JPH09288202A - Antireflection film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To greatly improve the weakness of an antireflection film formed of an amorphous fluororesin, i.e., the wear resistance and flaw resistance thereof and to provide the antireflection film which sufficiently withstands the use with the full-surface panel of a CRT display etc., by providing the surface of the antireflection film with an overcoating layer of a thickness at which the antireflection performance is not affected at all. SOLUTION: This film is formed of a plastic substrate 1 which has light transparency, a high-refractive index layer 2 which is consists essentially of metal alkoxide and colloidal metal oxide and/or metal halide applied on this substrate 1 and has antistatic performance, an antireflection layer 3 which consists of an amorphous fluororesin of a refractive index (nd) of <=1.36 applied on this high-refractive index layer 2 and a coating layer 4 which consists essentially of the org. polysiloxane applied on this antireflection film and has surface activatability. The excellent wear resistance, flaw resistance, adhesion property and light transparency are obtd. by forming such film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection film for producing a plastic material having excellent light transmitting property.

[0002]

2. Description of the Related Art A plastic material having a light-transmitting property is also used for an optical filter, an optical lens, etc., but since it has a refractive index in the range of 1.45 to 1.60, it is completely transparent. However, it causes about 7 to 10% optical reflection.

This light ray reflection causes a decrease in light ray transmittance, a ghost phenomenon due to reflection, and a difficulty in seeing an object through the light.

As a method of removing or reducing this reflection, a λ / 4 film such as magnesium fluoride or silica having a low refractive index or a λ / 4 film such as titanium oxide or zirconium oxide having a high refractive index is formed by a vacuum deposition method. Multilayer coats have been used in combination with.

For coating a small object such as an optical lens, the film quality and the productivity are good, but C
For a large plate such as an RT-display full-scale panel, the number of charges per one time into the vapor deposition kettle becomes extremely small, which causes a problem of high cost.

On the other hand, as another method, a method of obtaining an antireflection film by dissolving a solvent-soluble amorphous fluororesin in a suitable solvent and forming a film by a dipping method is also known. According to this method, it is relatively easy to coat a large plate, but the hardness of the resin itself is poor, and a λ / 4 wavelength film, that is, 100 to 200.
Since a film having a thickness of nm is easily peeled off, it is impossible to use the film exposed to the outside. In addition, since the fluororesin has the characteristics of strong water repellency, strong oil repellency, and electric insulation, there is a problem in that it is easily charged with static electricity and easily adsorbs dust.
However, the biggest problem is that the antireflection performance is slightly inferior to the vacuum deposition method.

[0007]

SUMMARY OF THE INVENTION The present invention provides an antireflection film formed of an amorphous fluororesin with an overcoat layer having a thickness that does not affect the antireflection performance. The present invention provides an antireflection film that significantly improves the weakness, that is, the abrasion resistance and the scratch resistance, and can withstand the use of CRT display full-scale panels and the like.

A combination of a metal alkoxide and a colloidal metal oxide and / or an inorganic precursor thereof is used as an under layer of an antireflection film formed of an amorphous fluororesin, and an epoxy resin is added if necessary. By providing one or two high refractive index layers in combination, an antireflection film having an antistatic effect is provided without impairing the strong water repellency and strong oil repellency that are the characteristics of fluororesins, and
The entire visible region (4
It is possible to achieve low reflectance in the range of 0 to 700 nm), and an object thereof is to provide an antireflection film similar to vacuum deposition by a film forming method by dipping using a sol-gel method.

[0009]

According to the present invention, a light-transmissive plastic substrate, a metal alkoxide and a colloidal metal oxide and / or a metal halide coated on the substrate, and optionally an epoxy resin. And a high refractive index layer having an antistatic property as a main component, an antireflection layer of an amorphous fluororesin having a refractive index (nd) of 1.36 or less coated on the high refractive index layer, and the antireflection Wear resistance, scratch resistance, adhesion and translucency, which is characterized by comprising a coating layer containing a fluorine-based material having a surface-active ability and having organopolysiloxane as a main component coated on the film. An excellent antireflection film is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In FIG. 1 showing an example of an antireflection film of the present invention, the antireflection film is a transparent plastic substrate 1, a high refractive index layer 2 and a high refractive index layer provided on the substrate. The antireflection layer 3 is provided on the upper side and the coat layer 4 is provided on the antireflection layer.

In FIG. 2 showing another example of the antireflection film of the present invention, the antireflection film is a transparent plastic substrate 1, a first high refractive index layer 2a provided on the substrate, and a first high refractive index layer 2a. A second high refractive index layer 2b provided on the high refractive index layer of
The antireflection layer 3 is provided on the second high refractive index layer, and the coating layer 4 is provided on the antireflection layer.

