JPS6247601A - Antireflection film - Google Patents

Abstract

PURPOSE:To permit large-capacity and mass production by coating three layers of thin films having specified refractive indices and film thicknesses on a transparent base material by liquid and using a colloidal dispersion of pulverous antimony oxide particles for liquid compsn. to form the 1st and 2nd layers of thin films. CONSTITUTION:A middle refractive index thin film 11 having the refractive index na and film thickness da expressed by formula I is formed on the transparent base material resin 14, the high refractive index thin film 12 having the refractive index nb and film thickness db expressed by formula II is formed on the thin film 11 and the low refractive index thin film 13 having the refractive index nc and film thickness dc expressed by formula III is formed on the thin film 12. (m) denotes a positive integer, l, (n) denote odd positive integers, lambda1-lambda3 denote respectively independently wavelength of visible regions. The thin films 11-13 are obtd. by coating the liquids and curing the coatings by heating, drying or active energy rays. The colloidal dispersion of pulverous antimony oxide particles dispersed into water or other solvents is used as the component for the liquid compsn. for forming the films 11, 12. The antireflection film which permit the large-capacity and mass production is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an antireflection coating VC applied on a transparent substrate.

[Summary of the invention]

The present invention provides an anti-reflection film for reducing surface reflection of a transparent substrate, which comprises three layers of thin films with different refractive indexes on at least a portion of the transparent substrate. A colloidal dispersion of fine antimony oxide particles dispersed in water or other bath medium is used to coat a thin film with a higher refractive index than the transparent base material layer by coating and curing a liquid composition. By using this material, we improve physical properties such as uniformity, hardness, surface resistance, scratch resistance, water resistance, dyeability, etc., and provide an anti-reflection film that can be produced in large volumes such as M1 dog grade. It is something to do.

[Conventional technology]

Many methods have been proposed for anti-reflection ■Theory and layered structure. Vacuum evaporation can be used to create a thin film of gold or fluoride compounds. PVD methods such as sputter deposition, ion blating, and various CVD techniques are commonly used.

On the other hand, in addition to these physical vapor deposition methods, there is a method for obtaining an antireflection film by coating it in liquid form and curing it.
Japanese Unexamined Patent Publication No. 59-49501 proposes an antireflection film consisting of three layers. These methods are based on the total height of a composition consisting of titanium alcoholade and colloidal silica.
An antireflection effect is achieved by using a composition consisting of a silane coupling agent, an epoxy compound, and colloidal silica as a material for a refractive index thin film.

Furthermore, Japanese Patent Laid-Open No. 57-37301 proposes a lens made of synthetic resin with a single or multi-layer anti-reflection film made of synthetic resin. Titanium, tantalum, etc., Alcolade, melamine resin, etc. are used as materials for the thin film.

Also, anti-reflection 8! on base materials other than transparent materials! A liquid composition containing tetraisopropoxy titanium is applied and heated on the olfactory crystal silicon 0 coating surface of a solar cell to form a thin film of titanium oxide as a decomposition product. There is a method to obtain anti-reflection effect (RCA,
Review, Vol. 1m41, No. 2. I'133～
180 (1980)) [Points and objects to be solved by the invention] However, among the above-mentioned conventional techniques, vacuum evaporation method,
Methods of forming anti-reflection film by sputter deposition, ion blating, CVD, etc. (1) require a high degree of vacuum, which imposes restrictions on the size and material of the substrate to be treated; It also takes a long time to manufacture,
Productivity and economy are low.

(2) Thin film materials are mainly inorganic compounds, and while they form a dense, hard film, they are inferior in flexibility, and if there is a difference in the O-line expansion coefficient from the base material, cracks may occur due to changes in the environmental temperature, or molding Cracks occur when article Th1G is mechanically bent.

(3) The base material to which the thin film material firmly adheres is very limited, and it is very difficult to obtain sufficient adhesion to the resin base or film.

(4) Due to poor processing properties such as dyeing and coloring, coloring is limited to vapor deposition materials that have an absorption band in the visible region.

In addition, it is impossible to create a vermilion color after anti-reflection processing.

It has the following problems.

Furthermore, in the method disclosed in Japanese Patent Application Laid-Open No. 58-46301,
Since the antireflection thin film is formed from two layers, there are the following problems depending on the application.

