CN102057459A - Glass tube for fluorescent lamp, fluorescent lamp, and lighting system - Google Patents

Glass tube for fluorescent lamp, fluorescent lamp, and lighting system Download PDF

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Publication number
CN102057459A
CN102057459A CN200980121553XA CN200980121553A CN102057459A CN 102057459 A CN102057459 A CN 102057459A CN 200980121553X A CN200980121553X A CN 200980121553XA CN 200980121553 A CN200980121553 A CN 200980121553A CN 102057459 A CN102057459 A CN 102057459A
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China
Prior art keywords
glass
oxide
lamp
fluorescent
glass tube
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Pending
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CN200980121553XA
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Chinese (zh)
Inventor
元家淳志
北嘉之
谷内昭
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Publication of CN102057459A publication Critical patent/CN102057459A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/30—Vessels; Containers
    • H01J61/302—Vessels; Containers characterised by the material of the vessel
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2453—Coating containing SnO2
    • 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
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C03C17/2456—Coating containing TiO2
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/30—Vessels; Containers
    • H01J61/35—Vessels; Containers provided with coatings on the walls thereof; Selection of materials for the coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/70—Lamps with low-pressure unconstricted discharge having a cold pressure < 400 Torr

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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)
  • Glass Compositions (AREA)
  • Vessels And Coating Films For Discharge Lamps (AREA)
  • Manufacture Of Electron Tubes, Discharge Lamp Vessels, Lead-In Wires, And The Like (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Disclosed is a glass tube for a fluorescent lamp that can realize a reduction in thickness of a bulb of a fluorescent lamp. The glass tube for a fluorescent lamp comprises a tube body formed of a glass comprising 60 to 75 wt% of silicon oxide and 5 to 18 wt% of an alkaline earth metal oxide and a film that is formed at least on the outer peripheral face of the tube body and is formed of at least one oxide selected from tin oxide, titanium oxide, zirconium oxide, and silicon oxide.

Description

Fluorescent-lamp-use glass tube, fluorescent lamp and lighting device
Technical field
The present invention relates to fluorescent-lamp-use glass tube, fluorescent lamp and lighting device.
Background technology
In recent years, from the viewpoint of earth environment protection, require resource-savingization and cut down CO 2Discharge rate.As resource-savingization in the field of fluorescent lamps and reduction CO 2The method of discharge rate is considered glass shell (below abbreviate " shell " as) thin-walled property.That is, when with shell (bulb) thin-walled property, owing to reduced the use amount of the glass of the material that becomes shell, so can realize resource-savingization.In addition, thus since the amount of the combustion gas that the amount by the glass that reduce to use is consumed by melting furnace when producing glass reduce, so also can realize CO 2The reduction of discharge rate.
On the other hand, when with the shell thin-walled property, so easily make the fluorescent lamp breakage because strength of glass reduces.In order to solve such problem, for example in patent documentation 1, propose to have the overlay film that constitutes by oxides such as zirconias with the surface formation of shell at bulb scheme with the strength of glass that improves this shell.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2001-332222 communique.
Summary of the invention
The problem that invention will solve
The result that the inventor confirms by experiment is that under the situation of the bulb that does not form luminescent coating, when forming overlay film on the surface at shell, strength of glass improves.But under the situation of the fluorescent lamp that forms luminescent coating, even form overlay film on the surface of shell, strength of glass can not improve yet.Therefore, under the situation of fluorescent lamp, be difficult to realize the thin-walled property of shell.
The present invention is in view of above-mentioned problem, and its main purpose is, a kind of fluorescent-lamp-use glass tube that can make the shell thin-walled property of fluorescent lamp is provided.Other purposes of the present invention are, provide a kind of and are suitable for resource-savingization and cut down CO 2The fluorescent lamp of discharge rate and lighting device.
The scheme that is used to deal with problems
In order to reach above-mentioned purpose, fluorescent-lamp-use glass tube of the present invention is characterized in that possessing: tube body is made of the glass of the alkaline-earth metals oxide of the silica that contains 60～75wt% and 5～18wt%; And overlay film, be formed on the outer peripheral face at least of described tube body, constitute by at least a oxide that is selected from tin oxide, titanium oxide, zirconia and silica.
In addition, the containing ratio of the oxide that the application put down in writing is exactly the value that oxide converts unless otherwise specified.In addition, comprise lower limit and higher limit in the number range of being put down in writing in this application.For example, be under the situation of 60～75wt% in number range, this number range comprises 60wt% and 75wt%.In addition, in the oxide of glass that constitutes tube body and formation overlay film, in impurity levels, also can comprise above-mentioned material in addition.
Fluorescent-lamp-use glass tube of the present invention contains the above alkaline-earth metals oxide of 5wt% owing to constitute the glass of tube body, so can make the shell thin-walled property of fluorescent lamp.
Because alkali metal metal ion as monovalence in glass exists, so the degree of excursion in the network-like structure of glass is big.Particularly because the atomic radius of sodium is little, so degree of excursion is bigger.Like this, the alkali metal that degree of excursion is big easily as alkali composition elution from glass (elute) to glass surface.When particularly glass becomes high temperature, because the degree of excursion of metal ion becomes big, so the easy elution of alkali composition.
