CN103492331A - High-refractive-index glass - Google Patents

High-refractive-index glass Download PDF

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Publication number
CN103492331A
CN103492331A CN201280020313.2A CN201280020313A CN103492331A CN 103492331 A CN103492331 A CN 103492331A CN 201280020313 A CN201280020313 A CN 201280020313A CN 103492331 A CN103492331 A CN 103492331A
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Prior art keywords
glass
refractive index
high refractive
quality
sro
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虫明笃
村田隆
柳濑智基
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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    • 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
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays

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  • 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)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Ceramic Engineering (AREA)
  • Glass Compositions (AREA)

Abstract

This high-refractive-index glass is characterized by having a glass composition which contains, in terms of mass%, 0-10% B2O3, 0.001-35% SrO, 0.001-30% ZrO2+TiO2, and 0-10% La2O3+Nb2O5 and in which the mass ratio of BaO/SrO is 0-40 and the mass ratio of SiO2/SrO is 0.1-40, and by having a refractive index nd of 1.55-2.3.

Description

Glass of high refractive index
Technical field
The present invention relates to glass of high refractive index, for example relate to the glass of high refractive index of applicable organic el device, particularly organic EL illuminating.
Background technology
In recent years, used the indicating meter of organic EL luminous element, illumination gradually to receive publicity.These organic el devices have: the substrate (sheet glass) of the nesa coating by having formed ITO, FTO etc. has sandwiched the structure (for example,, with reference to patent documentation 1) of organic illuminating element.In this structure, if current flowing in organic illuminating element, the hole in organic illuminating element and electronics junction are carried out luminous.The light sent enters sheet glass by nesa coating, in sheet glass, in repeated reflection, is radiated into outside.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-149460 communique
Summary of the invention
Invent problem to be solved
Yet the refractive index n d of organic illuminating element is 1.8～1.9, the refractive index n d of ELD is 1.9～2.0.With respect to this, the refractive index n d of glass substrate is generally 1.5 left and right.Therefore, organic el device in the past is due to the refringence at glass substrate-ITO interface, and causes following problem: reflectivity is high, can't effectively take out the light occurred by organic illuminating element.
If use glass of high refractive index as sheet glass, can make the refringence at the interface of sheet glass-ELD diminish.
As glass of high refractive index, be known that the middle opticglass that use such as optical lens.The uses such as optical lens apply thermal treatment again to utilizing the drop method of forming etc. to be shaped to spherical drop glass, and extrusion forming is the opticglass of regulation shape.Although d is high for this opticglass refractive index n, liquid phase viscosity is low, if thereby not with speed of cooling the fast drop method of forming etc. carry out moulding, glass can devitrification during moulding.Therefore, in order to address the above problem, need to improve the devitrification resistance of glass of high refractive index.
Yet, along with the slimming of OLED display etc. is maximized, require little, the large-area sheet glass of thickness of slab.In order to obtain such sheet glass, need to utilize float glass process or glass tube down-drawing (overflow downdraw, discharge orifice glass tube down-drawing) to carry out moulding.Yet glass of high refractive index in the past is because liquid phase viscosity is low, thereby can't utilize float glass process or glass tube down-drawing to carry out moulding, the thin plate maximization difficulty that becomes.In addition, even organic EL illuminating also requires the thin plate maximization.
On the other hand, if add oxide compound, particularly LaO, Nb in glass forms 2o 5, Gd 2o 3, can, in the reduction that suppresses to a certain degree liquid phase viscosity, improve the refractive index n d of sheet glass.Yet there is the problem that raw materials cost is high in such rare metal oxide.In addition, if add in a large number rare metal oxides in glass forms, devitrification resistance reduces, is difficult to make shaping glass sheets.In addition, add in a large number in the situation of rare metal oxide, scale resistance also reduces.
Therefore, technical task of the present invention is, provides and rare metal oxide (La particularly 2o 3, Nb 2o 5, Gd 2o 3) content irrelevant less, with the refractive index n d coupling of organic illuminating element, ELD and the good glass of high refractive index of devitrification resistance.
For the method for dealing with problems
The<the 1 invention >
The inventor etc. conduct in-depth research, and found that: by by each composition contain scope and specific refractory power is limited to specialized range, can solve above-mentioned technical task, as the 1st the invention, scheme has been proposed.That is, the glass of high refractive index of the 1st invention, is characterized in that, as glass, forms, and in quality, % contains B 2o 30～10%, SrO0.001～35%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～10%, mass ratio BaO/SrO is 0～40, mass ratio SiO 2/ SrO is 0.1～40, and refractive index n d is 1.55～2.3.At this, " ZrO 2+ TiO 2" refer to ZrO 2with TiO 2total amount." La 2o 3+ Nb 2o 5" refer to La 2o 3with Nb 2o 5total amount." refractive index n d " can utilize commercially available refractive index analyzer to be measured, for example, after the rectangular parallelepiped sample of making 25mm * 25mm * about 3mm, with the speed of cooling of 0.1 ℃/min to from (annealing point Ta+30 ℃) to the temperature province of (strain point Ps-50 ℃), carrying out anneal, then, in the immersion liquid that makes refractive index match under the state soaked between glass, use the refractive index analyzer KPR-2000 of Shimadzu Seisakusho Ltd.'s system, can be measured thus." annealing point Ta " refers to and utilizes the method mensuration of putting down in writing in ASTM C338-93 and the value obtained." strain point Ps " refers to and utilizes the method mensuration of putting down in writing in ASTM C336-71 and the value obtained.
The glass of high refractive index preferred liquid phase viscosity of the second, the 1 invention is 10 3.0more than dPas.At this, " liquid phase viscosity " refers to the value of utilizing the glass viscosity under platinum ball crystal pulling method mensuration liquidus temperature and obtaining." liquidus temperature " refers to value as described below: the glass powder that will remain in 50 orders (300 μ m) by standard sieve 30 orders (500 μ m) is put into the platinum boat, in temperature gradient furnace, keep after 24 hours, measure crystallization temperature and value.
The glass of high refractive index of the three, 1st invention is preferably tabular.At this, " tabular " can't restrictively explain, the glass of the film shape that comprise film shape that thickness of slab is little, for example along cylinder, arranges, also comprise that a face is formed with the glass of concaveconvex shape in addition.
The glass of high refractive index of the four, 1st invention preferably utilizes the float glass process moulding to form.
The glass of high refractive index preferably 10 of the five, 1st invention 4temperature during dPas is below 1250 ℃.At this, " 10 4.0temperature during dPas " refer to utilize platinum ball crystal pulling method measure and value.
The preferred strain point of glass of high refractive index of the six, 1st invention is more than 650 ℃.
The glass of high refractive index of the seven, 1st invention is preferred for set lights.
The glass of high refractive index of the eight, 1st invention is preferred for organic EL illuminating.
The glass of high refractive index of the nine, 1st invention is preferred for OLED display.
The glass of high refractive index of the ten, 1st invention, is characterized in that, as glass, forms, and in quality %, contains B 2o 30～8%, SrO0.001～35%ZnO0～12%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～5%, Li 2o+Na 2o+K 2o0～10%, mass ratio BaO/SrO is 0～20, mass ratio SiO 2/ SrO is 0.1～20, mass ratio (MgO+CaO)/SrO is 0～20, and refractive index n d is more than 1.58, liquid phase viscosity is 10 3.5dPas is above, strain point is more than 670 ℃.At this, " Li 2o+Na 2o+K 2o " refer to Li 2o, Na 2o, and K 2the total amount of O." MgO+CaO " refers to the total amount of MgO and CaO.
The glass of high refractive index of the 11,1st invention, is characterized in that, as glass, forms, and in quality %, contains SiO 210～50%, B 2o 30～8%, CaO0～10%, SrO0.001～35%, BaO0～30%, ZnO0～4%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～5%, Li 2o+Na 2o+K 2o0～2%, mass ratio BaO/SrO is 0～20, mass ratio SiO 2/ SrO is 1～15, mass ratio (MgO+CaO)/SrO is 0～20, and refractive index n d is more than 1.6, liquid phase viscosity is 10 4.0dPas is above, strain point is more than 670 ℃.
The set lights sheet glass of the 12,1st invention, is characterized in that, as glass, forms, and in quality %, contains SiO 20.1～60%, B 2o 30～10%, SrO0.001～35%, BaO0～40%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～10%, and refractive index n d is 1.55～2.3.
The organic EL illuminating sheet glass of the 13,1st invention, is characterized in that, as glass, forms, and in quality %, contains SiO 20.1～60%, B 2o 30～10%, SrO0.001～35%, BaO0～40%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～10%, and refractive index n d is 1.55～2.3.
The OLED display sheet glass of the 14,1st invention, is characterized in that, as glass, forms, and in quality %, contains SiO 20.1～60%, B 2o 30～10%, SrO0.001～35%, BaO0～40%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～10%, and refractive index n d is 1.55～2.3.
The glass of high refractive index of the 15,1st invention, is characterized in that, as glass, forms, and in quality %, contains SiO 235～60%, Li 2o+Na 2o+K 2o0～1.5%, SrO0.1～35%, BaO0～35%, TiO 20.001～25%, La 2o 3+ Nb 2o 5+ Gd 2o 30～9%, refractive index n d is 1.55～2.3.At this, " La 2o 3+ Nb 2o 5+ Gd 2o 3" refer to La 2o 3, Nb 2o 5, and Gd 2o 3total amount.
The glass of high refractive index of the 16,1st invention, is characterized in that, as glass, forms, and in quality %, contains SiO 235～60%, Li 2o+Na 2o+K 2o0～1.5%, SrO0.1～20%, BaO17～35%, TiO 20.01～20%, La 2o 3+ Nb 2o 5+ Gd 2o 30～9%, refractive index n d is 1.55～2.3.
The glass of high refractive index of the 17,1st invention preferably further contains the B of 0～3 quality % 2o 3.
The glass of high refractive index of the 18,1st invention preferably further contains the MgO of 0～3 quality %.
The glass of high refractive index of the 19,1st invention preferably further contains the ZrO of 1～20 quality % 2+ TiO 2.
