A liquid crystal display element having a transparent electrode substrate and a transparent electrod

专利摘要:
The liquid crystal display element comprises: A) a metal oxide layer; B) a silicon compound adjacent to the metal oxide layer, the epoxy compound having epoxy and alkoxysilyl groups, a complete or partial hydrolysis product thereof; B2) silicon compounds having amino and alkoxysilyl groups, their hydrolysis or condensation products; And B3) a cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer; C) a transparent conductive layer and D) a transparent polymer substrate. A transparent electrode substrate comprising a substrate (D), a metal oxide layer (A) and the cured polymer layer (B) is also provided.
公开号:KR19980018054A
申请号:KR1019970010210
申请日:1997-03-25
公开日:1998-06-05
发明作者:도루 하나다；가즈오 야하타；유지 다무라
申请人:이타가키 히로시；데이진 가부시키가이샤；
IPC主号:

专利说明:

A liquid crystal display element having a transparent electrode substrate and a transparent electrode substrate
1. Field of the Invention
The present invention relates to a liquid crystal display device having a transparent electrode substrate excellent in optical isotropy, smoothness, durability, chemical resistance or solvent resistance, water barrier property, gas barrier property, A touch panel, a photosensitive conductor, a flat fluorescent material,
1. Description of related field
BACKGROUND OF THE INVENTION Recently, portable information devices such as wireless paging receivers, portable telephones, electronic notebooks, and portable information terminals have become popular and business and lifestyle are rapidly changing. In order to improve the portability of the information device, it is required to make the information device thinner, lighter, and more durable.
Conventionally, a heavy, thick and fragile glass substrate is used for a transparent conductive substrate of an LCD device or a touch panel. As an alternative material, a transparent resin substrate has been proposed, and since the transparent resin substrate can be processed by a roll-to-roll system, there is an advantage of cost reduction for manufacturing of LCD and the like. However, transparent resin substrates are inferior to glass substrates in durability, chemical resistance 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 LDC element, gas barrier properties can be improved by providing a metal oxide layer on a transparent resin substrate. In the step of removing the resist after patterning the transparent electrode, in the step of contacting the metal oxide layer with the alkali solution to dissolve the metal oxide layer and form the liquid crystal alignment layer, the liquid crystal alignment layer containing N-methylpyrrolidone or another solvent There is a problem that the transparent resin substrate which is in contact with the solvent is damaged or swelled or swelled, for example.
In order to solve the above problems, there are several proposals for laminating a layer having gas barrier properties and endurance property on a transparent resin substrate. For example, Japanese Unexamined Patent Publication Nos. 5-52002 and 5-52003 propose a transparent substrate composed of a polymer film having improved adhesion and moisture barrier property and an oxygen gas barrier layer made of polyvinyl alcohol. However, the polyvinyl alcohol-based polymer layer disposed as the outermost layer does not have sufficient chemical resistance and thus causes problems during the production of the liquid crystal cell. By providing an additional layer of chemical resistance, the chemical resistance can be given, but the cost is increased.
Japanese Patent Application Laid-Open Nos. 2-137922 and 5-309794 provide a transparent substrate made of a flow chart 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. Although the solvent resistance of this transparent substrate is sufficient, the gas barrier property at high humidity is deteriorated due to the property of the gas barrier single-layer material, and the six-layer structure increases the manufacturing cost.
In addition, the following requirements are required for a transparent substrate of a liquid crystal display device, and there are problems in properties other than chemical resistance and gas barrier properties.
If the plate has low transparency or birefringence, coloration of display and deterioration of contrast occur.
If the surface smoothness of the substrate is low, the gap to the liquid-phase layer becomes uneven, the liquid crystal alignment may become disordered, or the substrate may become optically uneven. As a result, the display color becomes uneven.
Furthermore, if the smoothness, transparency and gas parasitism of the substrate are deteriorated by mechanical or thermal influences or by contact with the solvent, the benefits of brightness, the possibility of a wide range of shape degrees of freedom, , Pen-input devices, etc., because they are subject to substantial external mechanical or thermal influences. Particularly, in consideration of resistance to mechanical effects, excellent interlayer adhesion is required to maintain such favorable properties.
An object of the present invention is to provide a liquid crystal display element having a transparent resin substrate having excellent resistance to chemicals, solvent resistance, gas barrier property, transparency, smoothness, adhesiveness, and the like,
These and other objects and aspects of the present invention can be achieved by providing:
(I) A liquid crystal display element comprising two electrode substrates with a liquid crystal layer interposed therebetween, wherein at least one of the electrode substrates has the following composition:
A) a metal oxide layer,
B) B1) a silicon compound having an epoxy group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof,
B2) a silicon compound having an amino group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture 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) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm,
The transparent conductive layer (C) is formed on the liquid crystal layer side of the transparent polymer substrate (D), and the combination of the metal oxide layer (A) and the cured polymer layer (B) Is arranged between the substrates (D) or on a surface facing the transparent conductive layer (C) of the transparent polymer substrate (D).
(II) A liquid crystal display element comprising two electrode substrates with a liquid crystal layer interposed therebetween, wherein at least one of the electrode substrates has the following composition:
A) a metal oxide layer,
B) a cured polymer layer in contact with the metal oxide layer,
C) a transparent conductive layer, and
D) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm, wherein the transparent conductive layer (C) is formed on a liquid crystal layer surface of the transparent polymer substrate (D), and the metal oxide layer The combination of the cured polymer layer (B) is disposed between the transparent conductive layer (C) and the transparent polymer substrate (D), or disposed on a surface of the transparent polymer substrate (D) opposite to the transparent conductive layer (C)
The cured polymer layer is composed of a cross-linked polyvinyl alcohol polymer with units represented by the following formula (1)
[Chemical Formula 1]

Wherein p is an integer of 0 to 5,
q is an integer of 0 to 5,
A is
(2)

(3)

, Wherein R ⁷ and R ⁸ are independently hydrogen, methyl, ethyl or phenyl, and l is 0 or 1;
B is
[Chemical Formula 4]

, R is an integer of 0 to 5, s is an integer of 0 to 2,
* 2 and * 3 are sites bonded to each other.
(III) a transparent electrode substrate comprising the following components:
A) a metal oxide layer,
B) B1) a silicon compound having an epoxy group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof,
B2) a silicon compound having an amino group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof, and
B3) a cured polymer layer in contact with the metal oxide layer obtained from a crosslinking reaction of the polyvinyl alcohol polymer,
C) a transparent conductive layer, and
D) a transparent polymer substrate having a retardation of 30 mm or less with respect to a wavelength of 590 nm, wherein the combination of the metal oxide layer (A) and the cured polymer layer (B) is composed of the transparent conductive layer (C) (D) or on a surface facing the transparent conductive layer (C) of the transparent polymer substrate (D).
(IV) A transparent electrode substrate composed of the following components:
A) a metal oxide layer,
B) a cured polymer layer in contact with the metal oxide layer,
C) a transparent conductive layer, and
D) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm, wherein the combination of the metal oxide layer (A) and the cured polymer layer (B) (D) or disposed on a surface of the transparent polymer substrate (D) opposite to the transparent conductive layer (C)
The cured polymer layer is composed of a cross-linked polyvinyl alcohol polymer with units represented by the following formula (1)
(Formula 1)

Wherein p is an integer of 0 to 5,
q is an integer of 0 to 5,
A is
(2)

(Formula 3)

Wherein R ⁷ and R ⁸ are independently hydrogen, methyl, ethyl or phenyl, and l is 0 or 1;
B is
(Formula 4)

, R is an integer of 0 to 5, s is an integer of 0 to 2,
* 2 and * 3 are sites bonded to each other.
(V) Goods made up of:
(D) a substrate; And
(B) B1) a silicon compound having an epoxy group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof,
B2) a silicon compound having an amino group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof, and
B3) a cured polymer layer in contact with the metal oxide layer obtained from a crosslinking reaction of the polyvinyl alcohol polymer,
(VI) Process for preparing a coated article comprising the following steps:
a) B1) a silicon compound having an epoxy group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof,
B2) a silicon compound having an amino group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof, and
B3) a polyvinyl alcohol polymer;
B4) carboxylic acid;
B5) organic solvent; And
B6) water;
≪ / RTI >
b) coating the substrate with the composition; And
c) curing the coating compound by a cross-linking reaction between the compounds (B1) to (B3) to form a cured polymer layer on the substrate.
