KR100475418B1 - Liquid crystal display element with a transparent electrode substrate, and the transparent electrode substrate - Google Patents

Abstract

 The liquid crystal display device comprises: A) a metal oxide layer, B) a silicon compound adjacent to the metal oxide layer and having B1) an epoxy and alkoxysilyl group, a full or partial hydrolysis product thereof; B2) silicon compounds having amino and alkoxysilyl groups, hydrolysis or condensation products thereof; And B3) a cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer; At least one electrode substrate comprising C) a transparent conductive layer and D) a transparent polymer substrate. Also provided is a transparent electrode substrate comprising a substrate (D), a metal oxide layer (A), and the cured polymer layer (B).

Description

 Liquid crystal display and transparent electrode substrate having a transparent electrode substrate TECHNICAL FIELD [0001] AND THE TRANSPARENT ELECTRODE SUBSTRATE}

1. Field of Invention

The present invention relates to a liquid crystal display device having a transparent electrode substrate excellent in optical isotropy, smoothness, durability, chemical or solvent resistance, moisture barrier, gas barrier, flexibility and the like. The present invention relates to a transparent electrode substrate suitable for not only liquid crystal display (LCD) devices but also touch panels, photosensitive conductors, planar phosphors, organic electroluminescent devices, and the like.

1. Description of related fields

Recently, portable information devices such as wireless call receivers, mobile phones, electronic notebooks and portable information terminals have become popular, and work and lifestyle have changed rapidly. In order to improve the portability of the information apparatus, it is required to make the information apparatus thinner, lighter and more durable.

In the related art, heavy, thick and fragile glass substrates have been used for the transparent electronic substrates of LCD devices or touch panels. As an alternative material, a transparent resin substrate has been proposed, and since the transparent resin substrate can be processed in a roll-to-roll system, there is an advantage of cost reduction for the manufacture of an LCD or the like. However, transparent resin substrates are inferior to glass substrates in durability, chemical or solvent resistance, gas barrier properties, and other properties.

For example, in the case of a transparent resin substrate used as an electrode for an LCD element, gas barrier properties can be improved by providing a metal oxide layer to the transparent resin substrate. In the step of removing the resistor after patterning the transparent electrode, the metal oxide layer is in contact with the alkaline solution to dissolve the metal oxide layer, and in the step of forming the liquid crystal alignment layer, liquid crystal alignment containing N-methylpyrrolidone or another solvent. The coating composition for the layer is used, so that the transparent resin substrate in contact with the solvent is damaged, for example whitening or swelling.

In order to solve the above problems, there are several proposals for laminating a layer having gas barrier properties and chemical resistance on a transparent resin substrate. Japanese Patent Laid-Open Nos. 5-52002 and 5-52003, for example, propose a transparent substrate comprising a polymer film and an oxygen gas barrier layer made of polyvinyl alcohol having improved adhesion and further moisture barrier properties. . However, the polyvinyl alcohol-based polymer layer disposed as the outermost layer does not have sufficient chemical resistance, thus causing problems during liquid crystal cell manufacture. By providing an additional chemical resistant layer, chemical resistance can be given but the cost is increased.

Japanese Patent Laid-Open Nos. 2-137922 and 5-309794 provide a transparent substrate comprising as a stack a transparent polymer film, an anchor layer, a gas barrier layer made of an ethylene-vinyl alcohol copolymer, and a solvent resistant layer in this order. . Solvent resistance is sufficient in this transparent substrate, but gas barrier properties at high humidity are degraded due to the properties of the gas barrier layer material, and the six-layer structure increases the manufacturing cost.

In addition, the following matters are required for the transparent substrate of the liquid crystal display, and besides the chemical resistance and gas barrier property, there are problems with properties.

If the substrate is low in transparency or birefringent, coloration of the display and a decrease in contrast occur.

If the surface smoothness of the substrate is low, the gap for the liquid crystal layer may be nonuniform, the liquid crystal alignment may be disordered, or the substrate may be optically nonuniform. As a result, the display color becomes nonuniform.

Moreover, if the smoothness, transparency, and gas barrier properties of the substrate are degraded by mechanical or thermal influences or by contact with the solvent, the benefits of lightness, a wide range of shape freedom, and the possibility of curve display are likely to result in radio call receivers, cell phones, electronic notebooks. It cannot be obtained in application to pen-input devices or the like, since they are subjected to substantial external mechanical or thermal influences. In particular, considering resistance to mechanical influences, excellent interlayer adhesion is required to maintain this advantageous property.

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal display device having a transparent resin substrate which is excellent in chemical or solvent resistance, gas barrier property, transparency, smoothness, adhesiveness, etc. mentioned above, and has low manufacturing costs due to the low number of laminated layers. .

 The above and other objects and aspects of the present invention can be achieved by providing:

(I) a liquid crystal display device comprising two electrode substrates having a liquid crystal layer interposed therebetween, at least one of the electrode substrates comprising: a component;

A) a metal oxide layer,

B) B1) a silicon compound having an epoxy group and an alkoxysilyl group, its full or partial hydrolysis product, its full or partial condensation product, or a mixture thereof,

   B2) silicon compounds having amino groups and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof, and

   B3) a cured polymer layer adjacent to the metal oxide layer obtained from the crosslinking reaction of the polyvinyl alcohol polymer,

C) a transparent conductive layer, and

D) made of a transparent polymer substrate with a delay of 30 nm or less for a wavelength of 590 nm,

The transparent conductive layer (C) is formed on the liquid crystal layer surface of the transparent polymer substrate (D), and the combination of the metal oxide layer (A) and the cured polymer layer (B) is the transparent conductive layer (C) and the transparent polymer. The substrate D is disposed between the substrates D or on a surface of the transparent polymer substrate D opposite to the transparent conductive layer C.

(II) a liquid crystal display device comprising two electrode substrates having a liquid crystal layer interposed therebetween, wherein at least one of the electrode substrates comprises:

A) a metal oxide layer,

B) a cured polymer layer adjacent to the metal oxide layer,

C) a transparent conductive layer, and

D) made of a transparent polymer substrate with a delay of 30 nm or less for a wavelength of 590 nm,

The transparent conductive layer (C) is formed on the liquid crystal layer surface of the transparent polymer substrate (D), and the combination of the metal oxide layer (A) and the cured polymer layer (B) is the transparent conductive layer (C) and the transparent polymer. It is disposed between the substrate (D), or disposed on the surface opposite to the transparent conductive layer (C) of the transparent polymer substrate (D),

The cured polymer layer is made of a crosslinked polyvinyl alcohol polymer having a unit represented by the following formula (3):

 Wherein p is an integer from 0 to 5,

q is an integer from 0 to 5,

A is

or

In which R ⁷ and R ⁸ independently represent hydrogen, methyl, ethyl or phenyl, and l is 0 or 1;

B is

 In the formula, r is an integer of 0 to 5, s is an integer of 0 to 2,

 * 2 and * 3 are sites joined to each other.

(III) a transparent electrode substrate composed of the following components:

A) a metal oxide layer,

B) B1) a silicon compound having an epoxy group and an alkoxysilyl group, its full or partial hydrolysis product, its full or partial condensation product, or a mixture thereof,

B2) silicon compounds having amino groups and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof, and

B3) a cured polymer layer adjacent to the metal oxide layer obtained from the crosslinking reaction of the polyvinyl alcohol polymer,

C) a transparent conductive layer, and

D) made of a transparent polymer substrate with a delay of 30 mm or less for a wavelength of 590 nm,

The combination of the metal oxide layer (A) and the cured polymer layer (B) is disposed between the transparent conductive layer (C) and the transparent polymer substrate (D), or the transparent conductive layer (C) of the transparent polymer substrate (D) It is arranged on the side opposite to).

(IV) a transparent electrode substrate consisting of the following components:

A) a metal oxide layer,

B) a cured polymer layer adjacent to the metal oxide layer,

C) a transparent conductive layer, and

D) made of a transparent polymer substrate with a delay of 30 nm or less for a wavelength of 590 nm,

The combination of the metal oxide layer (A) and the cured polymer layer (B) is disposed between the transparent conductive layer (C) and the transparent polymer substrate (D), or the transparent conductive layer (C) of the transparent polymer substrate (D) On the side opposite to),

The cured polymer layer is made of a crosslinked polyvinyl alcohol polymer having a unit represented by the following formula (3):

(Formula 3)

Wherein p is an integer from 0 to 5,

q is an integer from 0 to 5,

A is

or

In which R ⁷ and R ⁸ independently represent hydrogen, methyl, ethyl or phenyl, and l represents 0 or 1;

B is

In the formula, r is an integer of 0 to 5, s is an integer of 0 to 2,

* 2 and * 3 are sites joined to each other.

(V) Articles consisting of:

(D) a substrate; And

(B) B1) a silicon compound having an epoxy group and an alkoxysilyl group, its full or partial hydrolysis product, its full or partial condensation product, or a mixture thereof,

B2) silicon compounds having amino groups and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof, and

B3) a cured polymer layer formed on the surface of the substrate obtained from the crosslinking reaction of the polyvinyl alcohol polymer,

(VI) A method of making a coated article consisting of

a) B1) a silicon compound having an epoxy group and an alkoxysilyl group, its full or partial hydrolysis product, its full or partial condensation product, or a mixture thereof,

B2) silicon compounds having amino groups and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof, and

B3) polyvinyl alcohol polymer;

B4) carboxylic acid;

B5) organic solvents; And

B6) water;

Preparing a coating composition consisting of;

b) coating the substrate with the coating composition; And

c) curing the coating composition by a crosslinking reaction between the compounds (B1) to (B3) to form a cured polymer layer on the substrate.

(VII)

B1) silicon compounds having epoxy groups and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof,

B2) silicon compounds having amino groups and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof, and

B3) polyvinyl alcohol polymer;

B4) carboxylic acid;

B5) organic solvents; And

B6) water;

Coating composition consisting of.

A liquid crystal display device is a display device in which a liquid crystal material is sealed between two substrates having an electrode pattern and a voltage is applied between the electrodes to electro-optically adjust the liquid crystal material and to make a display such as letters and images. The substrate of the liquid crystal display device is typically inorganic glass, but the liquid crystal display device using the plastic substrate can make the device thinner and lighter, display the curve, provide strength, and reduce the manufacturing cost. It is becoming.

1 shows an example of a liquid crystal display device, wherein the upper substrate 11 and the lower substrate 13 are disposed to face each other, and the outer peripheral portions of the substrates 11 and 13 are sealed with a sealing material 15, and a gap is formed. The material 21 is dispersed between the substrates 11 and 13, and the liquid crystal cell 17 is thus formed so that the liquid crystal material 19 is filled. The polarizing plate is provided to interpose the cell 17 to form a TN-type liquid crystal display element, but the present invention is not limited to this kind of liquid crystal display element.

Each of the upper and lower substrates 11 and 13 has a transparent conductive layer 23 on its inner surface and an alignment layer thereon.

2 shows a cross section of a commercially available transparent polymer electrode substrate. The transparent polymer electrode substrate is composed of a polycarbonate film 1, an anchor layer 2, a gas barrier layer 3 of ethylene-vinyl alcohol copolymer, a solvent-resistant layer 4 and a transparent conductive layer 5 of ITO. The polycarbonate film 1 is about 100 μm thick and the other layers 2 to 4 are several μm thick.

The liquid crystal display device of the present invention consists of two electrode substrates, at least one of which consists of a metal oxide layer (A), a cured polymer layer (B), a transparent conductive layer (C) and a transparent polymer substrate (D).

Transparent Polymer Substrate (D)

The transparent polymer substrate (D) used in the present invention is not particularly limited as long as it has an optical isotropy or a delay of 30 nm or less with respect to a wavelength of 590 nm. The delay is expressed as the product of Δn · d, where Δn represents the difference in refractive index of the birefringence over the wavelength of 590 nm, which can be measured with conventional devices, and d represents the thickness of the substrate. If the delay is 30 nm or more, there are problems of coloring and viewing angle. Preferably the delay is 20 nm or less. The dispersion of the delayed phase axis is preferably within ± 30 °, more preferably within ± 15 °.

Materials capable of satisfying the above conditions include polyester resins, polycarbonate resins, polyarylate resins, polysulfone resins such as polysulfones, polyether sulfones and polyallyl sulfones, polyolefin resins, acetates such as cellulose triacetate Resins, polystyrene resins, acrylic resins, and various thermosetting resins. Of these, a transparent polymer substrate made of polycarbonate resin as a main component is most preferred in view of high optical transparency and low optical anisotropy.

The thickness of the transparent polymer substrate is usually 30 μm to 800 μm.

Metal Oxide Layer (A)

The metal oxide layer (A) used in the present invention may be made of an insulating metal oxide such as oxides of silicon, aluminum, magnesium, and zinc. The transparent insulating metal oxide layer may be attached by known sputtering, vapor deposition, ion plating, plasma enhanced CVD, or the like. Silicon oxide is particularly preferred as the metal oxide for the moisture barrier layer in terms of transparency, surface smoothness or uniformity, flexibility, layer stress, cost and the like.