The glass of high refractive index of the 20,1st invention preferably utilizes the glass tube down-drawing moulding to form.At this, " glass tube down-drawing " has overflow downdraw, discharge orifice glass tube down-drawing, again draws down method etc.
The<the 2 invention >
Present inventors etc. are furtherd investigate, and found that by the glass compositing range is limited to specialized range, can solve above-mentioned technical task, as the 2nd invention, have proposed scheme.That is, the glass of high refractive index of the 2nd invention, is characterized in that, as glass, forms, and in quality %, contains SiO 230～60%, B 2o 30～15%, Al 2o 30～15%, Li 2o0～10%, Na 2o0～10%, K 2o0～10%, MgO+CaO+SrO+BaO+ZnO20～60%, TiO 20.0001～20%, ZrO 20～20%, La 2o 3+ Nb 2o 50～10%, refractive index n d is 1.55～2.3.At this, " MgO+CaO+SrO+BaO+ZnO " refers to MgO, CaO, SrO, BaO, reaches the total amount of ZnO." La 2o 3+ Nb 2o 5" refer to La 2o 3with Nb 2o 5total amount." refractive index n d " can utilize refractive index analyzer to be measured, for example, after the rectangular parallelepiped sample of making 25mm * 25mm * about 3mm, with the speed of cooling of 0.1 ℃/min to from (annealing point Ta+30 ℃) to the temperature province of (strain point Ps-50 ℃), carrying out anneal, then, when the immersion liquid that refractive index n d is mated is soaked between glass, use the refractive index analyzer KPR-200 of Kalnew company system, can be measured thus." annealing point Ta " refer to utilize the method for putting down in writing in ASTM C338-93 measured and value." strain point Ps " refer to utilize the method for putting down in writing in ASTM C336-71 measured and value.
The glass of high refractive index of the 2nd invention contains SiO 230～60%, B 2o 30～15%, Al 2o 30～15%, MgO+CaO+SrO+BaO+ZnO20～60%, TiO 20.0001～20%, ZrO 20～20%.If so, when can improve refractive index n d, improve devitrification resistance.
The glass of high refractive index of the 2nd invention contains La 2o 3+ Nb 2o 50～10%.If so, when can make cheapization of raw materials cost, easily improve devitrification resistance, acid resistance.
The glass of high refractive index of the 2nd invention contains Li 2o0～10%, Na 2o0～10%, K 2o0～10%.If so, acid resistance improves, and in utilizing sour etching work procedure, due to the stripping of alkali composition, glass is difficult for gonorrhoea.In addition, utilize sour etching work procedure to be included in the manufacturing process etc. of OLED display etc., if the acid resistance of sheet glass is low, in this etching work procedure, sheet glass suffers erosion and produces gonorrhoea.If sheet glass produces gonorrhoea, sheet glass is loss of transmission, and it is difficult that the high-precision refinement of indicating meter becomes.
The refractive index n d of the glass of high refractive index of the 2nd invention is 1.55～2.3.If so, easily with the refractive index n d of organic illuminating element, nesa coating, mate, can effectively the light sent from organic illuminating element be fetched into to outside.
The glass of high refractive index of the second, the 2 invention is preferred: form as glass, in quality %, contain SiO 235～60%, B 2o 30～15%, Al 2o 30～15%, Li 2o0～10%, Na 2o0～10%, K 2o0～10%, MgO+CaO+SrO+BaO+ZnO20～60%, TiO 20.0001～20%, ZrO 20.0001～20%, La 2o 3+ Nb 2o 50～10%, refractive index n d is 1.55～2.3.
The glass of high refractive index of the three, 2nd invention is preferred: form as glass, in quality %, contain SiO 235～60%, B 2o 30～15%, Al 2o 30～15%, Li 2o0～1%, Na 2o0～1%, K 2o0～1%, Li 2o+Na 2o+K 2o0～1%, MgO+CaO+SrO+BaO+ZnO20～50%, BaO0.1～35%, TiO 20.0001～20%, ZrO 20.0001～20%, La 2o 3+ Nb 2o 50～10%, refractive index n d is 1.55～2.3.At this, " Li 2o+Na 2o+K 2o " refer to Li 2o, Na 2o, and K 2the total amount of O.
The glass of high refractive index of the four, 2nd invention preferably comprises the above B of 1 quality % 2o 3.
The glass of high refractive index of the five, 2nd invention preferably comprises the above MgO of 1 quality %.
The glass of high refractive index of the six, 2nd invention is preferably tabular.If so, easily be applicable to the substrate of the various device of OLED display, organic EL illuminating, organic thin film solar cell etc.At this, " tabular " can't limitedly explain, the glass of the film shape that comprise film shape that thickness of slab is little etc., for example along cylinder, arranges, also comprise that a face is formed with the glass of concaveconvex shape in addition.
The glass of high refractive index preferred liquid phase viscosity of the seven, 2nd invention is 10 3.0more than dPas.In organic EL illuminatings etc., there are the following problems: according to the difference a little of the surface smoothness of sheet glass, current density change when electric current applies, cause the inequality of illumination.In addition, also can produce following problem: in order to improve the surface smoothness of sheet glass, if glass surface is ground, tooling cost is surging.Therefore, if liquid phase viscosity is made as to above-mentioned scope, utilize overflow downdraw etc. easily to make shaping glass sheets, consequently, even grind and also easily make the good sheet glass of surface smoothness.At this, " liquid phase viscosity " refers to the viscosity of utilizing platinum ball crystal pulling method to measure the glass under liquidus temperature and the value obtained." liquidus temperature " refers to value as described below: the glass powder that will remain in 50 orders (300 μ m) by standard sieve 30 orders (500 μ m) is put into the platinum boat, in temperature gradient furnace, keeps 24 hours, measure crystallization temperature and value." overflow downdraw " is following method: melten glass is overflowed from the both sides of stable on heating tubular structure thing, and the melten glass after making to overflow, in the interflow, lower end of tubular structure thing, makes shaping glass sheets along the below elongation moulding.
The glass of high refractive index of the eight, 2nd invention preferably utilizes float glass process or glass tube down-drawing moulding to form.At this, " glass tube down-drawing " has overflow downdraw, discharge orifice glass tube down-drawing etc.
The glass of high refractive index of the nine, 2nd invention preferably at least one mask has the surface of not grinding, and its surperficial surface roughness Ra is below.At this, " surface roughness Ra " refers to the method mensuration of utilizing based on JIS B0601:2001 and the value obtained.
The invention effect
According to above-mentioned the 1st invention and the 2nd invention, can provide rare metal oxide (La particularly 2o 3, Nb 2o 5, Gd 2o 3) the poor while, with the refractive index n d of organic illuminating element, ELD coupling and the good glass of high refractive index of devitrification resistance.
Embodiment
The<the 1 embodiment >
With regard to the 1st working of an invention mode (below, be called the 1st embodiment.) glass of high refractive index that relates to, as glass, form, in quality %, contain B 2o 30～10%, SrO0.001～35%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～10%, mass ratio BaO/SrO is 0～40, mass ratio SiO 2/ SrO is 0.1～40.Below explanation limits the reason that contains scope of each composition as described above.In addition, in the following explanation that contains scope, the % mark, except situation about being particularly limited, means quality %.
B 2o 3content be preferably 0～10%.If B 2o 3containing quantitative change many, refractive index n d, Young's modulus easily reduce.Therefore, B 2o 3applicable upper range be below 8%, below 5%, below 4%, below 3%, less than below 2%, 1%, particularly less than 1%.
The content of SrO is preferably 0.001～35%.SrO is in alkaline earth metal oxide, and rejection ratio improves the large composition of effect of refractive index n d than increased devitrification resistance the time.Yet if SrO's is many containing quantitative change, refractive index n d, density, thermal expansivity uprise, or lack the one-tenth balance-dividing that glass forms, devitrification resistance easily reduces.Therefore, the applicable upper range of SrO is below 30%, below 25%, below 20%, below 15%, below 12%, below 10%, particularly below 8%.The applicable lower range of SrO is more than 0.01%, more than 0.1%, more than 1%, more than 2%, more than 3%, more than 3.5%, particularly more than 4%.
TiO 2+ ZrO 2content be preferably 0.001～30%.If TiO 2+ ZrO 2many containing quantitative change, likely devitrification resistance easily reduces, or density, thermal expansivity become too high.On the other hand, if TiO 2+ ZrO 2content tail off, refractive index n d easily reduces.Therefore, TiO 2+ ZrO 2applicable upper range be below 25%, below 20%, below 18%, below 15%, below 14%, particularly below 13%.TiO 2+ ZrO 2applicable lower range be more than 0.01%, more than 0.5%, more than 1%, more than 3%, more than 5%, more than 6%, particularly more than 7%.
TiO 2content be preferably 0～30%.TiO 2it is the composition that improves refractive index n d.Yet, if TiO 2many containing quantitative change, tend to density, thermal expansivity becomes too high, or the easy step-down of devitrification resistance or loss of transmission.Therefore, TiO 2applicable upper range be below 25%, below 15%, below 12%, particularly below 8%.TiO 2applicable lower range be more than 0.001%, more than 0.01%, more than 0.5%, more than 1%, particularly more than 3%.
ZrO 2content be preferably 0～30%.ZrO 2it is the large composition of effect that improves refractive index n d and improve near the viscosity of liquidus temperature.Yet, if ZrO 2containing quantitative change many, density too uprises, or devitrification resistance easily reduces.Therefore, ZrO 2applicable upper range be below 15%, below 10%, below 7%, particularly below 6%.ZrO 2applicable lower range be more than 0.001%, more than 0.01%, more than 0.5%, more than 1%, more than 2%, particularly more than 3%.
La 2o 3+ Nb 2o 5content be preferably 0～10%.If La 2o 3+ Nb 2o 5many containing quantitative change, refractive index n d easily uprises, if but its content is greater than 10%, likely lack the one-tenth balance-dividing that glass forms and devitrification resistance reduces or raw materials cost rises and the manufacturing cost of glass is surging.Particularly in the purposes of illumination etc., owing to requiring cheap glass, thereby the rising of raw materials cost, therefore not preferred.Therefore, La 2o 3+ Nb 2o 5applicable lower range be below 9%, below 8%, below 5%, below 3%, below 2%, below 1%, below 0.5%, particularly below 0.1%.