(VII)
B1) a silicon compound having an epoxy group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof,
B2) a silicon compound having an amino group and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof, and
B3) a polyvinyl alcohol polymer;
B4) carboxylic acid;
B5) organic solvent; And
B6) water;
≪ / RTI >
1 is a 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,
Fig. 3 schematically shows a hybrid reaction of a polyvinyl alcohol polymer and an alkoxysilane,
Figures 4A and 4B show the oxygen permeability of the gas barrier layer,
5 is a cross-sectional view of a cross-section of a gas-gauge laminate of a polycarbonate film and a SiOx layer,
Figures 6a-c show the combined effect of hybrid and SiOx layers,
Figure 7 shows the alkaline resistance of the hybrid layer,
Figure 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,
Figures 10a to 10d and 11a to 11f show various arrangements of the components (A) to (D) of the present invention.
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 make a display such as characters and images. A substrate of a liquid crystal display element is usually inorganic glass, but a liquid crystal display element using a plastic substrate can be made thinner and lighter, curved display can be performed, strength is provided, and the main purpose is to reduce manufacturing cost Dragging.
1 shows an example of a liquid crystal display element in which an upper substrate 11 and a lower substrate 13 are arranged so as to face each other and an outer peripheral portion of the substrates 11 and 13 is sealed with a sealing material 15, ) Material 21 is dispersed between the substrates 11 and 13, and the liquid crystal cell 17 is formed in this way to fill the liquid crystal material 19. The polarizing plate is provided to interpose the cell 17 to form a TN-type 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 the 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 an ethylene-vinyl alcohol copolymer, a solvent-containing layer 4 and a transparent conductive layer 4 of ITO. The polycarbonate film 1 is about 100 탆 thick and the other layers 2 to 4 are several 탆 thick.
The liquid crystal display element of the present invention is composed of two electrode substrates, and at least one of them comprises a metal oxide layer (A), a cured polymer layer (B), a transparent conductive layer (C) and a transparent polymer substrate (D).
The transparent polymer substrate (D)
The transparent polymer (D) used in the present invention is not particularly limited as long as it has optical isotropy or a retardation of 30 nm or less with respect to a wavelength of 590 nm. The retardation is expressed as the product of [Delta] n d, where [Delta] n represents the refractive index difference of the birefringence for a wavelength of 590 nm, which can be measured with a conventional device, and d represents the thickness of the substrate. If the delay is more than 30nm, there is a problem of coloring and view 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 which can satisfy the above conditions include polyester resins, polycarbonate resins, polyarylate resins, polysulfone resins such as polysulfone, polyethersulfone and polyarylsulfone, polyolefin resins, acetate such as cellulose triacetate Polystyrene resins, acrylic resins, and various thermosetting resins. Of these, a transparent polymer substrate composed of a polycarbonate resin as a main component is most preferable from the viewpoints of high optical transparency and low optical anisotropy.
The thickness of the transparent polymer substrate is usually 30 μm to 800 μm.
The metal oxide layer (A)
The metal oxide layer (A) used in the present invention may be composed of an insulating metal oxide such as oxides of silicon, aluminum, magnesium and zinc. The transparent insulating metal oxide layer may be deposited by known sputtering, vapor deposition, ion plating, plasma enhanced CVD, and the like. Silicon oxide is particularly preferable as the metal oxide for the moisture barrier layer from the viewpoint of transparency, surface smoothness or uniformity, flexibility, layer stress, cost, and the like.
The composition of the silicon oxide can be analyzed and determined by X-ray photoelectron spectroscopy, X-ray microscopy, Auger electron analyzer, Rutherford back scattering, etc. The silicon oxide having an average composition represented by SiOx (1.5fxf2) It is preferable for light transmission and flexibility. If the value of x is less than 1.5, flexibility and transparency are deteriorated. The silicon oxide having an average composition represented by SiOx (1.5fxf2) may further contain other metals such as magnesium, iron, nickel, chromium, titanium, aluminum, indium, zinc, tin, antimony, tungsten, molybdenum and copper. The silicon oxide may further contain a fluoride or carbon to increase flexibility. The amount of such additive 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 permeates the substrate, thereby reducing gas barrier properties. If the thickness exceeds 200 nm, the transparency of the layer is lowered, the flexibility is poor, and cracking is caused, so that the gas barrier property is reduced.
The cured polymerized layer (B)
The cured polymer layer (B) used in the present invention has the following components:
B1) a silicon compound having an epoxy and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof or a mixture thereof; And
B3) Polyvinyl alcohol polymer
By the cross-linking reaction.
The cured polymer layer (B) is formed adjacent to or in contact with the metal oxide layer.
The components (B1) to (B3) are described below:
The polyvinyl alcohol polymer (B3)
The polyvinyl alcohol-based polymer (B3) of the present invention may be a known one, and is commercially available. Preferably, the polyvinyl alcohol polymer (B3) comprises at least 50 mol% of the polyvinyl alcohol component and / or the polyvinyl alcohol-copolymer component.
Examples of the polyvinyl alcohol copolymer include a vinyl alcohol-vinyl acetate copolymer, a vinyl alcohol-vinyl butylal copolymer, an ethylene-vinyl alcohol copolymer, and a vinyl alcohol-based alcohol having a silyl group in two molecules.
In general, polyvinyl alcohol, an ethylene-vinyl alcohol copolymer having a saponification degree of 80% or more and a polyvinyl alcohol polymer having a silyl group in its molecule are preferable.
The ethylene-vinyl alcohol copolymer four ethylene content is preferably 50% or less. If the ethylene content exceeds 50%, the desired gas barrier monolayer of the cured polymer layer can be obtained.
The polyvinyl alcohol polymer having a silyl group in the molecule has a reactive silyl group represented by the following formula (5)
[Chemical Formula 5]
Wherein R ¹¹ represents hydrogen, an alkyl, acyl, alkali metal or alkaline earth metal having 1 to 10 carbon atoms, R ¹² represents alkyl having 1 to 10 carbon atoms, and r is an integer of 1 to 3.
The silyl group in the molecule may be an end group of the polyvinyl alcohol polymer. The position, distribution, etc. of the silyl group in the molecule are not limited unless the silyl group is bonded to the polyvinyl alcohol polymer through the 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 tends to adversely become viscous and gel.
The polymerization degree and saponification degree of the polyvinyl alcohol polymer of the present invention are not particularly limited, but the average polymerization degree is preferably 100 to 5000, and the saponification degree is preferably 70% or more, and 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 difficult to coat.
If the saponification degree is too low, sufficient gas barrier property can not be obtained.
Silicon compound (B1) having an epoxy and alkoxysilyl group
The compound (B1) of the present invention is a silicon compound having an epoxy group and a silyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof. Preferred silicon compounds having epoxy and alkoxysilyl groups are represented by the following formula 1:
[Chemical Formula 6]
Wherein R < ¹ > is alkylene having from 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 group and an alkoxysilyl group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyltripropoxysilane, glycidoxymethyltributoxysilane , 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltripropoxysilane, 2-glycidoxyethyltributoxysilane, 1-glycidoxy Ethyl trimethoxysilane, 1-glycidoxyethyltriethoxysilane, 1-glycidoxyethyltripropoxysilane, 1-glycidoxymethyltributoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltributoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyl Triethoxysilane, 1-glycidoxy (3,4-epoxycyclohexyl) methyltriethoxysilane, (3, 4-epoxycyclohexyl) methyltriethoxysilane, (3, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3-epoxycyclohexyl) ethyltrimethoxysilane, 2- Epoxycyclohexyl) ethyl triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3,4-epoxycyclohexyl) (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) - (3,4-epoxycyclohexyl ) 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-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
These silicon compounds may be used alone or in combination.