In the present invention, the high refractive index layers 2, 2a, 2b, etc. provided on the plastic substrate are mainly composed of a metal alkoxide, a colloidal metal oxide and / or a metal halide, and, if necessary, an epoxy resin. The high refractive index layer also has antistatic performance.

The antireflection layer 3 has a refractive index (nd)
An amorphous fluororesin of 1.36 or less is used, and as the coating layer 4, a composition containing an organic polysiloxane as a main component and a fluorine-based material having a surface-active ability is used.

According to the present invention, a metal alkoxide, a colloidal metal oxide and / or a metal halide, and optionally an epoxy resin as a main component are provided under the antireflection layer made of the above amorphous fluororesin. By providing a high refractive index layer to
It is possible to impart antistatic performance and prevent the tendency of adsorbing dust and the like, which is a drawback of the amorphous fluororesin, without impairing oil repellency and stain resistance.

Further, since the high-refractive index layer is provided under the low-refractive-index antireflection layer, the reflectance of light rays can be suppressed to a further low level, which is exceptional as an antireflection film by the sol-gel coating method. Excellent antireflection performance is obtained.

Furthermore, not only a strong film can be formed by combining a colloidal metal oxide and / or a metal halide with a metal alkoxide, but also by combining an epoxy resin, if necessary.
Adhesion to various plastic substrates has improved, and the higher refractive index of the lower layer can be adjusted freely, making it possible to create multilayer antireflection coatings compatible with various transparent plastic substrates.

The low refractive index of the amorphous fluororesin effective as an antireflection coating is due to the large content of fluorine atoms in the molecule. However, the presence of this fluorine atom makes the surface of the film extremely water and oil repellent, and even if a hard coating agent or similar coating material is formed on it, it will be repelled, resulting in polka dots. Film cannot be formed. In addition, the water repellency is very high, which makes it easy to be charged with static electricity and easily adsorb dust in the air.

However, as a low molecular weight copolymer of (meth) acrylate having a perfluoroalkyl group and ethylene glycol (meth) acrylate, a material having hydrophilic and fluorophilic surface-active ability is fluorine. It showed complete wettability on the resin surface, and by adding these, it became possible to coat the surface of the fluororesin with the organic polysiloxane material.

Moreover, due to the characteristics of the organic polysiloxane material, the slipperiness of the surface is greatly improved, scratch resistance and abrasion resistance are obtained, and the film which is the first difficulty of the amorphous fluororesin is formed. I was able to improve my weakness. Furthermore, it has been found that water resistance and alcohol resistance can be obtained by using a polysiloxane having a perfluoroalkyl group.

The plastic substrate 1 is not particularly limited, but from the viewpoint of optical characteristics, polymethylmethacrylate, polycarbonate, polyallyldiglycolcarbonate, polystyrene or the like can be used, which is transparent or colored with an oil-soluble dye. Is used. For the purpose of improving the familiarity and adhesion between the fluororesin and the substrate, it is possible to use a primer-coated product in the present invention.

In the present invention, colloidal metal oxides used as a component of the high refractive index layer 2 and imparting an antistatic effect to the antireflection film due to its hydrophilicity include silica sol, titania sol, alumina sol, zirconium oxide sol, Antimony oxide sol and the like can be mentioned, but in consideration of the adjustment of the refractive index, the dispersibility in an organic solvent, the stability of the coating liquid, and further the wettability and the adhesiveness with the plastic substrate and the amorphous fluororesin, Silica sol, alumina sol and antimony oxide sol are preferred. Further, these colloidal metal oxides can be easily produced by hydrolyzing a metal chloride in an organic solvent.

Further, in the present invention, as the metal halide used as a component of the high refractive index layer 2 for the purpose of increasing the refractive index, metal chloride or metal bromide is used, more specifically, Antimony trichloride, zirconium tetrachloride, bismuth trichloride, titanium tetrabromide, antimony tribromide and the like can be mentioned, but considering the high refractive index, dispersibility in an organic solvent, and stability of the coating liquid, Antimony trichloride, bismuth trichloride and antimony tribromide are preferred.

The metal alkoxide used as a binder for adhering these colloidal metal oxides to a plastic substrate and an amorphous fluororesin is represented by the following formula (1) M (OR) _m (1) In the formula, M represents a metal, R represents a hydrocarbon group having 1 to 5 carbon atoms, and m represents a valence (3 or 4) of the metal M.

As the metal M, aluminum, titanium,
Zirconium, tin, etc. are suitable. Specific examples of the metal alkoxide include aluminum ethoxide, aluminum isopropoxide, aluminum butoxide, aluminum t-butoxide, tin t-butoxide,
Titanium methoxide, titanium ethoxide, titanium n-
Propoxide, titanium isopropoxide, titanium n
-Butoxide, titanium isobutoxide, zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and the like can be mentioned.

These metal alkoxides are very unstable substances because they are characterized by rapidly reacting with water to form a precipitate. By reacting these with β-diketones to form chelate compounds, they can be used as stable coating compositions.

