JP2970294B2 - CRT and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-definition CRT having an antireflection film and a method of manufacturing the same.

[0002]

2. Description of the Related Art Recently, from the viewpoint of improving the performance of cathode ray tubes, various surface treatment films have been produced on the surface of cathode ray tubes. Anti-reflection film and anti-static film
This is a typical example. Above all, the anti-reflection film suppresses the reflection of external light, prevents reflection on the CRT, and improves visibility, and is important in terms of the function of the CRT. Among anti-reflection films, a non-glare film that forms fine irregularities on the surface and physically diffusely reflects external light is typical. As a method of forming the antireflection film or the antistatic film, there are a CVD method, a sputtering method, and the like. However, a large-scale vacuum device is required, and a large-area face surface of a cathode ray tube, which is proceeding in the direction of larger panels, is required. It is not suitable as a film forming method, and there are many problems in terms of productivity and the like. For this reason, at present, a method of forming these films by using a coating solution prepared by a sol-gel method or the like and spraying or spin-coating the solution is mainly used (Japanese Patent Application Laid-Open Nos. 61-118946, 62). No. 143348). As the material of the antireflection film, there are many materials having a SiO ₂ thin film formed on the outermost surface. These films generate an inorganic polymer precursor in a solution using a metal alkoxide such as Si (OR) ₄ as a raw material, spray-coat the solution on the cathode ray tube face, and then heat-treat the solution at about 150 to 180 ° C. The organic matter in the film is thermally decomposed and cured by heating to form Si having surface irregularities.
This is for forming an O ₂ film. A film with irregularities formed on the surface of the formed film is called a non-glare film. The irregularities on the surface of the non-glare film reflect external light on the CRT face by diffusing and reflecting external light. This makes it easier to see the displayed image. In addition, as these films, a film in which two or more layers are stacked in addition to a single-layer film can be used. In some cases, a conductive film is formed under the non-glare film to prevent the surface of the CRT from being charged, thereby improving the performance of the CRT. In addition, there is a color CRT in which an organic material is contained in a non-glare film or a film containing an organic dye is formed below the non-glare film in order to make the color more clear. In general, a thin film preparation method by a sol-gel method requires high-temperature heating to cure the film. One of the low-temperature film formation techniques is a method described in JP-A-3-18893. In this method, a solution containing an organometallic compound and water is irradiated with an electromagnetic wave of a specific wavelength to apply a solution of the metal oxide prepolymer to form a thin film, or after applying a reaction solution,
Irradiation with light energy of a specific wavelength forms a prepolymer, and oxidizes in an ozone atmosphere to form a film. This document does not describe an antireflection film of a cathode ray tube.

[0003]

In the above-described method for producing a coating film for a display by the usual method, since the raw material contains an organic substance, heat treatment at a high temperature is required to remove these impurities and to densify the thin film. is necessary. Therefore, during the heat treatment process, Si defects, which are structural defects, are likely to occur in the generated SiO ₂ film. This Si defect is
Since light is emitted by the wavelength of visible light, light is emitted by R, G, and B lights, particularly in a color cathode ray tube, and this causes a problem in that the screen becomes unclear. Also, from the viewpoint of the cathode ray tube manufacturing process, high heat treatment gives rise to problems such as the occurrence of thermal distortion inside the product and the deterioration of the emission characteristics of the electron gun. In addition, due to the difference in the coefficient of thermal expansion between the non-glare film and the CRT panel,
There were problems such as cracks in the formed film and peeling of the film. For that purpose, it is necessary to raise and lower the baking temperature in the cathode ray tube manufacturing process at about 5 ° C./min, which takes time and labor for temperature adjustment and baking. In addition, since a large furnace is required for heat treatment, the film production equipment becomes large-scale, and there has been a problem in terms of manufacturing cost. SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a high-definition CRT having a dense antireflection film manufactured at a low temperature, a method of manufacturing the same, and an apparatus therefor. .