The silicon compound (B2) having amino and alkoxysilyl groups
The compound (B2) of the present invention is a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof. Preferred silicon compounds having amino and alkoxysilyl groups are represented by the following formula (7)
(7)
Wherein R < ⁴ > is alkylene having from 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- Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, Aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 2-aminopropyltripropoxysilane, 2-aminoethyltributoxysilane, 1-aminoethyl Aminopropyltriethoxysilane, 1-aminopropyltripropoxysilane, 1-aminopropyltributoxysilane, N-aminomethylaminomethyltriethoxysilane, N-aminomethylaminomethyltriethoxysilane, Propoxy silane, N-aminomethane Aminomethyl-2-aminoethyltrimethoxysilane, N-aminomethyl-2-aminoethyltriethoxysilane, N-aminomethyl- Aminomethyl-3-aminopropyltriethoxysilane, N-aminomethyl-3-aminopropyltrimethoxysilane, N-aminomethyl- Aminopropyltriethoxysilane, N-aminopropyltriethoxysilane, N- (2-aminoethyl) - N-aminopropyltriethoxysilane, N- Aminoethyltrimethoxysilane, N- (2-aminoethyl) -2-aminoethyltriethoxysilane, N- (2-aminoethyl) Aminoethyltrimethoxysilane, N- (2-aminoethyl) -1-aminoethyltriethoxysilane, N- (2-aminoethyl) Aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, 3-diethylenetriaminopropyltriethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, trimethoxysilylpropyldiethylenetriamine, and the like .
Particularly preferred silicon compounds (B2) having amino and alkoxysilyl groups are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methyl- Methoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl-3-aminopropylmethyldimethoxysilane.
These silicon compounds having amino and alkoxysilyl groups may be used alone or in combination.
The hydrolysis and condensation products (B1) and (B2)
The complete or partial hydrolysis product, or the complete or partial condensation product, of the silicon compound is obtained through a so-called sol-gel reaction of the silicon compound. The condensation product of the silicon compound may include not only the condensation product between the silicon compounds but also the condensation product between the unreacted silicon compound and the complete or partial hydrolysis product of the silicon compound.
The compounds (B1) and (B2) used as the starting material may be the silicon compound itself or a hydrolysis product or condensation product already prepared.
The 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, an alkali such as sodium hydroxide, or only water. The hydrolysis can be carried out after mixing the silicon compound and the solvent to make the hydrolysis uniform. If heating or cooling is required, it can be carried out during hydrolysis. Alternatively, after hydrolysis by heating and / or evaporation, a solvent such as an alcohol may be removed or an appropriate solvent may be further added.
Crosslinking reaction
By reacting the above-mentioned compounds (B1) to (B3) according to the present invention, the cured polymer layer has a combination of excellent chemical resistance, solvent resistance, gas barrier property and adhesive property, optical isotropy, surface smoothness, durability, moisture barrier property, Lt; / RTI >
By using a combination of the silicon compound (B1) having epoxy and alkoxysilyl groups and the silicon compound (B2) having amino and alkoxysilyl groups in this reaction,
(1) not only the reaction of the silanol period of the alkoxysilyl group,
(2) the reaction between the epoxy and the amino term,
(3) It is believed that the reaction between the silanol group of the alkoxysilyl group and the hydroxyl group of the polyvinyl alcohol polymer occurs as the main reaction. Thus, the reaction between the two kinds of silicon compounds and the crosslinking product of the polyvinyl alcohol polymer results in the formation of a cured product, and as a result, the reaction product exhibits excellent chemical resistance or solvent properties and other properties.
Crosslinked polymer
As a result of this reaction, it is believed that the reaction product of the present invention comprises a chemical bond represented by the following formula:
(Formula 1)
Wherein p is an integer of 0 to 5,
q is an integer of 0 to 5,
A is
(2)
(Formula 3)
, Wherein R ⁷ and R ⁸ are independently hydrogen, methyl, ethyl or phenyl, and 1 is 0 or 1;
B is
(Formula 4)
, R is an integer of 0 to 5, s is an integer of 0 to 2,
* 2 and * 3 are sites bonded to each other.
The structure of the main crosslinking of the present invention may further include a structure consisting of the above-described structural formula (3) or a structure represented by the following structural formulas (8) and (9)
[Chemical Formula 8]
[Chemical Formula 9]
Wherein the symbol is as defined in Chemical Formula (1).
The composition of component (B)
It is preferable that the ratio between the compounds (B1) to (B3) used satisfies the following formula.
_{1/9 f (B 3) / [} (B 1) + (B 2)] f 9/1, and a weight ratio of _{1/9 f (b 1) / [} (b 2) f 9/1, the molar ratio
Wherein B ₁ to B ₃ each represent the weight of the compounds (B ₁ ) to (B ₃ ); b ₁ represents the amount of the compound (B1) based on the mole of the epoxy group; and b ₂ represents the amount of the compound (B2) based on the total moles of amino and imino groups. More specifically, B ₁ and B ₂ are calculated on the basis of the weights of the following compounds (6a) and (7a), respectively:
(Formula 6a)
(Formula 7a)
For example, when 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 B ₁ is 90 parts by weight.
When the ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] exceeds 9/1, the water resistance and chemical resistance are liable to be lowered. When the ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] is less than 9/1, the gas barrier properties are reduced. The preferable range of the ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] is 2/8 to 8/2, more preferably 1/3 to 3/1. 1/9 (B ₃ ) / [(B ₁ ) + (B ₂ )] 4/1 is preferable for interlayer adhesion when the transparent conductive layer C is laminated on the cured polymer layer (B). When silyl-containing polyvinyl alcohol is used, the preferred ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] is 2/1 to 1/9.
The combined effect of the properties of component (B) and components (A) and (B)
The cured polymer layer (B) obtained by the cross-linking reaction has excellent chemical resistance or solvent resistance, gas barrier property and adhesiveness, as well as other properties required for a transparent electrode substrate.
As described above, the polyvinyl alcohol-based polymer may have gas barrier properties, but is deteriorated in water or a high humidity atmosphere and has poor adhesion to polycarbonate or other polymer substrate and metal oxide layer. Some of these defects can be improved by adding a chemical resistant layer, an anchor layer and an anchor layer, but that adds manufacturing cost and gas breakdown is still not high enough.
The data shown in the following table are properties of a transparent polymer substrate, one of which is a commercially available product based on an ethylene-vinyl alcohol copolymerization system (prior art), and one obtained by the present invention (present invention). The properties shown are measured by the method described below in the Examples.
[table]
It is possible that the transparent electrode substrate has the following excellent chemical resistance:
i) a haze value change of 1% or less when N-methylpyrrolidone is contacted with the cured polymer layer side of the transparent electrode substrate at 25 占 폚 for 10 minutes and subsequently washed;
ii) no deterioration when a 3.5% -NaOH aqueous solution was contacted with the cured polymer layer side of the transparent electrode substrate at 25 占 폚 for 10 minutes and subsequently rinsed; And
iii) No deterioration when a 5.0% -HCl aqueous solution was contacted with the cured polymer layer side of the transparent electrode substrate at 25 占 폚 for 10 minutes and subsequently rinsed.
Moreover, the cured polymer layer (B) can be bonded to a transparent polymer substrate, especially a polycarbonate and a metal oxide layer, particularly silicon oxide.
As can be seen from the above table, the gas barrier properties (cm ³ / m ² / atm / day), solvent resistance and adhesiveness are improved in the present invention.
These improved properties of the present invention are basically obtained by the component (B) alone, but the properties of the commercial product are obtained by the combination of the chemical resistant layer and the anchor layer of the polyvinyl alcohol polymer (as shown in Fig. 2, 6 Lt; / RTI > layers 2 to 4 are added). The gas barrier properties as described above of the present invention are obtained by the combination of the component (B) and the metal oxide layer (A), but according to the present invention, the addition of only three layers, as shown in Fig. 9, Better properties can be obtained.