La 2o 3it is the composition that improves refractive index n d.If La 2o 3containing quantitative change many, likely devitrification resistance easily reduces, in addition, density, thermal expansivity become too high.Therefore, La 2o 3content be preferably below 10%, below 9%, below 8%, below 5%, below 2%, below 1%, below 0.5%, particularly below 0.1%.
Nb 2o 5it is the composition that improves refractive index n d.If Nb 2o 5containing quantitative change many, likely devitrification resistance easily reduces, in addition, density, thermal expansivity become too high.Therefore, Nb 2o 5content be preferably below 10%, below 9%, below 8%, below 5%, below 2%, below 1%, below 0.5%, particularly below 0.1%.
Mass ratio (La 2o 3+ Nb 2o 5)/(ZrO 2+ TiO 2) be preferably 0～30.Mass ratio (La 2o 3+ Nb 2o 5)/(ZrO 2+ TiO 2) larger, when can suppress the reduction of devitrification resistance, improve refractive index n d, if but this value is excessive, lack the one-tenth balance-dividing that glass forms, and devitrification resistance reduces, or raw materials cost becomes too high.Therefore, mass ratio (La 2o 3+ Nb 2o 5)/(ZrO 2+ TiO 2) applicable upper range be below 20, below 10, below 5, below 2, below 1, below 0.1, particularly below 0.01.
Mass ratio BaO/SrO is 0～40.If mass ratio BaO/SrO is excessive, likely devitrification resistance reduction, or density, thermal expansivity become too high.On the other hand, if mass ratio BaO/SrO is too small, likely refractive index n d reduces, or lacks the one-tenth balance-dividing that glass forms, and devitrification resistance reduces.Therefore, the applicable upper range of mass ratio BaO/SrO is below 30, below 20, below 10, below 8, particularly below 5.The applicable lower range of mass ratio BaO/SrO is more than 0.1, more than 0.5, more than 1, more than 2.5, particularly more than 3.
BaO is in alkaline earth metal oxide, can extremely not reduce the viscosity of glass and improve the composition of refractive index n d.The content of BaO is preferably 0～40%.If BaO's is many containing quantitative change, refractive index n d, density, thermal expansivity easily uprise.Yet, if the content of BaO surpasses 40%, lacking the one-tenth balance-dividing that glass forms, devitrification resistance easily reduces.Therefore, the applicable upper range of BaO be preferably below 35%, below 32%, below 30%, below 29.5%, below 29%, particularly below 28%.Wherein, if the content of BaO tails off, be difficult to obtain desired refractive index n d, and be difficult to guarantee high liquid phase viscosity.Therefore, the applicable lower range of BaO be preferably more than 0.5%, more than 1%, more than 2%, more than 5%, more than 10%, more than 15%, more than 17%, more than 20%, more than 23%, particularly more than 25%.
Mass ratio SiO 2/ SrO is 0.1～40.If mass ratio SiO 2/ SrO is excessive, and refractive index n d easily reduces.On the other hand, if mass ratio SiO 2/ SrO is too small, and likely devitrification resistance easily reduces, or density, thermal expansivity become too high.Therefore, mass ratio SiO 2the applicable upper range of/SrO is below 30, below 20, below 15, below 10, below 9, particularly below 8.Mass ratio SiO 2the applicable lower range of/SrO is more than 0.5, more than 1, more than 2, more than 2.5, particularly more than 3.
SiO 2content be preferably 0.1～60%.If SiO 2containing quantitative change many, meltbility, formability easily reduce, in addition, refractive index n d easily reduces.Therefore, SiO 2content be preferably below 55%, below 53%, below 52%, below 50%, below 49%, below 48%, particularly below 45%.On the other hand, if SiO 2content tail off, be difficult to form the eyed structure of glass, vitrifying become the difficulty.In addition, the viscosity of glass too reduces, and is difficult to guarantee high liquid phase viscosity.Therefore, SiO 2content be preferably more than 3%, more than 5%, more than 10%, more than 15%, more than 20%, more than 25%, more than 30%, more than 35%, particularly more than 40%.
Al 2o 3content be preferably 0～20%.If Al 2o 3containing quantitative change many, in glass, easily separate out the devitrification crystallization, liquid phase viscosity easily reduces, in addition, refractive index n d easily reduces.Therefore, Al 2o 3applicable upper range be below 15%, below 10%, below 8%, particularly below 6%.In addition, if Al 2o 3content tail off, lack the one-tenth balance-dividing that glass forms, on the contrary the easy devitrification of glass.Therefore, Al 2o 3applicable lower range be more than 0.1%, more than 0.5%, more than 1%, particularly more than 3%.
The content of MgO is preferably 0～10%.MgO, for improving the composition of refractive index n d, Young's modulus, strain point, is also the composition that reduces high temperature viscosity simultaneously, if but add in a large number MgO, likely liquidus temperature rises and devitrification resistance reduces, or density, thermal expansivity become too high.Therefore, the applicable upper range of MgO is below 5%, below 3%, below 2%, below 1.5%, below 1%, particularly below 0.5%.
The content of CaO is preferably 0～10%.If CaO's is many containing quantitative change, density, thermal expansivity easily uprise, and if then the content of CaO become too much, lack the one-tenth balance-dividing of glass composition, devitrification resistance easily reduces.Therefore, the applicable upper range of CaO is below 9%, particularly below 8.5%.In addition, if the content of CaO tails off, meltbility reduces, or the Young's modulus reduction, or refractive index n d easily reduces.Therefore, the applicable lower range of CaO is more than 0.5%, more than 1%, more than 2%, more than 3%, particularly more than 4%.
Mass ratio (MgO+CaO)/SrO is preferably 0～20.If it is large that mass ratio (MgO+CaO)/SrO becomes, when can maintain high refractive index nd, make the glass low density, or high temperature viscosity is reduced, but liquidus temperature also easily uprises, is difficult to maintain high liquid phase viscosity.Therefore, the applicable upper range of mass ratio (MgO+CaO)/SrO is below 10, below 8, below 5, below 3, below 2, particularly below 1.
The content of ZnO is preferably 0～12%.If ZnO's is many containing quantitative change, density, thermal expansivity become too high, or lack the one-tenth balance-dividing that glass forms, and devitrification resistance reduces, or high temperature viscosity becomes and too reduce, and are difficult to guarantee high liquid phase viscosity.Therefore, the applicable upper range of ZnO is below 8%, below 4%, below 2%, below 1%, below 0.5%, below 0.1%, particularly below 0.01%.
La 2o 3+ Nb 2o 5+ Gd 2o 3content be preferably 0～10%.If La 2o 3+ Nb 2o 5+ Gd 2o 3many containing quantitative change, refractive index n d easily uprises, if but its content is greater than 10%, likely lack the one-tenth balance-dividing that glass forms and devitrification resistance reduces, or raw materials cost rises and the manufacturing cost of glass.Particularly, in the purposes of illumination etc., owing to requiring cheap glass, thereby raw materials cost rises, therefore not preferred.Therefore, La 2o 3+ Nb 2o 5+ Gd 2o 3applicable lower range be below 9%, below 8%, below 5%, below 3%, below 2%, below 1%, below 0.5%, particularly below 0.1%.
Gd 2o 3content be preferably 0～10%.Gd 2o 3the composition that improves specific refractory power, if but Gd 2o 3many containing quantitative change, density, thermal expansivity become too high, or lack the one-tenth balance-dividing that glass forms, devitrification resistance reduces, or high temperature viscosity becomes too low, is difficult to guarantee high liquid phase viscosity.Therefore, Gd 2o 3applicable upper range be below 8%, below 4%, below 2%, below 1%, below 0.5%, below 0.1%, particularly below 0.01%.
Li 2o+Na 2o+K 2the content of O is preferably 0～15%.Li 2o+Na 2o+K 2o is the composition that makes the viscosity reduction of glass, is also the composition of adjusting thermal expansivity in addition, if but add in a large number Li 2o+Na 2o+K 2o, the viscosity of glass too reduces, and is difficult to guarantee high liquid phase viscosity.Therefore, Li 2o+Na 2o+K 2the applicable upper range of O is below 10%, below 5%, below 2%, below 1.5%, below 1%, below 0.5%, particularly below 0.1%.
As finings, can add 0～3% the As that is selected from 2o 3, Sb 2o 3, CeO 2, SnO 2, F, Cl, SO 3group in one or two or more kinds.Wherein, with regard to As 2o 3, Sb 2o 3, and F, particularly As 2o 3with Sb 2o 3, from the viewpoint of environment, preferably control as possible its use, the preferred less than 0.1% of content separately.If consider above viewpoint, as finings, be preferably SnO 2, SO 3, and Cl.SnO particularly 2content be preferably 0～1%, 0.01～0.5%, particularly 0.05～0.4%.In addition, SnO 2+ SO 3the content of+Cl is preferably 0～1%, 0.001～1%, 0.01～0.5%, particularly 0.01～0.3%.At this, " SnO 2+ SO 3+ Cl " refer to SnO 2, SO 3, and the total amount of Cl.
PbO is the composition that high temperature viscosity is reduced, but, from the viewpoint of environment, preferably controls as possible its use, and its content is preferably below 0.5%, more preferably not enough 1000ppm (quality).
Bi 2o 3be the composition that high temperature viscosity is reduced, but, from the viewpoint of environment, preferably control as possible its use, its content is preferably below 0.5%, more preferably not enough 1000ppm (quality).
Certainly the scope that contains be applicable to of each composition can be combined and forms applicable glass compositing range, but, wherein from the viewpoint of refractive index n d, devitrification resistance, manufacturing cost etc., particularly applicable glass compositing range is as described below.
(1) form as glass, in quality %, contain SiO 220～50%, B 2o 30～8%, CaO0～10%, SrO0.01～35%, BaO0～30%, ZnO0～4%, ZrO 2+ TiO 20.001～20%, La 2o 3+ Nb 2o 50～3%, Li 2o+Na 2o+K 2o0～1%, mass ratio BaO/SrO is 0～20, mass ratio SiO 2/ SrO is 1～15, mass ratio (MgO+CaO)/SrO is 0～10.