[0004]

In order to achieve the above object, according to the present invention, at least a part of the surface of a substrate contains silicon oxide as a main component, and does not substantially emit light even when irradiated with light having a wavelength in a visible light region. A high-definition CRT provided with an antireflection film was produced. Further, in the antireflection film containing silicon oxide as a main component, the structural defects of silicon are reduced by 10%.
^A film having a density of ¹⁰ −10 ¹⁴ / cm ³ was formed to obtain a high-definition CRT. Further, the antireflection film according to the present invention contains silicon oxide as a main component and contains all Si-
Among the O-Si units, the ratio of the bent Si-O-Si unit is 30% or less, and the rest is linear Si-O-Si.
It is characterized in that an antireflection film as a unit is produced. Further, the antireflection film of the present invention contains silicon oxide as a main component, is characterized in that absorption of ultraviolet light at 190 nm is smaller than 250 nm, and a peak corresponding to Si—O—Si symmetric stretching vibration is higher than 812 cm ^−1. It appears on the wavelength side. A high-definition cathode-ray tube provided with the above-described anti-reflection film, comprising a metal oxide other than silicon oxide and containing at least one of indium oxide, zinc oxide and antimony oxide, and having a conductive coating film. It can be. Further, the above antireflection film can be manufactured by spray-coating a solution containing silicon alkoxide by a sol-gel method on a cathode ray tube face surface, heating at a low temperature and irradiating with ultraviolet light to form irregularities on the produced surface. it can. In order to prepare the thin film, in the present invention, a coating film of a metal alkoxide solution represented by M (OR) n is formed on the panel surface of a cathode ray tube by a sol-gel method, and the coating film is cured by irradiation with ultraviolet light. And a method of manufacturing a high-definition CRT having a non-glare film characterized by forming a fine uneven film. In the present invention, an antistatic film is formed on at least the panel surface of the CRT, and the M (OR) is formed on the panel surface of the CRT on which the antistatic film is formed by a sol-gel method.
forming a coating film of a solution using a metal alkoxide represented by n as a raw material, and curing the coating film by irradiation with ultraviolet light to form a fine uneven film. Things. In the method of manufacturing a cathode ray tube having a non-glare film, the non-glare film may contain an organic dye, or a film containing an organic dye may be formed as a base film on the surface of the cathode ray tube panel. Irradiation with ultraviolet light is preferably performed in an atmosphere of 100 ° C. or lower. Further, in the present invention, as a device for manufacturing a CRT having the non-glare film, a coating device for applying a non-glare film forming solution to a CRT panel surface is provided, and a device for transferring the CRT after applying the solution is provided, Is provided with an ultraviolet light irradiation means for irradiating light. It is preferable that the above-mentioned manufacturing apparatus is provided with a heating means capable of heating the surface of the coating film when the coating film is irradiated with ultraviolet light.

[0005]

The point of the present invention is to use light energy instead of heat energy in the sol-gel method for forming a coating film of a metal alkoxide sol and converting it into an inorganic film by heat energy. That is, a non-glare film formed by curing by light irradiation is provided on the surface of the CRT panel. In general, the sol-gel method is based on a hydrolysis reaction and a condensation reaction in a solution using a metal alkoxide as a raw material, and forms an inorganic polymer precursor in the solution. Is what you get. In the present invention, in this sol-gel reaction, the energy necessary for breaking the metal-alkoxy group bond is applied by ultraviolet light irradiation, and the sol-gel reaction can be completed. In addition, after this solution is formed, irradiation with light having a shorter wavelength than that for generating ozone can be performed to obtain an oxide thin film having a uniform stoichiometric ratio at a low temperature. By using this method, a dense thin film can be obtained at a lower temperature than in the past, so that it is optimal as a method for producing a CRT surface treatment film. In the present invention, heating may be used in combination with ultraviolet light irradiation. The heating temperature in this case is lower than before, for example, 1
A temperature of 00 ° C. or less is sufficient, and heating for a short time (about 10 to 15 minutes) is sufficient, so that there is almost no influence of heat on the inside of the cathode ray tube. Therefore, there is no adverse effect on the emission characteristics of the electron gun of the cathode ray tube, and thermal distortion of the whole cathode ray tube can be avoided. Further, generation of film peeling and the like due to the heat treatment can also be removed. Further, since the processing time can be shortened at a low temperature, a drastic reduction in manufacturing cost and equipment cost can be expected. In particular, in the case of heating, according to the present method, since the temperature may be low, the heating rise temperature can be made faster than before. For example, in the conventional method, 1
Since the heat treatment was performed at 60 ° C., the heating rise temperature was extremely slow at 5 ° C./min. According to this method, the heating temperature may be 100 ° C. or less, so the heating temperature is 2
Can be more than doubled.

