JPS6217701A - Liquid crystal display device with anti-reflection film - Google Patents

Abstract

PURPOSE:To improve the coloring and the drying properties of the titled device, and the productivity of the titled device by incorporating a prescribed amount of an organic radical component or a resinous compd. component binded to a metallic atom, and a prescribed amount of a metallic component binded to an metal oxide or an organic chain to the constituting components of each thin films of the antireflection coating composed of three thin layers respectively. CONSTITUTION:The antireflection film composed of the three thin films is formed on the liquid crystal display device. Each components of constituting the three layers composed of the thin films (a), (b) and (c) are composed of at least 20wt% the org. radical component or the resinous compd. binded to the metallic atom and <80wt% the metallic atom binded to the metal oxide or the organic chain respectively. Each thin films composed of the three layers (a), (b) and (c) have the optical characteristics satisfying formulas I-III. In formulas I-III, na, nb, and nc are each refractive indexs of the three layers respectively. The symbols of da, db and dc are each film thicknesses of the prescribed three layers, the lambda1, lambda2, and lambda3 are each independent wave lengths of the visible range, (m) is an integer, (l) and (n) are each positive odd numbers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a liquid crystal display device having a good anti-reflection film on an external glass substrate and/or a glass substrate of a liquid crystal cell.

[Summary of the invention]

The present invention aims to improve the clarity of the screen by forming three layers of thin films with different refractive indexes on the external glass substrate of a liquid crystal display device and/or the glass substrate of a liquid crystal cell. Since it is composed of at least 20% by weight of organic matter, it has excellent impact resistance, alkali resistance, heat resistance, easy processability, and dyeability. In order to carry out the entire curing reaction,
Compared to vapor deposition and other conventional techniques, this method enables large-capacity and mass production.

[Conventional technology]

Conventionally, the technology of applying an anti-reflection film to the liquid crystal cells of liquid crystal display devices has not been used in segment-type display systems or matrix-type display systems, and is known to be used on the glass substrate of original addressless liquid crystal display devices. It is being No antireflection film was provided on the external glass substrate of the liquid crystal display device.

Regarding the theory of anti-reflection coating and its product 1 method, many methods have been proposed, including methods of forming thin films of metal oxides, fluorides, etc. using vacuum evaporation, and PVD such as sputter deposition and ion blating. methods and various CVD techniques are common.

On the other hand, in addition to these physical vapor deposition methods, there is a method for obtaining an antireflection film by applying it in liquid form and curing it.
JP-A-59-49501 proposes an antireflection film consisting of three layers. In these methods, a composition consisting of titanium alcoholade and colloidal silica is used as a material for a high refractive index thin film, and a composition consisting of a silane coupling agent, an epoxy compound, and colloidal silica is used as a total low refractive index thin film material. The anti-reflection effect is fully realized.

Furthermore, Japanese Patent Application Laid-Open No. 57-57501 discloses a single layer made of a synthetic resin layer. Synthetic resin lenses coated with 11 or multilayer antireflection films have been proposed, and in this method, Alcolade such as titanium, tantalum, etc., melamine resin, etc. are used as materials for the high refractive index thin film.

[Problem that the invention seeks to solve]

However, among the conventional techniques mentioned above, methods for forming thin films with anti-reflection films by vacuum evaporation, sputter evaporation, ion blating, CVD, etc. require: (1) a high degree of vacuum; There are restrictions on size and materials,
This method is not suitable as a thin film forming method for liquid crystal display panels, which tend to have larger capacities. In addition, it takes a long time to manufacture, and the productivity and economic efficiency are low.

(2) 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, it is impossible to color or dye the product after anti-reflection treatment.

It has the following problems.

Also, JP-A-58-46301, JP-A-59-4
The method disclosed in Japanese Patent No. 9501 has a problem in the adhesion of each layer. Furthermore, since the coating film has poor flexibility, cracks may occur depending on the processing conditions.

Furthermore, the method disclosed in the examples of JP-A-57-57501 has all the problems of not having a sufficient antireflection effect and having insufficient water resistance.