As shown in Fig. 3, the polyvinyl alcohol polymer has flexibility and gas barrier properties. By crosslinking a polyvinyl alcohol polymer with an alkoxysilane to form an interpolymer, chemical resistance and abrasion resistance are imparted to the interpolymer because the crosslinked polymer has a microscopically homogeneously bonded structure.
Further, by selecting a specific silicon compound (silane-coupler-type compound) as a crosslinking agent, the above-described improvement is increased.
Gas Carbon Monoxide:
Referring to Fig. 4A, the oxygen permeability of a gas barrier monolayer formed on a polycarbonate membrane (PC) is shown. Is an ethylene-vinyl alcohol copolymer indicated in the prior art. The line labeled H / PC is a hybrid layer of polyvinyl alcohol. The oxygen permeation of the hybrid layer at low humidity is superior to the prior art. The line denoted SiOx / PC is a SiOx layer, but this can be further improved by increasing the thickness of SiOx. Here, it is theoretically expected that the lamination of the hybrid layer and the SiOx layer will provide the oxygen permeability shown by the dashed line, as indicated by H / SiOx / PC (theoretical value). However, the actual measured oxygen permeability of the laminate of the hybrid layer and the SiOx layer is shown as a solid line, as indicated by H / SiOx / PC (measured), which is significantly better than the theoretical value and is even lower at high humidity (90% RH). Therefore, the gas barrier properties exceeding the target value can be obtained by a combination of the hybrid layer and the SiOx layer (metal oxide layer).
Figure 4b shows a similar oxygen transmission rate of the gas barrier monolayer with respect to temperature changes. The combination of the hybrid layer and the SiOx layer also has gas cross-talk beyond the target.
This synergistic effect is obtained by the lamination of the hybrid layer and the SiOx layer as shown in Fig. 5, in which 41 denotes a polycarbonate film with a thickness of 100 mu m, 42 denotes a SiOx layer with a thickness of 0.01 mu m, 2 占 퐉 thick hybrid layer. One of the reasons for the synergistic effect is thought to be as follows. That is, as shown in FIG. 6A, the SiOx layer has pinholes, and the lamination of the hybrid layers fills the pinholes. This combination provides a synergistic effect of gas barrier properties because the hybrid layer itself has not only gas barrier properties but also excellent adhesion to the SiOx layer, but the present invention is not limited to a particular theory.
Adhesion:
As described above, the hybrid layer has excellent adhesion to the SiOx layer or the metal oxide layer. Also, the hybrid layer has excellent adhesion to an organic layer such as a polycarbonate film.
Therefore, the cured polymer layer (B) of the present invention adheres to a polymer layer, particularly a polycarbonate, and a metal oxide layer, particularly silicon oxide. It is believed that the epoxy groups and amino groups contribute to the adhesion of the cured polymer layer to the polycarbonate layer and the silanol groups contribute to the adhesion of the cured polymeric layer to the silicon oxide layer.
As a result, the cured polymer layer (B), which is a gas barrier layer and a chemical resistant layer, can be formed between any kind of organic layer and metal oxide layer without an anchor layer.
Drug or solvent:
The hybrid layer has improved chemical resistance or solvent resistance to NMP and acid.
However, the hybridization of a hybrid layer such as polyvinyl alcohol with a typical alkoxysilane such as tetramethoxysilane (TMOS) does not have excellent chemical resistance or solvent resistance to alkali as shown in Fig. According to the present invention, the alkali resistance of the hybrid layer is obtained by selecting two specific types of alkoxysilanes and using two types of alkoxysilanes in combination.
These two alkoxysilanes are silicon compounds (B1) having epoxy and alkoxysilyl groups and silicon compounds having amino and alkoxysilyl groups (B2) as described in detail above.
Figure 8 schematically shows the reaction times of the compounds (Bl) to (B3). The epoxy group of the silicon compound (B1) and the alkoxysilyl group react with each other and react with the hydroxyl group of the polyvinyl alcohol polymer (B3), but the amino group of the silicon compound (B2) reacts only with the epoxy group of the silicon compound Lt; / RTI > does not react with other functional groups of the general formulas (B1) to (B3). This specific reactivity of the reaction and properties of the functional groups of the compounds (B1) to (B3) is believed to provide an advantageous effect on other excellent properties such as gas barrier properties, adhesion, as well as excellent alkali resistance.
As a result, the laminate structure shown in Fig. 9 provides an ideal result for a transparent polymer electrode substrate, 41 represents a polycarbonate film with a thickness of 100 mu m, 42 represents a SiOx layer with a thickness of 0.01 mu m, Of the silicon compound (B1) and (B2) and the polyvinyl alcohol polymer (B3).
A particular mode of combination of compounds (Bl) to (B3)
Therefore, such improvements are obtained by the specific properties of component (B).
More specifically, the crosslinking of a polyvinyl alcohol polymer with an alkoxysilane and further with a silane coupler type compound can increase gas barrier property, 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) having a specific functional group is used together with the polyvinyl alcohol polymer (B3), and all the gas diaphragms, solvent resistance, A sufficient improvement is obtained unexpectedly.
A crosslinking reaction between a polyvinyl alcohol polymer and a silane coupler is known, and a silicon compound having an epoxy group and an alkoxysilyl group is used as a silane coupler. However, in practice silicon compounds with amino and alkoxysilyl groups do not provide a presumably superior cross-linked polymer and are therefore not used as a silane coupler in cross-linking polyvinyl alcohol polymers in particular. Although there are many other alkoxysilanes and silane couplers, there is a problem that a silicon compound (B1) having an epoxy and an alkoxysilyl group and a silicon compound (B2) having an amino group and an alkoxysilyl group as a crosslinking agent for use in polyvinyl alcohol, It is not known that it can provide superior solvent resistance and other properties over combinations of silane couplers or even two or more other silane couplers.
Therefore, the reaction between the compounds (B1) to (B3) is carried out in such a way that the polyvinyl alcohol polymer (B3) and any silane coupler comprising (B1) or (B2) The reaction between silane couplers is fundamentally different.
The reaction between the compounds (B1) to (B2) is as described below, and the cross-linking or the structure is as shown by the general formula (3). The resulting crosslinked structure of the polymer is novel.
Moreover, the above-mentioned specific combination of silicon compound and polyvinyl alcohol polymer for a transparent electrode polymer substrate, especially a liquid crystal cell, as well as a certain advantageous effect has 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 constituted by a small number of layers.
Other components of component (B)
Carboxylic acid:
When the ratio (b1) / (b2) is 1/9 to 9/1, more preferably 1/4 to 4/1, and more preferably 1/6 to 6/1, the adhesiveness of the cured polymer layer, , Chemical resistance, water resistance, durability and other components. If the amount of one of the compounds (B1) and (B2) exceeds the amount of the other components, the properties of the cured polymer layer are degraded.
Since the compound (B2), that is, the silicon compound having an amino group and a hydroxysilyl group is a condensation catalyst for hydrolysis of the compound (B1), that is, a silicon compound having an epoxy and a hydroxysilyl group, and also functions as a polymerization catalyst for the epoxy group, (B2) to the hydrolysis product of component (B1) causes immediate reaction and gelation of the coating composition. In order to prevent this, it is preferable to add a carboxylic acid to the component (B2) to form a weak acid salt of the organic acid and to increase the pot life. The carboxylic acid may be formic acid, acetic acid, propionic acid, lactic acid, and the like. Acetic acid is most preferred due to its acidity and volatility.
Generally, the amount of the carboxylic acid is in the range of 0.01 to 10 mol, preferably 0.1 to 5.0 mol per mol of the total number of moles of amino and imino groups. If the amount is less than 0.01 mol, the pot life of the composition is shortened and gelation may occur. If the amount exceeds 10 moles, the curing of the composition may become insufficient and the properties of the cured polymer layer may deteriorate.
menstruum:
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-based polymer dissolving solvent is preferably 30% by weight or more of the total solvent. When an ethylene-vinyl alcohol copolymer is used, water / propanol may be used as a solvent for the copolymer, and the mixing weight ratio of the water-propanol is preferably 3/7 to 7/3. Any solvent which is compatible with the polyvinyl alcohol polymer and in which the compounds (B1) and (B2) are soluble can be used in combination with the solvent. Examples of such solvents are alcohols, cellosolves, ketones, amides, and the like. Among them, alcohols such as butanol, ketones such as cellosolve and cyclohexanone such as 1-methoxy-2-propanol are preferable solvents for providing excellent surface smoothness. These additional solvents themselves may be used alone or in combination.