A further advantage of the present invention is that a non-glare film having a uniform stoichiometric ratio can be produced at a low temperature.
The structural defect of SiO _{2 in} the film can be greatly reduced as compared with the conventional one. Heat treatment at high temperature by ordinary method (150-180 ° C or higher)
In this case, since a SiO ₂ structural defect (E ′ center or the like) is generated in the film, when light in the visible light region shines, the entire region emits fluorescence. In the case of a color cathode ray tube, this fluorescent light impairs the clarity of the three primary colors of red, blue and green, and this is a serious problem when developing a high definition cathode ray tube. According to the present invention, a film having very few structural defects can be obtained.
In light emission, a film that does not substantially generate fluorescence is obtained. Therefore, in the non-light emitting film according to the present invention, the colors of R, G, and B emitted from the inside of the CRT can be transmitted to the viewer from the screen clearly. On the other hand, the film produced by the conventional method
The fluorescent light is continuously emitted for several hours by irradiation with light in the visible light region. For this reason, the CRT surface becomes unclear. When the emission spectrum of the phosphor of the cathode ray tube is measured, the spectrum of B and G becomes considerably wider in the case where the conventional film is formed due to the overlap of the excess fluorescence. However, when the film of the present invention is formed,
Since there is no extra fluorescence, the half width of the spectrum is as narrow as 80 nm or less, which leads to an improvement in color purity.

[0007] Further, since this structural defect is a defect in the SiO ₂ network structure, it greatly affects the mechanical strength and water resistance of the film. The strength and water resistance of the membrane
This is a particularly important element because a non-glare film as an anti-reflection film is formed on the outermost surface of the CRT panel. Since the SiO ₂ film according to the present invention has few structural defects, the strength and water resistance of the film are improved. The structural defect of the film and its quantification can be measured by electron spin resonance spectrum (ESR). The amount of Si defects estimated by ESR is 10 ¹⁰ -10 ¹⁴ / cm ³ . As shown in FIG. 4, the SiO ₂ film according to the present invention can be transparent up to 160 nm. However, a conventional heat-treated film has absorption in the ultraviolet region and is strong on the shorter wavelength side than 200 nm. Absorption occurs. This is said to be absorption based on the structural defect of the SiO ₂ film, and the presence of the structural defect of the film can be known from the absorption spectrum. According to the method of the present invention, light irradiation during heat treatment eliminates absorption in the ultraviolet region of 200 nm or less and fluorescence generated upon irradiation with visible light. This means that the irradiation with light has eliminated the structural defect of the film. It was also found that the molecular structure of the film was different between the light-irradiated film and the heat-treated film. Information on the molecular structure of the membrane
^It can be obtained by measurement of ²⁹ Si solid state NMR or Raman spectroscopy. For example, Raman spectroscopy can provide information on the flexibility and strength of the Si—O—Si bond in the SiO ₂ film. If peaks of both the Si—O—Si symmetric stretching vibration and the antisymmetric stretching vibration are observed in the Raman spectrum, the Si—O—Si bond in the film contains many bent bonds. If only the symmetric stretching vibration is observed and the peak of the inverse symmetric stretching vibration is not observed, the Si—O—Si bond in the film consists of only a linear bond. Since the bent Si—O—Si bond has a large strain,
The strength of the film containing a large amount of this is low. Water resistance also deteriorates because water molecules easily attack the Si-O-Si bond having a large strain. On the other hand, the stronger the peak position of the Raman shift is on the higher wave number side, the stronger the coupling is formed. As described above, the change in the molecular structure of the film can be semi-quantitatively known from the peak intensity, the type of vibration, and the position of the Raman shift in Raman spectroscopy. In films prepared at room temperature by the sol-gel method, weak symmetric stretching vibration and strong antisymmetric stretching vibration are observed, and a large amount of unstable Si-O-Si bonds with unstable strain is observed in the film. You. Heat-treat this film,
When the treatment temperature is gradually increased, the peak intensity ratio of the two is reversed, and in the film heat-treated at several hundred degrees Celsius, strong symmetric stretching vibration is observed, but inverse symmetric stretching vibration is not observed. That is, an unstable bent Si-
It can be seen that the molecular structure changed from the O-Si bond to a stable linear Si-O-Si bond. On the other hand, in the case of light irradiation, a change in spectrum similar to that in the case of heat treatment was observed, but it was found that the temperature at which the change occurred was less than half. That is, by irradiating light, a stable film can be obtained at a lower temperature than before. Among films made by irradiating light, a film having sufficient strength as an anti-reflection film has a bent Si-O of all the Si-O-Si units.
It was found that the proportion of -Si units was 30% or less, and the balance was linear Si-O-Si units. That is,
A film having a sufficient strength can be obtained with a film having a ratio of not less than this ratio. As described above, according to the present invention, a non-glare film having no (small) Si defects in the SiO ₂ film and having a linear SiO ₂ network structure without distortion in the film can be produced. Thereby, a high-definition CRT can be provided. In addition, it goes without saying that the present method can be applied not only to the non-glare film but also to an anti-reflection film of a laminated film utilizing the light interference effect. Alternatively, laser light may be used as a light irradiation light source.

