JP6671732B2 - Borosilicate glass, glass frit using the same, and glass molded article using the glass frit - Google Patents
Borosilicate glass, glass frit using the same, and glass molded article using the glass frit Download PDFInfo
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- JP6671732B2 JP6671732B2 JP2019013536A JP2019013536A JP6671732B2 JP 6671732 B2 JP6671732 B2 JP 6671732B2 JP 2019013536 A JP2019013536 A JP 2019013536A JP 2019013536 A JP2019013536 A JP 2019013536A JP 6671732 B2 JP6671732 B2 JP 6671732B2
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- 239000011521 glass Substances 0.000 title claims description 145
- 239000005388 borosilicate glass Substances 0.000 title claims description 59
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 42
- 239000002131 composite material Substances 0.000 claims description 31
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 36
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 34
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 34
- 239000000203 mixture Substances 0.000 description 30
- 239000011787 zinc oxide Substances 0.000 description 29
- 238000002425 crystallisation Methods 0.000 description 28
- 230000008025 crystallization Effects 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 23
- 229910052697 platinum Inorganic materials 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 18
- 235000012239 silicon dioxide Nutrition 0.000 description 18
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 17
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 17
- 239000004327 boric acid Substances 0.000 description 17
- 229910000019 calcium carbonate Inorganic materials 0.000 description 17
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 description 17
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 17
- 229910001887 tin oxide Inorganic materials 0.000 description 17
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 16
- 229910000018 strontium carbonate Inorganic materials 0.000 description 16
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 15
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 15
- 229960001633 lanthanum carbonate Drugs 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 description 14
- 230000000536 complexating effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 13
- 239000001095 magnesium carbonate Substances 0.000 description 13
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 13
- 229910000484 niobium oxide Inorganic materials 0.000 description 13
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 238000013329 compounding Methods 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003303 reheating Methods 0.000 description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 239000005084 Strontium aluminate Substances 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Glass Compositions (AREA)
Description
本発明は、ホウケイ酸ガラス及びそれを用いたガラスフリット、並びに該ガラスフリットを用いたガラス成形品に関する。 The present invention relates to borosilicate glass, a glass frit using the same, and a glass molded product using the glass frit.
近年、高残光輝度を示す蓄光体が開発され、これを利用した蓄光体複合体が安全標識などに利用されるようになってきた。屋外で使用される複合体は耐候性の高いガラスフリットを使用したもの（ガラス蓄光体複合体）が主として用いられている。蓄光体用途を拡大するためには高輝度化が重要であり、高輝度を示す複合体の開発が行われている。 In recent years, luminous bodies exhibiting high afterglow luminance have been developed, and luminous body composites using the luminous bodies have come to be used for safety signs and the like. As a composite used outdoors, a composite using a glass frit having high weather resistance (glass phosphorescent composite) is mainly used. It is important to increase the luminance in order to expand the use of the phosphor, and a composite exhibiting high luminance is being developed.
蓄光体とガラスフリットとの複合体（ガラス蓄光体複合体）として、特許文献１には二酸化珪素、アルミナ、酸化硼素、アルカリ金属酸化物、希土類元素酸化物からなるフリットを使用することが記載されている。また、特許文献２には、酸化ケイ素、酸化アルミニウム、酸化ホウ素、アルカリ金属酸化物を主成分とし、その含有量範囲が規定されたフリットを使用することが記載されている。これらの文献には屈折率は考慮されておらず、いずれも屈折率は１．６０未満である。 Patent Literature 1 describes using a frit composed of silicon dioxide, alumina, boron oxide, an alkali metal oxide, and a rare earth element oxide as a composite of a phosphor and a glass frit (glass phosphor composite). ing. Patent Literature 2 discloses that a frit having silicon oxide, aluminum oxide, boron oxide, and alkali metal oxide as main components and having a specified content range is used. No refraction index is taken into account in these documents, and in each case the refraction index is less than 1.60.
高輝度なガラス蓄光体複合体を得るためには、蓄光体の発光を有効に取り出すために屈折率が蓄光体に近いガラスフリットを用いることが好ましい。アルミン酸ストロンチウム系高輝度蓄光体の屈折率は１．６５以上であり、最も一般的な、組成が７４ＳｉＯ２−１４Ｎａ２Ｏ−１１ＣａＯ−１Ａｌ２Ｏ３であり、屈折率が１．５１であるビンガラスに比べて高い。 In order to obtain a high-luminance glass phosphor composite, it is preferable to use a glass frit having a refractive index close to that of the phosphor to effectively extract light emitted from the phosphor. Refractive index of the strontium aluminate high luminance phosphorescent article is 1.65 or more, the most common, the composition is 74SiO 2 -14Na 2 O-11CaO- 1Al 2 O 3, a refractive index of 1.51 Higher than bottle glass.
現在使用されているガラスフリットは使用する蓄光体に比べて屈折率が低いため、発光をすべて取り出せていない。発光を有効に取り出すには屈折率を蓄光体にそろえることが好ましい。このためガラスフリットの屈折率は１．６４以上にすることが好ましい。複合体作製のためには、通常作製したガラスフリットを粉砕し、蓄光体と混合して再加熱される。この際、通常のガラス加工においては、結晶化温度域以上で加熱されるために結晶化は問題になりにくい。一方、ガラスフリットを蓄光体と複合化する際には、ガラスフリットが溶融して表面の光散乱が起こらなくなるように粘性が１０６ｄＰａｓ程度になる温度以上に加熱することが好ましく、また加熱によるガラスフリットと蓄光体との反応による劣化を防止するために複合化温度としてガラスフリットの粘性が１０５ｄＰａｓ程度になる温度以下に設定することが好ましいが、この温度域は特に結晶化の核生成及び成長が起きやすい温度であり、ガラス蓄光体複合体を作製する際には、高屈折率成分はガラス中で結晶化しやすく、再加熱によって結晶相が生じやすい。結晶相が生じると蓄光体からの発光を散乱させて有効に光を取り出せず、残光輝度が低下する。このため、通常の高屈折率ガラスは結晶化を起こすため使用することはできない。 The currently used glass frit has a lower refractive index than the phosphor used, and thus cannot emit all light. In order to extract light emission effectively, it is preferable to make the refractive index uniform with the phosphor. Therefore, the refractive index of the glass frit is preferably set to 1.64 or more. In order to produce a composite, usually, the produced glass frit is pulverized, mixed with a luminous body, and reheated. At this time, in normal glass processing, crystallization hardly causes a problem because the glass is heated at a temperature higher than a crystallization temperature range. On the other hand, when the glass frit is combined with the luminous body, it is preferable to heat the glass frit to a temperature of at least about 10 6 dPas so that the glass frit is melted and light scattering on the surface does not occur. In order to prevent the glass frit from deteriorating due to the reaction between the glass frit and the phosphor, the compounding temperature is preferably set to a temperature at which the viscosity of the glass frit becomes about 10 5 dPas or less. When the glass phosphorescent composite is manufactured, the high refractive index component is easily crystallized in the glass, and a crystal phase is easily generated by reheating. When a crystal phase is generated, light emitted from the phosphor is scattered, so that light cannot be effectively extracted, and the afterglow luminance decreases. For this reason, ordinary high refractive index glass cannot be used because it causes crystallization.
本発明は、ガラス組成を工夫することで、再加熱の際の結晶化を起こさずに屈折率を蓄光体に合わせたガラスを作製し、高輝度の蓄光体−ガラス複合体を提供しようとするものである。 The present invention seeks to provide a high-luminance phosphorescent-glass composite by devising a glass composition to produce a glass whose refractive index is adjusted to that of a phosphorescent body without causing crystallization upon reheating. Things.