Therefore, the present invention aims to solve all of these problems.
The purpose is to provide excellent anti-reflection properties to improve the clarity of the screen, and to be highly economical.
Suitable for producing large-capacity panels with large area gold, and moreover,
It has an anti-reflection coating yk that can be mass-produced.

All liquid crystal display devices are available.

[Means for solving problems]

The liquid crystal display device having the anti-reflection film of the present invention has the following three features: α) on the surface of the external glass substrate and/or the glass substrate of the liquid crystal cell from the substrate toward the atmosphere; In forming an antireflection film consisting of a thin film, b) the constituent components of each of the thin films (■, ■, θ) each contain at least 20% by weight of an organic group component or a resin compound component bonded to metal atoms; It consists of less than % by weight of metal atoms bonded to metal oxide or organic chains, and the optical characteristics of the three layers C)■, [B], and [C] are respectively ■
1.55 (le α (1,80 le α, dα = tλ1/4 (
B, ) @ 1.65 (nA (2,25 n b , cl b = mA2/4 (nm) le b >
α θ 1.40 (c (1,50 nc, dc=nλs/4 (nm)
The refractive index of the floor, da, cLb, and da are respectively, ■141i
, @) layer, 0 layer thickness (rL, ) 1-represented, fold is a positive integer, t.

is a positive odd number, λ1. λ8. λ, each independently satisfies the condition of the wavelength in the visible region (represents WL>1. Also, Lα> (refractive index of the substrate)), and each of LL) ■, [B], and [C] The thin film is an optical thin film formed by applying a coating solution consisting of a solution or a colloidal suspension and curing it by heating, drying, or active energy rays, and then laminating it on the glass substrate of the liquid crystal display device. do.

The antireflection film in the present invention is applied to the glass substrate of a liquid crystal display device, but even clearer images can be obtained by applying the antireflection film to both the external glass substrate and the glass substrate of the liquid crystal cell.

As an anti-reflection film, three thin films with different refractive indexes are formed on the entire substrate, but the optical function of the thin film depends on the coating assembly used to form each thin film and its application and curing methods. Its performance is decisive. In the present invention, the coating material for forming the entire 0 layer and 0 layer is a suspension solution in which fine metal oxide particles are colloidally dispersed in a solvent, metal alcoholades, metal chelates, metal acylates, and their hydrolysis. Condensates, polymers such as natural resins and synthetic resins, and reactive compounds such as polymerizable monomers, thermosetting reactive compounds, coupling reactive monomers, condensation monomers, etc. Both consist of one component.

The above metal oxide dispersed in a total solvent has a particle size of 1
Including colloidal silica consisting of ~100mμ silica particles, alumina sol, zirconium oxide sol,
Antimony pentoxide sol, titanium oxide sol, tin oxide sol, iron oxide sol, chromium trioxide sol, cerium oxide sol,
Examples include yttrium trioxide sol and tantalum oxide sol. Furthermore, dispersions of oxides such as hafnium, thorium, vanadium, niobium, molybdenum, lead, and zinc can also be used. Furthermore, for the purpose of improving conductivity, it is also possible to add a given characteristic to the fine particles by doping them with other metal oxides.

Examples of metal compounds having organic residues include silane coupling agents represented by the general formula R%Bi, -α-b, and tetraalkoxysilane. These hydrolysates, partial condensates, etc. also have similar properties. Here R1
is an alkyl group, an alkenyl group, a phenyl group, a halogen group, etc., and R1 is an epoxy group, an amino group, an amide group,
Indicates an organic group containing a mercapto group, a methacryloyloxy group, a cyano group, a group having a nuclear halogenated aromatic ring, etc.
Ha, ha l: Ige: 4. Indicates hydrolyzable groups such as flukoxyl group, alkoxyalkoxyl group, and acyloxy group. Also, α and h are each I11 or 2, and α+b is 1
to 3. Examples of these compounds include tetrafunctional silanes such as tetramethoxysilane, methyltrimethoxysilane, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, β-(5,4 -Epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxy7rane, γ-mercaptoglobiltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-B-(aminoethyl)-γ-amino Propyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-cyanoglobiltrimethoxysilane, γ-morpholinoglobiltrimethoxysilane, N
Examples include trifunctional silanes such as -phenylaminopropyltrimethoxysilane, and trifunctional silanes in which a portion of the trifunctional silane is substituted with a methyl group, an ethyl group, or a bivinyl group.

