JP2000227603A - Liquid crystal display device and transparent conductive substrate suitable for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive substrate having excellent durability, chemical resistance, gas barrier property, good transparency, optical isotropy and interlayer adhesion property, and having high insulating surface resistance when a transparent conductive layer is etched. SOLUTION: This transparent conductive substrate consists of a laminated film including a transparent polymer substrate (S) and a hardened resin layer (U), and a transparent conductive layer (E) disposed in contact with the hardening resin layer (U) of the laminated film. The substrate has the following properties. (a) The transmittance for whole rays is >=80%, (b) the transparent polymer substrate (S) is 0.01 to 1.0 mm thick, (c) the retardation of the transparent polymer substrate (S) is <=20 nm, (d) the transparent conductive layer (E) is 1 nm to 1 μm thick, and (e) the surface of the hardened resin layer (U) in contact with the transparent conductive layer (E) has >=1.0×1013 Ω/unit sq. surface resistance under conditions of at 50 deg.C and 30% RH, and >=1.0×1012 Ω/unit sq. surface resistance at 50 deg.C and 90% RH.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly reliable liquid crystal display device and a transparent conductive substrate useful as an electrode substrate constituting the liquid crystal display device.
Since this transparent conductive substrate has high gas barrier properties and high stability under high temperature and high humidity, in addition to the liquid crystal display element, an electrode substrate in a flat panel display field such as a photoconductive photoreceptor, a surface light emitter, and an EL element. Can be suitably used.

[0002]

2. Description of the Related Art In recent years, in the field of flat panel displays such as liquid crystal display elements, improvement of breakage resistance, weight reduction,
Due to the demand for thinner, on a film made of transparent polymer,
A semiconductor film such as an oxide of indium oxide, tin oxide, or tin-indium alloy, a metal film such as an oxide film of gold, silver, or a palladium alloy, and a film formed by combining the semiconductor film and the metal film are transparent. The use of a transparent conductive substrate provided as a conductive layer as an electrode substrate of a liquid crystal display element has been studied. In such a substrate, in a panel assembling process,
High chemical resistance to various organic solvents, acids, and alkalis used during patterning of electrodes, lamination of alignment films, and various washings is required. In addition, a high gas barrier property is usually required to improve the reliability of bubbles generated inside the liquid crystal cell of the panel. Regarding this gas barrier property, for example, WO 94/23332, JP 2796573, and JP 27901
No. 44 describes a substrate in which an organic gas barrier layer such as a vinyl alcohol polymer or a vinylidene chloride polymer and an inorganic gas barrier layer such as silicon oxide or aluminum oxide are laminated on a transparent polymer substrate. However, even when these organic or inorganic gas barrier layers are used as a single layer, a plurality of such layers are stacked, or a combination of organic and inorganic gas barrier layers is used, the same as a conventionally used glass substrate is used. Gas barrier properties of
In particular, it is difficult to achieve steam barrier properties. In fact, when a panel using such a substrate is left for a long time in a high-temperature, high-humidity environment, water vapor enters the liquid crystal cell,
There has been a problem that the impedance between two opposing electrodes of the liquid crystal cell and between two adjacent electrodes in the plane of the substrate is reduced, and display defects such as image bleeding and crosstalk are likely to occur on the panel.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel and highly reliable liquid crystal display device. Another object of the present invention is to provide a transparent conductive substrate suitable for a liquid crystal display element in which display quality is hardly deteriorated even when left for a long time in a high temperature and high humidity environment. Still another object of the present invention is to provide a novel transparent conductive substrate having excellent gas barrier properties.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the above-mentioned problems are due to the humidity dependence of the surface insulation resistance of the underlayer of the transparent conductive layer and the transparent conductive substrate. It has been found that the above problem can be solved by controlling the gas barrier property of the present invention, and the present invention has been completed.

That is, the present invention relates to a liquid crystal display device having two electrode substrates and a liquid crystal layer disposed between the electrode substrates, wherein the electrode substrate comprises: (i) a transparent polymer substrate (S);
A cured resin layer (U) and a transparent conductive layer (E),
(ii) the cured resin layer (U) and the transparent conductive layer (E) are laminated in contact with each other; (iii) the surface of the cured resin layer (U) in contact with the transparent conductive layer (E) is at 50 ° C. The surface resistance under a 30% RH environment is 1.0 × 10 ¹³ Ω / □ or more,
Surface resistance value is 1.0 × 1 under 0 ° C. 90% RH environment
It is attained by a liquid crystal display element characterized by being at least 0 ¹² Ω / □.

The present invention also provides a laminated film comprising a transparent polymer substrate (S) and a cured resin layer (U), and a transparent conductive layer (E) disposed in contact with the cured resin layer (U) of the laminated film. This is achieved by a transparent conductive substrate comprising the following (a) to (e). (A) The total light transmittance is 80% or more. (B) The thickness of the transparent polymer substrate (S) is 0.01 to 1.0.
mm (c) The retardation of the transparent polymer substrate (S) is 20
nm or less (d) The thickness of the transparent conductive layer (E) is 1 nm to 1 μm. (e) The surface of the cured resin layer (U) in contact with the transparent conductive layer (E) has a surface resistance value of 50 ° C. and 30% RH. Is 1.0 × 10 ¹³ Ω / □ or more, and the surface resistance under a 50 ° C. 90% RH environment is 1.0 × 10 ¹² Ω / □ or more.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A liquid crystal display device according to the present invention mainly comprises two electrode substrates and a liquid crystal layer disposed between the electrode substrates. A representative example is shown in FIG. This electrode substrate is in contact with the cured resin layer (U) on a laminated film having excellent gas barrier properties having a gas barrier layer (X) and a cured resin layer (U) on a transparent polymer substrate (S). It is a transparent conductive substrate on which the transparent conductive layer (E) is disposed. By using this transparent conductive substrate as an electrode substrate, a highly reliable liquid crystal display element that is unlikely to cause deterioration in display quality even when left in a high-temperature and high-humidity environment for a long time is provided. This transparent conductive substrate is also one of the present invention. FIG. 2 shows a typical example of such a transparent conductive substrate. The transparent conductive layer (E) 27, the cured resin layer (U) 29, the transparent polymer substrate (S) 31, the cured resin layer (B) 33, the gas barrier layer (X) 35, and the cured resin layer (C) 37 They are provided in contact in order.

[0008] Such a transparent conductive substrate has a low water absorption and good transparency with a total water absorption of 2% or less and a total light transmittance of 80% or more. Therefore, it can be suitably used not only as an electrode substrate of a liquid crystal display element, which is expected to have high reliability and gas barrier properties, but also as an electrode substrate in a flat panel display field such as a photoconductive photoreceptor, a surface light emitter, and an EL element. it can.

[Transparent Polymer Substrate (S)] The material constituting the transparent polymer substrate (S) is not particularly limited as long as it is a transparent polymer having good transparency and heat resistance. Examples of such a transparent polymer include polyester resins, polycarbonate resins, polyarylate resins, polysulfone resins such as polysulfone, polyethersulfone and polyallylsulfone, polyolefin resins, and acetate resins such as cellulose triacetate. , Polyacrylate resins, various thermosetting resins and the like are preferable. Among them, a film or a sheet containing a polycarbonate-based resin or a polyarylate-based resin as a main component is more preferable from the viewpoint of the above-mentioned transparency, heat resistance, and relatively low optical anisotropy. The polycarbonate resin obtained by the casting method is particularly preferable because it has excellent surface flatness and excellent optical isotropy.

