JP3077778B2 - Electrode substrate for liquid crystal display device and liquid crystal display device using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode substrate for a liquid crystal display and a liquid crystal display using the same.

[0002]

2. Description of the Related Art In general, plastic materials are light in weight, and excellent in impact resistance, workability and mass productivity, and in recent years, demand for optical filters, optical lenses, optical discs and other optical element materials has been increasing. It is getting. Currently, transparent resins such as methyl methacrylate, polystyrene, and polycarbonate are mainly used as plastic materials for these optical elements. However, these thermoplastic resins not only have poor heat resistance represented by heat deformation temperature, but also have poor solvent resistance and low elastic modulus.

[0003] In addition, plastic optical elements generally have the drawback of low surface hardness in addition to the above problems as compared with inorganic glass, and many attempts to improve this have already been proposed. For example, a method of providing a polyorganosilane hard coat film or an acrylic hard coat film on the surface of a plastic substrate (US Pat.
997, USP 4,211,823, JP-A-57-16
8922, JP-A-59-38262, JP-A-59-51908, JP-A-59-51954, JP-A-59-78240, and JP-A-59-8
9368, JP-A-59-102964, JP-A-59-109528, and JP-A-59-1206.
63, JP-A-59-155439, JP-A-59-174629, and JP-A-59-193969.
JP-A-59-204669).

However, in the technology of providing a silane-based and acrylic-based hard coat film disclosed in JP-A-59-38262 and JP-A-59-51908, the heat resistance is somewhat improved. However, the degree was insufficient. On the other hand, as a substrate for a liquid crystal display device, use of a transparent plastic material instead of a glass substrate has been studied. FIG. 1 shows a conventional technology (Japanese Unexamined Patent Publication No.
FIG. 20 is a cross-sectional view showing a configuration of a liquid crystal display device according to No. 204545). This liquid crystal display device is 0.1 to 0.4 m
mt thermoplastic resin substrate 2 [for example, PES (polyether sulfone), PMMA (polymethyl methacrylate), PC (polycarbonate), or P
ET (polyethylene terephthalate)]
x undercoat film 3 is deposited to a thickness of 150 angstroms, and ITO transparent conductive film 4 is further evaporated to a thickness of 200 angstroms.
A liquid crystal is sealed between the two obtained substrates.

However, a film is formed by sputtering.
SiOx undercoat and ITO transparent conductive film
The formed thermoplastic resin substrate 2 is sheeted in the same manner as the glass substrate.
When entering into the existing liquid crystal display device manufacturing process with leaves,
The problem occurred. 1. Alkaline treatment and heating treatment after photoetching
In the process, SiOx undercoat and ITO
Cracks occur in the deposited film and subsequent processing cannot be performed. K
Even if a display device without racks can be created,
In the species reliability test (high temperature and high humidity storage, thermal shock etc.), IT
Cracks occur in the O film and the ITO electrode breaks,
Cracks occur in the SiOx film
Bubbles are formed. 2. 0.4mmt thickness due to the use of thermoplastic resin
Even so, the substrate does not have a certain degree of hardness (so-called waist).
It is difficult to perform the same single-wafer processing as the secondary substrate. Furthermore, the softening and opening of the substrate
Since the starting temperature is about 100 ° C, warpage in the heating process
Deformation in the bonding process
The gap cannot be made uniform and display unevenness occurs. 3. Insufficient gas barrier properties of SiOx undercoat
In some cases, O _TwoAnd H_TwoGas such as O invades,
This leads to the generation of air bubbles.

An object of the present invention is to provide an electrode substrate for a liquid crystal display device having excellent heat resistance, abrasion resistance and transparency, and a liquid crystal display device using the same. And

[0007]

According to the present invention, there is provided an electrode substrate for a liquid crystal display device, comprising a transparent cross-linked resin substrate, a cured film containing inorganic fine particles, a metal oxide film, an ITO film.
And have a film in this order. And contains inorganic fine particles
The cured film is a siloxane-based cured film containing fine silica particles.
It is. Further, another electrode base for a liquid crystal display device according to the present invention.
The plate is made of inorganic fine particles on a transparent cross-linked resin substrate.
Cured film containing particles, metal nitride film, metal oxide film,
An ITO film is provided in this order. Further, according to the present invention,
Still another electrode substrate for a liquid crystal display device has a transparent cross-linked structure.
A cured resin containing inorganic fine particles is placed on a substrate made of
A film, a metal oxide film, and an ITO film are provided in this order.
And the resin of the crosslinked structure is a maleimide-based
It is a resin obtained by copolymerization of not less than weight%. A liquid crystal display device according to the present invention is a liquid crystal display device in which liquid crystal is injected between two alignment-treated electrode substrates, and has the above-mentioned electrode substrate for a liquid crystal display device as an electrode substrate.

[0008] The transparent crosslinked resin (hereinafter abbreviated as transparent crosslinked resin) in the present invention is not particularly limited, but a transparent crosslinked resin having a glass transition temperature of 160 ° C or higher has good heat resistance. Therefore, it is preferably used.
Here, the glass transition temperature is a temperature at which a polymer changes from an amorphous glass state to a rubber state. Various properties such as elastic modulus, expansion coefficient, heat capacity, refractive index, and dielectric constant change with the transition temperature as a boundary, and it is possible to measure the glass transition temperature from the change in these properties. It can be evaluated by a known method such as scanning calorimetry (DSC) (for example, JIS K7121). In the case of measuring the glass transition temperature by differential scanning calorimetry, the glass transition temperature can be obtained by evaluating the transparent crosslinked resin itself or the one obtained by heat-treating the resin. It is also possible to regard the glass transition temperature of a resin provided with a transparent coating as the glass transition temperature of the transparent resin.

