CN102057461A - 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
CN102057461A
CN102057461A CN2009801215525A CN200980121552A CN102057461A CN 102057461 A CN102057461 A CN 102057461A CN 2009801215525 A CN2009801215525 A CN 2009801215525A CN 200980121552 A CN200980121552 A CN 200980121552A CN 102057461 A CN102057461 A CN 102057461A
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China
Prior art keywords
glass
oxide
lamp
fluorescent
glass tube
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CN2009801215525A
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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 CN102057461A publication Critical patent/CN102057461A/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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • 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
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic 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)

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, a first 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, and a second film that is stacked on the first film and is formed of a hydrophobic lubricant or a surfactant having an HLB value of not more than 13.

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 angle of the environment of preserving our planet, require to save resource and reduce CO 2Discharge capacity.Just in field of fluorescent lamps, be used to save resource and reduce CO 2The method of discharge capacity can be considered glass bulb (being designated hereinafter simply as " bulb ") is made thin-walled property.That is, behind the glass bulb thin-walled property, will reduce as the use amount of the glass of bulb material, thereby can realize the saving of resource.In addition, after employed amount of glass reduced, the gas quantity that melting furnace consumes when producing glass also reduced thereupon, thereby also can realize CO 2The minimizing of discharge capacity.
Yet, can predict, in case with the bulb thin-walled property, strength of glass will descend.Therefore, must try every possible means to improve the strength of glass of bulb.Disclose a kind of method that is used to improve strength of glass in the patent documentation 1, reduced this surperficial coefficient of friction, improved the marresistance energy of glass container thus thereby on the surface of glass container, form the overlay film that constitutes by lubricant.Glass is as long as the surface is not injured, and its intensity is just very high, therefore, has improved the marresistance energy, has been not easy injuredly, and then the strength of glass of glass container is improved.
And then disclose following discovery in the patent documentation 1: preferably use the hydrophobicity lubricant in the above-mentioned overlay film, if use hydrophilic lubricant, then the marresistance of glass container can improve not quite.In addition, following method being disclosed also wherein: because the hydrophobicity lubricant is poor to the tack of glass, therefore, at first forms the overlay film that is made of metal oxide on glass surface, form the overlay film that is made of the hydrophobicity lubricant on this overlay film.
The prior art document
Patent documentation
Patent documentation 1: No. 3895519 communique of patent
But, find that though formed overlay film that is made of metal oxide and the overlay film that is made of the hydrophobicity lubricant on the tube face, the strength of glass of bulb does not still improve after the use said method is produced the fluorescent lamp bulb.Therefore, be difficult to realize the thin-walled property of bulb.
Summary of the invention
The present invention is in view of above-mentioned problem, and its objective is provides a kind of fluorescent-lamp-use glass tube that can realize the thin-walled property of fluorescent lamp bulb.Another object of the present invention provides and a kind ofly is suitable for saving resource and reduces CO 2The fluorescent lamp of discharge capacity and lighting device.
To achieve these goals, fluorescent-lamp-use glass tube of the present invention is characterised in that to have: tube body is made of the glass of the alkaline-earth metals oxide of the silica that contains 60～75wt% and 5～18wt%; The 1st overlay film is formed on the outer peripheral face at least of described tube body, is made of at least a kind of oxide selecting among tin oxide, titanium oxide, zirconia and silica; The 2nd overlay film is layered on described the 1st overlay film, is made of smaller or equal to 13 surfactant hydrophobicity lubricant or HLB.
In addition, if no special instructions, the containing ratio of the oxide of putting down in writing among the application all is the value after peroxide converts.In addition, the number range of putting down in writing among the application comprises lower limit and higher limit.For example, if number range is set to 60～75wt%, then this number range comprises 60wt% and 75wt%.In addition, at the glass that constitutes tube body with constitute in the oxide of the 1st overlay film, also it doesn't matter even comprise impurity except that above-mentioned substance.
In the fluorescent-lamp-use glass tube of the present invention, the glass that constitutes tube body contains the above alkaline-earth metals oxide of 5wt%, so the bulb of fluorescent lamp can be realized thin-walled property.
Alkali metal form with monovalent metallic ion in glass exists, and therefore, its mobility in the network configuration of glass is bigger.Especially, sodium is bigger because of the little mobility of its atomic radius.Like this, the alkali metal that mobility is big easily from glass as the alkaline components stripping to glass surface.After the alkaline components that comes out of stripping made the 1st overlay film be subjected to chemical erosion (chemical damage) by this way, the polarity on overlay film surface can increase, and therefore the hydrophily of the 1st overlay film improves, and consequently, the tack of the 2nd overlay film descends.Like this, the coefficient of friction of tube face increases, thereby the marresistance of bulb can descend, and the strength of glass of bulb descends.The inventor finds, even more than be exactly to form the 1st overlay film that is made of metal oxide and the 2nd overlay film that is made of the hydrophobicity lubricant on the tube face of fluorescent lamp, the strength of glass of bulb also can not get the reason place of improving.