本発明者らは、上記した目的を達成すべく誠意研究を重ねてきた。その結果、ガラス組成を特定の成分とすることにより、蓄光体との複合化の際に必要な温度域で結晶化が起こらず透明性の高い複合体を作製できることを見出した。本発明は、このような知見に基づき、さらに研究を重ね、完成させたものである。すなわち、本発明は、以下の構成を包含する。
項１．ＳｉＯ2及びＢ2Ｏ3を主成分とするホウケイ酸ガラスであって、
ＳｉＯ2及びＢ2Ｏ3の合計含有量が４５モル％以上であり、
Ｎｂ2Ｏ5、ＺｒＯ2及びＬａ2Ｏ3よりなる群から選ばれる少なくとも２種と、ＴｉＯ2とを含有し、
Ｎｂ2Ｏ5の含有量が０〜３．８モル％であり、ＺｒＯ2の含有量が０〜４．３モル％であり、Ｌａ2Ｏ3の含有量が０〜４モル％であり、ＴｉＯ2の含有量が０．５〜３．８モル％であり、
ＺｎＯの含有量が０〜１７％であり、ＢａＯの含有量が１〜８モル％である、ガラス蓄光体複合体用のホウケイ酸ガラス。
項２．Ｎｂ2Ｏ5が含まれる場合の含有量は０．５〜３．８モル％であり、ＺｒＯ2が含まれる場合の含有量は０．５〜４．３モル％であり、Ｌａ2Ｏ3が含まれる場合の含有量は０．５〜４．０モル％である、項１に記載のガラス蓄光体複合体用のホウケイ酸ガラス。
項３．ＴｉＯ2の含有量が０．５〜２．８モル％である、項１又は２に記載のガラス蓄光体複合体用のホウケイ酸ガラス。
項４．Ｎｂ2Ｏ5の含有量が０〜２．８モル％である、項１〜３のいずれかに記載のガラス蓄光体複合体用のホウケイ酸ガラス。
項５．ＺｎＯの含有量が０〜７．５モル％である、項１〜４のいずれかに記載のガラス蓄光体複合体用のホウケイ酸ガラス。
項６．ＺｎＯの含有量が０〜３．８モル％である、項１〜５のいずれかに記載のガラス蓄光体複合体用のホウケイ酸ガラス。
項７．項１〜６のいずれかに記載のホウケイ酸ガラスからなるガラスフリット。
項８．屈折率が１．６４以上である、項７に記載のガラスフリット。
項９．粘度が１０5〜１０6ｄＰａｓとなる温度に３０分間加熱した際に結晶化しない、項７又は８に記載のガラスフリット。
項１０．項７〜９のいずれかに記載のガラスフリットと、蓄光体とを含有する、ガラス成形品。
The present inventors have been conducting sincere research to achieve the above-mentioned object. As a result, it has been found that by using a glass composition as a specific component, a composite having high transparency can be produced without causing crystallization in a temperature range necessary for composite with a phosphorescent body. The present invention has been completed by further research based on such findings. That is, the present invention includes the following configurations.
Item 1. A borosilicate glass containing SiO 2 and B 2 O 3 as main components,
The total content of SiO 2 and B 2 O 3 is 45 mol% or more,
Containing at least two members selected from the group consisting of Nb 2 O 5 , ZrO 2 and La 2 O 3 , and TiO 2 ,
Content of Nb 2 O 5 is 0 to 3.8 mol%, the content of ZrO 2 is 0 to 4.3 mol%, the content of La 2 O 3 is 0-4 mol%, The content of TiO 2 is 0.5 to 3.8 mol%,
A borosilicate glass for a glass phosphor composite, wherein the content of ZnO is 0 to 17% and the content of BaO is 1 to 8 mol%.
Item 2. The content of the case that contains Nb 2 O 5 is an 0.5 to 3.8 mole%, the content of the case that contains ZrO 2 is 0.5 to 4.3 mol%, La 2 O 3 The borosilicate glass for a glass phosphor composite according to item 1, wherein the content when is contained is 0.5 to 4.0 mol%.
Item 3. The content of TiO 2 is 0.5 to 2.8 mol%, the glass phosphorescent article borosilicate glass for composite according to claim 1 or 2.
Item 4. Content of Nb 2 O 5 is 0 to 2.8 mol%, the glass phosphorescent article borosilicate glass for composite according to any one of claim 1 to 3.
Item 5. Item 5. The borosilicate glass for a glass phosphor composite according to any one of Items 1 to 4, wherein the content of ZnO is 0 to 7.5 mol%.
Item 6. Item 6. The borosilicate glass for a glass phosphor composite according to any one of Items 1 to 5, wherein the content of ZnO is 0 to 3.8 mol%.
Item 7. Item 7. A glass frit comprising the borosilicate glass according to any one of Items 1 to 6.
Item 8. Item 8. The glass frit according to Item 7, having a refractive index of 1.64 or more.
Item 9. Item 7. The glass frit according to Item 7 or 8, wherein the glass frit does not crystallize when heated to a temperature at which the viscosity becomes 10 5 to 10 6 dPas for 30 minutes.
Item 10. Item 10. A glass molded article containing the glass frit according to any one of Items 7 to 9 and a phosphorescent body.
本発明によれば、ガラス蓄光体複合体を作製した際に発光を有効に取り出すために屈折率を向上させつつも、ガラス蓄光体複合体を作製する際の加熱の際の結晶化を抑制することができる。 ADVANTAGE OF THE INVENTION According to this invention, while producing a glass luminous body composite, while improving a refractive index in order to take out light emission effectively, suppressing crystallization at the time of heating at the time of producing a glass luminous body composite is suppressed. be able to.
１．ホウケイ酸ガラス
本発明のホウケイ酸ガラスは、ＳｉＯ２及びＢ２Ｏ３を主成分とするホウケイ酸ガラスであって、
ＳｉＯ２及びＢ２Ｏ３の合計含有量が４５モル％以上であり、
Ｎｂ２Ｏ５、ＴｉＯ２、ＺｒＯ２及びＬａ２Ｏ３よりなる群から選ばれる少なくとも３種を含有し、ＺｒＯ２の含有量が０〜４．３モル％である。
1. Borosilicate glass The borosilicate glass of the present invention is a borosilicate glass containing SiO 2 and B 2 O 3 as main components,
The total content of SiO 2 and B 2 O 3 is 45 mol% or more,
Nb 2 O 5, containing TiO 2, at least 3 kinds selected from ZrO 2 and La 2 O 3 the group consisting of the content of ZrO 2 is 0 to 4.3 mol%.
本発明のホウケイ酸ガラスにおいて、ＳｉＯ２は、ガラスを構成する主成分であり、よりガラスを安定化させるとともに、より屈折率を低下させない観点から、その含有量は、２０〜５０モル％が好ましく、２５〜４５モル％がより好ましい。 In the borosilicate glass of the present invention, SiO 2 is a main component constituting the glass, and from the viewpoint of further stabilizing the glass and not lowering the refractive index, the content is preferably 20 to 50 mol%. And 25 to 45 mol% is more preferable.
本発明のホウケイ酸ガラスにおいて、Ｂ２Ｏ３は、ガラスを構成する主成分であり、蓄光体との複合化のために必要な温度をより低くし、屈折率をより向上させ、ガラスをより安定にするとともに、蓄光体との反応性をより低下させる観点から、その含有量は、７〜３０モル％が好ましく、１０〜２７モル％がより好ましい。 In the borosilicate glass of the present invention, B 2 O 3 is a main component constituting the glass, and lowers the temperature required for compounding with the phosphorescent body, further improves the refractive index, and further improves the glass. From the viewpoint of stabilizing and further reducing the reactivity with the phosphor, the content is preferably from 7 to 30 mol%, more preferably from 10 to 27 mol%.
本発明のホウケイ酸ガラスにおいて、ＳｉＯ２及びＢ２Ｏ３の合計含有量は、４５モル％以上（特に４５〜６５モル％）、好ましくは５０〜６０モル％である。ＳｉＯ２及びＢ２Ｏ３の合計含有量が少なすぎるとガラスを安定化させることができない。一方、ＳｉＯ２及びＢ２Ｏ３の合計含有量が多すぎると屈折率を十分に向上させることができないとともに、蓄光体との複合化のために必要な温度を十分に低くできないために蓄光体との複合化の際に蓄光体が劣化してしまう。 In the borosilicate glass of the present invention, the total content of SiO 2 and B 2 O 3 is 45 mol% or more (particularly 45 to 65 mol%), preferably 50 to 60 mol%. If the total content of SiO 2 and B 2 O 3 is too small, the glass cannot be stabilized. On the other hand, if the total content of SiO 2 and B 2 O 3 is too large, the refractive index cannot be sufficiently improved, and the temperature required for complexing with the phosphor can not be sufficiently reduced. The phosphorescent body is deteriorated in the case of compounding with the phosphor.
