JPH09110476A - Display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a display device provided with a filter having reflection preventive property, excellent in resistances to soiling and scuffing and in workability, etc. SOLUTION: This display device is provided with the filter having reflection preventive property wherein the outermost surface of a single layered or multi- layered reflection preventive film 2 formed on a glass base 1 is covered with a compound 3 consisting of perfluoro-polyether or its derivative having a polar group at the terminal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cathode ray tube (CRT) or other display device provided with a filter having an antireflection property which is excellent in stain resistance, scratch resistance and work resistance. Is.

[0002]

2. Description of the Related Art When an object is viewed through a transparent material, it is troublesome that the reflected light is strong and the reflected image is clear. For example, in a spectacle lens, a reflected image called a ghost or a flare is generated to cause discomfort to the eyes. Or Further, in the case of a looking glass or the like, there is a problem that the contents are not clear due to the reflected light on the glass surface.

Conventionally, a method of coating a substance having a refractive index different from that of a substrate on a substrate by a vacuum deposition method or the like to prevent reflection has been performed. In this case, it is known that the selection of the thickness of the substance coating the base material is important in order to maximize the antireflection effect.

For example, in the case of a single-layer film, a substance having a lower refractive index than that of a base material is required to be １ ／ of the optical wavelength for the optical film thickness.
It is known that selecting an odd multiple thereof gives a minimum reflectance, that is, a maximum transmittance. Here, the optical film thickness is given by the product of the refractive index of the film forming material and the film thickness of the film. Furthermore, it is possible to form multiple antireflection layers, and some proposals have been made regarding the selection of the film thickness in this case (Optical Technology Contact Vol.
9, No.8, p.17 (1971)).

On the other hand, JP-A-58-46301, JP-A-59-49501, and JP-A-59-50401.
The publication describes a method for forming an antireflection film composed of a plurality of layers which satisfies the above-mentioned conditions of optical film thickness, using a liquid composition.

[0006]

An antireflection film formed on a glass substrate by a vacuum deposition method, a sputtering method or the like is mainly composed of an inorganic oxide or an inorganic halide as a film forming material, and the antireflection film is essentially Has high surface hardness, on the other hand, fingerprints, sweat, or hair liquid,
There is a drawback that stains caused by cosmetics such as hair sprays are easily conspicuous, and these stains are difficult to remove. In addition, there is a problem that the scratch formed when coming into contact with any hard object becomes thick because the surface slippage is poor. In addition, there is a problem in that raindrops and water droplets adhere to water, so that they spread greatly when they adhere to water, and objects such as spectacle lenses appear to be distorted over a large area.

In order to impart a hard surface hardness to the antireflection films described in JP-A-58-46301, JP-A-59-49501 and JP-A-59-50401, the outermost surface is required in order to impart a hard surface hardness. It is necessary to contain 30% by weight or more of an inorganic material typified by silica fine particles in the film, but an antireflection film obtained from such a film composition has a poor surface slippage and is scratched by abrasion of cloth or the like. It has problems such as easy sticking.

Various surface treatment agents have been proposed and commercially available for the purpose of improving these problems, but all of them are soluble in water or various solvents and temporarily impart a function. It was not durable and poor in durability. JP-A-3-266801 reports that a fluorine-based resin layer is formed in order to impart water repellency. However, although these fluorinated resins certainly increase the water repellency, they did not provide satisfactory results against friction or abrasion.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a display device provided with a filter having antireflection property which is excellent in stain resistance, scratch resistance, workability and the like. And

[0010]

The present inventor has arrived at the invention described below as a result of extensive studies to solve the above problems. That is, the display device of the present invention which solves the above problems is formed from a perfluoropolyether or a derivative thereof having a polar group at the terminal on the outermost surface of a single-layer or multilayer antireflection film formed on a glass substrate. And a filter having an antireflection property, which is coated with the compound.

In a first aspect of the display device of the present invention, the glass substrate is a glass panel of the display device,
A single-layer or multi-layer antireflection film is directly formed on the surface of the glass panel, and the outermost surface thereof is further coated with a compound consisting of a perfluoropolyether having a polar group at the terminal or a derivative thereof.