In addition, go out alkaline components from the glass stripping of tube body and be not limited only to heat treated the sintering circuit.In the manufacturing process of fluorescent lamp, connection operation that also has other the bulb sealing process that seals such as the bulb bending operation that bulb is bent, to the end of glass tube, glass tube is connected with each other etc. need be implemented the operation of heat treated to glass tube, and these operations also can cause alkaline components that stripping takes place easily.In addition, so-called crooked bulb refers to glass tube with straight shape and carries out the non-linear shape bulb that forms after the bending machining, for example ring-type bulb, U font bulb, helical lamp envelope etc.
Fluorescent-lamp-use glass tube of the present invention has suppressed the stripping of the alkaline components that alkaline-earth metal causes.Alkaline-earth metal form with bivalent metal ion in glass exists, and therefore, its mobility in the network configuration of glass is little.In addition, ionic radius is also bigger.Therefore, in glass, hindered alkali-metal moving.If the content of alkaline-earth metal is more than 5wt%, then in the manufacturing process of fluorescent lamp, even glass tube is subjected to heat treated, alkaline components also is difficult to stripping from the glass of tube body.Therefore, the 1st overlay film is not easy to be subjected to chemical erosion, and consequently, the tack of the 2nd overlay film can not descend, and therefore, the marresistance of bulb can not can descend, and strength of glass can not descend yet.In addition, the containing ratio of alkaline-earth metals oxide is more preferably 5～18wt%, further is more preferably 10～18wt%, most preferably is 12～18wt%.
Fig. 1 and Fig. 2 are the composition of glass of the expression tube body that constitutes the fluorescent-lamp-use glass tube relevant with execution mode and the figure of characteristic.As depicted in figs. 1 and 2, when the containing ratio of the alkaline-earth metal of the glass that constitutes tube body when 5wt% is above, the marresistance of bulb can be very high, the strength of glass of bulb is enough big.On the other hand, under the situation of the not enough 5wt% of described containing ratio, the marresistance of bulb can be low, and the strength of glass of bulb is big inadequately.
In the fluorescent-lamp-use glass tube of the present invention, therefore the containing ratio of the alkaline-earth metals oxide of the glass of formation tube body also is easy to processing below 18wt%.
After the containing ratio of alkaline-earth metal improved in the glass, the variation that viscosity takes place along with variations in temperature will increase.That is, become easy cooling and the glass that is not easy to process.If use this glass to constitute tube body, glass tube will become and be difficult for processing.In order to form the glass tube that is easy to process, the alkaline-earth metal containing ratio that constitutes the glass of tube body must be controlled at below the 18wt%.In addition, the softening temperature of the glass that is easy to process is in 650～720 ℃ the scope, and processing temperature is in 960～1050 ℃ the scope.Being more preferably softening temperature is in 670～700 ℃ the scope and processing temperature is in 960～1000 ℃ the scope.
As depicted in figs. 1 and 2, when the containing ratio of alkaline-earth metal under the situation below the 18wt%, can access softening temperature and processing temperature and be in the glass that is easy to process in the above-mentioned scope.On the other hand, when described containing ratio surpasses under the situation of 18wt%, just become the glass that is difficult for processing.
The 1st overlay film needs only and is made of at least a kind of oxide selecting among tin oxide, titanium oxide, zirconia and silica, but especially preferably is made of tin oxide.If the 1st overlay film is made of tin oxide, then the glass of tube body just can not be colored or devitrification.On the other hand, if the 1st overlay film is made of zirconia, then the composition in zirconium and the glass reacts and plays the karyogenesis thing effect of crystallization, and the nucleus of this zirconium probably can cause the glass devitrification of tube body through the heat treated of back and grow.In addition, if the 1st overlay film is made of titanium oxide, then the crystal particle diameter when titanium occurs under the situation of growth significantly, and the glass of tube body probably can be colored and turn white.
The lubricant of the 2nd overlay film employing hydrophobicity or HLB get final product smaller or equal to 13 surfactant formation.
The hydrophobicity lubricant can be for example olefine kind resin and high melting point paraffin etc.This is because therefore the glass branchpoint of olefine kind resin (transition point) height, and the fusing point height of high melting point paraffin, also are not easy to destroy the 2nd overlay film even glass tube is implemented heat treated.
Olefine kind resin can be for example polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer etc.
High melting point paraffin can be for example microwax, paraffin, Tissuemat E, Fischer-Tropsch (Fischer-Tropsch) paraffin, polyethylene polypropylene copolymer, ester type waxes etc.In addition, preferably 100～450 ℃ of the fusing points of high melting point paraffin are more preferably 200～450 ℃, further preferably 300～450 ℃.
HLB (Hydrophile-Lipophile Balance: can be for example soap, alkylbenzenesulfonate, alkyl sulfate, alkyl ether sulphate salts, alkylsurfuric acid triethanolamine, fatty diglycollic amide, polyoxyethylene alkyl ether, alkyl trimethyl ammonium salt etc. hydrophilic lipophilic balance) smaller or equal to 13 surfactant.In addition, said here HLB refers to the HLB value that calculates by Griffin (Griffin) method.
In addition, in an execution mode of fluorescent-lamp-use glass tube of the present invention, alkaline-earth metals oxide is at least a kind of oxide selecting among magnesium oxide and calcium oxide.In this case, can produce glass tube with low cost.This is because magnesium oxide oxide and calcium oxide oxide can be obtained from the natural crystal of dolomite and so on, so can obtain with the price that is lower than other alkaline-earth metals oxides.