(1) To achieve a high antireflection effect, thickness control 'fc Vk must be performed with great precision, and manufacturing variations are large.

(2) It is difficult to obtain a greenish reflective interference color, which is particularly desired for eyeglass lenses.

Furthermore, JP-A-58-46301, JP-A-59
In the method according to Publication No. 49501, organic titanium compounds such as titanium alcoholade compounds and chelate compounds are used as high refractive index thin film materials. Since complete condensation polymerization occurs, it is difficult to obtain a thin film of titanium oxide at the curing temperature in the examples, and the presence of unreacted oxygen such as alcolade causes considerable problems in terms of adhesion and various durability.

Furthermore, in the method of forming a thin film using metal alcoholade, unreacted 17) -OR groups and -OR groups remain on the surface side of the thin film O, which poses a problem particularly in terms of water resistance. Therefore, if the base material has thermal stability such as single crystal silicon used in solar cells or infinite glass, high temperature heating is possible and the problem of film durability can be solved. In the case of thermoplastic resins such as plastics, it is difficult to use metal alcolades due to limitations as a coating base material.

Furthermore, the method disclosed in the Tentsumugi example of JP-A-57-37301 has problems in that the antireflection effect is not sufficient and the water resistance is not sufficient.

Therefore, the present invention is intended to solve these problems, and its purpose is to provide an antireflection film that has excellent antireflection properties and is highly adhesive and durable. .

〔problem? Means to solve]

The anti-reflection film of the present invention includes the following steps: α) When applying an anti-reflection film consisting of a three-layer Q thin film to at least a portion of a transparent base material, from the base material toward the atmosphere side, b) ) The optical properties of the three layers of ■, @, and ○ are respectively ■ 1.55
<71α< 1.80 na X da = Aλ1/4 Cnm>@1.6
5 < nb < 2.25 nb X db = mλ2/4 (?L77L)
nb > na 61.40 < nc < 1.50 nc
[B]hen.

The refractive index of the 0 layer, da, clb, and dc are each
Ii @ (g) I, h, θ layer Di thickness (nm) kN
L, m'a positive O positive integer, n is odd positive integer, λl,
λ2 and λ3 are each independently visible wavelength (in nm)
, and na〉(substrate ■ refractive index). 1, =) e D layer, @ layer, θ layer O Each thin film is applied in liquid form, obtained by heating, drying, or curing with active energy rays, and d) Furthermore, the liquid composition for forming ■I':ia@/Wk contains as a component water or other 7) Antimony oxide fine particles dispersed in a bath medium. O-Floyd dispersion has all the features and characteristics provided by it.

Here, the transparent base material includes glass molded products and PMMA.
It is a synthetic resin molded article used for optical purposes such as polycarbonate, polyethylene terephthalate, diethylene glycol bisallyl carbonate, polystyrene, high refractive index resin having nuclear substituted phenyl & Th in the molecule, allyl resin, etc., and its shape, film, It is possible to use panels, lenses, sheets, and other arbitrary articles processed. These base materials can be modified to improve adhesion with the antireflection thin film by modifying the surface of the base material in accordance with 7) t-1 or 8 firing. The coating surface treatment methods include treatment with alkaline liquid-resistant or strong oxidizing agents (Japanese Patent Publication No. 38-13784, etc.), treatment with ozone TL (T]5P3227605), treatment with flame loaded with electric charge ( JP-A-48-84879), plasma gas treatment (JP-A-53-137)
Publication No. 269).

Treatment with oxidizing agent and reducing agent (JP-A-48-81966
Jy Publication) - Treatment with an alkali metal solution containing polyethylene glycol (Japanese Patent Application No. 59-119682) In addition, corona discharge, sputtering, ultraviolet rays, electron beams,
Examples include active military irradiation with radiation, etc.
Depending on the substrate material and surface condition, known surface treatments can be applied.

In addition, if the base material is relatively easily damaged such as synthetic resin,
In order to improve the abrasion resistance, a wear-resistant Q cured coating can be applied in advance, and an antireflection thin film can be laminated thereon.