Usually, in the manufacturing process of fluorescent lamp, comprise sintering (sintering) operation of firing luminescent coating.Owing in sintering circuit, glass tube is carried out heat treated, thus the alkali composition easily from the glass that constitutes tube body elution to the surface of tube body.Like this, when the elution of alkali composition, overlay film is subjected to chemical erosion (chemical damage), and the performance of the raising strength of glass of this overlay film reduces.Even the inventor finds out that above is that the surface at shell forms overlay film, the reason that strength of glass also can not improve under the situation of fluorescent lamp.
In addition, the alkali composition is not limited to heat treated according to sintering circuit from the glass elution of tube body.In the manufacturing process of fluorescent lamp, exist in addition the end of the shell bending operation make the shell bending, sealed glass tube the package closure operation, connect connection operation between the glass tube etc. glass tube carried out the operation of heat treated, by these operation alkali compositions also elution easily.In addition, so-called crooked shell is meant that the glass tube with linearity carries out bending machining and the shell of the non-linear shape that forms for example is ring-type shell, U font shell, spiral shell etc.
Fluorescent-lamp-use glass tube of the present invention suppresses the elution of alkali composition by alkaline-earth metal.Because alkaline-earth metal metal ion as divalence in glass exists, so the degree of excursion in the network-like structure of glass is little.In addition, ionic radius is also bigger.Therefore, in glass, can hinder alkali-metal moving.If contain the above alkaline-earth metal of 5wt%, though then in the manufacturing process of fluorescent lamp glass tube be heated processing, the alkali composition also is difficult to elution from the glass of tube body.Therefore, overlay film is difficult to be subjected to chemical erosion, and the performance of the raising strength of glass of overlay film is difficult to reduce.In addition, the containing ratio of alkaline-earth metals oxide is 5～18wt% more preferably, and more preferably 10～18wt% most preferably is 12～18wt%.
Fig. 1 and Fig. 2 are the composition of glass of tube body of the expression lantern pane pipe that constitutes execution mode and the figure of characteristic.As depicted in figs. 1 and 2, under the containing ratio of the alkaline-earth metal of the glass that constitutes tube body was situation more than the 18wt%, the strength of glass of shell was abundant.On the other hand, under the situation of the not enough 5wt% of described containing ratio, the strength of glass of shell is insufficient.
Fluorescent-lamp-use glass tube of the present invention is because the containing ratio of the alkaline-earth metals oxide of the glass of formation tube body is below the 18wt%, so processability is also good.
When glass uprised at the containing ratio of alkaline-earth metal, the viscosity that is caused by temperature changed change greatly.That is, become the glass of the poor in processability of easy cooling.When constituting tube body by such glass, the processability of glass tube is variation also.In order to become the good glass tube of processability, need make the containing ratio of the alkaline-earth metal of the glass that constitutes tube body is below the 18wt%.In addition, the softening temperature of the glass that processability is good is in 650～720 ℃ scope, and processing temperature is in 960～1050 ℃ scope.More preferably, softening temperature is in 670～700 ℃ scope, and processing temperature is in 960～1000 ℃ scope.
As depicted in figs. 1 and 2, under the containing ratio of alkaline-earth metal is situation below the 18wt%, can obtain the good glass of softening temperature and the processing temperature processability in above-mentioned scope.On the other hand, surpass under the situation of 18wt%, become the glass of poor in processability at described containing ratio.
Though overlay film especially preferably is made of tin oxide as long as be made of at least a oxide that is selected from tin oxide, titanium oxide, zirconia and silica.If overlay film is made of tin oxide, then the glass of tube body can painted or devitrification (devitrification).On the other hand, when overlay film is made of zirconia, the reaction of composition in zirconium and the glass, and work as the karyogenesis thing of crystallization, the nuclei of crystallization of this zirconium are grown by the heat treated of back, and worry can cause the glass devitrification of tube body.In addition, when overlay film is made of titanium oxide, under the situation of the bigger growth of crystallization particle diameter of titanium, worry that the glass of tube body can be partially white and painted.
In addition, in a mode of fluorescent-lamp-use glass tube of the present invention, it is characterized in that alkaline-earth metals oxide is at least a oxide that is selected from magnesium oxide and calcium oxide.In this case, can make glass tube with low cost.This be because, because magnesium oxide oxide and calcium oxide oxide can obtain from the such natural crystal of dolomite (dolomite), so can obtain more at an easy rate than other alkaline-earth metals oxides.
In addition, in a mode of fluorescent-lamp-use glass tube of the present invention, it is characterized in that alkaline-earth metals oxide is magnesium oxide and calcium oxide, described calcium oxide is 0.5～3 with respect to described magnesian mol ratio.In this case, can constitute tube body with the less glass of elution that is difficult to devitrification and alkali composition.Because calcium is bigger than magnesium ion radius, so the effect of the elution of inhibition alkali composition is big.On the other hand, when calcium is too much, calcium and alkali-metal crystallization can be produced, the glass easy devitrification that becomes can be made.Therefore, be preferably in the scope of described mol ratio.