Specific examples of the β-diketone include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, acetylacetone, and the like, most preferably ethyl acetoacetate. . β-diketone is a metal alkoxide,
It is used in a molar ratio of 0.5 to 2.0 mol, more preferably 0.8 to 1.2 mol.

Further, a compound obtained by chelating a metal alkoxide may be used after being hydrolyzed. Mineral acids such as hydrochloric acid, nitric acid and sulfuric acid, or organic acids such as acetic acid and oxalic acid may be used as an aqueous solution for hydrolysis.

In the hydrolysis, the acidic aqueous solution used is preferably 0.5 mol to 2.0 mol, and more preferably 0.5 mol to 1.0 mol, based on 1 mol of the metal alkoxide chelate compound. At this time, if the water content is large, the stability of the coating liquid becomes poor.

The high-refractive index layer formed of only the chelate compound of metal alkoxide has a weak film strength, so that it is somewhat difficult to use it as an optical thin film by itself. Further, it is difficult to increase the film thickness only with the chelate compound of metal alkoxide, and in order to compensate for the drawback and to impart an antistatic effect due to its hydrophilic property, a colloidal metal oxide is added. Further, by adding a metal halide, a higher refractive index can be achieved. Furthermore, by adding an epoxy resin, it is possible to prevent cracks due to thickening of the film and to ensure adhesion with a plastic substrate.

An organic solvent can be used as a solvent in the coating composition for a high refractive index layer in the present invention. The organic solvent is not particularly limited as long as it is compatible with the metal alkoxide and colloidal metal oxide. Examples of the solvent include alcohols, ketones, esters, aromatic hydrocarbons and the like. Specific examples include methanol, isopropanol, methyl ethyl ketone, isobutyl acetate, toluene and the like. Using these solvents, the concentration is adjusted so that the total solid content concentration is 1 to 30% by weight based on the total weight.

As a coating method, a dipping method which can easily form a thin film can be preferably used. Generally, the coated thin film is preferably heat-treated at a temperature of about 70 to 140 ° C.

The perfluoro amorphous fluororesin having a refractive index n ₃ of 1.36 or less may be any perfluoro amorphous fluororesin having a ring structure in its main chain.
As a suitable example of this perfluoro amorphous fluororesin,
The following formula (2) in the main chain

[0033]

Embedded image R; perfluoroalkylene group p; number of zero or one q; repeating unit of number of zero or one, the following formula (3)

[0034]

Embedded image R: a repeating unit of a perfluoroalkylene group and / or the following formula (4)

[0035]

Embedded image R: A perfluorofluorine resin containing at least one repeating unit of a perfluoroalkylene group.

In this perfluorofluororesin, even if all of the repeating units are composed of the above cyclic repeating units, or a part of the repeating units is composed of the cyclic repeating units and the other part of the repeating units is linear. It may consist of perfluoromonomer units.

The above-mentioned perfluoro amorphous fluororesin can be obtained by a method known per se, for example, cyclopolymerization of perfluoroether monomer having double bonds at both ends, or cyclic perfluoromonomer. It can be obtained by radical polymerization. A copolymer can be obtained by coexisting with another perfluoromonomer during these polymerizations.

The perfluoroether monomer having double bonds at both ends is represented by the following formula (5): CF ₂ ═CF-(— CF ₂ —) _n —O — (— CF ₂ —) _m —CF═CF ₂ (5) (n = 1 to 5, m = 1 to 5, n + m = 1 to 6)
Examples thereof include perfluoroallyl vinyl ether, perfluorodiallyl ether, perfluorobutenyl vinyl ether, perfluorobutenyl allyl vinyl ether, perfluorodibutenyl ether and the like.

Another type of perfluoroether monomer having double bonds at both ends is represented by the following formula (6) CF ₂ ═CFO—R—O—CF═CF ₂ (6) R; perfluoroalkylene group The perfluoroalkylene glycol divinyl ether represented by can be mentioned, and examples thereof include perfluoroethylene glycol divinyl ether and perfluorotetramethylene glycol divinyl ether.

On the other hand, as the cyclic perfluoromonomer,
For example, the following formula (7)

[0041]

Embedded image R: a monomer represented by a perfluoroalkylene group, particularly perfluoro-2,2-dimethyl-1,3-dioxole.

Examples of other monomers used for the copolymerization include tetrafluoroethylene, hexafluoropropylene, perfluorovinylpropyl ether, perfluoroallyl butyl ether, perfluorodivinyl ethyl ether, perfluorovinyl allyl ether and the like. It

Suitable examples of amorphous fluororesins include, but are not limited to, cyclic ethers and perfluoro-2,2-.
Examples thereof include copolymers with dimethyl-1,3-dioxole, copolymers of tetrafluoroethylene and cyclic perfluoroether, and cyclized copolymers of perfluorovinylallyl ether.