Further, in a second aspect of the display device of the present invention, the filter is provided on the gullal panel of the display device.
The surface opposite to the surface on which the antireflection film is formed is adhered. Further, in a third aspect of the display device of the present invention, the filter is arranged on the front surface of the glass panel of the display device so that the surface opposite to the surface on which the antireflection film is formed faces. .

Further, the flat display device of the present invention is a compound comprising a perfluoropolyether having a polar group at a terminal or a derivative thereof on the outermost surface of a single-layer or multi-layer antireflection film formed on a glass substrate. Is provided with a filter having antireflection property.

In the cathode ray tube of the present invention, the outermost surface of a single-layer or multi-layer antireflection film formed on a glass substrate is coated with a compound consisting of a perfluoropolyether having a polar group at the terminal or a derivative thereof. And a filter having antireflection property.

[0015]

In the present invention, the antireflection property is improved by coating the outermost surface of a single-layer or multilayer antireflection film formed on a glass substrate with a perfluoropolyether compound having a polar group at the end. The wear resistance or stain resistance of the display device filter having the above is improved.

When the compound is coated on the outermost surface of the antireflection film, the polar group at the terminal of the compound is strongly adsorbed on the surface of the antireflection film to cover the surface of the antireflection film, thereby exhibiting good durability. . On the other hand, since the perfluoropolyether chain of this compound exhibits hydrophobicity, it is oriented in a direction away from the film surface, and when the foreign matter comes in contact with the outer surface, the shock is mitigated and the surface moves by swaying gently in the shock direction. Scratches can be avoided, and at the same time, good stain resistance is imparted due to the high water repellency of the perfluoropolyether chain or the low wettability to various media.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail based on embodiments. In the display device of the present invention, the outermost surface of a single-layer or multi-layer antireflection film formed on a glass substrate is coated with a compound comprising a perfluoropolyether having a polar group at the terminal or a derivative thereof. And a filter having an antireflection property.

In the present invention, various combinations can be used as the single-layer or multilayer antireflection film. In particular, the film structure of the substance forming the lower layer than the outermost layer film (that is, the part farthest from the glass substrate) has required performance such as heat resistance, antireflection property, reflected light color, durability, surface hardness, etc. Can be arbitrarily determined experimentally. The outermost layer film of the reflective film is not particularly limited, but it is desirable that the outermost layer film is mainly made of SiO ₂ or MgF ₂ , and more preferably SiO ₂ . When the outermost layer film is mainly composed of SiO ₂ or MgF ₂ , more sufficient surface hardness can be obtained and
This is because the stain resistance and the scratch resistance, which are the objects of the present invention, and the durability of these performances are remarkably exhibited.

As methods for forming various inorganic substances including SiO ₂ for forming these antireflection films, there are various PVD (Physical Vapor Deposition) methods typified by vacuum deposition, ion plating and sputtering. Inorganic substances suitable for the PVD method include SiO ₂ and Al ₂
O ₃ , ZrO ₂ , TiO ₂ , TaHf ₂ , SiO, Ti
O, Ti ₂ O ₃ , Y ₂ O ₃ , Yb ₂ O ₃ , MgO, Ce
Inorganic oxides such as O ₂ are preferably applied.

Further, the film thickness of the outermost layer of the reflection film should be determined depending on the required performance other than the antireflection effect. Particularly, for the purpose of maximizing the antireflection effect, the outermost layer is formed. It is preferable to select the optical film thickness of the film to be ¼ of the target light wavelength or an odd multiple thereof, from the viewpoint of giving the minimum reflectance, that is, the maximum transmittance.

On the other hand, the structure of the layer below the outermost layer film in the reflective film is not particularly limited. That is, it is possible to form the outermost layer film directly on the glass substrate, but in order to make the antireflection effect more remarkable, a higher refractive index than the outermost layer film on the glass substrate. It is effective to form one or more coating layers. Also, some proposals have been made regarding selection of the film thickness and refractive index of such an antireflection film having a multilayer structure (for example, Optical Technology Contact Vol. 9, No. 8, p. 17 (1971). )), And can be appropriately selected based on these known techniques.

