JP5182191B2 - Paint for fluorescent lamp, coating film using the same, method for producing coating film, and fluorescent lamp - Google Patents

Description

  The present invention relates to a coating material for a fluorescent lamp, a coating film using the coating material, a method for producing the coating film, and a fluorescent lamp, and more specifically, an adhesive strength between phosphors and an adhesive strength between the phosphor and a translucent sealing tube. Coating for fluorescent lamp for forming a coating film capable of improving the coating, coating film using this coating for fluorescent lamp, coating film manufacturing method, adhesion strength between phosphors and phosphor and translucent The present invention relates to a fluorescent lamp capable of improving the mechanical strength of a phosphor layer and preventing problems such as peeling by improving the adhesive strength with a conductive sealing tube.

Conventionally, when a phosphor layer is formed by attaching a phosphor to the inner surface of a glass tube of a fluorescent lamp, a phosphor slurry in which the phosphor is suspended in a solution containing a binder is applied to the inner surface of the glass tube, and then dried and fired. The phosphor layer is formed through the process.
From the viewpoints of resource saving, energy saving, working environment, disaster prevention, etc., there are fluorescent lamp paints that use water-soluble binders as binders, but these water-soluble binders are phosphors to glass tubes compared to organic solvent binders. There is a problem that the adhesion strength of the phosphor is low and the phosphor layer is peeled off from the glass tube.

  Therefore, in order to improve the adhesive strength between the phosphors and the adhesive strength between the phosphor and the translucent sealing tube, strontium borate, water-soluble rare earth compounds and colloidal alumina, water-soluble rare earth compounds and boric acid, There has been proposed a paint to which a binder such as colloidal alumina is added (for example, see Patent Documents 1 to 3).

JP 2004-207100 A Japanese Patent No. 2760202 Japanese Patent No. 2783077

However, even in conventional fluorescent lamp paints to which a binder such as strontium borate is added, the adhesive strength between the phosphors reaches a practical level, but the adhesive strength of the phosphor to the glass tube still reaches the practical level. There was no problem.
In addition, low melting point glass generally used as a binder at present needs to be fired at 650 ° C. or higher in order to develop a binding force. There was a problem of heat deterioration.
In this case, if the firing temperature can be lowered to 600 ° C. or lower, there is an advantage that there is no possibility that the phosphor is thermally deteriorated and the luminance of the fluorescent lamp is improved. However, the present situation is that no such binder has been proposed yet.

  The present invention has been made in view of the above circumstances, and a sufficient binding force can be obtained at a low temperature of 600 ° C. or less, and there is no possibility that the phosphor is thermally deteriorated. An object of the present invention is to provide a fluorescent lamp paint capable of improving the bonding strength of a phosphor to a sealing tube and preventing defects such as peeling, a coating film using the same, a method for producing the coating film, and a fluorescent lamp. And

  As a result of intensive studies in order to solve the above problems, the present inventors bonded phosphors as a binding substance that bonds these phosphors to a light-transmitting sealing tube such as a glass tube. If the aluminum oxide fine particles surface-treated with the organosilicon compound are used, the dispersibility of the binding substance in the coating is improved, and a sufficient binding force can be obtained even when baked at a low temperature of 600 ° C. or less. It is found that there is no possibility that the phosphor is thermally deteriorated, and that the bonding strength of the phosphor to the light-transmitting sealing tube such as a glass tube is improved, and that troubles such as peeling of the phosphor layer can be prevented, The present invention has been completed.

  That is, the fluorescent lamp paint of the present invention is a fluorescent lamp paint comprising a binder and a solvent for adhering the phosphors to each other and adhering these phosphors to the translucent sealing tube. And the said binding material is the aluminum oxide microparticles | fine-particles surface-treated with the organosilicon compound, It is characterized by the above-mentioned.

The fluorescent lamp paint of the present invention preferably further contains a phosphor.
The solvent is preferably a low boiling point organic solvent.

  The coating film of the present invention is formed by using a fluorescent lamp paint containing the phosphor of the present invention.

  In the method for producing a coating film of the present invention, a fluorescent lamp paint containing the phosphor of the present invention is applied onto a substrate to form a coating film, and then the coating film is dried or dried and heat-treated. It is characterized by doing.

  The fluorescent lamp of the present invention is characterized in that the coating film of the present invention is formed inside a translucent sealing tube.

