JPS634201A - Antireflection film - Google Patents

Abstract

PURPOSE:To obtain a preventive film having an excellent antireflection characteristic by providing an antireflection film consisting of two layers of thin films having the optical characteristics varying from a transparent base material toward the atm. side to at least part of the base material. CONSTITUTION:The antireflection film is constituted of two layers of the thin films; a high-refractive index thin film 11 and low-refractive index thin film 12, at the time of depositing said antireflection film on the surface of a plastic lens 13. The optical characteristic of the layer 11 in such constitution is specified to 1.55<na<2.25, 0.8Xmlambda0/4<nada<1.2Xmlambda0/4 and the optical characteristic of the layer 2 is specified to 1.35Xna<1.50, 0.8Xlambda0/4<nbdb<1.2Xlambda0/4, where na and nb are refractive indices, da and db are the film thickness expressed by nm, 1 and 2 are the design wavelength of nm unit in a visible wavelength region. na is the value larger than the refractive index of the base material. The essential component of the liquid compsn. is specified to the colloidal liquid prepd. by dispersing titanium oxide particles having 1-100mmu grain size in a solvent.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to an antireflection coating applied on a transparent substrate.

[Summary of the invention]

The present invention relates to an antireflection film for reducing surface reflection of a transparent substrate. In other words, it relates to an antireflection film formed by applying and curing a liquid composition made of specific components in a process of applying two thin films with different refractive indexes to at least part of a transparent substrate. It is. More specifically, a colloidal dispersion of titanium oxide fine particles dispersed in water or other solvent and a specific organosilane compound are essential conditions for the coating solution to form a thin film with a higher refractive index than the transparent base material layer. By using organic titanium compounds and organic titanium compounds, various physical properties such as excellent adhesion, hardness, chemical resistance, scratch resistance, water resistance, and dyeability are achieved.

[Conventional technology]

Many methods have been proposed regarding the theory of anti-reflection coatings and their lamination methods.
Common methods include methods for forming thin films such as tsuride, PVD methods such as sputter deposition and ion blating, and various OVD techniques.

- On the other hand, in addition to these physical vapor deposition methods, JP-A-58-46301 and JP-A-60-23036 disclose a two-layer method for obtaining an antireflection film by coating and curing in liquid form. Anti-reflection film consisting of JP-A-559-49
Publication No. 5C proposes an antireflection film consisting of three layers. @These methods use a composition consisting of titanium alcoholade and colloidal silica as a material for a high refractive index thin film, and a silane coupling agent and an epoxy compound. By using a composition consisting of colloidal silica and colloidal silica as a material for a low refractive index thin film, an antireflection effect is exhibited. A synthetic resin lens coated with an antireflection film has been proposed, and in this method, Alcolade such as titanium or tantalum, melamine resin, etc. are used as the material for the high refractive index thin film.

In addition, as an example of providing an antireflection film on a substrate other than a transparent material, a liquid composition containing titanium tetraisopropoxy is applied to the surface of single crystal silicon of a solar cell and heated, and titanium oxide is produced as a decomposition product. There is a way to form a thin film and obtain the antireflection effect of a single layer (RCA, Revie
w, Vol, 41, Nu 2, P 133-180
(1980)) [Problems to be solved by the invention] However, among the above-mentioned conventional techniques, methods for forming antireflection thin films by vacuum evaporation, sputter evaporation, ion blating, CVD, etc. are: (1) highly sophisticated; Since this requires a degree of vacuum, there are restrictions on the size and material of the substrate to be treated. In addition, it takes a long time to manufacture, and the productivity and economic efficiency are low. If there is a difference, cracks may occur due to changes in environmental temperature or when the molded article is mechanically bent.

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

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

Furthermore, dyeing after anti-reflection treatment is not possible.

It has the following problems.

Also, JP-A-58-46501, JP-A-60-2
In the method for forming a two-layer antireflection film in JP-A No. 5056, and a three-layer antireflection film in JP-A-59-49501, organic titanium compounds such as titanium tricholate compounds and chelate compounds or high These titanium compounds are used as materials for refractive index thin films, but in order to completely condensate and polymerize these titanium compounds, it is usually necessary to heat them to 350°C or higher, and at the curing temperature in the example, complete condensation cannot be achieved. Although this is difficult and is presumed to be due to residual unreacted sulfurate, the resulting film has poor adhesion, water resistance,
It has the problem of poor durability such as scratch resistance. Further, in the method of forming a thin film using other metal alcolades, unreacted 10H groups and -OR groups remain in the thin film, which causes problems particularly in terms of water resistance. For this reason, thermally stable base materials such as single-crystal silicon used in solar cells and inorganic glass can be heated to high temperatures and solve the problem of film durability, but plastics In the case of thermoplastic resins such as, it is difficult to use metal alcolade due to limitations as a coating base material.Furthermore, in the method disclosed in the example of JP-A-57-57501, it is difficult to use reflective There are problems in that the preventive effect is not sufficient and the water resistance is also not sufficient.