In addition, functional silane compounds containing perfluoroalkyl groups are suitable, especially for forming a low refractive index layer.

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

An example of this is titanate coupling agent -? Useful are aluminum coupling agents, alcoholades, acylates, and chelating compounds such as zirconium, mental, tin, and indium. In addition, alcoholades, acylates, chelating compounds, etc. of hafnium, thorium, vanadium, niobium, chromium, molybdenum, manganese, iron, cerium, lanthanum, lead, zinc, etc., which can be prepared by methods similar to these, can also be used.

These preferred compounds include tetrainpropyl titanate, tetra-loop titanate, tetrakis(2
-ethylhexyl) titanate, diisopropyl bis(acetylacetone) titanate, di-luptyl bis(triethanolamine) titanate, dihydroxy bis(lactate) titanium, isopropyl octylene glycol tetanate, isopropyl triisostearoyl titanate, inglobuldecyl Benzene 7 sul; f-nyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphate) titanate, tetraoctyl bis(ditridecyl phosphate) titanate, tetra(2,2-diallyloxymethyl-1-butyl) ) bis(di-tridecyl)phosphate titanate,
Bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate ethylene titanate, inglobil trioctinoltitanate, isopropyl dimethacrylylisostearoyl titanate, isopropyl instearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl Titanium coupling agents such as phenyl titanate, isopropyl tri(N-aminoethyl/aminoethyl) titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene natanate, and titanium alcohol which is partially hydrolyzed and condensed with Alcolade. Examples of organic titanium compounds include alcoholades whose organic groups are substituted with other alcohols, acylates whose organic groups are substituted with organic acids, ethyl acetoacetate, ethylene glycol, salicylaldehyde, tartaric acid, Coordinating compounds with chelating compounds such as lactic acid and diacetone alcohol can also be used.

Examples of zirconium compounds include alcoholades such as tetraisoglobil zirconate and tetra-louptyl zirconate, their partially condensed prepolymers, diimpropyl bis(acetylacetone) zirconate, bis(acetylacetone) zirconate, and bis(acetylacetone) zirconate. Chelate compounds such as
Organic zirconium compounds are available that have a similar substitution fund as titanium compounds.

Furthermore, compounds such as tantalum, tin, and aluminum can be treated as organic metals similar to those mentioned above except that they have coordination numbers of 5 and 2.3, respectively. Namely, alcoholades such as pentaethoxytantalum, pentabutoxytantalum, jetoxytin, dibutoxytin, triethoxyaluminum, triisopropoxyaluminum, chelates with ligands such as acetylacetone, lactic acid, oxalic acid, tartaric acid, maleic acid, acylates, etc. Examples include substituted compounds such as ethylene glycol.

In addition to these, antimony, iron, chromium, cerium, yttrium, hafnium, thorium, vanadium,
Alcolade, acylate, and chelate compounds of metals selected from niobium, molybdenum, lead, and zinc can also be used.

Further, the organic residue components of the above-mentioned compounds may be substituted with a polymeric material containing a binding residue component such as polyacrylic acid, polyvinyl alcohol, polyethylene glycol, polyvinylamine, etc., without any problem.

Next, the basic purpose of polymeric materials such as natural resins and synthetic resins is to serve as a stabilizer for gold J4 atoms, or to impart flexibility, dyeability, and toughness.

Examples of materials include celluloses such as carboxyalkylated cellulose, terpene-based fats, yv-cose derivatives,
Natural polymers such as polyamino acids, chitin, chitosans, starches, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylic esters, polymethacrylic esters, polyvinylamine, polyurethane, polyvinylpyrrolidone, polyvinylpyridine, polyvinylimidazole, etc. Synthetic polymers with all polar groups, polystyrene, bisphenol H, yt4 +) carr
Examples include aromatic polymers such as tl-nate, high refractive index polymers such as polysal7ones, and low refractive index polymers such as fluororesins.