  According to the fluorescent lamp coating material of the present invention, aluminum oxide fine particles whose surface is treated with an organosilicon compound as a binding substance for adhering phosphors to each other and adhering these phosphors to a translucent sealing tube Therefore, the dispersibility of the binding substance in the paint can be improved, and sufficient binding force can be obtained even when baked at a low temperature of 600 ° C. or less, and the phosphor may be thermally deteriorated. In addition, the adhesive strength between the phosphors and the adhesive strength between the phosphors and the translucent sealing tube can be improved.

Further, dispersibility can be improved without adding a dispersant, and binding power can be expressed. Further, it is possible to prevent the phosphor film from being colored by the dispersant when the firing temperature is reduced and the unburned residue in the low-melting glass.
Therefore, by using this fluorescent lamp paint, it is possible to improve the bonding strength of the phosphor to the translucent sealing tube, and to provide a coating film capable of preventing problems such as peeling of the phosphor layer. It can be easily formed at a low temperature of ℃ or less.

  Furthermore, if the phosphor is contained, the operation of mixing the slurry containing the phosphor becomes unnecessary, and the operation when forming the coating film can be simplified.

According to the coating film of the present invention, since it is formed using the fluorescent lamp paint containing the phosphor of the present invention, it is possible to prevent the phosphor from being thermally deteriorated, and the fluorescence to the translucent sealing tube. The bonding strength of the body can be improved, and problems such as peeling off of the phosphor layer can be prevented.
Moreover, since the phosphor is contained in the fluorescent lamp paint, the operation of mixing the slurry containing the phosphor becomes unnecessary, and the operation when forming the coating film can be simplified.

According to the method for producing a coating film of the present invention, a fluorescent lamp paint containing the phosphor of the present invention is applied onto a substrate to form a coating film, and then the coating film is dried or dried. And since the heat treatment, there is no thermal deterioration of the phosphor, the bonding strength of the phosphor to the translucent sealing tube can be improved, and a coating film that can prevent defects such as peeling of the phosphor layer, It can be formed easily without increasing the manufacturing cost.
In addition, since the fluorescent material is included in the fluorescent lamp coating material, the operation of mixing the slurry containing the fluorescent material becomes unnecessary, and the operation for forming the coating film can be simplified.

According to the fluorescent lamp of the present invention, since the coating film of the present invention is formed inside the translucent sealing tube, it is possible to prevent thermal degradation of the phosphor, and the translucent sealing tube of the phosphor layer Therefore, it is possible to improve the bonding strength with respect to the film, and thus prevent problems such as peeling.
As a result, it is possible to provide a highly reliable fluorescent lamp that does not cause thermal degradation of the phosphor and does not cause problems such as peeling.

It is a longitudinal cross-sectional view which shows the fluorescent lamp of one Embodiment of this invention. It is a cross-sectional view which shows the fluorescent lamp of one Embodiment of this invention.

The fluorescent lamp paint of the present invention, a coating film using the same, a method for producing the coating film, and a mode for carrying out the fluorescent lamp will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

"Fluorescent lamp paint"
The fluorescent lamp paint of the present embodiment is a fluorescent lamp paint comprising a binder and a solvent for adhering the phosphors to each other and adhering these phosphors to the translucent sealing tube. The binding material is aluminum oxide fine particles that are surface-treated with an organosilicon compound.

Here, as the aluminum oxide fine particles surface-treated with the organosilicon compound, silicone-coated aluminum oxide fine particles having a surface coated with silicone will be described as an example.
The silicone-coated aluminum oxide fine particles have a surface formed on the surface by a surface treatment with a methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer.
This film is mainly composed of silicone obtained by heat-treating the above methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer.

The average particle diameter of the aluminum oxide fine particles is preferably 10 nm or more and 500 nm or less, more preferably 20 nm or more and 200 nm or less.
Here, the reason why the preferable average particle diameter of the aluminum oxide fine particles is 10 nm or more and 500 nm or less is that the specific surface area becomes large when the average particle diameter of the aluminum oxide fine particles is less than 10 nm. On the other hand, if the average particle diameter of the aluminum oxide fine particles exceeds 500 nm, the phosphors and between the phosphor and the translucent sealing tube are adversely affected. This is because the adhesive strength cannot be sufficiently expressed.