In addition, in an execution 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, and described calcium oxide and described magnesian mol ratio are 0.5～3.In this case, can constitute and be not easy devitrification, the less glass tube body of alkaline components stripping.The ratio of ionic radii magnesium of calcium is big, therefore, suppresses the effective of alkaline components stripping.And on the other hand,, will produce calcium and alkali-metal crystallization, the easy devitrification of glass if calcium is too much.Therefore, preferably be in the scope of above-mentioned mol ratio.
As depicted in figs. 1 and 2, under the situation of calcium oxide and magnesian mol ratio (CaO/MgO) less than 0.5, the softening temperature of glass or processing temperature sometimes are not in the suitable scope, the easy variation of processability.In addition, if calcium oxide and magnesian mol ratio (CaO/MgO) surpass 3, then glass sometimes can devitrification.
In addition, in an execution mode of fluorescent-lamp-use glass tube of the present invention, it is characterized in that the contained alkali metal oxide of glass that constitutes tube body amounts to 8～20wt%.If the containing ratio of alkali metal oxide surpasses 20wt%, conductance then described later sometimes can surpass 57 μ S/cm, becomes the relatively large glass of alkaline components stripping quantity easily.If the not enough 8wt% of the containing ratio of alkali metal oxide, then the processing temperature of glass sometimes can not be in the suitable scope, the easy variation of processability.
In addition, in an execution mode of fluorescent-lamp-use glass tube of the present invention, it is characterized in that, constitute in the oxide of the 1st overlay film and have tetragonal crystal structure more than the 50wt%.In the oxide that constitutes the 1st overlay film, surpass half and have under the situation of tetragonal crystal structure, can further improve the strength of glass of bulb, help further to improve the thin-walled property of bulb.Under crystal structure oxide was tetragonal situation, the reason that strength of glass is improved was, as the SiO of the main component of glass 2System of crystallization, promptly the crystal structure of cristobalite is a tetragonal system, therefore, is set at same tetragonal system if will form the crystal structure of the oxide of the 1st overlay film, just can improve the film forming on the glass surface.In addition, this be because: if crystal structure is a tetragonal system, the 1st overlay film that is then generated will combine securely with glass, therefore, phenomenon such as is not easy to peel off.
When the oxide that constitutes the 1st overlay film is under the situation of tin oxide, this tin oxide is SnO preferably 2State rather than SnO state.This be because, SnO 2Be stable tetragonal crystallization, and SnO change the crystallization of cubic system easily into.In addition, when by the temperature of the glass tube of overlay film under the situation more than 500 ℃, be difficult to reach the state of SnO.
In addition, in an execution 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 the relation of t≤0.7 or t/ φ≤0.42.In this case, because wall thickness, bulb is damaged especially easily, and structure of the present invention can play a role.
Fluorescent lamp of the present invention has the bulb that the fluorescent-lamp-use glass tube that uses above-mentioned record is made.Therefore, be difficult to breakage.
Lighting device of the present invention has 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 fluorescent lamp manufacturing process is heated processing, its performance that improves the strength of glass of overlay film can not descend yet.
Therefore, can realize the thin-walled property of the bulb 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 correlation test result's of the thickness of expression the 1st overlay film influence that the strength of glass and the gonorrhoeaization of glass tube produced figure.
Fig. 4 is the partial sectional view of the lamp of expression present embodiment.
Fig. 5 is the perspective view of summary structure of the lighting device of expression present embodiment.
Fig. 6 is the figure that is used to illustrate fluorescent lamp manufacturing method, (a) be the figure that is used to illustrate the fluorophor working procedure of coating, (b) being the figure that is used to illustrate sintering circuit, (c) is the figure that is used to illustrate the bulb sealing process, (d) is the figure that is used to illustrate the bulb 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 alkali stripping quantity.
To be the expression alkali stripping quantity that utilizes the alkali dissolution test method of JIS regulation to measure to obtain measure the figure of the dependency relation of the conductance that obtains with utilizing alkali dissolution test method among the application to Fig. 9.
Embodiment
Below based on fluorescent-lamp-use glass tube (being designated hereinafter simply as " glass tube "), fluorescent lamp and the lighting device of description of drawings embodiments of the present invention.
[structure of glass tube, fluorescent lamp and lighting device]
＜glass tube 〉
Glass tube of the present invention by tube body, be formed on the 1st overlay film on the outer peripheral face of this tube body and the 2nd overlay film that is layered on the 1st overlay film at least and constitute.
Tube body is wall thickness t[mm preferably] and external diameter φ [mm] satisfy the relation of t≤0.7 or t/ φ≤0.42.Especially, preferably 0.4≤t≤0.6,1≤φ≤10.
The thickness of the 1st overlay film is 5～100nm preferably, is more preferably 5～50nm.Fig. 3 is the correlation test result's of the thickness of expression the 1st overlay film influence that the strength of glass and the gonorrhoeaization of glass tube produced figure.As shown in Figure 3, when the thickness (embodiment 14～20,23～25) under the situation more than the 5nm of overlay film, be evaluated as relevant " zero " with strength of glass, and under the situation of not enough 5nm (embodiment 21,22), be evaluated as relevant " △ " with strength of glass.In addition, when the thickness of the 1st overlay film under the situation below the 50nm, do not generate gonorrhoea at the heating position when in processes such as bulb sealing process, glass tube being heated, and surpass under the situation of 50nm when the thickness of the 1st overlay film, generated gonorrhoea at the heating position.In addition, gonorrhoea is considered to because the coating particle of tin oxide because of heating the result of particle growth has taken place, and this gonorrhoea can cause the bad order of fluorescent lamp, and and then hinder visual examination to situation such as injured, therefore do not wish to see.