Therefore, the present invention aims to solve these problems, and aims to have excellent anti-reflection properties, adhesion, hardness, chemical resistance, scratch resistance, water resistance, and dyeing resistance. An object of the present invention is to provide an antireflection film consisting of two layers with excellent properties.

[Means for solving problems]

The anti-reflection film of the present invention includes the following steps: α) When applying an anti-reflection film consisting of two thin films of (i) and O to at least a portion of a transparent base material from the base material toward the atmosphere, b) [i] The optical properties of the two layers of ] and [b] are as follows: 155<n<2.25 α8×λ. < na d'< t2 X Toro@
t 55 < n b < t 5008×-λo
(n, d b < t 2 X aλ.

(Here, n a 'i n B are [A] layer, [
The refractive indexes, d, and d of the [b] layer and [b] layer are respectively
Represents the thickness of the layer (in nm), m is 1 or 2, R0
represents the design wavelength (in nanometer units) in the visible wavelength region, and n is the refractive index of the base material. ), C) Each of the thin films of the [a] layer and the [b] layer is applied in liquid form and obtained by heating and drying or curing with active energy rays, and d) Further, the layer 0 is formed. The main components of the liquid composition for this purpose are: 1) A colloidal dispersion of fine titanium oxide particles having a particle size of 1 to 100 ynμ dispersed in water or other solvent.

(However, R1 is an alkyl group, an alkenyl group, a phenyl group,
halogen group, etc., and R2 represents an organic group including an epoxy group, a ryomino group, an amide group, a mercapto group, a methacryloyloxy group, a cyano group, a group having a nuclear halogenated aromatic ring, etc., and X represents a halogen group, Indicates a hydrolyzable group such as an alkoxyl group, an alkoxyalkoxyl group, and a ryosyloxy group.
is 1 to 5. ) A silane coupling agent represented by

(OR3)0 (However, R3 is hydrogen or a hydrocarbon having 1 to 6 carbon atoms.

R4 is an organic group having at least one carboxylic acid ◇
C is 1.2 or 5. ) is a titanium hydroxy acid coordination compound 0 When formed into a thin film, 1) is 99 to 90% by weight, 2) is 9.9 to 90% by weight, 111) or 0.1 to 20% by weight.

Here, the transparent base material includes glass molded products, PMM
A, polycarbonate, polyethylene tele, 7 tallate, diethylene glycol bisallyl carbonate resin,
Synthetic resin molded articles used for optical purposes such as polystyrene, high refractive index resins having nuclear-substituted phenyl groups in the molecule, allyl resins, etc., and can be shaped into films, panels, lenses, sheets, and other arbitrary articles. A processed product can be used. These base materials can be used as they are, or their surfaces can be modified as necessary to improve adhesion to the antireflection thin film.

As methods for this surface treatment, treatment with an alkaline solution or strong acid with oxidizing power (% Publication No. 58-13784, etc.), treatment with ozone (USF No. 5227605)
, Treatment with charged flame (Japanese Patent Application Laid-Open No. 48-848
No. 79), treatment with plasma gas (4?
-137269), treatment with an oxidizing agent and a reducing agent (
JP-A-48-81966), treatment with an alkali metal solution containing polyethylene glyfur (Japanese Patent Application No. 59-81)
119682), other examples include corona discharge, sputtering, and irradiation with active electromagnetic waves such as ultraviolet rays, electron beams, and radiation.Depending on the material and surface condition of the base material,
It can be used after being subjected to known surface treatment.

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

These methods include, for example, Japanese Patent Application No. 59-1060.
There are methods of forming a surface hardening film as disclosed in No. 92 and Japanese Patent Application Laid-Open No. 59-231501. Optical substrates with colored films or films with light control performance (Japanese Unexamined Patent Publication No. 59-4
6625) can also be used.