[0008]

【Example】

(Example 1) Tetraethoxysilane, water, ethanol,
Nitric acid was mixed at a molar ratio of 1: 12: 45: 0.25 to obtain a raw material solution. After making this solution,
The face of the cathode ray tube was spray-coated. On this thin film, 254 nm (10 m
W / cm ² ) and then 184 nm (1 mW / cm ² ) light
Irradiated for 0 minutes. On the display screen of the cathode ray tube, unnecessary light emission of the non-glare film due to light emission of the phosphors (R, G, B) does not occur, so that a cathode ray tube with extremely high color and tone can be manufactured. FIG. 1 shows the emission spectrum of the phosphor (R, G, B). The CRT of the present invention (dotted line) has a smaller half-width than that of the conventional CRT (solid line), and therefore has improved color purity. The surface has a height of 0.2-
Since a film having an anti-reflection function having irregularities of about 0.3 μm and a width of about 30 μm was produced, a high-definition CRT with a reflectance of 1% or less and little reflection could be produced. Next, the properties of the anti-reflection film manufactured in this example and the anti-reflection film manufactured by the conventional method using only heat treatment are shown in comparison. FIG. 2 shows that the film heat-treated at 160 ° C.
3 shows an emission spectrum of the non-glare film when irradiating visible light of m. It has a peak around 530 nm and shows a broad emission spectrum over the entire visible light region. Since this light emission extends over the entire visible light region, the screen is in a state where green-white light emission has occurred. FIG. 3 shows the luminescence intensity plotted against time. This emission lasts for a fairly long time. This emission overlaps with the spectrum of the phosphor RGB emission of the color cathode ray tube, thereby causing an image to be unclear.
On the other hand, such light emission is not observed in a film formed by light irradiation. For this reason, it has become possible to produce a high-definition CRT. This light emission is known to be due to the defect structure of the film, and ESR confirmed the presence of the E 'center. The amount was 10 ¹⁷ pieces / cm ³ . On the other hand, its existence is not confirmed in the light irradiation film. FIG. 4 shows the absorption spectrum of the film. The heat-treated film has absorption in the ultraviolet region, and its absorption intensity rises from around 200 nm. This absorption is called absorption based on the structural defect of SiO _{2, and} the structural defect of the heat-treated film is estimated from the absorption spectrum. On the other hand, such absorption is not observed in the light-treated film. FIG. 5 shows a change in Raman spectrum of a light-irradiated film from which information on the molecular structure of the film can be obtained. In the figure, (a), (b) and (c) are Si-O-Si, respectively.
Symmetrical stretching vibration, Si-OH, Si-O-Si inverse symmetrical stretching vibration. When light is irradiated, the peak of (c) decreases,
It can be seen that the peak of (a) has increased. (C) is a peak corresponding to a bent Si—O—Si bond, and it is presumed that the bent structure gradually changes to a linear structure. Similar changes occur in conventional methods at high processing temperatures. Estimation of the flexibility and linearity of the Si—O—Si unit in the 90 ° C. light-treated film from this spectrum revealed that the bent Si—O—Si unit was 10%.
The remainder was found to be linear Si-O-Si units. FIG. 6 shows the change in the Si—O—Si symmetric stretching vibration peak position in FIG. As the processing temperature increases, this peak position shifts to a higher wavenumber side, and it is observed that the coupling is strengthened. The peak position of the 90 ° C. light-treated film is 81
2.5 cm ^-1, which is comparable to a 160 ° C. heat treated film. In other words, a low-temperature, strong network structure comparable to that processed at a high temperature was obtained by light treatment.