The thickness of the 2nd overlay film is 10～300nm preferably.Thickness above or the 2nd overlay film reaches more than the 500nm if the thickness of the 1st overlay film reaches 500nm, and then the transmitance of the visible light of glass tube will descend, and therefore, uses the transmitance of the visible light of the bulb that this glass tube is made also will descend.Consequently, the light of fluorescent lamp takes out decrease in efficiency, and the total light flux of this fluorescent lamp also descends.In addition, if the thickness of the 1st overlay film below 5nm, then the tack of the 2nd overlay film can variation.In addition, if the thickness of the 2nd overlay film below 5nm, then the marresistance of bulb can descend.
In addition, the 1st overlay film and the 2nd overlay film not only can be formed on the outer peripheral face of tube body, also can be formed on inner peripheral surface or the end face.In addition, the 1st overlay film and the 2nd overlay film not necessarily will be formed in the Zone Full of outer peripheral face, when becoming bulb, also can not formed the 1st overlay film and the 2nd overlay film on the part of coverings such as lamp holder.
Tube body preferably forms by having 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%, iron oxide (Fe 2O 3): 0.01～0.2wt%, antimony oxide (Sb 2O 3): 0～1wt%, cerium oxide (CeO 2): 0～1wt%.
SiO 2Be the main component that forms the glass bone, very few, then glass adhesion can descend, and it is poor that processability became.In addition, too much, then the viscosity of glass meeting hardening is difficult to distortion.SiO 2The preferable range of containing ratio be 60～75wt%.
Al 2O 3Be the composition that improves chemical durability, very few, its chemical durability can variation.In addition, too much, the glass quality that can become is inhomogeneous, and texture increases.Al 2O 3The preferable range of containing ratio be 0.5～5wt%.
B 2O 3Can be composition arbitrarily, a small amount of interpolation can reduce the coefficient of expansion, plays the effect that reduces devitrification.But, too much, then cause the setting temperature to descend, it is narrow that range of working temperature becomes, and causes processing difficulties.B 2O 3The preferable range of containing ratio be 0～5wt%.
Na 2The interpolation of O can be played effect that reduces viscosity or the effect that increases the coefficient of expansion, and is very few, then can't obtain these effects.In addition, too much, then chemical durability is with variation.Na 2The preferable range of the containing ratio of O is 3～17wt%.
K 2The interpolation of O can be played and Na 2The effect that O is identical, but it compares Na to the influence degree that increases the coefficient of expansion 2O is big.In addition, by making itself and Na 2The mixed base effect has been given play in the O coexistence, and also performance improves the effect of resistivity.Very few, then can't obtain these effects, too much, it is excessive that the coefficient of expansion can become.K 2The preferable range of the containing ratio of O is 1～12wt%.
By adding Li 2O can obtain and Na 2O or K 2The effect that O is identical, but Na is compared in the increase of the coefficient of expansion 2O is little.In addition, by making itself and Na 2O or K 2The mixed base effect is further brought into play in the O coexistence, and also performance further improves the effect of resistivity.Very few, its effect can't realize that too much, glass probably phase-splitting can take place.Li 2The preferable range of the containing ratio of O is 0.5～7wt%.
MgO, CaO also have the effect that improves chemical durability after the interpolation except having the effect that suppresses above-mentioned alkaline components stripping.Very few, its effect can't realize that too much, glass probably 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 also influence the raising of the resistivity of glass except having the effect that suppresses above-mentioned alkaline components stripping, electrical insulating property is provided.If the containing ratio of these materials surpasses 10wt%, the just easy devitrification of glass.Preferable range is: SrO is that 0～8wt%, BaO are that 0～10wt%, ZnO are 0～10wt%, as long as in this scope, just can access and be more suitable for the glass that fluorescent lamp uses.
ZrO can be a composition arbitrarily, has the effect that improves hardness after the interpolation.Too much, glass probably can produce crystallization.The preferable range of the containing ratio of ZrO is 0～5wt%.
Fe 2O 3Be the material of sneaking into, can refine by raw material and adjust its addition, can absorb ultraviolet ray after the interpolation as the impurity of various raw materials.Very few, its effect can't realize that too much, glass probably can be colored.Fe 2O 3The preferable range of containing ratio be 0.01～0.2wt%.
Sb 2O 3Can be composition arbitrarily, it has the effect that can clarify the gas that raw material produces efficiently in glass furnace, and too much, glass probably can be colored.Sb 2O 3The preferable range of containing ratio be 0～1wt%.
CeO 2Can be composition arbitrarily, can absorb ultraviolet ray after the interpolation, but too much, probably can be painted because of ultraviolet irradiation, promptly produce so-called negative sense (solarization) effect.CeO 2The preferable range of containing ratio be 0～1wt%.