The mechanical properties of the transparent crosslinked resin are preferably 20 when the flexural modulus at room temperature is used as an index.
0 kg / mm ² or more, more preferably 330 kg
/ Mm ² or more. Furthermore, the transparency of the transparent cross-linked resin, when represented by the total light transmittance at the time of non-coloring as an index,
It is preferably at least 60%, more preferably at least 80%. The transparent cross-linked resin can be made into a composite system with an inorganic substance or the like as long as the transparency is not impaired.
It may contain an inorganic bond such as a siloxane bond or a phosphazene bond.

The components of the transparent crosslinked resin having a glass transition temperature of 160 ° C. or higher include, for example, (i) polymethacrylic acid,
Polyolefin resins represented by polymethacrylic resins such as polycarboxyphenyl methacrylamide and polystyrene resins such as poly (biphenyl) styrene; (ii) poly (2,6-dimethyl-1,4-phenylene oxide) Polyether resins represented by (iii)
Polycarbonate resins represented by poly (oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene), (iv) poly (oxy-2,2,2)
Polyester-based resins represented by 4,4-tetramethyl-1,3-cyclobutyleneoxyterephthaloyl),
(v) poly (oxy-1,4-phenylenesulfonyl-
1,4-phenylene), poly (oxy-1,4-phenyleneisopropylidene-1,4-phenyleneoxy)
1,4-phenylenesulfonyl-1,4-phenylene)
(Vi) Polyamide resin represented by poly (iminoisophthaloylimino-4,4′-biphenylene), (vii) Poly (thio-1,
4-phenylene sulfonyl-1,4-phenylene), (viii) unsaturated polyester resin, (ix) epoxy resin, (x) melamine resin, (xi) phenolic resin, xii) diallyl phthalate resin, (xiii) polyimide resin, (xiv) polyphosphazene resin and the like.

By introducing a crosslinked structure into these polymer groups,
It is possible to obtain a transparent crosslinked resin exhibiting the above thermal characteristics. In particular, from the viewpoint of transparency and moldability, a polyolefin-based resin is preferable, and a polyolefin-based copolymer obtained by polymerizing a composition containing a polyfunctional monomer having two or more unsaturated groups is more preferable. Used. The copolymer contains 20 to 98% by weight of a maleimide monomer represented by the general formula (A) and 2 to 80% by weight of a polyfunctional monomer having two or more unsaturated groups. And a copolymer obtained by polymerizing a composition in which the total weight ratio of the monomer represented by the formula (A) and the polyfunctional monomer having two or more unsaturated groups is 30% by weight or more. Coalescing is preferably used.

[0012]

Embedded image In the formula, R ¹ and R ² represent a substituent selected from hydrogen, a methyl group and an ethyl group. R ³ represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different. When R ³ is a hydrocarbon group, specific examples include (i) a linear alkyl group such as a methyl group, an ethyl group, a propyl group, an octyl group, and an octadecyl group;
Branched alkyl groups such as isopropyl group, sec-butyl group, tert-butyl group and isopentyl group, (iii) alicyclic hydrocarbon groups such as cyclohexyl group and methylcyclohexyl group, (iv) phenyl group and methylphenyl group And (v) an aralkyl group such as a benzyl group and a phenethyl group. Note that R ¹ , R ² and R
³ may be substituted with various substituents such as a halogeno group (such as fluorine, chlorine, and bromine), a cyano group, a carboxyl group, a sulfonic acid group, a nitro group, a hydroxy group, and an alkoxy group.

Specific examples of the compound represented by formula (A) include N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, −
p-methylphenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenyl Maleimide, N
-O-chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide,
No-carboxyphenylmaleimide, Np-carboxyphenylmaleimide, Np-nitrophenylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-isopropylmaleimide and the like.

These monomers can be used alone or as a mixture of two or more. From the viewpoints of yellowing and weather resistance after the heat resistance test, among these maleimide compounds, alkylmaleimide and cycloalkylmaleimide are preferable, and N-iso-propylmaleimide and N-cyclohexylmaleimide are particularly preferable. Further, from the viewpoint that the monomer solution can be easily prepared at the time of cast polymerization and the above properties can be satisfied, N-
The combination of N-alkylmaleimide and N-alicyclic alkylmaleimide, such as the combination of iso-propylmaleimide and N-cyclohexylmaleimide, is most preferred. The ratio of N-alkylmaleimide to N-alicyclic alkylmaleimide when used in combination should be appropriately determined experimentally depending on the type and amount of the polyfunctional monomer having two or more unsaturated groups. However, in order to exhibit the effect of the combination, N-
It is preferable to use N-alicyclic maleimide in the range of 10 to 500 parts by weight based on 100 parts by weight of the alkylmaleimide.

The polyfunctional monomer having two or more unsaturated groups is a monomer having two or more unsaturated functional groups copolymerizable with the maleimide. Examples of the copolymerizable functional group include a vinyl group, a methylvinyl group, an acryl group, and a methacryl group. In addition, a monomer containing two or more different copolymerizable functional groups in one molecule is also included in the polyfunctional monomer.

Preferred specific examples of the polyfunctional monomer having two or more unsaturated groups include (i) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate.
Acrylate, glycerol (di / tri) (meth) acrylate, trimethylolpropane (di / tri) (meth) acrylate, pentaerythritol (di / tri /
Di-, tri-, tetra- (meth) acrylates of polyhydric alcohols such as tetra) (meth) acrylate, (ii)
aromatic polyfunctional monomers such as p-divinylbenzene and o-divinylbenzene, (iii) esters such as (meth) acrylic acid vinyl ester and (meth) acrylic acid allyl ester, and (iv) butadiene, hexadiene, pentadiene and the like. Dienes, (v) a monomer having a phosphazene skeleton into which a polymerized polyfunctional group is introduced from dichlorophosphazene as a raw material, and (vi) a polyfunctional monomer having a heteroatom cyclic skeleton such as triallyl isocyanurate.