The composition of silicon oxide can be analyzed and determined by X-ray photoelectron spectroscopy, X-ray microscopy spectroscopy, auger electron spectroscopy, Rutherford scattering and the like. Silicon oxide with an average composition represented by SiO _x (1.5 ≦ _x ≦ 2) is preferred for visible light transmission and flexibility. If the value of x is less than 1.5, flexibility and transparency are degraded. Silicon oxide with an average composition represented by SiO _x (1.5 ≦ _x ≦ 2) may further include other metals such as magnesium, iron, nickel, chromium, titanium, aluminum, indium, zinc, tin, antimony, tungsten, molybdenum, copper Can be. Silicon oxide may further contain fluoride or carbon to increase flexibility. The amount of such additives is 30% by weight or less.

The thickness of the metal oxide layer is preferably 2 nm to 200 nm. If the layer thickness is less than 2 nm, it is difficult to form a uniform layer, and the formed layer may have pores through which the gas penetrates the substrate, thereby reducing gas barrier properties. If the thickness exceeds 200 nm, the transparency of the layer is lowered and the flexibility is poor, causing cracking, thereby reducing gas barrier properties.

Cured Polymer Layer (B)

The cured polymer layer (B) used in the present invention comprises the following components:

B1) silicon compounds having epoxy and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof;

B2) silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products or mixtures thereof; And

B3) polyvinyl alcohol polymer

 It is formed by the crosslinking reaction of.

 The cured polymer layer (B) is formed adjacent to or in contact with the metal oxide layer.

Components (B1) to (B3) are described below:

Polyvinyl Alcohol Polymer (B3)

The polyvinyl alcohol polymer (B3) of the present invention may be a known one, and commercially available. Preferably, the polyvinyl alcohol polymer (B3) comprises at least 50 mol% of a polyvinyl alcohol component and / or a polyvinyl alcohol-copolymer component.

Examples of polyvinyl alcohol-copolymers include vinyl alcohol-vinylacetate copolymers, vinyl alcohol-vinylbutyl alcohol copolymers, ethylene-vinyl alcohol copolymers, and vinyl alcohol alcohols having silyl groups in the molecule.

Generally, polyvinyl alcohol, ethylene-vinyl alcohol copolymer having a saponification degree of 80% or more, and polyvinyl alcohol polymer having a silyl group in the molecule are preferable.

The ethylene content in the ethylene-vinyl alcohol copolymer is preferably 50% or less. If the ethylene content exceeds 50%, the desired gas barrier property of the cured polymer layer cannot be obtained.

The polyvinyl alcohol polymer having a silyl group in a molecule has a reactive silyl group represented by the following Chemical Formula 4:

Wherein R ¹¹ represents hydrogen, alkyl having 1 to 10 carbon atoms, acyl, alkali metal or alkaline earth metal, R ¹² represents alkyl having 1 to 10 carbon atoms, r is an integer from 1 to 3.

 The intramolecular silyl group may be an end group of the polyvinyl alcohol polymer. The site, distribution, and the like of the intramolecular silyl group are not limited as long as the silyl group is bonded to the polyvinyl alcohol polymer through a non-hydrolyzable bond. The content of silyl is preferably 5 mol% or less, more preferably 1 mol% or less. If the silyl content is too high, the coating composition disadvantageously becomes viscous and tends to gel.

Although the degree of polymerization and the degree of saponification of the polyvinyl alcohol polymer of the present invention are not particularly limited, the average degree of polymerization is preferably 100 to 5000, and the degree of saponification is preferably 70% or more, more preferably 80% or more. If the degree of polymerization is too low, the coating layer becomes brittle. If the degree of polymerization is too high, the coating solution becomes too viscous and coating is difficult. If the degree of saponification is too low, sufficient gas barrier property is not obtained.

Silicon compounds having an epoxy and alkoxysilyl group (B1)

Compound (B1) of the present invention is a silicon compound having an epoxy group and a silyl group, a full or partial hydrolysis product thereof, a full or partial condensation product thereof, or a mixture thereof. Preferred silicon compounds having epoxy and alkoxysilyl groups are represented by the following general formula (1):

Wherein R ¹ is alkylene having 1 to 4 carbon atoms,

R ² and R ³ are independently alkyl having 1 to 4 carbon atoms,

X is glycidoxy or epoxycyclohexyl,

n is 0 or 1;

Examples of the silicon compound (B1) having an epoxy and an alkoxysilyl group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltripropoxysilane, glycidoxymethyltributoxysilane , 2-glycidoxy oxytrimethoxysilane, 2-glycidoxy oxyethyl triethoxysilane, 2-glycidoxy ethyltripropoxysilane, 2-glycidoxy oxyethyl tributoxy silane, 1-glycidoxy Ethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane, 1-glysidoxyethyltripropoxysilane, 1-glycidoxyoxytrimethylbutoxysilane, 3-glycidoxyoxypropyltrimethoxysilane, 3-glycidoxyoxytriethoxysilane, 3-glycidoxyoxytripropoxysilane, 3-glycidoxyoxytributoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxyoxy Triethoxysilane, 1-glycidoxy Cipropyltriprooxysilane, 1-glycidoxyoxytributoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3 , 4-epoxycyclohexyl) methyltripropoxysilane, (3,4-ethoxycyclohexyl) methyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) ethyltributoxysilane, 3- ( 3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltripropoxysilane, 3- (3,4-epoxycyclohexyl) propyltributoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, 4 -(3,4-epoxycyclohex ) Butyl tree propoxysilane, and the like of 4- (3,4-epoxycyclohexyl) butyl-tree-butoxysilane, diethoxy-3-glycidoxypropyl methyl silane.

Particularly preferred silicon compounds (B1) having epoxy and alkoxysilane groups are 3-glycidoxy oxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

The silicon compounds may be used alone or in combination.

Silicon compounds having amino and alkoxysilyl groups (B2)

Compounds (B2) of the present invention are silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof. Preferred silicon compounds having amino and alkoxysilyl groups are represented by the following general formula (2):

Wherein R ⁴ is alkylene having 1 to 4 carbon atoms,

R ⁵ and R ⁶ are independently alkyl having 1 to 4 carbon atoms,

Y is hydrogen or aminoalkyl,

m is 0 or 1;

Examples of the silicon compound (B2) having an amino group and an alkoxysilyl group include aminomethyltriethoxysilane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltripropoxysilane, 2- Aminoethyltributoxysilane, 1-aminoethyltrimethoxysilane, 1-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxy Silane, 3-aminopropyltributoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 2-aminopropyltripropoxysilane, 2-aminoethyltributoxysilane, 1-aminoethyl Trimethoxysilane, 1-aminopropyltriethoxysilane, 1-aminopropyltripropoxysilane, 1-aminopropyltributoxy silane, N-aminomethylaminomethyltriethoxysilane, N-aminomethylaminomethyltri Propoxysilane, N-aminometh Tyl-2-aminoethyltrimethoxysilane, N-aminomethyl-2-aminoethyltriethoxysilane, N-aminomethyl-2-aminoethyltripropoxysilane, N-aminomethyl-3-aminopropyltrimeth Methoxysilane, N-aminomethyl-3-aminopropyltriethoxysilane, N-aminomethyl-3-aminopropyltripropoxysilane, N-aminomethyl-2-aminopropyltrimethoxysilane, N-aminomethyl- 2-aminopropyltriethoxysilane, N-aminomethyl-2-aminopropyltripropoxysilane, N-aminopropyltrimethoxysilane, N-aminopropyltriethoxysilane, N- (2-aminoethyl)- 2-aminoethyltrimethoxysilane, N- (2-aminoethyl) -2-aminoethyltriethoxysilane, N- (2-aminoethyl) -2-aminoethyltripropoxysilane, N- (2- Aminoethyl) -1-aminoethyltrimethoxysilane, N- (2-aminoethyl) -1-aminoethyltriethoxysilane, N- (2-aminoethyl) -1-aminoethyltripropoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltripropoxysilane, N- (3-aminopropyl) -2-aminoethyltri Methoxysilane, N- (3-aminopropyl) -2-aminoethyltriethoxysilane, N-methyl-3-aminopropyl) -2-aminoethyltripropoxysilane, N-methyl-3-aminopropyltri Methoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-diethylenetriaminopropyltriethoxy Silane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, trimethoxysilylpropyldiethylenetriamine, and the like.

Particularly preferred silicon compounds having amino and alkoxysilyl groups (B2) are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methyl-3-aminopropyltri Methoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.

The silicon compounds having these amino and alkoxysilyl groups can be used alone or in combination.

Hydrolysis and Condensation Products of Compounds (B1) and (B2)

The complete or partial hydrolysis product, or complete or partial condensation product of the silicon compound is obtained through the so-called sol-gel reaction of the silicon compound. Condensation products of silicon compounds can include not only condensation products between silicon compounds, but also condensation products between unreacted silicon compounds and complete or partially hydrolyzed products of silicon compounds.

Compounds (B1) and (B2) used as starting materials may be silicon compounds themselves or may be already prepared hydrolysis or condensation products.

Hydrolysis of the silicon compound can be carried out using, for example, an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid, or an alkali such as sodium hydroxide, or only water. Hydrolysis can be performed after mixing a silicon compound and a solvent, in order to make hydrolysis uniform. If heating or cooling is required, it can be carried out during hydrolysis. Alternatively, solvents such as alcohols can be removed or further suitable solvents can be added after hydrolysis by heating and / or evaporation.

Crosslinking reaction

By reacting the compounds (B1) to (B3) according to the present invention, the cured polymer layer has excellent chemical or solvent resistance, gas barrier property and adhesiveness, in addition to optical isotropy, surface smoothness, durability, moisture barrier property, flexibility, and the like. May have a combination.

In this reaction, by using a combination of a silicon compound (B1) having an epoxy and an alkoxysilyl group and a silicon compound (B2) having an amino and an alkoxysilyl group,

(1) reactions between silanol groups of alkoxysilyl groups,

(2) reaction between epoxy and amino groups,

(3) It is believed that the reaction between the silanol of the alkoxysilyl group and the hydroxy group of the polyvinyl alcohol polymer occurs as the main reaction. Thus, a cured product is formed from the reaction between the two kinds of silicon compounds and the crosslinked product of the polyvinyl alcohol-based polymer, whereby the reaction product exhibits excellent chemical or solvent resistance and the remaining properties.

Cross-polymer

As a result of the above reaction, it is believed that the reaction product of the present invention includes a chemical bond represented by the following Chemical Formula 3:

(Formula 3)

Wherein p is an integer from 0 to 5,

q is an integer from 0 to 5,

A is

 or

In which R ⁷ and R ⁸ independently represent hydrogen, methyl, ethyl or phenyl, and l is 0 or 1;

B is

In the formula, r is an integer of 0 to 5, s is an integer of 0 to 2,

* 2 and * 3 are sites joined to each other.

The structure of the main crosslinking of the present invention may be a structure consisting only of Chemical Formula 3, or may further include structures represented by the following Chemical Formulas 5 and 6:

Wherein the symbols are as defined in formula (3).

Composition of Component (B)

It is preferable that the ratio between the compounds (B1) to (B3) used satisfies the following formula.

1/9 ≦ (B ₃ ) / [(B ₁ ) + (B ₂ )] ≦ 9/1, weight ratio, and

1/9 ≤ (b ₁ ) / [(b ₂ ) ≤ 9/1, molar ratio

Wherein B ₁ to B ₃ each represent the weight of the compound (B1) to (B3); b ₁ represents the amount of the compound (B1) based on the mole of the epoxy group; b ₂ represents the amount of compound (B2) based on the total moles of amino and imino groups. More specifically, B ₁ and B ₂ are respectively calculated based on the weight of the following compounds (Formulas 1 ′ and 2 ′):

 [Formula 1 ']

 [Formula 2 ']

For example, if 100 parts by weight of the compound (B1) represented by the formula (1) is used, B ₁ represents the weight of the compound having the structure represented by the formula (1 ') which is a complete condensation product, and therefore B ₁ is 90 parts by weight.

When the ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] exceeds 9/1, the water resistance and the chemical resistance tend to decrease. If the ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] is less than 1/9, gas barrier properties are reduced. The preferred range of ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] is 2/8 to 8/2, more preferably 1/3 to 3/1. When the transparent conductive layer (C) is laminated on the cured polymer layer (B), 1/9 <(B ₃ ) / [(B ₁ ) + (B ₂ )] <4/1 is preferred for interlayer adhesion. If silyl-containing polyvinyl alcohol is used, the preferred ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] is 2/1 to 1/9.

Properties of Component (B) and Complex Effects of Components (A) and (B)

The cured polymer layer (B) obtained by the crosslinking reaction has excellent chemical or solvent resistance, gas barrier property and adhesiveness, as well as other properties required for a transparent electrode substrate.

As described above, polyvinyl alcohol-based polymers may have gas barrier properties but deteriorate in water or high humidity atmosphere, and have poor adhesion to polycarbonate or other polymer substrates and metal oxide layers. Some of these drawbacks can be improved by adding a chemical resistant layer and an anchor layer, but it adds manufacturing costs and the gas barrier property is still not high enough.

The data shown in the following table are properties of the transparent polymer substrate, one of which is a commercial product based on an ethylene-vinyl alcohol copolymer-based polymer ("prior art"), and one of which is the object of the present invention ("target"). And one obtained by the present invention ("the present invention"). Properties shown are measured by the method described below in the Examples.