As depicted in figs. 1 and 2, under the situation of calcium oxide with respect to magnesian mol ratio (CaO/MgO) less than 0.5, the softening temperature of glass or processing temperature can not be included preferred range in sometimes, the easy variation of processability.In addition, when calcium oxide surpasses 3 with respect to magnesian mol ratio (CaO/MgO), make the glass devitrification sometimes.
In addition, in a mode of fluorescent-lamp-use glass tube of the present invention, it is characterized in that the glass that constitutes tube body adds up to the alkali metal oxide that contains 8～20wt%.When the containing ratio of alkali metal oxide surpassed 20wt%, conductance described later had sometimes surpassed 57 μ S/cm, becomes the many glass of elution amount of alkali composition easily.If the not enough 8wt% of the containing ratio of alkali metal oxide, then the processing temperature of glass can not be included preferred range in sometimes, the easy variation of processability.
In addition, in a mode of fluorescent-lamp-use glass tube of the present invention, it is characterized in that the crystal structure that has the quadratic crystal class more than the 50wt% of the oxide of formation overlay film.Have in the plurality of the oxide that constitutes overlay film under the situation of crystal structure of quadratic crystal class, can improve the strength of glass of shell more, can further realize the thin-walled property of shell.At the crystal structure of oxide is that the reason that the situation lower-glass intensity of quadratic crystal class improves is: because as the SiO of the principal component of glass 2The crystal class be that its crystal structure of cristobalite (cristobalite) is the quadratic crystal class, so if making the crystal structure of the oxide that forms overlay film is same quadratic crystal class, then the film forming to glass surface can improve.In addition because: if because crystal structure is the quadratic crystal class, and then the overlay film of Sheng Chenging combines securely with glass, peel off etc. so be difficult to generation.
At the oxide that constitutes overlay film is under the situation of tin oxide, and preferably this tin oxide is not SnO but SnO 2State.This be because, SnO 2As the crystallization of quadratic crystal class and stablize, but SnO changes the crystallization of cubic crystal class easily into.In addition, under the situation more than 500 ℃, be difficult to become the state of SnO in the temperature of the glass tube that carries out overlay film.
In addition, in a mode of fluorescent-lamp-use glass tube of the present invention, it is characterized in that the wall thickness t[mm of tube body] and external diameter φ [mm] satisfy t≤0.7 or, the relation of t/ φ≤0.42.In this case, because wall thickness, so particularly shell is damaged easily, it is effective that formation of the present invention becomes.
Fluorescent lamp of the present invention possesses the shell of the fluorescent-lamp-use glass tube making of using above-mentioned record.Therefore, be difficult to breakage.
Lighting device of the present invention possesses the fluorescent lamp of above-mentioned record.Therefore, be difficult to breakage.
The invention effect
Even fluorescent-lamp-use glass tube of the present invention glass tube in the manufacturing process of fluorescent lamp is heated processing, the performance of the raising strength of glass of overlay film can not reduce yet.Therefore, can realize the thin-walled property of the shell of fluorescent lamp.
Description of drawings
Fig. 1 is the composition of glass of tube body of the expression lantern pane pipe that constitutes present embodiment and the figure of characteristic.
Fig. 2 is the composition of glass of tube body of the expression lantern pane pipe that constitutes present embodiment and the figure of characteristic.
Fig. 3 is the experimental result of the strength of glass of glass tube and the influence that gonorrhoeaization is brought is given in expression at the thickness of overlay film figure.
Fig. 4 is the biopsy cavity marker devices plane graph of the lamp of expression present embodiment.
Fig. 5 is the stereogram of schematic configuration of the lighting device of expression present embodiment.
Fig. 6 is the figure of explanation fluorescent lamp manufacturing method, (a) is the figure of explanation fluorophor working procedure of coating, (b) is the figure of explanation sintering circuit, (c) is the figure of explanation package closure operation, (d) is the figure of explanation shell bending operation.
Fig. 7 is the figure of assay method that is used to illustrate the thickness of overlay film.
Fig. 8 is the figure that is used to illustrate the assay method of the alkali cleaning amount of carrying.
Fig. 9 is the alkali cleaning amount of putting forward of (alkaline elution) test method determination and the dependency relation of the conductance of carrying test method determination by the application's alkali cleaning are put forward in expression by the alkali cleaning of JIS regulation figure.
Embodiment
Below, describe based on fluorescent-lamp-use glass tube (being designated hereinafter simply as " glass tube "), fluorescent lamp and the lighting device of accompanying drawing embodiment of the present invention.
[formation of glass tube, fluorescent lamp and lighting device]
＜glass tube＞
The overlay film that glass tube of the present invention comprises tube body and is formed at the outer peripheral face at least of this tube body.
Its wall thickness of tube body t[mm] and external diameter φ [m] preferably satisfy the relation of t≤0.7 or t/ φ≤0.42.Be preferably 0.4≤t≤0.6,1≤φ≤10 especially.
