した後、成形するこ
とを特徴とする紫外線吸収無色透明ソーダライムシリカ
系ガラスの製造方法。4. Soda ash 26 per 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 017 to 0.07 parts by weight and 1.0 to 2.0 parts by weight of sodium sulfate, and a coloring frit containing V 2 O 5 and Se are contained in a feeder. A method for producing a transparent and colorless soda lime silica glass absorbing ultraviolet light, which comprises adding a colored frit, stirring and shaping.
が、溶融ガラス１００重量部に対し、５〜１５重量％の
Ｖ2Ｏ5を含有する着色フリット０.４〜１.７重量部、
１.０〜１.３重量％のＳｅを含有する着色フリット１.
０〜３.１重量部及び０.１〜０.５重量％のＣｏを含有
する着色フリット０〜０.２重量部である請求項４に記
載の紫外線吸収無色透明ソーダライムシリカ系ガラスの
製造方法。5. The coloring frit added in the feeder is 0.4 to 1.7 parts by weight of a coloring frit containing 5 to 15% by weight of V 2 O 5 based on 100 parts by weight of the molten glass.
Colored frit containing 1.0-1.3% by weight Se 1.
5. The production of a colorless frit containing 0 to 3.1 parts by weight and 0 to 0.2 parts by weight of a colored frit containing Co of 0.1 to 0.5% by weight according to claim 4. Method.
が、溶融ガラス１００重量部に対し、５〜１５重量％の
Ｖ2Ｏ5と０.００６〜０.０５重量％のＣｏを含有する着
色フリット０.４〜１.７重量部及び１.０〜１.３重量％
のＳｅを含有する着色フリット１.０〜３.１重量部であ
る請求項４に記載の紫外線吸収無色透明ソーダライムシ
リカ系ガラスの製造方法。6. A colored frit added in feeder, with respect to the molten glass 100 parts by weight, the colored frits 0 containing 5-15 wt% V 2 O 5 and from 0.006 to 0.05 wt% of Co. 4 to 1.7 parts by weight and 1.0 to 1.3% by weight
5. The process for producing a colorless frit with ultraviolet absorption and colorless soda lime silica according to claim 4, wherein the colored frit containing Se is 1.0 to 3.1 parts by weight.
が、溶融ガラス１００重量部に対し、５〜１５重量％の
Ｖ2Ｏ5を含有する着色フリット０.４〜１.７重量部及び
１.０〜１.３重量％のＳｅと０.００３３〜０.０２重量
％のＣｏを含有する着色フリット１.０〜３.１重量部で
ある請求項４に記載の紫外線吸収無色透明ソーダライム
シリカ系ガラスの製造方法。7. A colored frit added in feeder, with respect to the molten glass 100 parts by weight, the colored frit 0.4 to 1.7 parts by weight and 1.0 containing V 2 O 5 of 5 to 15 wt% The ultraviolet-absorbing colorless and transparent soda-lime-silica-based glass according to claim 4, which is 1.0 to 3.1 parts by weight of a colored frit containing 1.3% by weight of Se and 0.0033 to 0.02% by weight of Co. Manufacturing method.