These methods include, for example, Japanese Patent Application No. 58-1554.
55, Japanese Patent Publication No. 57-2735, etc., there is a method of completely forming a surface hardening film. In addition, optical substrates with coatings having N chromogen and dimming performance (Japanese Patent Laid-Open No. 59-46
623) can also be used.

In the present invention, three thin films with different refractive indexes are formed on a transparent substrate as an anti-reflection film. The optical properties of each thin film are determined by the liquid Amg material used to form it and its application and curing methods.

In order to form each layer of (1), (2), and (3) in the present invention, antimony oxide O fine particles θ are used as a component of the liquid composition.
The colloidal dispersion is essential as a high refractive index component. In addition, it is also an important component for obtaining coating film '7) water resistance, durability, and dyeability.

In addition to this, colloidal silica with silica fine particles completely dispersed in a solvent, metal compounds containing organic residues and their hydrolyzed condensates, natural resins, polymers such as synthetic toilet fat, polymerizable crystalline bodies, and mature Use at least one component selected from reactive compounds such as hardening-reactive single-particles to improve the refractive index! 1. It is possible to improve the dyeing properties or improve the stainability.

Here, the colloidal sol of antimony oxide fine particles is
Antimony pentoxide or antimony trioxide fine particles obtained by a gas phase method and dispersed in a dispersion medium, or a colloidal sol obtained by a liquid phase method can be used. The particle size of the fine particles of this sol is 1 to 100 m1t, preferably 1 to 50 m1t.
Antimony oxide of μ is useful 9 particle size is 100 to 71
If it is more than μ, the eardrum will become cloudy, and if it is less than 1 mμ, the water resistance of the eardrum will decrease. As a dispersion medium for antimony oxide fine particles, in addition to water, methanol, ethanol, inglobanol, selonlube, etc., carboxylic acid O such as acetic acid can also be used. In addition, particularly when water is used as a dispersion medium, sol fine particles stabilized with acetic acid, nitric acid, sulfuric acid, amine, etc. are useful.

The antimony oxide fine particles must be contained in the formed thin film at least 10 times or more in the 0th layer, and at least 40 times or more in the 0th layer. This is because if the content is less than that, it will be difficult to obtain the desired refractive index required for an antireflection thin film.

Next, as colloidal silica, the particle size is 1 to 10077.
Although silica (1) containing 1 µm silica fine particles is suitable for obtaining the desired hardness, a colloidal dispersion containing 0 metal oxide fine particles can also be used in place of colloidal silica.

In addition, as a metal compound having all organic residues, the general formula E
Examples include silane coupling agents combined with eaRh*, 8 i 4-α-, tetraalkoxysilane, and the like.

These hydrolysates, partial condensates, etc. also have similar O properties. Here, R1 is an alkyl group, an alkenyl group, a phenyl group, a halogen group, etc., or R? represents an organic group including an epoxy group, an amine group, an amide group, a mercapto group, a methacryloyloxy group, a cyan group, a group having a halogenated aromatic group, and X represents a halogen group, an alkoxyl group, an alkoxyalkoxyl group, an acyloxy represents a hydrolyzable group such as a group, and α and b are each 0.1 or 2,
α+b is 1 and 3. Examples of these compounds include tetrafunctional silanes such as tetramethoxysilane, methyltrimethoxysilane, r-chloropropyltrimethoxysilane, vinyltrimethoxysilane, r-methacryloyloxypropyltrimethoxysilane, βf3.4-epoxycyclohexyl ) Ethyltrimethoxysilane #r-
Dalicidoxypropyltrimethoxysilane, γ-methylcaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-r
- Trifunctional silanes such as aminopropyltrimethoxysilane, r-ureidoglobiltrimethoxysilane, γ-cyanopropyltrimethoxysilane, r-molfluorinobrobiltrimethoxysilane, and N-phenylaminoglobiltrimethoxysilane , and trifunctional silanes in which a portion of the trifunctional silane is substituted with a methyl group, an ethyl group, or a vinyl group. In addition, a functional silane compound containing a perfluoroalkyl group is suitable, especially for forming a low refractive index layer.

Furthermore, metal compounds containing all organic residues other than silane are generally useful for forming thin films with a high refractive index.

Examples of this include titanate coupling agents, aluminum coupling agents, alcoholades, acylates, and chelating compounds such as zirconium, tantalum, tin, and indium.