As the polycarbonate resin, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), the following formula [I]

[0011]

Embedded image

A polycarbonate resin containing the bisphenol represented by the formula (II) as a bisphenol component is exemplified. Here, R ¹ , R ² , R ³ and R ⁴ are the same or different and are a hydrogen atom or a methyl group, and X is a cycloalkylene group having 5 to 10 carbon atoms, an araalkylene group having 7 to 15 carbon atoms, 1 to 5 haloalkylene groups.

Specific examples of X include 1,1-cyclopentylene, 1,1-cyclohexylene, 1,1- (3,3,5-trimethyl) cyclohexylene, norbornane-2,2- Diyl, tricyclo [5.2.1.0 ^2,6 ] decane-8,8′-diyl, especially 1,1-cyclohexylene, because of availability of raw materials.
1,1- (3,3,5-trimethyl) cyclohexylene is preferably used. As the aralkylene group, phenylmethylene, diphenylmethylene, 1,1-
(1-phenyl) ethylene, 9,9-fluorenylene. As the haloalkylene group, 2,2-
Hexafluoropropylene, 2,2- (1,1,3,3
-Tetrafluoro-1,3-dicyclo) propylene and the like are preferably used. These may be one kind or two or more kinds. Among them, 1,1- (3,3,5-trimethyl) cyclohexylene or 9,9-fluorenylene is preferable from the viewpoint of heat resistance and optical characteristics required for a liquid crystal display device.

The above bisphenol components can be used in combination of two or more.

The polycarbonate resin may be a copolymer or a combination of two or more.

As such a polycarbonate resin,
(I) a homopolymer in which the bisphenol component is bisphenol A, (ii) bisphenol A, and in the above formula [I], X is 1,1- (3,3,5-trimethyl) cyclohexylene or 9,9-fluorenylene. A copolymer comprising a certain bisphenol is more preferred. The composition of such a copolymer is preferably bisphenol A of 10%.
~ 90 mol%.

The thickness of the transparent polymer substrate (S) is 0.01 to
Preferably, the film or sheet has a thickness of 1.0 mm. When the thickness is smaller than 0.01 mm, the panel does not have sufficient rigidity and is easily deformed at the time of panel processing, and is difficult to handle. On the other hand, if it is larger than 1.0 mm, deformation is unlikely to occur, but when the liquid crystal display element is assembled, a double image becomes conspicuous and display quality is impaired. The preferred thickness is 0.02
It is in the range of 0.7 mm.

When the transparent conductive substrate is used as an electrode substrate for a liquid crystal display panel, it preferably has the following excellent optical isotropy, transparency, and non-water absorption. (I) Retardation value is 30 nm or less (preferably 20 nm or less) (ii) Variation of the slow axis is within ± 30 degrees (preferably ±
(Iii) The total light transmittance is 80% or more (preferably 85%)
(Iv) The water absorption is 2% or less (preferably 1% or less) Here, the retardation value is the difference Δn between the refractive index of birefringence at a wavelength of 590 nm measured using a known measuring device and the film thickness. This is expressed by the product △ n · d with d.

The transparent polymer substrate preferably has a low water absorption. When the water absorption is high, the substrate contains water in the high-temperature and high-humidity durability test, and the surface resistance of the base of the transparent conductive layer is reduced, so that display defects of the panel are likely to occur. Such a problem can be considerably suppressed by laminating a gas barrier layer described later, but in order to obtain high reliability at high temperature and high humidity, the water absorption of the transparent polymer substrate is 0.7% or less. Is more preferable.

[Gas Barrier Layer (X)] When the above transparent conductive substrate is used as an electrode substrate for a liquid crystal display element,
It is important to laminate at least one organic or inorganic gas barrier layer (X) on at least one surface of the transparent polymer substrate. As an organic gas barrier layer,
For example, polyvinyl alcohol, vinyl alcohol-based polymers such as vinyl alcohol-ethylene copolymers, acrylonitrile-based polymers such as polyacrylonitrile, acrylonitrile-methyl acrylate copolymer and acrylonitrile-styrene copolymer, or polyvinylidene chloride and the like Polymers. The organic gas barrier layer can be usually formed by wet-coating a coating composition obtained by dissolving these polymers in an organic solvent on the transparent polymer substrate (S). As a coating method, for example, a known method such as a reverse roll coating method, a microgravure coating method, a direct gravure coating method, a kiss coating method, and a die coating method can be used. Further, by diluting the coating composition with an appropriate organic solvent, it is possible to adjust the viscosity of the coating liquid and the thickness of the gas barrier layer.

The organic gas barrier layer is used so that the water vapor permeability of the entire transparent conductive substrate after removing the transparent conductive layer from the transparent conductive substrate of the present invention in a high-temperature and high-humidity environment is as small as possible. The film thickness may be adjusted according to the material, but usually 1 to 50 μm is preferable.

The inorganic gas barrier layer may be formed, for example, of a metal oxide containing one or more metals selected from the group consisting of silicon, aluminum, magnesium, zinc, zirconium, titanium, yttrium, and tantalum. , Metal nitrides of silicon, aluminum, and boron, or mixtures thereof. Among them, a gas barrier property, transparency, surface smoothness, flexibility, film stress, the ratio of the number of oxygen atoms to the number of silicon atoms is 1.5 to 2.0 from the viewpoint of cost and the like. Metal oxide is good. The ratio of the number of oxygen atoms to the number of silicon atoms in the silicon oxide is analyzed and determined by X-ray photoelectron spectroscopy, X-ray microspectroscopy, Auger electron spectroscopy, Rutherford backscattering, or the like. When this ratio is smaller than 1.5, the transparency is reduced.
2.0 is preferred. Further, when magnesium oxide and / or magnesium fluoride is contained in the silicon oxide in an amount of 5 to 30% by weight based on the total weight, the transparency can be further increased. These inorganic gas barrier layers can be formed by a vapor deposition method of depositing a material from a gas phase such as a sputtering method, a vacuum deposition method, an ion plating method, or a plasma CVD method to form a film. Among them, the sputtering method is preferred from the viewpoint that particularly excellent gas barrier properties can be obtained.

The thickness of the inorganic gas barrier layer is from 2 nm to
A range of 1 μm is preferred. The thickness of the metal oxide layer is 2 nm
If it is less than 1, it is difficult to form a uniform film, and a portion where the film is not formed occurs, so that the gas permeability increases. On the other hand, when the thickness is more than 1 μm, not only is the transparency lacking, but also when the transparent conductive substrate is bent, cracks are generated in the gas barrier layer to increase the gas permeability. In particular,
As described later, when X is sandwiched between the cured resin layers (B) and (C) made of (P) or (Q) so that X is as thin as 5 to 200 nm, preferably 5 to 50 nm, High gas barrier properties can be obtained.

According to the present invention, in the transparent conductive substrate, on the side opposite to the surface on which the cured resin layer (U) of the transparent polymer substrate (S) is laminated, the cured resin having a higher water absorption than (S). By laminating the resin layer (B), a panel can be obtained in which display degradation hardly occurs even when left in a high temperature and high humidity environment for a long time. Here, as the (B) layer, a thermosetting resin such as a silicon-containing resin (P) or (Q) described later, an epoxy resin, a melamine resin, a urethane resin, an alkyd resin,
A radiation curable resin such as an ultraviolet curable acrylic resin can be used.