＜fluorescent lamp 〉
Fig. 4 is the partial sectional view of the ring-type fluorescent lamp of expression one embodiment of the present invention.As shown in Figure 4, the ring-type fluorescent lamp (FCL30ECW/28) 10 of one embodiment of the present invention has: ring-type bulb 20; Be sealed in the bar (stem) 30,31 ' at these bulb 20 both ends; With the lamp holder of installing across these two ends 40.
Bulb 20 is processed by glass tube of the present invention, has stacked gradually protective layer (not shown) and luminescent coating (not shown) on its inner surface, and the argon gas of one of the amalgamation goldc grains 21 that is used to supply with mercury vapour and rare gas has been enclosed in inside.On each bar 30,30 ' electrode 31,31 ' that is made of filament coil and pair of lead wires has been installed.Lamp holder 40 has: the body 41 that holds the end of bulb 20; With a plurality of connecting pins 42 that are arranged on this body 41.
＜lighting device 〉
Fig. 5 is the perspective view of the lighting device of expression one embodiment of the present invention.As shown in Figure 5, the lighting device 100 of present embodiment has above-mentioned fluorescent lamp 10 as light source.Fluorescent lamp 1 is accommodated in the device body 101, is lighted by the lamp device 102 that is installed on this device body 101.
[manufacture method of glass tube and lamp]
The manufacture method of＜glass tube 〉
At first, multiple frit is in harmonious proportion in above-mentioned proportion of composing scope, obtains raw mix.Then, raw mix is dropped in the glass furnace, make its fusing and vitrifying with 1500～1600 ℃, obtain the glass melts of vitreousness.Then, make glass melts be shaped to tubulose, and cutting processing is preliminary dimension, obtains glass tube by trombone slide methods such as Dan Na (Danner) trombone slide methods.
The 1st overlay film is to form to the glass tube that is in the trombone slide process by the vapor spray evaporation that in the draft chamber organic metal heating is produced.For example, organic metal is heated with 180 ℃, produced the 10g steam in the clock time, resulting steam flow velocity with 5L/min in 1 second time is sprayed on the glass tube, form the 1st overlay film at 1 minute.By regulating gasification temperature, organometallic use amount, spray velocity, spray time etc., can control the thickness of the 1st overlay film.In addition, also can adopt the method that organic metal is sprayed with sprayer behind the water-soluble or organic solvent or adopt tube body dipping and the method that applies are formed the 1st overlay film.
Employed organic metal is the organic metal that for example contains metal ingredients such as tin, titanium, zirconium or element silicon in the forming process of the 1st overlay film.Particularly, can enumerate as 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.
Under the situation of using the hydrophobicity lubricant, the 2nd overlay film is to form by for example hydrophobicity lubricant emulsification and liquid of being made in water or organic solvent etc. being coated on the glass tube.Film covering method uses method of spraying with sprayer or the method that tube body is flooded and applies.In addition, using under the situation of surfactant, for example using the method for spraying or tube body dipping and the method that applies are carried out overlay film with sprayer.
The manufacture method of＜lamp 〉
Fig. 6 is the figure that is used to illustrate fluorescent lamp manufacturing method, (a) be the figure that is used to illustrate the fluorophor working procedure of coating, (b) being the figure that is used to illustrate sintering circuit, (c) is the figure that is used to illustrate the bulb sealing process, (d) is the figure that is used to illustrate the bulb bending operation.
At first, in the fluorophor working procedure of coating, shown in Fig. 6 (a), on inner surface, be formed with the glass tube 21 inner fluorophor suspension-turbid liquids 50 that inject 3 wavelength of diaphragm, utilize described fluorophor suspension-turbid liquid 50 to soak the inner surface of described glass tube 21.Then, be blown into hot blast (25～30 ℃) to glass tube 21 inside thus after making fluorophor suspension-turbid liquid 50 dryings, shown in Fig. 6 (b), in gaseous environment is controlled in stove about 550～660 ℃, fired about 1 minute, form luminescent coating.Like this, glass tube is heated processing in sintering circuit, so the easy stripping of alkaline components.
Then, in the bulb sealing process, after near the luminescent coating glass tube 21 both ends removed, shown in Fig. 6 (c), insertion rod 30,31 ' back and seal respectively at described both ends.In bulb bending operation thereafter, according in gaseous environment is controlled in stove about 700～900 ℃, carrying out bending machining like that shown in Fig. 6 (d), make it become ring-type the glass tube 21 of straight shape.Like this, in the bulb bending operation, glass tube is heated processing, so the easy stripping of alkaline components.
, in deairing step, via unencapsulated blast pipe 32 foreign gas of bulb 20 inside discharged, make bulb 20 inside reach state, charge into argon gas then near vacuum thereafter.And then, enclose in the operation at mercury alloy, in bulb, drop into amalgamation goldc grains 21 from blast pipe 32.
[evaluation method]
Carry out the evaluation of fluorescent-lamp-use glass tube according to method as follows.
The thickness of＜overlay film 〉
The hot junction plated film instrument (HOT END COATING MEASUREMENT SYSTEM:HECM-S) that the thickness of overlay film uses American Glass Research company to make is measured.