In addition, hafnium, which can be prepared by a similar O method to these,
Thorium, vanadium, niobium, chromium, molybdenum,
Alcolades, acylates, chelating compounds, etc. of manganese, iron, cerium, lanthanum lead, zinc, etc. can also be used.

Next, the main purpose of polymeric materials such as natural resins and synthetic resins is to impart flexibility, dyeability, and toughness.

Examples of ttRO include celluloses such as carboxyalkylated cellulose, terpene thread resins, glucose conductors, polyamino acids, chitin, chitosans, natural polymers such as starches, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, and polyacrylics. Synthetic polymers with negative groups such as acid esters, polymethacrylic acid esters, polyvinylamines, polyurethanes, polyvinylpyrrolidone, polyvinylpyridine, polyvinylimidazole, aromatic polymers such as polystyrene, bisphenol A# polycarbonate, and polysal 7-ones. ■ Examples include high refractive index polymers and low refractive index polymers such as fluororesins.

Also, the viscosity v! Examples of reactive compounds added to improve properties, toughness, and durability include precured polyfunctional acrylates and Q epoxy compounds such as ethylene glycol diglycidyl ether. can.

Further, it is preferable that at least 20 parts of the above-mentioned organic component be contained in the formed thin film.

In other words, if the tension is less than 20, the elasticity is insufficient.
Poor durability such as heat resistance and impact resistance. Furthermore, it is difficult to obtain sufficient adhesion between each layer of the thin film.

In addition, there is no upper limit, but if there are many organic components,
Hardness tends to be poor, and it is difficult to maintain a high refractive index of the high refractive index layer. Therefore, it is desirable to determine the type and content of the organic component within the range, taking into consideration the intended use.

The liquid composition in the present invention is as described above! In addition to the 7:l thin film forming product O, an appropriate solvent is added in consideration of the problem of coating workability. As the solvent, a solution containing 1 to 20% by weight Q solid content using a solvent such as alcohols, ketones, selonlubes, formamides, water, Freon, etc. is suitable, but is not necessarily limited. .

Further, surfactants, ultraviolet absorbers, antioxidants, chicktroping agents, pigments, dyes, antistatic agents, conductive particles, etc. can also be added.

The composition thus obtained is coated and coated by a known method.
A variety of improved coating methods can be used to form a coating film by curing, such as dry coating, flow coating, dip coating, spin coating, roll coating, and spray coating.

Drying and curing are determined depending on the base material and components used, but preferably at 40°C to 130°C for 10 minutes to
Curing by heating for 10 hours is practical.

Further, in order to promote the crosslinking and polymerization reaction of the reactive group Q in the components used, curing can also be carried out by irradiation with infrared rays, ultraviolet rays, r-rays, or electron beams.

It is also useful to subject the base material to a surface treatment such as plasma treatment or alkali treatment before coating the (1), @, and (theta) layers of the present invention for the purpose of improving their adhesion.

The refractive index of the antireflection thin film in the present invention is the first
layer, the second layer, and the third layer each have a refractive index of 1.55 to 1.55.
80 and 1.65 to 2.25 and 1.4σ to 1.5
0, and the second layer has the highest refractive index, followed by the first layer and the third layer. Furthermore, it is safe to select a value for na that is higher than the refractive index of the base material. On the other hand, the film thickness can be directly set as desired by adjusting it with a solvent or coating method, so it can be selected from any combination of film thicknesses depending on the combination of refractive indexes.In particular, the optical film thickness of each layer is Odd integer multiples of a quarter of the wavelength are preferred; deviations from these optical conditions are not preferred because the antireflection properties are poor.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of high refractive index coating 1 (Al) In a reaction flask, 60.0% of acetic acid was added. Add a colloidal dispersion of antimony pentoxide fine particles using acetic acid as a dispersion medium (sli-uniform particle size 15±1 mμm5b20).
After adding 50.08 ffl (S-containing ffl: 19.17%) and stirring thoroughly, 3°432 of γ-glycidoxypropyltrimethoxysilane was added and stirring was performed at room temperature for 1 hour. After that, methyl cellosolve 140.1? , and 0.022 of a silicone surfactant were added to prepare a coating liquid. ■ Application/10) Viscosity fly. 4 centistokes (20° C.), and the solid content concentration was 5.1 type needles.