(2) form as glass, in quality %, contain SiO 235～50%, B 2o 30～5%, CaO0～9%, SrO1～35%, BaO0～29%, ZnO0～3%, ZrO 2+ TiO 21～15%, La 2o 3+ Nb 2o 50～0.1%, Li 2o+Na 2o+K 2o0～0.1%, mass ratio BaO/SrO is 0～10, mass ratio SiO 2/ SrO is 1～10, mass ratio (MgO+CaO)/SrO is 0～5.
(3) form as glass, in quality %, contain SiO 235～50%, B 2o 30～3%, CaO0～9%, SrO2～20%, BaO0～28%, ZnO0～1%, ZrO 2+ TiO 23～15%, La 2o 3+ Nb 2o 50～0.1%, Li 2o+Na 2o+K 2o0～0.1%, mass ratio BaO/SrO is 0～8, mass ratio SiO 2/ SrO is 2～10, mass ratio (MgO+CaO)/SrO is 0～3.
(4) form as glass, in quality %, contain SiO 235～50%, B 2o 30～1%, CaO0～8.5%, SrO4～15%, BaO0～28%, ZnO0～0.1%, ZrO 2+ TiO 26～15%, La 2o 3+ Nb 2o 50～0.1%, Li 2o+Na 2o+K 2o0～0.1%, mass ratio BaO/SrO is 0～8, mass ratio SiO 2/ SrO is 2～10, mass ratio (MgO+CaO)/SrO is 0～3.
(5) contain SiO 235～55%, B 2o 30～8%, SrO0.001～35%, ZnO0～12%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～5%, Li 2o+Na 2o+K 2o0～10%, mass ratio BaO/SrO is 0～20, mass ratio SiO 2/ SrO is 0.1～20, mass ratio (MgO+CaO)/SrO is 0～20.
(6) form as glass, in quality %, contain SiO 235～55%, B 2o 30～5, MgO0～5%, ZrO 20～10%, Li 2o+Na 2o+K 2o0～2%, SrO0.1～20%, BaO0～30%, TiO 20.001～15%, La 2o 3+ Nb 2o 5+ Gd 2o 30～9%, mass ratio (La 2o 3+ Nb 2o 5)/(ZrO 2+ TiO 2) be 0～5, mass ratio BaO/SrO is 0～10.
(7) form as glass, in quality %, contain SiO 235～55%, B 2o 30～5, MgO0～5%, ZrO 20～10%, Li 2o+Na 2o+K 2o0～2%, SrO0.1～20%, BaO0～30%, TiO 20.001～15%, La 2o 3+ Nb 2o 5+ Gd 2o 30～9%, mass ratio (La 2o 3+ Nb 2o 5)/(ZrO 2+ TiO 2) be 0～5, mass ratio BaO/SrO is 0～10, mass ratio SiO 2/ SrO is 0.1～10, mass ratio (MgO+CaO)/SrO is 0～2.
In the glass of high refractive index of the 1st embodiment, refractive index n d is more than 1.55, be preferably more than 1.58, more than 1.6, more than 1.63, more than 1.65, particularly more than 1.66.If refractive index n d less than 1.55, uprise at the reflectivity of ITO-glass interface, can't effectively take out light.On the other hand, if refractive index n d surpasses 2.3, the reflectivity at air-glass surface uprises, even glass surface is implemented to roughened processing, also is difficult to improve the taking-up efficiency of light.Therefore, refractive index n d be preferably below 2.3, below 2.2, below 2.1, below 2.0, below 1.9, particularly below 1.75.
In the glass of high refractive index of the 1st embodiment, liquidus temperature is preferably below 1200 ℃, below 1150 ℃, below 1130 ℃, below 1110 ℃, below 1090 ℃, below 1070 ℃, particularly below 1050 ℃.In addition, liquid phase viscosity is preferably 10 3.0dPas is above, 10 3.5dPas is above, 10 3.8dPas is above, 10 4.0dPas is above, 10 4.1dPas is above, 10 4.2dPas is above, particularly 10 4.3more than dPas.If so, glass is difficult to devitrification during moulding, easily utilizes float glass process to make shaping glass sheets.
The glass of high refractive index of the 1st embodiment is preferably tabular.In addition, thickness be preferably that 1.5mm is following, 1.3mm following, 1.1mm is following, 0.8mm is following, 0.6mm is following, 0.5mm is following, 0.3mm is following, particularly below 0.2mm.Thickness of slab is less, flexible higher, more easily improves the designability of set lights, if but thickness of slab extremely diminish, sheet glass is easily damaged.Therefore, more than thickness of slab is preferably 10 μ m, particularly more than 30 μ m.
The glass of high refractive index of the 1st embodiment is preferably and utilizes the float glass process moulding to form.If so, grinding also can be cheap and manufacture in large quantities the sheet glass that surface quality is good.
Except float glass process, as the forming method of sheet glass, for example can adopt, glass tube down-drawing (overflow downdraw, discharge orifice glass tube down-drawing, again draw down method etc.), offset method etc.
The glass of high refractive index of the 1st embodiment preferably, according to HF etching, sandblast etc., carries out roughened processing to a face.The surface roughness Ra of roughened treated side is preferably
Figure BDA0000401934640000131
above,
Figure BDA0000401934640000132
Figure BDA0000401934640000133
above,
Figure BDA0000401934640000134
above, particularly
Figure BDA0000401934640000135
above.If make the side of roughened treated side for contact with the air of organic EL illuminating etc., roughened treated side becomes reflection-free configuration, thereby is difficult to return in organic luminous layer at the light of organic luminous layer generation, consequently, can improve the taking-up efficiency of light.In addition, can also, according to the hot-work of pressing again etc., to glass surface, give concaveconvex shape.If so, can form reflection configuration accurately at glass surface.As long as concaveconvex shape is considered refractive index n d, is adjusted its interval and the degree of depth simultaneously.Further, can also there is in the glass surface laminating resin molding of concaveconvex shape.
If the employing atmospheric plasma processes, can, on the basis of the condition of surface that maintains a surface, carry out roughened processing to another surface uniform ground.In addition, as the gas source of atmospheric plasma processes, preferably use gas (for example, the SF that contains F 6, CF 4).If so, because generation contains the plasma that HF is gas, thereby the efficiency of roughened processing improves.
In addition, in the situation that glass surface forms reflection-free configuration, even do not carry out roughened processing, also can obtain same effect during moulding.
In the glass of high refractive index of the 1st embodiment, density is preferably 5.0g/cm 3below, 4.8g/cm 3below, 4.5g/cm 3below, 4.3g/cm 3below, 3.7g/cm 3below, 3.5g/cm particularly 3below.If so, can make the glass lightweight, and make the equipment lightweight.In addition, " density " can utilize known Archimedes's method to be measured.
In the glass of high refractive index of the 1st embodiment, thermal expansivity is preferably 30 * 10 -7～100 * 10 -7/ ℃, 40 * 10 -7～90 * 10 -7/ ℃, 60 * 10 -7～85 * 10 -7/ ℃, 65 * 10 -7～80 * 10 -7/ ℃, 68 * 10 -7～78 * 10 -7/ ℃, particularly 70 * 10 -7～78 * 10 -7/ ℃.In recent years, in organic EL illuminating, organic el device, dye sensitization solar battery, from improving the viewpoint of the key element designed, require to have flexible sheet glass.In order to improve the flexible of sheet glass, need to reduce the thickness of slab of sheet glass, but in this case, if the thermal expansivity of the nesa coating of sheet glass and ITO, FTO etc. does not mate, the easy warpage of sheet glass.In addition, in the situation that make the OLED display of using oxide compound TFT, if the thermal expansivity of oxide compound TFT and sheet glass does not mate, likely sheet glass produces warpage, or the film of oxide compound TFT produces be full of cracks.Therefore, if make thermal expansivity in above-mentioned scope, easily prevent such situation.At this, " thermal expansivity " refers to, the mean value under the temperature range of 30～380 ℃, such as utilizing dilatometer etc. to be measured.
In the glass of high refractive index of the 1st embodiment, strain point is preferably more than 630 ℃, more than 650 ℃, more than 670 ℃, more than 690 ℃, particularly more than 700 ℃.If so, glass is difficult for the thermal treatment thermal contraction because of the high temperature in the manufacturing process of equipment.Particularly in the situation that use oxide compound TFT etc. make OLED display, in order to make the stay in grade of oxide compound TFT, need the thermal treatment of 600 ℃ of left and right, if but limit as described above strain point,, in this thermal treatment, can reduce the thermal contraction of glass.
In the glass of high refractive index of the 1st embodiment, 10 2.5temperature during dPas is preferably below 1400 ℃, below 1350 ℃, below 1300 ℃, below 1250 ℃, particularly below 1200 ℃.If so, meltbility improves, thereby easily obtains the glass of bubble excellent quality, and the manufacture efficiency of sheet glass improves.
In the glass of high refractive index of the 1st embodiment, 10 4.0temperature during dPas is below 1250 ℃, below 1200 ℃, below 1150 ℃, below 1110 ℃, particularly below 1060 ℃.If so,, in the moulding that utilizes float glass process, can reduce mold temperature.Consequently, but cold operation, the refractory body long lifetime used in forming part, the manufacturing cost of sheet glass easily reduces.
If the manufacture method of the glass of high refractive index of illustration the 1st embodiment, at first form according to desired glass, the modulation frit, make glass batch materials.Then, after making this glass batch materials melting, clarification, the gained melten glass is shaped to desired shape.Then, carry out as required anneal, be processed into desired shape.