 [table]

   Property  Prior art   goal  Invention  Gas cut off: O ₂ (50% RH)   0.5   <0.2   0.01 O ₂ (90% RH)  10.5  <10  <0.05  Chemical resistance:    NMP  2 minutes  > 3 minutes  > 5 minutes    alkali  No change  No change  No change    mountain  No change  No change  No change  Adhesive to SiO _x    0/100  100/100  100/100   Polycarbonate  100/100  100/100  100/100

 It is possible for the transparent electrode substrate to have the following excellent chemical resistance:

i) Change in haze value of 1% or less when N-methylpyrrolidone was contacted with the cured polymer layer surface of the transparent electrode substrate at 25 ° C. for 10 minutes and then washed with water:

ii) no deterioration when the aqueous 3.5% -NaOH solution was brought into contact with the cured polymer layer surface of the transparent electrode substrate for 10 minutes at 25 ° C .; And

iii) No deterioration when the 5.0% -HC1 aqueous solution was brought into contact with the cured polymer layer surface of the transparent electrode substrate for 10 minutes at 25 ° C.

Furthermore, the cured polymer layer (B) can adhere to transparent polymer substrates, in particular polycarbonate and metal oxide layers, in particular silicon oxide.

As can be seen from the table above, gas barrier properties (cm ³ / m ² / atm / day), solvent resistance and adhesion are improved in the present invention.

These improved properties of the present invention are basically obtained by component (B) alone, but the properties of commercial products are obtained by the combination of a polyvinyl alcohol-based polymer, a chemical resistance layer and an anchor layer (as shown in FIG. 2). It can be seen that six layers (2-4 are added). The gas barrier properties as described above of the present invention are obtained by the combination of component (B) and metal oxide layer (A), but according to the present invention the properties of the prior art are only three additional layers as shown in FIG. Better properties can be obtained.

As shown in FIG. 3, the polyvinyl alcohol polymer has flexibility and gas barrier properties. By crosslinking the polyvinyl alcohol-based polymer with the alkoxysilane to form the interpolymer, chemical resistance and abrasion resistance are provided to the interpolymer since the crosslinked polymer has a structure that is microscopically uniformly bonded.

In addition, by selecting a specific silicon compound (silane-coupler-type compound) as the crosslinking agent, the improvement as described above is increased.

Gas barrier property:

Referring to FIG. 4A, the oxygen transmission rate of the gas barrier layer formed on the polycarbonate film PC is shown. The line marked "prior art" is an ethylene-vinyl alcohol copolymer. The line marked "H / PC" is a hybrid layer of polyvinyl alcohol. Oxygen permeation of the hybrid layer at low humidity is superior to the prior art. The line labeled "SiO _x / PC" is a SiO _x layer, but this can be further improved by increasing the thickness of SiO _x . Here, the stacking of the hybrid layer and the SiO _x layer is theoretically expected to provide an oxygen permeability shown in dashed lines as indicated by " H / SiO _x / PC (theoretical value) &quot;. However, the actual measured oxygen permeability of the stack of hybrid and SiO _x layers is shown in solid lines as indicated by “H / SiO _x / PC (actual values)”, which is significantly better than theoretical and even at high humidity (90% RH). Consistently low. Therefore, the gas barrier property beyond the target value can be obtained by the combination of the hybrid layer and the SiO _x layer (metal oxide layer).

4B shows a similar oxygen permeability of the gas barrier layer with respect to temperature change. The combination of hybrid layer and SiO _x layer also has gas barrier properties beyond the target.

This synergistic effect is obtained by lamination of the hybrid layer and the SiO _x layer as shown in FIG. 5, where 41 represents a 100 μm thick polycarbonate film, and 42 represents a 0.01 μm thick SiO _x layer. , 43 represents a hybrid layer having a thickness of 2 μm. One of the reasons for the synergy is thought to be as follows. That is, as shown in FIG. 6A, the SiO _x layer has pinholes and the stack of hybrid layers fills the pinholes. Since the hybrid layer itself has not only gas barrier property but also excellent adhesion to the SiO _x layer, this combination provides a synergistic effect of gas barrier property, but the present invention is not bound to a specific theory.

Adhesive:

As described above, the hybrid layer has excellent adhesion to the SiO _x layer or metal oxide layer. The hybrid layer also has excellent adhesion to organic layers such as polycarbonate films.

Therefore, the cured polymer layer (B) of the present invention adheres to a polymer layer, in particular a polycarbonate, and a metal oxide layer, in particular silicon oxide. It is believed that the epoxy group and the amino group contribute to the adhesion of the cured polymer layer to the polycarbonate layer, and the silanol group contributes to the adhesion of the cured polymer layer to the silicon oxide layer.

As a result, the cured polymer layer (B), which is a gas barrier layer and a chemical resistance layer, can be formed between any kind of organic layer and the metal oxide layer without an anchor layer.

Chemical or solvent resistant:

Hybrid layers have improved chemical or solvent resistance to NMPs and acids.

However, hybridization of hybrid layers, such as polyvinyl alcohol, with typical alkoxysilanes such as tetramethoxysilane (TMOS), does not have good chemical or solvent resistance to alkalis as shown in FIG.

According to the present invention, the alkali resistance of the hybrid layer is obtained by selecting two specific alkoxysilanes and using a combination of the two alkoxysilanes.

These two alkoxysilanes are silicon compounds having an epoxy and alkoxysilyl group (B1) and a silicon compound having an amino and alkoxysilyl group (B2) as described above in detail.

8 schematically shows the reaction between functional groups of compounds (B1) to (B3). The epoxy and alkoxysilyl groups of the silicon compound (B1) react with each other and the hydroxyl group of the polyvinyl alcohol polymer (B3), but the amino group of the silicon compound (B2) only reacts with the epoxy group of the silicon compound (B1) and the compound It should be noted that it does not react with other functional groups of (B1) to (B3). This particular reactivity of the reaction and properties of the functional groups of the compounds (B1) to (B3) is believed to provide not only good alkali resistance, but also beneficial effects on other good properties such as gas barrier properties, adhesion and the like.

As a result, the laminate structure shown in FIG. 9 provides an ideal result for the transparent polymer electrode substrate, where 41 represents a polycarbonate film having a thickness of 100 μm, 42 represents a SiO _x layer having a thickness of 0.01 μm, and 45 represents 2 The hybrid layer of the silicon compound (B1) and (B2) of a micrometer thickness, and a polyvinyl alcohol-type polymer (B3) is shown.

Specific Embodiments of Combinations of Compounds (B1) to (B3)

Therefore, the above improvement is obtained by the specific property of component (B).

More specifically, crosslinking of polyvinylalcohol-based polymers with alkoxysilanes and even more silane coupler-type compounds may increase gas barrier properties, slight chemical resistance and adhesion, but is not sufficient. However, according to the present invention, a specific combination of two silicon compounds (B1) and (B2) with specific functional groups is used together with the polyvinyl alcohol-based polymer (B3), and together with all gas barrier properties, solvent resistance and adhesion properties, A full improvement of the other required properties is surprisingly obtained.

The crosslinking reaction of a polyvinyl alcohol-type polymer and a silane coupler is well known, and the silicon compound which has an epoxy and an alkoxy silyl group is used as a silane coupler. However, in practice, silicon compounds having amino and alkoxysilyl groups do not provide a presumably good crosslinked polymer, and therefore are not used as silane couplers, particularly in crosslinking polyvinylalcohol-based polymers. In addition, although there are many other alkoxysilanes and silane couplers, as a crosslinking agent used in polyvinyl alcohol, silicon compounds (B1) having epoxy and alkoxysilyl groups and silicon compounds (B2) having amino and alkoxysilyl groups are polyvinyl alcohol-based. It is not known that it can provide better solvent resistance and other properties than a polymer and any silane coupler or even a combination of two or more silane couplers.

Therefore, the reaction between the compounds (B1) to (B3) may be combined with the reaction of the polyvinyl alcohol polymer (B3) with any silane coupler including (B1) or (B2), or a combination thereof (B1) with (B1) Unless B2), it is also fundamentally different from the reaction between two or more silane couplers.

The reaction between the compounds (B1) to (B2) is as described below, and the crosslinking or structure is as shown in the formula (3). The resulting crosslinked structure of the polymer is novel.

Moreover, the use of such specific combinations of silicon compounds and polyvinyl alcohol-based polymers for transparent electrode polymer substrates for certain liquid crystal cells, as well as advantageous specific effects, have never been presented in this field.

According to the present invention, not only the properties of the transparent electrode substrate are improved, but also the transparent electrode substrate can be economically advantageously composed of a few layers.

Other components of component (B)

Carboxylic acid:

If the ratio (b ₁ ) / (b ₂ ) is 1/9 to 9/1, more preferably 1/4 to 4/1, still more preferably 1/6 to 6/1, the adhesiveness of the cured polymer layer It may be excellent in heat resistance, chemical resistance, water resistance, durability and other properties. If the amount of one of the compounds (B1) and (B2) exceeds the amount of the other compound, the above properties of the cured polymer layer are lowered.

Compound (B2), i.e., a silicon compound having amino and hydroxysilyl groups, is a condensation catalyst for the hydrolysis of compound (B1), i.e. a silicon compound having epoxy and hydroxysilyl groups, and at the same time acts as a polymerization catalyst for epoxy groups. The addition of component (B2) to the hydrolysis product of component (B1) causes an immediate reaction and gelation of the coating composition. In order to prevent this, it is preferable to add carboxylic acid to component (B2) to form weak acid salts of organic acids and increase pot life. The carboxylic acid may be formic acid, acetic acid, propionic acid, lactic acid and the like. Acetic acid is most preferred because of its acidity and volatility.

In general, the amount of carboxylic acid ranges from 0.01 to 10 moles, preferably 0.1 to 5.0 moles per mole of the total moles of amino and imino groups. If the amount is less than 0.01 mole, the pot life of the composition is shortened and gelation may occur. If the amount exceeds 10 mol, curing of the composition may become insufficient, and the properties of the cured polymer layer are degraded.

solvent:

The solvent includes a solvent capable of dissolving the polyvinyl alcohol polymer, for example, water, dimethylimidazole, and the like. The content of the polyvinyl alcohol polymer dissolving solvent is preferably 30% by weight or more of the total solvent. If an ethylene-vinyl alcohol copolymer is used, water / propanol may be used as the solvent for the copolymer, and the mixing weight ratio of water to propanol is preferably 3/7 to 7/3. Any solvent that is compatible with the polyvinyl alcohol polymer and in which the compounds (B1) and (B2) can be dissolved can be used in combination with the above solvents. Examples of such solvents are alcohols, cellosolves, ketones, amides and the like. Among them, alcohols such as butanol, cellosolves such as 1-methoxy-2-propanol, and ketones such as cyclohexanone are preferred solvents for providing excellent surface smoothness. These additional solvents themselves can be used alone or in combination.

The amount of the solvent is preferably in the range of 200 to 99900 parts by weight relative to 100 parts by weight of the total solid content of the compounds (B1) to (B3). If the amount of the solvent is less than 200 parts by weight, the stability of the coating solution is lowered. When the amount of the solvent exceeds 99900 parts by weight, the solids content in the coating solution is lowered to limit the thickness of the coating layer that can be obtained.

Curing agent:

Curing agents may be optionally added. The curing agent is aluminum such as aluminum acetylacetonate, aluminum ethylacetylacetate bisacetylacetate, aluminum bisacetoacetateacetylacetonate, aluminum di-n-butoxydmonoethylacetoacetate and aluminum di-i-propoxide monomethylacetoacetate Chelate compounds; Alkali metal salts of carboxylic acids such as sodium carboxylate, potassium carboxylate and potassium formate; Amine carboxylates such as dimethylamine acetate, ethanol acetate and dimethylaniline formate; Tertiary ammonium salts such as benzyltrimethylammonium hydroxide, tetramethylammonium acetate and benzyltrimethylammonium acetate; Metal carboxylic acids such as tin octanoate; Amines such as triethylamine, triethanolamine and pyridine; And 1,8-diazabicyclo [5,4,0] -7-undecene. These curing agents may be used alone or in combination.

additive:

In addition, various additives may be optionally added. For example, surfactants such as silicon-based compounds, fluorine-containing surfactants and organic surfactants can be used to improve the surface smoothness of the layer.

Epoxy resins, melamine resins, aramid resins, colloidal silica and the like which are compatible with the coating composition may be added as the modifier. These additives can improve various properties of the cured polymer layer, such as heat resistance, weather resistance, water resistance, durability, adhesion, chemical resistance, or solvent resistance.

Coating solution for component (B):

Thus, as can be seen from the above description, according to the invention, the coating solution for forming the cured polymer layer (B layer) is preferably:

(B1) silicon compounds having epoxy and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products or mixtures thereof;

(B2) silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products or mixtures thereof;

(B3) polyvinyl alcohol polymer;

(B4) carboxylic acid;

(B5) an organic solvent; And

(B6) water

Is made of.

Other optional components are described elsewhere herein.