Further, in order to achieve a very high gas barrier property required for a liquid crystal display device, the above-mentioned metal oxide containing silicon oxide as a main component is used as a gas barrier layer (X). Cured resin layer (B) composed of a silicon-containing resin and a cured resin layer (C) composed of
It is preferable that (X) is provided in contact with (X) so as to sandwich it. As the silicon-containing resin, a vinyl alcohol-containing polysiloxane resin (P) or an organic polysiloxane resin (Q) is preferable, and at least one of the cured resin layers (B) and (C) is more preferably (P). With such a layer structure, the gas permeability of the entire substrate can be reduced even when a metal oxide mainly composed of a silicon oxide having a small thickness is used, and in particular, the water vapor permeability is reduced to 0.1 g / m 2.
² / day or less.

The vinyl alcohol-containing polysiloxane resin (P) can be obtained by using a coating composition containing a vinyl alcohol polymer and a silicon compound containing an epoxy group and a silicon compound containing an amino group.

Here, the vinyl alcohol-based polymer is
A vinyl alcohol copolymer containing 50 mol% or more of vinyl alcohol as a monomer component, or a homopolymer of vinyl alcohol. Examples of the vinyl alcohol copolymer include a vinyl alcohol-vinyl acetate copolymer, a vinyl alcohol vinyl butyral copolymer, an ethylene-vinyl alcohol copolymer, and a polyvinyl alcohol having a silyl group in a molecule. Among them, when an ethylene-vinyl alcohol copolymer is used, a vinyl alcohol-containing polysiloxane resin (P) having further excellent chemical resistance, water resistance and durability can be obtained.

The vinyl alcohol-based polymer is dissolved in an organic solvent such as water, alcohol, dimethylimidazoline or the like to form a component of the coating composition. For example, the ethylene-vinyl alcohol copolymer is preferably dissolved in a mixed solvent containing water and propanol as main components and used as a component of the coating composition.

The silicon compound containing an epoxy group is selected from the group consisting of a silicon compound having an epoxy group and an alkoxysilyl group, a (partly) hydrolyzate thereof, a (partly) condensate thereof, and a mixture thereof. II].

[0030]

X-R ¹¹ -Si (R ¹² ) _n (OR ¹³ ) _{3 -n} [II] wherein R ¹¹ is an alkylene group having 1 to 4 carbon atoms, and R ¹² and R ¹³ are 1 to 3 carbon atoms. And X is a glycidoxy group or an epoxycyclohexyl group, and n is 0 or 1.

Particularly preferred silicon compounds containing an epoxy group are 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These compounds may be used alone or in combination of two or more.

The amino group-containing silicon compound is selected from the group consisting of a silicon compound having an amino group and an alkoxysilyl group, a (partial) hydrolyzate thereof, a (partial) condensate thereof, and a mixture thereof. III].

[0033]

Y—HN—R ¹⁴ —Si (R ¹⁵ ) _m (OR ¹⁶ ) _3-m [III] where R ¹⁴ is an alkylene group having 1 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ are carbon atoms. 1-4 alkyl groups, Y is a hydrogen atom or an aminoalkyl group, and m is 0 or 1.

Of these, particularly preferred amino group-containing silicon compounds are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, and 3-aminopropylmethyldiethoxysilane. , N- (2-aminoethyl)-
3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. These compounds may be used alone or in combination of two or more.

In the present invention, the (partial) hydrolyzate of the epoxy group-containing silicon compound and the amino group-containing silicon compound and the (partial) condensate thereof are one of the above-mentioned epoxy group-containing silicon compound and amino group-containing silicon compound. A part or all of which is hydrolyzed, a condensate in which part or all of the hydrolyzate is subjected to a condensation reaction, and an epoxy group-containing silicon compound and an amino group-containing silicon compound of a raw material that is not hydrolyzed with the condensate These are condensation products, which are obtained by a so-called sol-gel reaction. Here, the hydrolyzate is obtained by mixing with an aqueous acidic solution such as an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid, or water. The coating liquid is preferably diluted with various organic solvents such as alcohols, esters, ethers, ketones, and cellosolves in consideration of storage stability and coating stability.

The mixing ratio of the silicon compound containing an epoxy group and the silicon compound containing an amino group is expressed by a molar equivalent of an epoxy group E
1/6 <Ep in the ratio of p, amino equivalent molar equivalent conversion amount Ap
/ Ap <6/1 is preferable. If the mixing ratio is out of this range, adhesion, heat resistance, solvent resistance, water resistance,
The durability decreases. When such a mixture of the epoxy group-containing silicon compound and the amino group-containing silicon compound is mixed with the polyvinyl alcohol-based polymer, they are mixed so that the weight ratio after curing becomes 20% by weight or more and less than 95% by weight. When the amount is less than 20 parts by weight, water resistance and chemical resistance tend to be inferior, and when it is 95% by weight or more, gas barrier properties tend to decrease. Here, the weight after curing of the mixture of an epoxy group-containing silicon compound and an amino group-containing silicon ^{compound, X-R 11 -Si (R} 12) nO (3-n) / 2 and Y-HN
-R ¹⁴ is a weight represented by _{^{-Si (R 15) m O (}} 3-m) / 2. Here, this weight conversion formula was defined as above, assuming that all of the alkoxysilyl groups in each silicon compound had undergone hydrolysis and condensation reactions.

In particular, by laminating the polyvinyl alcohol-containing polysiloxane resin in contact with at least one surface of a gas barrier layer composed of the above-described metal oxide containing silicon oxide as a main component, the gas barrier property is further improved. improves.

The coating composition contains a vinyl alcohol polymer, an epoxy group-containing silicon compound, an amino group-containing silicon compound, an organic solvent, a catalyst such as acetic acid, and the like.
It may contain stabilizers and leveling agents. The concentration of acetic acid in the composition is preferably in the range of 0.2 to 5 molar equivalent times the molar concentration of amino groups and / or imino groups in the coating composition. In addition, the amounts of the organic solvent, the stabilizer, and the leveling agent may be adjusted in consideration of workability and the thickness of the obtained cured product layer.

This composition is coated on a substrate such as (S),
Then, by subjecting this to a curing reaction by heating or the like, (P) can be obtained. The heating temperature is usually not lower than room temperature and not higher than the glass transition temperature of (S). By this heating, a so-called sol-gel reaction of the epoxy group-containing silicon compound and the amino group-containing silicon compound proceeds, and a part or all of the vinyl alcohol-based polymer reacts to obtain a cured film.

The thickness of the polyvinyl alcohol-containing polysiloxane resin (P) can be appropriately selected generally from the range of 0.01 to 20 μm.

The organic polysiloxane resin (Q) can be obtained by using a coating composition containing a silicon compound containing an epoxy group and a silicon compound containing an amino group.

The organic polysiloxane resin (Q) is preferably obtained by subjecting an organosilicon compound represented by the following formula (IV) or a hydrolyzate thereof to a so-called sol-gel reaction.

[0043]

Equation 5] R ¹⁷ _a R ¹⁸ _b SiX _{4-a over b} [IV]

Here, R ¹⁷ is an organic group having 1 to 10 carbon atoms, R ¹⁸ is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 6 carbon atoms, X is a hydrolyzable group, a and b are 0 or 1. Examples of the organosilicon compound represented by the above formula (3) include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminomethyltriethoxysilane, 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, N-aminomethyl-3-aminopropyltrimethoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and the like can be mentioned. These compounds can be used alone or in combination of two or more. Among them, it is preferable to use a mixture of the epoxy group-containing silicon compound of the above formula (1) and the amino group-containing silicon compound of the above formula (2) as a main component. Here, the mixing ratio of the epoxy group-containing silicon compound and the amino group-containing silicon compound is
It is preferable in terms of chemical resistance and interlayer adhesion that the ratio of the epoxy group molar equivalent conversion amount Eq and the amino group molar equivalent conversion amount Aq be within the range of 5/95 <Eq / Aq <95/5. In particular, by forming a gas barrier layer made of a metal oxide containing silicon oxide as a main component on the organic polysiloxane-based resin layer, the gas barrier property is further improved.