In the present invention, a 0 layer and a 0 layer thin film having different refractive indexes are formed on a transparent substrate as an antireflection film, and the optical function of the thin film depends on the liquid composition used to form each thin film. The material and its coating and curing methods determine the optical properties of each thin film.

In the present invention, the liquid composition for forming the zero layer includes colloidal silica in which silica particles are dispersed in a solvent;
Silane compounds having organic residues and their hydrolyzed condensates,
It consists of at least one component selected from polymers such as natural resins and synthetic resins, and reactive compounds such as polymerizable monomers and thermosetting reactive monomers, and also has a refractive index higher than that of the transparent base material. The liquid composition for forming the layer is composed of at least one selected from the above compounds, a colloidal dispersion of titanium oxide fine particles dispersed in water or another solvent, and a titanium organic compound.

Therefore, the titanium oxide fine particles which are the main component of the liquid composition for forming the zero layer are preferably colloidal dispersions of titanium oxide fine particles having a particle size of 1 to 100 mμ dispersed in water or other solvent. The main purpose of the titanium oxide fine particles is to obtain a thin film having a high refractive index in a two-layer antireflection film.

The titanium oxide fine particles used have a particle size of 1 to 100 mμ, more preferably a particle size of 5 to 50 mμ. That is, if the particle size is 100 mμ or more, the thin film after curing becomes cloudy or colored due to the wavelength of light in the visible region, making it unsuitable as an antireflection film for transparent materials. Furthermore, if the particle size is less than 1 mμ, the hardness of the thin film after curing will be insufficient and the durability of the film will be poor.

In addition to water, alcohol dispersion media such as methanol, ethanol, isopropyl alcohol, and methyl cellosolve, and carboxylic acids such as acetic acid, propionic acid, and butyric acid are used as dispersion media for the titanium oxide fine particles. In addition, when water is used as a dispersion medium, metal oxide fine particles stabilized with acetic acid, nitric acid, sulfuric acid, organic acids (oxalic acid, tartaric acid, apple acid, citric acid, amino acids, etc.) are used. You can also do that.

The titanium oxide fine particles must be contained in the layer in an amount of 99 to 90% by weight; however, if the content of the titanium oxide particles is less than 9.9% by weight, it is not required as an antireflection thin film. This is because it is difficult to obtain a desired refractive index, and if the content exceeds 90% by weight, cracks will occur in the thin film.

Titanium oxide fine particles are an essential component for obtaining a thin film with a high refractive index and sufficient hardness.

The silane coupling agent represented by H% is such that R' is an alkyl group, an alkenyl group, a phenyl group, a halogen group, etc.
R2 represents an organic group including an epoxy group, an amino group, an amide group, a mercapto group, a methacryloyloxy group, a cyano group, a group having a nuclear halogenated aromatic ring, or a halogen group, an acyloxy group, an alkoxyalkoxyl group, Indicates a hydrolyzable group such as a siloxy group. Also, 1.
b is each 0.1 or 2, and a + b is 1 to 5
It is. Examples of these compounds include tetrafunctional silanes such as tetramethoxysilane, methyltrimethoxysilane,
Methyltriethoxysilane, r-chloropropyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, β-(5
, 4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane, r-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-cyanopropyltrimethoxysilane, γ - Trifunctional silane such as mol 7 olinobrobyltrimethoxysilane, N-7 2-22 aminopropyl trimethoxysilane, trifunctional silane in which a part of the above trifunctional silane is substituted with a methyl group, ethyl group, or vinyl group etc. Moreover, these hydrolysates, partial condensates, etc. also have similar properties.

This silane compound needs to be contained in the 0 layer in an amount of 99 to 909 to 90% by weight. This is because if the content of the silane compound is less than 99% by weight, cracks will occur in the thin film. Moreover, if the content is 90% by weight or more, it is difficult to obtain the desired refractive index required for an antireflection thin film.

This silane compound is an essential component for providing hardness and toughness to thin films.

Next, as a titanium organic compound, - general formula % formula %) There is a titanium hydroxy acid coordination compound represented by

Here, R3 is hydrogen or a hydrocarbon having 1 to 6 carbon atoms, R
4 represents an organic group having at least one carboxylic acid. Further, O is 1.2 or 3. Examples of these compounds include titanium organic compounds coordinated with glycolic acid, lactic acid, glyceric acid, malic acid, tartaric acid, citric acid, glyoxylic acid, pyruvic acid, acetoacetic acid, and the like.