Coating Method to Form Layer of Component (B)

The cured polymer layer (B) is:

a) preparing a coating composition consisting of the components (B1) to (B6) described above;

b) coating the substrate with the coating composition; And

c) curing the coating composition by a crosslinking reaction between components (B1) to (B3) to form a cured polymer layer on the substrate.

Is formed on the substrate.

More specifically, the method is:

Preparing an aqueous solution of a polyvinyl alcohol polymer (B3);

Adding acetic acid to said aqueous solution of copolymer;

First adding a silicon compound (B1) having an epoxy and an alkoxysilyl group to the solution and hydrolyzing the added silicon compound; And

Next, adding silicon compound (B2) having amino and alkoxysilyl groups to the solution and hydrolyzing the added silicon compound

It is preferable that it consists of.

Transparent conductive layer (C)

The transparent conductive layer (C) used in the present invention is preferably a metal oxide in terms of transparency, conductivity and mechanical properties. For example, tin oxide, cadmium, molybdenum, tungsten, fluoride and the like added indium oxide, cadmium oxide, and tin oxide, zinc oxide and titanium oxide added aluminum as a dopant may be mentioned. . Among them, a layer of indium oxide (ITO) containing tin oxide in an amount of 2 to 15% by weight is particularly preferred because it has excellent transparency and conductivity. The transparent conductive layer C may be formed by deposition, sputtering, ion beam sputtering, ion plating, or the like.

The thickness of the transparent conductive layer (C) is preferably 15 to 180 nm. If it is less than 15 nm, the layer is discontinuous and the conductivity is insufficient. If it exceeds 180 nm, transparency and flexibility are degraded.

Arrangement of components (A) to (D) in the electrode substrate

In the liquid crystal display device of the present invention, the electrode substrate is composed of components (A) to (D), and the transparent conductive layer (C) is positioned on the liquid crystal layer surface of the transparent polymer substrate (D). The transparent conductive layer C is patterned, and the liquid crystal alignment layer is formed thereon when used.

The metal oxide layer (A) and the cured polymer layer (B) are formed adjacent to or in contact with each other, whereby excellent gas barrier properties and solvent resistance can be obtained, as well as unexpectedly improved gas barrier properties. Since the polyvinyl alcohol polymer deteriorates with water, the gas barrier property of the polyvinyl alcohol polymer layer is lowered under high humidity conditions. By crosslinking a polyvinyl alcohol polymer with a specific combination of silicon compounds, the gas barrier properties and solvent resistance of the polyvinyl alcohol polymer-containing layer are ethylene-vinyl alcohol copolymers used as gas barrier layers in commercial liquid crystal labeling devices using resin electrode substrates. Compared with In addition, by combining the cured polymer layer (B) and the metal oxide layer (A) of the present invention, the gas barrier property can be kept low even under high humidity conditions, because the metal oxide layer is not degraded by water. This is the reason for using the combination of the cured polymer layer (B) and the metal oxide layer (A) as a gas barrier layer.

Furthermore, by forming the cured polymer layer (B) and the metal oxide layer (A) adjacent to each other, the obtained gas barrier property is larger than the addition of the gas barrier properties of the two layers, and a synergistic effect is obtained.

4A and 4B show oxygen permeability of the gas barrier layer with respect to relative humidity. Each gas barrier layer tested was formed on a polycarbonate substrate. The gas permeability of polymer layer (B) (hereinafter referred to as "H layer" or "hybrid layer") obtained from polyvinyl alcohol-based polymer (B3) crosslinked with silicon compounds (B1, B2) is ethylene- at 50% RH. It is significantly lower compared to the vinyl alcohol copolymer layer but increases with increasing humidity. Here, the gas permeability of the metal oxide layer, which is a silicon oxide layer, is considerably low and constant regardless of humidity, but not low enough, and deteriorates with a solvent such as alkali. The gas permeability of the laminate of the metal oxide layer and the hybrid layer is theoretically expected as shown by the dotted line in FIG. 4A. However, the actual gas permeability of the laminate was significantly lower than expected as indicated by the solid line in FIG. 4A. The gas permeability of the laminate of the invention is much lower than the ethylene-vinyl alcohol copolymer layer, regardless of humidity.

In the present invention, the position and order of the combination of the hybrid layer (B) and the metal oxide layer (A) of the electrode substrate are different from those of the components (A) to (D) except that the transparent conductive layer is located at the outermost side with respect to the liquid crystal layer surface. It is not limited.

However, the stacking order of components (C) / (B) / (A) / (D) is preferred, because the cured polymer layer (B) has a metal oxide layer (A) and a polymer substrate from the transparent conductive layer surface and the liquid crystal layer surface. (D) is for protection. The order of layers (A) and (B) may be reversed. Another preferred order is (C) / (A) / (B) / (D) or (C) / (D) / (A) / (B) or (C) / (D) / (B) / (A May be).

In practice, components (B) and (C) may be repeatedly formed on one and / or both sides of the substrate D, depending on the desired properties. In such substrates, certain preferred examples of the stacking order are (C) / (B) / (A) / (D) / (B), (B) / (A) / (D) / (B) / (C) , (C) / (A) / (B) / (D) / (B), (A) / (B) / (D) / (B) / (C), (C) / (B) / ( A) / (B) / (D) / (B), (B) / (A) / (B) / (D) / (B) / (C). Of course, any other order may be adopted.

10A-10D and 11A-11F are some examples of the preferred stacking order of components (A)-(D). The other order is not illustrated, because it is clear without example.

In addition, one or more additional layers may optionally be added or inserted into the stack to improve certain properties of the stack or electrode substrate. In particular, it is preferred that the anchor layer α is inserted to improve adhesion of any of the components (A) to (D) to the other layer components. In addition, any gas barrier layer and / or solvent or chemical layer may be used in combination with components (A) and (B). A protective layer may also be provided on the electrode substrate.

Anchor layer

The anchor layer α may be a silane coupler, a thermoplastic resin, a radiation curable resin or a thermosetting resin.

Silane Coupler:

Silane couplers are advantageous when used as silicon containing layers. The silane coupler is an organosilicon compound represented by Formula 7:

Wherein R ¹¹ represents an organic group having at least one of vinyl, methacryloxy, epoxy, amino, imino and mercapto, R ¹² represents a hydrolyzable substituent, such as alkoxy and halogen, n is a Is an integer.

Examples of silane couplers include vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (2-methoxy-ethoxy) silane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3-gly Seedoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-mercaptopropyl-trimethoxysilane, and (dimethoxy Methoxymethylsilylpropyl) -ethylenediamine, but is not limited thereto.

Thermoplastic:

The thermoplastic resin may be, for example, a phenoxy resin, a polyester resin, a polyurethane resin, a polyacrylic resin, or the like.

Radiation curable resin:

The radiation curable resin for the anchor layer is a resin that can be cured by irradiation with ultraviolet rays, electron beams, or the like. Radiation curable resins include resins having unsaturated double bonds such as acryloyl, methacryloyl and vinyl in the molecule or unit. Resins with acryloyl are preferred due to their reactivity.

The radiation-curable resin may be a single compound or a mixture of compounds. For solvent resistance it is desirable to contain a multifunctional acrylate component having at least two acryloyl groups in the molecule or unit. Examples of multifunctional acrylate components include acrylate monomers such as dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate and trimethylolpropanetriacrylate, Or multifunctional acrylate oligomers obtained by polyester-modified or urethane-modified.

The radiation curable resin layer is formed as follows. Coating compositions are prepared by adding photoinitiators and inhibitors, other additives such as leveling agents and UV absorbers, and modifying agents such as thermoplastics and plasticizers to the radiation curable resin composition. Organic solvents are optionally added to adjust the concentration and viscosity of the coating solution. Coating methods can be, for example, dip coating, spray coating, flow coating, roll coating, bar coating, spin coating, etc., which are pre-dried and then exposed to radiation. Thus, a hardened layer is obtained.

If the resin is cured with UV rays, photoinitiators are essential. The initiator is, for example, diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -morpholinopropane-1,2-hydroxy-2-methyl-1-phenylpropan-1-one And benzoin-based compounds such as acetophenone, benzoin and benzyl dimethyl ketal, such as 1-hydroxycyclohexylphenyl ketone; Thioxane-based compounds such as 2,4-dichlorothioxone; Known light co-initiators such as trimethanolamine, methyldiethanolamine and ethyl 4-dimethylamine benzoate can be optionally added in an appropriate amount to improve curability.

The thickness of a radiation curable layer becomes like this. Preferably it is 2-8 micrometers, More preferably, it is less than 2-6 micrometers. If it is less than 2 micrometers, solvent resistance is inadequate. If it exceeds 8 mu m, curing hardly occurs due to curing shrinkage.

Thermosetting Resin:

The thermosetting resin for the anchor layer is typically an epoxy resin, an isocyanate curable urethane resin, or the like. Preferred among these are cured phenoxy resins, phenoxy ether resins or phenoxy ester resins obtained by curing a phenoxy resin, phenoxy ether resin, or phenoxy ester resin with a polyfunctional isocyanate compound.

Although the thickness of a thermosetting resin layer is not limited, Solvent resistance is inadequate when it is less than 3 micrometers. The upper limit of the layer is determined by the balance between cost and solvent resistance and preferably 20 µm or less, even 10 µm or less.

The thermosetting resin layer is formed as follows. Coating solutions are prepared by adding optional additives such as reactive diluents, particulates and leveling agents and modifying agents such as thermoplastics and plasticizers to the thermosetting resin composition. Organic solvents are optionally added to adjust the concentration and viscosity of the coating solution. The coating method may be, for example, dip coating, spray coating, flow coating, roll coating, bar coating, spin coating, and the like, and heat treatment at 120 ° C. for at least 3 minutes, more preferably at 130 ° C. for at least 5 minutes. Form.

The solvent resistant protective layer may be a radiation cured layer or thermosetting layer which may be similar to the radiation cured layer or thermosetting layer for the anchor layer.

Particulate-containing layer

Optionally, a layer containing an inorganic or organic particulate layer may be provided on the laminated substrate.

The polymer substrate can be processed into a roll-to-roll system, which is advantageous for saving costs. However, if the surface of the membrane is too smooth, the membrane has poor sliding properties due to large contact area with the roll, etc., and the membrane is deformed or bent by blocking while winding the membrane, resulting in increased damage.

By adding fine particles to the layer of the membrane, in particular the outermost layer of the membrane, the slidability of the membrane can be improved by reducing the contact surface area with the roll or the like, so that deformation or bending of the membrane during membrane winding can be prevented.

This fine particle-containing layer is preferably formed in at least one outermost layer of the laminated film.

This particulate-containing layer can be formed by coating a coating solution to which inorganic or organic fine particles are added to a substrate and curing the coated layer.

The coating solution to which the inorganic or organic fine particles are added may be a coating solution for forming the above-mentioned cured polymer layer (B layer), or may be another coating solution.

Preferably, the inorganic fine particles include silica and alumina because the decrease in transparency by them is relatively low. The average particle size of the inorganic fine particles is preferably in the range of 0.5 to 5 mu m when the layer is cured.

Preferred organic particulates include acrylic resins, styrene resins, urethane resins, polycarbonate resins, nylon resins and the like. The average particle size of the organic fine particles is preferably in the range of 0.5 to 5 mu m. If it is smaller than 0.5 mu m, the sliding performance is insufficient. If it is larger than 5 mu m, the optical properties are degraded.

The content of the inorganic or organic fine particles is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the fine particle-containing cured layer. If it is less than 0.01 weight part, glidability will become inadequate. If it exceeds 5 parts by weight, optical properties such as haze value are lowered.

The thickness of the inorganic or organic fine particle-containing layer is preferably in the range of 0.5 to 30 μm. If too thin, the layer may have particle defects. If too thick, excellent slidability is hardly obtained.

Other components of the LCD device

The transparent electrode substrate composed of the components (A) to (D) of the present invention is used for at least one of the electrode substrates of the liquid crystal display device, but both electrode substrates are transparent composed of the components (A) to (D) of the present invention. It may be an electrode substrate. The other substrate may be made of a substrate other than the component B of the present invention. Other substrates are not transparent and may be made of nonpolymers.

Another aspect of the invention

According to an aspect of the present invention as described above, there is also provided a transparent electrode substrate composed of the components (A) to (D) as described above. The transparent electrode substrate may be useful not only for liquid crystal display devices but also for other electric devices using the transparent electrode substrate, for example, touch panels, electroluminescent devices, planar phosphors, and the like.

Moreover, component (B) as described above provides excellent transparency, water resistance, flexibility and other mechanical properties with significant chemical or solvent resistance, gas barrier properties and adhesion. Thus, the layer of component B can be used as a coating layer for articles made of not only resins, but also other materials such as metals, ceramics, paper, and the like. In this article, the metal oxide layer (A) and the transparent conductive layer (C) are not essential but optional. The shape of the article is not limited to sheets or films.

One preferred embodiment of this article is a polymer substrate consisting of a metal oxide layer (A), a cured polymer layer (B) adjacent to the metal (D) (see FIG. 5).

Other preferred embodiments of this article are a transparent polymer layer (D), a metal oxide layer (A) on one side of layer (D), a first cured polymer layer (B-1) in contact with the metal oxide layer (A), and a layer (D). A polymer substrate composed of a second cured polymer layer (B-2) formed on the other side of the substrate (see FIG. 9). In FIG. 9, 41 represents layer (D), 42 represents layer (A), and 45 represents cured layers (B-1, B-2).