The organic polysiloxane resin (Q) can be produced in the same manner as in the above (P). The thickness of the organic polysiloxane resin (Q) is generally 0.01 to
It can be appropriately selected from the range of 20 μm.

[Cured resin layer (U)] Cured resin layer (U)
Is used by laminating a transparent conductive layer (E) thereon. This (U) is 1.0 × 10 ¹³ at 50 ° C. and 30% RH environment.
Ω / □ and 1.0 × 10 ¹² Ω in a 50 ° C. 90% RH environment
Since it has a surface resistance of // or more, a display defect of the liquid crystal panel does not occur for a long time, and a highly stable and highly reliable liquid crystal display device can be provided. When the surface resistance at 50 ° C. 90% RH is to produce a liquid crystal panel using a 1 × 10 ¹² Ω / □ under the transparent conductive substrate, a display panel such as display bleeding and crosstalk at high temperature and high humidity durability test of the panel Defects are more likely to occur.

The cured resin layer (U) has a polar group, a water absorbing property,
It is preferable to reduce ionic impurities as much as possible. The more polar groups such as hydroxyl group, amino group, amide group, carbonyl group and the like, the higher the water absorption, and the more the contamination with ionic impurities, the more the surface resistance decreases. However, if some polar groups do not exist, the interlayer adhesion of the transparent conductive substrate cannot be ensured. The water absorption varies depending on the structure of the cured resin layer and the film forming conditions, and it is more preferable that the resin is crosslinked at a high density. Further, from the viewpoint of productivity, a thermosetting resin capable of obtaining sufficient properties by a short-time heat treatment is more preferable. Contamination such as ionic impurities needs to be reduced as much as possible in the process of manufacturing the transparent conductive substrate as well as the purification of the raw material of the cured resin layer (U). In addition, it is more preferable that the dielectric constant of the cured resin layer (U) be as low as possible, particularly for a liquid crystal panel that performs display by high frequency driving.

The cured resin layer (U) must have chemical resistance, transparency, and good interlayer adhesion. For example, the cured resin layer (U) may be made of silicon-containing resin, epoxy resin, melamine resin, urethane resin, alkyd resin, etc. A radiation-curable resin such as a thermosetting resin and an ultraviolet-curable acrylic resin can be used.

According to the present invention, such a cured resin layer (U)
There has in the infrared absorption spectrum, the absorbance of absorption based on O-H stretching vibration having a peak near 3500 cm ^-1 and (a), a peak near 3000 cm ^-1 C-
Absorbance (b) of absorption based on H stretching vibration and 1600c
The absorbance (c) of absorption based on -NH _{2 in-} plane bending vibration having a peak near m ^-1 and the absorbance (d) derived from Si-O having a peak near 1130 cm ^-1 are represented by the following formula (1). , (2) and (3), the insulation resistance of the (U) surface after the transparent electrode layer is removed by etching or the like is extremely high in a high-temperature and high-humidity environment. Therefore, when a transparent conductive substrate is used as an electrode substrate, sufficient insulation can be ensured in a circuit pattern formed by etching or the like, even if the distance between adjacent electrodes on the substrate surface is reduced. As a result, it is possible to obtain a liquid crystal display device having high reliability and high definition in a high-temperature, high-humidity environment.

[0050]

(6) 0.01 <(a) / (b) <1.0 (1) 0.01 <(c) / (b) <0.5 (2) 0.01 <(d) / (b) ) <2.0 (3)

As for the absorbance (b) derived from the C—H stretching vibration, when the stretching vibration of the same bond is adjacent, two symmetric and asymmetric absorptions are recognized, but the C—H stretching with the largest absorbance is observed. Let the vibration be (b). In addition to the above characteristics, the cured resin layer (U) has excellent adhesion to the transparent conductive layer. As a result, resistance to chemicals such as acids, alkalis, and NMP required in a liquid crystal display panel manufacturing process is good. When the above-mentioned formulas (1), (2) and (3) are not satisfied, it is difficult to obtain these good characteristics at the same time.

[0052] The above-mentioned polyvinyl alcohol-containing polysiloxane resin (P) and the organic polysiloxane resin (Q) are preferred as materials giving such a silicon-containing resin.
Here, in the case of the polysiloxane resin (P), when the mixing ratio of the epoxy group-containing silicon compound and the amino group-containing silicon compound is expressed as an epoxy group molar equivalent conversion amount UEp and an amino group molar equivalent conversion amount Uap, 50 / 50 <UEp / U
When the mixture of the epoxy group-containing silicon compound and the amino group-containing silicon compound is mixed with the polyvinyl alcohol-based polymer, the weight ratio of the solid content after curing becomes 50% by weight or more. Mixing is more preferred. In addition, the organic polysiloxane resin (Q)
In the case of, the mixing ratio of the alkoxysilane having an epoxy group and the alkoxysilane having an amino group is determined by converting the epoxy group molar equivalent conversion amount UEq and the amino group molar equivalent conversion amount UA
When q, 50/50 ≦ UEq / UAq ≦ 95/5
It is more preferable to mix them within the range. A particularly preferred range is 65/35 ≦ UEq / UAq ≦ 85/15.

The epoxy resin is preferably a novolak type epoxy resin from the viewpoint of solvent resistance. As the curing agent for curing the epoxy resin, a known agent can be applied. For example, a curing agent such as an amine-based, polyaminoamide-based, acid and acid anhydride, imidazole, mercaptan, and phenol resin is used. Among them, polymers having an acid anhydride and an acid anhydride structure or aliphatic amines are preferably used from the viewpoint of solvent resistance, optical properties, thermal properties, etc., and more preferably a polymer having an acid anhydride and an acid anhydride structure It is. Further, it is preferable to add an appropriate amount of a known curing catalyst such as a tertiary amine or imidazole in order to increase the reaction rate.

The radiation-curable resin refers to a resin that cures when irradiated with radiation such as ultraviolet light or an electron beam. Specifically, the radiation-curable resin has an acryloyl group, a methacryloyl group, a vinyl group, etc. A resin containing a saturated double bond. Among these, an acrylic resin containing an acryloyl group is particularly preferable from the viewpoint of reactivity. The radiation-curable resin may use one kind of resin or a mixture of several kinds of resins, but has two or more acryloyl groups in the molecule or unit structure from the viewpoint of solvent resistance. It is preferable to use an acrylic resin. Such polyfunctional acrylate resins include, for example, urethane acrylate, ester acrylate, epoxy acrylate, and the like, but are not limited thereto. In particular, from the viewpoint of increasing the surface insulation resistance in a high-temperature and high-humidity environment, an acrylic resin containing units of the following formulas (V) and / or (VI) and having at least two or more acryloyl groups is preferable.

[0055]

Embedded image

A known hydrolyzate of an alkoxysilane or a silane coupling agent may be mixed with such an epoxy resin or radiation curable resin for the purpose of imparting further adhesion and solvent resistance. When the ultraviolet curing method is used, an appropriate amount of a known photoreaction initiator is added to the radiation-curable resin.

The thickness of the cured resin layer (U) can be appropriately selected in a range of generally 0.01 to 20 μm, preferably 0.03 to 10 μm.