で表されるメチルハイドロジェンポリシロキサン・ジメチルポリシロキサン共重合体は、ｍが０以上かつｎが１以上で、かつ、１≦ｍ＋ｎ≦２０を満たす数であることが必要であり、好ましくは、５≦ｍ＋ｎ≦２０、更に好ましくは、１０≦ｍ＋ｎ≦２０である。 The following formula (1) used for surface treatment of the aluminum oxide fine particles

The methyl hydrogen polysiloxane / dimethylpolysiloxane copolymer represented by the formula (1) is required to be a number satisfying 1 ≦ m + n ≦ 20, and m is 0 or more and n is 1 or more, 5 ≦ m + n ≦ 20, more preferably 10 ≦ m + n ≦ 20.

Here, the reason why m is 0 or more, n is 1 or more, and satisfies 1 ≦ m + n ≦ 20 is that when the value of m + n exceeds 20, the molecular chain becomes too long. This is because the surface-treated aluminum oxide fine particles easily react with each other and cause aggregation and granulation.
In addition, since the molecular chain is long, the previously coated methyl hydrogen polysiloxane / dimethyl polysiloxane copolymer is sterically hindered and remains as an unreacted hydrogen atom.

  The coating amount of the methyl hydrogen polysiloxane / dimethyl polysiloxane copolymer is not particularly limited, but is preferably 1% by mass to 40% by mass with respect to the aluminum oxide fine particles to be surface-treated, more preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass.

  The reason for limiting the use amount as described above is that if the use amount is less than 1% by mass, the surface coverage of the aluminum oxide fine particles is small, so that the dispersibility and the binding force with the phosphor can be improved. It is not possible. Moreover, when the amount used exceeds 40% by mass, the methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer becomes excessive, so that a polymerization reaction easily occurs, and as a result, the thickness of the coating is not uniform, This is because there is a risk of enlargement.

The method for surface-treating the aluminum oxide fine particles with a methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer is not particularly limited as long as the method is a method in which these are mixed and then heat-treated.
As a method and conditions for mixing these, a method in which both components can be sufficiently brought into contact and can be uniformly stirred can be applied.
Examples of the mixing means that can be used here include a ball mill, a Henschel mixer, an air blender, a mortar, an atliner, a vibration mill, a vibration rod mill, an ang mill, a pot mill, a rotary ball mill, and a hybridizer.

In this mixing step, a solvent may be used as necessary. The solvent that can be used is preferably a low-boiling solvent because it needs to be removed after obtaining aluminum oxide fine particles whose surface is coated with silicone. Examples of the low boiling point solvent include lower alcohol (C ≦ 4), dichloromethane, toluene, xylene, normal hexane, cyclohexane, acetone, 2-butanone, dimethylcyclopolysiloxane (C = 3, 4) and the like. it can.
The amount of the solvent to be used is not particularly limited, but it is desirable that the amount be as small as possible in view of the later removal.

  The heat treatment conditions are not particularly limited as long as the aluminum oxide fine particles and the methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer are completely reacted with each other. 5 to 5 hours, more preferably 70 to 250 ° C for 0.5 to 3.5 hours.

The method for the heat treatment is not particularly limited as long as the aluminum oxide fine particles and the methylhydrogenpolysiloxane / dimethylpolysiloxane copolymer are completely reacted. As this heat treatment apparatus, for example, an air dryer, a vacuum dryer, a spray dryer, an evaporator, or the like is preferably used.
In this heat treatment, the temperature raising condition and the cooling condition are not particularly limited as long as the condition that the aluminum oxide fine particles and the methyl hydrogen polysiloxane / dimethyl polysiloxane copolymer are completely reacted can be satisfied.

The solvent used in the fluorescent lamp paint basically contains one or two of water and a low-boiling organic solvent.
Said low boiling-point organic solvent is used in order to improve a drying rate, and is an organic solvent which has a boiling point of 150 degrees C or less under a normal pressure (1 atmosphere).
Examples of the low-boiling organic solvent include lower alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol; methyl acetate, ethyl acetate, propyl acetate, 1-butyl acetate, and acetate-2- Esters such as butyl; ethers such as diethyl ether, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve); ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetyl acetone; toluene, xylene, etc. 1 type (s) or 2 or more types selected from these aromatic hydrocarbons are used.

  Among these solvents, water, lower alcohols, ketones and the like are preferable, and water, methanol, ethanol, 1-propanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, ethylene glycol monomethyl ether ( Methyl cellosolve) and the like are preferably used.