The amount of the solvent is preferably in the range of 200 to 99900 parts by weight based on 100 parts by weight of the total solids content of the compounds (B1) to (B3). When 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 is more than 99900 parts by weight, the solid content in the coating solution is low and the thickness of the coating layer that can be obtained is limited.
Hardener:
The curing agent may be optionally added. The curing agent is selected from the group consisting of aluminum acetylacetonate, aluminum ethyl acetylacetate bisacetylacetate, aluminum bisacetoacetate acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate 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 carboxylates 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:
Various additives can also be added selectively. Surfactants such as, for example, silicon compounds, fluorine-containing surfactants and organic surfactants can be used to improve the surface smoothness of the layer.
Admixed epoxy resin, melamine resin, aramid resin, colloidal silica and the like which are used with the coating composition may be added as a modifier. These additives can improve various properties of the cured polymer layer, for example, heat resistance, weather resistance, water resistance, durability, adhesiveness, chemical resistance, solvent resistance and the like.
Coating solution for component (B):
Thus, as can be seen from the above description, according to the present invention, the coating solution for forming the curing composition layer (layer B) is preferably:
(B1) a silicon compound having an epoxy and an alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof or a mixture thereof;
(B2) a silicon compound having an amino and an alcoholic silyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof or a mixture thereof;
(B3) a polyvinyl alcohol polymer;
(B4) carboxylic acid;
(B5) an organic solvent; And
(B6) water
.
Other optional components are described elsewhere herein.
A coating method for forming a layer of component (B)
The cured polymer layer (B)
a) preparing a coil composition comprising components (B1) to (B6) as described above;
b) coating the substrate with a coating composition; And
c) curing the coating composition by a cross-linking reaction between components (B1) to (B3) to form a cured polymer layer on the substrate
On the substrate.
More particularly, the method comprises:
Preparing an aqueous solution of the polyvinyl alcohol-based polymer (B3);
Adding acetic acid to the aqueous solution of the copolymer;
First, the solution is added to the silicon compound (B1) having an epoxy and alkoxysilyl groups and the hydrolysis of the added silicon compound is performed; And
Next, a silicon compound (B2) having an amino and an alkoxysilyl group is added to the solution and a step of hydrolyzing the added silicon compound
.
The transparent conductive layer (C)
The transparent conductive layer (C) used in the present invention is preferably a metal oxide from the viewpoints of transparency, conductivity and mechanical properties. For example, mention may be made of indium oxide, cadmium oxide, and tin oxide doped with tin, tellurium, cadmium, molybdenum, tungsten, fluoride or the like as a dopant, zinc oxide and aluminum oxide to which aluminum is added as a dopant. 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 vapor 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 becomes discontinuous and the conductivity is insufficient. If it exceeds 180 nm, transparency and flexibility are deteriorated.
The arrangement of the components (A) to (D) in the electrode substrate
In the liquid crystal display element of the present invention, the electrode substrate is composed of the 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 behind it when used.
The metal oxide layer (A) and the cured polymer layer (B) are formed adjacent to each other or in contact with each other, whereby excellent gas barrier properties and solvent resistance can be obtained, and the obtained gas barrier properties are improved unexpectedly. Since the polyvinyl alcohol polymer deteriorates with water, the gas barrier properties of the polyvinyl alcohol polymer layer deteriorate under high-humidity conditions. The gas barrier property and the solvent resistance of the polyvinyl alcohol polymer-containing layer are improved by cross-linking the polyvinyl alcohol polymer and a specific combination of silicon compounds with an ethylene-vinyl alcohol copolymer used as a gas barrier layer in a commercially available liquid crystal display element using a resin electrode substrate ≪ / RTI > Further, by combining the cured polymer layer (B) and the metal oxide layer (A) of the present invention, the gas barrier properties can be kept low even under high humidity conditions because the metal oxide layer is not deteriorated by water. This is why the combination of the cured polymer layer (B) and the metal oxide layer (A) is used as the gas barrier single layer.
Furthermore, by forming the cured polymer layer (B) and the metal oxide layer (A) adjacent to each other, the obtained gas barrier properties are larger than those in which the gas barrier properties of the two layers are increased and the synergistic effect is obtained.
4A and 4B show the oxygen permeability of the gas-gaseous monolayer relative to the relative humidity. Each tested gas barrier layer was formed on a polycarbonate substrate. The polymer layer B (hereinafter referred to as the H layer or the hybrid layer) separated from the polyvinyl alcohol polymer (B3) crosslinked with the silicon compounds (B1 and B2) has a higher thermal conductivity than the ethylene-vinyl alcohol copolymer layer at 50% It is significantly lower 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 sufficiently low, and deteriorated by a solvent such as alkali. The gas permeability of the metal oxide layer and the hybrid layer is theoretically expected as indicated by the dotted line in Fig. 4A. However, the actually obtained gas permeability of the laminate was considerably lower than expected, as indicated by the solid line in Fig. 4A. The gas permeability of the laminate of the present invention is much lower than that of the ethylene-vinyl alcohol copolymer layer regardless of humidity.
In the present invention, the position and sequence of the combination of the hybrid layer (B) and the metal oxide layer (A) of the electrode substrate are different from each other in that the transparent conductive layer among the components (A) to (D) It is not limited.
However, the lamination order of the component (C) / (B) / (A) / (D) is preferable because the cured polymer layer (B) (D). The order of layers (A) and (B) may be reversed. (A) / (B) or (C) / (D) / (B) / (A) ).
In practice, the 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 a substrate, some preferred examples of the stacking order are (C) / (B) / (A) / (D) / (B), (B) (B) / (D) / (B) / (C) / (C) / (B) / A) / (B) / (D) / (B), (B) / (A) / (B) / (D) / (B) / (C). Of course, any other sequence can be adopted.
Figs. 10A to 10D and Figs. 11A to 11F are examples of preferred lamination orders of the components (A) to (D). The other order is not an example, because it is obvious without an example.
In addition, one or more additional layers may be selectively added to or inserted into the laminate to improve certain properties of the laminate or electrode substrate. Specifically, it is preferable to improve the adhesion of the component (A) to the component (D) to the other layer component by inserting the anchor layer ( ). In addition, any gas barrier 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 floor
The anchor layer 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 a silicon compound layer. The silane coupler is an organosilicon compound represented by Formula 10:
[Chemical formula 10]
Wherein R ¹¹ represents an organic group having at least one of vinyl, methacryloxy, epoxy, amino, imino and mercapto, R ¹² represents a hydrolysable substituent such as alkoxy and halogen, and n represents an integer of 1 to 2 to be.
Examples of silane couplers are vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (2-methoxy-ethoxy) silane, 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-hydroxyethyl) -3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and Ethoxymethylsilylpropyl) -ethylenediamine. ≪ / RTI >
Thermoplastic resin:
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 or electron beams. Radiation-curable resins include resins having unsaturated double bonds such as acryloyl, methacryloyl and vinyl in a molecule or unit. A resin having acryloyl is preferable due to the reactivity.
The radiation-curable resin may be a single compound or a mixture of compounds. It is preferred that the composition contains a multifunctional acrylate component having two or more acryloyl moieties in the molecule or unit for solvent resistance. Examples of polyfunctional acrylate components include acrylate monomers such as dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate and trimethylolpropane triacrylate , Or a polyfunctional acrylate oligomer obtained by polyester-modification or urethane-modification.
The radiation curable resin is formed as follows. The coating composition is prepared by adding a photoinitiator and other additives such as an inhibitor, a leveling agent and a UV absorber, a modifier such as a thermoplastic resin and a plasticizer to the radiation curable resin composition. The organic solvent is optionally added to adjust the concentration and viscosity of the coating solution. The coating method can be, for example, dip coating, flow coating and roll coating, bar coating, spin coating, and the like, and is preliminarily dried and then exposed to radiation. Thus a cured layer is obtained.