As concretely available ones, "Teflon AF" manufactured by Mitsui DuPont Fluorochemical Co., Ltd., "Cytop" manufactured by Asahi Glass Co., Ltd., "Florard FC-722" manufactured by Sumitomo 3M Ltd., DuPont "Teflon AF
1600 "and the like.

As the solvent, perfluorooctane, perfluorohydrofuran, etc. have a good balance in volatilization speed, and the above resin can be dissolved at a concentration of 1 to 5% to prepare a coating solution.

In the present invention, the organopolysiloxane material used as the overcoat layer and imparting abrasion resistance and scratch resistance includes silanol groups, alkoxy groups, acetyl groups, phenyl groups, polyether groups, and peroxy groups. Examples thereof include methylpolysiloxane or dimethylpolysiloxane having a fluoroalkyl group or the like in the side chain.

Functional groups such as silanol groups, alkoxy groups (methoxy groups, ethoxy groups, etc.), acetyl groups, etc. in polysiloxane impart crosslinkability to polysiloxane, while phenyl groups cause heat resistance to polysiloxane. It is effective for imparting properties and durability, the polyether group imparts a surface-active effect, and the perfluoroalkyl group imparts chemical resistance and water resistance. The polysiloxane used is preferably one having crosslinking reactivity.

Specifically, as the available organosiloxanes, silicone oil BY16-817 (silanol group) manufactured by Toray Dow Corning Co., Ltd., SH
Examples thereof include 510 (phenyl group), SF8421 (polyether group), FS1265 (fluoroalkyl group), but the present invention is not limited to this example.

Further, as the additive for lowering the surface tension or interfacial tension of the organosiloxane material and coating it on the amorphous fluororesin, any one of the fluorocarbon materials having the surface active ability is used. Preferred examples include fluorinated alkyl esters having a perfluoro group and a hydrophilic group as side chains, and fluorinated aliphatic polymer esters having a perfluoro group and a lipophilic group as side chains.

Fluorinated alkyl esters that can be specifically obtained include "Florard FC430" and "Florard FC43" manufactured by Sumitomo 3M Limited.
1 ", and examples of the fluorinated aliphatic polymer ester include" Florard FC740 "manufactured by Sumitomo 3M Limited. However, the present invention is not limited to this material.

The amount of the fluorine-based material having surface active ability used is not particularly limited as long as it is sufficient to ensure sufficient wetting on the amorphous fluororesin film, but generally, an organic siloxane-based material is used. As a standard, 0.5 to 10.0% by weight, preferably 1.0 to 3.0% by weight may be used.

The organic siloxane-based material and the fluorine-based material having a surface active ability are preferably dissolved in an organic solvent and used for coating in the form of a solution. As the organic solvent, a solvent that does not dissolve or soften the amorphous fluororesin is preferable, and an easily volatile solvent such as an alcohol solvent, an ester solvent, or a mixture thereof is used. The solid content concentration in the solution is preferably about 0.05 to 3.0% by weight.

In this case, a catalyst such as dibutyltin laurate or tin octoate may be used in a catalytic amount in order to accelerate the curing of the organosiloxane material.

As the resin having a high refractive index, a polystyrene resin, a polycarbonate resin, an aromatic polyester resin, a polysulfone resin, a polyarylate resin, a phenoxy resin, an epoxy resin and chlorides or bromides thereof, etc. Can be given. Of these resins,
A phenoxy resin or an epoxy resin is excellent in adhesiveness to a plastic substrate and is also preferable as a binder for dispersing a metal oxide.

Epoxy resins are resins based on epoxy resins derived from epichlorhydrin and polyhydric phenols or polyhydric alcohols, and include epoxy resin itself and carboxyl group terminal. A modified epoxy resin such as an epoxy ester, epoxy vinyl, epoxy amide, or epoxy urethane formed by modifying a hydroxyl group terminal, an amide group terminal, or an isocyanate group terminal is used. The phenoxy resin is similar to the epoxy resin in that it is derived from epichlorohydrin and polyhydric phenol (bisphenol), but it has a much higher molecular weight and is more thermoplastic. It is different from resin.

Specific available epoxy resins for coating materials include "Epiclon 85" manufactured by Dainippon Ink and Chemicals Co., Ltd.
0 ", manufactured by Toray Dow Corning Co., Ltd., silicone resin" SR2410 "," SR2411 "," SR211 "
5 "," Kaneka Zemlac YC3 "manufactured by Kaneka Fuchi Chemical Co., Ltd.
315 ”,“ YC3835 ”and the like. Of course, the invention is not limited to this example.

In the present invention, the film thickness of the high refractive index layer is 50.
˜400 nm, the film thickness of the amorphous fluororesin antireflection layer is 50 to 200 nm, and the film thickness of the coating layer containing organic polysiloxane as a main component is 200 nm or less, preferably 100 n.
m or less. When the high refractive index layer is provided in multiple layers, the thickness of the first high refractive index layer is 50 to
600 nm, the thickness of the second high refraction layer is 100 to 40
It is preferably 0 nm.