The thickness of overlay film is preferably 5～100nm, more preferably 5～50nm.The figure of the experimental result of Fig. 3 influence that to be expression bring the strength of glass and the gonorrhoeaization of glass tube at the thickness of overlay film.As shown in Figure 3, be that (embodiment 14～20,23～25) about the evaluation of strength of glass for " zero ", but (embodiment 21,22) are the evaluation of " △ " about strength of glass under the situation of not enough 5nm under the situation more than the 5nm at the thickness of overlay film.In addition, under the thickness of overlay film was situation below the 50nm, when in package closure operation etc. glass tube being heated, heating part can not produce gonorrhoea, but is surpassing under the situation of 50nm and can produce gonorrhoea at heating part.In addition, though so generally to consider gonorrhoea be that the grain growth produces because the coated particle of tin oxide is by heating, such gonorrhoea can cause the bad order of fluorescent lamp, and then can hinder the visual examination of damage etc., so not preferred.
Because when the thickness of overlay film becomes 500nm when above, the visible light transmittance reduction of glass tube is so use the transmissivity of the shell of this glass tube making also to reduce.Using this shell to make under the situation of fluorescent lamp, the taking-up efficient of light reduces, and the full luminous flux of lamp reduces.In addition, overlay film not only forms at the outer peripheral face of tube body, also can form at inner peripheral surface, end face.In addition, the Zone Full that overlay film need not to spread all over outer peripheral face forms, and the part that can be not be covered by lamp holder etc. when becoming shell forms.
Tube body is preferably formed by the following glass of forming.Silica (SiO 2): 60～75wt%, aluminium oxide (Al 2O 3): 0.5～5wt%, boron oxide (B 2O 3): 0～5wt%, lithia (Li 2O): 0.5～7wt%, sodium oxide molybdena (Na 2O): 3～17wt%, potassium oxide (K 2O): 1～12wt%, magnesium oxide (MgO): 1～4wt%, calcium oxide (CaO): 1～7.3wt%, strontium oxide strontia (SrO): 0～8wt%, barium monoxide (BaO): 0～10wt%, zinc oxide (ZnO): 0～10wt%, zirconia (ZrO): 0～5wt%, acidifying iron (Fe 2O 3): 0.01～0.2wt%, antimony oxide (Sb 2O 3): 0～1wt%, cerium oxide (CeO 2): 0～1wt%.
SiO 2Principal component for the skeleton that forms glass has served as after a little while, and the viscosity of glass descends, and processability is poor excessively.In addition, served as for a long time, the viscosity hardening of glass and be difficult to the distortion.SiO 2The preferable range of containing ratio be 60～75wt%.
Al 2O 3For making the good composition of chemical durability, served as after a little while its chemical durability variation.In addition, served as for a long time, glass becomes inhomogeneous and the lines increase.Al 2O 3The preferable range of containing ratio be 0.5～5wt%.
B 2O 3Be any composition,, have the effect that makes the coefficient of expansion reduce and reduce devitrification by a spot of interpolation.But owing to served as for a long time, the setting temperature descends, and range of working temperature is narrow, becomes difficult so add trade union.B 2O 3The preferable range of containing ratio be 0～5wt%.
Na 2O has by interpolation makes the effect of viscosity reduction, the effect that the coefficient of expansion is increased, and has served as after a little while, can not obtain its effect.In addition, served as for a long time the chemical durability variation.Na 2The preferable range of the containing ratio of O is 3～17wt%.
K 2Though thereby O can obtain and Na by adding 2The identical such effect of O, but the influence degree of the increase of the coefficient of expansion compares Na 2O is big.In addition, by with Na 2The O coexistence can be brought into play the mixed base effect, also can bring into play the effect that improves resistivity.Served as after a little while, can not obtain its effect, served as for a long time, the coefficient of expansion is excessive.K 2The preferable range of the containing ratio of O is 1～12wt%.
Li 2Though thereby O can obtain and Na by adding 2O, K 2The identical such effect of O, but Na is compared in the increase of the coefficient of expansion 2O is little.In addition, by with Na 2O, K 2The O coexistence can be brought into play further mixed base effect, also can bring into play the effect of further raising resistivity.Served as after a little while, can not obtain its effect, served as for a long time, worried that glass can phase-splitting.Li 2The preferable range of O containing ratio is 0.5～7wt%.
MgO, CaO also have the effect that improves chemical durability by interpolation except that the effect of the elution with the alkali composition that suppresses above-mentioned.Served as after a little while, can not obtain its effect, served as for a long time, worried that glass can devitrification.The preferable range of the containing ratio of MgO is 1～4wt%, and the preferable range of the containing ratio of CaO is 1～7.3wt%.
SrO, BaO and ZnO are except the effect of the elution that suppresses above-mentioned alkali composition, and the resistivity of glass is improved the material that also influences, and have also given electrical insulating property.When they containing ratio than 10wt% for a long time, the easy devitrification of glass.Preferable range is that SrO is that 0～8wt%, BaO are that 0～10wt%, ZnO are 0～10wt%, as long as in this scope, just can obtain the preferred glass as fluorescent-lamp-use.