In addition, the set lights sheet glass that the 1st working of an invention mode relates to, is characterized in that, as glass, forms, and in quality %, contains SiO 20.1～60%, B 2o 30～10%, SrO0.001～35%, BaO0～40%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～10%, and refractive index n d is 1.55～2.3.In addition, the organic EL illuminating sheet glass that the 1st working of an invention mode relates to, is characterized in that, as glass, forms, and in quality %, contains SiO 20.1～60%, B 2o 30～10%, SrO0.001～35%, BaO0～40%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～10%, and refractive index n d is 1.55～2.3.Further, the OLED display sheet glass that the 1st working of an invention mode relates to, is characterized in that, as glass, forms, and in quality %, contains SiO 20.1～60%, B 2o 30～10%, SrO0.001～35%, BaO0～40%, ZrO 2+ TiO 20.001～30%, La 2o 3+ Nb 2o 50～10%, and refractive index n d is 1.55～2.3.Above-mentioned sheet glass for set lights, sheet glass for organic EL illuminating, and OLED display identical with the glass of high refractive index illustrated in above-mentioned the 1st embodiment substantially with the technical characterictic of sheet glass, thereby detailed.
Embodiment 1
Below, describe the 1st inventive embodiment in detail.In addition, following embodiment is simple illustration.The 1st invention is not subject to any restriction of following embodiment.
Table 1～4 mean the 1st inventive embodiment (sample No.1～19).
[table 1]
Figure BDA0000401934640000161
[table 2]
Figure BDA0000401934640000171
[table 3]
Figure BDA0000401934640000181
[table 4]
Figure BDA0000401934640000191
At first, the glass composition according to record in table 1～4, after the modulation frit, be supplied to glass melting furnace by the gained glass batch materials, 1500～1600 ℃ of meltings 4 hours.Then, the gained melten glass is flowed out on carbon plate, be shaped to tabular after, the anneal of being stipulated.Finally, to the gained sheet glass, estimate various characteristics.
Density is for measuring the value obtained according to known Archimedes's method.
Thermal expansivity is for being used dilatometer, measure mean thermal expansion coefficients under 30～380 ℃ and value.As measuring sample, use the cylindric sample (end face carries out R processing) of φ 5mm * 20mm.
Strain point Ps measures for the method according to putting down in writing in ASTM C336-71 the value obtained.In addition, strain point Ps is higher, and thermotolerance is higher.
Annealing point Ta softening temperature Ts measures for the method according to putting down in writing in ASTM C338-93 the value obtained.
High temperature viscosity 10 4.0dPas, 10 3.0dPas, and 10 2.5temperature during dPas is for utilizing platinum ball crystal pulling method to measure the value obtained.In addition, these temperature are lower, and meltbility is more excellent.
Liquidus temperature TL is value as described below: will put into the platinum boat at the residual glass powder of 50 orders (300 μ m) by standard sieve 30 orders (500 μ m), keep in temperature gradient furnace 24 hours, measure crystallization temperature and value.In addition, liquid phase viscosity log 10η TL refers to the viscosity of utilizing platinum ball crystal pulling method to measure the glass under liquidus temperature and the value obtained.In addition, liquid phase viscosity is higher, liquidus temperature is lower, and devitrification resistance, formability are more excellent.
Refractive index n d is value as described below: after at first making the rectangular parallelepiped sample of 25mm * 25mm * about 3mm, with the speed of cooling of 0.1 ℃/min to from (annealing point Ta+30 ℃) to the temperature province of (strain point Ps-50 ℃), carrying out anneal, then, when the immersion liquid of refractive index n d coupling is soaked between glass, the refractive index analyzer KPR-2000 that utilizes Shimadzu Seisakusho Ltd.'s system measure and value.
Embodiment 2
Form according to the glass of putting down in writing in sample No.3, after the modulation frit, the gained glass batch materials is dropped into to continuous working kiln, melting at the temperature of 1500～1600 ℃.Then, the gained melten glass is utilized to the moulding of float glass process, obtained the sheet glass of thickness 0.5mm.
Form according to the glass of putting down in writing in sample No.4, after the modulation frit, the gained glass batch materials is dropped into to continuous working kiln, melting at the temperature of 1500～1600 ℃.Then, the gained melten glass is utilized to the moulding of float glass process, obtained the sheet glass of thickness 0.5mm.
Form according to the glass of putting down in writing in sample No.6, after the modulation frit, the gained glass batch materials is dropped into to continuous working kiln, melting at the temperature of 1500～1600 ℃.Then, the gained melten glass is utilized to the moulding of float glass process, obtained the sheet glass of thickness 0.5mm.
The<the 2 embodiment >
With regard to the 2nd working of an invention mode (below, be called the 2nd embodiment.) glass of high refractive index that relates to, as glass, form, in quality %, contain: SiO 230～60%, B 2o 30～15%, Al 2o 30～15%, Li 2o0～10%, Na 2o0～10%, K 2o0～10%, MgO+CaO+SrO+BaO+ZnO20～60%, TiO 20.0001～20%, ZrO 20～20%, La 2o 3+ Nb 2o 50～10%.Below explanation limits the reason that contains scope of each composition as described above.In addition, in the explanation that contains scope of each composition, except situation about being particularly limited, % means quality %.
SiO 2content be 30～60%.If SiO 2containing quantitative change many, meltbility, formability easily reduce, in addition, refractive index n d easily reduces.Therefore, SiO 2content on be limited to below 60%, be preferably below 50%, below 48%, below 45%, particularly below 43%.On the other hand, if SiO 2content tail off, be difficult to form the glass mesh structure, vitrifying become the difficulty.In addition, except the viscosity of glass too reduces, be difficult to guarantee beyond high liquid phase viscosity, acid resistance also easily reduces.Therefore, SiO 2content under be limited to more than 30%, be preferably more than 35%, more than 38%, particularly more than 40%.
B 2o 3content be 0～15%.If B 2o 3containing quantitative change many, Young's modulus easily reduces, in addition, strain point easily reduces.Further impaired except the one-tenth balance-dividing of glass composition, beyond devitrification resistance easily reduces, acid resistance also easily reduces.Therefore, B 2o 3content on be limited to below 15%, be preferably below 10%, below 8%, particularly below 6%.On the other hand, if B 2o 3content tail off, the glass metal phase viscosity easily reduces.Therefore, B 2o 3applicable lower limit content be more than 0.1%, more than 0.5%, more than 1%, more than 1.5%, more than 2%, more than 3%, particularly more than 4%.
Mass ratio B 2o 3/ SiO 2be preferably 0～1.If mass ratio B 2o 3/ SiO 2become large, be difficult to guarantee high liquid phase viscosity, in addition, chemical reagent resistance easily reduces.Therefore, mass ratio B 2o 3/ SiO 2applicable upper range be below 1, below 0.5, below 0.2, below 0.15, particularly below 0.13.On the other hand, if mass ratio B 2o 3/ SiO 2diminish, the one-tenth balance-dividing that glass forms is impaired, and devitrification resistance easily reduces.Therefore, mass ratio B 2o 3/ SiO 2applicable lower range be more than 0.01, more than 0.02, more than 0.03, more than 0.04, more than 0.05, particularly more than 0.10.
Al 2o 3content be 0～15%.If Al 2o 3content too much, the one-tenth balance-dividing that glass forms is impaired, devitrification resistance easily reduces.In addition, acid resistance easily reduces.Therefore, Al 2o 3content on be limited to below 15%, be preferably below 10%, below 8%, particularly below 6%.On the other hand, if Al 2o 3content tail off, the viscosity of glass too reduces, and is difficult to guarantee high liquid phase viscosity.Therefore, Al 2o 3applicable lower limit content be more than 0.5%, more than 1%, more than 2%, particularly more than 4%.
Li 2the content of O is 0～10%.If Li 2o's is many containing quantitative change, and liquid phase viscosity easily reduces, and in addition, strain point easily reduces.In addition, in utilizing sour etching work procedure due to the stripping of alkali composition, the easy gonorrhoea of glass.Therefore, Li 2on the content of O, be limited to below 10%, be preferably below 8%, below 5%, below 4%, below 3%, less than below 2%, 1%, particularly less than 1%, expectation does not contain in fact.At this, " do not contain in fact Li 2o " refer to the Li of glass in forming 2the situation containing quantity not sufficient 1000ppm (quality) of O.
Na 2the content of O is 0～10%.If Na 2o's is many containing quantitative change, and liquid phase viscosity easily reduces, and in addition, strain point easily reduces.In addition, in utilizing sour etching work procedure due to the stripping of alkali composition, the easy gonorrhoea of glass.Therefore, Na 2on the content of O, be limited to below 10%, be preferably below 8%, below 5%, below 4%, below 3%, less than below 2%, 1%, particularly less than 1%, expectation does not contain in fact.At this, " do not contain in fact Na 2o " refer to the Na of glass in forming 2the situation containing quantity not sufficient 1000ppm (quality) of O.
K 2the content of O is 0～10%.If K 2o's is many containing quantitative change, and liquid phase viscosity easily reduces, and in addition, strain point easily reduces.In addition, in utilizing sour etching work procedure due to the stripping of alkali composition, the easy gonorrhoea of glass.Therefore, K 2be limited to below 10% on the content of O, be preferably below 8%, below 5%, below 4%, below 3%, less than below 2%, 1%, particularly less than 1%, expectation does not contain in fact.At this, " do not contain in fact K 2o " refer to the K of glass in forming 2the situation containing quantity not sufficient 1000ppm (quality) of O.
Li 2o+Na 2o+K 2the content of O is preferably 0～10%.If Li 2o+Na 2o+K 2o's is many containing quantitative change, and liquid phase viscosity easily reduces, and in addition, strain point easily reduces.In addition, in utilizing sour etching work procedure due to the stripping of alkali composition, the easy gonorrhoea of glass.Therefore, Li 2o+Na 2o+K 2on the content of O, be limited to below 10%, below 8%, below 5%, below 4%, below 3%, below 2%, below 1%, less than 1% particularly, expectation does not contain in fact.At this, " do not contain in fact Li 2o+Na 2o+K 2o " refer to the Li of glass in forming 2o+Na 2o+K 2the situation containing quantity not sufficient 1000ppm (quality) of O.
The content of MgO is preferably 0～20%.MgO is the composition that improves refractive index n d, Young's modulus, strain point, is also the composition that reduces high temperature viscosity, if contain in a large number MgO, likely liquidus temperature rises and devitrification resistance reduction or density, thermal expansivity become too high simultaneously.Therefore, the applicable upper limit content of MgO is below 20%, below 10%, particularly below 6%.On the other hand, if the content of MgO tails off, meltbility reduces, or the Young's modulus reduction, or refractive index n d easily reduces.Therefore, the applicable lower limit content of MgO is more than 0.1%, more than 0.5%, more than 1%, more than 1.5%, more than 2%, particularly more than 3%.