The cured resin layer (U) can be produced by a conventional method in which a composition obtained by mixing a curable resin in an organic solvent is applied onto a substrate, and the composition is cured by heating or irradiation with ultraviolet rays. it can. In particular, when (P) or (Q) is used as the silicon-containing resin, it can be produced by the above-described method.

[Laminated Film] According to the present invention, the laminated film comprising the transparent polymer substrate (S) and the cured resin layer (U) further comprises a gas barrier layer (X). By disposing the transparent conductive layer (E) in contact with (U), a transparent conductive substrate having the above-mentioned excellent properties and good gas barrier properties is provided. That is, such a laminated film, the surface of the U layer shows a high resistance value even under high temperature and high humidity, and good gas barrier properties,
The water absorption is 2% or less. In particular, the water vapor permeability under an environment of 40 ° C. and 90% RH is 1 g / m ² / day or less, preferably 0.1 g / m ² / day or less, and (U)
Has a high insulation resistance under a high temperature and high humidity environment.

[Transparent Conductive Layer (E)] As the transparent conductive layer (E), a known metal film, metal oxide film and the like can be applied. Among them, from the viewpoint of transparency, conductivity and mechanical properties, Metal oxide films are preferred. For example, indium oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium, etc. are added as impurities,
Metal oxide films such as cadmium oxide and tin oxide, zinc oxide to which aluminum is added as an impurity, and titanium oxide are given. Above all, a thin film of indium oxide mainly composed of tin oxide and containing 2 to 15% by weight of zinc oxide,
It is excellent in transparency and conductivity, and is preferably used.

The thickness of the transparent conductive layer (E) is set according to the desired surface resistance, and is 1 nm to 1 μm, preferably 10 nm to 500 nm.

In the transparent conductive substrate of the present invention, when (P) and (Q) are used as the cured resin layers (B) and (C),
For example, (E) / (S) / (X), (E) / (X) /
(S) / (X), (E) / (S) / (P) / (X) /
(Q), (E) / (S) / (Q) / (X) / (P),
(E) / (S) / (P) / (X) / (P), (E) /
(P) / (X) / (Q) / (S) / (P) / (X) /
(Q), (E) / (P) / (X) / (Q) / (S) /
(Q) / (X) / (P), (E) / (P) / (X) /
(Q) / (S) / (P) / (X) / (P), (E) /
(Q) / (X) / (P) / (S) / (P) / (X) /
(Q), (E) / (Q) / (X) / (P) / (S) /
(Q) / (X) / (P), (E) / (Q) / (X) /
(P) / (S) / (P) / (X) / (P), (E) /
(P) / (X) / (P) / (S) / (P) / (X) /
(Q), (E) / (P) / (X) / (P) / (S) /
(Q) / (X) / (P), (E) / (P) / (X) /
(P) / (S) / (P) / (X) / (P), (E) /
(U) / (S) / (X), (E) / (U) / (X) /
(S) / (X), (E) / (U) / (S) / (P) /
(X) / (Q), (E) / (U) / (S) / (Q) /
(X) / (P), (E) / (U) / (S) / (P) /
(X) / (P), (E) / (U) / (P) / (X) /
(Q) / (S) / (P) / (X) / (Q), (E) /
(U) / (P) / (X) / (Q) / (S) / (Q) /
(X) / (P), (E) / (U) / (P) / (X) /
(Q) / (S) / (P) / (X) / (P), (E) /
(U) / (Q) / (X) / (P) / (S) / (P) /
(X) / (Q), (E) / (U) / (Q) / (X) /
(P) / (S) / (Q) / (X) / (P), (E) /
(U) / (Q) / (X) / (P) / (S) / (P) /
(X) / (P), (E) / (U) / (P) / (X) /
(P) / (S) / (P) / (X) / (Q), (E) /
(U) / (P) / (X) / (P) / (S) / (Q) /
(X) / (P), (E) / (U) / (P) / (X) /
A transparent conductive substrate laminated in the order of (P) / (S) / (P) / (X) / (P) is preferable. Among them,
(E) / (U) / (S) / (P) / (X) / (Q),
(E) / (U) / (S) / (Q) / (X) / (P),
The liquid crystal display device manufactured using the transparent conductive substrate having the configuration of (E) / (U) / (S) / (P) / (X) / (P) has only one gas barrier layer (X). Despite not being laminated, display degradation hardly occurs even when left for a long time in a high temperature and high humidity environment. Then, in the assembling process of the liquid crystal display element, it is preferable because it has good chemical resistance to various organic solvents and acids and alkalis in various patterning processes and lamination of an alignment film and various washing processes, and good interlayer adhesion can be obtained.

In addition, chemical treatment such as lamination of various undercoat layers for enhancing adhesion between layers, or physical treatment such as corona treatment, plasma treatment, UV irradiation, etc., within a range not to decrease the effect of the present invention. A processing method may be performed. In particular, it is preferable to use the cured resin layer (A) as the anchor layer between (U) and (S) because the adhesiveness is further increased. As such a cured resin layer (A), a urethane resin is preferable.

When the transparent conductive substrate of the present invention is handled in the form of a film roll, a layer for imparting slipperiness to the film may be provided on the surface opposite to the surface on which the transparent conductive layer is laminated, or a knurling treatment may be performed. It is valid.

Further, a color filter layer may be provided on the transparent conductive substrate of the present invention, for example, for the purpose of imparting a color display function to a liquid crystal display device produced using the same. The color filter can be formed by a known technique such as a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. The color filter layer is formed on a layer other than the layer between the transparent conductive layer (E) and the cured resin layer (U) of the transparent conductive substrate, or on the outermost surface opposite to the surface on which the transparent conductive layer (E) is laminated. This is preferable because the operation reliability of the liquid crystal panel can be easily secured.

[0066]

The transparent conductive substrate of the present invention is excellent in transparency, optical isotropy, chemical resistance, interlayer adhesion, gas barrier property, and displays even when left for a long time in a high temperature and high humidity environment. It is extremely useful as a transparent conductive substrate capable of providing a liquid crystal panel in which deterioration of quality is unlikely to occur. Therefore, a liquid crystal display device using such a transparent conductive substrate as an electrode substrate has excellent stability over a long period of time and good display quality.

[0067]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, parts and% are by weight unless otherwise specified. Various measurements in the examples were performed as described below.

Surface resistance: The entire transparent conductive layer of the transparent conductive substrate was completely removed by etching, and the surface resistance of the cured resin layer (U) which was the underlayer of the transparent conductive layer on the transparent conductive substrate was measured. 50 ° C., 30% RH surface resistance R30
And the surface resistance R90 at 50 ° C. and 90% RH is
8009 RESISTIVIT made by Keithley
The measurement was performed using Y TEST FIXTURE and Model 6517A manufactured by Keithley. Etching was performed using a 10% hydrochloric acid aqueous solution.

Water vapor barrier property: Permtran W1A manufactured by MOCON was used to measure the water vapor permeability under an atmosphere of 40 ° C. and 90% RH.

Water absorption: The water absorption of the transparent polymer substrate (S), the entire transparent conductive substrate, and the cured resin layer (B) were measured by a method according to ASTM D570.

