JPH0968603A - Antireflection filter and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antireflection filter and a display device having a prevention effect against contamination by hands or water and having excellent lubricating property and wear resistance by the effect of a lubricant. SOLUTION: This antireflection filter consists of a transparent base body and a single-layer or multilayered antireflection film essentially comprising a UV-curing resin. A perfluoropolyether having polar groups at molecular ends is held in this antireflection film. In the display device 1, a display screen 2 and/or the front plate of the screen is coated with a single or multilayered antireflection film essentially comprising a UV-curing resin. The antireflection film holds perfluoropolyether having polar groups at molecular ends.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antireflection filter excellent in stain resistance, scratch resistance, workability, etc., and an antireflection film formed on a display screen and / or a display of its front plate. Display device.

[0002]

2. Description of the Related Art When seeing an object through a transparent material, it is troublesome that the reflected image is strong and the reflected image is clear. Or Further, in the case of looking glass or the like, there is a problem that the contents are unclear due to the reflected light on the glass surface.

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

For example, in the case of a single-layer coating, a substance having a low refractive index is used as a base material and a quarter of the light wavelength for an optical thin film
Or, it is known that selecting an odd multiple thereof gives a minimum reflectance, that is, a maximum transmittance.

Here, the optical thin film is given by the product of the refractive index of the film forming material and the film thickness of the film.
Further, it is possible to form a multi-layered antireflection layer, and some proposals have been made regarding the selection of the film thickness in this case (Optical Technology Contact Vol. 9, No. 8, pp17).
[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 conditions for the optical thin film, using a liquid composition.

In recent years, an optical article having antireflection property based on plastic has been devised and put into practical use by taking advantage of advantages such as light weight, safety and easy handling.
Most of them employ a film structure having silicon dioxide as a surface film.

[0008]

In the antireflection film formed by the vapor deposition method, the film forming material is mainly an inorganic oxide or an inorganic halide, and the antireflection film is essentially high in a plastic substrate. Although it has a surface hardness, it has the drawback that stains due to hand marks, fingerprints, sweat, hair liquid, hair spray, etc. are conspicuous and are hard to stain. Further, there is a problem that the scratches become thick due to poor surface slippage.

Further, since the wettability to water is great, when raindrops or water droplets adhere, it spreads widely, and there is a problem that an object looks distorted over a large area in a spectacle lens or the like. Further, when the inorganic oxide is formed by the vapor deposition method, a vacuum device is required, which increases the cost. Therefore, it is desirable that the problems of the stain resistance and abrasion resistance can be solved by applying a lubricant on the antireflection film on which the inorganic protective film is not formed.

JP-A-58-46301 and JP-A-5-301
In order to provide a hard surface hardness even in the antireflection film described in JP-A No. 9-49501 and JP-A No. 59-50401, the outermost layer film contains 30% by weight or more of an inorganic material typified by silica fine particles. However, the antireflection film obtained from such a film composition has problems such as poor surface slippage and being easily scratched by abrasion of cloth or the like.

Various kinds of surface treatment agents have been proposed and commercially available for the purpose of improving these problems. However, since they are dissolved by water or various solvents, they are temporarily provided with a function, and they are permanently used. The durability was poor.

Further, Japanese Patent Application Laid-Open No. 3-266801 has a report of forming a fluororesin in order to impart water repellency.

However, although these fluorinated resins certainly increase the water repellency, satisfactory results have not been obtained with respect to friction or wear.

Therefore, the present invention has an effect of preventing stains such as hand stains and water stains, and due to the effect of the above-mentioned lubricant, slipperiness,
It is an object of the present invention to provide an antireflection filter and a display device having excellent wear resistance.

[0015]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, a single-layer or multi-layer antireflection film mainly composed of an ultraviolet curable resin is provided. By holding perfluoropolyether having a polar group at the end of the film, it has the effect of preventing stains on hands, scales, etc., and due to the effect of the above lubricant, it has excellent anti-reflection properties with excellent slipperiness and abrasion resistance. The inventors have found that a filter and a display device can be obtained, and completed the present invention.

That is, in the antireflection filter according to the present invention, a single-layer or multi-layer antireflection film mainly composed of an ultraviolet curable resin is provided on a transparent substrate, and the antireflection film has a polar group at the end. It is characterized in that the fluoropolyether is retained.