The component A of the metal oxide layer in this application for the article is not essential as mentioned above, but it is of course advantageous to use it in combination.

One of the most useful applications of component (B) as a coating is as a solvent resistant layer or gas barrier coating, especially for pharmaceutical or food containers or packaging.

The coated layer of component (B) at 40 ° C., 90% RH below 10 cm ³ / m ² / day / atm in addition to the chemical resistances (i) to (iii) mentioned above for the transparent electrode substrate Oxygen permeability.

Example

The invention is further illustrated with reference to the examples, but is not limited thereto. The cured polymer layer of component (B) of the present invention is preferably formed adjacent to the metal oxide layer of component (A) on the transparent electrode substrate, but the cured polymer of component (B) formed on the substrate without the metal oxide layer It should be appreciated that the layers are also novel and are within the scope of the present invention.

Parts and percentages are based on weight unless otherwise stated in the Examples.

In the Examples, evaluation was made in the following manner.

Appearance of the component (B) layer:

Visual inspection determined pigmentation and coating defects.

Transparency:

The light transmission of parallel light was calculated | required with the wavelength of 550 nm using the spectrophotometer (Hitachi Ltd, U-3500). Haze value was Nippon Denshoku k.k. Obtained using COH-300A.

Optical isotropy:

 Nippon Sepctroscopy Corp. The delay with respect to the wavelength of 590 nm was calculated | required using the multi-wavelength birefringence measuring apparatus M-150.

Surface Smoothness:

WYCO Corp. Surface smoothness was determined using TOPO-3D.

Ra is the centerline average surface roughness of the layer measured at a magnification of 256 mu m length and 1 mu m pitch at 400 magnification by phase-transfer interference method.

Chemical or solvent resistant (1):

The sample was immersed in an aqueous 3.5% -NaOH solution at 25 ° C. for 10 minutes, washed with running water, dried, and inspected for appearance of the sample.

Chemical or solvent resistant (2):

The sample was immersed in a 5.0%-HC1 solution at 25 ° C. for 10 minutes, washed with running water and dried, and then the appearance of the sample was examined.

When the transparent conductive layer (C) was formed, this evaluation was performed on the sample before forming the layer (C).

Chemical or solvent resistant (3):

Test (1):

For the laminate having a transparent conductive layer, the laminate was immersed in N-methylpyrrolidone (NMP) at 25 ° C. for 10 minutes, the appearance change was examined, the change in haze value was measured, and the tolerance change was measured. If peeling off, the decrease in surface smoothness, or cloudiness of the coating layer was visually inspected, or if the change in haze value was greater than 1%, it was evaluated as "deteriorated appearance".

Test (2):

For a laminate without a transparent conductive layer, a few drops of NMP were added dropwise to the laminate with the cured polymer layer (B) plane at 80 ° C, left at 80 ° C for 1 minute, and washed with running water to examine the appearance.

Test (3):

For a laminate without a transparent conductive layer, a few drops of NMP were added dropwise to the laminate with the cured polymer layer (B) plane at 80 ° C, left at 80 ° C for 10 minutes, and washed with running water to examine the appearance.

Water vapor barrier:

Water vapor barrier and the following gas barrier properties were measured for the cured polymer layer without forming the transparent electrode layer.

Water vapor permeability was measured by Modern Control Corp. It was calculated | required in 40 degreeC and 90% RH atmosphere using Permatoran W1A by (MOCON Corp.).

Gas barrier properties (1):

Oxygen permeability was measured by MOCON Corp. It was calculated | required in 30 degreeC and 50% RH atmosphere using OX-TRAN 2/20 of the agent.

Gas barrier properties (2):

Oxygen permeability was measured by MOCON Corp. It was calculated | required in 30 degreeC and 90% RH atmosphere using the OX-TRAN 2/20 of the agent.

Adhesive:

The sample surface was cut into a matrix at 1 mm pitch to form 100 small square sections. Cellophane adhesive tape (Cello tape, manufactured by Nichiban k.k.) was applied to the cut samples and was quickly peeled off at a 90 ° angle from the surface. The number of small square sections on the sample was counted to assess adhesion. The score "100/100" means complete adhesion and "0/100" means complete peeling (according to JIS K5400).

Flexibility:

The sample was wound and unrolled in a glass tube having a diameter of 10 mm ø and the sample appearance was examined. If cracks occur (particularly if cracks larger than 5 mm occur on the surface of the transparent conductive electrode), they are evaluated as defective.

durability:

The temperature and humidity control apparatus was heated at 60 ° C. and 90% RH for 100 hours and then cooled to examine the appearance of the cured layer.

Sliding:

A 50 cm wide and 50 m long film was wound on a roll and the film was examined for deformation or bending.

Examples 1 to 8

A polycarbonate resin having a bisphenol A composed of bisphenol A and having a molecular weight of 37,000 was dissolved in methylene chloride at a concentration of 20% by weight, and cast on a polyester film having a thickness of 175 μm by die casting. The cast film was dried to have a residual solvent concentration of 13% by weight and peeled from the polyester film. The polycarbonate film thus obtained was dried with a balanced tension in the transverse direction so that the solvent concentration remaining in the drying oven at 120 ° C. was 0.08% by weight.

The transparent polycarbonate film thus obtained had a thickness of 103 μm and a 550 nm light transmittance of 91%.

On the surface of the polycarbonate film as a substrate, a SiO chip was deposited under a vacuum of 5 x 10 ^-5 torr to deposit a metal oxide layer (A layer). The attached silicon oxide layer had an average composition of SiO _x (x is about 1.7 or 1.3).

Next, a polymer cured layer (B layer) was formed on the metal oxide layer by preparing a coating solution as described later. The composition of the coating solution is shown in the table and the silicon compounds (B1) and (B2) listed in the table are compounds before hydrolysis.

On the SiO _1.7 layer formed on the polycarbonate film or polycarbonate film, a coating solution aged at room temperature for 24 hours after coating was coated by Meyer bar, and the coated layer was heated at 130 ° C. for 2 minutes to form a cured polymer layer (B Layer).

(Example 1)

In this example, layer B was formed on a substrate of transparent polymer film or polycarbonate.

The coating solution for layer B was silanol-containing polyvinyl alcohol (R1130, manufactured by Kraray Corp. Ltd.) as polyvinyl alcohol polymer (B3), 3-glycidoxy as silicon compound (B1) having epoxy and alkoxysilyl groups. Silicon compound (B2) having propyltrimethoxysilane and amino and alkoxysilyl group, consisting of aminopropyltrimethoxysilane, weight ratio (B ₃ ) / “(B ₁ ) + (B ₂ )] is 2/1; , Molar ratio (b ₁ ) / (b ₂ ) is 1/1, wherein B ₁ to B ₃ represent the weights of the compounds (B1) to (B3), b ₁ represents the molar amount of the epoxy group, and b ₂ is The total molar amount of amino and imino groups is shown.

The coating solution was added acetic acid to a mixture of polyvinyl alcohol and distilled water, water was evaporated, stirred to make the mixture homogeneous, and aminopropyltrimethoxysilane was added dropwise to the solution to carry out the hydrolysis, and the solution was stirred for 30 minutes. Was stirred and prepared by addition of 3-glycidoxyoxytrimethoxysilane.

As can be seen from Table 1, all evaluations of the laminate were good.

(Example 2)

In this example, layer B was formed on a transparent polymer film of polycarbonate.

The coating solution for layer B consisted of the same polyvinyl alcohol polymer (B3) as in Example 1, a silicon compound (B1) having an epoxy and an alkoxysilyl group, and a silicon compound (B2) having an amino and an alkoxysilyl group (B2). B ₃ ) / [(B ₁ ) + (B ₂ )] was 2/1, and the molar ratio (b ₁ ) / (b ₂ ) was 3/2.

The coating solution was added acetic acid to a mixture of polyvinyl alcohol and distilled water, water was evaporated, stirred to make the mixture homogeneous, and aminopropyltrimethoxysilane was added dropwise to the solution to carry out the hydrolysis, and the solution was stirred for 30 minutes. Prepared by stirring. To this solution was added slowly with stirring 0.01 N hydrochloric acid, and an isopropyl alcohol solution of 3-glycidoxyoxytrimethoxysilane stirred for 30 minutes was added.

As can be seen from Table 1, all evaluations of the laminate were good.

(Example 3)

In this embodiment, a silicon oxide layer was attached to the polycarbonate film as the metal oxide layer (A layer), and then B layer was formed on the A layer.

The process is carried out except that the composition of the coating solution used has a weight ratio of 2/1 (B ₃ ) / [(B ₁ ) + (B ₂ )] and a molar ratio of 1/2 (b ₁ ) / (b ₂ ) Was the same as in Example 2.

As can be seen from Table 1, all evaluations of the laminate were good. In particular, gas barrier properties have been significantly improved by providing a silicon oxide layer (layer A).

(Example 4)

In this embodiment, a silicon oxide layer was attached to the polycarbonate film as the metal oxide layer (A layer), and then B layer was formed on the A layer.

The process consists of the composition of the coating solution used consisting of aminopropyltriethoxysilane as component (B2), with a weight ratio of 2/1 (B ₃ ) / [(B ₁ ) + (B ₂ )] and 1/2 It was the same as Example 2 except having a molar ratio of (b ₁ ) / (b ₂ ).

As can be seen from Table 1, all evaluations of the laminate were good. In particular, gas barrier properties have been significantly improved by providing a silicon oxide layer (layer A).

(Example 5)

In this embodiment, a silicon oxide layer was attached to the polycarbonate film as the metal oxide layer (A layer), and then B layer was formed on the A layer.

The process consists of the composition of the coating solution used consisting of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as component (B1) and aminopropyltrimethoxysilane as component (B2), 2 / It was the same as Example 2 except having a weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] of 1 and a molar ratio (b ₁ ) / (b ₂ ) of 1/1.

As can be seen from Table 1, all evaluations of the laminate were good. In particular, gas barrier properties have been significantly improved by providing a silicon oxide layer (layer A).

(Example 6)

In this embodiment, a silicon oxide layer was attached to the polycarbonate film as the metal oxide layer (A layer), and then B layer was formed on the A layer.

The manufacturing process of the coating solution is composed of the same components (B1) and (B3) and aminopropyltriethoxysilane as the component (B2) as in Example 5, the weight ratio of 1/1 (B ₃ It was the same as Example 2 except having a molar ratio (b ₁ ) / (b ₂ ) of 1/1) / [(B ₁ ) + (B ₂ )].

As can be seen from Table 2, all evaluations of the laminate were good. In particular, gas barrier properties have been significantly improved by providing a silicon oxide layer (layer A).

(Example 7)

In this embodiment, the silicon oxide layer was attached to the polycarbonate film as the metal oxide layer (A layer), and then the B layer was formed on the A layer.

The process for preparing the coating solution was made of the same compound (B1) and (B3) and aminopropyltriethoxysilane as the compound (B2) as in Example 6, and the weight ratio (B ₃ ) / [( B ₁ ) + (B ₂ )] and the same as Example 2 except that it has a molar ratio (b ₁ ) / (b ₂ ) of 1/1.

The preparation of the coating solution was carried out with the same compounds (B1) and (B3) and compound (B2) as in Example 1 with N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl ) -3-amino-propylmethyldimethoxysilane, a weight ratio of 3/1 (B ₃ ) / [(B ₁ ) + (B ₂ )] and a molar ratio of 1/2 (b ₁ ) / (b ₂ Same as Example 1 except for having a).

As can be seen from Table 2, all evaluations of the laminate were good. In particular, gas barrier properties have been significantly improved by providing a silicon oxide layer (layer A).

(Example 8)

In this embodiment, the silicon oxide layer was attached to the polycarbonate film as the metal oxide layer (A layer), and then the B layer was formed on the A layer.

The procedure was the same as in Example 7, except that the polyvinyl alcohol used was Gocenol NM-11Q (more than 99% soap) from Nippon Synthetic Chemical Industry Ltd.

As can be seen from Table 2, all evaluations of the laminate were good, but the alkali resistance (solvent resistance 1) was slightly reduced.

(Comparative Examples 1 to 5)

The same procedure as in Examples 1-8 was carried out except that the coated layer (s) were as shown in Table 3.

(Comparative Example 1)

In this comparative example, a cured polymer layer containing no polyvinyl alcohol polymer (B3) was formed on a transparent polymer film of polycarbonate.

The coating solution for the cured polymer layer consisted only of 3-glycidoxyoxytrimethoxysilane (B1) and 3-aminopropyltrimethoxysilane (B2).

As can be seen from Table 3, gas barrier properties and durability were poor.

(Comparative Example 2)

In this comparative example, a silicon oxide film was attached to the polycarbonate film as a metal oxide layer (A layer), and then a cured polymer layer containing no amino and hydrosilyl groups (B2) was formed on the A layer.

The coating solution consisted of silanol-containing polyvinyl alcohol (B3) and 3-aminopropyltrimethoxysilane (B2) only as used in Example 1.