This titanium organic compound is present in the 0 layer with α1-201-2
Preferably, it contains 0% by weight. More preferably, it is used in a content of 1 to 10% by weight, but this is because if the content of the titanium organic compound is less than 1% by weight or more than 20% by weight, sufficient hardness cannot be imparted to the thin film. It is.

This titanium organic compound is an essential component for obtaining a thin film with sufficient hardness.

Next, as components for forming the 0 layer, in addition to the organic silane compound, colloidal silica, epoxy compound, curing catalyst, etc., there are also functional silane compounds containing AK and perfluoroalkyl groups that form a low refractive index layer. Can be mentioned.

Here, the colloidal silica has a particle size of 1 to 100 m.
A material containing μ silica fine particles is suitable for obtaining the desired hardness and transparency, and known dispersion media such as methanol, ethanol, isopropyl alcohol, etc. can be used.

This colloidal silica is a useful component for obtaining a thin film having a low refractive index and sufficient hardness.

Epoxy compounds include diglycidyl ethers of difunctional alcohols such as (poly)ethylene glycol, (poly)propylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol, or trifunctional alcohols such as glycerin and trimethylolpropane. ◇ In general, curing catalysts for silanol or epoxy groups include the following: O-9-butylamine, triethylamine, guanidine, biguanide, and other amines; glycine and other curing catalysts. Amino acids, metal acetylacetonates such as aluminum acetylacetonate, chromium acetylacetonate, titania acetylacetonate, cobalt acetylacetonate, acetic acid) IJ ram, zinc naphthenate, cobalt naphthenate, zinc octylate, octyl Organic acid metal salts such as acid tin, 5nCf
i4% AfiCffi8, Fool,, T i OA
,, Lewis acids such as Zn0Q□, 5bai3, etc., but regarding all the characteristics, magnesium perchlorate,
Are better.

In addition to the above-mentioned thin film forming material, an appropriate solvent is added to the liquid composition in the present invention, taking into consideration the problem of coating workability. As a solvent, using a solvent such as alcohols, ketones, heptarosols, formamides, water, or 7 leone,
Solutions containing 1 to 20% solids by weight are preferred, but not necessarily limited.

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

The composition thus obtained is applied by a known method,
Form a coating film by curing ◎ That is, 70
-Foot, dip coat, spin cord, roll coat, spray: I-) Oh! Drying and curing are determined by the ingredients used, but preferably from 40°C to 130°C.
Therefore, curing by heating for 10 minutes to 10 hours is practical.

Further, in order to promote crosslinking and polymerization reactions of reactive groups in the components used, curing can also be carried out by irradiation with infrared rays, ultraviolet rays, gamma rays, or electron beams.

The refractive index of the antireflection thin film in the present invention is the first
The refractive index of the layer and the second layer are 155 to 2.55 and 135 to 150, respectively, and the refractive index of the first layer must be selected to be higher than the refractive index of the base material. The smaller the refractive index of the layer, the better the anti-reflection properties.The film thickness can be set to any value by adjusting it with a solvent or coating method, so it can be used as desired depending on the combination of refractive indexes. In particular, the optical thickness of each layer is selected from combinations of film thicknesses of
or for a 1/2 layer, - a quarter of the design wavelength.
It is preferable that the article having the thin film obtained as described above can be dyed with a disperse dye.

〔Example〕

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

Example t (1) Preparation of coating liquid for high refractive index (A1) In a reaction flask, add 206.28% of isopropyl alcohol.
, r-glycidoxypropyltrimethoxysilane 5.1
9 F, α05N hydrochloric acid water t42? was added and stirred at room temperature for 1 hour to perform hydrolysis. Thereafter, a colloidal dispersion of titanium oxide fine particles using water as a dispersion medium (average particle diameter 12 ± 1μ, titanium oxide content 10%) was added to the above mixture. ) 56.56"? and stirring, 0.75" dihydroxybis(tartrate) titanium and 0.02f silicone surfactant were added in this order and stirred at room temperature for 1 hour to prepare a coating liquid. The viscosity of the coating liquid is 2.4 centistokes (2
0° C.), and the solid content concentration was 3.2% by weight.

(2) Preparation of coating liquid for low refractive index (A2) Place isopropanol 232°521 into a reaction flask, and add methyltriethoxysilane (KBm-1) with stirring.
5, Shin-Etsu Chemical ■) 34.05 P, 0, 05 N hydrochloric acid water 12.41 ? was added and stirred at room temperature for 1 hour.