In addition, examples of reactive compounds added to adjust viscosity, modify properties, and obtain toughness and durability include precured polyfunctional acrylates, epoxy compounds such as ethylene glycol diglycidyl ether, and lactones. and reactive monomers such as incyanates.

Furthermore, a curing catalyst that promotes the reaction of these reactive groups can be added to shorten the curing time and increase the crosslink density.

These organic components are present in the formed thin film at least
It is necessary to contain an amount of 201 St-. That is, 20
If the weight is less than t, the elasticity will not be sufficient and durability such as crack resistance will be poor. Furthermore, sufficient adhesion between each layer of the thin film is often not achieved. Furthermore, although there is no upper limit to the upper limit, those containing a large amount of M components tend to have poor hardness, and it becomes difficult to maintain a high refractive index of the high refractive index layer.

Therefore, the type and content of the M organic component should be determined within the range, taking into consideration the intended use.

These materials are used after being diluted with an appropriate solvent.

That is, solutions containing 1 to 20% by weight of solids using alcohols, esters, ketones, cellosolves, formamides, water, Freon, and other solvents are preferred, but there are limitations. isn't it.

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

The composition thus obtained is applied by a known method,
A coating film is formed by curing. That is, flow coating, dip coating, spin cording, roll coating, and various improved coating methods can be used.

Further, drying and curing are determined depending on the components used, but curing by Calorie heat at 40° C. to 130° C. 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.

In addition, in order to improve the adhesion of layers 1, 2, and 6 of the present invention, treatment with an alkaline solution or strong acid with oxidizing power, ozone treatment, treatment with charged flame, or plasma gas treatment may be applied. Treatment with one or more suitable methods of surface treatment, such as treatment with oxidizing agents and reducing agents, can be carried out.

The refractive index of the antireflection thin film in the present invention is the first
The refractive index of the layer, the 21i#, and the third layer is 1.55 to 1.55, respectively.
1.80, and 1.65 to 2.25 and 1.40
~1.50, and the refractive index is the highest in the second r@,
Next, it becomes lower in the first layer and the third layer. Further, it is necessary to select a value of the refractive index higher than the refractive index of the base material. On the other hand, the film thickness can be set to any value by adjusting it with a solvent or coating method, so it is selected from any combination of film thicknesses depending on the combination of refractive indexes, but in particular, the optical film thickness of each layer is is preferably an integral multiple of -4/4 of the visible wavelength. If these optical conditions are not met, the antireflection properties will be poor, which is not preferable.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

Example 1 (1) Preparation of coating liquid for high refractive index (A1) 155 tf of ethanol was placed in a reaction flask, and while stirring, γ
-Glycidoxyglobil(methyl)dimethoxysilane 1
0t, ethanol-dispersed colloidal 7 Lika (Oscar 12
32. Catalyst chemical synthesis (book, solid content concentration 30%)5. Of, tetramer of tetrabutyl titanate (TBT-B4
After obtaining 1 difference in Japan (...) 50ff7JQ, I left it at room temperature for 1 day and night.

Next, 100 methyl ethyl ketone? and silicone surfactant α022 were added to form a coating liquid. The viscosity of this coating liquid is 1.5 centistokes (20°C),
The solid content concentration was 67% by weight.

(2) Preparation of low refractive index coating liquid (A2) Add ethanol (60?) to a reaction flask and add γ-
Glycidoxyglobiltrimethoxy7 silane 1i9F, inglobilbil alcohol-dispersed colloidal silica (Oscar 1432 Catalyst chemical formation (... solid content - 1i30%)
After adding 102, 5v of hydrochloric acid (105 liters) was added dropwise. After aging this solution at room temperature for a day and night,
Silicone surfactant ll02f and methyl ethyl ketone 100ff were added, and with further stirring, glycerol diglycidyl ether a4ft, magnesium perchlorate α
15? was added and dissolved. The viscosity of this coating liquid is 1.4
centistokes (20° C.) and solid content concentration was 11% by weight.

(8) Preparing the medium refractive index coating liquid (A5) The refractive index coating liquid (A5) is composed of (A1) and (A2).
100 each? These were mixed to obtain (A5).