本発明のホウケイ酸ガラスにおいては、高屈折率成分として、Ｎｂ２Ｏ５、ＴｉＯ２、ＺｒＯ２及びＬａ２Ｏ３よりなる群から選ばれる少なくとも３種を含有する。高屈折率成分は、多ければ多いほどガラスの屈折率を向上させることができるが、１種の成分を多く含ませると、蓄光体と複合化する際に結晶化しやすいため、上記高屈折率成分を少量ずつ、多くの種類を含ませることが好ましい。このため、本発明においては、上記の高屈折率成分のうち少なくとも３種を含有する。 The borosilicate glass of the present invention contains, as the high refractive index component, at least three kinds selected from the group consisting of Nb 2 O 5 , TiO 2 , ZrO 2 and La 2 O 3 . The higher the refractive index component is, the more the refractive index of the glass can be improved. However, if a large amount of one kind of component is contained, it is easy to crystallize when compounded with a luminous body. It is preferable to include a large number of types in small amounts. For this reason, in the present invention, at least three of the above high refractive index components are contained.
これらの高屈折率成分のなかでも、最も屈折率を向上させることができることから、少なくともＮｂ２Ｏ５を含むことが好ましい。つまり、Ｎｂ２Ｏ５を含み、さらに、ＴｉＯ２、ＺｒＯ２及びＬａ２Ｏ３の少なくとも２種を含有することが好ましい。なかでも、Ｎｂ２Ｏ５、ＴｉＯ２及びＬａ２Ｏ３を含有するか、Ｎｂ２Ｏ５、ＴｉＯ２及びＺｒＯ２を含有するか、Ｎｂ２Ｏ５、ＴｉＯ２、ＺｒＯ２及びＬａ２Ｏ３を含有することが好ましい。 Among these high refractive index components, it is preferable to include at least Nb 2 O 5 because the refractive index can be improved most. That is, it preferably contains Nb 2 O 5 and further contains at least two of TiO 2 , ZrO 2 and La 2 O 3 . Among them, Nb 2 O 5 , TiO 2 and La 2 O 3 , Nb 2 O 5 , TiO 2 and ZrO 2 , Nb 2 O 5 , TiO 2 , ZrO 2 and La 2 O 3 Is preferable.
高屈折率成分のうち、Ｎｂ２Ｏ５は、最も屈折率を向上させる効果を有するが、蓄光体との複合化の際に必要な温度域で結晶化をより抑制するために含有量は多すぎないことが好ましい。また、Ｌａ２Ｏ３と併用する場合は、より結晶化しやすくなるため、含有量をより低くすることが好ましい。このため、Ｎｂ２Ｏ５の含有量は、より屈折率を向上させるとともに、より結晶化を抑制する観点から、０〜３．８モル％（特に０．５〜３．８モル％）が好ましく、０〜２．８モル％（特に０．５〜２．８モル％）がより好ましい。また、Ｌａ２Ｏ３と併用する場合は、Ｎｂ２Ｏ５の含有量は、０〜２．８モル％（特に０．５〜２．８モル％）が好ましく、０〜２．５モル％（特に０．５〜２．５モル％）がより好ましいが、ＺｎＯの含有量が少ない（０〜１７モル％、特に０〜７．５モル％）場合は、０〜３．８モル％（特に０．５〜３．８モル％）とすることもできる。 Among the high refractive index components, Nb 2 O 5 has the effect of improving the refractive index most, but its content is large in order to further suppress crystallization in the temperature range necessary for complexing with the phosphor. Preferably not too much. When used in combination with La 2 O 3 , crystallization is more likely to occur, so the content is preferably made lower. For this reason, the content of Nb 2 O 5 is preferably 0 to 3.8 mol% (particularly 0.5 to 3.8 mol%) from the viewpoint of further improving the refractive index and further suppressing crystallization. , 0 to 2.8 mol% (particularly, 0.5 to 2.8 mol%). When used in combination with La 2 O 3 , the content of Nb 2 O 5 is preferably 0 to 2.8 mol% (particularly 0.5 to 2.8 mol%), and 0 to 2.5 mol% (Especially 0.5 to 2.5 mol%), but when the content of ZnO is small (0 to 17 mol%, particularly 0 to 7.5 mol%), 0 to 3.8 mol% ( In particular, it can be 0.5 to 3.8 mol%).
高屈折率成分のうち、ＴｉＯ２は、屈折率を向上させる効果を有するが、蓄光体との複合化の際に必要な温度域で結晶化をより抑制するとともに、着色をより抑制するために含有量は多すぎないことが好ましい。このため、ＴｉＯ２の含有量は、より屈折率を向上させるとともに、蓄光体との複合化の際に必要な温度域でより結晶化を抑制し、着色をより抑制する観点から、０〜３．８モル％（特に０．５〜３．８モル％）が好ましく、０〜２．８モル％（特に０．５〜２．８モル％）がより好ましい。 Among the high refractive index components, TiO 2 has an effect of improving the refractive index. However, in order to further suppress crystallization in a temperature range necessary for compounding with the phosphor and to further suppress coloring. Preferably, the content is not too high. For this reason, the content of TiO 2 is preferably from 0 to 3 from the viewpoint of further improving the refractive index, further suppressing crystallization in a temperature range necessary for complexing with the luminous body, and further suppressing coloring. 0.8 mol% (especially 0.5 to 3.8 mol%) is preferable, and 0 to 2.8 mol% (especially 0.5 to 2.8 mol%) is more preferable.
高屈折率成分のうち、ＺｒＯ２は、屈折率及び耐火性（熱膨張率）を向上させる効果を有するが、含有量が多いと蓄光体との複合化の際に必要な温度域で結晶化する。このため、ＺｒＯ２の含有量は、０〜４．３モル％（特に０．５〜４．３モル％）、好ましくは０〜３．３モル％（特に１．５〜３．３モル％）である。 Among the high refractive index components, ZrO 2 has an effect of improving the refractive index and the fire resistance (thermal expansion coefficient), but if the content is large, it is crystallized in a temperature range necessary for complexing with a phosphorescent material. I do. For this reason, the content of ZrO 2 is 0 to 4.3 mol% (particularly 0.5 to 4.3 mol%), preferably 0 to 3.3 mol% (particularly 1.5 to 3.3 mol%). ).
高屈折率成分のうち、Ｌａ２Ｏ３は、屈折率を向上させる効果を有するが、蓄光体との複合化の際に必要な温度域で結晶化をより抑制するために含有量は多すぎないことが好ましい。また、Ｎｂ２Ｏ５と併用する場合は、より結晶化しやすくなるため、含有量をより低くすることが好ましい。このため、Ｌａ２Ｏ３の含有量は、より屈折率を向上させるとともに、蓄光体との複合化の際に必要な温度域でより結晶化を抑制する観点から、０〜４モル％（特に０．５〜４モル％）が好ましく、０〜２モル％（特に０．５〜２モル％）がより好ましい。また、Ｎｂ２Ｏ５と併用する場合は、Ｌａ２Ｏ３の含有量は、０〜２モル％（特に０．５〜２モル％）が好ましく、０〜１．５モル％（特に０．５〜１．５モル％）がより好ましいが、ＺｎＯの含有量が少ない（０〜１７モル％、特に０〜７．５モル％）場合は、０〜４モル％（特に０．５〜４モル％）とすることもできる。 Among the high refractive index components, La 2 O 3 has an effect of improving the refractive index, but its content is too large in order to further suppress crystallization in a temperature range necessary for complexing with the phosphor. Preferably not. When used in combination with Nb 2 O 5 , crystallization is more likely to occur, so that the content is preferably made lower. For this reason, the content of La 2 O 3 is from 0 to 4 mol% (particularly, from the viewpoint of further improving the refractive index and further suppressing crystallization in a temperature range necessary for complexing with the phosphor. 0.5 to 4 mol%), and more preferably 0 to 2 mol% (particularly 0.5 to 2 mol%). Further, when used in combination with Nb 2 O 5, the content of La 2 O 3 is 0 to 2 mol% (particularly 0.5 to 2 mol%), more preferably 0 to 1.5 mol% (particularly 0. More preferably, the content of ZnO is small (0 to 17 mol%, particularly 0 to 7.5 mol%), and 0 to 4 mol% (particularly 0.5 to 4 mol%). Mol%).