After this, methanol-dispersed colloidal silica (methanol silica sol, manufactured by Nissan Chemical, solid content concentration 30%) 2tO
OP was added and stirred at room temperature for 30 minutes. Then,
Added silicone surfactant. The viscosity of this coating liquid was 14 centistokes (20° C.), and the solid content concentration was 6.3% by weight.

In addition, the above coating liquids (A1) and (A2) are each filtered with a membrane filter after liquid preparation.
Large particles and insoluble matter were removed.

(3) Coating and curing of anti-reflection film with 5% hydroxide) Diethylene glycol bisallyl carbonate resin plastic/lens (thickness 0.2, refractive index t50, total light transmittance 92%), an antireflection film was provided by the following method.

First, the lens was immersed in a coating liquid (AI) for high refractive index thin films, and coating was carried out at a liquid temperature of 10° C. and a lifting speed of 12 cm/min. After lifting, 40℃ at 100℃
The lens was cured for 3 minutes to obtain a high refractive index layer.Subsequently, the lens was immersed in a strongly acidic aqueous solution for 3 minutes, thoroughly rinsed with water, and dried. Thereafter, the lens was immersed in a low refractive index thin film coating liquid (A2), and coating was performed at a liquid temperature of 8° C. and a pulling rate of 2 C1 n/min. After pulling it up, it was cured at 160° C. for 30 minutes to obtain a two-layer antireflection film.

(4) Test results The total light transmittance of the lens thus obtained was 9'
15%, and the Y radiation interference color was green.

Further, the antireflection-treated lens was dyed at 90° C. for 3 minutes using a dye bath containing a commercially available disperse dye mixed with three colors, red, blue, and yellow, dispersed and dissolved in water. The total light transmittance of this lens was 54.8%, indicating good stainability.

Furthermore, the obtained lenses were tested by the method described below, and the results are shown in Table 1.

α) Adhesion The adhesion between the anti-reflection film and the transparent substrate is
A cross-cut tape test was conducted according to D-0202. ◎ That is, using a knife, cut the surface of the transparent substrate after anti-reflection treatment into 1-word intervals, and mark the 1- squares with 1-
Form 00 pieces. Next, a cellophane adhesive tape (Nitto Kagaku ■) was strongly pressed onto it, and then it was suddenly pulled off from the surface in a 90° direction, and the remaining squares of the coat film were used as an adhesion index.

b) Scratch resistance: A load of 2 oar was applied with #0000 steel wool, the surface was rubbed 100 times, and the degree of scratches was visually evaluated in the following stages. No scratches.

B: 1 to 10 scratches within the above range OC: 10 to 100 scratches within the above range.

D: Countless scratches are present, but a smooth surface remains O E: No smooth surface remains due to scratches on the surface.

C) Water resistance and chemical resistance: It was immersed in water, alcohol, and kerosene for 48 hours, and the surface condition was examined.

d) Weather resistance: The surface condition was examined after being exposed to a sunshine weather meter using a xenon lamp for 400 hours.

The appearance was examined, and those with no abnormalities were evaluated as good.The adhesion of the antireflection film after the hot water test was evaluated by the cross-cut tape test described above.

In addition, if the thin films obtained by applying each of the coating liquids (A1) and (A2) were 11.12 layers each, the refractive index and film thickness were as follows.〇Thin line Refractive index Film thickness ( nm) 1 1 1, 7 3 I
SO, 312t 4 2
9 t 5 Example 2゜(1) Hard coat processing α) Preparation of hard coat liquid γ-Glycidoxypropyl methyljethoxysilane 10
6.85' was cooled to 10°C and heated to 50,05 with stirring.
15.5 liters of an aqueous N-hydrochloric acid solution was gradually added dropwise, and after completion of the addition, the mixture was further stirred at room temperature for 1 hour to effect hydrolysis.

This solution, epoxy resin (9 Epicoat 827', manufactured by Shell Chemical ■) 252, epoxy resin (Evolai) 3
002", cocoal 58.9 f, benzyl alcohol 295?, methanol 31 (1'), silicone surfactant t5? were added and mixed, and methanol-dispersed colloidal silica (average particle size 12 ± 1 mμ, solid content 50 %) 4
16.7g! and aluminum acetylacetonate) 1
After adding 2.5 f and stirring thoroughly, a hard coat liquid was obtained.

b) Application and curing of hard coat liquid After performing argon gas plasma treatment (AOOW, 20 seconds) on the same diethylene glycol bisallyl carbonate resin plastic as used in Example 1, the hard coat liquid was applied by dipping. It was coated and dried by heating at 93° C. for 4 hours to obtain a hard coat layer.