Example 2 Tetraethoxysilane, water,
Ethanol and nitric acid in a molar ratio of 1: 12: 45: 0.2
Of tin oxide (Sb / Sn = 5 mol%) containing antimony oxide having a diameter of 0.1 μm or less is added in an equal amount to tetraethoxysilane, and they are uniformly dispersed. The solution was used. This solution was spray-coated on the surface of a cathode ray tube to form a film. 90 ° C for this film
While heating at 254 nm, light of 254 nm (10 mW / cm ² ) and then 184 nm (1 mW / cm ² ) were irradiated for 10 minutes.
The prepared film is in a state in which fine particles of tin oxide containing conductive antimony oxide are uniformly dispersed in a SiO ₂ matrix. The resistance of this film is 10
It was ⁹ Ω / □. The antistatic and antireflection film produced using this method showed good performance without adverse effects on the inside of the cathode ray tube due to high heat treatment, which had been a problem in the past. FIG. 7 shows the charging characteristics in which the induced voltage observed on the outermost surface of the panel attenuates after the CRT is switched on and then off. In the figure, (a) is for only the anti-reflection film, and (b) is for this embodiment. Those containing no tin oxide require 5 minutes or more for the induced voltage to become zero, whereas those provided with the film of this example provide:
It was confirmed that the induced voltage became 0 in a few seconds. The film of this example also had a good antireflection function.

Example 3 Tetraethoxysilane, water,
Ethanol and nitric acid in a molar ratio of 1: 12: 45: 0.2
5 and mixed with an equal amount of fine particles of indium oxide (Sn / In = 5 mol%) containing tin oxide having a diameter of 0.1 μm or less with respect to tetraethoxysilane to uniformly disperse them. To obtain a raw material solution. This solution was spray-coated on the surface of a cathode ray tube to form a film. The film was irradiated with light of 254 nm (10 mW / cm ² ) and then at 184 nm (1 mW / cm ² ) for 10 minutes while heating at 90 ° C.
The prepared film has a state in which fine particles of indium oxide containing conductive tin oxide are uniformly dispersed in a SiO ₂ matrix. The resistance of this film is 10
⁹ Ω / □. The antistatic and antireflection film produced using this method showed good performance without adverse effects on the inside of the cathode ray tube due to high heat treatment, which had been a problem in the past. This film does not emit light when the switch is turned on,
Since it has both antireflection and antistatic functions, a high-definition CRT was obtained.

Example 4 Tetraethoxysilane, water,
Ethanol and nitric acid in a molar ratio of 1: 12: 45: 0.2
Of fine particles of tin oxide (Sb / Sn = 5 mol%) containing antimony oxide having a diameter of 0.1 μm or less are added to tetraethoxysilane in an equal amount, and they are uniformly dispersed to obtain a raw material. The solution was used. This solution was spray-coated on the surface of a cathode ray tube to form a film. Next, tetraethoxysilane, water, ethanol, and nitric acid are used in a molar ratio.
A solution mixed at a ratio of 1: 12: 45: 0.25 was spray-coated on the face of the cathode ray tube. On this thin film, 254 nm (10 mW /
cm ² ) and then at 184 nm (1 mW / cm ² ) for 10 minutes. The cathode ray tube has a two-layer film, the lower layer is an antistatic film, and the upper layer is a film having an antireflection function. This cathode-ray tube had high definition because there was no knitted light emission in the visible light region. In addition, both antireflection and antistatic functions were good.

Example 5 Tetraethoxysilane, water,
Ethanol and nitric acid in a molar ratio of 1: 12: 45: 0.2
To the solution mixed at a ratio of 5 was added about 5 mol% of an ethanol solution of a quinacudrine-based light-fast organic dye having an absorption wavelength near 570 nm, based on tetraethoxysilane. This solution was spin-coated on a CRT (150 r
pm) to form a film. Then, on this film, tetraethoxysilane, water, ethanol and nitric acid in a molar ratio of 1: 1:
Example 1 was prepared by mixing a solution mixed at a ratio of 12: 45: 0.25.
An anti-reflection film was formed in the same manner as shown in the above. The cathode ray tube manufactured in this manner has a film having absorption at 550-570 nm, which is the highest in human luminous sensitivity, and therefore absorbs light in the vicinity of 550-570 nm of extraneous light to enhance the antireflection function. . Thus, a high-definition cathode ray tube was manufactured.