The surface of the above antireflection film is coated with perfluoropolyether having a polar group at the terminal,
It is characterized in that a perfluoropolyether having a polar group at the terminal is internally added to the antireflection film.

On the other hand, a single-layer or multi-layer antireflection film mainly composed of an ultraviolet curable resin is provided on the surface of the display screen and / or its front plate, and this antireflection film has a perfluoropolyether having a polar group at the terminal. Is held.

The surface of the antireflection film is coated with perfluoropolyether having a polar group at the terminal, and
It is characterized in that a perfluoropolyether having a polar group at the terminal is internally added to the antireflection film.

Here, the antireflection film can be combined in various ways. In particular, the film constitution of the substance forming the lower layer than the surface layer film should be experimentally determined according to the required performance such as heat resistance, antireflection property, reflected light color, durability and surface hardness.

The film thickness of the surface layer film should be determined depending on the required performance other than the antireflection effect. In particular, the optical thin film of the surface layer film is used for the purpose of maximizing the antireflection effect. It is preferable to select 1/4 or an odd multiple of the target light wavelength from the viewpoint of giving a minimum reflectance, that is, a maximum transmittance.

In the present invention, the surface film provided on the transparent substrate is a single-layer or multi-layer antireflection film mainly made of UV (Ultra Violet) curing resin, and the surface of the film is made of perfluoropolyether having a polar group at the end. Or a compound internally added to an ultraviolet curable resin.

Here, the perfluoropolyether having a polar group at the terminal is preferably a carboxylic acid salt having a long chain amino group at the terminal, but is not particularly limited thereto. The molecular weight of the perfluoropolyether having a polar group at the terminal 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, 1000 to 5000 is used.

The repeating unit structure of the perfluoropolyether of the present invention is shown by the following structural formula, but is not necessarily limited thereto.

[0025]

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[0026]

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[0027]

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[0028]

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The film thickness of the film made of perfluoropolyether having a polar group at the terminal is not particularly limited, but it is 0 in view of the balance between the antireflection property and the static contact angle with water and the surface hardness. 0.5 nm to 10 n
m is preferred.

As a coating method, a method used in ordinary coating work can be applied, but spin coating, dip coating and curtain flow are used from the viewpoint of uniformity of antireflection effect and control of reflection interference color. Coating, spray coating and the like are preferably used.

Further, from the viewpoint of workability, a method of impregnating a material such as paper cloth with a liquid and applying and casting it is also preferably used.

These organic substance-containing effect substances are usually diluted with a volatile solvent and applied.

The solvent used is not particularly limited, but it should be determined in consideration of the stability and volatility of the composition before use. In the case of perfluoropolyether containing no long chain hydrocarbons, the solvent is limited to CFCs or perfluoroalkanes, but the lubricant or solvent containing long chain hydrocarbons dissolves in ordinary organic solvents. It is also possible to use not only the species but also a mixture of two or more species.

In the present invention, the transparent substrate may be any substrate as long as it is made of an organic polymer, but it has optical properties such as transparency, refractive index, dispersion, and impact resistance.
From the viewpoint of physical properties such as heat resistance and durability, especially polymethylmethacrylate and its copolymers, polycarbonate,
Diethylene glycol bisallyl carbonate (CR-
39), di (meth) acrylate polymers of (brominated) bisphenol A and copolymers thereof, polymers of urethane-modified monomers of mono (meth) acrylate of (brominated) bisphenol A and copolymers thereof, polyesters in particular Polyethylene terephthalate, polyethylene naphthalate and unsaturated polyester, acrylonitrile-styrene copolymer, vinyl chloride, polyurethane, epoxy resin and the like are preferable. Also, an aramid resin can be used.

Further, the above-mentioned plastic coated with a coating material such as a hard coat can be preferably applied to an antireflection film by using it as a base material. In particular, the coating material of the present invention can improve various physical properties such as adhesion, hardness, chemical resistance, durability, and color resistance.

Further, in order to improve the hardness, it is possible to use those to which various materials which have hitherto been known as the surface-hardened coating of plastic are applied (Japanese Patent Publication No. 50-28).
092, Japanese Patent Publication No. 50-28446, Japanese Patent Publication No. 50-39449, Japanese Patent Publication No. 51-24368, Japanese Patent Publication No. 52-112698, Japanese Patent Publication No. 57-2.
No. 735), and further, an acrylic crosslinked product obtained from (meth) acrylic acid and pantaerythritol.