By controlling the refractive index and thickness of each layer, the antireflection performance can be maximized. The refractive index of the plastic substrate is n _S , the refractive index of the first high refractive index layer is n ₃ , and its thickness is d ₃ (unit: nm),
When the refractive index of the second high refractive index layer is n ₂ , its thickness is d ₂ , the refractive index of the antireflection layer is n ₁ , and its thickness is d ₁ ,
The following layer structure is preferable.

In the case of the antireflection film of FIG. 1, the following formulas (8) and (9) n ₃ · n _S ² = n ₁ ² (8) and n ₁ · d ₁ = n ₃ · d ₃ = λ / 4 It is preferable to provide the high refractive index layer and the antireflection layer so as to substantially satisfy (9).

Next, in the case of the antireflection film of FIG. 2, the following formulas (10) and (11) n ₁ · n ₃ = n ₂ · (n ₀ · n _s ) ^1/2 (10) n ₀ is the refractive index of air, and n ₁ · d ₁ = n ₂ · d ₂ = n ₃ · d ₃ = λ / 4 (11) It is preferable to provide an antireflection layer.

In the case of the antireflection film shown in FIG. 2, the following equations (12) and (13) n ₃ ² · n _S = n ₀ · n ₁ ² ··· (12) and n ₁ · d ₁ = n _{2 · d 2/2 = n 3} · d 3 = λ / 4 ·· (13) so as to substantially satisfy, can be provided a high refractive index layer and an antireflection layer.

[0062] When the antireflection film of Figure 2, the following equation (14) and ^{_{(15) n 3 2 · n}} S = n 0 · n 1 2 ‥ (14) and n ₁ · d _{1/3 = N 2 · d 2/2} = n 3 · d 3 = λ / 4 ‥ (15) so as to substantially satisfy, can be provided a high refractive index layer and an antireflection layer.

[0063]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described with reference to the following examples.

Amorphous fluororesin coating liquid (coating liquid 1)
Preparation of Teflon AF-1600 (manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.) at a concentration of 2%, which is a mixed solvent of perfluorooctane and perfluorohydrofuran with a boiling point of 102 ° C., Fluorinert FC-75 (Sumitomo 3M Limited). )) To prepare a coating liquid (coating liquid 1).

Preparation of coating liquid for high refractive index layer (coating liquid 2) of the first layer 1.8 wt% of aluminum sol 10 (manufactured by Kawaken Fine Chemical Co., Ltd.), titanium tetrabutoxide monomer (Wako Pure Chemical Industries ( (Manufactured by Co., Ltd.) is 4.2% by weight, ethyl acetoacetate is 3% by weight, and ethyl cellosolve is 10% by weight, and is prepared using methanol (coating solution 2).

Preparation of coating liquid for high refractive index layer (coating liquid 3) of the second layer 0.7% by weight of aluminum sol 10 (manufactured by Kawaken Fine Chemical Co., Ltd.), titanium tetrabutoxide monomer (Wako Pure Chemical Industries ( (Manufactured by K.K.) of 6.3% by weight, ethyl acetoacetate of 3% by weight, and ethyl cellosolve of 10% by weight are prepared using methanol (coating solution 3).

Preparation of coating liquid for high refractive index layer (coating liquid 4) of the first layer Titanium tetrabutoxide monomer (Wako Pure Chemical Industries, Ltd.)
(Manufactured by Dai Nippon Ink Chemical Co., Ltd.), 6.0% by weight, Epicron 850 (manufactured by Dainippon Ink and Chemicals, Inc.) 2.0% by weight, ethyl acetoacetate 2.5% by weight, Epicron B-570 (Dainippon Ink and Chemicals ( Co., Ltd.) to prepare 0.2% by weight of isobutyl acetate (coating solution 4).

Preparation of Coating Solution for High Refractive Index Layer (Coating Solution 5) of Second Layer Antimony trichloride (III) was dissolved in ethanol to a concentration of 1.5% by weight, and 0.05N hydrochloric acid was used. And hydrolyze to prepare antimony sol (Preparation liquid 1).
Titanium tetrabutoxide monomer (Wako Pure Chemical Industries, Ltd.)
3.0% by weight, ethyl acetoacetate 3.0% by weight
Is prepared using isopropyl alcohol (Preparation liquid 2). Preparation liquid 1 and preparation liquid 2 are mixed in equal weights (coating liquid 5).

Preparation of Overcoat Liquid (Coating Liquid 6) Isopropyl alcohol was added so that dimethyl silicone oil "BY16-817" (manufactured by Toray Down Corning Co., Ltd.) having silanol groups at both ends was 0.2% by weight. And dibutyl acetate are diluted with a mixed solvent having a weight ratio of 2: 3, and 3% by weight of polysiloxane of fluorinated alkyl ester "Florard FC430" (manufactured by Sumitomo 3M Limited) is added (Coating liquid 6 ).