The content of CaO is preferably 0～15%.If CaO's is many containing quantitative change, density, thermal expansivity easily uprise, and in addition, the one-tenth balance-dividing that glass forms is impaired, and devitrification resistance easily reduces.Therefore, the applicable upper limit content of CaO is below 15%, below 13%, below 11%, below 9.5%, particularly below 8%.On the other hand, if the content of CaO tails off, meltbility reduces, or the Young's modulus reduction, or refractive index n d easily reduces.Therefore, the applicable lower limit content of CaO is more than 0.5%, more than 1%, particularly more than 2%.
The content of SrO is preferably 0～25%.If SrO's is many containing quantitative change, refractive index n d, density, thermal expansivity easily uprise, and in addition, the one-tenth balance-dividing that glass forms is impaired, and devitrification resistance easily reduces.Therefore, the applicable upper limit content of SrO is below 25%, below 18%, below 14%, particularly below 12%.On the other hand, if the content of SrO tails off, meltbility easily reduces, and in addition, refractive index n d easily reduces.Therefore, the applicable lower limit content of SrO is more than 0.1%, more than 0.5%, more than 1%, more than 2%, more than 5%, more than 7%, particularly more than 9%.
BaO is in alkaline earth metal oxide, does not make as possible the viscosity reduction of glass and the composition of raising refractive index n d, and its content is preferably 0.1～60%.If BaO's is many containing quantitative change, refractive index n d, density, thermal expansivity easily uprise, and in addition, the one-tenth balance-dividing that glass forms is impaired, and devitrification resistance easily reduces.Therefore, the applicable upper limit content of BaO is below 60%, below 53%, below 48%, below 44%, below 40%, below 39%, below 36%, below 35%, below 34%, particularly below 33%.On the other hand, if the content of BaO tails off, be difficult to obtain desired refractive index n d, and be difficult to guarantee high liquid phase viscosity.Therefore, the applicable upper limit content of BaO is more than 0.1%, more than 1%, more than 2%, more than 5%, more than 10%, more than 15%, more than 20%, more than 23%, particularly more than 25%.
The content of ZnO is preferably 0～20%.ZnO is the composition that improves refractive index n d, strain point, is also the composition that reduces high temperature viscosity simultaneously, if but add in a large number ZnO, likely liquidus temperature rises and devitrification resistance reduction or density, thermal expansivity become too high.Therefore, the applicable upper limit content of ZnO is below 20%, below 10%, below 5%, below 3%, particularly below 1%.
The content of MgO+CaO+SrO+BaO+ZnO is 20～60%.If MgO+CaO+SrO+BaO+ZnO's is many containing quantitative change, density, thermal expansivity easily uprise, and in addition, the one-tenth balance-dividing that glass forms is impaired, and devitrification resistance easily reduces.Therefore, on the content of MgO+CaO+SrO+BaO+ZnO, be limited to below 60%, be preferably below 55%, below 50%, below 48%, particularly below 45%.On the other hand, if the content of MgO+CaO+SrO+BaO+ZnO tails off, glass becomes unstable.Therefore, the content of MgO+CaO+SrO+BaO+ZnO under be limited to more than 20%, be preferably more than 30%, more than 35%, particularly more than 40%.
TiO 2it is the composition that improves refractive index n d.TiO 2content be 0.0001～20%.Yet, if TiO 2many containing quantitative change, the one-tenth balance-dividing that glass forms is impaired, devitrification resistance easily reduces.In addition, transmissivity reduces, in the situation that be applicable to OLED display, likely luminous efficiency reduces.Therefore, TiO 2content on be limited to below 20%, be preferably below 10%, below 7%, particularly below 5%.On the other hand, if TiO 2content tail off, be difficult to obtain desired refractive index n d.Therefore, TiO 2content under be limited to more than 0.0001%, be preferably more than 0.001%, more than 0.01%, more than 0.02%, more than 0.05%, more than 0.1%, more than 1%, particularly more than 2%.
ZrO 2it is the composition that improves refractive index n d.ZrO 2content be 0～20%.Yet, if ZrO 2many containing quantitative change, the one-tenth balance-dividing that glass forms is impaired, devitrification resistance easily reduces.Therefore, ZrO 2content on be limited to below 20%, be preferably below 10%, below 7%, particularly below 5%.On the other hand, if ZrO 2content tail off, be difficult to obtain desired refractive index n d.Therefore, ZrO 2applicable lower limit content be more than 0.0001%, be preferably more than 0.001%, more than 0.01%, more than 0.02%, more than 0.05%, more than 0.1%, more than 1%, particularly more than 2%.
La 2o 3it is the composition that improves refractive index n d.La 2o 3content be preferably 0～10%.If La 2o 3containing quantitative change many, density, thermal expansivity easily uprise, in addition, devitrification resistance, acid resistance easily reduce.In addition, raw materials cost rises, and the manufacturing cost of sheet glass is easily surging.Therefore, La 2o 3applicable upper limit content be below 10%, below 5%, below 3%, below 2.5%, particularly below 1%.
Nb 2o 5it is the composition that improves refractive index n d.Nb 2o 5content be preferably 0～10%.If Nb 2o 5containing quantitative change many, density, thermal expansivity easily uprise, in addition, devitrification resistance easily reduces.In addition, raw materials cost rises, and the manufacturing cost of sheet glass is easily surging.Therefore, Nb 2o 5applicable upper limit content be below 10%, below 5%, below 3%, particularly below 1%.
Gd 2o 3content be preferably 0～10%.Gd 2o 3it is the composition that improves refractive index n d.Yet, if Gd 2o 3many containing quantitative change, density, thermal expansivity become too high or lack the one-tenth balance-dividing that glass forms, devitrification resistance reduces or high temperature viscosity too reduces, and is difficult to guarantee high liquid phase viscosity.Therefore, Gd 2o 3applicable upper limit content be below 10%, below 5%, below 3%, particularly below 1%.
La 2o 3+ Nb 2o 5content be 0～10%.If La 2o 3+ Nb 2o 5containing quantitative change many, density, thermal expansivity easily uprise, in addition, devitrification resistance easily reduces, and then is difficult to guarantee high liquid phase viscosity.In addition, raw materials cost rises, and the manufacturing cost of sheet glass is easily surging.Therefore, La 2o 3+ Nb 2o 5content on be limited to below 10%, be preferably below 8%, below 5%, below 3%, below 1%, below 0.5%, particularly below 0.1%.
The content of rare metal oxide is preferably in total amount 0～10%.If rare metal oxide is many containing quantitative change, density, thermal expansivity easily uprise, and in addition, devitrification resistance, acid resistance easily reduce, and are difficult to guarantee high liquid phase viscosity.In addition, raw materials cost rises, and the manufacturing cost of sheet glass is easily surging.Therefore, the applicable upper limit content of rare metal oxide is below 10%, below 5%, below 3%, particularly below 1%.
Except mentioned component, can also add following composition.
As finings, can add 0～3% the As that is selected from 2o 3, Sb 2o 3, CeO 2, SnO 2, F, Cl, SO 3group in one or two or more kinds.Wherein, with regard to As 2o 3, Sb 2o 3, and F, from the viewpoint of environment, preferably control as possible its use, the preferred less than 0.1% of content separately.If consider above viewpoint, as finings, be preferably SnO 2, SO 3, Cl, and CeO 2.
SnO 2content be preferably 0～1%, 0.001～1%, particularly 0.01～0.5%.
SO 3content be preferably 0～1%, 0～0.5%, 0.001～0.1%, 0.005～0.1%, 0.01～0.1%, particularly 0.01～0.05%.As SO 3the importing raw material, can use saltcake.In addition, also can use the vitriolated raw material of bag.
The content of Cl is preferably 0～1%, 0.001～0.5%, particularly 0.01～0.4%.
SnO 2+ SO 3the content of+Cl is preferably 0～1%, 0.001～1%, 0.01～0.5%, particularly 0.01～0.3%.At this, " SnO 2+ SO 3+ Cl " refer to SnO 2, SO 3, and the total amount of Cl.
CeO 2content be preferably 0～6%.If CeO 2containing quantitative change many, devitrification resistance easily reduces.Therefore, CeO 2applicable upper limit content be below 6%, below 5%, below 3%, below 2%, particularly below 1%.On the other hand, if CeO 2tail off, as finings, lack effect.Therefore, CeO 2applicable lower limit content be more than 0.001%, more than 0.005%, more than 0.01%, more than 0.05%, particularly more than 0.1%.
PbO is the composition that reduces high temperature viscosity, but, from the viewpoint of environment, preferably controls as possible its use.The content of PbO is preferably below 0.5%, expectation does not contain in fact.At this, " not containing in fact PbO " refers to the situation containing quantity not sufficient 1000ppm (quality) of the PbO in the glass composition.
Can also combine each composition be applicable to contain scope, form applicable glass compositing range.Wherein, applicable glass compositing range is as described below.
(1) in quality %, contain: SiO 230～60%, B 2o 30～15%, Al 2o 30～15%, Li 2o0～10%, Na 2o0～10%, K 2o0～10%, MgO+CaO+SrO+BaO+ZnO20～60%, TiO 20.1～20%, ZrO 20～20%, La 2o 3+ Nb 2o 50～10%,
(2) in quality %, contain: SiO 235～45%, B 2o 32～8%, Al 2o 34～8%, Li 2o1～8%, Na 2o0～5%, K 2o0～8%, MgO+CaO+SrO+BaO+ZnO30～48%, TiO 21～7%, ZrO 20.1～5%, La 2o 3+ Nb 2o 50～5%.
In the glass of high refractive index of the 2nd embodiment, refractive index n d is more than 1.55, be preferably more than 1.58, more than 1.60, particularly more than 1.63.If refractive index n d less than 1.55,, due to the reflection at nesa coating-sheet glass interface, can't effectively take out light.On the other hand, if refractive index n d higher than 2.3, the reflectivity at air-sheet glass interface uprises, even glass surface is carried out to roughened processing, also is difficult to light is fetched into to outside.Therefore, refractive index n d be below 2.3, be preferably below 2.2, below 2.1, below 2.0, below 1.9, particularly below 1.75.