本発明のホウケイ酸ガラスには、ＺｎＯが含まれていてもよい。ＺｎＯは、ガラス転移温度を低減することができる（蓄光体との複合化の際に必要な温度を低減することができるため結晶化をより抑制することができる）とともに、屈折率を向上させる効果も有する。ただし、ガラスが柔らかくなると結晶化しやすくなるとともに、Ｎｂ２Ｏ５とＬａ２Ｏ３とを併用する場合は、より結晶化しやすくなるため含有量は多すぎないことが好ましい。なお、屈折率向上の観点からはＺｎＯの含有量は多いほうが好ましいが、結晶化抑制の観点からはＺｎＯの含有量は少ないほうが好ましい。このため、ＺｎＯの含有量は、結晶化抑制の観点からは、０〜１７モル％が好ましく、０〜７．５モル％がより好ましく、０〜３．８モル％がさらに好ましい。また、ＺｎＯの含有量は、屈折率向上の観点からは、０〜１７モル％が好ましく、５〜１６モル％がより好ましく、８〜１５モル％がさらに好ましい。 The borosilicate glass of the present invention may contain ZnO. ZnO can reduce the glass transition temperature (the temperature required for complexing with the phosphor can be reduced, so that crystallization can be further suppressed) and the effect of improving the refractive index. Also have. However, when the glass is soft, it is easy to crystallize, and when Nb 2 O 5 and La 2 O 3 are used in combination, it is preferable that the content is not too large because the glass is more easily crystallized. In addition, from the viewpoint of improving the refractive index, the content of ZnO is preferably higher, but from the viewpoint of suppressing crystallization, the content of ZnO is preferably lower. Therefore, the content of ZnO is preferably from 0 to 17 mol%, more preferably from 0 to 7.5 mol%, and still more preferably from 0 to 3.8 mol%, from the viewpoint of suppressing crystallization. Further, the content of ZnO is preferably from 0 to 17 mol%, more preferably from 5 to 16 mol%, and still more preferably from 8 to 15 mol%, from the viewpoint of improving the refractive index.
本発明のホウケイ酸ガラスには、Ａｌ２Ｏ３が含まれていてもよい。Ａｌ２Ｏ３は、耐水性を向上させる効果を有する。Ａｌ２Ｏ３を含ませる場合、その含有量は、より耐水性を向上させる観点から、０．２〜５モル％が好ましく、０．５〜３モル％がより好ましい。 The borosilicate glass of the present invention may contain Al 2 O 3 . Al 2 O 3 has an effect of improving water resistance. When Al 2 O 3 is contained, the content is preferably from 0.2 to 5 mol%, more preferably from 0.5 to 3 mol%, from the viewpoint of further improving the water resistance.
本発明のホウケイ酸ガラスには、アルカリ金属酸化物が含まれていてもよい。アルカリ金属酸化物としては、例えば、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等が挙げられ、ガラス転移温度を低減する（蓄光体との複合化の際に必要な温度を低減することができるため結晶化をより抑制する）とともにガラスを安定化しやすい効果を有するが、含有量が多すぎると屈折率及び耐水性が低下しやすく、蓄光体との複合化の際に必要な温度域で結晶化もしやすい。また、Ｌｉ２ＯとＺｎＯとを併用する場合は結晶化しやすいが、本態様ではＺｎＯの含有量が少ないため、Ｌｉ２Ｏの含有量を若干多めにしても結晶化を抑制することができる。このような観点から、Ｌｉ２Ｏの含有量は３〜２０モル％（特に５〜１５モル％）が好ましく、Ｎａ２Ｏの含有量は１〜５モル％（特に２〜４モル％）が好ましく、Ｋ２Ｏの含有量は０〜５モル％（特に０〜３モル％）が好ましい。また、アルカリ金属酸化物の含有量は５〜３０モル％が好ましく、７〜２５モル％がより好ましい。 The borosilicate glass of the present invention may contain an alkali metal oxide. Examples of the alkali metal oxide include Li 2 O, Na 2 O, and K 2 O, and reduce the glass transition temperature (the temperature required for complexing with a phosphorescent material can be reduced. In addition, it has the effect of stabilizing the glass as well as having the effect of easily stabilizing the glass. It is easy to change. When Li 2 O and ZnO are used together, crystallization is easy. However, in this embodiment, since the content of ZnO is small, crystallization can be suppressed even if the content of Li 2 O is slightly increased. From such a viewpoint, the content of Li 2 O is preferably 3 to 20 mol% (particularly 5 to 15 mol%), and the content of Na 2 O is 1 to 5 mol% (particularly 2 to 4 mol%). Preferably, the content of K 2 O is 0 to 5 mol% (particularly 0 to 3 mol%). Further, the content of the alkali metal oxide is preferably from 5 to 30 mol%, more preferably from 7 to 25 mol%.
本発明のホウケイ酸ガラスには、アルカリ土類金属酸化物が含まれていてもよい。アルカリ土類金属酸化物としては、例えば、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ等が挙げられ、ガラスを安定化しやすい効果を有するが、含有量が多すぎると耐水性が低下しやすく、蓄光体との複合化の際に必要な温度域で結晶化もしやすい。このような観点から、ＭｇＯの含有量は０〜５モル％（特に１〜４モル％）が好ましく、ＣａＯの含有量は４〜１５モル％（特に５〜１０モル％）が好ましく、ＳｒＯの含有量は０〜５モル％（特に１〜４モル％）が好ましく、ＢａＯの含有量は１〜８モル％（特に２〜６モル％）が好ましい。また、アルカリ土類金属酸化物の含有量は５〜２５モル％が好ましく、６〜２０モル％がより好ましい。 The borosilicate glass of the present invention may contain an alkaline earth metal oxide. Examples of the alkaline earth metal oxide include MgO, CaO, SrO, and BaO, which have an effect of easily stabilizing the glass. Crystallization is also easy in the temperature range required for complexing. From such a viewpoint, the content of MgO is preferably 0 to 5 mol% (particularly 1 to 4 mol%), the content of CaO is preferably 4 to 15 mol% (particularly 5 to 10 mol%), and the content of SrO is The content is preferably 0 to 5 mol% (particularly 1 to 4 mol%), and the content of BaO is preferably 1 to 8 mol% (particularly 2 to 6 mol%). The content of the alkaline earth metal oxide is preferably from 5 to 25 mol%, more preferably from 6 to 20 mol%.
本発明のホウケイ酸ガラスには、ＣａＦ２が含まれていてもよい。ＣａＦ２は、ガラス転移温度を低減する（蓄光体との複合化の際に必要な温度を低減する）効果を有するが、含有量が多すぎるとフッ化物の結晶が析出しやすい。このような観点から、ＣａＦ２の含有量は０〜７モル％（特に１〜５モル％）が好ましい。 The borosilicate glass of the present invention may contain CaF 2 . CaF 2 has the effect of reducing the glass transition temperature (reducing the temperature required for complexing with the phosphor), but if the content is too large, fluoride crystals are likely to precipitate. From such a viewpoint, the content of CaF 2 is preferably 0 to 7 mol% (particularly 1 to 5 mol%).
本発明のホウケイ酸ガラスには、ＳｎＯ２が含まれていてもよい。ＳｎＯ２は、欠陥の生成による黒化を抑制する効果を有するが、含有量が多すぎると蓄光体との複合化の際に必要な温度域で結晶化しやすい。このような観点から、ＳｎＯ２の含有量は０〜２モル％（特に０．１〜１モル％）が好ましい。 The borosilicate glass of the present invention may contain SnO 2 . SnO 2 has an effect of suppressing blackening due to the generation of defects, but if the content is too large, it is likely to crystallize in a temperature range necessary for complexing with a luminous body. From this viewpoint, the content of SnO 2 0 to 2 mol% (particularly 0.1 to 1 mol%) is preferable.