In the above polyolefin copolymer composition, the monomer represented by the above-mentioned general formula (A) is contained in an amount of 20 to 9%.
Preferably, the content is 8% by weight. 20 content
When the amount is less than the weight percentage, properties such as sufficient heat resistance, mechanical strength, and optical isotropy may not be satisfied. On the other hand, when the content exceeds 98% by weight, the degree of crosslinking is reduced, and the solvent resistance, low water absorption and the like may be insufficient. This content is more preferably from 30 to 80% by weight, and even more preferably from 40 to 60% by weight.

The polyfunctional monomer having two or more unsaturated groups is preferably contained in the crosslinked polymer composition at a ratio of 2 to 80% by weight. If less than 2% by weight,
Crosslinking does not proceed sufficiently, and a decrease in heat resistance, solvent resistance and the like tends to be observed. If it exceeds 80% by weight,
In some cases, a problem such as a decrease in impact resistance and a significant decrease in properties as plastic may occur.

In the above-mentioned polyolefin copolymer composition, mechanical strength, optical isotropy, refractive index,
Various copolymerizable monomers are preferably used in combination for the purpose of lowering water absorption, improving dyeability, improving heat resistance, improving impact resistance, and the like. Examples of monomers that can be used in combination include aromatic vinyl monomers, olefin vinyl monomers, (meth) acrylic acid and its ester monomers, and polycarboxylic anhydrides. Specific examples of such an aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinyltoluene, chlorostyrene, bromostyrene, and the like. Usually, styrene, α-methylstyrene and p-
Methylstyrene is used. As other vinyl monomers, (i) acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, (ii) methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, t-butyl methacrylate And (meth) acrylic acid (ester) monomers such as benzyl methacrylate, acrylic acid and methacrylic acid, and (iii) maleic anhydride.

The total content of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups in the polyolefin copolymer composition is as follows: It is preferably at least 30% by weight, more preferably at least 40% by weight. If the amount is less than 30% by weight, a polymer having insufficient transparency, heat resistance, chemical resistance, impact resistance and the like may be obtained.

For the purpose of improving the light resistance, oxidation deterioration resistance and antistatic property, it is also useful to add various ultraviolet absorbers, antioxidants and antistatic agents to the transparent crosslinked resin in the present invention. In particular, it is preferable to copolymerize a monomer having an ultraviolet absorbing property or an antioxidant property, since these properties can be improved without lowering chemical resistance and heat resistance. Preferred examples of such a monomer include a benzophenone ultraviolet absorber having an unsaturated double bond, a phenylbenzoate ultraviolet absorber having an unsaturated double bond, and a (meth) acryl monomer having a hindered amino group as a substituent. Is mentioned.
These copolymerized monomers are preferably used in the range of 0.5 to 20% by weight. When the amount is less than 0.5% by weight, the effect of addition is not recognized, and when it exceeds 20% by weight, heat resistance and mechanical strength tend to be reduced.

The method for polymerizing the transparent cross-linked resin is not particularly limited, and it can be polymerized by a generally known method.
When the transparent crosslinked resin is a polyolefin-based copolymer, polymerization can be carried out by maintaining the above monomer mixture under a predetermined temperature condition in the presence or absence of a radical initiator. Various methods such as bulk polymerization, solution polymerization, suspension polymerization, and cast polymerization can be used. The degree of polymerization of the transparent crosslinked resin of the present invention is not particularly limited,
The higher the polymerization rate, the better. Considering post-processing such as solution coating such as transparent cured film and vacuum evaporation,
The polymerization rate is preferably 90% or more. Polymerization of transparent resin is 30
The polymerization can be carried out in a temperature range from to 250 ° C, but the polymerization rate can be increased by setting the polymerization temperature to 130 ° C or higher, more preferably 150 ° C or higher.

There is no particular limitation on the molding method of the transparent cross-linked resin, but an effective molding method includes a casting polymerization method. In consideration of mechanical properties, the thickness of the substrate made of the transparent cross-linked resin is preferably 0.1 to 5 mm, more preferably 0.1 to 0.8 mm. The cured film of the electrode substrate for a liquid crystal display device is a film containing an organic polymer in addition to the inorganic fine particles. Specific examples of the organic polymer constituting the cured film include acrylic resin, silicone resin, polyurethane resin, epoxy resin,
Examples include melamine resins, polyolefin resins, celluloses, polyvinyl alcohol resins, urea resins, nylon resins, polycarbonate resins, and the like. These resins can be used alone or in combination of two or more kinds, and can be three-dimensionally cross-linked using various curing agents, cross-linking agents and the like. Particularly for applications where surface hardness is important, it is preferable to use a curable resin. For example, a single resin or a composite resin such as an acrylic resin, a silicone resin, an epoxy resin, a polyurethane resin, and a melamine resin is preferably used. Is done. When various properties such as surface hardness, heat resistance, chemical resistance, and transparency are taken into consideration, it is preferable to use a silicone resin as the organic polymer, and an organosilicon compound represented by the following general formula (B) or More preferably, a polymer obtained from the hydrolyzate is used.

R ⁴ _a R ⁵ _b SiX _4-ab (B) wherein R ⁴ is an organic group having 1 to 10 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon. X is a hydrolyzable group, and a and b are 0 or 1. Examples of the organosilicon compound represented by the general formula (B) include (i) methyl silicate, ethyl silicate, n-propyl silicate, iso-propyl silicate, n-butyl silicate, sec-butyl silicate, and t-butyl silicate Such as tetraalkoxysilanes and hydrolysates thereof, (ii) methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-c Propyltriethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercapto Propyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyl Trimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β -Glycidoxyethyltriethoxysilane,
α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane,
α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-
Glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane,
(3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyl Trimethoxysilane,
trialkoxysilanes such as γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriemethoxysilane, Triacyloxysilane or triphenoxysilanes or hydrolysates thereof, and (iii) dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloro Propylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethy Xysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxy Methylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane,
β-glycidoxyethylmethyldiethoxysilane, α-
Glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycidoxypropyl Methyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane Dialkoxysilanes, such as γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, diphenoxysilane or diacyloxysilanes or a hydrolyzate thereof. Degradation products.