In the glass of high refractive index of the 2nd embodiment, density is preferably 5.0g/cm 3below, 4.8g/cm 3below, 4.5g/cm 3below, 4.3g/cm 3below, 3.7g/cm 3below, 3.5g/cm 3below, 3.4g/cm particularly 3below.If so, can make the equipment lightweight.
In the glass of high refractive index of the 2nd embodiment, the thermal expansivity under 30～380 ℃ is preferably 45 * 10 -7～110 * 10 -7/ ℃, 50 * 10 -7～100 * 10 -7/ ℃, 60 * 10 -7～95 * 10 -7/ ℃, 65 * 10 -7～90 * 10 -7/ ℃, 65 * 10 -7～85 * 10 -7/ ℃, particularly 67 * 10 -7～80 * 10 -7/ ℃.In recent years, in organic el device etc., from improving the viewpoint of the key element designed, exist and give flexible situation to sheet glass.In order to improve the flexible of sheet glass, need to reduce the thickness of sheet glass, in this case, and if the thermal expansivity of sheet glass and nesa coating does not mate, the easy warpage of sheet glass.Therefore, as the thermal expansivity by under 30～380 ℃ is set as above-mentioned scope, easily prevent such situation.
In the glass of high refractive index of the 2nd embodiment, strain point is preferably more than 600 ℃, particularly more than 630 ℃.In the equipment of organic thin film solar cell etc., when forming nesa coating, at high temperature process, can form the high and low-resistance film of the transparency.Yet glass of high refractive index in the past is because thermotolerance is insufficient, thereby be difficult to take into account the transparency and low resistance.Therefore, if strain point is made as to above-mentioned scope,, in the equipment of organic thin film solar cell etc., can take into account the transparency and low-resistance while, glass is difficult for because of the thermal treatment thermal contraction in the manufacturing process of equipment.
In the glass of high refractive index of the 2nd embodiment, 10 2.5temperature during dPas is preferably below 1450 ℃, below 1400 ℃, below 1350 ℃, below 1300 ℃, below 1250 ℃, particularly below 1200 ℃.If so, meltbility improves, thereby the manufacture efficiency of glass improves.
In the glass of high refractive index of the 2nd embodiment, liquidus temperature is preferably below 1200 ℃, below 1150 ℃, below 1130 ℃, below 1110 ℃, below 1090 ℃, below 1070 ℃, below 1050 ℃, below 1040 ℃, below 1000 ℃, particularly below 980 ℃.In addition, liquid phase viscosity is preferably 10 3.5dPas is above, 10 3.8dPas is above, 10 4.0dPas is above, 10 4.2dPas is above, 10 4.4dPas is above, 10 4.6dPas is above, 10 4.8dPas is above, particularly 10 5.0more than dPas.If so, glass is difficult for devitrification during moulding, easily utilizes float glass process or overflow downdraw to make shaping glass sheets.
The glass of high refractive index of the 2nd embodiment is preferably tabular.In addition, thickness (tabular situation is thickness of slab) be preferably that 1.5mm is following, 1.3mm following, 1.1mm is following, 0.8mm is following, 0.6mm is following, 0.5mm is following, 0.3mm is following, 0.2mm is following, particularly below 0.1mm.Thickness is less, flexible higher, more easily makes the set lights of designability excellence, if but thickness becomes extremely little, and glass is easily damaged.Therefore, more than thickness is preferably 10 μ m, particularly more than 30 μ m.
The glass of high refractive index of the 2nd embodiment, preferably in the situation that tabular, has the surface (particularly the effective surface of at least one face is whole is grinding) of not grinding at least one mask.The theoretical strength of glass is original just very high, even in most cases also can cause destroying well below the stress of theoretical strength.This is because operation after moulding, such as glass surface in grinding step etc., produce the little defect that is called as lattice Lifei mobile (Griffith flow).Therefore, if ground glass surface not can not damage the physical strength of original glass, thereby glass is survivable.In addition, owing to can making grinding step simplify or it being omitted, thereby can make cheap for manufacturing costization of sheet glass.
In the glass of high refractive index of the 2nd embodiment, the surface roughness Ra on the surface of not grinding is preferably
Figure BDA0000401934640000271
below,
Figure BDA0000401934640000272
below,
Figure BDA0000401934640000273
below, particularly below.If surface roughness Ra is greater than
Figure BDA0000401934640000275
the quality of the nesa coating formed on its surface reduces, and is difficult to obtain luminous uniformly.
The glass of high refractive index of the 2nd embodiment is preferably and utilizes glass tube down-drawing, particularly the overflow downdraw moulding forms.If so, do not grind and can manufacture the sheet glass that surface quality is good yet.Its reason is because the state forming with free surface forms in the situation that overflow downdraw should become that surperficial face does not contact with the tubular fire thing.As long as the structure of tubular structure thing, material can realize desired size, surface accuracy, be not particularly limited.In addition, in order to carry out elongation moulding downwards, the method that melten glass is applied to power also is not particularly limited.For example, can adopt the thermotolerance roller that makes to have fully large width at state backspin contact with melten glass then the method for extension, can also adopt a plurality of paired thermotolerance rollers only with near the end face of melten glass are contacted and the method for extending.In addition, except overflow downdraw, as glass tube down-drawing, can also adopt the discharge orifice glass tube down-drawing.If so, easily make the sheet glass that thickness of slab is little.At this, " discharge orifice glass tube down-drawing " refers to following method: when from the gap of essentially rectangular shape, flowing out melten glass, below carry out elongation moulding, make the method for shaping glass sheets.
The glass of high refractive index of the 2nd embodiment preferably utilizes the float glass process moulding to form.If so, can be cheap and make in large quantities large-scale sheet glass.
Except above-mentioned forming method, for example can also adopt, again draw down method, float glass process, offset method etc.
The glass of high refractive index of the 2nd embodiment preferably, according to HF etching, sandblast etc., carries out roughened processing to a face.The surface roughness Ra of roughened treated side is preferably above, above, above, particularly
Figure BDA0000401934640000284
above.If make the side contacted with air that roughened treated side is organic EL illuminating etc., roughened treated side becomes reflection-free configuration, thereby the light produced in organic luminous layer is difficult to return in organic luminous layer, consequently, can improve the taking-up efficiency of light.In addition, can also give concaveconvex shape (such as the hot-work of pressing again etc.) to glass surface.If so, can form reflection configuration accurately at glass surface.Concaveconvex shape so long as consider refractive index n d, is adjusted its interval and the degree of depth simultaneously and is got final product.Further, can also make to have resin molding and the glass surface laminating of concaveconvex shape.
In addition, if carry out roughened processing by atmospheric plasma processes, can maintain the condition of surface of a face, and another side is carried out to roughened processing equably.In addition, as the gas source of atmospheric plasma processes, preferably use gas (for example, the SF that contains F 6, CF 4).If so, because generation contains the plasma that HF is gas, thereby the efficiency of roughened processing improves.
Further, also form the method for concaveconvex shape during preferred moulding at a face.In this case, do not need to carry out in addition independently roughened processing, the efficiency of roughened processing improves.
Then, illustration is manufactured the method for the glass of high refractive index of the 2nd embodiment.At first according to desired glass, form, the modulation frit, make glass batch materials.Then, after making this glass batch materials melting, clarification, be configured as desired shape.Then, be processed into desired shape.
Embodiment 3
Below, describe the 2nd inventive embodiment in detail.In addition, following embodiment is simple illustration.The 2nd invention is not limited in any way the following examples.
Table 5～12 mean the 2nd inventive embodiment (sample No.20～55) and comparative example (sample No.56).
[table 5]
[table 6]
Figure BDA0000401934640000301
[table 7]
Figure BDA0000401934640000311
[table 8]
Figure BDA0000401934640000321
[table 9]
Figure BDA0000401934640000331
[table 10]
Figure BDA0000401934640000341
[table 11]
Figure BDA0000401934640000351
[table 12]
Figure BDA0000401934640000361
At first, the glass composition according to record in table 5～12, after the modulation frit, be supplied to the gained glass batch materials in glass melting furnace, 1500 ℃ of meltings 4 hours.Then, the gained melten glass is flowed out on carbon plate, be shaped to tabular after, the anneal of being stipulated.Finally, to the gained sheet glass, estimate various characteristics.
Refractive index n d is value as described below: after at first making the rectangular parallelepiped sample of 25mm * 25mm * about 3mm, with the speed of cooling of 0.1 ℃/min to from (annealing point Ta+30 ℃) to the temperature province of (strain point Ps-50 ℃), carrying out anneal, then, when the immersion liquid of refractive index n d coupling is soaked between glass, the refractive index analyzer KPR-2000 that utilizes Shimadzu Seisakusho Ltd.'s system measured and value.
Density is for utilizing known Archimedes's method to measure the value obtained.
Thermal expansivity is for being used dilatometer, measure mean thermal expansion coefficients under 30～380 ℃ and value.As measuring sample, use the cylindric sample (end face carries out R processing) of φ 5mm * 20mm.
Strain point Ps is for utilizing the method for putting down in writing in ASTM C336-71 to measure the value obtained.In addition, strain point Ps is higher, and thermotolerance is higher.
Annealing point Ta softening temperature Ts is for utilizing the method for putting down in writing in ASTM C338-93 to measure the value obtained.
High temperature viscosity 10 4.0dPas, 10 3.0dPas, 10 2.5dPas, and 10 2.0temperature during dPas is for utilizing platinum ball crystal pulling method to measure the value obtained.In addition, these temperature are lower, and meltbility is more excellent.
Liquidus temperature TL is value as described below: will put into the platinum boat at the residual glass powder of 50 orders (300 μ m) by standard sieve 30 orders (500 μ m), keep in temperature gradient furnace 24 hours, measure crystallization temperature and value.In addition, liquid phase viscosity log 10the value that η TL obtains for the viscosity of utilizing platinum ball crystal pulling method to measure the glass under liquidus temperature.In addition, liquid phase viscosity is higher, liquidus temperature is lower, and devitrification resistance, formability are more excellent.