Infrared absorption spectrum: The cured resin layer (B) as an underlayer of the transparent conductive layer (E) was scraped off the surface of the sample from which the transparent conductive layer (E) of the transparent conductive substrate was completely removed by etching. This was dried for 1 hour under the condition of 60 ° C. DRY for the purpose of removing adsorbed water.
The infrared absorption spectrum was measured by the r method. The measurement sample was 0.3 parts by weight with respect to 100 parts by weight of KBr.
The parts were mixed in parts by weight. The measuring device used was FT-IR manufactured by PerkinElmer. C-H with 3500 cm ^-1 absorbance of the absorption attributed to the 0-H stretching vibration having a peak near the (a), a peak near 3000 cm ^-1
Absorbance (b) of absorption attributed to stretching vibration and 1600
cm ^-1 absorbance of absorption attributed to -NH ₂ plane deformation vibration having a peak near the (c), the absorbance of absorption derived from Si-O having a peak near 1100 cm ^-1 (d)
Was measured.

Transparency: Wavelength 55 using an ordinary spectrophotometer
The light transmittance of a parallel light of 0 nm was measured.

Optical Isotropy: The retardation value for light having a wavelength of 590 nm was measured using a multi-wavelength birefringence measuring apparatus M-150 manufactured by JASCO.

Interlayer adhesion: ASTM D2196-68
The adhesion between the respective layers constituting the transparent conductive substrate was evaluated by a method conforming to the above.

Liquid crystal panel reliability: A liquid crystal display device as shown in FIG. 1 was prepared and evaluated. The laminated film 11 on the upper side and the laminated film 13 on the lower side are disposed so as to face each other. The periphery of the laminated films 11 and 13 is sealed with the sealing material 15 and the gap material 21 is dispersed to form the liquid crystal cell 17. The liquid crystal cell 17 contains liquid crystal substance 1
9 was enclosed. Then, a polarizing plate was disposed so as to sandwich the liquid crystal cell 17, thereby forming an STN type liquid crystal display element. The upper transparent film 11 is provided with a patterned transparent conductive layer 23 to constitute the transparent conductive substrate of the present invention. The lower laminated film 13 is provided with an unpatterned transparent conductive layer 23 to constitute the transparent conductive substrate of the present invention. An alignment film 25 is formed on the inner surface of each laminated film.

On the transparent conductive substrate, display electrodes for 160 × 100 dots were formed on the transparent conductive layer by photolithography. Next, an orientation film of 1000 ° was formed on the electrode surface, and rubbing treatment was performed so that each twist was 220 °. Next, plastic beads of 6.5 μm are used as a gap agent and dispersed on the surface of the electrode so as to have a dispersion density of 150 / mm ^2, and two transparent conductive substrates are attached with the electrode surface inside using an epoxy adhesive. Together, a cell was produced. Next, a nematic liquid crystal containing a chiral nematic liquid crystal was injected into the cell from the injection port, the cell gap was made uniform by a pressure method, and the injection port was sealed. Next, polarizing plates were attached to both sides of the cell to obtain a liquid crystal panel. The liquid crystal panel thus obtained was left under an environment of 50 ° C. and 90% RH for 250 hours, and it was examined whether or not the impedance of the liquid crystal cell was reduced.

The following abbreviations were used for the compound names described below. BisA-PC: polycarbonate containing 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BisA) as a bisphenol component BisA / BCF-PC: bisphenol A and 9,9-bis (4-
(Hydroxy-3-methylphenyl) fluorene (BCF)
BisA / IP-PC containing bisphenol A as a bisphenol component: bisphenol A and 3,3,5-trimethyl-1,1-di (4-phenol) cyclohexylidene
Polycarbonate copolymer containing (IP) as a bisphenol component PES: Polyethersulfone ITO: Indium tin oxide ECHETMOS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane APTMOS: 3-amino Propyltrimethoxysilane EVOH: Ethylene vinyl alcohol copolymer (“EVAL” manufactured by Kuraray) DCPA: Dimethylol tricyclodecane diacrylate (“Light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.) EA: Epoxy acrylate (manufactured by Showa Polymer) "Ripoxy R
UA: Urethane acrylate (“NK Oligo U-15HA” manufactured by Shin-Nakamura Chemical) PhR: Phenoxy resin (“PAP manufactured by Phenoxy Associates”)
HEN ") PI: Polyisocyanate (" Coronate "manufactured by Nippon Polyurethane Industry)

[Example 1] Polycarbonate (BisA-PC) having an average molecular weight of 37,000 and a Tg of 155 ° C, in which the bisphenol component consists solely of BisA, was dissolved in methylene chloride so as to be 20% by weight. Then, this solution was cast on a polyester film having a thickness of 175 μm by a die coating method. Next, it was dried in a drying oven until the residual solvent concentration became 13% by weight, and was peeled off from the polyester film. Then, the obtained polycarbonate film was dried in a drying oven at a temperature of 120 ° C. while balancing the longitudinal and horizontal tensions until the residual solvent concentration in the film became 0.08% by weight.

The thus obtained transparent polymer substrate (S)
Had a thickness of 100 μm and a light transmittance at a wavelength of 550 nm of 91%.

Next, a coating composition for forming the polyvinyl alcohol-containing polysiloxane resin layer (P) was prepared as follows.

Component (P1) 100 parts of EVOH was added to water 72
The mixture was heated and dissolved in a mixed solvent of 0 part and 1080 parts of n-propanol to obtain a homogeneous solution. 0.1 parts of a leveling agent (SH30PA manufactured by Dow Corning Toray Co., Ltd.) and 39 parts of acetic acid were added to this solution, and then the component (P2)
One part was added and stirred for 10 minutes. Further, the components (P
3) 77 parts of APTMOS was added and stirred for 3 hours to obtain a coating composition.

The composition of the coating composition is (P1) /
[(P2) + (P3)] = 1/2, (P2) / (P3)
= 2/1. This coating composition was coated on one side of the transparent polymer substrate (S) described above,
A heat treatment was performed at 3 ° C. for 3 minutes to form a (P) layer having a thickness of 0.05 μm.

Next, a gas barrier layer (X) made of a 250 ° -thick SiO ₂ film was laminated on the layer (B) by DC magnetron sputtering.

Further, the coating composition for providing the polysiloxane resin (Q) was prepared as follows.

720 parts by weight of water, 2-propanol 108
After adding 88 parts by weight of acetic acid to 0 parts by weight of the mixed solvent,
(Q1) 640 parts by weight of ECHEMOS and (Q2) AP
154 parts by weight of TMOS were sequentially added and stirred for 3 hours to obtain a coating composition. The composition of the coating composition is
(Q1) / (Q2) = 3/1. This coating composition is coated on both sides of a film on which (P) and (X) are laminated, and heat-treated at 130 ° C. for 3 minutes,
A (Q) layer having a thickness of 2 μm was formed.

Next, a transparent conductive layer (E) made of an ITO film having a thickness of 130 nm is provided on the surface of the film opposite to the surface on which (X) is laminated by a DC magnetron sputtering method. A substrate was obtained. The evaluation results of the obtained transparent conductive substrate were good as shown in Table 1.

Further, the liquid crystal display device manufactured using the transparent conductive substrate of the present invention did not show any visual defects such as alignment deterioration and the like in a high-temperature storage test at 80 ° C. for 1000 hours, and the current consumption was 20% of the initial value. Within the range, showing high reliability.

[Embodiment 2] The configuration of the substrate was changed to (E) / (U)
Except for / (S) / (Q) / (X) / (P), a transparent conductive substrate was obtained in the same manner as in Example 1. The evaluation results of the obtained transparent conductive substrate were good as shown in Table 1.

[Embodiment 3] The structure of the substrate was changed to (E) / (U)
Except for / (S) / (P) / (X) / (P), a transparent conductive substrate was obtained in the same manner as in Example 1. The evaluation results of the obtained transparent conductive substrate were good as shown in Table 1.