(3) Coating and curing of antireflection film The hard coated lens was subjected to argon gas plasma treatment (aaow) in the same manner as described above.

20 seconds), an antireflection film was provided in the same manner as in Example 1.

(4) Test results The total light transmittance of the lens thus obtained was 97.
．． 0%, and the reflected interference color was green.

In addition, this anti-reflection-treated lens was dyed at 90°C for 3 minutes using a dye bath containing a commercially available disperse dye mixed with red, blue, and yellow in water for 3 minutes. The light transmittance was 55.2%, indicating good dyeability.

Furthermore, the obtained lenses were tested in the same manner as in Example 1, and the results are shown in Table 1.

The thickness of each thin film obtained by applying each of the coating liquids (A1) and (A2) was the same as in Example 1.

Example 3 (1) Preparation of coating liquid for high refractive index (B1) In a reaction flask, methyl cellosolve 194, 82? , γ
-Glycidoxyprobyltrimethoxysilane 4.65
? , add 1.27 P of 0.05 N hydrochloric acid, and leave at room temperature for 1.
Hydrolysis was carried out by stirring for hours.

Thereafter, 48.6 IP of colloidal dispersion of titanium oxide fine particles using water as a dispersion medium used in Example 1 was added and stirred.
Dihydroxybis(lactate) titanium 0.65 ? and silicone surfactant [102F were added in this order,
The mixture was stirred at room temperature for 1 hour to obtain a coating liquid. The viscosity of this coating liquid is H12, 7 centistokes (
20° C.), and the solid content concentration was 3.5% by weight.

(2) Preparation of coating liquid for low refractive index (B2) Put 255.00 P of ethanol into a reaction flask, and add r-glycidoxypropyltrimethquinsilane Z while stirring.
072, α05N hydrochloric acid water t94? After stirring for 1 hour at room temperature, isopropyl alcohol-dispersed colloidal silica (Oscar 1432, Catalyst Kasei Co., Ltd.) was added.
Add 29.7 Of (solid content concentration 30%) and stir at room temperature.
Stirring was performed for 0 minutes. After that, glycerol diglycidyl ether 5.94P, magnesium perchlorate 0.5
5? , 0.02 P of silicone surfactant was added and dissolved. The viscosity of this coating liquid was 19 centistokes (20° C.), and the solid content was m degrees Bi6%.

After the coating solutions (B1) and (B2) were prepared, they were each passed through a membrane filter to remove giant particles and insoluble matter.

(3) Coating and curing of anti-spray film A commercially available inorganic glass panel (diameter 12Cl
11. Thickness 0.2, refractive index t52, total light transmittance 92
%) was provided with an anti-reflection film by the following method.

First, the lens was immersed in a coating liquid (B1) for high refractive index thin film, and the coating was carried out under the condition that the liquid temperature was raised by 10°C and the rate of increase was 8 am/min. Got the rate layer.

Subsequently, the lens was immersed in a strongly acidic aqueous solution for 3 minutes, thoroughly rinsed with water, and dried. Thereafter, the lens was immersed in a low refractive index thin film coating liquid (B2) K at a liquid temperature of 9°C and a lifting speed of 2°C. Coating was carried out at a rate of 11/min. After pulling it up, it was cured at 130° C. for 30 minutes to obtain a two-layer antireflection film.

(4) Test results The total light transmittance of the inorganic glass panel thus obtained was 978%, and the reflection interference color was yellow-green.

In addition, if the thin films obtained by applying each of the coating solutions (B1) and (B2) were each 21.22 layers, the refractive index and film thickness were as follows - Thin film Refractive index Film thickness (nm ) 21 177 14&92 2
1, 4 3 9 α 9
Example 4 (1) Coating and curing of antireflection film Seiko Blacks Diamond Coat I (manufactured by Seiko Epson) was treated with argon gas plasma (400W, 2
0 seconds), an antireflection film was provided in the same manner as in Example 3.

(2) Test results The total light transmittance of the lens thus obtained was 97
．． 5%, and the reflected interference color was green.