In order to adjust the drying speed of the fluorescent lamp paint, a high boiling point organic solvent may be added.
This high-boiling organic solvent is an organic solvent having a boiling point exceeding 150 ° C. under normal pressure (1 atm). For example, N-methyl-2-pyrrolidinone, ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol monobutyl ether ( Butyl cellosolve), formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and the like.

In this fluorescent lamp paint, it is preferable to add a dispersant in order to further improve dispersibility.
Examples of the dispersant include water-soluble polymers such as polycarboxylates, polyalkyl sulfates, and polyvinyl alcohol (PVA).

This fluorescent lamp paint may further contain a phosphor.
The phosphor is preferably a fine particle containing a phosphor, and the fine particle containing the phosphor is composed of one or more of a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor. Fine particles containing a phosphor are preferred.
The average particle size of the fine particles containing the phosphor is preferably 0.05 μm or more and 5 μm or less, more preferably 0.05 μm or more and 3 μm or less.

Here, as the red light emitting phosphor, for example, Y ₂ O ₃ : Eu, Y (PV) O ₄ : Eu, YVO ₄ : Eu, Y ₂ O ₂ S: Eu, (Y, Gd) BO ₃ : Eu etc. are mentioned.
Examples of the green light emitting phosphor include (Ba, Eu) (Mg, Mn) Al ₁₀ O ₁₇ , LaPO ₄ : Ce, Tb, Zn ₂ SiO ₄ : Mn, ZnS: Cu, Al, CeMgAl ₁₁ O. ₁₉ : Tb, GdMgB ₅ O ₁₀ : Ce, Tb, and the like.
Examples of blue light emitting phosphors include (Sr, Ca, Ba, Mg) ₅ (PO ₄ ) ₃ Cl: Eu, (Ba, Sr, Eu) (Mg, Mn) Al ₁₀ O ₇ , Sr _10. (PO ₄ ) ₆ Cl ₂ : Eu, ZnS: Ag, Al, BaMgAl ₁₀ O ₁₇ : Eu, and the like.
The content of each of the red light-emitting phosphor, the green light-emitting phosphor, and the blue light-emitting phosphor may be appropriately set according to the light emission characteristics of the target fluorescent lamp.

In this case, the mass of the silicone-coated aluminum oxide fine particles in the paint is preferably 0.5% by mass or more and 3.5% by mass or less, more preferably 1.0% by mass with respect to the phosphor. And 2.5% by mass or less.
Here, the reason why the mass of the silicone-coated aluminum oxide fine particles is preferably 0.5% by mass or more and 3.5% by mass or less with respect to the phosphor is that the phosphor is less than 0.5% by mass. This is because the bonding strength between the phosphors and the translucent sealing tube is insufficient, while when it exceeds 3.5% by mass, the initial luminance of the fluorescent lamp decreases.

  In this fluorescent lamp paint, a surfactant, an organic polymer such as a resin, a low melting point glass such as zinc borosilicate glass, etc. may be added depending on the application and specifications within the range that does not deteriorate the characteristics of the fluorescent lamp. Good.

According to the fluorescent lamp paint of the present embodiment, the binding material for adhering the phosphors to each other and adhering these phosphors to the translucent sealing tube is subjected to surface treatment with an organosilicon compound. Since the fine particles are used, the dispersibility of the binding substance in the paint can be improved, and a sufficient binding force can be obtained even when baked at a low temperature of 600 ° C. or less, and the phosphor may be thermally deteriorated. In addition, the adhesive strength between the phosphors and the adhesive strength between the phosphors and the translucent sealing tube can be improved.
Therefore, by using this fluorescent lamp paint, it is possible to improve the bonding strength of the phosphor to the translucent sealing tube, and to provide a coating film capable of preventing problems such as peeling of the phosphor layer. It can be easily formed at a low temperature of ℃ or less.

  Furthermore, if it is set as the fluorescent lamp coating material containing a fluorescent substance, the operation which mixes the slurry containing a fluorescent substance becomes unnecessary, and the operation at the time of forming a coating film can be simplified.

"Manufacturing method of coating film and coating film"
There are the following two methods (1) and (2) in the method for producing a coating film of the present embodiment.
(1) The above-mentioned fluorescent lamp paint (not containing a phosphor) and a slurry containing a phosphor are mixed to produce a mixed paint, and then this mixed paint is applied onto a substrate to form a coating film. Then, the coating film is dried or dried and heat-treated.