Example 4 Polycarbonate copolymer (BiA / BCF = 1/1 (molar ratio) and Tg of 225 ° C.)
A transparent conductive substrate was obtained in the same manner as in Example 2 except that a transparent polymer substrate (S) made of sA / BCF-PC) having a thickness of 150 μm was used. The evaluation results of the obtained transparent conductive substrate were good as shown in Table 1.

[0091]

[Table 1]

Example 5 BisA / IP = 2/3 (molar ratio)
And a polycarbonate copolymer having a Tg of 205 ° C (BisA / I
(P-PC) 200 µm thick transparent polymer substrate (S)
A transparent conductive substrate was obtained in the same manner as in Example 2 except for using. The evaluation results of the obtained transparent conductive substrate were good as shown in Table 2.

Example 6 A transparent conductive substrate was obtained in the same manner as in Example 5, except that the (P) layer and the (U) layer were laminated using a coating composition adjusted as follows. . In the same manner as in Example 1, component (P1) EVOH
Was obtained. After 0.1 part of the leveling agent used in Example 1 and 28 parts of acetic acid were added to this solution, the components (P
2) 229 parts of ECHETMOS were added and stirred for 10 minutes. Further, 56 parts of the component (P3) APTMOS was added to this solution and stirred for 3 hours to obtain a coating composition. The composition of the coating composition is (P1) / [(P2) + (P
3)] = 1/2, (P2) / (P3) = 3/1.
The evaluation results of the obtained transparent conductive substrate were good as shown in Table 2.

Example 7 As a gas barrier layer (X), a layer made of silicon oxide containing 10% by weight of magnesium fluoride formed by a vapor deposition method (thickness: 1000 °).
A transparent conductive substrate was obtained in the same manner as in Example 6, except that the above procedure was repeated. The evaluation results of the obtained transparent conductive substrate were good as shown in Table 2.

[0095]

[Table 2]

Example 8 Example 2 was repeated except that the cured resin layer (U) was laminated to a thickness of 4 μm by the following method.
In the same manner as in the above, a transparent conductive substrate was obtained. 10 parts by weight of DCPA, 10 parts by weight of EA, 10 parts by weight of UA, 30 parts by weight of 1-methoxy-2-propanol, 1 part as an initiator
2 parts by weight of -hydroxycyclohexyl phenyl ketone was mixed to obtain a coating composition. After coating this composition and heating at 60 ° C. for 1 minute, a cured resin layer (U) was formed using a high-pressure mercury lamp. The evaluation results of the obtained transparent conductive substrate were good as shown in Table 3.

Example 9 Example 2 was repeated except that the cured resin layer (U) was laminated to a thickness of 4 μm by the following method.
In the same manner as in the above, a transparent conductive substrate was obtained. 20 parts by weight of DCPA, 10 parts by weight of UA, 30 parts by weight of 1-methoxy-2-propanol, and 2 parts by weight of 1-hydroxycyclohexylphenyl ketone as an initiator were mixed to obtain a coating composition. Coat this composition,
After heating for 1 minute, a cured resin layer (U) was formed using a high-pressure mercury lamp. The evaluation results of the obtained transparent conductive substrate were good as shown in Table 3.

Example 10 A transparent conductive substrate was obtained in the same manner as in Example 2 except that the (Q) layer was not provided between the S and (X) layers. As shown in Table 3, the evaluation results of the obtained transparent conductive substrate showed that although the interlayer adhesion between the (S) substrate and the (X) layer was slightly insufficient, the reliability of the liquid crystal panel formed using this substrate was low. The properties were also relatively good.

Example 11 A transparent conductive substrate was obtained in the same manner as in Example 2 except that the (P) layer was not provided. The evaluation results of the obtained transparent conductive substrate were relatively good as shown in Table 3.

[0100]

[Table 3]

[Comparative Example 1] A transparent conductive substrate was obtained in the same manner as in Example 1 except that the (P) layer and the (U) layer were laminated using a coating composition adjusted as follows. . After adding 353 parts by weight of acetic acid to a mixed solvent of 720 parts by weight of water and 1080 parts by weight of 2-propanol, (Q
1) 478 parts by weight of ECHETMOS and 706 parts by weight of (Q2) APTMOS were sequentially added and stirred for 3 hours to obtain a coating composition. The composition of the coating composition is (Q1) / (Q2)
= １ ／. As shown in Table 4, the evaluation result of the obtained transparent conductive substrate was 50% of the underlayer of the transparent conductive layer (E).
The surface insulation resistance at a temperature of 90 ° C. and a relative humidity of 90% was low, and the reliability of a liquid crystal panel manufactured using this substrate was poor.

Comparative Example 2 A transparent conductive substrate was obtained in the same manner as in Example 8, except that a 200 μm PES produced by a melt extrusion molding method was used as the transparent polymer substrate (S). As shown in Table 4, the evaluation results of the obtained transparent conductive substrate showed that the water absorption of the substrate was high and the reliability of the liquid crystal panel manufactured using this substrate was poor.

[0103]

[Table 4]

INDUSTRIAL APPLICABILITY As described above, the liquid crystal display element of the present invention comprises a transparent conductive layer including a cured resin layer located under the transparent conductive layer and having excellent insulating properties under a high temperature and high humidity environment. Since the conductive substrate is used as the electrode substrate, the display quality is hardly deteriorated for a long time, and the substrate has very high reliability. The transparent conductive substrate has good gas barrier properties, and can be suitably used as an electrode substrate in the field of flat panel displays such as a photoconductive photoreceptor, a surface light emitter, and an EL element.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing a specific example of a liquid crystal display device of the present invention.

FIG. 2 is a cross-sectional view schematically showing a specific example of the transparent conductive substrate of the present invention.

[Explanation of symbols]

 11, 13 laminated film 15 sealing material 17 liquid crystal cell 19 liquid crystal material 21 gap material 23 transparent conductive layer 25 alignment film 27 transparent Conductive layer (E) 29: Cured resin layer (U) 31: Transparent polymer substrate (S) 33: Cured resin layer (B) 35: Gas barrier layer (X) 37: Cured resin layer (C)

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hitoshi Mikoshiba 4-3-2 Asahigaoka, Hino-shi, Tokyo Teijin Incorporated Tokyo Research Center (72) Inventor Toshiaki Yatabe 4-2-2 Asahigaoka, Hino-shi, Tokyo Teijin Tokyo Research Center Co., Ltd.

Claims (24)