The viscosity of this liquid is 1.5 centistokes (20℃),
The solid content concentration was &8fi:1%.

(4) Creation of external glass substrate with anti-reflection film All anti-reflection treatments were applied to the external glass substrate (refraction $1.54) of a liquid crystal display watch.Prior to this, (A1), (A2),
(A5) Each coating liquid gold is completely filtered using a Menz line filter to remove large particles and insoluble matter before use.

First, dipping was performed in a coating liquid for medium refractive index (A3). The liquid temperature at this time was 11℃, and the pulling speed was 3
It was cfRZ. After dipping, the glass substrate gold, 8
Dry cured at 0°C for 25 minutes.

Subsequently, this glass substrate gold was dissolved in 5% NaOH aqueous solution.
After being immersed for a minute and subjected to alkali treatment, it was thoroughly washed with water, dried, and then dipped in a high refractive index coating liquid (A1). The liquid temperature at this time was 10℃, and the pulling speed was 4/4
It was a minute. After dipping, it was dried and cured at 80° C. for 25 minutes.

The above two-layer thin film-coated glass substrate was treated with a 1.05N hydrochloric acid aqueous solution for 4 minutes, thoroughly dried, and subjected to low refractive index coating solution (A2)'tt-delag. The liquid temperature at this time was 11°C, and the pulling rate was 55 F/min. After dipping, wait for 60 minutes at 80℃, then continue for 60 minutes at 130℃.
Dry and harden.

The external glass substrate of the liquid crystal display watch thus obtained exhibits a green reflective interference color, and the visible light transmission is 9a.
It was 2 chi.

The adhesion of the thin film was evaluated using a cross-cut tape test, a hot water boiling test, an unexpected exposure test (1 month), and a sunshine weather meter test (500 hours), and the results showed good results. Furthermore, (person 3), (A1
) and (A2), respectively.
1.12.13, the refractive index and film thickness are: Thin film Refractive index Film thickness (rL,) 11 1.67 7912
1.82 7513 1.49
It was 87.

Example 2 Example 1 was used except that an external glass substrate (refractive index 1.54) tl of a color liquid crystal display device used for automobile dash board displays was used as a substrate on which an antireflection film was applied.
The same anti-reflection coating was applied to all parts. These initial characteristics were as good as in Example 1, and an improvement in screen clarity was observed.

Example 3 In addition to the antireflection film, (A1), (A2), and
(,A3)', and these thin films were laminated on a glass substrate of a large-capacity liquid crystal display cell by the following method.

In the liquid crystal cell before liquid crystal injection, the injection port was sealed, and the thin films (A3), (A1), and (A2) were sequentially dipped in the same manner as in Example 1, and after heating and curing, the liquid crystal injection port was opened. After all of the liquid crystal material was injected, the injection port was completely sealed again. The mechanical properties were as good as in Example 1.2.

Example 4 (1) Preparation of coating liquid for high refractive index (B1) In a flask for reaction, Ingrovil alcohol 45? , a solution of tetrabutoxyzirconium in ethyl acetate (trade name “
Atron NZr” made by Japan No. 1, 15% i containing Zr01)
100j', 12.5F of γ-glycidoxyglobyltrimethoxysilane, and 40f'i of acetylacetone were added, and the mixture was stirred at room temperature for 2 hours. Subsequently, 25f of zirconium oxide sol (ZrO, containing 20%, acetic acid stabilized product, manufactured by Nichichi Kagaku Co., Ltd.) as a water-gold dispersion medium was mixed with 151 g of glacial acetic acid,
The denatured solution was added dropwise to the reaction solution while stirring 60 f'i of methanol. Subsequently, α022 ammonium perchlorate was added to prepare a coating liquid.

The viscosity of this coating liquid is 1.8 centistokes (20℃)
The solid content concentration was 43% by weight.

(2) Preparation of low refractive index coating liquid (B2) As a low refractive index coating liquid, a commercially available fluorosilicone coating agent (trade name "KP-801") was used.

Shin-Etsu silicone (manufactured by Akai, solid content concentration 5%) was applied all around (8
) Preparation of coating liquid for medium refractive index (B3) (*
2) 50F and (B1) 751 were mixed to form a medium refractive index coating liquid (B3).