ZrO is any composition, has the effect that improves hardness by interpolation.Served as for a long time, worried that glass can crystallization.The preferable range of the containing ratio of ZrO is 0～5wt%.
Fe 2O 3Be the material of sneaking into, but can adjust its addition,, can absorb ultraviolet ray by adding by refining raw material as the impurity of various raw materials.Served as after a little while, can not obtain its effect, served as for a long time, worried that glass can be painted.Fe 2O 3The preferable range of containing ratio be 0.01～0.2wt%.
Sb 2O 3Be any composition, have the gas that in glass melting furnace, makes from the raw material generation and purify the effect of (clarify) effectively, but served as for a long time, worry that glass can be painted.Sb 2O 3The preferable range of containing ratio be 0～1wt%.
CeO 2Be any composition, have by interpolation and absorb ultraviolet effect, but served as for a long time that worry can cause because of ultraviolet irradiation painted so-called over-exposed (solarization).CeO 2The preferable range of containing ratio be 0～1wt%.
＜fluorescent lamp＞
Fig. 4 is the biopsy cavity marker devices plane graph of the ring-type type fluorescent lamp of expression an embodiment of the present invention.As shown in Figure 4, the ring-type type fluorescent lamp (FCL30ECW/28) 10 of an embodiment of the present invention possess ring-type shell 20, be sealed in the stem stem 30,31 ' and cross over its both ends and the lamp holder 40 installed at the both ends of this shell 20.
Shell 20 processes glass tube of the present invention; the surface stacks gradually matcoveredn (not shown) and luminescent coating (not shown) within it, encloses in inside and is useful on the amalgamation goldc grains 21 of supplying with mercury vapor, as the argon gas of an example of rare gas.Be equipped with the electrode 31,31 ' that constitutes by heater winding and pair of lead wires at each stem stem 30,30 '.Lamp holder 40 possesses the main part 41 of the end of accommodating shell 20 and is arranged at a plurality of connecting pins 42 of this main part 41.
＜lighting device＞
Fig. 5 is the stereogram of the lighting device of expression an embodiment of the present invention.As shown in Figure 5, the lighting device 100 of present embodiment possesses above-mentioned fluorescent lamp 10 as light source.Fluorescent lamp 1 is contained in the apparatus main body 101, lights by the lighting unit 102 that is installed on this apparatus main body 101.
[manufacture method of glass tube and lamp]
The manufacture method of＜glass tube＞
At first, multiple frit is mixed in the scope of above-mentioned composition and obtain raw mix.Then, raw mix is dropped into glass melting furnace, under 1500～1600 ℃, make its fusion, carry out vitrifying, obtain the glass solution (glass melt) of vitreousness., glass solution by danner process pipe pulling methods such as (Danners) be configured as tubulose, cut off the size that is processed as regulation, obtain glass tube thereafter.
The formation of overlay film is that steam that organic metal the produces glass tube in draft chamber (draft chamber) pipe being stretched sprays and evaporation carries out by heating.For example, organic metal is heated with 180 ℃, 10g is vaporized by carrying out in per 1 minute, and the steam that obtains was sprayed for 1 second with flow velocity 5L/min in glass tube, forms overlay film.The thickness of overlay film can be controlled by regulating vaporized temperature, organometallic use amount, jet velocity, injecting time etc.In addition, the method that also can spray by the soln using injector that will make organic metal be dissolved in water, organic solvent, dip pipe main body and the method that applies form overlay film in the solution of dissolving.
As the organic metal of the formation that is used for overlay film, can use and for example contain tin, titanium, zirconium or silicon as the organic metal of metal ingredient.Specifically, can enumerate: butter of tin titanium tetrachloride zirconium chloride silicon tetrachloride, dimethyltin chloride, dimethyl titanium chloride, dimethyl zirconium dichloride, dimethyl silicon dichloride, acetylacetone,2,4-pentanedione tin, titanium acetylacetone, acetylacetone,2,4-pentanedione zirconium, acetylacetone,2,4-pentanedione silicon etc.
The manufacture method of＜lamp＞
Fig. 6 is the figure of explanation fluorescent lamp manufacturing method, (a) is the figure of explanation fluorophor working procedure of coating, (b) is the figure of explanation sintering circuit, (c) is the figure of explanation package closure operation, (d) is the figure of explanation shell bending operation.
At first, in the fluorophor working procedure of coating, shown in Fig. 6 (a), in being formed with the glass tube 21 of diaphragm, inner surface flows into the fluorophor suspension-turbid liquid 50 of 3 wavelength, and the inner surface of above-mentioned glass tube 21 is wetting by above-mentioned fluorophor suspension-turbid liquid 50.Then, in glass tube 21, be blown into hot blast (25～30 ℃), make fluorophor suspension-turbid liquid 50 dryings, then shown in Fig. 6 (b), in environment is controlled in stove about 550～660 ℃, fired about 1 minute, form luminescent coating.Like this, in sintering circuit, because glass tube is carried out heat treated, so easy elution alkali composition.