In coating the perfluoropolyether compound having a polar group at the terminal in the present invention, the surface of the antireflection film to be coated is preferably cleaned. At the time of this cleaning, stain removal with a surfactant, degreasing with an organic solvent, steam cleaning with Freon, etc. are applied. In addition, various pretreatments, chemical treatments with acids, alkalis, etc. may be mentioned for the purpose of improving adhesion and durability.

The antireflection filter obtained by the present invention is less likely to be stained and is less conspicuous than an ordinary antireflection film.
Furthermore, it has the advantages that it is easy to remove dirt, or that it has good surface slippage and is not easily scratched. In addition to these performances, it is durable against abrasion, so it is an antireflection filter and display. Used as a device.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Specific embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to these embodiments. The parts in the examples represent parts by weight.

This embodiment is applied to a display device equipped with a cathode ray tube (hereinafter referred to as CRT). As a display device using such a CRT, for example, a basic configuration of a main part of a display device 1 using a monochrome CRT is as shown in FIG. In FIG. 6, the CRT
Reference numeral 1a denotes a panel portion (display screen) 2 whose interior is kept in a vacuum and whose inner surface is coated with a phosphor, and a conductive film provided on the inner surface to keep the electron beam traveling space at an equipotential and a conductive film on the outer surface. It has a funnel portion 3 which forms a high withstand voltage smoothing capacitor and a neck portion 5 in which an electron gun 6 is provided.

Video signal V supplied via terminal 12
D is amplified by the video amplifier 10 and sent to the electron gun 6. An electron beam ed corresponding to the video signal VD is emitted from the electron gun 6. Further, the deflection circuit 11 drives the deflection yoke 4 according to the horizontal and vertical synchronization signals extracted from the video signal VD in the video amplifier 10.
The trajectory of the electron beam ed emitted from the electron gun 6 is bent by the magnetic field generated from the deflection yoke 4 driven by the deflection circuit 11, and the phosphor screen inside the panel portion 2 is scanned while the phosphor screen is being scanned. The fluorescent substance of is made to emit light. The scanning direction of the electron beam ed in the case of FIG. 6 is perpendicular to the paper surface.

In such a display device, the display screen 2
The surface is coated with a single-layer or multi-layer antireflection film mainly composed of an ultraviolet curable resin, and the surface of the antireflection film is coated with a compound consisting of a perfluoropolyether having a polar group at the terminal.

Specifically, it was manufactured as in the following examples.

In the present embodiment, the coating film is formed on the display screen 2 which is the panel portion of the CRT 1a. However, the present invention may form a coating film on the front plate of the display screen 2. Of course, both the display screen 2 and the front plate may be coated. The present invention also provides CR
In addition to display devices having T, OA such as liquid crystal displays, plasma displays, light emitting diode displays, etc.
It is widely applied to equipment.

[0045]

EXAMPLES An example of a method of manufacturing an antireflection filter will be specifically described below.

(1) Preparation of Antireflection Film A 100 μm thick transparent polyethylene terephthalate (PET) film was used as a substrate. On one side of this polyethylene terephthalate (PET), a hard coat layer and an acrylic resin layer for ensuring surface hardness are formed in advance to a thickness of 2 μm.

The hard coat treatment here is generally to coat an acrylic crosslinkable resin raw material and crosslink and cure it with ultraviolet rays or electron beams.
The epoxy resin raw material is applied and heat-cured.

(2) Preparation of coating composition containing perfluoropolyether having polar groups at the terminals 0.4 parts of perfluoropolyether having terminal polar groups (number average molecular weight 2000, compound in the table) and hexane 3
After 80 parts and 20 parts of alcohol were added and mixed to form a uniform solution, the solution was filtered with a membrane filter to obtain a coating composition.

(3) Coating and Drying The surface of the antireflection film obtained in (1) above is dip coated with the coating composition prepared in (2) at a pulling rate of 5 cm / min to obtain an optical article having antireflection properties. Obtained.

(4) Performance Evaluation The performance of the obtained optical article was tested according to the following method. In addition, as comparative examples, tests were carried out for those not coated with perfluoropolyether having a polar group at the terminal and those coated with a fluororesin. The results are shown in Table 2.
Shown in

(A) Contamination resistance test 5 ml of tap water was dropped on the filter surface, allowed to stand for 48 hours in a room temperature atmosphere, and the remaining state of scales when observed with a cloth was observed. 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 slipperiness The scratching condition when scratching the surface with a pencil was evaluated. The determination method is as follows. In Tables 1 and 2 described later, ◯, Δ, and x represent the following meanings, respectively. ○
= No scratches; Δ = Scratch when strengthened; × = Scratch after weakening (c) Difficulty in sticking to the hand The difficulty in sticking to the plaque was visually evaluated.