Fig. 7 is the figure of assay method that is used to illustrate the thickness of overlay film.Be ready to be cut into the glass tube of 20cm as sample, shown in Fig. 7 (a), at near near the position, 3 place the both ends of this glass tube and the central part, respectively according to mode shown in Fig. 7 (b), uniformly-spaced (devices spaced apart forms about 90 ° anglec of rotation) spaced apart in the circumferential direction, measure (amount to 12 points) on 4 points, the mean value of measured value of getting these 12 points is as thickness.In addition, suppose that the angle of incidence of light degree at each point is 45 °.
In the plated film instrument of hot junction, thickness adopts its distinctive unit, i.e. ctu(coating thickness units: represent that coating film thickness unit) 1ctu is equivalent to 0.2～0.3nm of SI unit.In this application, suppose that 1ctu is scaled 0.25nm.
＜strength of glass 〉
At first, in experiment, use external diameter to be the straight glass tube that is formed with the 1st overlay film and the 2nd overlay film on 3mm, the outer peripheral face as 4mm, internal diameter.The 1st overlay film be by with the dimethyltin chloride powder with 120 ℃ of heating 1 minute, and with the steam that produced at draft chamber's internal spraying to the glass tube that is in the trombone slide process and the overlay film that constitutes by tin oxide that forms, thickness is 100nm.The 2nd overlay film be with sprayer to being in glass tube in the trombone slide process and spraying and the overlay film that the various materials by illustrated in figures 1 and 2 that form constitute, thickness is 30nm.
Then, the glass tube that has formed overlay film is put into the quartz ampoule that internal diameter is 20mm, this quartz ampoule rotary speed with 20rpm in 500 ℃ of environment was rotated 5 minutes, utilize the friction of glass tube and quartz ampoule to make the glass tube surface injured.
The bending strength of the glass tube after use Autograph AG-IS(island Tianjin company manufacturing thereafter) mensuration is injured.With left and right sides span 40mm fixing glass pipe, load load at the central part of this glass tube with the load speed of 1mm/min then, thereby the value when obtaining glass tube and breaking is carried out the mensuration of bending strength thus.
In addition, when the injured bending strength that makes has descended under the situation more than 30%, be judged to be with regard to thinking the strength of glass deficiency " * ", under the situation of intensity decreases less than 30%, be judged to be " △ " (bending strength descend 15% or more but under the situation of less than 30%) with regard to thinking that strength of glass is enough or be judged to be " zero " (bending strength decline more than 0% but under the situation of less than 15%).In addition, the reason that is judged to be the strength of glass deficiency under bending strength has descended the situation more than 30% is: the glass tube more than 30% is made fluorescent lamp if the use bending strength has descended, and then the rate of finished products in the operation will significantly descend.
＜gonorrhoea 〉
The evaluation of gonorrhoea is by visual enforcement, when visual, can't see under the situation of gonorrhoea and be judged to be " zero ", and when visual finding next be judged to be " * " of situation of gonorrhoea.
＜marresistance energy 〉
The evaluation of marresistance energy is implemented according to following program.At first, 2 glass tubes that block to 10cm are contacted with 90 ° of angles, carry out 20 frictions.To through the part of friction be placed on light microscope under amplification 4 times after observe thereafter.Its result if find to have formed scratch, then is judged to be " * ", if do not find scratch, then is judged to be " zero ".
＜softening point temperature and setting temperature 〉
Softening point temperature and setting temperature in order to measure glass go out sample according to following program making.At first, the raw mix that frit is formed through mediation moves in the platinum crucible, and with this platinum crucible heating 3 hours, fusing formed glass in 1500 ℃ electric furnace.The fusing back is injected in the mould, through cooling (annealing) gradually in 12 hours, thereby fully eliminates distortion.Use cutter etc. that the glass blocks after the moulding is processed into the sample shape that is suitable for carrying out following illustrated every mensuration, measure respectively.
Softening point temperature is that glass viscosity is 10 7.65The temperature of dPa s, glass will show flowability after reaching more than this temperature.With regard to fluorescent-lamp-use glass, softening point temperature preferably in 650 ℃～720 ℃ scope, is more preferably in 670～700 ℃ scope.If softening point temperature is lower than 650 ℃, then in the working procedure of coating of fluorophor, when heating for the adhesive volatilization that makes the fluorophor suspension-turbid liquid, bulb will be out of shape because of being heated.On the other hand,, just glass tube must be heated to high temperature man-hour sealing to add, have to improve the burning capacity of melting furnace if softening point temperature is higher than 720 ℃.
The setting temperature is that glass viscosity reaches 10 4The temperature of dPa s is processed glass below the temperature at this.With regard to fluorescent-lamp-use glass, the setting temperature preferably in 960 ℃～1050 ℃ scope, is more preferably in 960～1000 ℃ scope.If processing temperature is lower than 1000 ℃, then range of working temperature will narrow down, so poor in processability.On the other hand, if the setting temperature is higher than 1050 ℃, it is too high that the temperature of glass melting will become, thereby the processability variation, and the cost of melting process also raises.
＜alkali stripping quantity 〉
The assay method of alkali stripping quantity is normally for example used the test method (the JIS R3502 of Japanese Industrial Standards) of glass wares based on the chemical analysis of JIS.This method is exactly at first to use mortar etc. that glass sample is ground into Powdered (particle diameter is 250～420 μ m) to obtain glass dust and mince in simple terms, then using alcohol that this glass dust is minced cleans, from mincing, removes in glass dust the glass attritive powder, glass dust after then will cleaning minces and heated 60 minutes in boiled water, from this glass dust minces, separate out alkaline components, obtain the alkali dissolution fluid., use sulfuric acid this alkali dissolution fluid carried out acid-base titration, converse the alkali stripping quantity according to the titration value that obtains thus thereafter.