In the present invention, the surface of each of these single-layer or multilayer antireflection films is coated with a compound consisting of a perfluoropolyether having a polar group at the terminal or a derivative thereof. Here, the molecular structure of perfluoropolyether is not particularly limited,
The repeating units include those having perfluoroalkyloxy groups of various chain lengths, preferably C1 to C3.
A perfluoroalkyloxy group is used as a repeating unit. Specifically, for example, as a monofunctional one, there are the following,

[0023]

Embedded image

The polyfunctional ones are as follows.

[0025]

Embedded image

In the above chemical structural formula, l, m, n,
k, p and q each represent an integer of 1 or more. However, as described above, the molecular structure of the perfluoropolyether is not limited to those exemplified above. The polar group disposed at one end or both ends of such a perfluoropolyether is not particularly limited, and examples thereof include an amino group, a carboxyl group, a hydroxyl group, an alkoxysilano group, and a phosphoric acid group. However, preferably, with respect to the material constituting the outermost surface film of the reflective film coating the compound consisting of the perfluoropolyether or its derivative, it is desirable that it exhibits good affinity and adsorptivity, For example, when the outermost surface film of the reflective film is mainly composed of SiO ₂ , the amino group, the carboxyl group, the hydroxyl group, the alkoxysilano group, the phosphoric acid group, etc., and the outermost surface film is mainly composed of MgF ₂ . The same applies to the case.

The compound consisting of perfluoropolyether having a polar group at the terminal or a derivative thereof, which is used when the outermost layer of the reflective film is mainly composed of SiO ₂ , is bonded to a long-chain hydrocarbon group at the terminal. Particularly preferred is the form of a carboxylate having an amino group. The compound consisting of such a perfluoropolyether derivative having a long-chain hydrocarbon group is not only excellent in workability due to increase in usable solvent as described later, but also capable of imparting more excellent scratch resistance. is there.

The molecular weight of the compound consisting of a perfluoropolyether having a polar group at the terminal or a derivative thereof is not particularly limited, but from the viewpoint of stability and ease of handling, the number average molecular weight is 500 to 10,000, more preferably, The thing of about 1000-5000 is used.

Further, the film thickness of the film formed of the compound comprising a perfluoropolyether having a polar group at the terminal or a derivative thereof is not particularly limited, either, but the antireflection property and the stillness to water. 0.5 nm from the balance with the contact angle and the relationship with the surface hardness
˜100 nm, more preferably 1 nm to 20 nm.

As the coating method, various methods used in ordinary coating work can be applied, but spin coating, dip coating, from the viewpoint of uniformity of antireflection effect and control of reflection interference color, Curtain flow coating is preferably used. Further, from the viewpoint of workability, a method of impregnating a material such as paper or cloth with a liquid and applying and casting it is also preferably used.

In such a coating operation, the compound consisting of perfluoropolyether having a polar group at the terminal or its derivative is usually diluted with a volatile solvent before use. The solvent used is not particularly limited, but in use, it should be determined in consideration of the stability of the composition, the wettability of the reflective film with respect to the outermost layer film, volatility and the like. In the case of a perfluoropolyether or a derivative thereof which does not contain a long chain hydrocarbon group, the solvent is limited to a fluorocarbon or a perfluoroalkane group, but a perfluoropolyether derivative containing a long chain hydrocarbon group is , Ordinary organic solvents, for example, alcohol solvents such as ethyl alcohol and ketone solvents such as acetone,
Alternatively, since it also dissolves in a hydrocarbon solvent such as hexane, these can be used alone or as a mixture of two or more kinds. Incidentally, in applying the compound comprising a perfluoropolyether having a polar group at the terminal or a derivative thereof according to the present invention, it is preferable that the surface of the antireflection film to be applied is cleaned. Further, stain removal with a surfactant, degreasing with an organic solvent, the above cleaning with a fluorine-based gas, etc. are applied. It is also an effective means to perform various pretreatments for the purpose of improving adhesion and durability, and as a particularly preferably used method, activated gas treatment,
Examples include chemical treatment with acid or alkali.