If the resin is cured by UV radiation, photoinitiators are essential. Initiators include, for example, benzoin compounds such as acetophenone, benzoin and benzyl dimethyl ketal such as diethoxyacetophenone and 1-hydroxycyclohexyl phenyl ketone; Dioxane-based compounds such as 2,4-dichlorothioxanone. Known photo-initiators such as trimethanolamine, methyldiethanolamine and ethyl 4-dimethylamine benzoate can be selectively added in appropriate amounts to improve the curability.
The thickness of the radiation curable layer is preferably 2 to 8 占 퐉, more preferably 2 to 6 占 퐉. If it is less than 2 탆, the solvent resistance is insufficient. If the thickness is less than 8 μm, curing will be unfavorable due to curing shrinkage.
Thermosetting resin:
The thermosetting resin for the anchor layer is usually an epoxy resin, an isocyanate-curable urethane resin, or the like. Of these, a cured phenoxy resin, phenoxy ether resin or phenoxy ester resin obtained by curing a phenoxy resin, a phenoxy ether resin or a phenoxy ester resin with a polyfunctional isocyanate compound is preferable.
The thickness of the thermosetting resin layer is not limited, but if it is less than 3 탆, the solvent resistance is insufficient. The upper limit of the layer is determined by a balance between the cost and the solvent resistance, and it is preferably 20 占 퐉 or less, more preferably 10 占 퐉 or less.
The thermosetting resin layer is formed as follows. The coating solution is prepared by adding to the thermosetting resin composition an optional additive such as a reactive diluent, fine particles and a leveling agent, and a modifier such as a thermoplastic resin and a plasticizer. The organic solvent is 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, etc., and heat-treated at 120 ° C. for 3 minutes or more, more preferably at 130 ° C. for 5 minutes or more to form a thermosetting layer do.
The solvent resistant protective layer may be a radiation cured layer or a thermosetting layer which may be similar to the radiation cured layer or thermosetting layer for the anchor layer.
The particulate-
Alternatively, a layer containing an inorganic or organic fine particle layer may be provided on the laminated substrate.
Polymer substrates are advantageous in terms of cost savings because they can be processed into a roll-to-roll system. However, if the surface of the film is too smooth, the film has poor slipperiness due to a large contact area with the roll, etc., and the film is deformed or bent by blocking during winding the film, resulting in increased damage.
By adding fine particles to the outermost layer of the film, particularly the outermost layer of the film, the slidability of the film can be improved by, for example, reducing the area of contact with the roll, so that deformation and bending of the film in the film winding layer can be prevented.
The particulate-containing layer is preferably formed on at least one outermost layer of the laminated film.
This particulate-containing layer can be formed by coating a substrate with a coating solution containing inorganic or organic fine particles 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 (layer B) or other coating solution.
Preferably the inorganic microparticles comprise silica and alumina, because the reduction 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 fine particles include acrylic resin, styrene resin, urethane resin, polycarbonate resin, nylon resin 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 占 퐉, the slidability becomes insufficient. If it is larger than 5 탆, the optical properties are deteriorated.
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 part by weight, the slipperiness becomes insufficient. If it exceeds 5 parts by weight, the optical properties such as the 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 mu m. If it is too thin, the layer may have particle type defects. If it is too thick, it is difficult to obtain excellent smoothness.
Other components of LCD elements
Although the transparent electrode substrate composed of the constituent elements (A) to (D) of the present invention is used for at least one of the electrode substrates of the liquid crystal display element, both electrode substrates are transparent electrodes made of the constituent elements (A) to (D) Substrate. The other substrate may be a substrate without the component (B) of the present invention. Other substrates may be non-transparent and non-polymeric.
Other aspects of the invention
According to an aspect of the present invention, as described above, there is also provided a transparent electrode substrate made up of the above-described components (A) to (D). This transparent electrode substrate can be used not only for a liquid crystal display element but also for other electric devices using a transparent electrode substrate, for example, a touch panel, an electroluminescence device, a planar fluorescent material, and the like.
Moreover, component B as described above provides excellent transparency, water resistance, flexibility and other mechanical properties along with significant chemical resistance or solubility, gas barrier properties and adhesion. Therefore, the layer of the component (B) can be used not only as a resin but also as a coating layer of an article made of other materials such as metals, ceramics, paper and the like. In this article, the metal oxide layer (A) and the metal conductive layer (C) are not essential but optional. The shape of the article is not limited to a sheet or a film.
One preferred embodiment of this article is a polymer substrate consisting of a metal oxide layer (A) and a cured polymer layer (B) fixed to the metal (D) (see Fig. 5).
Another preferred embodiment of the article comprises a transparent polymer layer (D), a metal oxide layer (A) on one side of the layer (D), a first cured polymer layer (B-1) in contact with the metal oxide layer And a second cured polymer layer (B-2) formed on the other side of the substrate (see Fig. 9). 9, reference numeral 41 denotes a layer (D), 42 denotes a layer (A), and 45 denotes a cured layer (B-1, B-2).
In this application for the article, the metal oxide layer is not essential as component (A) 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 or gas barrier coating, especially for medicines or food containers or packaging.
The coated layer of the above-mentioned component (B) has a resistance of not more than 10 cm ³ / m ² / day / atm at 40 ° C and 90% RH in addition to the chemical resistance (i) to (iii) Oxygen permeability.
Example
The invention is further illustrated but not limited by the following examples. Although the cured polymer layer of the component (B) of the present invention is preferably formed in contact with the metal oxide layer of the component (A) in the transparent electrode substrate, the cured polymer layer of the component (B) formed on the substrate without the metal oxide layer And are within the scope of the present invention.
Unless specifically stated otherwise in the examples, parts and percentages are based on weight.
The examples were evaluated in the following manner.
Appearance of the component (B) layer:
Coloring and coating defects were determined by visual inspection.
Transparency:
Using a spectrophotometer (Hitachi Ltd, U-3500), the light transmission of parallel light at a wavelength of 550 nm was obtained. The haze value was calculated using Nippon Denshoku k.k. COH-300A. ≪ tb > < TABLE >
Optically isotropic:
Nippon Sepctroscopy Corp. The retardation for 590 nm was determined using a multi-wavelength birefringence meter M-150.
Surface smoothness:
WYCO Corp. The surface smoothness was determined by using TOPO-3D manufactured by Tosoh Corporation.
Ra is the centerline average surface roughness of a layer measured at a magnification of 400 at a magnification of 256 占 퐉 and a layer at a pitch of 1 占 퐉 according to a phase transition interference method.
Drug or solvent (1):
The sample was immersed in a 3.5% -NaOH aqueous solution at 25 DEG C for 10 minutes, washed with flowing water, dried and examined for the appearance of the sample.
Drug or solvent (2):
The sample was immersed in a 5.0% -HCl aqueous solution at 25 DEG C for 10 minutes, washed with flowing water, dried and examined for the appearance of the sample.
When the transparent conductive layer C was formed, this evaluation was performed on the sample before the layer C was formed.
Drug or solvent (3):
Test (1):
For the laminate having the transparent conductive layer, the laminate was immersed in N-methylpyrrolidone (NMP) at 25 DEG C for 10 minutes, the change in appearance was examined, the change in the haze value was measured, and the change in resistance was measured. If peeling is observed, reduction in surface smoothness or haze of the coating layer is determined by visual inspection, or if the change in haze value is larger than 1%
And evaluated by appearance.
Test (2):
For the laminate without a transparent layer, a few drops of NMP were dropped onto the laminate from the cured polymer layer (B) side at 80 DEG C, left at 80 DEG C for 1 minute, and washed with running water to examine the appearance.
Test (3):
For the laminate without a transparent layer, a few drops of NMP were dropped onto the laminate at 80 占 폚 and the surface of the cured polymer layer (B), left at 80 占 폚 for 10 minutes, and washed with running water to examine the appearance.
Water vapor barrier property:
The water vapor barrier property and the following gas barrier property were measured for the water vapor polymer layer not having a transparent electrode layer.