Then, in the package closure operation, after near the luminescent coating the both ends of glass tube 21 is removed, shown in Fig. 6 (c), stem stem 30,30 ' and seal is inserted at above-mentioned both ends respectively.In shell bending operation thereafter, shown in Fig. 6 (d), bending machining is a ring-type in environment is controlled in stove about 700～900 ℃ with rectilinear glass tube 21.Like this, in the shell bending operation, because glass tube is carried out heat treated, so the easy elution of alkali composition.
Thereafter, in deairing step, via unencapsulated blast pipe 32, from the inner foreign gases of discharging of shell 20, in making shell 20, become state near vacuum after, add argon gas.And then, enclose in the operation at mercury alloy, from blast pipe 32 amalgamation goldc grains 21 is dropped in the shell.
[evaluation method]
The evaluation of fluorescent-lamp-use glass tube is carried out with following such method.
The thickness of＜overlay film＞
The thickness of overlay film uses the hot junction coating meter (HOT END COATING MEASUREMENT SYSTEM:HECM-S) of U.S. glass research company (American Glass Research) system to measure.
Fig. 7 is the figure of assay method that is used to illustrate the thickness of overlay film.As sample, preparation is cut into the glass tube of 20cm, shown in Fig. 7 (a), near the both ends of this glass tube and central portion near three places respectively shown in Fig. 7 (b), on circumferentially, vacate uniformly-spaced (vacating at interval) and measure (adding up to 12 points) with 4, on average be used as thickness with this measured value of 12 in the about 90 ° mode of the anglec of rotation.In addition, the incident angle to the light of each point is made as 45 °.
In the coating meter of hot junction, thickness is by the ctu(coating thickness units as unique unit: expression coating layer thickness unit), 1ctu is 0.2～0.3nm by SI unit.Convert as 1ctu=0.25nm in this application.
＜strength of glass＞
At first, in experiment, use external diameter as 4mm, internal diameter as 3mm and be formed with the glass tube of the straight line of overlay film at outer peripheral face.Overlay film forms in the following way: heated 1 minute down at 120 ℃ by the powder with dimethyltin chloride, the steam that produces is ejected into the glass tube of managing in stretching in the draft chamber, thereby form the overlay film of the thickness 100nm that is made of tin oxide.
Then, put into the quartz ampoule of internal diameter 20mm with finishing glass tube that overlay film forms, this quartz ampoule is rotated with the rotating speed of 5 minutes 20rpm under 500 ℃ environment, by making glass tube and quartz ampoule mutual friction mutually, thereby the surface that makes glass tube in spite of wound.
, use universal testing machine (Autograph) AG-IS(island Tianjin company make thereafter), the bending strength of the glass tube after is in spite of wound measured.The mensuration of bending strength is carried out in the following way: glass tube is fixed with left and right sides span 40mm, and at the central portion of this glass tube with loading speed 1mm/min load loading, obtain the value of glass tube when destroyed.
And, because in spite of wound and bending strength descends under the situation more than 30%, insufficient and be evaluated as " * " as strength of glass, under the situation of less than 30% that only descends, fully be evaluated as " △ " (bending strength descends more than 15% and the situation of less than 30%) or " zero " (bending strength descends more than 0% and the situation of less than 15%) as strength of glass.In addition, the inadequate reason of situation lower-glass intensity that descends more than 30% in bending strength is: when such glass tube was made fluorescent lamp more than 30% because of descending when the use bending strength, the rate of finished products in the operation can remarkable decline.
＜gonorrhoea＞
The valency of gonorrhoea is undertaken by visual, visually is evaluated as " zero " under the situation of gonorrhoea, is evaluated as " * " visual under the situation of gonorrhoea not having.
＜softening point temperature and setting temperature＞
For softening point temperature and the setting temperature of measuring glass, make sample according to order as follows.At first, the raw mix that the hybrid glass raw material is obtained is transferred to platinum crucible, and this platinum crucible was carried out fusion to realize vitrifying through 3 hours in 1500 ℃ electric furnace.Flow into metal die after the fusion, and with the degree of being out of shape abundant elimination through cooling off (annealing) in 12 hours gradually.The piece of the glass that is shaped is used cutter etc., and being shaped is processed as each sample shape measured that is suitable for the following describes, and implements each mensuration.
Softening point temperature is that the viscosity of glass becomes 10 7.65The temperature of dPas, if become this more than temperature, then glass can obtain flowability.Softening point temperature as fluorescent-lamp-use preferably in 650 ℃～720 ℃ scope, more preferably in 670～700 ℃ scope.When softening point temperature is lower than 650 ℃, pay in (printing) operation in the burning of fluorophor, when heating for the adhesive volatilization that makes the fluorophor suspension-turbid liquid, shell is owing to distortion has taken place this heat.On the other hand, when softening point temperature is higher than 720 ℃, must make man-hour glass tube become high temperature sealing to add, the burning capacity of melting furnace is improved.