These organosilicon compounds may be used alone or in combination.
More than one species can be added. In particular, for the purpose of imparting dyeability, the use of an organosilicon compound containing an epoxy group or a glycidoxy group is preferable, and provides high added value. In addition to the silicone resin, acrylic-based resins, polyurethane-based resins, epoxy-based resins, and melamine-based coating-forming components containing a silicone-based resin as a main component, as long as they do not impair transparency and satisfy surface hardness. Resins, polyolefin resins, celluloses, polyvinyl alcohol resins, urea resins, nylon resins, polycarbonate resins, and the like can be added.

The organosilicon compound lowers the curing temperature,
In order to further accelerate the curing, it is preferable to use it after hydrolysis. The hydrolysis can be obtained by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid and stirring. The degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution. At the time of hydrolysis, it is preferable to add pure water or an acidic aqueous solution in an amount equal to or more than 3 moles of the hydrolyzable group contained in the compound represented by the general formula (B) from the viewpoint of accelerating curing.

At the time of hydrolysis, alcohol and the like are generated, so that hydrolysis can be carried out without a solvent.
Further, for the purpose of performing the hydrolysis more uniformly, it is also possible to carry out the hydrolysis after mixing the organosilicon compound and the solvent. Further, depending on the purpose, it is possible to remove the alcohol or the like after hydrolysis in an appropriate amount by heating and / or reducing the pressure, and then use it, or to add an appropriate solvent thereafter.

It is preferable that the above composition is usually diluted with a volatile solvent and applied as a liquid composition. Although what is applied as a solvent is not particularly limited, it is required that the surface properties of the object to be applied are not impaired in use. Furthermore, stability of the composition, wettability to the substrate,
The solvent should be determined in consideration of volatility and the like. Further, the solvent may be used as a mixture of not only one kind but also two or more kinds. Examples of the solvent include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and aprotic polar solvents.

Inorganic fine particles are added to the transparent film for the purpose of improving the surface hardness, adjusting the refractive index, improving the mechanical strength, and improving the thermal characteristics. Such inorganic fine particles are not particularly limited as long as they do not impair transparency in a film state. A particularly preferred example from the viewpoint of improving workability and imparting transparency is a sol dispersed in a colloidal state. More specific examples include silica sol and antimony oxide sol.

The amount of the inorganic fine particles to be added is not particularly limited.
It is preferable that the content is not less than 80% by weight and not more than 80% by weight. 1
If the content is less than 80% by weight, no obvious effect of the addition is observed. If the content is more than 80% by weight, problems such as poor adhesion to the plastic substrate and cracks in the coating itself may occur, resulting in reduced impact resistance. There is.

The particle size of the inorganic fine particles is not particularly limited, but is usually 1 to 200 μm, preferably 5 to 100 μm.
μ, more preferably 20 to 80 μm. When the particles having an average particle diameter of more than 200 μm are used, the resulting coating film tends to be poor in transparency and turbid. Further, in order to improve the dispersibility of the particulate inorganic material, various kinds of fine particle surface treatments may be performed, and there is no problem even if various surfactants, amines and the like are added.

Various curing agents may be used in combination with the coating composition used at the time of forming the cured film for the purpose of accelerating curing and curing at a low temperature. As the curing agent, various epoxy resin curing agents or various organic silicon resin curing agents are used. Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds, various metal complex compounds, metal alkoxides, various salts such as organic carboxylate and carbonate of alkali metals, and salts of organic acids. Examples thereof include oxides and radical polymerization initiators such as azobisisobutyronitrile. These curing agents can be used as a mixture of two or more kinds. Among these curing agents, an aluminum chelate compound is particularly useful from the viewpoint of the stability of the coating composition, the presence or absence of coloring of the film after coating, and the like.

The aluminum chelate compound referred to here is, for example, an aluminum chelate compound represented by the general formula AlX _n Y _3-n . Where X in the formula is O
L (L represents a lower alkyl group), Y is a general formula M ¹ CO
A ligand derived from a compound represented by CH ₂ COM ² (M ¹ and M ² are both lower alkyl groups);
³ COCH ₂ COOM ⁴ (M ³ and M ⁴ are both lower alkyl groups) are at least one selected from ligands derived from the compounds represented by n, and n is 0, 1 or 2.

As the aluminum chelate compound represented by the general formula AlX _n Y _3-n , various compounds can be mentioned, and particularly preferred from the viewpoints of solubility in the composition, stability, and effect as a curing catalyst. Are aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate and the like. These can be used as a mixture of two or more kinds.

Various types of surfactants are added to the coating composition used for forming the cured film in order to improve the flow at the time of application and improve the smoothness of the transparent film to lower the coefficient of friction of the film surface. It is also possible. As the surfactant, a block or graft copolymer of dimethylpolysiloxane and alkylene oxide, a fluorine-based surfactant, and the like are particularly effective.

An inorganic oxide other than the inorganic fine particles may be added to the coating composition used for forming the cured film, as long as the film performance and transparency are not significantly reduced. The combined use of these additives can improve various properties such as adhesion to a substrate, chemical resistance, surface hardness, and durability. Examples of the inorganic material that can be added include a metal alkoxide represented by the following general formula (C);
A chelate compound and / or a hydrolyzate thereof may be mentioned.

M (OR) _m (C) Here, M is silicon, titanium, zircon, antimony, tantalum, germanium, aluminum, or the like. R is an alkyl group, an acyl group, or an alkoxyalkyl group. m is the same value as the number of charges of the metal M. Further, it is possible to add an ultraviolet absorber for the purpose of improving light resistance, and an antioxidant for the purpose of improving heat deterioration.