First, the light lamp paint containing no phosphor and the slurry containing the phosphor are mixed to prepare a mixed paint.
The slurry containing the phosphor is a slurry in which the above-described phosphor is dispersed in any one or two of the above-described solvents, that is, water and a low-boiling organic solvent. Here, in the fluorescent lamp paint, The mass of the silicone-coated aluminum oxide fine particles is 0.5% by mass or more and 3.5% by mass or less, more preferably 1.0% by mass or more and 2.5% by mass or less with respect to the phosphor in the slurry. In this way, the mixing ratio (mass ratio) between the fluorescent lamp paint and the slurry containing the phosphor is set.

  Here, the fluorescent lamp coating material and the fluorescent lamp are adjusted so that the mass of the silicone-coated aluminum oxide fine particles in the fluorescent lamp coating material is 0.5% by mass or more and 3.5% by mass or less with respect to the phosphor in the slurry. The reason for setting the mixing ratio (mass ratio) with the slurry containing the body is that when the mass of the silicone-coated aluminum oxide fine particles is less than 0.5% by mass with respect to the phosphor in the slurry, This is because the adhesive strength between the translucent sealing tube is insufficient and, on the other hand, when the mass exceeds 3.5% by mass with respect to the phosphor in the slurry, This is because the luminance decreases.

Next, this mixed paint is applied onto a substrate to form a coating film.
Here, the base material may be any base material that can withstand the heat treatment temperature, and a glass base material, a translucent ceramic base material, and the like are suitable. However, considering the fluorescent lamp application, it conforms to the specifications of the fluorescent lamp. A possible glass tube is preferred.
As a coating method, a usual wet coating method such as a spin coating method, a roll coating method, a spray coating method, a bar coating method, a dip coating method, a meniscus coating method, a suction coating method, a flow coating method, or the like can be used. In particular, when a coating film is formed on the inner surface of a glass tube like a fluorescent lamp, a suction coating method, a flow coating method, or the like is preferably used.

Next, the coating film is dried in the atmosphere or dried and heat-treated.
The drying temperature may be a temperature at which the low-boiling organic solvent (or the low-boiling organic solvent and the high-boiling organic solvent) contained in the paint is sufficiently dissipated, and is, for example, room temperature (25 ° C.) to 150 ° C.
In this drying step, the coating film only needs to be sufficiently dried, may be dried only by heating, or may be blown with air. Specifically, hot air may be blown by air blow at normal temperature.

When the heat treatment is performed, the heat treatment temperature is set to a temperature in the range of 500 ° C. to 600 ° C. for a predetermined time in a range in which the fluorescent lamp is not defective.
Further, this heat treatment step may be performed simultaneously with the phosphor layer when the phosphor layer and the coating film of the present invention are sequentially formed on the substrate.
Thus, the coating film of this embodiment can be obtained.

(2) A method of coating the fluorescent lamp-containing coating material containing the phosphor on the substrate to form a coating film, and then drying or drying and heat-treating the coating film.
The method (2) uses a fluorescent lamp paint containing a phosphor instead of using a mixed paint in which a fluorescent lamp paint (not containing a phosphor) and a slurry containing a phosphor are mixed. The point is only different from the above method (1), and the other points are exactly the same.
Also by this method, the coating film of this embodiment can be obtained.

According to any of the coating film manufacturing methods described above, a coating film that can improve the bonding strength of the phosphor to the light-transmitting sealing tube and prevent defects such as peeling of the phosphor layer is manufactured. It can be formed easily without increasing the cost.
The coated film thus obtained has improved the bonding strength with the translucent sealing tube, and thus there is no risk of peeling from the translucent sealing tube, and the phosphor layer is stable for a long period of time. Can be maintained.

  Further, according to this coating film, even when heat treatment is performed at a low temperature in the range of 500 ° C. to 600 ° C., it is possible to prevent the phosphor from being thermally deteriorated, and the phosphor of the translucent sealing tube can be prevented. Bonding strength can be improved and problems such as peeling of the phosphor layer can be prevented.

"Fluorescent lamp"
The fluorescent lamp of the present embodiment is one in which the above-mentioned coating film is formed inside a translucent sealing tube. By adopting such a configuration, there is no thermal deterioration of the phosphor, and the phosphor is bonded to each other. The strength and the adhesive strength between the phosphor and the translucent sealing tube are improved, and there is no possibility of problems such as peeling off of the phosphor layer.