The viscosity of this coating liquid is 1.6 centistokes (20℃)
The solid content concentration was 6.5% by weight.

(4) Creation of external glass substrate with anti-reflection film applied on the entire external glass substrate (refractive index: 1.54) of a liquid crystal display device for a calculator. Coating and surface treatment (B
6), (B1), and (B2) were performed in the same order as in Example 1. In addition, the temperature and lifting speed of the coating liquid are (B3), 10"C3an 7 minutes, (B1) 1
1℃, 55cM/min, (B2) 10℃, 3c! It was run at R/min.

The reflection interference color of the external glass substrate thus obtained was blue-green, and the visible light transmittance was 9a3. Furthermore, (B
3), (B1), and (B2) have 21, 22, and 23 layers, respectively, and the refractive index and film thickness are as follows: Thin film Refractive index Film thickness (4 winds) 21 1.65 76.022
1.84 7Q, 325 1.47
It was 811L2.

Example 5 As the antireflection film, (B1), (B2) of Example 4,
Using (B3), these thin films were laminated on an external glass substrate of a liquid crystal display type of a pocket-type liquid crystal color television (made by Suwa Seiko Kin, trade name: "Television"). The lamination method was the same as in Example 4. The film properties were as good as in Example 47, and an improvement in image clarity was observed.

Comparative Example 1 The visible light transmittance of an external glass substrate used in commercially available liquid crystal display devices such as watches and calculators was measured and found to be 91.7.
It was ~94.0%.

Comparative Example 2 Laminated on a glass plate (refractive index 1.54) by S10* + "Otr A40s t" vacuum evaporation method.

Various performances such as adhesion between the substrate and the antireflection film were good, but the size of the substrate was limited.

〔Effect of the invention〕

As described above, according to the present invention, by applying an anti-reflection film to the external glass substrate of the liquid crystal display device and/or the glass substrate of the liquid crystal cell, the anti-reflection film can be applied to the external glass substrate of the liquid crystal display device and/or the glass substrate of the liquid crystal cell. 1 of thin films with different refractive indices, and each thin film has at least 2
It is a thin film consisting of 0% by weight of organic components, and the thin film is formed by applying the entire coating solution and drying and curing, so it has excellent colorability and dyeability, and can be produced in large quantities. The present invention provides an economical anti-reflection film, and at the same time has the effect of improving screen clarity due to the anti-reflection film.

[Brief explanation of drawings]

FIG. 1 shows a cross-sectional view of a liquid crystal display watch having an antireflection film according to Example 1. 11... Medium refractive index thin film 12... High refractive index thin film 13... Low refractive index thin film 14... External glass substrate 15.17... ...Polarizing plate 16...TN liquid crystal cell 18...Light reflecting plate 19...Cell glass substrate FIG. 2 shows the entire reflection spectrum of Example 1. The third column shows a cross-sectional view of a liquid crystal cell having the entire antireflection film of Example 5. that's all

Claims (1)

[Claims] (1) a) The surface of the external glass substrate of the liquid crystal display device and/or the glass substrate of the liquid crystal cell is made of three thin films of [a], [b], and [c] from the substrate toward the atmosphere. In a liquid crystal display device having an anti-reflection film formed with an anti-reflection film, b) each of the constituent components of the thin film in [a], [b], and [c] is bonded to at least 20% by weight of metal atoms, respectively; consisting of an organic group component or a resin compound component and less than 80% by weight of metal oxide or metal atoms bonded to an organic chain; c) The chemical properties of each of the thin films in [a], [b], and [c] are [ 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, and nc are the [a] layer and [b] layer, respectively.
layer, [C] The refractive index of the layer, da, db, dc are respectively [A]
Represents the film thickness (nm) of layer, [b] layer, and [c] layer, where m is a positive integer, l and n are positive odd numbers, and λ_1, λ_2, and λ_3 are each independently wavelengths in the visible region (nm). represents. Also, na
>(refractive index of the substrate). ) A liquid crystal display device having an antireflection film that satisfies the following conditions.