The setting temperature is that the viscosity of glass becomes 10 4The temperature of dPas.Glass is processed below the temperature at this.The setting temperature, more has in the scope that is selected in 960～1000 ℃ preferably in 960 ℃～1050 ℃ scope as fluorescent-lamp-use.When the operation temperature is lower than 1000 ℃, owing to range of working temperature narrows down, so poor in processability.On the other hand, when the setting temperature was higher than 1050 ℃, because the temperature of glass melting is too high, so the processability variation, in addition, the cost of fusion operation also uprised.
＜alkali cleaning the amount of carrying＞
As the method for measuring the alkali cleaning amount of putting forward, can enumerate the test method (the JIS R of Japanese Industrial Standards 3502) of using glass wares based on the chemical analysis of JIS usually.When simply this method being described, at first, use mortars (mortar) etc. are pulverized the glass test portion and are minced for Powdered (particle diameter 250～420 μ m) obtain glass dust, then, this glass dust minced clean, and mince from glass dust and to remove the glass micropowder, then with ethanol, with the heating 60 minutes of mincing in boiling water bath of the glass dust after cleaning, and make the alkali composition mince elution and obtain the alkali cleaning extract from this glass dust., this alkali cleaning extract with sulfuric acid carried out acid-base titration, according to the titration value that the obtains alkali cleaning amount of carrying that converts thereafter.
In the test method based on such JIS, when according to the cleaning of ethanol when insufficient, because meeting residual glass micropowder in glass dust minces, so, because of the total surface area of the glass in the existence distilled water of this glass micropowder significantly increases, existence can not be measured the problem of the correct alkali cleaning amount of putting forward.In addition, the glass test portion need be pulverized for Powdered, remove complicated operation such as glass micropowder, acid-base titration by cleaning.Therefore, wish the assay method of high accuracy more and the easy alkali cleaning amount of carrying.
Therefore, inventor waits and to have established again than based on the test method of the JIS assay method of high accuracy and the easy alkali cleaning amount of carrying more.In the assay method of the present invention, block glass test portion is impregnated in the distilled water, make the alkali composition from the elution of glass test portion to distilled water, the conductance of the alkali cleaning extract that obtains is measured, and according to this measured value conversion alkali cleaning amount of carrying.
Fig. 8 is the figure that is used to illustrate the assay method of the alkali cleaning amount of carrying of the present invention.Use Fig. 8 that the concrete order of assay method of the present invention is described.
At first, the glass test portion is cut into bulk, contains wet process making temperature keep 75～85 ℃, humidity to keep placing 45～50 hours in 85～95% the constant temperature and humidity cabinet.In addition, in order to improve the mensuration precision, near the value the center that is set at temperature, humidity and standing time above-mentioned each scope in more preferably impregnation being handled promptly 80 ℃, 90%, 48 hour.
Then, as shown in Figure 8, retain 70～80 ℃ the distilled water 2 of 100ml in tank 1, the glass test portion 3 that end is contained wet process in this distilled water 2 flooded 1 hour.In assay method of the present invention, because elution alkali composition in the distilled water 2 of 70～80 ℃ of such lower temperatures, so compare with the test method based on JIS of from the distilled water of boiling, forcing elution alkali composition, can measure the alkali cleaning amount of putting forward of the occupation mode that conforms to actual glass.
Glass test portion 3 is included 4500～5500mm in the summation of surface area 2Scope in mode, be preferably about 5000mm 2Mode adjust dipping.For example, will be cut into 8 of glass test portion 3 dippings of the rectangular shape of about 15 * 15 * 2.5mm.
, from distilled water 2 take glass test portion 3, obtain the alkali cleaning extract thereafter.And, this alkali cleaning extract is stabilized to 25 ℃, use the sensor type liquid infiltration shape electric conductivity measuring machine 4(trade name of commercially available portable type: Twin Cond B-173) conductance is measured.
Fig. 9 is expression by the alkali cleaning amount of carrying measured based on the test method of the JIS chart with the dependency relation of conductance by determination of test method of the present invention.Above-mentioned alkali cleaning amount of carrying and conductance are in so as shown in Figure 9 dependency relation.It is generally acknowledged the shell to fluorescent lamp, the suitable alkali cleaning amount of carrying is the following glass of 270 μ g/g, but as can be seen from Figure 9, is 57 μ S/cm corresponding to the conductance of the alkali cleaning amount of carrying of 270 μ g/g.Therefore, we can say that conductance is that the following glass of 57 μ S/cm is suitable as the glass that shell is used.
That is, conductance is to represent the numerical value of the alkali cleaning amount of carrying of glass indirectly, we can say in order to be as fluorescent-lamp-use and preferred glass preferably is below the 57 μ S/cm in 25 ℃.When conductance than 57 μ/when cm is high, the variety of issue that is caused by the generation of mercury alloy becomes remarkable.
In the said determination method,, control the summation of the surface area that impregnated in the glass in the distilled water easily owing to use block glass test portion.Therefore, can be with beguine according to the higher precision determination alkali cleaning amount of carrying of the test method of JIS.In addition, because assay method of the present invention is by the electric conductivity measuring alkali cleaning amount of carrying, so, measure precision and also can not reduce even the alkali cleaning amount of carrying is more.