  FIG. 1 is a longitudinal sectional view showing a fluorescent lamp according to an embodiment of the present invention. FIG. 2 is a transverse sectional view of the fluorescent lamp. In the figure, 1 is a translucent sealing tube made of a glass tube sealed at both ends. 2 is a protective film having an electron emission function formed on the entire inner wall (inner surface) of the translucent sealing tube 1, and 3 is a red light emission formed on the entire inner surface of the protective film 2 according to the present invention. A phosphor layer comprising a phosphor, a phosphor composed of a mixture of a green light-emitting phosphor and a blue light-emitting phosphor, and silicone-coated aluminum oxide fine particles as a binding material, 4 is a translucent sealing tube 1 Electrodes 5 and 5 respectively provided on both end sides are lead wires electrically connected to the electrode 4.

G is a sealed gas sealed in the translucent sealing tube 1, and this sealed gas G is composed of a rare gas such as mercury, neon, or argon, or an inert gas such as nitrogen.
Further, the protective film 2 is included in the function of emitting electrons from the electron-emitting material by applying a high-frequency high voltage between the electrodes 4 and 4, and the material and gas G included in the translucent sealing tube 1. It is a film having a function of preventing amalgam from reacting with mercury.

In this fluorescent lamp, since the phosphor layer 3 made of the coating film of the present embodiment is formed on the inner wall of the translucent sealing tube 1, the red light emitting phosphor, the green light emitting phosphor and the blue light emitting phosphor are formed. There is no thermal degradation, and the adhesive strength between red-based phosphors, green-based phosphors and blue-based phosphors and the adhesive strength between these phosphors and translucent sealing tubes are improved. There is no risk of problems such as peeling off of the phosphor layer.
Therefore, the maintenance ratio of the initial luminance is high, and stable luminance can be obtained over a long period.

  In order to manufacture this fluorescent lamp, a coating film for forming a protective film is applied to the inner wall of the translucent sealing tube 1 to form a coating film, and this coating film is dried or dried and heat-treated to form the protective film 2. Then, the above-mentioned mixed paint is applied on the protective film 2 and dried or dried and heat-treated to form the phosphor layer 3, and then the electrodes 4, 4 in the translucent sealing tube 1. Are further introduced, and a rare gas and mercury are introduced to seal the translucent sealing tube 1 to obtain a fluorescent lamp.

  In the fluorescent lamp of this embodiment, the protective film 2 having an electron emission function is formed on the entire inner wall of the translucent sealing tube 1, and the phosphor layer 3 is formed on the protective film 2. The fluorescent lamp of the present embodiment is not limited to this. In the fluorescent lamp of the present invention, for example, the phosphor layer 3 may be first formed on the inner wall of the translucent sealing tube, and the protective film 3 may be formed on the phosphor layer 3. Alternatively, a three-layer structure in which the phosphor layer 3 and the protective film 2 are sequentially laminated may be employed.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

（ただし、ｎは１０以上かつ２０以下の数）
で表されるジメチルポリシロキサン（ＤＭＰＳ）を添加し、室温（２５℃）にてヘンシェルミキサーで１０００ｒｐｍの攪拌回転数で３０分間混合し、次いで、温度を１００℃に上昇させるとともに回転数を２０００ｒｐｍに上げて１時間攪拌し、酸化アルミニウム微粒子の表面を７％シリコーン処理し、結着用物質であるシリコーン被覆酸化アルミニウム微粒子を作製した。 "Example 1"
The following formula (2) is applied to aluminum oxide (Al ₂ O ₃ ) fine particles having an average particle diameter of 20 nm.

(Where n is a number between 10 and 20)
Dimethylpolysiloxane (DMPS) is added and mixed at room temperature (25 ° C.) with a Henschel mixer for 30 minutes at a stirring rotation speed of 1000 rpm, then the temperature is raised to 100 ° C. and the rotation speed is increased to 2000 rpm. The resulting mixture was stirred for 1 hour, and the surface of the aluminum oxide fine particles was treated with 7% silicone to produce silicone-coated aluminum oxide fine particles as a binding substance.

  Next, the silicone-coated aluminum oxide fine particles were dispersed in normal butyl acetate containing 1.0% by mass of nitrocellulose using a bead mill, and then the beads were separated. The content of the silicone-coated aluminum oxide fine particles was 1.5%. It adjusted so that it might become mass%, and the dispersion liquid was produced.