The cured film is obtained by curing the coating composition, and the curing is performed by a heat treatment. The heating temperature is appropriately selected in consideration of the composition of the coating composition and the heat resistance of the transparent crosslinked resin, but is preferably 50 to 250 ° C. As a method for applying the coating on the transparent crosslinked resin, a commonly used coating method such as brush coating, dip coating, roll coating, spray coating, spin coating, and flow coating can be easily used.

In applying the coating composition,
It is also an effective means to carry out various pretreatments for the purpose of improving cleaning, adhesion and water resistance. Particularly preferred pretreatments include an activation gas treatment, a chemical treatment, and an ultraviolet treatment. These pre-processing
It is sufficiently possible to carry out the combination continuously or stepwise.

The activation gas treatment is a treatment with ions, electrons or excited gas generated under normal pressure or reduced pressure. Methods for generating these activation gases include, for example, corona discharge, direct current under reduced pressure,
There are low frequency, high frequency or high voltage discharge by microwave. The gas used here is not particularly limited, but specific examples include oxygen, nitrogen, hydrogen, carbon dioxide, sulfur dioxide, helium, neon, argon, freon, steam, ammonia, carbon monoxide, Chlorine, nitric oxide, nitrogen dioxide and the like. These can be used even if two or more kinds are mixed. Among the above, preferred gases include those containing oxygen, and may be gases that exist in nature such as air. More preferably, pure oxygen gas is effective for improving the adhesion.
Furthermore, it is also possible to raise the temperature of the substrate to be treated during the treatment.

Specific examples of chemical treatment include (i) alkali treatment with caustic soda, (ii) acid treatment with hydrochloric acid, sulfuric acid, potassium permanganate, potassium dichromate, and the like, and (iii) organic solvent treatment. Can be The thickness of the cured film is not particularly limited, but is preferably between 0.1 and 50 μm from the viewpoint of maintaining the adhesive strength and hardness. Particularly preferably, it is 0.3 to 10 μm. In applying the coating, the coating composition is used after being diluted with various solvents for the purpose of controlling the workability and the thickness of the coating. As the diluting solvent, for example, water, alcohol, ester, ether, halogenated hydrocarbon, dimethylformamide, dimethylsulfoxide and the like can be variously used according to the purpose, and a mixed solvent can be used as necessary. . Water, alcohol, dimethylformamide, ethylene glycol, diethylene glycol, triethylene glycol,
Polar solvents such as benzyl alcohol, phenethyl alcohol and phenyl cellosolve are preferably used.

The transparency of the substrate having the cured film is preferably 60% or more, more preferably 80%, when the total light transmittance is expressed as an index. In applications where optical isotropy is important, the birefringence of the electrode substrate for a liquid crystal display is preferably 30 nm or less, more preferably 15 nm or less. The metal oxide film provided on the substrate having the cured film is made of Si, A
An oxide of a metal selected from l and Ti is preferred. Between the metal oxide film and the cured film, a silicon nitride film,
It is also possible to provide a metal nitride film such as a silicon oxynitride film. The thickness of the metal oxide film is preferably 100 from the viewpoint of imparting gas barrier properties to the substrate.
~ 2000 angstroms, more preferably 300 ~
1200 Angstroms.

On the substrate having the metal oxide film obtained as described above, ITO (Indium Tin Ox) was formed.
As a method of forming the (ide, indium / tin mixed oxide) film, a method such as a vacuum evaporation method, an ion plating method, and a sputtering method such as a DC method or a magnetron method can be used. The thickness of the ITO film is not particularly limited, but may be 1 depending on the resistance value and the film formation time.
It is preferable to appropriately select from the range of 50 to 5000 Å. The surface structure of the ITO film is I
In consideration of the durability of the TO film, it is preferable that the TO film be formed in a grain shape. The grain shape refers to a structure in which a grain boundary as shown in FIG. 3 is observed on the surface of the ITO film by morphological observation using an electron microscope, an atomic force microscope, or the like. In addition,
The grain preferably has a diameter of 300 to 2000 angstroms.

The thickness of the electrode substrate for a liquid crystal display device is preferably from 0.1 to 5 mm, more preferably from 0.1 to 0.8 mm, in consideration of mechanical characteristics. The electrode substrate for a liquid crystal display device of the present invention comprises: (i) TN (Twis)
ted Nematic) type, STN (Super T)
twisted Nematic, ferroelectric liquid crystal (FL)
C: Ferroelectric Liquid Cr
simple matrix type such as istal) type, (ii) MIM
(Metal-Insulator-Metal) type,
TFT (Thin-Film Transistor)
The present invention can be applied to liquid crystal displays of an active matrix type or the like. Since the manufacturing process is relatively simple, it is preferably used for a simple matrix type liquid crystal display.

As a method of manufacturing a liquid crystal display device using the electrode substrate for a liquid crystal display device of the present invention, a known method can be applied. For example, in the case of a simple matrix type liquid crystal display [Liquid Crystal Device Handbook (edited by the 142nd Committee of the Japan Society for the Promotion of Science, published by Nikkan Kogyo Shimbun, 198)
9) p. 531], after cleaning the substrate, forming a transparent conductive film, fine processing of the transparent conductive film (resist coating, development, etching, resist cleaning and removal), alignment film formation, rubbing treatment, cleaning, sealing agent printing, substrate bonding, Heating / pressurizing,
A liquid crystal display device can be obtained by sequentially performing steps such as vacuum degassing, liquid crystal injection, sealing an injection port, dividing a liquid crystal cell, and attaching a polarizing plate and a light reflecting plate. In these liquid crystal display manufacturing processes, the manufacturing conditions should be set in consideration of various characteristics such as heat resistance and mechanical characteristics of the liquid crystal display substrate.