(2) Preparation of coating liquid for low refractive index (A2) Pour 85.729 k of ethanol into a reaction flask, and add r-prisidoxyglobil (methyl) sil under stirring.
) Kishishiray8.57F, 0.051J Hydrochloric acid 1.
251P was added and hydrolysis was carried out for 1 hour while stirring.

After this, ethanol-dispersed colloidal silica (Oscar 12)
32 #catalyzed FM, ■, solid content concentration 30 cm) 202 was added and stirred at room temperature for 30 minutes. Then, methyl cellosolve 85.72 F, silicone surfactant 0.0
29e was added to prepare a coating liquid. 1ff of this application
The lo viscosity was 1.3 centistokes (20°C), and the solids concentration was 6.2 centistokes.

(3) Preparation of coating liquid for medium refractive index (A3) All preparations were made in the same manner except that the additive stitches in the previous section (1) were changed as shown below.

Acetic acid 50.03f Colloidal dispersion of antimony pentoxide fine particles using acetic acid as a dispersion medium 26.08f γ-Glycidoxyprobyltrimethoxysilane
7.14 F Methyl Cellosolve 116.75 F The viscosity of this coating liquid was 1.4 centistokes (warmed), and the solid content concentration was 5.2 centistokes.

In addition, the above coating liquids (1), (2), (3)
) was prepared using a membrane filter to remove giant particles and insoluble matter.

(4) Application and curing of antireflection film (5% hydroxide) A flat plate of diethylene glycol bisallyl carbonate resin (diameter 10mm, thickness 0.5mm) immersed in an aqueous IJ solution for 5 minutes and treated with alkali.
An antireflection film was provided on the substrate (with a refractive index of 1.50 and a total light transmittance of 92 cm) using the following method.

First, add this resin to the coating solution (A-3) for medium refractive index thin film. Coating was carried out under the following conditions: the liquid was immersed at 1110° C. and the pulling speed was 3 cm 1 minute. Pulling 1. Curing at 100℃ for 30 minutes,
A medium refractive index layer was obtained.

Next, the resin was immersed in a strong hydrochloric acid aqueous solution for 3 minutes, thoroughly washed with water and dried, and then coated with a high refractive index thin film coating solution (A-1).
Coating 2 was carried out at a liquid temperature of 10° C. and a lifting speed of 3 crn/min. After pulling it up, it was cured at 100° C. for 40 minutes to form a high refractive index layer.

Finally, the resin was immersed in a strong hydrochloric acid aqueous solution for 2 minutes, thoroughly washed with water, and dried.
), and coating was performed under the conditions of a liquid temperature of 7° C. and a pulling rate of 2 crn/min. After pulling it up, it was cured at 120° C. for 20 minutes to obtain an antireflection film consisting of three layers.

(5) Test result anti-reflection film? The total light transmittance of the diethylene glycol bisallyl carbonate resin provided was 96.3 cm,
Is the reflective interference color green? presented.

When the adhesion was evaluated by a cross-cut tape test, there was no gap at all, and the results of water resistance, scratch resistance (÷0000 steel wool, l() times scratches), and hot water resistance (60°C) were also good. Ta.

In addition, if the thin films obtained by applying the can liquids of (A3), (AI), and (A2) are 11 and 12.13 layers, respectively,
The refractive index and film thickness were as follows.

Thin film Refractive index Film thickness (nm) 11 1.61 79.4 12 1.70 71.6 J3 1.49 85.8 Example 2 (1) Preparation of coating liquid for high refractive index (B1) Inside flask for reaction , isopropyl alcohol '17.9
A colloidal dispersion of antimony pentoxide fine particles using isopropyl alcohol as a dispersion medium (average particle diameter 21 ± 1 mμs, 5bZO5 containing company 23.5 cm) was prepared with stirring.
After adding 42.55 F and stirring, γ-glycidoxyglobyl(methyl)dimethoxysilane 1°791.0
．． 0.74M' of 05N hydrochloric acid was added, and the mixture was stirred at room temperature for 2 hours. Then, under stirring, methyl ethyl ketone 116
．． 88F, glycerol diglycidyl ether 1.25
1. 0.0272 of magnesium perchlorate was added and dissolved. The viscosity of this coating liquid was 1.3 centistokes (20°C), and the solid content value was 4.8 centistokes.