Example 1 A coating solution 2 was pulled up at a speed of 200 mm / mi onto a polymethylmethacrylate cast substrate having a thickness of 2 mm which had been subjected to a primer treatment with a silane coupling agent in advance.
The film was formed by n. Next, the coating liquid 1 is pulled up at a speed of 200
An antireflection film was formed at mm / min. Further, the coating liquid 6 was overcoated at 100 mm / min. This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having antireflection performance. The surface reflectance was 0.1% T (measurement wavelength: 550 nm), the pencil hardness was 3H, and no scratches were formed even when strongly rubbed with a nail. Further, the surface specific resistance value was 2 × 10 ¹¹ Ω · cm, and it had an antistatic effect. The refractive index and the thickness of each layer substantially satisfied the expressions (8) and (9).

Example 2 A coating liquid 2 was pulled up to a polymethylmethacrylate cast substrate having a thickness of 2 mm, which had been preliminarily treated with a silane coupling agent, at a speed of 200 mm / mi.
The film was formed by n. Next, the coating liquid 3 is pulled up at a speed of 120
The film was formed at mm / min. Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min. Further, as in Example 1, the coating liquid 6 was applied at 100 mm / min.
I overcoated it. This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having an antireflection function. The surface reflectance is 0.1% T (550 nm) and is 400 to
The average surface reflectance at 700 nm was 1.0% T, which showed excellent antireflection performance in the entire visible region. Pencil hardness is 3
With H, even if it was rubbed strongly with a nail, no scratch was given. Also,
This surface specific resistance value was 5 × 10 ¹¹ Ω and had an antistatic effect. The refractive index and the thickness of each layer are calculated by the formula (1
0) and (11) were substantially satisfied.

Example 3 A coating liquid 2 was pulled up at a speed of 200 mm / mi onto a polymethylmethacrylate cast substrate having a thickness of 2 mm, which had been subjected to a primer treatment with a silane coupling agent in advance.
The film was formed by n. Next, the coating liquid 3 is pulled up at a speed of 200
It was coated twice at mm / min. Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min. Further, as in Example 1, the coating liquid 6 was applied at 100 mm /
Overcoated with min. This substrate is 100 ℃, 1
After heat treatment for a time, a substrate having antireflection performance was obtained. The surface reflectance is 0.2% T (measurement wavelength 500 nm), and the average surface reflectance at 400 to 700 nm is 0.7.
% T, which showed excellent antireflection performance in the entire visible region. The pencil hardness was 3H, and even if it was strongly rubbed with a nail, no scratch was given. The surface resistivity was 5 × 10 ¹⁰ Ω, which had an antistatic effect. The refractive index and the thickness of each layer substantially satisfy the expressions (12) and (13).

Example 4 A coating liquid 2 was pulled up at a speed of 200 mm / mi onto a polymethylmethacrylate cast substrate having a thickness of 2 mm, which had been subjected to a primer treatment with a silane coupling agent in advance.
n coating 3 times. Next, the coating liquid 3 was coated twice at a pulling rate of 200 mm / min. Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min. Further, as in Example 1, 100 parts of the coating liquid 6 was added.
Overcoating was performed at mm / min. 100 this board
Heat treatment was performed at 1 ° C. for 1 hour to obtain a substrate having antireflection performance. Surface reflectance is 0.2% T (measurement wavelength 550n
m), and the average surface reflectance at 400 to 700 nm was 0.7% T, which showed excellent antireflection performance in the entire visible region. The pencil hardness was 3H, and even if it was strongly rubbed with a nail, no scratch was given. The surface resistivity is 5 × 10 ^10.
It was Ω · cm and had an excellent antistatic effect. The refractive index and the thickness of each layer substantially satisfy the expressions (14) and (15).

Example 5 Primer treatment with a silane coupling agent in advance
2mm thick polymethylmethacrylate cast
The coating liquid 4 is pulled up to the substrate and the speed is 200 mm / mi.
The film was formed by n. Next, the coating liquid 1 is pulled up at a speed of 200
An antireflection film was formed at mm / min. Furthermore, coating liquid
6 was overcoated at 100 mm / min. This group
The plate is heat-treated at 100 ° C for 1 hour for anti-reflection performance.
A substrate having is obtained. Surface reflectance is 0.1% T (measurement wavelength
550 nm), the pencil hardness is 4H, and it is rubbed strongly with a nail.
But it didn't hurt at all. Also, this surface resistivity
Is 5 × 10 ¹²Ω · cm, has a slight antistatic effect
I was The refractive index and the thickness of each layer are expressed by the formula (8) and
(9) was substantially satisfied.