As can be seen from Table 3, alkali resistance (chemical resistance 1), NMP resistance (solvent resistance 3) and durability were poor, and adhesiveness was slightly poor.

(Comparative Example 3)

In this comparative example, a cured polymer layer containing no silicon compound (B2) having amino and hydrosilyl groups was formed on a transparent polymer film of polycarbonate.

The coating solution consisted of silanol-containing polyvinyl alcohol (B3) and 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane (B1) only as used in Example 1.

As can be seen from Table 3, alkali resistance (solvent resistance 1), NMP resistance (solvent resistance 3), adhesiveness and durability were poor.

(Comparative Example 4)

In this comparative example, a polycarbonate film was evaluated in which a silicon oxide layer (A layer) was attached as the metal oxide layer of SiO _1.7 but the cured polymer layer was not formed on the A layer.

Solvents 1-3 and oxygen barrier properties were low.

(Comparative Example 5)

In this comparative example, a polycarbonate film was evaluated in which a silicon oxide layer (A layer) was attached as the metal oxide layer of SiO _1.3 but the cured polymer layer was not formed on the A layer.

Solvents 1-3 and oxygen barrier properties were low.

Examples 9-15

(Example 9)

In the same manner as in Examples 3 to 5, a polycarbonate film with a metal oxide layer (A layer) of silicon oxide was used also in this example.

Next, a polymer cured layer (B layer) was formed on the metal oxide layer by preparing a coating solution as described later. The composition of the coating solution is shown in Tables 4 and 5, and the silicon compounds (B1) and (B2) listed in Tables 4 and 5 are compounds before hydrolysis.

The coating solution for forming the cured polymer layer (B layer) was prepared as follows: 100 weight of ethylene-vinyl alcohol copolymer (EVOH-F, Kuraray, ethylene copolymerization rate 32%) as polyvinyl alcohol polymer (B3). Part was added to a mixed solvent of 720 parts by weight of water, 1080 parts by weight of n-propanol and 100 parts by weight of n-butanol, and heated to obtain a uniform solution. 0.1 parts by weight of silicone oil (SH30PA, manufactured by Toray Dow Corning Silicone Corp.) and 62.4 parts by weight of acetic acid were added to the solution, followed by 2- (3,4-epoxy) as a silicon compound (B1) having epoxy and alkoxysilyl groups. 85.8 parts by weight of cyclohexyl) ethoxytrimethoxysilane was added and the solution was stirred for 10 minutes. Then, 62.4 parts by weight of 3-aminopropyltrimethoxysilane was added to the solution as silicon compound (B2) having amino and alkoxysilyl groups, and the solution was stirred for 3 hours to form a coating solution for forming a cured polymer layer (B layer). Got it. The coating solution had a weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] of 1/1 and a molar ratio (b ₁ ) / (b ₂ ) of 1/1.

On the SiO _1.7 layer (A layer) formed in the polycarbonate film, a coating solution was coated by Meyer bar, and the coated layer was heated at 130 ° C. for 3 minutes to form a cured polymer layer (B layer).

The obtained laminate is evaluated and the results are shown in Table 4.

As can be seen from Table 4, all the evaluations were good.

(Examples 10 to 13)

The same procedure as in Example 9 was repeated, but the composition of the coating solution was changed as shown in Table 4, and the weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] was 2/1 in Example 10. 1/2 in Example 11, 1/3 in Example 12, 1/9 in Example 13, and the molar ratio (b ₁ ) / (b ₂ ) was 1/1 in Examples 10 to 13.

The obtained laminate is evaluated and the results are shown in Table 4.

As can be seen from Table 4, all the evaluations were good.

(Example 14)

The same procedure as in Example 9 was repeated, but compound (B1) was changed to 3-glycidoxyoxytrimethoxysilane, and the weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] was 1/1. And the molar ratio (b ₁ ) / (b ₂ ) was 1/1.

The obtained laminate is evaluated and the results are shown in Table 4.

As can be seen from Table 4, all the evaluations were good.

(Example 15)

The same coating composition as in Example 9 was coated on both surfaces of the polycarbonate film having the silicon oxide layer as in Example 9 in the same manner as in Example 9.

The obtained laminate was evaluated and the results are shown in Table 4.

As can be seen from Table 4, the evaluations were all good. The layer B had excellent adhesion to both the silicon oxide layer and the polycarbonate film, and the obtained laminate had excellent chemical resistance to both surfaces thereof.

Examples 16-21

(Examples 16 to 20)

The same polycarbonate film as Example 9 was used, but no silicon oxide film was formed thereon. Coating solutions of Examples 16 to 20 were the same as Examples 9 to 12 and 14, respectively. The formation method of the cured polymer layer was the same as in Example 9.

Evaluation of the obtained laminated body was shown in Table 5, and all were favorable.

(Example 21)

The same method as in Example 9 was repeated, but a polycarbonate film was changed to a polyester film having a thickness of 12 µm.

The obtained laminate is evaluated and the results are shown in Table 5.

As can be seen in Table 4 all evaluations were good.

Comparative Examples 6 to 10

 In Comparative Examples 6 to 10, the procedure of Example 9 was repeated, but the solution for forming the cured polymer was changed as shown in Table 6.

(Comparative Example 6)

This is a comparative example without adding the silane compounds (B1) and (B2). Therefore, the weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] was 1/0.

In evaluation, NMP resistance (chemical resistance 3) and adhesiveness were poor.

(Comparative Example 7)

It did not add the silane compound (B2) having amino and alkoxysilyl groups, the weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] is 2/1, and the molar ratio (b ₁ ) / (b ₂ ) Is a comparative example of 1/0.

In evaluation, alkali resistance (chemical resistance 1), NMP resistance (chemical resistance 3), and adhesiveness were poor.

(Comparative Example 8)

It did not add the silane compound (B1) having epoxy and alkoxysilyl groups, the weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] is 2/1, and the molar ratio (b ₁ ) / (b ₂ ) Is a comparative example in which 0/1.

In evaluation, appearance, haze value, alkali resistance (chemical resistance 1), NMP resistance (chemical resistance 3), and adhesiveness were poor.

(Comparative Example 9)

The coating solution for forming the cured polymer layer as in Example 9 was coated on the polycarbonate film having the silicon oxide layer as in Example 9, but the coated side was the opposite side to the silicon oxide layer side.

In the evaluation shown in Table 6, the gas barrier layer was poor.

(Comparative Example 10)

Evaluation was made about the polycarbonate film alone used in Example 9.

Examples 22-24

 (Example 22)

The same polycarbonate film having the silicon oxide layer as in Example 3 was used.

The first coating solution for forming the cured polymer layer (B layer) is applied to the silicon oxide layer (A layer) of the substrate by the microgravure method, and heated at 130 ° C. for 3 hours to form a cured polymer having a thickness of 2 μm. A layer was formed. The prepared first coating solution was the same as in Example 16.

The second coating solution for forming the protective layer was applied to the silicon oxide layer (A layer) and the B layer of the substrate preliminarily dried at 50 ° C. for 1 minute by the microgravure method, and applied to a high pressure mercury lamp of 160 W / cm. Thereafter, UV rays were irradiated and cured at a total exposure amount of 800 mJ / cm 2 to form a protective layer having a thickness of 4 μm. The second coating solution was 100 parts by weight of trimethylolpropane triacrylate (Aronix M-309, manufactured by Toa Synthetic Chemical Corp.), and 7 parts by weight of 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Chiba-Geigy) as a photoinitiator. And 0.02 parts by weight of silicone oil (SH28PA, manufactured by Toray Dow Corning Corporation) as a leveling agent, and the mixture was prepared by diluting the mixture with 1-methoxy-2-propanol and methanol to a solid content of 35% by weight.

The thus obtained roll of the laminate having a polyester film as the substrate was fixed with a sputtering apparatus vacuumed at a pressure of 1.3 mPa. A mixed gas of Ar and O ₂ (1.4 vol% of O ₂ content) was added and the temperature was adjusted to 9.27 Pa. DC sputtering was carried out using an ITO target (SnO ₂ content 5% by weight) at an applied current density of 1 W / cm ₂ to attach a transparent conductive layer of ITO having a thickness of 130 μm to the cured polymer layer in contact with the polycarbonate film.

Thus, a transparent conductive laminate (transparent electrode substrate) was obtained and evaluated.

The results are shown in Table 7.

(Example 23)

Although the process of Example 22 was repeated, 100 parts by weight of the first coating solution, 100 parts by weight of the polyvinyl alcohol polymer (B3) (R1130, made by Kraray, less than 1% silyl content) of silyl 1300 parts by weight of water and n-propanol It was thermally dissolved in 600 parts by weight of a mixture to form a uniform solution, cooled to room temperature, 0.1 parts by weight of silicone oil (SH30PA, manufactured by Toray Dow Corning Silicone Corp.) and 124.8 parts by weight of acetic acid were added as a leveling agent, and then 3-amino. 124.8 parts by weight of propyltrimethoxysilane (B2) was added to the solution and stirred for 3 hours, 171.6 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (B1) was further added, followed by stirring for 3 hours. It was prepared by. The composition had a weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] of 1/2 and a molar ratio (b ₁ ) / (b ₂ ) of 1/1.

The results are shown in Table 7.

(Example 24)

Example 22 was repeated, but the second coating solution was coated, heated at 180 ° C. for 5 minutes, and then heated at 130 ° C. for 5 minutes to obtain a protective layer having a thickness of 5 μm. The second coating solution was mixed with 20 parts by weight of phenoxy ester resin (PKHM-30, manufactured by Union Carbide Corporation), 40 parts by weight of methyl ethyl ketone and 20 parts by weight of 2-ethoxyethyl acetate, followed by polyfunctional isocyanate (Coronate L, 20 parts of Nippon Polyisocyanate) were added to the mixture to prepare.

The results are shown in Table 7.

Comparative Examples 11 and 12

(Comparative Example 11)

The process of Example 22 was repeated but did not form a cured polymer layer prepared from the first coating solution.

The results are shown in Table 7.

(Comparative Example 12)

Although the process of Example 22 was repeated, the cured polymer layer was formed by changing the first coating solution into a polyvinyl alcohol polymer (Gocenol NM-11Q, manufactured by Nippon Synthetic Chemical Corp.).

The results are shown in Table 7.

In Tables 7 to 10 the following abbreviations are used.

PVA: Polyvinyl Alcohol

SP: silyl-containing polyvinyl alcohol (R1130, Kraray)

P: highly saponified polyvinyl alcohol (Gocenol NM-110, Nippon Synthetic Chemical Industry)

E: ethylene-vinyl alcohol copolymer (EVAL F104, Kraray)

ECHETMOS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

APTMOS: 3-aminopropyltrimethoxysilane

H (2): layer B of Example 1

X 200: SiO _X Layer of Example 3

TF-PC: Polycarbonate film of Example 1

SX 70: SiO _x Layer of Example 28

G: with filler

Si content: `` (B ₁ + B ₂ ) / (B ₁ + B ₂ + B ₃ )] x 100 (weight)

B1 amount: `` b ₁ / (b ₁ + b ₂ )] x 100 (mol)

Examples 25-27

 (Example 25)

The polycarbonate film having a silicon oxide layer (A layer) having a thickness of 20 μm was the same as in Example 3.

A first coating solution was prepared to form a cured polymer layer (B layer). The coating solution was applied to both sides of the polycarbonate having a silicon oxide layer (A layer) by a microgravure method, and heated at 130 ° C. for 2 minutes to obtain a cured polymer layer having a thickness of 2 μm.

The first coating solution was the same as that used to form the cured polymer layer (layer B) of Example 9.

An ITO layer was deposited on the cured polymer layer (B layer) formed in the silicon oxide layer in the same manner as in Example 22.

The laminate thus obtained was evaluated and the results are shown in Table 8.

(Example 26)

Although the process of Example 25 was repeated, one of the cured polymer layers formed on the silicon oxide layer was prepared using a second coating solution, while the other cured polymer layer formed directly on the polycarbonate film was the same as that of Example 30. It was prepared by the coating solution.

The second coating solution was thermally dissolved in a mixture of 1300 parts by weight of water and 600 parts by weight of n-propanol in 100 parts of silyl-containing polyvinyl alcohol-based polymer (R1130, manufactured by Kraray, with a silyl content of less than 1%), cooled to room temperature, and leveled. 0.1 parts by weight of zero silicone oil (SH30PA, manufactured by Toray Dow Corning Silicone Corp.), 124.8 parts by weight of acetic acid, and then 171.6 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (B1) were added to the solution. After stirring for 10 minutes, 124.8 parts by weight of 3-aminopropyltrimethoxysilane (B2) was further added to the solution, followed by stirring for 3 hours. The composition had a weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] of 1/2 and a molar ratio (b ₁ ) / (b ₂ ) of 1/1.

The laminate thus obtained was evaluated and the results are shown in Table 8.

(Example 27)

The procedure of Example 25 was repeated but no silicon oxide layer was formed.

The laminate thus obtained was evaluated and the results are shown in Table 8.

Comparative Example 13

Although the process of Example 25 was repeated, the cured polymer layer formed was made of a polyvinyl alcohol polymer (Gocenol NM-1Q, Nippon Synthetic Chemical).

The laminate thus obtained was evaluated and the results are shown in Table 8.