[Claims] 1. A liquid crystal display device having two electrode substrates and a liquid crystal layer disposed between the electrode substrates, wherein the electrode substrate comprises: (i) a transparent polymer substrate (S), a cured resin layer ( U)
And (ii) the cured resin layer (U) and the transparent conductive layer (E) are laminated in contact with each other,
(iii) The surface of the cured resin layer (U) in contact with the transparent conductive layer (E) has a surface resistance value of 1.0 × 10 ¹³ Ω / □ or more in a 50 ° C. and 30% RH environment, 90% RH
A liquid crystal display device having a surface resistance value of 1.0 × 10 ¹² Ω / □ or more in an environment. 2. The electrode substrate further includes a gas barrier layer (X), has a water absorption of 2% or less, and has a temperature of 40 ° C.
Water vapor permeability of 1 g / m ² / da under 0% RH environment
2. The liquid crystal display device according to claim 1, wherein y is equal to or less than y. 3. The cured resin layer (U) has an absorbance (a) attributed to OH stretching vibration near 3500 cm ⁻¹ in an infrared absorption spectrum and a C—H stretching near 3000 cm ^−1. Absorbance attributed to vibration (b)
And the absorbance (c) attributed to the -NH _{2 in-} plane bending vibration near 1600 cm ⁻¹ and the absorbance (d) derived from Si—O near 1100 cm ⁻¹ are represented by the following formula (1). 3. The liquid crystal display element according to claim 1, wherein the liquid crystal display element is a silicon-containing cured resin layer satisfying the relationship of (2), (2) and (3). ## EQU1 ## 0.01 <(a) / (b) <1.0 (1) 0.01 <(c) / (b) <0.5 (2) 0.01 <(d) / (b) ) <2.0 (3) 4. The cured resin layer (U) is a vinyl alcohol-containing polysiloxane resin (P) obtainable from a coating composition containing a vinyl alcohol-based polymer, an epoxy group-containing silicon compound and an amino group-containing silicon compound.
Or an organic polysiloxane resin (Q) obtainable from a coating composition containing a silicon compound containing an epoxy group and a silicon compound containing an amino group.
4. The liquid crystal display device according to any one of items 1 to 3. 5. The electrode substrate further comprises a cured resin layer (B), and the transparent polymer substrate (S), the cured resin layer (B), the gas barrier layer (X) and the cured resin layer (C) are contacted in this order. The liquid crystal display device according to any one of claims 2 to 4, wherein 6. The cured resin layer (B) is a vinyl alcohol-containing polysiloxane resin (P) obtainable from a coating composition containing a vinyl alcohol-based polymer, an epoxy group-containing silicon compound and an amino group-containing silicon compound.
Or, it is composed of an organic polysiloxane resin (Q) obtainable from a coating composition containing a silicon compound containing an epoxy group and a silicon compound containing an amino group, and the cured resin layer (C) is composed of the above (P) or (Q) A liquid crystal display device according to claim 5. 7. The gas barrier layer (X) is made of a metal oxide containing silicon oxide as a main component and having a ratio of the number of oxygen atoms to the number of silicon atoms of 1.5 to 2.0. A liquid crystal display device according to any one of the above. 8. The transparent polymer substrate (S) contains polycarbonate or polyarylate as a main component, has a total light transmittance of 80% or more, and has a retardation of 20 nm.
The liquid crystal display device according to claim 1, wherein: 9. An interlayer other than the interlayer between the transparent conductive layer (E) and the cured resin layer (U) of the electrode substrate, or the transparent conductive layer (E).
The liquid crystal display device according to any one of claims 1 to 8, further comprising a color filter layer on the outermost surface opposite to the surface on which is laminated. 10. A laminated film comprising a transparent polymer substrate (S) and a cured resin layer (U) and a transparent conductive layer (E) arranged in contact with the cured resin layer (U) of the laminated film. And a transparent conductive substrate satisfying the following (a) to (e). (A) The total light transmittance is 80% or more. (B) The thickness of the transparent polymer substrate (S) is 0.01 to 1.0.
mm (c) The retardation of the transparent polymer substrate (S) is 20
nm or less (d) The thickness of the transparent conductive layer (E) is 1 nm to 1 μm. Is 1.0 × 10 ¹³ Ω / □ or more, and the surface resistance under a 50 ° C. 90% RH environment is 1.0 × 10 ¹² Ω / □ or more. 11. The transparent conductive film according to claim 10, wherein the laminated film further has a gas barrier layer (X) made of a metal oxide, a metal nitride or a mixture thereof, and satisfies the following (f) to (g). Substrate. (F) The water absorption is 2% or less (g) The thickness of the gas barrier layer (X) is 5 to 200 nm 12. The cured resin layer (U) has an absorbance (a) attributed to O—H stretching vibration near 3500 cm ⁻¹ in the infrared absorption spectrum and a C—H stretching near 3000 cm ^−1. Absorbance attributed to vibration (b)
And the absorbance (c) attributed to the -NH _{2 in-} plane bending vibration near 1600 cm ^-1 and the absorbance (d) derived from Si-O near 1100 cm ^-1 are represented by the following formula (1). The transparent conductive substrate according to claim 10, wherein the transparent conductive substrate is a silicon-containing cured resin layer that satisfies the relationships of (2) and (3). ## EQU2 ## 0.01 <(a) / (b) <1.0 (1) 0.01 <(c) / (b) <0.5 (2) 0.01 <(d) / (b) ) <2.0 (3) 13. The cured resin layer (U) is a vinyl alcohol-containing polysiloxane obtainable from a radiation-curable resin or a coating composition containing a vinyl alcohol-based polymer, an epoxy group-containing silicon compound and an amino group-containing silicon compound. Organic polysiloxane resin (Q) obtainable from resin (P) or a coating composition containing an epoxy group-containing silicon compound and an amino group-containing silicon compound (Q)
The transparent conductive substrate according to claim 10, wherein: 14. The transparent conductive substrate according to claim 10, wherein the laminated film has a water vapor permeability of 0.1 g / m ² / day or less at 40 ° C. and 90% RH. 15. A cured resin layer (B) is disposed on the transparent polymer substrate (S) on the side opposite to the side on which the cured resin layer (U) is disposed, in contact with (S), and (B) The transparent conductive substrate according to any one of claims 10 to 14, wherein the water absorption of ()) is higher than the water absorption of (S). 16. The transparent polymer substrate (S) has a water absorption of 1%.
The transparent conductive substrate according to claim 15, wherein: 17. The cured resin layer (B) may be a vinyl alcohol-containing polysiloxane resin (P) or an epoxy resin obtained from a coating composition containing a vinyl alcohol-based polymer, an epoxy group-containing silicon compound and an amino group-containing silicon compound. 17. The transparent conductive substrate according to claim 15, comprising an organic polysiloxane resin (Q) obtainable from a coating composition containing a group-containing silicon compound and an amino group-containing silicon compound. 18. The laminated film further includes a cured resin layer (C) made of a silicon-containing resin, and the gas barrier layer (X) is disposed in contact with the cured resin layer (B) and the cured resin layer (C). The transparent conductive substrate according to claim 15. 19. The silicon-containing resin is a vinyl alcohol-containing polysiloxane resin (P) or an epoxy group-containing silicon obtainable from a coating composition containing a vinyl alcohol-based polymer, an epoxy group-containing silicon compound and an amino group-containing silicon compound. 19. The transparent conductive substrate according to claim 18, which is an organic polysiloxane resin (Q) obtainable from a coating composition containing a compound and an amino group-containing silicon compound. 20. The gas barrier layer (X) having a thickness of 5 to 5
20. The transparent conductive substrate according to claim 19, which is in a range of 0 nm. 21. The gas barrier layer (X) is made of a metal oxide containing silicon oxide as a main component and having a ratio of the number of oxygen atoms to the number of silicon atoms of 1.5 to 2.0.
0. The transparent conductive substrate according to any one of the above items. 22. The transparent polymer substrate (S) contains polycarbonate or polyarylate as a main component, has a total light transmittance of 80% or more, and has a retardation of 20 n.
The transparent conductive substrate according to any one of claims 10 to 21, which is not more than m. 23. The cured resin layer (A) is disposed between the cured resin layer (U) and the transparent polymer substrate (S) so as to be in contact with (U) and (S). The transparent conductive substrate according to any one of the above. 24. A color on a layer other than the layer between the transparent conductive layer (E) and the cured resin layer (U) of the transparent conductive substrate, or on the outermost surface opposite to the surface on which the transparent conductive layer (E) is laminated. It has a filter layer, The Claims 10-23 characterized by the above-mentioned.
The transparent conductive substrate according to any one of the above.