(Embodiment 6) FIG. 8 is a schematic view of an apparatus for manufacturing a non-glare film of a high-performance CRT. The CRT for forming a coating film is attached to a fixed base 15 on a conveyor 14 moving in a hood 16, and the solution introduced from a film forming solution storage tank 18 is sprayed by a spray gun 13.
Spray coating is applied to the panel surface of the cathode ray tube 11. The CRT after the coating is formed is transferred by a conveyor 14 and transferred into a hood 16 provided with an ultraviolet lamp 17 for generating light having a wavelength corresponding to the metal alkoxide solution and ozone, and necessary for curing the film. Receiving the best light. The film forming solution storage tank 18 can contain a necessary film forming solution such as a non-glare film, a non-glare antistatic film, and a colored non-glare film, and can send it to the spray gun 13. This manufacturing apparatus is economical because there is no need for heating as in the prior art, and the apparatus can be downsized because a heating furnace is not required. In addition, curing can be further promoted by using heating of 100 ° C. or less at the time of irradiation with ultraviolet light. In this case, heating can be achieved sufficiently by inserting heated air into the hood 16. .

[0014]

According to the present invention, a dense antireflection film can be manufactured at a low temperature. Since this thin film has no defects in the film, it does not emit extra light even when irradiated with phosphor light. For this reason, a high-definition CRT with improved color purity can be manufactured as compared with the conventional one. In addition, since the film can be formed at a very low temperature in a short time, it has a great effect on cost reduction.

[Brief description of the drawings]

FIG. 1 is a comparison of emission spectra of color television phosphors (dotted line—light treated film, solid line—heat treated film).

FIG. 2 is an emission spectrum of a heat-treated film.

FIG. 3 is a time change of an emission spectrum of a heat-treated film.

FIG. 4 shows absorption spectra of a light-treated film and a heat-treated film (a-heat-treated film, b-light-treated film).

FIG. 5 is a graph showing a change in a Raman spectrum of a light-treated film.

FIG. 6 shows the processing temperature dependence of Si—O—Si symmetric stretching vibration in the optical processing film.

FIG. 7 shows a voltage induced on the surface of a cathode ray tube when a switch is applied.

FIG. 8 is a brown production facility.

[Explanation of symbols]

11 ... CRT, 12 ... Forming film, 13 ... Spray gun, 14 ... Conveyor, 15 ... Fixed table, 16 ... Hood, 1
7 ... Light irradiation lamp, 18 ... Film formation solution storage tank.

Continuation of front page (72) Inventor Ken Takahashi 4026 Kuji-cho, Hitachi City, Ibaraki Prefecture Hitachi, Ltd. Hitachi Research Laboratory (56) References JP-A-61-118932 (JP, A) JP-A-3-197572 (JP) JP-A-64-41149 (JP, A) JP-A-1-154445 (JP, A) JP-A-5-107403 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) H01J 29/88 H01J 29/89 C03C 17/25

Claims (4)

(57) [Claims] 1. A cathode ray tube comprising: a glass substrate; and an antireflection film formed by spray-coating a solution containing silicon alkoxide on the glass substrate by a sol-gel method and then irradiating with light while performing heat treatment. CRT which comprises an organic dye barrier layer absorbs light of 5 5 0-5 7 0nm. 2. A glass substrate was a solution spray coating a containing silicon alkoxide by a sol-gel method on the glass substrate, a cathode ray tube consisting of an anti-reflection film formed by irradiation with heat treatment, the glass 5 between the substrate and the antireflection film 5 0-5 7
A cathode ray tube having a film containing an organic dye that absorbs 0 nm light . 3. A coating step of forming a coating film of a metal alkoxide solution represented by M (OR) n (M: metal, R: lower alkyl group, n: integer) by a sol-gel method; CRT production method having an antireflection film characterized by comprising a curing step of curing by ultraviolet irradiation with heat treatment. 4. A means for applying a solution for forming an anti-reflection film on a panel surface of a cathode ray tube, a means for transferring the cathode ray tube after the application of the solution, a means for heating the coating film, and a heat treatment for the coating film. An apparatus for producing a CRT having an anti-reflection film, comprising a light irradiation means for photo-curing the coating film.