Examples 28-31

 (Example 28)

The polycarbonate film used as the substrate was the same as in Example 1 except that the film thickness was 100 µm.

The cured polymer layer (B layer) was coated on both sides of the polycarbonate film by the microgravure method and heated at 130 ° C. for 2 minutes to obtain a laminated substrate having the cured polymer layer (B layer) on both sides. .

The coating composition used in this example was the same as in Example 9.

The laminated substrate was fixed with the sputtering apparatus vacuumed at 1.3 mPa pressure. A mixed gas of Ar / O ₂ (O ₂ concentration of 12.0% by volume) was introduced into the sputtering chamber and the pressure was adjusted to 0.27 Pa. DC magnetron sputtering was performed at an applied current density of 1 W / cm 2 using a polycrystalline Si metal target to form a SiO ₂ layer having a thickness of 7 nm on one surface of the cured polymer layer of the substrate.

ITO was formed on this SiO ₂ layer. The process of forming the ITO layer was the same as in Example 22.

The laminate thus obtained was evaluated and the results are shown in Table 9.

(Example 29)

The procedure of Example 28 was repeated, but the first coating solution was changed to the next solution and the coating layer was heated at 130 ° C. for 3 minutes.

The first coating solution used in this example was prepared by the same procedure as in Example 26.

The laminate thus obtained was evaluated and the results are shown in Table 9.

(Example 30)

The polycarbonate film used was the same as in Example 28.

The first coating solution used in this example was the same as in Example 10. The first coating solution was coated on one surface of the polycarbonate film by a microgravure method and heated at 130 ° C. for 3 minutes to form a cured polymer layer (B layer) on one surface thereof.

On the other side of the polycarbonate, a second coating solution was prepared, and the second coating solution was coated on the other side of the polycarbonate film by the microgravure method, preheated at 50 ° C. for 1 minute, and 160 W at a total exposure amount of 800 mJ / cm 2. The coating layer was cured by irradiating with UV rays from a high-pressure mercury lamp of / cm to form a curing protective layer having a thickness of 4 µm to form a solvent-resistant protective layer.

The second coating solution used herein was 100 parts by weight of trimethylolpropane triacrylate (Alonix M-309, manufactured by Toa Synthetic Chemical Corp.), and 7 parts by weight of 1-hydroxycyclohexyl ketone (Irgacure 184, manufactured by Chiba Geigy Limited). And a silicone oil (SH28PA, manufactured by Toray Dow Corning Silicone Corp.) as a leveling agent, followed by dilution with 1-methoxy-2-propanol and methanol to a solid content of 35% by weight.

The same silicon oxide layer as in Example 28 was attached to the cured polymer (layer B) of the laminated substrate in the same manner as in Example 28. Then, the same ITO layer as Example 28 was attached to the solvent-resistant protective layer of the laminated substrate in the same manner as in Example 28.

The laminate thus obtained was evaluated and the results are shown in Table 9.

(Example 31)

The process of Example 28 was repeated, but the ITO layer was formed on the cured polymer layer (B layer) formed directly on the polycarbonate film, but not on the surface of the cured polymer layer (B layer) formed on the silicon oxide layer.

The laminate thus obtained was evaluated and the results are shown in Table 9.

Examples 32-38

(Example 32)

The polycarbonate film used as the substrate was the same as in Example 1.

On both sides of the polycarbonate, the first coating solution for forming the cured polymer layer (layer B) used in Example 9 was coated and cured.

The laminate thus obtained was fixed with a vapor deposition apparatus and a 20 nm thick SiO _x layer (x is about 1.7) (A layer) was cured polymer layer of the substrate from a deposition source of a mixture of Si and SiO ₂ under a vacuum of 1.3 mPa. Attached to one side. The lower layer of this cured polymer layer served as an anchor layer.

The first coating solution was again coated on the silicon oxide layer and heated at 130 ° C. for 2 minutes to form a second cured polymer layer (layer B) having a thickness of 2 μm.

An ITO layer was formed on this second cured polymer layer in the same manner as in Example 22.

Thus, the first cured polymer layer (B layer) / polycarbonate film (D layer) / the first cured polymer layer (B layer or anchor layer) / SiO _x layer (A layer) / second cured polymer layer (B layer) A laminated structure of the / ITO layer (C layer) was obtained.

The laminate thus obtained was evaluated and the results are shown in Table 10.

(Example 33)

Example 32 Repeat the procedure but, to change to an anchor layer of a silane coupler 1 is the cured polymer layer thickness 50㎚ (AP133, Nippon Unitika claim) that the anchor layer serves for the SiO _x layers, SiO _x layer is Si , were deposited a mixture of SiO ₂ and MgF ₂ by changing the metal oxide layer of a thickness 100㎚ mainly consisting of SiO _x, SiO _x content of the intra-layer MgF ₂ was about 10% by weight.

The laminate thus obtained was evaluated and the results are shown in Table 10.

(Example 34)

Example 32 was repeated, but the first cured polymer layer formed on both sides of the polycarbonate was changed to a UV cured layer having a thickness of 4 μm, and the solvent-resistant coating layer as used in Example 37 in the same manner as in Example 30. It formed using the coating solution for forming (trimethylol propane triacrylate base).

The laminate thus obtained was evaluated and the results are shown in Table 10.

(Example 35)

The same procedure as in Example 32 was repeated, but the cured polymer layer under the ITO layer was changed to the UV cured layer as used in Example 34.

The laminate thus obtained was evaluated and the results are shown in Table 10.

(Example 36)

The same procedure as in Example 32 was repeated, but the cured polymer layer was replaced with the solvent-resistant protective layer and the cured layer of Example 24 as an anchor layer under the metal oxide layer.

The laminate thus obtained was evaluated and the results are shown in Table 10.

(Example 37)

The same procedure as in Example 32 was repeated, but the fine particle-containing layer was further coated with a coating solution and heated at 130 ° C. for 2 minutes to form a thickness of 2 μm on the surface of the polycarbonate membrane opposite the ITO layer. This coating solution was the same as the coating solution of Example 32, but silica powder having an average particle size of 2 µm was added in an amount of 0.4 part, and the mixture was sufficiently stirred.

The laminate thus obtained was evaluated and the results are shown in Table 10.

(Example 38)

Although the procedure of Example 37 was repeated, the particulate-containing layer was prepared from a coating solution that was basically the same as the UV curable solution of Example 34, in which 0.2 parts of acrylic resin powder having an average particle size of 5 µm was added.

The laminate thus obtained was evaluated and the results are shown in Table 10.

Examples 39-41

The procedure of Example 26 was repeated except for the following. For the B layer in contact with the ITO layer, a polyvinyl alcohol polymer (EVAL F104, manufactured by Kuraray) and a compound as shown in Table 11 were used in the amounts indicated in Table 11. For the other B layer (B ′ layer) in contact with the SiO _x layer, polyvinyl alcohol-based polymer EVAL F104 and compounds as shown in Table 11 were used in the amounts indicated in Table 11.

Examples 42-46

The same procedure as in Example 9 was repeated, but the compounds as shown in Table 11 were used in the amounts indicated in Table 11.

In Table 11, the following abbreviations are used.

APMDEOS: 3-aminopropylmethyldiethoxysilane

MAPTMOS: N-methylaminopropyltrimethoxysilane

APTEOS: 3-aminopropyltriethoxysilane

AEAPTMOS: N- (2-aminoethyl) -3-aminopropyltrimethoxysilane

AEAPMDMOS: N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane

By using the transparent electrode substrate of the present invention, a liquid crystal display device having a transparent resin substrate having improved chemical resistance or solvent resistance, gas barrier property, transparency, smoothness, adhesion, etc., and having low manufacturing costs due to the small number of laminated layers can be obtained. Can be.

1 is a cross-sectional view of an example of a liquid crystal display element;

2 is a cross-sectional view of a commercially available transparent polymer electrode substrate,

3 schematically shows a hybridization reaction between a polyvinyl alcohol polymer and an alkoxysilane,

4A and 4B show oxygen permeability of the gas barrier layer,

5 is a cross-sectional view of a gas barrier layer lamination of a hybrid with a polycarbonate film and an SiO _x layer;

6a to 6c show the composite effect of the hybrid and SiO _x layers,

7 shows alkali resistance of the hybrid layer,

8 schematically shows the reaction of compounds (B1) to (B3),

9 is a cross-sectional view of an ideal transparent polymer substrate according to the present invention,

10A to 10D and 11A to 11F show various arrangements of components (A) to (D) of the present invention.

Claims (33)

 The liquid crystal layer consists of two electrode substrates interposed therebetween, wherein at least one of the electrode substrates comprises: A) a metal oxide layer, B) adjacent the metal oxide layer, B1) silicon compounds having epoxy and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; B2) silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; And B3) Cured polymer layer obtained from the crosslinking reaction of a polyvinyl alcohol-type polymer; C) a transparent conductive layer; And D) consists of a transparent polymer substrate having a delay of 30 nm or less for a wavelength of 590 nm, The transparent conductive layer (C) is formed on the liquid crystal layer surface of the transparent polymer substrate (D), and the combination of the metal oxide layer (A) and the cured polymer layer (B) is the transparent conductive layer (C) and the transparent polymer substrate. It is disposed between (D) or on the side opposite to the transparent conductive layer (C) of the transparent polymer substrate (D), The silicon compound (B1) having the epoxy and alkoxysilyl groups is represented by the formula (1), and the silicon compound (B2) having the amino and alkoxysilyl groups is represented by the formula (2). (Formula 1)

Wherein R ¹ is alkylene having 1 to 4 carbon atoms, R ² and R ³ are independently alkyl having 1 to 4 carbon atoms,   X is glycidoxy or epoxycyclohexyl,   n is 0 or 1; (Formula 2)

Wherein R ⁴ is alkylene having 1 to 4 carbon atoms, R ⁵ and R ⁶ are independently alkyl having 1 to 4 carbon atoms,   Y is hydrogen or aminoalkyl,   m is 0 or 1;  The liquid crystal display device according to claim 1, wherein the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula. 1/9 ≦ (B ₃ ) / [(B ₁ ) + (B ₂ )] ≦ 9/1 (by weight), and 1/9 ≤ (b ₁ ) / (b ₂ ) ≤ 9/1 (in moles) Wherein B ₁ to B ₃ each represent an amount expressed by the weight of the compounds (B1) to (B3), b ₁ represents the amount of the compound (B1) based on the moles of the epoxy group, and b ₂ is The amount of compound (B2) is shown based on the total moles of amino and imide groups.  The silicon compound represented by the formula (1) according to claim 1 or 2, wherein the silicon compound represented by the formula (1) is composed of 3-glycidoxyoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The silicon compound represented by the formula (2) is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N A liquid crystal display device selected from the group consisting of-(2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.  The polyvinyl alcohol polymer according to claim 1 or 2, wherein the polyvinyl alcohol polymer is selected from the group consisting of polyvinyl alcohol having a saponification degree of 80% or more, ethylene-vinyl alcohol copolymer and polyvinyl alcohol having a silyl group in a molecule thereof. Liquid crystal display device characterized in that. The liquid crystal display device according to claim 1 or 2, wherein the metal oxide layer comprises SiO _x (where x is 1.5 ≦ x ≦ 2.0).  The method according to claim 1 or 2, wherein the at least one electrode substrate comprises components (C) / (B) / (A) / (D) / (B) or (B) / (A) / (D) / A liquid crystal display device comprising the structures (B) / (C) in this order.  The method according to claim 1 or 2, wherein the at least one electrode substrate comprises components (C) / (A) / (B) / (D) / (B) or (A) / (B) / (D) / A liquid crystal display device comprising the structures (B) / (C) in this order.  The method according to claim 1 or 2, wherein the at least one electrode substrate comprises components (C) / (B) / (A) / (B) / (D) / (B) or (B) / (A) / A liquid crystal display device comprising the structures (B) / (D) / (B) / (C) in this order.  The liquid crystal display device according to claim 1 or 2, wherein the transparent polymer substrate is selected from the group consisting of polycarbonate, polyarylate, polysulfone and polyether sulfone.  The method according to claim 1 or 2, i) the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula: 1/9 ≦ (B ₃ ) / [(B ₁ ) + (B ₂ )] ≦ 9/1 (by weight), and 1/9 ≤ (b ₁ ) / (b ₂ ) ≤ 9/1 (in moles) Wherein B ₁ to B ₃ each represent an amount expressed by the weight of the compounds (B1) to (B3), b ₁ represents the amount of the compound (B1) based on the moles of the epoxy group, and b ₂ is The amount of Compound (B2) based on the total moles of amino and imide groups; ii) the silicon compound represented by the formula (1) is selected from the group consisting of 3-glycidoxyoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; iii) The silicon compound represented by the formula (2) is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; iv) the polyvinyl alcohol polymer is an ethyl-polyvinyl alcohol copolymer having an ethylene content of 10 to 50 mol%; v) the metal oxide layer comprises SiO _x (x is 1.5 ≦ x ≦ 2.0); vi) the transparent polymer substrate is selected from the group consisting of polycarbonate, polyarylate, polysulfone and polyether sulfone.  The method of claim 1 or 2, wherein the electrode substrate is i) the change in haze value is not more than 1% when N-methylpyrrolidone is contacted with and washed with the cured polymer layer surface of the electrode substrate at 25 ° C. for 10 minutes; ii) A 3.5% NaOH aqueous solution is contacted with the cured polymer layer surface of the electrode substrate at 25 ° C. for 10 minutes and satisfies a condition that does not deteriorate when washed with water.  The liquid crystal layer consists of two electrode substrates interposed therebetween, wherein at least one of the electrode substrates comprises: A) a metal oxide layer, B) a cured polymer layer adjacent the metal oxide layer; C) a transparent conductive layer; And D) consists of a transparent polymer substrate having a delay of 30 nm or less for a wavelength of 590 nm, The transparent conductive layer (C) is formed on the liquid crystal layer surface of the transparent polymer substrate (D), and the combination of the metal oxide layer (A) and the cured polymer layer (B) is the transparent conductive layer (C) and the transparent polymer substrate. It is arranged between (D) or on the surface facing the transparent conductive layer (C) of the transparent polymer substrate (D), The curable polymer layer is a liquid crystal display device comprising a crosslinked polyvinyl alcohol polymer having a unit represented by the formula (3). (Formula 3)