本発明のホウケイ酸ガラスには、Ｇｄ２Ｏ３が含まれていてもよい。Ｇｄ２Ｏ３は、Ｌａ２Ｏ３と同様の効果を有するが、含有量が多すぎると蓄光体との複合化の際に必要な温度域で結晶化しやすい。このような観点から、Ｇｄ２Ｏ３の含有量は０〜２モル％（特に０．１〜１モル％）が好ましい。 The borosilicate glass of the present invention may contain Gd 2 O 3 . Gd 2 O 3 has the same effect as La 2 O 3 , but if the content is too large, it tends to crystallize in a temperature range necessary for complexing with a phosphor. From this viewpoint, the content of Gd 2 O 3 is 0 to 2 mol% (particularly 0.1 to 1 mol%) is preferable.
２．ガラスフリット
本発明のホウケイ酸ガラスは、上記の組成を有していることから、本発明のホウケイ酸ガラスからなるガラスフリットは、種々の優れた特性を有している。
2. Glass Frit Since the borosilicate glass of the present invention has the above composition, the glass frit made of the borosilicate glass of the present invention has various excellent properties.
本発明のガラスフリットの屈折率は、１．６４以上（特に１．６４〜１．６７）が好ましく、１．６５以上（特に１．６５〜１．６６８）がより好ましい。屈折率を上記範囲内とすることにより、例えば、アルミン酸ストロンチウム系高輝度蓄光体の屈折率は１．６５以上であることから、本発明のガラスフリットの屈折率を蓄光体の屈折率に近づけ、蓄光体を含有するガラス成形品を製造した際に蓄光体の発光をより有効に取り出すことができる。特に、特許文献２に記載のガラスフリットは、屈折率が１．５２であることと比較すると、本発明のガラスフリットは、蓄光体に屈折率を近づけることができることから、蓄光体の発光をより有効に取り出すことができる。本発明のガラスフリットの屈折率は、アッベ屈折計を用いて屈折率１．７０以上の中間液を使用して測定するものとする。 The refractive index of the glass frit of the present invention is preferably 1.64 or more (particularly 1.64 to 1.67), more preferably 1.65 or more (particularly 1.65 to 1.668). By setting the refractive index within the above range, for example, the refractive index of the strontium aluminate-based high-luminance phosphor is 1.65 or more, so that the refractive index of the glass frit of the present invention is close to the refractive index of the phosphor. In addition, when a glass molded article containing a luminous body is manufactured, light emitted from the luminous body can be more effectively extracted. In particular, since the glass frit described in Patent Document 2 has a refractive index of 1.52, the glass frit of the present invention can make the refractive index close to that of the luminous body. Can be taken out effectively. The refractive index of the glass frit of the present invention is measured using an Abbe refractometer using an intermediate liquid having a refractive index of 1.70 or more.
本発明のガラスフリットの熱膨張係数は、耐熱性をより向上させる観点から、７．０×１０−６〜１５．０×１０−６（１／℃）が好ましく、７．５×１０−６〜１３．０×１０−６（１／℃）がより好ましく、７．８×１０−６〜１２．０×１０−６（１／℃）がさらに好ましい。本発明のガラスフリットの熱膨張係数は、熱膨張計を用いて測定するものとする。 The thermal expansion coefficient of the glass frit of the present invention is preferably from 7.0 × 10 −6 to 15.0 × 10 −6 (1 / ° C.) from the viewpoint of further improving heat resistance, and is preferably 7.5 × 10 −6. To 13.0 × 10 −6 (1 / ° C.) is more preferable, and 7.8 × 10 −6 to 12.0 × 10 −6 (1 / ° C.) is further preferable. The coefficient of thermal expansion of the glass frit of the present invention is measured using a thermal dilatometer.
本発明のガラスフリットのガラス転移温度は、耐熱性をより向上させるとともに、蓄光体との複合化の際に必要な温度を低減することができるため結晶化をより抑制することができる観点から、４３０〜６００℃が好ましく、４５０〜５７０℃がより好ましく、４６０〜５５０℃がさらに好ましい。本発明のガラスフリットのガラス転移温度は、熱膨張計を用いて測定するものとする。 The glass transition temperature of the glass frit of the present invention further improves heat resistance, and from the viewpoint of further suppressing crystallization because the temperature required for complexing with the phosphor can be reduced. 430-600 ° C is preferred, 450-570 ° C is more preferred, and 460-550 ° C is even more preferred. The glass transition temperature of the glass frit of the present invention is measured using a thermal dilatometer.
本発明のガラスフリットは、上記のような組成を有するホウケイ酸ガラスからなるため、蓄光体との複合化の際に必要な温度域において結晶化しにくい。具体的には、粘度が１０５〜１０６ｄＰａｓとなる温度（具体的には６５０〜８００℃）に３０分間加熱した際に結晶化しないことが好ましい。これにより、蓄光体との複合化の際に結晶化をより抑制することができる。 Since the glass frit of the present invention is made of borosilicate glass having the above-described composition, it is difficult to crystallize in a temperature range necessary for compounding with the phosphor. Specifically, it is preferable not to crystallize when heated at a temperature at which the viscosity becomes 10 5 to 10 6 dPas (specifically, 650 to 800 ° C.) for 30 minutes. This makes it possible to further suppress crystallization during compounding with the phosphor.
本発明のガラスフリットは、ガラスフリット製造原料（ガラスフリット（ホウケイ酸ガラス）の構成成分、又は該成分を含むもしくは焼成により該成分を生成しうる、天然鉱石、酸化物、水酸化物、炭酸塩、硝酸塩等）を、ガラスフリット組成が所望の組成となるように秤量して混合し、１０００〜１５００℃程度の温度で溶融させた後、溶融物を流し出してそのまま冷却（空気中で放冷）するか又は水中に入れて急冷することにより製造することができる。この後、必要に応じて、細かく粉砕（粗粉砕及び微粉砕）することにより粒径を制御してもよい。この場合、ガラスフリットの粒径は、取扱性を考慮して適宜選択することができるが、通常、平均粒径として、５〜１００μｍが好ましく、２５〜７５μｍがより好ましい。 The glass frit of the present invention is a raw material for producing glass frit (a constituent component of glass frit (borosilicate glass), or a natural ore, an oxide, a hydroxide, or a carbonate containing the component or capable of producing the component by firing). , Nitrates, etc.) are weighed and mixed so that the glass frit composition becomes a desired composition, melted at a temperature of about 1000 to 1500 ° C., and then the melt is poured out and cooled as it is (cooled in air) ) Or quenched in water. Thereafter, if necessary, the particle size may be controlled by finely pulverizing (coarse and fine pulverization). In this case, the particle size of the glass frit can be appropriately selected in consideration of handleability, but usually, the average particle size is preferably 5 to 100 μm, more preferably 25 to 75 μm.
本発明のガラスフリットは、上記のような特性を有していることから、蓄光体との複合化（蓄光体を含有するガラス成形品の製造）のために特に有用である。 Since the glass frit of the present invention has the above characteristics, it is particularly useful for compounding with a luminous body (manufacture of a glass molded article containing the luminous body).
３．ガラス成形品
本発明のガラス成形品は、本発明のガラスフリットと蓄光体とを含有する。
3. Glass molded article The glass molded article of the present invention contains the glass frit of the present invention and a luminous body.
本発明のガラスフリットは、上記説明したものである。 The glass frit of the present invention has been described above.
本発明のガラス成形品において、本発明のガラスフリットの含有量は、複合体の輝度を最大にするために蓄光体間の空隙を完全に埋めるという観点から、６０〜９０重量％が好ましく、７０〜８０重量％がより好ましい。 In the glass molded article of the present invention, the content of the glass frit of the present invention is preferably from 60 to 90% by weight from the viewpoint of completely filling the gaps between the luminous bodies in order to maximize the brightness of the composite, and 70% by weight. ~ 80 wt% is more preferred.
