JPH0227770B2 - BOGENMENOJUSURUINKYOKUSENKANNOSEIZOHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a cathode ray tube having an anti-glare surface that can be used for television receivers, office computer displays, etc., and an object thereof is to provide a cathode ray tube having an anti-glare surface that can be easily mass-produced at low cost. It is something to do. BACKGROUND ART Research and development have been carried out to improve the difficulty in viewing images of cathode ray tubes when direct or indirect sunlight or fluorescent light enters the tube. Generally, there are the following methods. (1) A method that uses the light scattering effect to physically or chemically roughen the glass surface of a cathode ray tube to form minute irregularities. (2) A method that utilizes the interference effect of light to form a thin film of metal oxide, metal fluoride, metal nitride, etc. in a single layer or in multiple layers on the glass surface using vacuum technology. (3) A method of blending pigments and dyes into the glass to utilize the light absorption effect. (Glass obtained by this method is called smoked glass.) Of the three methods above, the first method significantly reduces the light transmittance of the glass if it is roughened to the point that the image becomes difficult to see. This will reduce the number of
This method tends to cause variations in the degree of roughness on the glass surface, and is not a method that completely meets the purpose of the present invention. The second method is often applied to small parts such as lenses, but cathode ray tubes are large in size and volume, and the method itself uses vacuum technology.
Since mass production is inferior, the cost is high. Furthermore, although the light transmittance of the glass body is significantly improved, since the image of external light incident directly or indirectly is formed on the top surface of the cathode pipe, especially when the external light is strong,
The difficulty in viewing images cannot be completely resolved. The third method is essentially a method of reducing the light transmittance of the glass, and like the second method, it does not completely eliminate the difficulty in viewing images due to strong external light. The above-mentioned drawbacks of the present invention are improved, and the glass surface of the cathode ray tube is coated with at least one type of HPC.
A mixture containing at least a resin, at least one epoxy group-containing alkoxysilane compound, and at least one alkoxytantalum compound, and IPA
By applying a solution consisting of a solvent containing , and coating it with a cured film by hydrolysis or thermal decomposition, the surface exhibits excellent light scattering properties, and even when strong external light is incident, an image is formed on the surface. The problem disappeared, and the difficulty in seeing the image was completely resolved. Moreover, due to the coating, the light transmittance of the glass is reduced.
Since it is extremely small, within 1%, it is unlikely to affect the brightness of the cathode ray tube. This was achieved by forming an extremely uniform polyhedral-shaped uneven surface on the surface. Numerous experiments have revealed that a unique uneven surface can be obtained by applying a treatment solution made by dissolving HPC resin in a solvent containing IPA to a glass surface and firing it at an appropriate temperature. IPA is a semi-soluble solvent that does not completely dissolve HPC resin, so when the treatment liquid is applied to the glass surface, there may be variations in the content of HPC resin in the coating layer on the glass surface. It is thought that by subsequent firing, the variation in content is not resolved and forms a film, forming a unique uneven surface. Although this film exhibits excellent light scattering properties and high light transmittance, its adhesion to the glass, hardness, abrasion resistance, durability, etc. are insufficient. This can be improved by adding two or more hydrolyzable organometallic compounds. Various hydrolyzable organometallic compounds, such as
Si, Ti, Ta, Ge, Al, Cr, Nb, V, Mo, Hf,
Add monomers or polymers such as alkoxy compounds, allyloxy compounds, chelate compounds, etc. containing W, Ga, In, Sn, Sb, Fe, etc., stir thoroughly, and then apply to the glass surface by spraying or dipping at constant velocity. Apply by known methods such as pulling up method or spinner method, and apply for 50~
By heating and baking at 250℃ for 5 minutes to 3 hours,
The hydrolyzable organometallic compound is combined with the glass.
It chemically reacts with the HPC resin and the hydrolyzable organometallic compound to form a strong three-dimensional compound coating with an uneven surface. Therefore, the adhesion between the three-dimensional compound and the glass is good, the pencil hardness of the three-dimensional compound is as high as 5H to 6H, and it exhibits excellent durability against heat, humidity, and light. , and is unaltered by chemicals such as alcohol. As a result of many hydrolyzed organometallic compounds, at least two
It has been found that these components are indispensable in order to sufficiently ensure the properties of the three-dimensional compound. The epoxy group-containing alkoxysilane compound also serves to further lower the refractive index of the resulting three-dimensional compound while ensuring adhesion to glass.
In addition, the alkoxytantalum compound decomposes even under heating and baking conditions at lower temperatures, and the alkoxytantalum compound and the epoxy group-containing alkoxysilane compound,
The HPC resin and the glass body are reacted, and the epoxy group-containing alkoxysilane compound is reacted with the HPC resin and glass to form a film of a strong three-dimensional compound that has excellent adhesion to the glass. Unlike when the glass itself is made into smoked glass, the alkoxytantalum compound can be used to make plastics such as acrylic resin or polycarbonate resin smoked, and when this smoked plastic is attached to the glass surface of a cathode ray tube, its properties are further improved. to repel. In other words, as mentioned above, the alkoxytantalum compound is active even when fired at low temperatures, so it is possible to form a high-quality film on plastic, which only has heat resistance of around 100°C, just like glass. . When using a low-temperature hydrolyzable organometallic compound other than the alkoxytantalum compound, for example,
When hydrolyzable organometallic compounds such as Ti, Zr, V, Mo, Cr, Nb, Hf, W, and Ga are used, the resulting coating changes to various colors upon aging (under heating, humidification, etc.). Because it is easy to discolor, there is a limit to the amount that can be added. (If the amount added is within a few percent of the total weight of the hydrolyzable organometallic compound used, discoloration will be less noticeable.) Also, hydrolyzable organometallic compounds such as Al, In, Sn, and Sb are easily handled by hydrolysis. This method has disadvantages, and the lifespan of the processing liquid to be prepared is short, making it unsuitable. (Although organometallic compounds that are easily hydrolyzed can be stabilized and used with various chelating agents, stabilized compounds are difficult to decompose at low temperatures, so when using plastics with poor heat resistance. It is also possible to further increase the hardness of the resulting coating and improve the wear resistance of the coating, and it is particularly effective to use (R ₄ )lSi(OR ₃ )4-l. It is. As a result, the coating hardness was 6H.
~8H (pencil hardness), and when various plastics are used, the film becomes a scratch-preventing protective film.
(Here, l is a numerical value of 0, 1, 2, or 3.) The optical properties of glass with an anti-glare film that exhibits such excellent durability are as follows: (The present invention can be applied to the untreated product.) The gloss level is reduced to about 1/3 or less compared to the untreated product, and a strong external light image is no longer formed on the glass surface of the cathode ray tube. The reduction in light transmittance is within 1%, so the reduction cannot be recognized with the naked eye. As described above, the present invention has made it possible to manufacture a cathode ray tube having an anti-glare surface exhibiting excellent optical properties and durability. Note that the appropriate molecular weight of the HPC resin is 10,000 to 2,000,000, and the size of the uneven polyhedron obtained differs depending on the molecular weight. To give an example, a molecular weight of 60,000
When using HPC resin, the diameter of the circumscribed circle of the polyhedron is approximately 10 to 100 μm, and that of approximately 80% of the polyhedra is 50 to 100 μm.
The height difference is 0.2 to 1 μm, and that of about 80% of the polyhedrons is 0.5 to 0.8 μm. Also, the coating thickness is 0.2
~8μm is good, and the HPC resin is 0.1~20wt/V%. The amount of the hydrolyzable organometallic compound in the range of 0.5 to 20 times the weight of the HPC resin added was good. Further, with respect to R ₂ to _{R 4} , if they are outside the above limits, the solubility in the solvent may deteriorate or a high firing temperature is required, which is not optimal. Details will be described below in Examples. Example 1 The following ingredients were thoroughly stirred to prepare a treatment liquid. HPC resin (molecular weight approx. 60000) 2g SH6040 (Toray silicone product) 4g Ta (OC ₂ H ₅ ) ₅ 4g Si (OCH ₃ ) ₄ 1.5g IPA 80ml Methanol 20ml The glass surfaces of non-smoke and smoke cathode ray tubes were treated with the above treatment. The material was immersed in a liquid, pulled up at a constant speed of 15 cm/min, and immediately thereafter heated and baked at 140° C. for 30 minutes. As representative values, the optical properties of non-smoke glass before and after treatment are shown in Table 1.