The glass substrate used in the present invention may be any one as long as it is a substrate made of inorganic silicon oxide, but the optical properties such as transparency, refractive index and dispersion, and further impact resistance. From the viewpoint of physical properties such as heat resistance, heat resistance, and durability, silicate glass containing Sr (strontium) or Ba (barium) is particularly preferable for CRT, and alkali-free glass is preferable for liquid crystal display. Further, the glass substrate may be the panel glass itself of the display device as shown in the embodiments described below, or may be, of course, separate from the panel glass.

1 to 3 show sectional structures of a surface portion of a CRT as a display device according to an embodiment of the present invention. First, the outline of the CRT will be described. FIG.
As shown in FIG. 1, the CRT 10 is joined to a glass panel 12 having a fluorescent surface formed on its inner surface and the glass panel 12,
The neck portion has a funnel glass 14 in which an electron gun 16 is housed. The electron beam emitted from the electron gun 16 is deflected by the deflection yoke 18, and the glass panel 1
Through the aperture grille 20 as a color selection electrode mounted on the inner surface side of 2, the fluorescent screen is hit and emitted to display an image.

In the embodiment shown in FIG. 1, an antireflection film 2 is directly formed on the surface of a glass panel 1 of a cathode ray tube (CRT) as a display device, and a polar group having a polar group at the end is formed on the antireflection film 2. A surface coating layer 3 formed by coating a fluoropolyether compound is formed.

In another embodiment shown in FIG. 2, CR
It has a glass substrate 1B having a curvature corresponding to the curvature of the glass panel 1 of T, and the antireflection film 2 and the surface coating layer 3 similar to the above are formed on this glass substrate 1B. Then, the filter material having such a configuration is bonded to the glass panel 1 of the CRT via the adhesive layer 4 on the surface opposite to the surface on which the antireflection film is formed. The glass panel 1 and the glass substrate 1B
The adhesive for adhering and is not particularly limited, and various known adhesives can be used. For example, an epoxy adhesive, an acrylic adhesive, a silicone adhesive, etc. are used and their curing It is preferable that the refractive index of the layer (adhesive layer) is close to the refractive index of the panel, for example, the difference is within 0.8%.

In still another embodiment shown in FIG. 3, a glass substrate 1B is provided as in the embodiment shown in FIG. 2, and the same antireflection film 2 and surface as described above are provided on the glass substrate 1B. The coating layer 3 is formed. However, unlike the embodiment shown in FIG. 2, the filter material having such a configuration is such that the surface opposite to the surface on which the antireflection film is formed faces the front surface of the glass panel of the display device. , Just placed.

In the present invention, the target display device includes various display devices such as a flat display device such as a liquid crystal display device and a plasma display device, in addition to the CRT as described above. The display device provided with the filter having the antireflection property obtained according to the present invention is less likely to be stained and the stain is less noticeable than the display device having the ordinary antireflection film. Furthermore, it has the advantages that it is easy to remove dirt and that the surface has good slipperiness so that it is not easily scratched, and in addition to these performances, it is durable with respect to the wear of this filter.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, "parts" indicates parts by weight.

Example 1 (1) Preparation of Antireflection Film On the surface of a CRT panel glass, a 130 nm-thick ITO film was first deposited by sputtering as an antireflection film, and subsequently SiO ₂ was deposited to 80 nm to form the film. . (2) Preparation of Perfluoropolyether Compound-Containing Coating Composition Having Polar Groups at Terminals Perfluoropolyether having polar groups at terminals shown in Table 1 (number average molecular weight 2000, lubricant 1 in Table 1) Four
380 parts of hexane and 20 parts of ethanol were added to and mixed with each part to form a uniform solution, which was then filtered with a membrane filter to obtain a coating composition. (3) Application and drying of coating composition The surface of the antireflection film obtained in (1) above is dip coated with the coating composition obtained in (2) above at a pulling rate of 5 cm / min to improve antireflection properties. An optical article having the above was obtained. (4) Performance Evaluation The performance of the obtained optical article was evaluated by conducting a test according to the following method. Table 1 shows the results.

(A) Contamination resistance test 5 ml of tap water was dropped on the filter surface at room temperature of 25 ° C.
After being left in an atmosphere of ± 2 ° C for 48 hours, the remaining state of scale was observed when wiped with a cloth. The time when the scale could be removed was defined as good, and the time when the scale could not be removed was defined as bad.