蓄光体としては、特に制限はなく、ユーロピウム等で賦活され、マンガン、ジルコニウム、ニオブ、セリウム、プラセオジム、ネオジム、サマリウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウム等で共賦活されるとともに、一部をホウ素で置換してアルミン酸塩（マグネシウム塩、カルシウム塩、ストロンチウム塩、バリウム塩、亜鉛塩等）を使用できる。このような蓄光体としては、例えば、特開平７−１１２５０号公報、特開平８−７３８４５号公報等に記載されている蓄光体（蓄光性蛍光体、残光性蛍光体）等を使用できる。これらの蓄光体は、公知又は市販の蓄光体から適宜選択し、単一種又は複数種を混合し発光色等の発光特性を調整して用いることができる。蓄光体の発光色は、特に限定されず、例えば、青色、緑色、青緑色等の何れであってもよい。 The phosphorescent is not particularly limited, and is activated by europium or the like, and is activated by manganese, zirconium, niobium, cerium, praseodymium, neodymium, samarium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, etc. Alternatively, aluminates (magnesium salts, calcium salts, strontium salts, barium salts, zinc salts, etc.) can be used by partially substituting them with boron. As such a luminous body, for example, luminous bodies (luminous phosphors, afterglow phosphors) described in JP-A-7-11250 and JP-A-8-73845 can be used. These luminous bodies can be appropriately selected from known or commercially available luminous bodies, and a single kind or a mixture of a plurality of kinds can be used after adjusting the emission characteristics such as emission color. The emission color of the phosphor is not particularly limited, and may be, for example, any of blue, green, and blue-green.
蓄光体の平均粒子径は、特に制限はないが、大きい蓄光体のほうが、高い残光輝度が得られやすいことから、１〜４００μｍが好ましく、５０〜３００μｍがより好ましい。蓄光体の平均粒子径は、光学顕微鏡により測定するものとする。 The average particle diameter of the phosphor is not particularly limited, but is preferably from 1 to 400 µm, more preferably from 50 to 300 µm, since a larger phosphor can easily obtain high afterglow luminance. The average particle diameter of the luminous body is measured by an optical microscope.
本発明のガラス成形品において、蓄光体の含有量は、蓄光体間の空隙が完全に埋めて複合体の輝度を最大にするという観点から、１０〜４０重量％が好ましく、２０〜３０重量％がより好ましい。 In the glass molded product of the present invention, the content of the luminous body is preferably from 10 to 40% by weight, and more preferably from 20 to 30% by weight, from the viewpoint that voids between the luminous bodies are completely filled to maximize the brightness of the composite. Is more preferred.
本発明のガラス成形品は、例えば、本発明のガラスフリットと、必要に応じて微細に粉砕された蓄光体とを混合し、得られた混合物を、ガラスフリットのガラス転移点よりも１８０〜２８０℃（特に２００〜２５０℃）高い温度で焼成（溶融成形）することにより製造することができる。 The glass molded article of the present invention is obtained by, for example, mixing the glass frit of the present invention with a finely pulverized phosphor as needed, and setting the obtained mixture to 180 to 280 from the glass transition point of the glass frit. It can be manufactured by firing (melt molding) at a high temperature of 200C (especially 200 to 250C).
焼成（溶融成形）の際には、適宜な型に詰めてもよい。使用できる型としては、耐熱性の高い材質のものであればよく、金属製、セラミック製等の何れであってもよいが、得られるガラス成形品の取り出しやすさ等の点で、金属製、石膏製の型が好ましい。石膏製の型の場合は、焼成後、型を砕くことにより、ガラス成形品を容易に取り出すことができる。 During firing (melt molding), the material may be packed in an appropriate mold. As a mold that can be used, any material having high heat resistance may be used, and it may be made of metal, ceramic, or the like. Gypsum molds are preferred. In the case of a plaster mold, after firing, the molded glass article can be easily taken out by crushing the mold.
なお、本発明のガラスフリット及び蓄光体の他、さらに、有機バインダー、水、有機溶媒等を加えて混合又は混練し、これらの混合物又は混練物を必要に応じて上記の型に入れて焼成（溶融成形）してもよい。 In addition, in addition to the glass frit and the phosphorescent body of the present invention, an organic binder, water, an organic solvent, and the like are further added and mixed or kneaded. Melt molding).
有機バインダーとしては、例えば、カルボキシメチルセルロース、メチルセルロース、エチルセルロース等のセルロース系樹脂；アラビアゴム等の水溶性乃至親水性高分子；スキージーオイル、アクリル樹脂、ブチラール樹脂等が挙げられる。これらの有機バインダーは焼成時に焼失するものである。 Examples of the organic binder include cellulosic resins such as carboxymethylcellulose, methylcellulose, and ethylcellulose; water-soluble or hydrophilic polymers such as gum arabic; squeegee oil, acrylic resins, butyral resins, and the like. These organic binders burn off during firing.
本発明のガラス成形品は、上記のようにして製造したガラス成形品を再度粉砕して、適宜な大きさの蓄光体入りのガラスフリットとし、この蓄光体入りガラスフリットを所望の型に入れて、上記の温度で焼成（溶融成形）することで、再度ガラス成形品を製造してもよい。 The glass molded product of the present invention is obtained by pulverizing the glass molded product produced as described above again to obtain a glass frit containing a luminous body of an appropriate size, and putting the glass frit containing the luminous body into a desired mold. By firing (melt molding) at the above temperature, a glass molded article may be produced again.
本発明のガラス成形品の形状は特に制限されず、例えば、球状、半球状、楕球状、碁石状、平板状（底面が円形、四角形、三角形、星形、ハート形、花びら形状等）、角柱状、角錐状、円柱状、円錐状、不定形状等の何れであってもよい。 The shape of the glass molded product of the present invention is not particularly limited, and examples thereof include a spherical shape, a hemispherical shape, an oval shape, a stone-like shape, a flat shape (a bottom surface is a circle, a square, a triangle, a star, a heart, a petal, and the like), a corner. Any of a columnar shape, a pyramid shape, a columnar shape, a conical shape, an irregular shape and the like may be used.
本発明のガラス成形品の大きさも特に限定されない。本発明のガラス成形品の厚み（最大厚み）は、例えば、１〜３０ｍｍが好ましく、２〜１０ｍｍがより好ましい。 The size of the glass molded article of the present invention is not particularly limited. The thickness (maximum thickness) of the glass molded article of the present invention is, for example, preferably 1 to 30 mm, more preferably 2 to 10 mm.
本発明のガラス成形品は、その表面が透明ガラス層で被覆されていてもよい。本発明のガラス成形品の表面に透明ガラス層を設けることにより、表面を平滑化できるとともに、本発明のガラス成形品の表面付近に存在する蓄光体が空気、水等により変質及び／又は劣化することを防止することができる。この際、透明ガラス層は、本発明のガラスフリットからなるものを採用することが好ましい。透明ガラス層は、例えば、本発明のガラスフリットを含むコーティング組成物を用いて、本発明のガラス成形品の表面の一部又は全体に該コーティング組成物からなる被複層を設け、例えば７００〜８５０℃（特に７５０〜８３０℃）の温度で焼成することにより形成できる。 The surface of the glass molded product of the present invention may be covered with a transparent glass layer. By providing a transparent glass layer on the surface of the glass molded article of the present invention, the surface can be smoothed, and the phosphorescent substance near the surface of the glass molded article of the present invention is deteriorated and / or deteriorated by air, water, and the like. Can be prevented. At this time, it is preferable to employ a transparent glass layer made of the glass frit of the present invention. The transparent glass layer, for example, using a coating composition containing the glass frit of the present invention, to provide a multi-layer to be formed of the coating composition on a part or the entire surface of the glass molded article of the present invention, for example, 700 to It can be formed by firing at a temperature of 850 ° C (especially 750 to 830 ° C).
前記コーティング組成物は、例えば、本発明のガラスフリットを水溶きしたり、本発明のガラスフリットと有機バインダーと溶媒（水及び／又は有機溶剤）とを混練したりすることにより調製できる。有機バインダーとしては、前記例示のものを使用でき、焼成時に焼失する。また、コーティング組成物の形態は、塗布性等の観点から、分散液又はペーストが好ましい。 The coating composition can be prepared by, for example, dissolving the glass frit of the present invention in water, or kneading the glass frit of the present invention, an organic binder, and a solvent (water and / or organic solvent). As the organic binder, those exemplified above can be used, and are burned out during firing. The form of the coating composition is preferably a dispersion or a paste from the viewpoint of applicability and the like.