(2) Coating liquid for low refractive index (B2) ■ Preparation In the reaction flask, add ethanol 88.91? Put k,
While stirring, 2.53 r of r-glycidoxypropyltrimethoxysilane and 1.32 F of 0.05N hydrochloric acid were added, and the mixture was stirred at room temperature for 1 hour.

After this, colloidal silica dispersed in inpropyl alcohol (Oscar 1432.Catalyst Chemical ■, solid content concentration 30%)
a, 331, methyltriethoxysilane 13.30
9 was added, and the mixture was stirred at room temperature.

After sowing, 133.36 F of methyl cellosolve, 2.53 Ps of glycerol diglycidyl ether, and 0.0749 K of magnesium perchlorate were added and dissolved. The viscosity of this coating liquid was 1.6 centistokes (20° C.), and the solid content concentration was 5.2% by weight.

(3) Coating liquid for medium refractive index (B3) ■ Preparation Previous item α) ■ Prepared in the same manner in a pan except that the amounts added were changed as shown below.

Isopropyl alcohol 86.22 f Colloidal dispersion of antimony pentoxide fine particles using isopropyl alcohol as a dispersion medium 26.60 Pγ-glycidoxib a Viru(methyl)dimethoxysilane 5.35 F 0.05N hydrochloric acid water 1.02 Methyl ethyl ketone 129.33 y Glycerol diglycidyl ether 2.52 Magnesium perchlorate 0.057'? The viscosity of this coating liquid was 1.4 centistokes (20°C), and the solid content concentration was 5.0 centistokes.

Incidentally, after preparing the liquids of the above d-picoatings I (1), (2), and (3), each of them was filtered using a membrane filter to remove large particles and insoluble matter.

(4) A card coating α) Preparation of hard coating liquid r-glycidoxyprobyltrimethoxysilane 13.5
F, ethanol-dispersed colloidal silica (Oscar 12
32. To a solution consisting of Catalyst Chemical Formation (1), 22.5 f of solids (1 addition) and 135.3 t of methyl cellosolve, 0.
Hydrolysis was carried out by gradually dropping 3.699 g of 05N hydrochloric acid solution. After aging this solution at 0° C. for an hour, 9.02 g of glycerol diglycidyl ether, 0.1217 f of magnesium perchlorate, and 0.04 f of a silicone surfactant were added and stirred at room temperature for T3 hours to obtain a node coating solution.

b) Application of hard coat solution and curing with 5% hydroxide) Diethylene glycol bisallyl carbonate resin Praluns (refractive index 1.50, total light transmittance 92%) immersed in IJium aqueous solution for 5 minutes and subjected to alkali treatment 5 ) was immersed in the hard coat solution, and then applied at a pulling rate of 15 crn/min. Next, put it in a hot air drying oven at 2.80℃ for 1 hour and then at 130℃ for 1 hour. and hardened it.

At this time, (2) the thickness of the hard coat layer was 2.3 μm.

(5) Coating and Curing of Anti-Reflection Film After the lens obtained in the above (4) was subjected to argon gas plasma treatment (400 W, 20 seconds) for 1 fr, an anti-reflection film was provided by the following method.

After first applying O for a medium refractive index thin film (B-3), the lens was immersed, and the coating was performed under the conditions 't=H@10°C, pulling speed 3 cm, and 7 minutes. After pulling, curing was performed at 100° C. for 40 minutes to obtain a medium refractive index layer.

Subsequently, the lens was immersed in a strong acidic aqueous solution for 3 minutes, thoroughly washed with water and dried.Then, the lens was immersed in a high refractive index thin film coating solution (B-1) for 1 mx.

The coating was carried out under the following conditions: °C, pulling speed 3 cm, and 7 minutes.

After pulling, harden at 100℃ for 45 minutes to obtain a high refractive index of 1-
Fully laminated.

Finally, the lens was immersed in a strong acidic aqueous solution for 3 minutes, thoroughly rinsed with water, and then immersed in a coating solution for oil refractive index thin film (B-2) at a temperature of 8°C and a pulling rate of 2 F/min. Coating under O condition 2
went. After pulling it up, it was cured at 130° C. for 30 minutes to obtain an antireflection film consisting of three layers.