If alcohol wash is insufficient, meeting residual glass attritive powder during then glass dust minces, thereby the problem of this test method based on JIS is: the existence of this glass attritive powder causes the glass total surface area in the distilled water to increase considerably, thereby can't measure alkali stripping quantity accurately.In addition, need to carry out with glass sample be ground into Powdered, remove the glass attritive powder by cleaning, carry out loaded down with trivial details operation such as acid-base titration.Therefore, people wish to have the higher and simple alkali stripping quantity assay method of a kind of precision.
Therefore, the inventor has rebulid test method the precision higher and simpler alkali stripping quantity assay method of a kind of ratio based on JIS.Assay method of the present invention is impregnated into block glass sample in the distilled water, make alkaline components from the glass sample stripping to distilled water, measure the conductance of the alkali dissolution fluid obtain thus then, converse the alkali stripping quantity according to this measured value.
Fig. 8 is the figure that is used to illustrate the assay method of alkali stripping quantity of the present invention.Use Fig. 8 that the specific procedure of assay method of the present invention is described.
At first, glass sample being cut into bulk, is that 75～85 ℃, humidity are to place 45～50 hours in 85～95% the constant temperature and humidity cabinet in temperature, adds wet process.In addition, in order to improve the mensuration precision, be more preferably near the value the center that is set at temperature, humidity and standing time described each scope that to add in the procedure for wet processing, promptly 80 ℃, 90%, 48 hour.
Then, as shown in Figure 8, storage 100ml temperature is 70～80 ℃ a distilled water 2 in tank 1, will pass through the glass sample 3 that adds wet process and flood 1 hour in this distilled water 2.In assay method of the present invention, stripping alkaline components in the lower distilled water 2 of 70～80 ℃ of such temperature, this compares with force the test method based on JIS of stripping alkaline components in the distilled water of boiling, can measure the alkali stripping quantity according to the glass user mode of reality.
The surface area summation of glass sample 3 is adjusted into and is in 4500～5500mm 2Scope in, preferably be about 5000mm 2, flood then.For example, 8 glass samples 3 that are cut into the rectangular shape of about 15 * 15 * 2.5mm of dipping.
, from distilled water 2 take out glass sample 3, obtain the alkali dissolution fluid thereafter.Then, make this alkali dissolution fluid stabilize to 25 ℃, use the hand-hold type sensor type liquid infiltration formula electric conductivity measuring machine 4(trade name of selling on the market: Twin Cond B-173) measure conductance.
Fig. 9 is that expression utilizes the alkali stripping quantity that the determination of test method based on JIS obtains and utilizes the chart of the dependency relation of the conductance that determination of test method of the present invention obtains.
Described alkali stripping quantity and conductance have dependency relation shown in Figure 9.Think that at present the bulb of fluorescent lamp is suitable to use the glass of alkali stripping quantity below 270 μ g/g, but as can be known according to Fig. 9, with the corresponding conductance of alkali stripping quantity below the 270 μ g/g be 57 μ S/cm.Therefore, we can say that the glass of conductance below 57 μ S/cm is suitable to bulb glass.
That is to say that conductance is the numerical value of the alkali stripping quantity of secondary indication glass, for suitable glass as fluorescent-lamp-use, preferably in 25 ℃ of environment conductance below 57 μ S/cm.If conductance is higher than 57 μ S/cm, then the variety of issue that generation caused of mercury alloy will display.
The said determination method is used block glass sample, and therefore, control is immersed in the summation of the surface area of the glass in the distilled water easily.Therefore, compare with test method based on JIS, can be with higher precision determination alkali stripping quantity.In addition, therefore assay method of the present invention, even the alkali stripping quantity increases, is measured precision and also can not descended by electric conductivity measuring alkali stripping quantity.
In addition, in the said determination method, the block glass sample after the cutting is immersed in the distilled water, so do not need glass sample is ground into operation Powdered or that glass dust is minced and cleans.In addition, as long as simply the electrode of electric conductivity measuring machine 4 is immersed in the conductance that just can measure the alkali dissolution fluid in this alkali dissolution fluid, do not need loaded down with trivial details acid-base titration operation.Therefore, compare, operate simpler with assay method based on JIS.
＜increased devitrification resistance 〉
By whether having produced crystallization and devitrification in the Visual Confirmation glass, and estimate accordingly when being fused into glass, " zero " represents not devitrification, " * " expression devitrification.
The ratio of＜tetragonal crystallization 〉
At first, in experiment, use external diameter to be the straight glass tube that is formed with the 1st overlay film on 3mm, the outer peripheral face as 4mm, internal diameter.The 1st overlay film be by with 120 ℃ to 1 fen clock time of dimethyltin chloride heating, in the draft chamber with the vapor spray evaporation that produced to the glass tube that is in the trombone slide process and form, thickness reaches 100nm.