Next, a mixture of a red light-emitting phosphor, a green light-emitting phosphor and a blue light-emitting phosphor was added at a ratio of 1: 1 to the dispersion to prepare the fluorescent lamp paint of Example 1.
The composition of this fluorescent lamp paint is as follows.
Red light emitting phosphor 12.50%
Green light emitting phosphor 15.00%
Blue light emitting phosphor 22.50%
Nitrocellulose 0.50%
Binding material 0.75%
Normal butyl acetate 48.75%

Next, this fluorescent lamp paint was applied onto a hard glass so that the film thickness after drying was 20 μm. The obtained coating film was dried at room temperature (25 ° C.), and then at 600 ° C. for 5 hours. A flat sample of Example 1 was prepared by heat-treating for a minute to form a coating film.
Furthermore, a glass tube for a fluorescent lamp is prepared, and the fluorescent lamp paint is applied to the inner surface of the glass tube by a suction coating method so that the film thickness after drying becomes 20 μm. After drying at room temperature (25 ° C.), heat treatment was performed at 600 ° C. for 5 minutes. Thereafter, electrodes and lead wires were attached to the glass tube and sealed to produce a fluorescent lamp of Example 1.

"Example 2"
A fluorescent lamp paint of Example 2 was produced in the same manner as in Example 1 except that the surface treatment amount of the aluminum oxide fine particles by dimethylpolysiloxane (DMPS) was changed to 3%.
Next, using this fluorescent lamp paint, a flat sample and a fluorescent lamp of Example 2 were produced in the same manner as in Example 1.

"Example 3"
A fluorescent lamp paint of Example 3 was produced in the same manner as in Example 1 except that the surface treatment amount of the aluminum oxide fine particles with dimethylpolysiloxane (DMPS) was changed to 15%.
Next, using this fluorescent lamp paint, a flat sample and a fluorescent lamp of Example 3 were produced in the same manner as in Example 1.

（ただし、ｍが０以上かつｎが１以上で、かつ、１≦ｍ＋ｎ≦２０を満たす数）
で表されるメチルハイドロジェンポリシロキサン（ＭＨＰＳ）を添加し、室温（２５℃）にてヘンシェルミキサーで１０００ｒｐｍの攪拌回転数で３０分間混合し、次いで、温度を１００℃に上昇させるとともに回転数を２０００ｒｐｍに上げて１時間攪拌し、酸化アルミニウム微粒子の表面を７％シリコーン処理し、結着用物質であるシリコーン被覆酸化アルミニウム微粒子を作製した。 Example 4
The following formula (3) is applied to aluminum oxide fine particles (Al ₂ O ₃ ) having an average particle diameter of 20 nm.

(However, m is 0 or more, n is 1 or more, and 1 ≦ m + n ≦ 20)
Methyl hydrogen polysiloxane (MHPS) represented by the following formula is added and mixed at room temperature (25 ° C.) with a Henschel mixer for 30 minutes at a stirring rotational speed of 1000 rpm, then the temperature is raised to 100 ° C. and the rotational speed is increased. The temperature was increased to 2000 rpm and the mixture was stirred for 1 hour, and the surface of the aluminum oxide fine particles was treated with 7% silicone to produce silicone-coated aluminum oxide fine particles as a binding substance.

  Subsequently, using the silicone-coated aluminum oxide fine particles, a fluorescent lamp paint, a flat sample, and a fluorescent lamp of Example 4 were produced in the same manner as in Example 1.

“Comparative Example 1”
Aluminum oxide (Al ₂ O ₃ ) fine particles having an average particle size of 20 nm are dispersed in normal butyl acetate containing 1.0% by mass of nitrocellulose using a bead mill, and then the beads are separated to contain aluminum oxide fine particles. The ratio was adjusted to 1.5% by mass to prepare a dispersion.
Next, using this dispersion, in the same manner as in Example 1, a fluorescent lamp paint, a flat sample, and a fluorescent lamp of Comparative Example 1 were produced.

“Comparative Example 2”
Aluminum oxide (Al ₂ O ₃ ) fine particles having an average particle diameter of 20 nm are dispersed using a bead mill in normal butyl acetate containing 1.0% by mass of nitrocellulose and 0.1% by mass of a dispersant, and then beads Was adjusted so that the content of the aluminum oxide fine particles was 1.5% by mass to prepare a dispersion.
Next, using this dispersion, in the same manner as in Example 1, a fluorescent lamp paint, a flat sample, and a fluorescent lamp of Comparative Example 2 were produced.