An example of a method for manufacturing a liquid crystal display device will be described below. After washing the substrate on which the ITO film is formed, a photoresist is coated with a thickness of 2 to 3 μm by a roll coater, and prebaked at 80 to 130 ° C. Thereafter, exposure is performed using an arbitrary photomask. The photoresist development is performed with a 0.6N NaOH aqueous solution at a liquid temperature of 25 ° C., and an etching pattern is formed with an 8.6N HBr aqueous solution at 40 to 45 ° C. to obtain a transparent conductive film electrode.
A silica coating material is applied to the substrate on which the transparent conductive film electrode pattern is formed by offset printing to 500 to 1500.
A top coat is formed by printing with a film thickness of Å and baking at a peak setting of 150 to 170 ° C. for 60 minutes. With this film, it is possible to prevent leakage due to conductive foreign matter between the upper and lower ITO films.

As in the case of the top coat film treatment, an alignment film material such as polyimide is printed on the top coat film by offset printing to a thickness of 300 to 600 angstroms,
The alignment film is formed by baking at a peak of 150 to 170 ° C. for 90 minutes. The alignment film is rubbed in a certain direction with a chemical fiber cloth having a certain length of hair to make physical fine scratches. The directions of the upper and lower substrates (segment substrate, common substrate) are different from each other, and the rubbing direction cross angles of the upper and lower substrates are changed according to the requirements of various electro-optical characteristics. Thereafter, the substrate is washed with warm water at 40 to 50 ° C., and the process proceeds to the next step.

A thermosetting epoxy sealing material is printed on the upper substrate (segment substrate) in a predetermined pattern by screen printing. On the other hand, the lower substrate (common substrate)
Plastic beads, which are spacers for securing the thickness of the liquid crystal layer, are dispersed so as to be uniformly dispersed. Then, the two substrates are bonded so that the upper and lower electrode patterns overlap a predetermined position finish. After this, pressure 0.8-1.5kg
Hot pressing is performed at f / cm ^{2 at} a temperature of 100 to 140 ° C., and the seal is cured at 140 to 160 ° C. As a result, a cell in the form of a container in which a pair of substrates are adhered by a seal except for the injection port is obtained. The cell is set in an injection machine and evacuated, and the liquid crystal is impregnated in the cell injection port in the vacuum system, and the liquid crystal is injected by a pressure difference when the pressure is returned to the atmospheric pressure. After filling the cell with liquid crystal, the cell is sealed with a UV-curable epoxy material. A polarizing plate having a predetermined angle is attached to the pair of cells having been subjected to the surface treatment with a roller to obtain a liquid crystal display device shown in FIG.

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below with reference to embodiments. Example 1 (1) Preparation of resin molded plate First, a substrate made of a resin having a crosslinked structure was prepared. 26.5 g of isopropylmaleimide, 18.5 g of styrene, 5.0 g of divinylbenzene, and 0.05 g of azobisisobutyronitrile were mixed and dissolved, and cast-molded by cast polymerization. Cast polymerization was performed as follows.

2 of a size of 300 mm × 300 mm and a thickness of 5 mm
A soft vinyl chloride gasket was attached to the outer periphery of the two glass plates, and the two glass plates were assembled so that the distance between them was 0.4 mm. The monomer mixture was poured into the assembled glass plate, and was heated at 70 ° C. for 8 hours, at 100 ° C. for 1 hour, and further for 1 hour.
Polymerization was performed at 50 ° C. for 1 hour to obtain a molded plate (I) made of a resin having a crosslinked structure.

The glass transition temperature of this molded plate (I) is 18
The temperature was 0 ° C., and the total light transmittance was 90%. The flexural modulus at room temperature was 398 kg / mm ² , the flexural strength was 9 kg / mm ² , and the solvent resistance was good. (2) Formation of a cured film containing inorganic fine particles In a reactor equipped with a rotor, 95.3 g of γ-glycidoxypropyltrimethoxysilane was charged, and the temperature of the solution was kept at 10 ° C while stirring with a magnetic stirrer. 0.0
21.8 g of a 1N aqueous hydrochloric acid solution was gradually added dropwise. After dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

The silane hydrolyzate was added to methanol 216
g, dimethylformamide 216 g, silicone-based surfactant 0.5 g, bisphenol A type epoxy resin (trade name Epicoat 827, manufactured by Yuka Shell Epoxy Co., Ltd.)
After adding and mixing 5 g, 270 g of colloidal antimony pentoxide sol (average particle diameter 50 mμ) and 13.5 g of aluminum acetylacetonate were added, and the mixture was sufficiently stirred to obtain a coating composition (I).

Coating composition (I) on molded plate (I)
Was pre-cured at 100 ° C. for 10 minutes, and further heated at 110 ° C. for 4 hours to form a cured coating containing inorganic fine particles on the molded plate (I). (3) Formation of Metal Oxide Film and ITO Film A reactive magnetron sputtering method was used to form the metal oxide film and the ITO transparent conductive film.

As the sputtering device, a device was used in which a magnetron-type target was arranged on the outer periphery of a cylindrical bell jar, and a sputtering gas could be introduced from an introduction hole provided near the target. In this apparatus, targets of three different materials can be arranged as targets arranged on the outer periphery of the bell jar.
Films of different materials such as a film and an ITO film can be continuously formed while maintaining a vacuum.

Here, sputtering was performed by applying power to the target while maintaining the inside of the bell jar at a predetermined degree of vacuum. The substrate on which the film was to be formed was attached to a substrate holding jig installed in a bell jar, and the front surface of the target being sputtered was rotated at a constant speed. At this time, a heater for heating the substrate was installed on the wall surface inside the bell jar so that the substrate was kept at a constant temperature during sputtering.