Further, the antireflection-treated lens was dyed at 90° C. for 3 minutes using a dye bath containing a commercially available disperse dye mixed with three colors, red, blue, and yellow, dispersed and dissolved in water. The total light transmittance of this lens was 55.2%, indicating good dyeability.

Furthermore, the obtained lenses were tested in the same manner as in Example 1, and the results are shown in Table 1.

Example 5゜(1) Acrylic plate coated with anti-reflection film and hardened hard coat (product name: Aku,
Rewrite MR, made by Mitsubishi Shion■, 100111X30
00as, thickness 2wh, refractive index t49, total light transmittance 92%), an antireflection film was provided in the same manner as in Example 1.

(2) Test results The total light transmittance of the lens obtained by K in this way is 97
．． 8%, and the reflection interference color was green. ◎Comparative Example is the same as Example 1 except that dihydroxybis(tartrate) + tan was not added when preparing the coating liquid for high refractive index. A lens provided with an anti-reflection film was obtained in the same manner as in Table 1. The test results are shown in Table 1. Comparative Example 2 In Example 3, when preparing the coating liquid for high refractive index, dihydroxybis(lactate) titanium An inorganic glass panel provided with an antireflection film was obtained in the same manner as in Example 3, except that .

The test results are shown in Table 1.

Each symbol in Table 1 (1) indicates the following conditions: 〇〇: Good or no abnormality ∆: Some defects are visible by visual inspection.

×: The antireflection film is damaged.

(2) In the table, 1007100 indicates good adhesion, and O/100 indicates poor adhesion. [Effects of the Invention] As described above, according to the present invention, at least a part of the transparent base material has a refractive index. When applying an anti-reflection film consisting of two thin films with different ratios by coating and curing a liquid composition,
By using a colloidal dispersion of titanium oxide fine particles dispersed in water or other solvent as a main component as a coating liquid for forming a high refractive index thin film having a higher refractive index than the transparent base material layer, desired refraction can be achieved. compared to the conventional metal Alcorade, it has improved adhesion, hardness,
It has become possible to obtain an antireflection film with excellent physical properties such as chemical resistance, scratch resistance, water resistance, and dyeability.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view 11 of the antireflection film of Example 1.
...High refractive index thin film 12...Low refractive index thin film 13...Plastic lens Figure 2 is the reflection spectrum diagram of Example 60 and above.

Claims (1)

[Claims] (1) a) When applying an anti-reflection film consisting of two thin layers of [a] and [b] from the base material toward the atmosphere to at least a part of the transparent base material, b) [a] The optical properties of the two layers of [B] and [B] are respectively [B]1
．． 55<n_a<2.25 0.8×(m/4)λ_n<n_ad_a<1.2×(
m/4)λ_0[b]1.35×n_a<1.50 0.8×(1/4)λ_0<n_bd_b<1.2×(
1/4) λ_0 (where n_a and n_b are the refractive indexes of the [a] layer and [b] layer, respectively, and d_a and d_b are the film thicknesses (in nm units) of the [a] layer and [b] layer, respectively. , m is 1 or 2, and λ_0 is the design wavelength (in nm units) in the visible wavelength region.Also, n_a>(refractive index of the base material)) satisfies the condition c) [a] Each thin film of the layer and [B] layer is obtained by applying in liquid form and curing with heating and drying or active energy rays, and d) Furthermore, the main component of the liquid composition for forming the layer [B]. i) A colloidal dispersion of fine titanium oxide particles having a particle size of 1 to 100 mμ dispersed in water or other solvent. ii) General formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^1 is an alkyl group, alkenyl group, phenyl group, halogen group, etc., and R^2 is an epoxy group, amino group, amide group, mercapto group. , methacryloyloxy group,
It represents an organic group including a cyano group, a group having a halogenated aromatic ring, and x represents a hydrolyzable group such as a halogen group, an alkoxyl group, an alkoxyalkoxyl group, or an acyloxy group. Also, a and b are each 0, 1 or 2, and a
+b is 1 to 3. ) A silane coupling agent represented by iii) General formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^3 is hydrogen or a hydrocarbon having 1 to 6 carbon atoms. R^4 is an organic group having at least one carboxylic acid. c is , 1, 2 or 3). It contains one or more compounds represented by, and when formed into a thin film, i) is 99 to 90% by weight, ii) is 99 to 90% by weight, and iii) is 0.1 to 20% by weight. Anti-reflective coating.