紫外線吸収無色透明ソーダライムシリカ系ガラスを成形
してなるガラス瓶。8. A glass bottle formed by molding the ultraviolet-absorbing colorless and transparent soda lime silica-based glass according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27600897A JPH11116270A (en) | 1997-10-08 | 1997-10-08 | Ultraviolet-ray absorbing colorless transparent soda lime-silica glass, its production and glass bottle obtained by molding same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27600897A JPH11116270A (en) | 1997-10-08 | 1997-10-08 | Ultraviolet-ray absorbing colorless transparent soda lime-silica glass, its production and glass bottle obtained by molding same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11116270A true JPH11116270A (en) | 1999-04-27 |
Family
ID=17563504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27600897A Pending JPH11116270A (en) | 1997-10-08 | 1997-10-08 | Ultraviolet-ray absorbing colorless transparent soda lime-silica glass, its production and glass bottle obtained by molding same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11116270A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002066388A1 (en) * | 2001-02-20 | 2002-08-29 | Nihon Yamamura Glass Co., Ltd. | Ultraviolet ray absorbing colorless transparent soda-lime-silica glass, method for production thereof and glass container comprising said glass |
| JP2006273662A (en) * | 2005-03-29 | 2006-10-12 | Ishizuka Glass Co Ltd | Food storage container |
| JP2008171811A (en) * | 2007-01-05 | 2008-07-24 | Samsung Sdi Co Ltd | Glass frit, composition for sealing material, and light emitting device |
| JP2009511419A (en) * | 2005-10-18 | 2009-03-19 | エージーシー フラット グラス ユーロップ エスエー | Pellets for Se encapsulation |
-
1997
- 1997-10-08 JP JP27600897A patent/JPH11116270A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002066388A1 (en) * | 2001-02-20 | 2002-08-29 | Nihon Yamamura Glass Co., Ltd. | Ultraviolet ray absorbing colorless transparent soda-lime-silica glass, method for production thereof and glass container comprising said glass |
| JP2006273662A (en) * | 2005-03-29 | 2006-10-12 | Ishizuka Glass Co Ltd | Food storage container |
| JP2009511419A (en) * | 2005-10-18 | 2009-03-19 | エージーシー フラット グラス ユーロップ エスエー | Pellets for Se encapsulation |
| JP2008171811A (en) * | 2007-01-05 | 2008-07-24 | Samsung Sdi Co Ltd | Glass frit, composition for sealing material, and light emitting device |
| US8546281B2 (en) | 2007-01-05 | 2013-10-01 | Samsung Display Co., Ltd. | Glass plate with glass frit structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0721429B1 (en) | Glass compositions | |
| JP3451350B2 (en) | UV-absorbing colorless transparent soda lime silica glass | |
| EP0821659B1 (en) | Colored glass compositions | |
| EP0709344B1 (en) | Glass having low solar radiation and ultraviolet ray transmittance | |
| JP4829128B2 (en) | Soda-lime-silicate glass composition | |
| US5747398A (en) | Neutral colored glass compositions | |
| JPS6344696B2 (en) | ||
| CA2035268A1 (en) | Batch composition for making infrared and ultraviolet radiation absorbing green glass | |
| USRE25456E (en) | Ultraviolet light absorbing glass | |
| JP4731086B2 (en) | UV-absorbing colorless and transparent soda-lime silica glass | |
| EP2942331A1 (en) | Low-transmission dark mist green glass composition | |
| CZ302914B6 (en) | Blue colored glass, flat glass sheet and automotive window | |
| US2923636A (en) | Glass-making frit and method | |
| US6133179A (en) | Glass compositions of the silica-soda-lime type | |
| JPH11116270A (en) | Ultraviolet-ray absorbing colorless transparent soda lime-silica glass, its production and glass bottle obtained by molding same | |
| US3291621A (en) | Ultraviolet light-absorbing glass | |
| US6780803B2 (en) | Ultraviolet/infrared absorbent low transmittance glass | |
| JP2002249338A (en) | Ultraviolet ray absorbing colorless and transparent soda lime silica-base glass, method for manufacturing the same, and glass container formed from the same | |
| KR950004060B1 (en) | Green glasses for containers, capable of intercepting ultraviolet rays and near ultraviolet rays, and processes for the production of the same | |
| US6048812A (en) | Brown glass which absorbs ultraviolet radiation | |
| JP5624587B2 (en) | UV-absorbing colorless and transparent soda-lime silica glass | |
| AU704906B2 (en) | UV radiation absorbing package | |
| JPH02302336A (en) | Green glass and its utilization | |
| JP2000344543A (en) | Yellowish-brown-colored glass and its production | |
| JPS61136935A (en) | High manganese-content frit for decoloring |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040928 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070731 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20071120 |