前記コーティング組成物を用いた被複層の形成は、慣用の方法、例えば、印刷法（スクリーン印刷法等）、スプレー法、浸し掛け法、流し掛け法、刷毛法、筆塗り法、転写法等により行うことができる。 The formation of the multiple layers using the coating composition can be performed by a conventional method, for example, a printing method (such as a screen printing method), a spray method, a dipping method, a flowing method, a brush method, a brush coating method, a transfer method, and the like. Can be performed.
透明ガラス層の厚みは特に限定されず、目的に応じて適宜設定できるが、通常、１０〜２０００μｍが好ましく、２０〜２００μｍがより好ましい。 The thickness of the transparent glass layer is not particularly limited and can be appropriately set according to the purpose, but is usually preferably from 10 to 2000 μm, more preferably from 20 to 200 μm.
このような構成を有する本発明のガラス成形品は、本発明のガラスフリット（本発明のホウケイ酸ガラス）が上記構成を有していることから、製造時の結晶化を抑制することができるとともに、内在する蓄光体の発光を有効に取り出すことができる。このため、電力を用いない屋外照明、停電時の安全標識等の用途に有用である。 In the glass molded article of the present invention having such a configuration, since the glass frit of the present invention (the borosilicate glass of the present invention) has the above-described configuration, crystallization during production can be suppressed, and In addition, the light emission of the intrinsic phosphor can be effectively extracted. Therefore, it is useful for applications such as outdoor lighting that does not use electric power and safety signs at the time of a power failure.
以下、実施例及び比較例を挙げて本発明を更に詳細に説明するが、本発明は以下の実施例のみに限定されないことは言うまでもない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to only the following Examples.
実施例１
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、炭酸ランタン、水酸化アルミニウム、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、フッ化カルシウム、炭酸バリウム、酸化スズ、及び酸化ガドリニウムを所定量混合し、白金るつぼ内で１２００℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例１のガラスフリット（ホウケイ酸ガラス）を得た。
Example 1
Silicon dioxide, boric acid, niobium oxide, titanium oxide, lanthanum carbonate, aluminum hydroxide, calcium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, calcium fluoride, barium carbonate, tin oxide, and gadolinium oxide are mixed in a predetermined amount, The glass frit (borosilicate glass) of Example 1 having the composition shown in Table 1 was obtained by melting at 1200 ° C. in a platinum crucible and allowing it to cool in air.
実施例２
二酸化ケイ素、ホウ酸、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例２のガラスフリット（ホウケイ酸ガラス）を得た。
Example 2
Mix a predetermined amount of silicon dioxide, boric acid, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide. The glass frit (borosilicate glass) of Example 2 having the composition shown in Table 1 was obtained by melting at 1300 ° C. in a platinum crucible and allowing it to cool in air.
実施例３
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例３のガラスフリット（ホウケイ酸ガラス）を得た。
Example 3
Silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide The glass frit (borosilicate glass) of Example 3 having the composition shown in Table 1 was obtained by quantitatively mixing, melting at 1300 ° C. in a platinum crucible, and allowing to cool in air.
実施例４
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例４のガラスフリット（ホウケイ酸ガラス）を得た。
Example 4
Silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide The glass frit (borosilicate glass) of Example 4 having a composition shown in Table 1 was obtained by quantitatively mixing, melting at 1300 ° C. in a platinum crucible, and allowing to cool in air.
実施例５
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例５のガラスフリット（ホウケイ酸ガラス）を得た。
Example 5
Mix a predetermined amount of silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide. The glass frit (borosilicate glass) of Example 5 having the composition shown in Table 1 was obtained by melting at 1300 ° C. in a platinum crucible and allowing it to cool in air.
実施例６
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例６のガラスフリット（ホウケイ酸ガラス）を得た。
Example 6
Silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide The glass frit (borosilicate glass) of Example 6 having the composition shown in Table 1 was obtained by quantitatively mixing, melting at 1300 ° C. in a platinum crucible, and allowing to cool in air.
実施例７
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例７のガラスフリット（ホウケイ酸ガラス）を得た。
Example 7
Silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide The glass frit (borosilicate glass) of Example 7 having the composition shown in Table 1 was obtained by quantitatively mixing, melting at 1300 ° C. in a platinum crucible, and allowing it to cool in air.
実施例８
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１２５０℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例８のガラスフリット（ホウケイ酸ガラス）を得た。
Example 8
A predetermined amount of silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, strontium carbonate, barium carbonate, and tin oxide are mixed in a predetermined amount, and platinum is mixed. The glass frit (borosilicate glass) of Example 8 having the composition shown in Table 1 was obtained by melting at 1250 ° C. in a crucible and allowing it to cool in air.
実施例９
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、フッ化カルシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１２００℃で溶融し、空気中で放冷することで、表１に示す組成を有する実施例９のガラスフリット（ホウケイ酸ガラス）を得た。
Example 9
Predetermined amounts of silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, calcium fluoride, strontium carbonate, barium carbonate, and tin oxide The glass frit (borosilicate glass) of Example 9 having the composition shown in Table 1 was obtained by mixing, melting at 1200 ° C. in a platinum crucible, and allowing to cool in air.
参考例１
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表２に示す組成を有する参考例１のガラスフリット（ホウケイ酸ガラス）を得た。
Reference Example 1
A predetermined amount of silicon dioxide, boric acid, niobium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide are mixed in predetermined amounts. The glass frit (borosilicate glass) of Reference Example 1 having the composition shown in Table 2 was obtained by melting at 1300 ° C. in a platinum crucible and cooling in air.
参考例２
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表２に示す組成を有する参考例２のガラスフリット（ホウケイ酸ガラス）を得た。
Reference example 2
A predetermined amount of silicon dioxide, boric acid, niobium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide are mixed in predetermined amounts. Then, the glass frit (borosilicate glass) of Reference Example 2 having the composition shown in Table 2 was obtained by melting at 1300 ° C. in a platinum crucible and allowing it to cool in air.
比較例１
二酸化ケイ素、ホウ酸、酸化ニオブ、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１２５０℃で溶融し、空気中で放冷することで、表２に示す組成を有する比較例１のガラスフリット（ホウケイ酸ガラス）を得た。
Comparative Example 1
A predetermined amount of silicon dioxide, boric acid, niobium oxide, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide are mixed and 1250 in a platinum crucible. The glass frit (borosilicate glass) of Comparative Example 1 having the composition shown in Table 2 was obtained by melting at ℃ and allowing to cool in air.
比較例２
二酸化ケイ素、ホウ酸、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１２５０℃で溶融し、空気中で放冷することで、表２に示す組成を有する比較例２のガラスフリット（ホウケイ酸ガラス）を得た。
Comparative Example 2
A predetermined amount of silicon dioxide, boric acid, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide are mixed and mixed in a platinum crucible at 1250. The glass frit (borosilicate glass) of Comparative Example 2 having the composition shown in Table 2 was obtained by melting at ℃ and allowing to cool in air.
比較例３
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、フッ化カルシウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表２に示す組成を有する比較例３のガラスフリット（ホウケイ酸ガラス）を得た。
Comparative Example 3
Silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, calcium fluoride, basic magnesium carbonate, strontium carbonate, barium carbonate, and A predetermined amount of tin oxide was mixed, melted at 1300 ° C. in a platinum crucible, and allowed to cool in air, to obtain a glass frit (borosilicate glass) of Comparative Example 3 having a composition shown in Table 2.
比較例４
二酸化ケイ素、ホウ酸、酸化ニオブ、酸化チタン、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム、フッ化カルシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１１５０℃で溶融し、空気中で放冷することで、表２に示す組成を有する比較例４のガラスフリット（ホウケイ酸ガラス）を得た。
Comparative Example 4
Silicon dioxide, boric acid, niobium oxide, titanium oxide, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, potassium carbonate, calcium fluoride, strontium carbonate, barium carbonate, and tin oxide Was melted at 1150 ° C. in a platinum crucible and allowed to cool in air to obtain a glass frit (borosilicate glass) of Comparative Example 4 having a composition shown in Table 2.