Anti-HCl utilizes following methods estimated.At first, after optical grinding is carried out in the two sides of each glass specimen, after its part is covered, carry out under the following conditions the chemical reagent processing.After chemical reagent is processed, remove mask, utilize the surfaceness instrumentation to determine mask part and the difference of altitude that corrodes part, using this value as erosion amount.With regard to anti-HCl (erosion amount), if erosion amount surpasses 20 μ m, be evaluated as " * ", if, below 20 μ m, be evaluated as " zero ".With regard to anti-HCl (outward appearance), after optical grinding is carried out on the two sides to each glass specimen, carry out the chemical reagent processing under following condition after, the surface of visual observation glass specimen, by produce gonorrhoea or surface irregularity or crack be evaluated as " * ", will not have vicissitudinous being evaluated as " zero ".
The treatment condition of anti-HCl (erosion amount) are to flood 24 hours in the 10 quality %HCl aqueous solution of 80 ℃, and the treatment condition of anti-HCl (outward appearance) are to flood 24 hours in the 10 quality %HCl aqueous solution of 80 ℃.
It is as shown in the table, with regard to sample No.20～55, do not contain in fact alkali composition and rare metal oxide, and refractive index n d is more than 1.623, acid resistance is for good.In addition, with regard to sample No.20,24,27～37,39,43～45,47～55, liquid phase viscosity is 10 3.4more than dPas.Further, with regard to sample No.20～31, high irrelevant with refractive index n d, because density is low, thereby can realize the lightweight of equipment.In addition, because the thermal expansivity with nesa coating is approximate, thereby expect to suppress the warpage of sheet glass.In addition, also think that sample No.20～25,27～55 are because strain point is high, thereby the thermal contraction of the glass in can the manufacturing process of suppression equipment.On the other hand, sample No.56 is owing in glass forms, comprising in a large number rare metal oxide, thereby density is high, acid resistance is low.
Utilizability on industry
The refractive index n d of glass of high refractive index of the present invention is more than 1.55, and in addition, liquid phase viscosity is high.And, from the viewpoint of raw materials cost, can from forming, glass remove rare metal oxide, from the viewpoint of environment, can also from forming, glass remove As 2o 3, Sb 2o 3deng.Therefore, glass of high refractive index of the present invention is applicable to substrate for organic el device, particularly organic EL illuminating substrate.In addition, glass of high refractive index of the present invention can also as the substrate for flat panel display of liquid-crystal display etc., charge coupled cell (CCD), etc. the outer casing shell, used for solar batteries substrate etc. of image sensor of times contact-type solid-state imager (CIS) etc.

Claims (32)

1. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: B 2o 30%～10%, SrO0.001%～35%, ZrO 2+ TiO 20.001%～30%, La 2o 3+ Nb 2o 50%～10%,
Mass ratio BaO/SrO is 0～40, mass ratio SiO 2/ SrO is 0.1～40, and refractive index n d is 1.55～2.3.
2. glass of high refractive index according to claim 1, is characterized in that,
Liquid phase viscosity is 10 3.0more than dPas.
3. glass of high refractive index according to claim 1 and 2, is characterized in that,
It is tabular.
4. glass of high refractive index according to claim 3, is characterized in that,
It utilizes the float glass process moulding to form.
5. according to the described glass of high refractive index of claim 3 or 4, it is characterized in that,
10 4temperature during dPas is below 1250 ℃.
6. according to the described glass of high refractive index of any one in claim 1～5, it is characterized in that,
Strain point is more than 650 ℃.
7. according to the described glass of high refractive index of any one in claim 1～6, it is characterized in that,
It is for means of illumination.
8. glass of high refractive index according to claim 7, is characterized in that,
It is for organic EL illuminating.
9. according to the described glass of high refractive index of any one in claim 1～6, it is characterized in that,
It is for OLED display.
10. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: B 2o 30%～8%, SrO0.001%～35%, ZnO0%～12%, ZrO 2+ TiO 20.001%～30%, La 2o 3+ Nb 2o 50%～5%, Li 2o+Na 2o+K 2o0%～10%,
Mass ratio BaO/SrO is 0～20, mass ratio SiO 2/ SrO is 0.1～20, mass ratio (MgO+CaO)/SrO is 0～20, and refractive index n d is more than 1.58, liquid phase viscosity is 10 3.5dPas is above, strain point is more than 670 ℃.
11. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: SiO 210%～50%, B 2o 30%～8%, CaO0%～10%, SrO0.001%～35%, BaO0%～30%, ZnO0%～4%, ZrO 2+ TiO 20.001%～30%, La 2o 3+ Nb 2o 50%～5%, Li 2o+Na 2o+K 2o0%～2%,
Mass ratio BaO/SrO is 0～20, mass ratio SiO 2/ SrO is 1～15, mass ratio (MgO+CaO)/SrO is 0～20, and refractive index n d is more than 1.6, liquid phase viscosity is 10 4.0dPas is above, strain point is more than 670 ℃.
12. a means of illumination sheet glass, is characterized in that,
As glass, form, in quality, % contains: SiO 20.1%～60%, B 2o 30%～10%, SrO0.001%～35%, BaO0%～40%, ZrO 2+ TiO 20.001%～30%, La 2o 3+ Nb 2o 50%～10%, and refractive index n d is 1.55～2.3.
13. an organic EL illuminating sheet glass, is characterized in that,
As glass, form, in quality, % contains: SiO 20.1%～60%, B 2o 30%～10%, SrO0.001%～35%, BaO0%～40%, ZrO 2+ TiO 20.001%～30%, La 2o 3+ Nb 2o 50%～10%, and refractive index n d is 1.55～2.3.
14. an OLED display sheet glass, is characterized in that,
As glass, form, in quality, % contains: SiO 20.1%～60%, B 2o 30%～10%, SrO0.001%～35%, BaO0%～40%, ZrO 2+ TiO 20.001%～30%, La 2o 3+ Nb 2o 50%～10%, and refractive index n d is 1.55～2.3.
15. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: SiO 235%～60%, Li 2o+Na 2o+K 2o0%～1.5%, SrO0.1%～35%, BaO0%～35%, TiO 20.001%～25%, La 2o 3+ Nb 2o 5+ Gd 2o 30%～9%, refractive index n d is 1.55～2.3.
16. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: SiO 235%～60%, Li 2o+Na 2o+K 2o0%～1.5%, SrO0.1%～20%, BaO17%～35%, TiO 20.01%～20%, La 2o 3+ Nb 2o 5+ Gd 2o 30%～9%, refractive index n d is 1.55～2.3.
17. according to the described glass of high refractive index of claim 15 or 16, it is characterized in that,
Further contain B 2o 30 quality %～3 quality %.
18. according to the described glass of high refractive index of any one in claim 15～17, it is characterized in that,
Further contain MgO0 quality %～3 quality %.
19. according to the described glass of high refractive index of any one in claim 15～18, it is characterized in that,
Further contain ZrO 2+ TiO 21 quality %～20 quality %.
20. according to the described glass of high refractive index of any one in claim 15～19, it is characterized in that,
It is tabular.
21. according to the described glass of high refractive index of any one in claim 15～20, it is characterized in that,
Liquid phase viscosity is 10 3.0more than dPas.
22. according to the described glass of high refractive index of any one in claim 15～21, it is characterized in that,
It utilizes float glass process or glass tube down-drawing moulding to form.
23. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: SiO 230%～60%, B 2o 30%～15%, Al 2o 30%～15%, Li 2o0%～10%, Na 2o0%～10%, K 2o0%～10%, MgO+CaO+SrO+BaO+ZnO20%～60%, TiO 20.0001%～20%, ZrO 20%～20%, La 2o 3+ Nb 2o 50%～10%, refractive index n d is 1.55～2.3.
24. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: SiO 235%～60%, B 2o 30%～15%, Al 2o 30%～15%, Li 2o0%～10%, Na 2o0%～10%, K 2o0%～10%, MgO+CaO+SrO+BaO+ZnO20%～60%, TiO 20.0001%～20%, ZrO 20.0001%～20%, La 2o 3+ Nb 2o 50%～10%, refractive index n d is 1.55～2.3.
25. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: SiO 235%～60%, B 2o 30%～15%, Al 2o 30%～15%, Li 2o0%～1%, Na 2o0%～1%, K 2o0%～1%, Li 2o+Na 2o+K 2o0%～1%, MgO+CaO+SrO+BaO+ZnO20%～50%, BaO0.1%～35%, TiO 20.0001%～20%, ZrO 20.0001%～20%, La 2o 3+ Nb 2o 50%～10%, refractive index n d is 1.55～2.3.
26. a glass of high refractive index, is characterized in that,
As glass, form, in quality, % contains: SiO 235%～60%, B 2o 30%～15%, Al 2o 30%～15%, Li 2o0%～1%, Na 2o0%～1%, K 2o0%～1%, Li 2o+Na 2o+K 2o0%～1%, MgO+CaO+SrO+BaO+ZnO20%～50%, BaO0.1%～35%, TiO 20.0001%～20%, ZrO 20.0001%～20%, La 2o 30%～2.5%, La 2o 3+ Nb 2o 50%～8%, refractive index n d is 1.55～2.3.
27. according to the described glass of high refractive index of any one in claim 23～26, it is characterized in that,
Comprise the above B of 1 quality % 2o 3.
28. according to the described glass of high refractive index of any one in claim 23～27, it is characterized in that,
Comprise the above MgO of 1 quality %.
29. according to the described glass of high refractive index of any one in claim 23～28, it is characterized in that,
It is tabular.
30. according to the described glass of high refractive index of any one in claim 23～29, it is characterized in that,
Liquid phase viscosity is 10 3.0more than dPas.
31. according to the described glass of high refractive index of any one in claim 23～30, it is characterized in that,
It utilizes float glass process or glass tube down-drawing moulding to form.
32. according to the described glass of high refractive index of any one in claim 23～31, it is characterized in that,
At least one mask has the surface of not grinding, and this surperficial surface roughness Ra is
Figure FDA0000401934630000041
below.
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