Then, use X-ray diffraction device (RINT2000, the instrument manufacturing of electric enterprise of Co., Ltd. Neo-Confucianism) to observe the 1st overlay film that keeps the state on the glass tube that is formed on, confirm the crystal structure of the oxide of formation the 1st overlay film.In sweep speed is that 6 °/min, measurement range are to measure under 0 °～90 ° the condition, estimates SnO and SnO 2Crystal area proportion.The crystal structure of SnO becomes the crystal structure of cubic crystal based on the crystal structure of quadratic crystal after the part distortion, and SnO 2The crystal structure that then only has quadratic crystal.Therefore, the 1st overlay film of glass SnO preferably 2State.Thus, the disguise of the 1st overlay film of glass surface is improved, and can obtain bigger effect.Especially, its ratio SnO preferably 2/ SnO is more than or equal to 1.
[variation]
More than specifically understand fluorescent lamp of the present invention and fluorescent-lamp-use glass tube based on execution mode, 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 also is suitable for making photoflash lamp (flare), blast pipe etc. and adds the utensil that need carry out heat treated man-hour and require thin-walled property except being used to make the bulb.In addition, the glass that constitutes tube body both can be that soft glass also can be a hard glass, and under the situation of using the low soft glass of strength of glass, structure of the present invention is especially effective.
Fluorescent lamp of the present invention is not limited to above-mentioned execution mode, but can be widely used in various fluorescent lamps such as straight pipe type fluorescent lamp, ring-type fluorescent lamp, cold-cathode fluorescence lamp, dual ring-type fluorescent lamp, square fluorescent lamp, dual square fluorescent lamp, double fluorescent lamp.
Lighting device of the present invention is not limited to above-mentioned execution mode.The backlight and the image that can be applied to illumination on for example interior illuminator, outdoor illumination, the table, portable lighting, display light source, liquid crystal panel read lighting devices such as illumination.
Industrial applicibility
Fluorescent-lamp-use glass tube of the present invention can be widely used in various lighting uses.
Description of reference numerals
10 lamps
20 bulbs
21 fluorescent-lamp-use glass tubes
22 tube bodies
23 the 1st overlay films
24 the 2nd overlay films
100 lighting devices.

Claims (9)

1. fluorescent-lamp-use glass tube is characterized in that having:
Tube body is made of the glass of the alkaline-earth metals oxide of the silica that contains 60～75wt% and 5～18wt%;
The 1st overlay film is formed on the outer peripheral face at least of described tube body, is made of at least a kind of oxide selecting among tin oxide, titanium oxide, zirconia and silica; With
The 2nd overlay film is layered on described the 1st overlay film, is made of smaller or equal to 13 surfactant hydrophobicity lubricant or HLB.
2. fluorescent-lamp-use glass tube as claimed in claim 1 is characterized in that, described hydrophobicity lubricant is olefine kind resin or high melting point paraffin.
3. fluorescent-lamp-use glass tube as claimed in claim 1 or 2 is characterized in that, described alkaline-earth metals oxide is at least a kind of oxide selecting among magnesium oxide and calcium oxide.
4. fluorescent-lamp-use glass tube as claimed in claim 1 or 2 is characterized in that, described alkaline-earth metals oxide is magnesium oxide and calcium oxide, and described calcium oxide and described magnesian mol ratio are 0.5～3.
5. fluorescent-lamp-use glass tube as claimed in claim 1 is characterized in that, the contained alkali metal oxide of glass that constitutes described tube body amounts to 8～20wt%.
6. fluorescent-lamp-use glass tube as claimed in claim 1 is characterized in that, constitutes in the oxide of described the 1st overlay film to have tetragonal crystal structure more than the 50wt%.
7. fluorescent-lamp-use glass tube as claimed in 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.
8. a fluorescent lamp is characterized in that, has the bulb that uses fluorescent-lamp-use glass tube as claimed in claim 1 manufacturing to form.
9. a lighting device is characterized in that, has fluorescent lamp as claimed in claim 8.
CN2009801215525A 2008-06-09 2009-06-05 Glass tube for fluorescent lamp, fluorescent lamp, and lighting system Pending CN102057461A (en)

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JP2008-150288 2008-06-09
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105449420A (en) * 2015-12-09 2016-03-30 西安赛尔电子材料科技有限公司 Slender hole glass-sealing multi-pin electrical connector and preparation method of slender hole glass-sealing multi-pin electrical connector
CN115043600A (en) * 2022-06-28 2022-09-13 凯盛君恒药玻(重庆)有限公司 Online coating process and device for medium boron glass tube

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JPS5432521A (en) * 1977-08-17 1979-03-09 Asahi Denka Kogyo Kk Method of protecting glass
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.
CN101223115B (en) * 2005-07-12 2012-02-08 独立行政法人产业技术综合研究所 Glass composition for lamp, glass part for lamp, lamp and process for producing lamp or glass composition for lamp
JP2008024564A (en) * 2006-07-24 2008-02-07 Matsushita Electric Ind Co Ltd Method for producing glass for lamp, glass for lamp, glass tube for lamp and lamp

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105449420A (en) * 2015-12-09 2016-03-30 西安赛尔电子材料科技有限公司 Slender hole glass-sealing multi-pin electrical connector and preparation method of slender hole glass-sealing multi-pin electrical connector
CN115043600A (en) * 2022-06-28 2022-09-13 凯盛君恒药玻(重庆)有限公司 Online coating process and device for medium boron glass tube

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