Example 6 The coating liquid 4 was pulled up to a polymethylmethacrylate cast substrate having a thickness of 2 mm, which had been preliminarily treated with a silane coupling agent, at a speed of 200 mm / mi.
The film was formed by n. Next, the coating liquid 5 is pulled up at a speed of 120
The film was formed at mm / min. Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min. Further, as in Example 1, the coating liquid 6 was applied at 100 mm / min.
I overcoated it. This substrate was heat-treated at 100 ° C. for 1 hour to obtain a substrate having an antireflection function. The surface reflectance is 0.1% T (measurement wavelength 550 nm),
The average surface reflectance at 400 to 700 nm was 1.0% T, which showed excellent antireflection performance in the entire visible region. The pencil hardness was 3H, and even if it was strongly rubbed with a nail, no scratch was given. The surface resistivity is 5 × 10 ¹¹ Ω,
It had an antistatic effect. The refractive index and the thickness of each layer substantially satisfy the expressions (10) and (11).

Example 7 A coating solution 4 was pulled up at a speed of 200 mm / mi onto a polymethylmethacrylate cast substrate having a thickness of 2 mm, which had been subjected to a primer treatment with a silane coupling agent in advance.
The film was formed by n. Next, the coating liquid 5 is pulled up at a speed of 200
It was coated twice at mm / min. Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min. Further, as in Example 1, the coating liquid 6 was applied at 100 mm /
Overcoated with min. This substrate is 100 ℃, 1
After heat treatment for a time, a substrate having antireflection performance was obtained. The surface reflectance is 0.2% T (measurement wavelength 500 nm), and the average surface reflectance at 400 to 700 nm is 0.7.
% T, which showed excellent antireflection performance in the entire visible region. The pencil hardness was 3H, and even if it was strongly rubbed with a nail, no scratch was given. The surface resistivity was 5 × 10 ¹¹ Ω, which had an antistatic effect. The refractive index and the thickness of each layer substantially satisfy the expressions (12) and (13).

Example 8 A coating solution 4 was pulled up at a speed of 200 mm / mi onto a polymethylmethacrylate cast substrate having a thickness of 2 mm, which had been subjected to a primer treatment with a silane coupling agent in advance.
n coating 3 times. Next, the coating liquid 5 was coated twice at a pulling rate of 200 mm / min. Next, the coating liquid 1 was pulled up to form an antireflection film at a speed of 200 mm / min. Further, as in Example 1, 100 parts of the coating liquid 6 was added.
Overcoating was performed at mm / min. 100 this board
Heat treatment was performed at 1 ° C. for 1 hour to obtain a substrate having antireflection performance. Surface reflectance is 0.2% T (measurement wavelength 550n
m), and the average surface reflectance at 400 to 700 nm was 0.7% T, which showed excellent antireflection performance in the entire visible region. The pencil hardness was 3H, and even if it was strongly rubbed with a nail, no scratch was given. The surface resistivity is 5 × 10 ^10.
It was Ω · cm and had an excellent antistatic effect. The refractive index and the thickness of each layer substantially satisfy the expressions (14) and (15).

Comparative Example 1 A coating solution 1 was pulled up to a polymethylmethacrylate cast substrate having a thickness of 2 mm, which had been subjected to a primer treatment with a silane coupling agent in advance, at a speed of 200 mm / mi.
A single-layer antireflection film was formed by n. Next, coat liquid 6
Overcoating was performed at 00 mm / min. This board is
Heat treatment was performed at 00 ° C. for 1 hour to obtain a substrate having antireflection performance. The surface reflectance was 1.2% T (550 nm), the pencil hardness was 4H, and no scratch was given even when strongly rubbed with a nail. The surface resistivity was 10 ¹⁵ Ω · cm or more, and there was no antistatic effect.

[0079]

According to the present invention, one or two high refractive index layers containing a colloidal metal oxide are provided as an under layer of an antireflection film using an amorphous fluororesin, so that all visible light can be obtained. It is possible to provide an antireflection film having a constant and excellent antireflection performance in a region (400 to 700 nm) and an excellent antistatic performance. Furthermore, by providing an overcoat layer with a thickness that does not affect the antireflection performance at all, the weakness of the film strength, that is, abrasion resistance and scratch resistance, is greatly improved, and it is comparable to the inorganic vapor-deposited antireflection film. It is possible to provide an antireflection film that can sufficiently withstand use of a full-scale CRT display panel and the like.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of an antireflection film of the present invention.

FIG. 2 is a cross-sectional view showing another example of the antireflection film of the present invention.