 Wherein p is an integer from 0 to 5,  q is an integer from 0 to 5, A is the following formula

or

Wherein R ⁷ and R ⁸ are independently hydrogen, methyl, ethyl or phenyl, and l is 0 or 1, and B is the following formula

(Wherein r is an integer of 0 to 5 and s is an integer of 0 to 2), wherein * 2 and * 3 are positions bonded to each other.  13. The method of claim 12, wherein the cured polymer layer is obtained from a crosslinking reaction of a silicon compound having an epoxy and alkoxysilyl group represented by the formula (1) and a silicon compound having an amino and alkoxysilyl group represented by the formula (2). Liquid crystal display device. (Formula 1)

Wherein R ¹ is alkylene having 1 to 4 carbon atoms, R ² and R ³ are independently alkyl having 1 to 4 carbon atoms,   X is glycidoxy or epoxycyclohexyl,   n is 0 or 1; (Formula 2)

Wherein R ⁴ is alkylene having 1 to 4 carbon atoms, R ⁵ and R ⁶ are independently alkyl having 1 to 4 carbon atoms,   Y is hydrogen or aminoalkyl,   m is 0 or 1;  Ingredients of A) a metal oxide layer, B) adjacent the metal oxide layer, B1) silicon compounds having epoxy and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; B2) silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; And B3) Cured polymer layer obtained from the crosslinking reaction of a polyvinyl alcohol-type polymer; C) a transparent conductive layer; And D) consists of a transparent polymer substrate having a delay of 30 nm or less for a wavelength of 590 nm, The combination of the metal oxide layer (A) and the cured polymer layer (B) is disposed between the transparent conductive layer (C) and the transparent polymer substrate (D), or the transparent conductive layer (C) of the transparent polymer substrate (D) ) On the side opposite to The silicon compound (B1) having the epoxy and alkoxysilyl groups is represented by the formula (1), and the silicon compound (B2) having the amino and alkoxysilyl groups is represented by the formula (2). (Formula 1)

Wherein R ¹ is alkylene having 1 to 4 carbon atoms, R ² and R ³ are independently alkyl having 1 to 4 carbon atoms,   X is glycidoxy or epoxycyclohexyl,   n is 0 or 1; (Formula 2)

Wherein R ⁴ is alkylene having 1 to 4 carbon atoms, R ⁵ and R ⁶ are independently alkyl having 1 to 4 carbon atoms,   Y is hydrogen or aminoalkyl,   m is 0 or 1;  The transparent electrode substrate according to claim 14, wherein the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula. 1/9 ≦ (B ₃ ) / [(B ₁ ) + (B ₂ )] ≦ 9/1 (by weight), and 1/9 ≤ (b ₁ ) / (b ₂ ) ≤ 9/1 (in moles) Wherein B ₁ to B ₃ each represent an amount expressed by the weight of the compounds (B1) to (B3), b ₁ represents the amount of the compound (B1) based on the moles of the epoxy group, and b ₂ is The amount of compound (B2) is shown based on the total moles of amino and imide groups.  The method of claim 14 or 15, wherein the silicon compound represented by the formula (1) is selected from the group consisting of 3-glycidoxyoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The silicon compound represented by the formula (2) is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N A transparent electrode substrate, characterized in that it is selected from the group consisting of-(2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.  16. The polyvinyl alcohol polymer according to claim 14 or 15, wherein the polyvinyl alcohol polymer is selected from the group consisting of polyvinyl alcohol having a saponification degree of 80% or more, ethylene-vinyl alcohol copolymer and polyvinyl alcohol having a silyl group in a molecule. Transparent electrode substrate, characterized in that.  16. The transparent electrode substrate of claim 14 or 15, wherein the polyvinyl alcohol polymer is an ethylene-vinyl alcohol copolymer having an ethylene content of 10 to 50 mol%. 16. The transparent electrode substrate of claim 14 or 15, wherein the metal oxide layer comprises SiO _x (x is 1.5 ≦ x ≦ 2.0).  The transparent electrode substrate according to claim 14 or 15, wherein the transparent polymer substrate is selected from the group consisting of polycarbonate, polyarylate, polysulfone and polyether sulfone.  The component (C) / (B) / (A) / (D) / (B) or (B) / (A) / (D) / (B) / (C) according to claim 14 or 15. Transparent electrode substrate comprising the structure of this order.  The component (C) / (A) / (B) / (D) / (B) or (A) / (B) / (D) / (B) / (C) according to claim 14 or 15. Transparent electrode substrate comprising the structure of this order.  The component (C) / (B) / (A) / (B) / (D) / (B) or (B) / (A) / (B) / (D) according to claim 14 or 15. A transparent electrode substrate comprising the structure of / (B) / (C) in this order.  The method of claim 14 or 15, wherein any one of the metal oxide layer (A), the cured polymer layer (B) and the transparent conductive layer (C) is disposed on the transparent polymer substrate (D), the ( An anchor layer (α) selected from the group consisting of a silane coupler, a thermoplastic resin, a radiation-curable resin and a heat-curable resin is further disposed between D) and (A), (B) or (C). Transparent electrode substrate.  The method according to claim 14 or 15, i) the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula: 1/9 ≦ (B ₃ ) / [(B ₁ ) + (B ₂ )] ≦ 9/1 (by weight), and 1/9 ≤ (b ₁ ) / (b ₂ ) ≤ 9/1 (in moles) Wherein, B ₁ to B ₃ each represent an amount expressed by the weight of the compounds (B1) to (B3), b ₁ represents the amount of the compound (B1) based on the moles of the epoxy groups, b ₂ Represents the amount of compound (B2) based on the total moles of amino and imide groups); ii) the silicon compound represented by the formula (1) is selected from the group consisting of 3-glycidoxyoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; iii) The silicon compound represented by the formula (2) is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; iv) the polyvinyl alcohol polymer is an ethyl-polyvinyl alcohol copolymer having an ethylene content of 10 to 50 mol%; v) the metal oxide layer comprises SiO _x (x is 1.5 ≦ x ≦ 2.0); vi) The transparent polymer substrate is selected from the group consisting of polycarbonate, polyarylate, polysulfone and polyether sulfone.  The method according to claim 14 or 15, i) the change in haze value is not more than 1% when N-methylpyrrolidone is contacted with and washed with the cured polymer layer surface of the electrode substrate at 25 ° C. for 10 minutes; ii) A 3.5% NaOH aqueous solution is brought into contact with the cured polymer layer surface of the electrode substrate at 25 ° C. for 10 minutes and satisfies the condition that it does not deteriorate when washed with water.  The following ingredients: A) a metal oxide layer, B) a cured polymer layer adjacent to the metal oxide layer; C) a transparent conductive layer; And D) consists of a transparent polymer substrate having a delay of 30 nm or less for a wavelength of 590 nm, The combination of the metal oxide layer (A) and the cured polymer layer (B) is disposed between the transparent conductive layer (C) and the transparent polymer substrate (D), or the transparent conductive layer (C) of the transparent polymer substrate (D) Is arranged on the side opposite to The curable polymer layer is a transparent electrode substrate comprising a cross-linked polyvinyl alcohol polymer having a unit represented by the formula (3). (Formula 3)

Wherein p is an integer from 0 to 5, q is an integer from 0 to 5, A is the following formula

or

Wherein R ⁷ and R ⁸ are independently hydrogen, methyl, ethyl or phenyl, and l is 0 or 1, and B is the following formula

(Wherein r is an integer of 0 to 5 and s is an integer of 0 to 2), wherein * 2 and * 3 are positions bonded to each other.  28. The transparent material as claimed in claim 27, wherein the cured polymer layer is obtained from a crosslinking reaction of a silicon compound having an epoxy and alkoxysilyl group represented by the formula (1) and a silicon compound having an amino and alkoxysilyl group represented by the formula (2). Electrode substrate. (Formula 1)

Wherein R ¹ is alkylene having 1 to 4 carbon atoms, R ² and R ³ are independently alkyl having 1 to 4 carbon atoms,   X is glycidoxy or epoxycyclohexyl,   n is 0 or 1; (Formula 2)

Wherein R ⁴ is alkylene having 1 to 4 carbon atoms, R ⁵ and R ⁶ are independently alkyl having 1 to 4 carbon atoms,   Y is hydrogen or aminoalkyl,   m is 0 or 1;  A) a metal oxide layer, B) B1) silicon compounds having epoxy and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof;    B2) silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; And    B3) Cured polymer layer obtained from the crosslinking reaction of a polyvinyl alcohol-type polymer; And D) a transparent polymer substrate having a delay of 30 nm or less with respect to a wavelength of 590 nm, The metal oxide layer (A) and the cured polymer layer (B) are adjacent to each other, The silicon compound (B1) having the epoxy and alkoxysilyl groups is represented by the formula (1), and the silicon compound (B2) having the amino and alkoxysilyl groups is represented by the formula (2). (Formula 1)

Wherein R ¹ is alkylene having 1 to 4 carbon atoms, R ² and R ³ are independently alkyl having 1 to 4 carbon atoms,   X is glycidoxy or epoxycyclohexyl,   n is 0 or 1; (Formula 2)

Wherein R ⁴ is alkylene having 1 to 4 carbon atoms, R ⁵ and R ⁶ are independently alkyl having 1 to 4 carbon atoms,   Y is hydrogen or aminoalkyl,   m is 0 or 1;  The method of claim 29, i) oxygen permeability is below 10 cm ³ / m ² / day / atm at 40 ° C. and 90% RH; ii) the change in haze value is 1% or less when N-methylpyrrolidone is contacted with and washed with the cured polymer layer surface of the polymer substrate at 25 ° C. for 10 minutes; iii) 3.5% aqueous NaOH solution was brought into contact with the cured polymer layer surface of the polymer substrate at 25 ° C. for 10 minutes and was not degraded when washed; iv) A polymer substrate, wherein the 5.0% aqueous HCl solution is brought into contact with the cured polymer layer surface of the polymer substrate for 10 minutes at 25 ° C. and satisfies the condition that it does not deteriorate when washed with water.  D) a transparent polymer substrate having a delay of 30 nm or less for a wavelength of 590 nm; A) a metal oxide layer formed on the first surface of the transparent polymer substrate; B-1) adjacent to the metal oxide layer, B1) silicon compounds having epoxy and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; B2) silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; And B3) a first cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer; And B-2) on a second side of the transparent polymer substrate opposite the first side, B1) silicon compounds having epoxy and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; B2) silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; And B3) a second cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer, The silicon compound (B1) having the epoxy and alkoxysilyl groups is represented by the formula (1), and the silicon compound (B2) having the amino and alkoxysilyl groups is represented by the formula (2). (Formula 1)

Wherein R ¹ is alkylene having 1 to 4 carbon atoms, R ² and R ³ are independently alkyl having 1 to 4 carbon atoms,   X is glycidoxy or epoxycyclohexyl,   n is 0 or 1; (Formula 2)

Wherein R ⁴ is alkylene having 1 to 4 carbon atoms, R ⁵ and R ⁶ are independently alkyl having 1 to 4 carbon atoms,   Y is hydrogen or aminoalkyl,   m is 0 or 1;  B1) silicon compounds having epoxy and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; B2) silicon compounds having amino and alkoxysilyl groups, their full or partial hydrolysis products, their full or partial condensation products, or mixtures thereof; And B3) polyvinyl alcohol polymer B4) carboxylic acid; B5) organic solvents; And B6) water Coating composition, characterized in that consisting of.  The coating composition according to claim 32, wherein the compounds (B1) to (B3) are used in an amount satisfying the following formula. 1/9 ≦ (B ₃ ) / [(B ₁ ) + (B ₂ )] ≦ 9/1 (by weight), and 1/9 ≤ (b ₁ ) / (b ₂ ) ≤ 9/1 (in moles) Wherein B ₁ to B ₃ each represent an amount expressed by the weight of the compounds (B1) to (B3), b ₁ represents the amount of the compound (B1) based on the moles of the epoxy group, and b ₂ is The amount of compound (B2) is shown based on the total moles of amino and imide groups.

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