“Comparative Example 3”
Aluminum oxide (Al ₂ O ₃ ) fine particles having an average particle diameter of 20 nm are dispersed in normal butyl acetate containing 1.0% by mass of nitrocellulose using a bead mill, and then the beads are separated. The dimethylpolysiloxane (DMPS) represented by (2) is added to 7% by mass with respect to the aluminum oxide fine particles, and then adjusted so that the content of the aluminum oxide fine particles is 1.5% by mass. Then, a dispersion was prepared.
Next, using this dispersion, in the same manner as in Example 1, a fluorescent lamp paint, a flat sample, and a fluorescent lamp of Comparative Example 3 were produced.

“Comparative Example 4”
A low-melting glass (CBB: barium calcium borate) is dispersed in normal butyl acetate containing 1.0% by mass of nitrocellulose by using a bead mill, and then the beads are separated to obtain a low-melting glass (CBB) content. It adjusted so that it might become 1.5 mass%, and the dispersion liquid was produced.
Next, using this dispersion, in the same manner as in Example 1, a fluorescent lamp paint, a flat sample, and a fluorescent lamp of Comparative Example 4 were produced.

"Evaluation"
For each of Examples 1 to 4 and Comparative Examples 1 to 4, the binding force and coloration of the coating film in the flat sample, the luminance of the fluorescent lamp, and the stability of the fluorescent lamp paint were evaluated by the following methods.
Table 1 shows the compositions and evaluation results of the paints of Examples 1 to 4 and Comparative Examples 1 to 4.

(1) Binding force (adhesive strength)
An air peel strength test was performed and evaluated.
An air spray gun with a diameter of 2 mm was fixed at a position of 1.5 cm from the coating film, air was blown from the air spray gun to the coating film, and the air pressure at which the coating film was peeled off within 10 seconds from the start of spraying was measured. . Here, the peeling unevenness of the coating film was mainly evaluated.
The air pressure at the start of measurement was 0.1 MPa, and the air pressure was increased by 0.01 MPa.
The obtained measured values were evaluated in the following four stages.
◎: When exceeding 0.6 MPa ○: 0.4 MPa% or more and 0.6 MPa or less △: 0.2 MPa% or more and less than 0.4 MPa ×: Less than 0.2 MPa

(2) Coloring The coating film was visually observed, and “◯” was assigned when no coloring was observed, and “X” was indicated when coloring was observed.

(3) Luminance The fluorescent lamp was turned on, the luminance after 100 hours was measured, and this luminance was evaluated at a ratio where the luminance of the fluorescent lamp of Comparative Example 1 was 100% (reference).
The obtained ratio was evaluated in the following four stages.
A: When the luminance exceeds 108% compared to the luminance of Comparative Example 1, B: The luminance exceeds 102% compared with the luminance of Comparative Example 1 and is not more than 108%. Δ: The luminance is Comparative Example 1. 98% or more and 102% or less in comparison with the brightness of-: Test not possible (Lighting test could not be performed because film peeling occurred during lamp production)

(4) Stability of fluorescent lamp paint The mass of the precipitate of the dispersed species after one month from the preparation of the fluorescent lamp paint was measured, and the measured value was evaluated in the following four stages.
◎: Precipitation of dispersed species is less than 3% by mass per month ○: Precipitation of dispersed species is not less than 3% by mass and less than 5% by mass △: Precipitation of dispersed species is not less than 5% by mass and 10% by month Less than% ×: precipitation of dispersed species is 10% by mass or more per month

DESCRIPTION OF SYMBOLS 1 Translucent sealing tube 2 Protective film 3 Phosphor layer 4 Electrode 5 Lead wire G Filling gas

Claims (6)

A fluorescent lamp paint comprising a binder and a solvent for adhering the phosphors together and bonding the phosphors to the light-transmitting sealing tube,
A fluorescent lamp paint characterized in that the binding material is aluminum oxide fine particles surface-treated with an organosilicon compound.   The fluorescent lamp paint according to claim 1, further comprising a phosphor.   3. The fluorescent lamp paint according to claim 1, wherein the solvent is a low boiling point organic solvent.   A coating film formed by using the fluorescent lamp paint according to claim 2.   A method for producing a coating film, comprising: coating a fluorescent lamp paint according to claim 2 on a substrate to form a coating film, and then drying or drying and heat-treating the coating film.   A fluorescent lamp comprising the coating film according to claim 4 formed inside a translucent sealing tube.

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