◯ = not good even with stains; Δ = sticking but easy to remove; × = conspicuous after attaching Examples 2 to 10 Examples 2 to 10 are lubrication of the coating composition in Example 1. The same procedure as in Example 1 was performed except that Lubricants 2 to 10 were used instead of Agent 1. Table 1 shows the molecular structures of various lubricants and the experimental results.

[0054]

[Table 1]

Comparative Examples 1 to 5 Comparative Examples 1 to 5 were prepared in order to compare the above Examples 1 and 2 to which the present invention was applied with the stain resistance, the slip resistance, and the resistance to the touch. Then, comparative experiments were carried out on both of these examples and comparative examples. The results are shown in Table 2.

[0056]

[Table 2]

Here, Comparative Example 1 uses no surface coating agent, Comparative Example 2 uses polytetrafluoroethylene as the surface coating agent, and Comparative Example 3 uses polyvinyl chloride as the surface coating agent. Derin fluoride was used, Comparative Example 4 uses tetrafluoroethylene-ethylene copolymer as the surface coating agent, and Comparative Example 5 uses chlorotrifluoroethylene-ethylene copolymer as the surface coating agent. It is one that uses coalescence.

As is apparent from Table 1, Examples 1 to 1
At 0, the products using perfluoropolyether having a polar group at the terminal all showed excellent results in terms of stain resistance, slip resistance, and hard to handle.

On the other hand, in Comparative Examples 1 to 5, it was not possible to obtain the ones satisfying all of the stain resistance, the slip resistance, and the hardness of hand plaque.

Therefore, the surface film provided on the plastic substrate is a single-layer or multi-layer antireflection film mainly made of an ultraviolet curable resin, and a perfluoropolyether having a polar group at the end is added to the surface of the antireflection filter. By coating it on, it has the effect of preventing contamination such as hand marks and water marks.
Moreover, due to the effect of the lubricant, it becomes possible to provide an antireflection filter and a display device which are excellent in slipperiness and abrasion resistance.

[0061]

As is apparent from the above description, the antireflection filter according to the present invention is provided with a single-layer or multi-layer antireflection film mainly composed of an ultraviolet curable resin on a transparent substrate. Since the membrane holds perfluoropolyether having a polar group at the terminal, the following effects can be obtained.

(1) Fingerprints are less likely to be soiled by hand stains and are less noticeable.

(2) It can be easily removed even if it is dried by depositing water stains and the like.

(3) The surface slip property is good.

(4) It is hard to get dirt such as dust and is easy to use.

(5) It has durability against friction or abrasion.

On the other hand, the display device according to the present invention has the coating film formed on the surface of the display screen and / or the front plate thereof, and therefore, the respective effects (1) to (5) can be obtained. To be

[Brief description of drawings]

FIG. 1 is a diagram showing a configuration example of a display device to which the present invention is applied.

[Explanation of symbols]

 1 display device 1a CRT (cathode ray tube) 2 panel section (display screen)

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tomio Kobayashi 6-735 Kitashinagawa, Shinagawa-ku, Tokyo Sony Corporation

Claims (6)

[Claims] 1. A single-layer or multi-layer antireflection film mainly comprising an ultraviolet curable resin is provided on a transparent substrate, and the antireflection film holds perfluoropolyether having a polar group at the terminal. Anti-reflection filter characterized by. 2. The antireflection filter according to claim 1, wherein the surface of the antireflection film is coated with perfluoropolyether having a polar group at the terminal. 3. The antireflection filter according to claim 1, wherein perfluoropolyether having a polar group at the terminal is internally added to the antireflection film. 4. A single-layer or multi-layer antireflection film mainly composed of an ultraviolet curable resin is provided on the surface of a display screen and / or its front plate, and this antireflection film has perfluoropolyether having a polar group at the terminal. A display device characterized by being held. 5. The display device according to claim 4, wherein the surface of the antireflection film is coated with perfluoropolyether having a polar group at the terminal. 6. The display device according to claim 4, wherein a perfluoropolyether having a polar group at the terminal is internally added to the antireflection film.