(B) Surface slip property A mechanical pencil tip was evaluated for scratching when the surface was scratched under a load of 200 g. The judgment was based on the following criteria. ◯: No scratches, Δ: Fine scratches, ×: Marked scratches.

(C) Abrasion resistance test The surface of the preventive film was measured with steel wool # 0000 for 20
It was confirmed by scratching after rubbing 30 times under a load of 0 g. The judgment was based on the following criteria. ◯: No scratches, Δ: Fine scratches, ×: Marked scratches.

(D) Difficulty in sticking to the hands The resistance to sticking to the hands when the surface of the prevention film was touched was visually evaluated. The judgment was based on the following criteria. ◯: Not noticeable even if attached, Δ: Attached but can be easily removed, ×: Noticeable after attached.

Examples 2 to 10 Optical articles were obtained in the same manner as in Examples 1 except that the lubricants 2 to 10 shown in Table 1 were used instead of the lubricant 1 of the coating composition. I did. Table 1 shows the obtained results.

Comparative Examples 1 to 5 For comparison, the same performance evaluation as in Examples was carried out for the case where the perfluoropolyether compound having a polar group at the terminal was not coated and the case where it was coated with another fluororesin. It was Table 2 shows the obtained results.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

As described above, the display device according to the present invention has the following effects. (1) It is hard to be stained by fingerprints, hand marks, etc., and is not conspicuous, and these effects are permanently retained.

(2) It can be easily removed even if water stains adhere and are dried. (3) The surface slip property is good. (4) Dirt such as dust hardly adheres, and the usability is good. (5) There is durability against abrasion.

Therefore, according to the present invention, it is possible to provide a display device having an antireflection effect which has an effect of preventing stains such as hand stains and water stains and is excellent in slipperiness and abrasion resistance. .

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing a surface portion configuration of a CRT as an embodiment of a display device according to the present invention.

FIG. 2 is a cross-sectional view schematically showing a surface portion configuration of a CRT as another embodiment of the display device according to the present invention.

FIG. 3 is a cross-sectional view schematically showing a surface portion configuration of a CRT as still another embodiment of the display device according to the present invention.

FIG. 4 is a schematic sectional view of a CRT.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... CRT glass panel 1B ... Glass base material 2 ... Antireflection film 3 ... Surface coating layer of a perfluoropolyether compound having a polar group at the end 4 ... Adhesive layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Tomio Kobayashi Tomio Kobayashi 4-16-1 Okada, Atsugi-shi, Kanagawa Sony Corporation Atsugi 2nd Technology Center (72) Mitsunori Ueda 6-chome, Kitagawa, Shinagawa-ku, Tokyo 7th 35th Sony Corporation

Claims (6)

[Claims] 1. A single-layer or multi-layer antireflection film formed on a glass substrate is coated on its outermost surface with a compound consisting of a perfluoropolyether having a polar group at its terminal or a derivative thereof. A display device comprising a filter having antireflection property. 2. The glass base material is a glass panel of a display device, and a single-layer or multi-layer antireflection film is directly formed on the surface of the glass panel, and the outermost surface thereof has a perfluoro group having a polar group at the end. A compound comprising a polyether or a derivative thereof is coated.
The display device according to claim 1. 3. The display device according to claim 1, wherein the filter is bonded to a gullal panel of the display device on a surface opposite to a surface on which the antireflection film is formed. 4. The display device according to claim 1, wherein the filter is arranged on the front surface of the glass panel of the display device so that the surface opposite to the surface on which the antireflection film is formed faces. 5. A compound comprising a perfluoropolyether or a derivative thereof having a polar group at the terminal is coated on the outermost surface of a single-layer or multi-layer antireflection film formed on a glass substrate. A flat display device comprising a filter having antireflection property. 6. A single-layer or multi-layer antireflection film formed on a glass substrate is coated with a compound consisting of a perfluoropolyether having a polar group at its end or a derivative thereof on the outermost surface. A cathode ray tube comprising a filter having antireflection property.