Using the above-mentioned sputtering apparatus, a film was formed under the following processing conditions to prepare an electrode substrate (I) for a liquid crystal display device. a) Formation of Metal Oxide Film Metal Oxide Film: SiOx 600 Å Target Material: Si Introduced Gas: Ar and O ₂ Sputter Degree of Vacuum: 1.0 × 10 ⁻³ Torr Input Power: 0.3 Kw Substrate Temperature: 110 ° C. Sputtering rate: 10 angstroms / min b) Deposition of ITO film ITO film thickness: 1600 angstroms Target material: ITO (In + Sn oxide sintered body) Introduced gas: Ar and O ₂ sputtering degree of vacuum: 2.0 × 10 ^-3 Torr Input power: 3.0 Kw Substrate temperature: 110 ° C. Sputtering rate: 60 Å / min Example 2 Using the electrode substrate for a liquid crystal display device obtained in Example 1, a liquid crystal display device was prepared by the following method. .

After cleaning the liquid crystal display electrode substrate (I),
A photoresist was coated with a thickness of 2 μm by a roll coater, and prebaked at 100 ° C. Thereafter, exposure was performed using a photomask. Photoresist development was carried out using a 0.6N NaOH aqueous solution at a liquid temperature of 25 ° C, and using a 8.6N HBr aqueous solution at 40 ° C.
Etching patterning of the TO film was performed.

A silica coating material was printed on the patterned electrode substrate for liquid crystal display device (I) by offset printing to a thickness of 800 Å, and baked at 150 ° C. for 60 minutes to form a top coat film. . An alignment film material was printed on the top coat film by offset printing in a thickness of 400 angstroms similarly to the top coat film treatment, and baked at 150 ° C. for 90 minutes to form a film.

With a synthetic fiber cloth having a fixed hair length,
The alignment film was rubbed in a certain direction to make physical fine scratches.
The directions are different for the upper and lower substrates (segment substrate, common substrate). After this rubbing treatment, the substrate was washed with warm water at 40 ° C. Next, a thermosetting epoxy-based sealing material was printed on the upper substrate (segment substrate) in a predetermined pattern by screen printing. On the other hand, plastic beads as spacers for securing the thickness of the liquid crystal layer were sprayed on the lower substrate (common substrate) so as to be uniformly dispersed. Then, the two substrates were bonded so that the upper and lower electrode patterns overlapped at predetermined positions. Thereafter, hot pressing was performed at a pressure of 1.2 kgf / cm ² and a temperature of 140 ° C. to cure the seal at 140 ° C. Thus, 1
The pair of electrode substrates was in the form of a sealed container except for the inlet.

The cell of the above embodiment was set in an injection machine, and vacuum was drawn. The liquid crystal was impregnated at the cell injection port with a vacuum system, returned to atmospheric pressure, and the liquid crystal was injected by a pressure difference. After filling the cell with liquid crystal, the cell was sealed with a UV-curable epoxy material. A polarizing plate having a predetermined angle was attached to a cell filled with liquid crystal between the substrates by a roller to form a liquid crystal display device having the configuration shown in FIG. In addition,
In FIG. 2, 9 is a polarizing plate, 10 is a transparent cross-linked resin substrate, 11 is a cured film containing inorganic fine particles, 12 is a metal oxide film, 12 'is a metal nitride film, 13 is an ITO transparent conductive film electrode, 14 is a top coat, 15 is an alignment film, 16 is a seal, and 17 is a liquid crystal.

The liquid crystal display device (S
TN type), clear dot display was possible. Example 3 (1) Preparation of resin molded plate A substrate made of a resin having a crosslinked structure was prepared. 4.3.5 g of isopropylmaleimide, cyclohexylmaleimide.
0 g, styrene 15.5 g, divinylbenzene 6.0
g and azobisisobutyronitrile were mixed and dissolved, and cast-molded by cast polymerization. Cast polymerization was performed as follows.

[0062] 2 of 300 mm x 300 mm in size and 5 mm in thickness
A soft vinyl chloride gasket was attached to the outer periphery of the two glass plates, and the two glass plates were assembled so that the distance between them was 0.4 mm. The monomer mixture was poured into the assembled glass plate, and polymerized at 70 ° C. for 8 hours, at 100 ° C. for 1 hour, and further at 150 ° C. for 1 hour to obtain a molded plate (II) made of a resin having a crosslinked structure. Was.

The glass transition temperature of this molded plate (II) is 18
The temperature was 0 ° C., and the total light transmittance was 90%. The flexural modulus at room temperature was 398 kg / mm ² , the flexural strength was 9 kg / mm ² , and the solvent resistance was good. (2) Formation of cured film containing inorganic fine particles In a reactor equipped with a rotor, 91.1 g of γ-glycidoxypropylmethyldimethoxysilane was charged, and the liquid temperature was adjusted to 10%.
C. and 13.2 g of a 0.05 N hydrochloric acid aqueous solution was gradually added dropwise while stirring with a magnetic stirrer. After completion of the dropwise addition, the cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropylmethyldimethoxysilane.

To this silane hydrolyzate, 178.1 g of n-propyl alcohol, 29.7 g of benzyl alcohol,
59.5 g of diacetone alcohol, acetylacetone 2
3.7 g, a surfactant 1.3 g, 64.0 g of a bisphenol A epoxy resin (trade name: Epicoat 827, manufactured by Yuka Shell Epoxy Co., Ltd.) were added and mixed, and 426.5 g of a colloidal silica sol (average particle diameter: 50 mμ) was further added. Then, 7.5 g of aluminum acetylacetonate and 8.5 g of triethylene glycol were added, and the mixture was sufficiently stirred to obtain a coating composition (II).

Coating composition (II) on molded plate (II)
Is pre-cured at 100 ° C. for 10 minutes, and further heated at 110 ° C. for 4 hours to form a molded plate (I
A cured film containing inorganic fine particles was formed on I). (3) Formation of Metal Oxide Film and ITO Film A metal oxide film and an ITO film were formed using the sputtering apparatus of item (3) of Example 1 under the following processing conditions, and an electrode substrate for a liquid crystal display device was formed. (II) created.