Water vapor permeability was measured using a Modern Control Corp. (Permotan W1A manufactured by MOCON Corp.) at 40 DEG C and 90% RH atmosphere.
Gas carmaking (1):
Oxygen permeability was measured by MOCON Corp. OX-TRAN < / RTI > 2/20 in an atmosphere of 30 DEG C and 50% RH.
Gas carmaking (2):
Oxygen permeability was measured by MOCON Corp. OX-TRAN 2/20 manufactured by Mitsubishi Gas Chemical Co., Ltd. under the conditions of 30 ° C and 90% RH.
Adhesion:
The sample surface was cut into a matrix of 1 mm pitch to form 100 small rectangular sections. A cellophane adhesive tape (Cellotape, made by Niciban k.k.) was applied to the cut sample and rapidly peeled off the surface in a direction at an angle of 90 °. The number of small square sections on the sample was counted to evaluate the adhesion. Score 100/100 means complete adhesion and 0/100 means complete peel (according to JIS K5004).
Flexibility:
The sample was loosened and loosened in a glass tube with a diameter of 10 mm < 5 > If a crack is generated (particularly when a crack larger than 5 mm is generated in the transparent conductive electrode), it is evaluated as defective.
durability:
After heating for 100 hours at 60 DEG C and 90% RH with a temperature and humidity controller, the surface of the cured layer was inspected after cooling.
Runtime:
A film having a width of 50 cm and a length of 50 m was wound on a roll to examine the deformation and curvature of the film.
Examples 1 to 8
A polycarbonate having a bisphenol component of bisphenol A and having a molecular weight of 37,000 was dissolved in methylene chloride at a concentration of 20 wt% and cast into a polyester film having a thickness of 175 mu m by a die casting method. The cast film was dried to a residual solvent concentration of 13% by weight and peeled off from the polyester film. The polycarbonate film thus obtained was dried in a drying oven at 120 ° C with a balance of tension in the transverse and longitudinal directions so that the remaining solvent concentration became 0.08% by weight.
The thus-obtained transparent polycarbonate film had a thickness of 103 탆 and a light transmittance at 550 nm of 91%.
A SiO 2 chip was deposited on the surface of the polycarbonate film as a substrate under a vacuum of 5 × 10 ^-5 torr to attach a metal oxide layer (A layer). The attached silicon oxide layer had an average composition of SiO _x (x about 1.7 or 1.3).
Next, a polymer cured layer (layer B) was formed in the metal oxide layer by preparing a coating solution as described below. 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.
A coating solution aged at room temperature for 24 hours was coated on a SiO _1.7 layer formed on a polycarbonate film or a polycarbonate film by a Meyer bar and the coated layer was heated at 130 ° C for 2 minutes to form a cured polymer layer ).
(Example 1)
In this embodiment, the B layer was formed on a transparent polymer film or polycarbonate substrate.
The coating solution for the B layer was prepared by mixing polyvinyl alcohol (R1130, manufactured by Kraray Corp. Ltd.) containing silanol as the polyvinyl alcohol polymer (B3), 3-glycidoxypropylsilane (B1) containing epoxy and alkoxysilyl groups, (B ₃ ) / (B ₁ ) + (B ₂ ) is 2/1, and the weight ratio (B ₃ ) / (B ₁ ) + (B ₂ ) of the silicon compound Wherein the molar ratio b ₁ / b ₂ is 1/1, wherein B ₁ to B ₃ each represent the weight of the compound (B1) to (B3), b ₁ is the molar amount of the epoxy group, and b ₂ is the Represents the total molar amount.
The coating solution is prepared by adding acetic acid to a mixture of polyvinyl alcohol and distilled water, stirring the mixture to be homogeneous, adding aminopropyltrimethoxysilane to the solution to effect hydrolysis, stirring the solution for 30 minutes and adding 3- Glycidoxypropyltrimethoxysilane to the reaction mixture.
As can be seen in Table 1, all evaluations of the laminate were good.
(Example 2)
In this example, the B layer was formed on the transparent polymer film of polycarbonate.
The coating solution for the B layer was composed of the same polyvinyl alcohol polymer (B3) as in Example 1, the silicon compound (B1) having epoxy and alkoxysilyl groups and the silicon compound (B2) having amino and alkoxysilyl groups, B ₃ ) / [(B ₁ ) + (B ₂ )] was 2/1 and the molar ratio (b ₁ ) / (b ₂ ) was 3/2.
The coating solution was prepared by adding acetic acid to a mixture of polyvinyl alcohol and distilled water, stirring the mixture to be homogeneous, adding aminopropyltrimethoxysilane to the solution to effect the hydrolysis, and stirring the solution for 30 minutes . To this solution, 0.01N-hydrochloric acid was slowly added with stirring, and an isopropyl alcohol solution of 3-glycidoxypropyltrimethoxysilane stirred for 30 minutes was added.
As can be seen in Table 1, all evaluations of the laminate were good.
(Example 3)
In this example, a silicon oxide layer was deposited as a metal oxide layer (A layer) on the polycarbonate film, and then a B layer was formed on the A layer.
Procedure, except that the composition having a weight ratio of 2/1 of the coating solution used _{(B 3) / [(B} 1) + (B 2)] and the mole ratio of _{1/2 (b 1) / (b} 2) Was the same as that in Example 2.
As can be seen in Table 1, all evaluations of the laminate were good. In particular, the gas barrier properties were considerably improved by providing a silicon oxide layer (layer A).
(Example 4)
In this embodiment, a silicon oxide layer as a metal oxide layer (A layer) was attached to the polycarbonate film, and then a B layer was formed on the A layer.
(B ₃ ) / [(B ₁ ) + (B ₂ )] of 2/1 and 1/2 of the weight ratio of the component Was the same as that of Example 2 except that the molar ratio (b ₁ ) / (b ₂ ) was used.
As can be seen in Table 1, all evaluations of the laminate were good. In particular, the gas barrier properties were considerably improved by providing a silicon oxide layer (layer A).
(Example 5)
In this embodiment, a silicon oxide layer as a metal oxide layer (A layer) was attached to the polycarbonate film, and then a B layer was formed on the A layer.
The procedure is such that the composition of the coating solution used consists of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as component (B1) and aminopropyltrimethoxysilane as component (B2) Was the same as that of Example 2 except that the weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] and 1/1 molar ratio (b ₁ ) / (b ₂ )
As can be seen in Table 1, all evaluations of the laminate were good. In particular, the gas barrier properties were considerably improved by providing a silicon oxide layer (layer A).
(Example 6)
In this embodiment, a silicon oxide layer as a metal oxide layer (A layer) was attached to the polycarbonate film, and then a B layer was formed on the A layer.
Coating manufacturing process as the coating in Example 5 and the same components (B1) and (B3) and the component (B2) The composition of the solution is composed of silane on aminopropyl weight ratio of 1/1 of the solution (B ₃₎ / was the same as in example 2 except for having _{[(B 1) + (B} 2)] and the molar ratio of _{(b 1) / (b 2} ) of 1/1.
As can be seen from Table 2, all evaluations of the laminate were good. In particular, the gas barrier properties were considerably improved by providing a silicon oxide layer (layer A).
(Example 7)
In this example, a silicon oxide layer was deposited as a metal oxide layer (A layer) on the polycarbonate film, and then a B layer was formed on the A layer.
Coating production process is made the same as the compound (B1) and (B3) and the compound (B2) with the coating solution in Example 6 with the aminopropyl silane weight ratio of 1/1 of the solution (B ₃₎ / [(B ₁ ) + (B ₂ )] was the same as that of Example 2 except that it had a molar ratio (b ₁ ) / (b ₂ ) of 1/1.
The coating solution was prepared in the same manner as in Example 1 except for using the same compounds (B1) and (B3) as in Example 1 and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- ) -3-amino-propyl-methyl-dimethoxy silane made of a weight ratio of _{3/1 (B 3) / [(} B 1) + (B 2)] and the mole ratio of _{1/2 (b 1) / (b} 2) Was the same as that of Example 1.