(6) Test results The total light transmittance of the lens O obtained in this way is 9
6.5%, and the reflection interference color is green.

In addition, this anti-reflection lens was made using a dyeing bath in which a commercially available disperse dye mixed with three colors of red, evening, and yellow was dispersed and dissolved in water.
Stained at 10°C. The total light transmittance of this O lens is 5
It showed good stainability at 6.7%.

Furthermore, when we evaluated the adhesion using a cross-cut tape test, we found that there were no problems at all, and the water resistance and scratch resistance were excellent.
oo steel wool, scratched 10 times), warm water resistance (60℃
) results were also good.

In addition, the thin PIA obtained by applying the can liquids of (B3), (Bl), and (B2) were 21, 22, and 22, respectively.
The refractive index and film thickness were as follows.

Thin film Refractive index Film thickness (nm) 21 1.58 82.82
2 1.71 76.9 Z3 1.48 87.8 Heavenly Journey Example 3 (1) Coating liquid for high refractive index (CL) Put ethyl cellosolve 180.22 into an OK reaction flask, and add water while stirring. A colloidal dispersion of antimony triacetate fine particles using as a dispersion medium (average particle size 40 mA,
sbo, included! ! -27.3%) After adding 17.589k and stirring thoroughly, 1.71f of γ-glycidoxyprobyltriethoxysilane, 0.4 of 0.051J hydrochloric acid water
7y.

Ethanol-dispersed colloidal silica (Oscar 1232,
A coating liquid was prepared by adding a catalyst component, a solid content of 30°, 072°, and a silicone surfactant, 02f. The zero viscosity of this coating solution is 1.5 my, )-x(
20°C), and the solid content concentration was 5.91%.

(2) Low refractive index coating liquid (C2) (1) Preparation A commercially available O fluorosilicone coating agent (trade name "KP-801', manufactured by Shin-Etsu Silicone, solid content 3%) was used as the low refractive index coating liquid.

(3) Coating liquid for medium refractive index (C3) ■ Before preparation □ Coating liquid for high refractive index in Example 1 f & (
AI) 73.8 y and low refractive index coating liquid (A
2) 64.7tf was mixed to obtain a coating liquid for medium refractive index (C3). The viscosity of the coating liquid O was C4 cm Stokes (20° C.), and the solid content was 5.6% by weight.

In addition, the above coating liquids (1), (2), (
In 3), after preparing the liquid, each solution was filtered using a membrane filter to remove giant particles and insoluble matter.

(4) Application and curing of anti-reflection film (5 times hydroxide) A commercially available inorganic glass panel (diameter 12 cm
rn, thickness 0.2+wa, refractive index 1.52. An antireflection film was provided using the following method.

First, the glass panel was immersed in a coating liquid CC-3 for medium refractive index thin films, and coating was performed at a liquid @9°C and a pulling rate of 3/min. After pulling, harden at 100℃ for 5 minutes,
Medium refractive index layer fi! :Obtained.

Subsequently, the glass panel is immersed in a strong acidic aqueous solution for 3 minutes,
After thoroughly rinsing with water, it was immersed in a coating liquid for high refractive interlayer film (C-1), and coating was carried out under the conditions of liquid @ 10°C, pulling speed of 3 cm, and 1 minute. After pulling, curing was performed at 100° C. for 30 minutes, and a high refractive index layer was laminated.

Finally, the glass panel was treated with oxygen plasma gas (50
0W, lo seconds), the film was immersed in a low refractive index thin film coating solution (C-2) and coated at a temperature of 7° C. and a pulling rate of 2 crn/min. After pulling, the film was dried and cured at 100° C. to obtain a three-layer antireflection film.

(5) Test results The total light transmittance of the glass panel thus obtained was 97.5%, and the reflection interference color was reddish-purple.

In addition, when we evaluated adhesion using a cross-cut tape test, no problems were found, and water resistance and scratch resistance (
000 steel wool, 10 times m'tJA), and hot water resistance (60°C) ■The results were also good.

Note that the refractive index and film thickness were as follows, assuming that the thin films obtained by applying the can liquids of (C3), (C1), and (C2) were 31 and 32 Hi, respectively.