A) Formation of Metal Oxide Film Metal Oxide Film: 100 Å of SiNx and 500 Å of SiOx SiNx Film Target Material: Si Introduced Gas: N ₂ Sputtering Vacuum: 9.0 × 10 ^-3 Torr Input Power: 0.5 Kw Substrate temperature: 110 ° C. Sputtering rate: 12 Å / min SiOx film Target material: Si Introducing gas: Ar and O ₂ Sputtering vacuum: 1.0 × 10 ⁻³ Torr Input power: 0.3 Kw Substrate temperature : 110 ° C. Sputtering rate: 10 angstroms / min. B) Formation of ITO film An ITO film of 1600 angstroms was formed in the same manner as in item (3) b) of Example 1. Observation with a scanning electron microscope confirmed that the surface of the ITO film was in a grain shape (FIG. 3). Example 4 Example 2 except that an electrode substrate (II) for a liquid crystal display device was used.
A liquid crystal display device was obtained in the same manner as described above. This liquid crystal display device was capable of displaying clear dots. The reliability evaluation of this liquid crystal display device was performed at 40 ° C. and 95 ° C.
The sample was stored for a predetermined period of time in an atmosphere of% RH, and the state of electrode disconnection and generation of bubbles due to cracks in the ITO film was evaluated. Table 1 shows the results of the reliability evaluation. Comparative Example 1 A liquid crystal display having the structure shown in FIG. 1 was prepared using a thermoplastic resin plate (PES), and its reliability was evaluated under the same conditions as in Example 4. Table 1 shows the results of the reliability evaluation. In addition,
In FIG. 1, 1 is a polarizing plate, 2 is PES, 3 is SiOx
An undercoat, 4 is an ITO transparent conductive film electrode, 5 is a top coat, 6 is an alignment film, 7 is a seal, and 8 is a liquid crystal.

[0067]

[Table 1]

[0068]

According to the electrode substrate for a liquid crystal display device and the liquid crystal display device of the present invention, a cured coating of inorganic fine particles, a metal oxide film, an IT
Since the O film is provided in this order, heat resistance, scratch resistance, and transparency are improved.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device obtained in Comparative Example 1.

FIG. 2 is a schematic sectional view of a liquid crystal display device obtained in Example 2.

FIG. 3 is a photograph of a surface structure of an ITO film on an electrode substrate obtained in Example 3.

[Explanation of symbols]

 9: Polarizing plate 10: Transparent crosslinked resin substrate 11: Cured coating containing inorganic fine particles 12: Metal oxide film 12 ': Metal nitride film 13: ITO transparent conductive film electrode 14: Top coat 15: Alignment film 16: Sticker 17: LCD

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Makoto Iwamoto 22-22 Nagaikecho, Abeno-ku, Osaka City Inside Sharpe Co., Ltd. (72) Inventor Akihiro Kitabatake 1-8-27 Kusune, Higashiosaka City Sanyo Vacuum Industry Inside (72) Inventor Masahiro Tanimoto 1-8-27 Kusunone, Higashiosaka City Inside Sanyo Vacuum Industry Co., Ltd. (72) Inventor Shinichi Yamada 1-1-1 Sonoyama, Otsu City, Shiga Prefecture Toray Shiga Co., Ltd. Inside the business place (72) Inventor Masaki Maekawa 1-1-1, Sonoyama, Otsu-shi, Shiga Toray Shiga Works (56) References JP-A-60-25104 (JP, A) JP-A-63-127227 (JP) , A) JP-A-5-253955 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02F 1/1333 G02F 1/1343 G09F 9/00-9/46

Claims (11)

(57) [Claims] (1) A substrate made of a resin having a transparent cross-linked structure,
Hardened film, metal oxide film, ITO film containing inorganic fine particles
In this order, the cured film containing the inorganic fine particles contains silica fine particles.
An electrode substrate for a liquid crystal display device , which is a siloxane-based cured film . 2. On a substrate made of a transparent cross-linked resin,
Cured coating containing inorganic fine particles, metal nitride film, metal oxidation
An electrode for a liquid crystal display device having an object film and an ITO film in this order.
Polar board. 3. On a substrate made of a resin having a transparent crosslinked structure,
Hardened film, metal oxide film, ITO film containing inorganic fine particles
In this order, the resin having a crosslinked structure has a maleimide monomer content of 20% by weight.
% Of an electrode substrate for a liquid crystal display device , which is a resin obtained by copolymerization of at least 30% . 4. The method according to claim 1, wherein the resin having a crosslinked structure has a gas temperature of 160 ° C. or higher.
4. The resin according to claim 1, which is a resin having a lath transition temperature.
3. The electrode substrate for a liquid crystal display device according to item 1. 5. The surface structure of the ITO film has a grain shape.
The liquid according to any one of claims 1 to 4, which is formed.
Substrate for crystal display device. 6. A grain having a diameter of 300 to 2000 mm.
6. The liquid crystal display device according to claim 5, wherein the liquid crystal display device is a liquid crystal display device.
Electrode substrate. 7. The method according to claim 1, wherein said ITO film has a thickness of 150 to 5000 angstroms.
7. A method as claimed in claim 1, having a storm thickness.
3. The electrode substrate for a liquid crystal display device according to 1. 8. The method according to claim 1, wherein the metal oxide film has a thickness of 300 to 1200 nm.
8. The method according to claim 1, wherein the thickness of the first layer is equal to or greater than the thickness of the first layer.
An electrode substrate for a liquid crystal display device according to any one of the preceding claims. 9. The method according to claim 9, wherein said metal oxide film is made of Si, Al and Ti.
9. An oxide of a metal selected from the group consisting of:
An electrode substrate for a liquid crystal display device according to any one of the above. 10. The resin having a crosslinked structure of 0.1 to 0.8.
10. The resin according to claim 1, which is a resin having a thickness of 0.1 mm.
An electrode substrate for a liquid crystal display device according to any one of the preceding claims. 11. A liquid crystal between two aligned electrode substrates.
In a liquid crystal display device in which
And using the electrode substrate according to any one of claims 1 to 10.
Liquid crystal display device.