In addition, in the said determination method, because the glass test portion of the bulk of cutting is impregnated in the distilled water, be not operation Powdered or that glass dust is minced and cleans so do not need the glass test portion pulverized.In addition, the mensuration of the conductance of alkali cleaning extract can be undertaken by the shirtsleeve operation that only electrode of electric conductivity measuring machine 4 is impregnated into this alkali cleaning extract, does not need numerous and diverse acid-base titration operation.Therefore, simpler and easy than assay method operation based on JIS.
＜increased devitrification resistance＞
When fusion and vitrifying, whether produce crystallization and devitrification by Visual Confirmation glass, carrying out " zero " does not have devitrification, " * " that the evaluation of devitrification is arranged.
The ratio of the crystallization of＜quadratic crystal class＞
At first, in experiment, use external diameter as 4mm, internal diameter as 3mm and be formed with the glass tube of the straight line of overlay film at outer peripheral face.Overlay film forms in the following manner: the powder of dimethyltin chloride was heated 1 minute down at 120 ℃, the steam that produces is ejected into the glass tube of managing in stretching in the draft chamber, form the overlay film of thickness 100nm.
Then, the overlay film that keeps being formed at the state of glass tube is observed with the X-ray diffraction device, the crystal structure of the oxide that constitutes this overlay film is confirmed.
[variation]
More than, based on execution mode fluorescent lamp of the present invention and fluorescent-lamp-use glass tube are illustrated particularly, but fluorescent-lamp-use glass tube of the present invention, fluorescent lamp and lighting device are not limited to above-mentioned execution mode.
Fluorescent-lamp-use glass tube of the present invention is except that the purposes of making shell, and also being suitable for making oviduct (flare), blast pipe etc. has and adding heat treated and the purposes of the device of the requirement of thin-walled property in man-hour.In addition, the glass that constitutes tube body can also can be hard glass for soft glass, but special under the situation of the low soft glass of strength of glass, formation of the present invention is effective especially.
Fluorescent lamp of the present invention is not limited to above-mentioned execution mode, can extensively be used in all fluorescent lamps such as straight pipe type fluorescent lamp, ring-type type fluorescent lamp, cold-cathode fluorescence lamp, double ring-type type fluorescent lamp, positive square fluorescent lamp, the positive square fluorescent lamp of two-fold, double fluorescent lamp.
Lighting device of the present invention is not limited to above-mentioned execution mode.For example, can extensively be used on indoor lighting device, room external application lighting device, the table with illumination, portable with illumination, show that backlight and image with light source, liquid crystal panel read lighting devices such as usefulness illumination.
Utilizability on the industry
Fluorescent-lamp-use glass tube of the present invention can extensively be used in lighting use.
Description of reference numerals
10: lamp, 20: shell, 21: fluorescent-lamp-use glass tube, 22: tube body, 23: overlay film, 100: lighting device.

Claims (8)

1. fluorescent-lamp-use glass tube is characterized in that possessing:
Tube body is made of the glass of the alkaline-earth metals oxide of the silica that contains 60～75wt% and 5～18wt%; And
Overlay film is formed on the outer peripheral face at least of described tube body, is made of at least a oxide that is selected from tin oxide, titanium oxide, zirconia and silica.
2. fluorescent-lamp-use glass tube according to claim 1 is characterized in that, described alkaline-earth metals oxide is at least a oxide that is selected from magnesium oxide and calcium oxide.
3. fluorescent-lamp-use glass tube according to claim 1 is characterized in that, described alkaline-earth metals oxide is magnesium oxide and calcium oxide, and described calcium oxide is 0.5～3 with respect to described magnesian mol ratio.
4. fluorescent-lamp-use glass tube according to claim 1 is characterized in that the glass that constitutes described tube body contains the alkali metal oxide that adds up to 8～20wt%.
5. fluorescent-lamp-use glass tube according to claim 1 is characterized in that, constitutes the crystal structure that has the quadratic crystal class more than the 50wt% of oxide of described overlay film.
6. fluorescent-lamp-use glass tube according to claim 1 is characterized in that, the wall thickness t[mm of described tube body] and external diameter φ [mm] satisfy the relation of t≤0.7 or t/ φ≤0.42.
7. a fluorescent lamp is characterized in that, it possesses the shell that uses the described fluorescent-lamp-use glass tube of claim 1 to make.
8. a lighting device is characterized in that, it possesses the described fluorescent lamp of claim 7.
CN200980121553XA 2008-06-09 2009-06-05 Glass tube for fluorescent lamp, fluorescent lamp, and lighting system Pending CN102057459A (en)

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JPS5432521A (en) * 1977-08-17 1979-03-09 Asahi Denka Kogyo Kk Method of protecting glass
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JP4756429B2 (en) * 2001-04-04 2011-08-24 日本電気硝子株式会社 Compact fluorescent lamp glass and manufacturing method thereof.
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