比較例５
二酸化ケイ素、ホウ酸、酸化ジルコニウム、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表２に示す組成を有する比較例５のガラスフリット（ホウケイ酸ガラス）を得た。
Comparative Example 5
A predetermined amount of silicon dioxide, boric acid, zirconium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide are mixed together and a platinum crucible is prepared. The glass frit (borosilicate glass) of Comparative Example 5 having the composition shown in Table 2 was obtained by melting at 1300 ° C. and cooling in air.
比較例６
二酸化ケイ素、ホウ酸、酸化チタン、炭酸ランタン、水酸化アルミニウム、酸化亜鉛、炭酸カルシウム、炭酸リチウム、炭酸ナトリウム、塩基性炭酸マグネシウム、炭酸ストロンチウム、炭酸バリウム、及び酸化スズを所定量混合し、白金るつぼ内で１３００℃で溶融し、空気中で放冷することで、表２に示す組成を有する比較例６のガラスフリット（ホウケイ酸ガラス）を得た。
Comparative Example 6
A predetermined amount of silicon dioxide, boric acid, titanium oxide, lanthanum carbonate, aluminum hydroxide, zinc oxide, calcium carbonate, lithium carbonate, sodium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, and tin oxide are mixed, and a platinum crucible is mixed. The glass frit (borosilicate glass) of Comparative Example 6 having the composition shown in Table 2 was obtained by melting at 1300 ° C. and cooling in air.
屈折率
実施例１〜９、比較例１〜６及び参考例１〜２のガラスフリット（ホウケイ酸ガラス）について、アッベ屈折計を用いて屈折率１．７０以上の中間液を使用して屈折率（ｎｄ）を測定した。結果を表１及び２に示す。
Refractive index About the glass frit (borosilicate glass) of Examples 1-9, Comparative Examples 1-6, and Reference Examples 1-2, using an Abbe refractometer and using an intermediate liquid having a refractive index of 1.70 or more, a refractive index. (Nd) was measured. The results are shown in Tables 1 and 2.
熱膨張係数及びガラス転移温度
実施例１〜９、比較例１〜６及び参考例１〜２のガラスフリット（ホウケイ酸ガラス）について、熱膨張計を用いて熱膨張係数α及びガラス転移温度Ｔｇを測定した。結果を表１及び２に示す。
Thermal Expansion Coefficient and Glass Transition Temperature For the glass frit (borosilicate glass) of Examples 1 to 9, Comparative Examples 1 to 6, and Reference Examples 1 and 2, the thermal expansion coefficient α and the glass transition temperature Tg were measured using a thermal dilatometer. It was measured. The results are shown in Tables 1 and 2.
再加熱時結晶化
実施例１〜９、比較例１〜６及び参考例１〜２のガラスフリット（ホウケイ酸ガラス）について、蓄光体との複合化の際に必要な温度域である７００℃まで３０分間加熱し、結晶の析出の有無を目視及びＸ線回折測定により観測した。結晶の析出が観測されなかった場合を○、結晶の析出が観測された場合を×として、結果を表１及び２に示す。
Crystallization at the time of reheating The glass frit (borosilicate glass) of Examples 1 to 9, Comparative Examples 1 to 6, and Reference Examples 1 to 2 was heated to 700 ° C., which is a temperature range necessary for compounding with the phosphor. The mixture was heated for 30 minutes, and the presence or absence of crystal precipitation was observed visually and by X-ray diffraction measurement. The results are shown in Tables 1 and 2, where ○ indicates that no crystal precipitation was observed, and x indicates that crystal precipitation was observed.
以上の結果、実施例１〜９では、いずれも、屈折率は１．６５以上であり、蓄光体の屈折率と近い結果となった。また、実施例１〜９では、いずれも結晶化を起こしやすい７００℃での３０分間の再加熱においても結晶析出は見られなかった。このことから、実施例１〜９のガラスフリットは、蓄光体との複合化に適していることが示唆された。 As a result, in each of Examples 1 to 9, the refractive index was 1.65 or more, which was a result close to the refractive index of the phosphor. Further, in Examples 1 to 9, no crystal precipitation was observed even after reheating at 700 ° C. for 30 minutes in which crystallization easily occurs. From this, it was suggested that the glass frit of Examples 1 to 9 was suitable for compounding with a phosphorescent body.
一方、比較例１〜４及び参考例１〜２では、７００℃での再加熱により結晶化した。比較例１及び参考例１〜２ではニオブ系の結晶が析出し、比較例１〜２では亜鉛シリケートの結晶が析出し、比較例３では酸化ジルコニウム系の結晶が析出し、比較例４ではバリウム系の結晶が析出した。また、比較例４ではガラス転移温度が低すぎるため、かえって結晶化しやすくなっていることが示唆された。 On the other hand, in Comparative Examples 1-4 and Reference Examples 1-2, crystallization was caused by reheating at 700 ° C. In Comparative Example 1 and Reference Examples 1 and 2, niobium-based crystals were deposited, in Comparative Examples 1 and 2, zinc silicate crystals were deposited, in Comparative Example 3, zirconium oxide-based crystals were deposited, and in Comparative Example 4, barium was deposited. A system crystal was deposited. In Comparative Example 4, it was suggested that the glass transition temperature was too low, so that crystallization was rather easy.
比較例５〜６では、７００℃での再加熱によっても結晶化しなかったが、屈折率の改善効果が不十分であった。 In Comparative Examples 5 and 6, crystallization did not occur even by reheating at 700 ° C., but the effect of improving the refractive index was insufficient.
実施例１０
一例として、実施例１のガラスフリット（ホウケイ酸ガラス）１００重量部に対して、蓄光体（根本特殊化学製のユーロピウム、ジスプロシウム含有アルミン酸ストロンチウム、粒径１５０μｍ）を１０重量部混合し、エタノールを添加して均一混合後に白金皿に入れ、減圧下で６５０℃まで加熱した。
Example 10
As an example, 100 parts by weight of the glass frit (borosilicate glass) of Example 1 is mixed with 10 parts by weight of a luminous body (Europium, dysprosium-containing strontium aluminate, particle size 150 μm) with 100 parts by weight of ethanol, and ethanol is added. After the addition and uniform mixing, the mixture was placed in a platinum dish and heated to 650 ° C. under reduced pressure.
その結果、得られた複合体は、ガラスフリットと蓄光体との界面が見えにくく、半透明な複合体であり、蓄光体の発光を有効に取り出すことができることが示唆された。 As a result, it was suggested that the obtained composite was a translucent composite in which the interface between the glass frit and the phosphor was difficult to see, and that the light emitted from the phosphor could be effectively extracted.
Claims (10)
ＳｉＯ2及びＢ2Ｏ3の合計含有量が４５モル％以上であり、
Ｎｂ2Ｏ5、ＺｒＯ2及びＬａ2Ｏ3よりなる群から選ばれる少なくとも２種と、ＴｉＯ2とを含有し、
Ｎｂ2Ｏ5の含有量が０〜３．８モル％であり、ＺｒＯ2の含有量が０〜４．３モル％であり、Ｌａ2Ｏ3の含有量が０〜４モル％であり、ＴｉＯ2の含有量が０．５〜３．８モル％であり、
ＺｎＯの含有量が０〜１７％であり、ＢａＯの含有量が１〜８モル％である、ガラス蓄光体複合体用のホウケイ酸ガラス。 A borosilicate glass containing SiO 2 and B 2 O 3 as main components,
The total content of SiO 2 and B 2 O 3 is 45 mol% or more,
Containing at least two members selected from the group consisting of Nb 2 O 5 , ZrO 2 and La 2 O 3 , and TiO 2 ,
Content of Nb 2 O 5 is 0 to 3.8 mol%, the content of ZrO 2 is 0 to 4.3 mol%, the content of La 2 O 3 is 0-4 mol%, The content of TiO 2 is 0.5 to 3.8 mol%,
A borosilicate glass for a glass phosphor composite, wherein the content of ZnO is 0 to 17% and the content of BaO is 1 to 8 mol%.
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