[Explanation of symbols]

 1 translucent plastic substrate 2, 2a, 2b high refractive index layer 3 antireflection layer 4 coating layer

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location B32B 27/30 B32B 27/30 D C08J 7/04 CEW C08J 7/04 CEWK

Claims (10)

[Claims] 1. A light-transmissive plastic substrate, a high-refractive-index layer containing a metal alkoxide and a colloidal metal oxide and / or a metal halide coated on the substrate as main components and having antistatic properties, and An antireflection layer made of an amorphous fluororesin having a refractive index (nd) of 1.36 or less coated on the high refractive index layer, and an organic polysiloxane coated on the antireflection film as a main component and having a surface active ability. An antireflection film excellent in abrasion resistance, scratch resistance, adhesion and light transmission, characterized by comprising a coating layer containing a fluorine-based material having 2. The amorphous fluororesin is a copolymer of cyclic ether and perfluoro-2,2-dimethyl-1,3-dioxole or a copolymer of tetrafluoroethylene and cyclic perfluoroether or perfluorovinyl. The antireflection film according to claim 1, which is a cyclized copolymer with an allyl ether. 3. The high refractive index layer comprises a metal alkoxide having a high refractive index such as silane alkoxide, aluminum alkoxide, titanium alkoxide, zirconium alkoxide, silica sol, alumina sol, titania sol,
The refractive index (nd) can be freely adjusted within the range of 1.5 to 2.0 by combining with a colloidal metal oxide such as zirconia sol and / or a metal halide such as metal chloride or metal bromide. The antireflection film according to claim 1, which is a refractive index layer. 4. The antireflection film according to claim 1, wherein the high refractive index layer contains an epoxy resin having a high refractive index and having good adhesion to the plastic substrate. 5. A fluorine-based material having a surface-active ability of a coating layer is a fluorinated alkyl ester having a perfluoro group and a hydrophilic group in a side chain or a fluorinated fat having a perfluoro group and a lipophilic group in a side chain. The antireflection film according to any one of claims 1 to 4, which is a group polymer ester and has a coating layer having a thickness of 200 nm or less, preferably 100 nm or less. 6. The organic polysiloxane of the coating layer is methylpolysiloxane or dimethylpolysiloxane having a side chain of a silanol group, an alkoxy group, an acetyl group, a phenyl group, a polyether group, a perfluoroalkyl group and the like. Item 6. The antireflection film according to any one of items 1 to 5. 7. The refractive index of a plastic substrate is n_S, High yield
The refractive index of the folding layer is n ₁, Its thickness d₁(Unit is n
m), the refractive index of the antireflection layer is n_Three, Its thickness d _Threeage
Then, the following equations (8) and (9) n_Three・ N_S ^Two = N₁ ^Two (8) and n₁・ D₁= N_Three・ D_Three= Λ / 4 A three-layer antireflection film designed to (9). 8. A high refractive index layer is provided in two layers, the refractive index n _S of the plastic substrate, the refractive index of the first high refractive index layer is n ₁ , its thickness is d ₁ (unit is nm), When the refractive index of the high refractive index layer is n ₂ , its thickness is d ₂ , the refractive index of the antireflection layer is n ₃ , its thickness is d ₃ , and the refractive index of air is n ₀ , the following formula (10) and (11) n ₁ · n ₃ = n ₂ · (n ₀ · n _S ) ^1/2 ··· (10) and n ₁ · d ₁ = n ₂ · d ₂ = n ₃ · d ₃ = λ / 4 (( The antireflection film according to any one of claims 1 to 6, wherein a high refractive index layer and an antireflection layer are provided so that (11) is substantially satisfied. 9. A high refractive index layer is provided in two layers, the refractive index n _S of the plastic substrate, the refractive index of the first high refractive index layer is n ₁ , its thickness is d ₁ (unit is nm), When the refractive index of the high refractive index layer is n ₂ , its thickness is d ₂ , the refractive index of the antireflection layer is n ₃ , its thickness is d ₃ , and the refractive index of air is n ₀ , the following formula (12) and ^{_{(13) n 3 2 · n}} S = n 0 · n 1 2 ‥ (12) and _{n 1 · d 1 = n 2} · d 2/2 = n 3 · d 3 = λ / 4 ‥ (13) is substantially The antireflection film according to any one of claims 1 to 6, wherein the first and second high refractive index layers and the antireflection layer are provided so as to be satisfied. 10. provided two layers of high refractive index layer, the refractive index of the plastic substrate n _S, the refractive index of the first high refractive index layer n _1,
Its thickness is d ₁ (unit is nm), the refractive index of the second high refractive index layer is n ₂ , its thickness is d ₂ , and the refractive index of the antireflection layer is n.
₃ , its thickness is d ₃ , and the refractive index of air is n ₀ ,
Formula (14) and ^{_{(15) n 3 2 · n}} S = n 0 · n 1 2 ‥ (14) and n ₁ · d _1/3 = As _{n 2 · d 2/2 =} n 3 · d 3 = λ / 4 ‥ (15) is substantially satisfied, wherein providing the first and second high refractive index layer and antireflective layer Item 7. The antireflection film according to any one of items 1 to 6.