Thin film Refractive index Film thickness (nm) 311゜62 80.2 32 1.74 74゜7 33 1.45 89.7 Comparative example 1 (1) High refractive index coating liquid (Dl) ■ Prepared in reaction flask , inpropyl alcohol 127.4 f
, add 31.86 f of phenethyl alcohol, a
Stirring T, ethanol-dispersed colloidal silica (Oscar 1
232. Catalyst chemical formation (solid content addition) 6.679 and tetra-n-butyl titanate 34.04 f,
A coating solution was prepared by adding 0.04v of silicone surfactant and stirring for 1 hour. The viscosity of this coating solution was 1.9 centistokes (20°C), and the solid content was as follows:
It was 5.2 times.

(2) As a coating liquid for low refractive index (D2),
(A2) of Example 1'! It was used for.

(3) Coating liquid for medium refractive index (D3) O Preparation A coating liquid for medium refractive index (D3) was prepared in the same manner in a pan, except that the addition and addition omitted in the previous section α) were changed as shown below.

Inglobil alcohol 136.97r Phenethyl alcohol 24.17F Tanol dispersion: rC:x Idal silica 13.33t Tetra-n-
Butyl titanate 25.53f The viscosity of the coating liquid is 1
．． 6 centistokes (20°C), solid separation is 5.
It was triple 111 cm.

(4) Anti-reflection@O coating and hardening A diethylene glycol bisallyl carbonate resin O flat plate that was immersed in a 5% aqueous sodium hydroxide solution for 5 minutes and subjected to alkali treatment [eM] was coated with a coating solution for medium refractive index thin films (D-3). '), and coating was carried out under the conditions of liquid@10'C and pulling speed of 3-7 minutes.

After pulling, it was cured at 100°C for 1 hour to obtain a medium refractive index l1.
1t-obtained.

However, when the resin was immersed in a strongly acidic aqueous solution for 3 minutes and thoroughly washed with water, part of the medium refractive index thin film had disappeared, and when wiped with a cloth, the thin film was peeled off.

〔Effect of the invention〕

As described above, according to the present invention, an antireflection mk liquid composition consisting of three thin films with different refractive indexes is applied to at least a portion of a transparent substrate by coating and curing. a high refractive index thin film having a higher refractive index than the layer;
In order to form a medium refractive index thin film, the desired refractive index can be centrally expressed by using a colloidal dispersion of antimony oxide fine particles dispersed in water or other solvent as a liquid composition. In addition, compared to the case of using conventional metal Alcolade, it has improved adhesion, hardness, chemical resistance, scratch resistance, water resistance,
It has now become possible to obtain an antireflection film that has excellent physical properties such as dyeability and can be produced in large quantities.

[Brief explanation of the drawing]

Figure 1 is a cross-sectional view of the antireflection film of Example 1. 11...Medium refractive index thin film 12...High refractive index thin film 13-...Low refractive index thin film 14...Base material resin stripe Figure 2 is a reflection spectrum diagram of the surface of the antireflection film of Example 1. that's all

Claims (1)

[Claims] (1) a) When applying an anti-reflection film consisting of three thin films of [a], [b], and [c] from the base material toward the atmosphere on at least a part of the transparent base material, b ) The optical properties of the three layers [A], [B], and [C] are respectively [A] 1.55<na<1.80 na×da=lλ_1/4 (nm) [B]1.65<nb<2.25 nb×db=mλ_2/4(nm) nb>na [c]1.40<nc<1.50 nc×dc=nλ_3/4(nm) (Here, na, nb, nc are Respectively, [a] layer, [b]
layer, the refractive index of the [C] layer, da, db, and dc respectively represent the film thickness (nm) of the A layer, B layer, and [C] layer, m is a positive integer, and l and n are odd positive numbers. The integers λ_1, λ_2, and λ_3 each independently represent a wavelength (in nm) in the visible region. Also, na
>(refractive index of base material). c) Each thin film of the [a] layer, [b] layer, and [c] layer satisfies the conditions of
d) The liquid composition for forming the [a] layer and the [b] layer is dispersed in water or other solvent as a component. An antireflection film characterized in that it is provided by a colloidal dispersion of antimony oxide fine particles.