[Table] As shown in Table 1, although the decrease in light transmittance cannot be determined visually, the glossy surface of the treated surface
The reduction was reduced to almost 1/4, and even when an external light image, such as light from a fluorescent light, was incident on the treated surface, it did not form a bright image and the image could be clearly seen. Example 2 The following ingredients were thoroughly stirred to prepare a treatment liquid. HPC resin (molecular weight approx. 40000) 2g SH6040 (manufactured by Toray Silicone) 5g Ta (OC ₂ H ₅ ) ₅ 5g Ti (OC ₄ H ₉ ) ₄ 0.2g Si (OCH ₃ ) ₄ 1g IPA 80ml Methanol 20ml 100μm acrylic and polycarbonate Apply the treatment liquid to the film by spraying, and immediately after that
Firing was performed at ℃ for 1 hour. The optical properties of the obtained film are shown in Table 2.

[Table] The treated plastics were glued to smoked and non-smoke glass cathode ray tubes using adhesive. As in Example 1, even when a strong external light image was incident, no image was formed and the image could be clearly seen. Micrograph of the surface of the cathode ray tube of the present invention (×100)
is shown in the reference photo.

Claims (1)

[Claims] 1. A. General formula (Here R ₁ is H or [-CH ₂ -CH (CH ₃ -)
At least one type of hydroxypropyl cellulose (hereinafter abbreviated as HPC) represented by O] mH group, m and n are integers of 1 or more. (b) General formula At least one epoxy group-containing alkoxysilane compound selected from the group represented by: C. A solution consisting of a mixture containing at least one alkoxytantalum compound represented by the general formula Ta-(OR ₃ ) ₅ and a solvent containing isopropyl alcohol (hereinafter abbreviated as IPA) is applied to the glass surface of the cathode ray tube. A method for producing a cathode ray tube having an anti-glare surface, characterized in that the cathode ray tube is coated with a cured film by hydrolysis or thermal decomposition. [Here, R ₂ is a straight chain or branched alkylene group having up to 6 carbon atoms, R ₃ is a straight chain or branched alkyl group having up to 4 carbon atoms, and R ₄ is OR ₃ or a straight chain or branched alkylene group having up to 4 carbon atoms. straight-chain or branched alkyl groups. ]