As can be seen from Table 2, all evaluations of the laminate were good. In particular, the gas barrier properties were considerably improved by providing a silicon oxide layer (layer A).
(Example 8)
In this example, a silicon oxide layer was deposited as a metal oxide layer (A layer) on the polycarbonate film, and then a B layer was formed on the A layer.
The procedure was the same as in Example 7 except that the polyvinyl alcohol used was Gecenol NM-11Q (saponification degree of 99% or more) manufactured by Nippon Synthetic Chemical Industry Ltd.
As can be seen from Table 2, all the evaluation of the laminate was good, but the alkali resistance (solvent resistance 1) was slightly reduced.
(Comparative Examples 1 to 5)
The same procedure as in Examples 1 to 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 not containing the polyvinyl alcohol polymer (B3) was formed on a transparent polymer film of polycarbonate.
The coating solution for the cured polymer layer consisted solely of 3-glycidoxypropyltrimethoxysilane (B1) and 3-aminopropyltrimethoxysilane (B2).
As can be seen from Table 3, the gas barrier properties and durability were poor.
(Comparative Example 2)
In this comparative example, a silicon oxide film as the metal oxide layer (A layer) was attached to the polycarbonate film, and then a cured polymer layer not containing the silicon compound (B2) having amino and hydrosilyl groups was formed on the A layer.
The curing solution consisted only of the silanol-containing polyvinyl alcohol (B3) and 3-aminopropyltrimethoxysilane (B2) as used in Example 1.
As can be seen from Table 3, it was poor in alkali resistance (chemical resistance 1), NMP resistance (solvent resistance 3), durability and adhesive property.
(Comparative Example 3)
In this comparative example, a cured polymer layer not containing the silicon compound (B2) having amino and hydrosilyl groups was formed in the transparent polymer film of polycarbonate.
The coating solution consisted only of silanol-containing polyvinyl alcohol (B3) and 2- (3,4-ethoxycyclohexyl) ethyl trimethoxysilane (B1) as used in Example 1.
As can be seen from Table 3, it was poor in alkali resistance (solvent resistance 1), NMP resistance (solvent resistance 3), adhesion and durability.
(Comparative Example 4)
In this comparative example, a polycarbonate film having a silicon oxide layer (A layer) as a metal oxide layer of SiO _1.7 but not a cured polymer layer formed on the A layer was evaluated.
Solvent resistance 1 to 3 and oxygen barrier properties were low.
(Comparative Example 5)
In this comparative example, a polycarbonate film to which a silicon oxide layer (A layer) as a metal oxide layer of SiO _1.3 was adhered but a cured polymer layer was not formed on the A layer was evaluated.
Solvent resistance 1 to 3 and oxygen barrier properties were low.
Examples 9 to 15
(Example 9)
A polycarbonate film to which a metal oxide layer (A layer) of silicon oxide was adhered was used in this example as in Examples 3 to 5.
Next, a polymer cured layer (layer B) was formed in the metal oxide layer by preparing a coating solution as described below. 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.
A coating solution for forming a cured polymer layer (layer B) was prepared as follows: 100 parts by weight of an ethylene-vinyl alcohol copolymer (EVOH-F, manufactured by Kuraray Co., Ltd., ethylene copolymerization ratio: 32%) as the polyvinyl alcohol polymer (B3) 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 homogeneous solution. To this solution, 0.1 part by weight of silicone oil (SH30PA, manufactured by Toray Dow Corning Silicone Corp.) as a leveling agent and 62.4 parts by weight of acetic acid were added. Subsequently, a silicone compound (B1) having epoxy and alkoxysilyl groups was added, Cyclohexyl) ethoxytrimethoxysilane (85.8 parts by weight) was added and the solution was stirred for 10 minutes. Next, 62.4 parts by weight of 3-aminopropyltrimethoxysilane as the silicon compound (B2) having amino and alkoxysilyl groups was added to this solution, and the solution was stirred for 3 hours to obtain a coating solution for forming a cured polymer layer (layer B) The composition of the coating solution was 1/1 by weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] and 1/1 by molar ratio (b ₁ ) / (b ₂ ).
The coating solution was coated on the SiO _1.7 layer (A layer) formed on the polycarbonate film by Meyer bar and the coated layer was heated at 130 캜 for 3 minutes to form a cured polymer layer (B layer).
The obtained laminate was evaluated and the results are shown in Table 4. [
As can be seen in Table 4, all evaluations were good.
(Examples 10 to 13)
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, 11 to 1/2, 1/3 in Example 12 and 1/9 in Example 13, and the molar ratio (b ₁ ) / (b ₂ ) was 1/1 in Examples 10-13.
The obtained laminate was evaluated and the results are shown in Table 4. [
As can be seen in Table 4, all evaluations were good.
(Example 14)
The procedure of Example 9 was repeated, but the compound (B1) was changed to 3-glycidoxypropyltrimethoxysilane 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 was evaluated and the results are shown in Table 4. [
As can be seen in Table 4, all evaluations were good.
(Example 15)
The coating composition as in Example 9 was coated on both sides of the polycarbonate film having the silicon oxide layer as in Example 9 by the same procedure as in Example 9. [
The obtained laminate was evaluated, and the results are shown in Table 4. < tb > < TABLE >
As can be seen from Table 4, the evaluation was all good. The B layer 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.
[Table 1]
[Table 2]
[Table 3]
[Table 4]
Examples 16 to 21
(Examples 16 to 20)
A polycarbonate film as in Example 9 was used, but a silicon oxide film was not formed thereon. The coating solutions of Examples 16 to 20 were the same as those of Examples 9 to 12 and 14, respectively. The method of forming the cured polymer layer was the same as in Example 9.
The evaluation results of the obtained laminate are shown in Table 5 and all were good.
(Example 21)
The same procedure as in Example 9 was repeated, but the polycarbonate film was changed to a polyester film having a thickness of 12 占 퐉.
The resultant laminate was evaluated, and the results are shown in Table 5.
As can be seen in Table 4, all evaluations were good.
[Table 5]
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 in which silane compounds (B1) and (B2) were not added. Therefore, the weight ratio (B ₃ ) / [(B ₁ ) + (B ₂ )] was 1/0.
In the evaluation, the NMP property (chemical resistance 3) and the adhesion property were poor.
(Comparative Example 7)
It was not added to the silane compound (B2) with the amino groups and alkoxysilyl groups, a weight ratio of _{(B 3) / [(B} 1) + (B 2)] 2/1 and the molar ratio of _{(b 1) / (b 2} ) Is 1/0.
In evaluation, it was poor in alkali resistance (chemical resistance 1), NMP resistance (chemical resistance 3) and adhesion.
(Comparative Example 8)
It was not added to the silane compound (B1) with an epoxy and alkoxysilyl groups, a weight ratio of _{(B 3) / [(B} 1) + (B 2)] 2/1 and the molar ratio of _{(b 1) / (b 2} ) Is 0/1.
In the evaluation, appearance, haze value, alkali resistance (chemical resistance 1), NMP resistance (chemical resistance 3), and adhesion 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 surface was opposite to the silicon oxide layer surface.
In the evaluation shown in Table 6, the gas barrier single layer was defective.
(Comparative Example 10)
The evaluation was made on the polycarbonate membrane alone used in Example 9.
[Table 6]
Examples 22 to 24
(Example 22)
A polycarbonate film having the same silicon oxide layer as in Example 3 was used.
The first curing solution for forming the cured polymer layer (layer B) was applied to the silicon oxide layer (A layer) by the Micro Gravia method and heated at 130 캜 for 3 hours to form a cured polymer Layer. The first coating solution prepared 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 DEG C for 1 minute by the microgravure method, and the coating solution was applied by a high pressure mercury lamp of 160 W / And then irradiated with UV rays at a total exposure dose of 800 mJ / cm < 2 > to form a protective layer having a thickness of 4 [micro] m. The second coating solution was prepared by mixing 100 parts by weight of trimethylolpropane triacrylate (Aronix M-309, manufactured by Toa Synthetic Chemical Corp.), 7 parts by weight of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Chiba-Geigy) And 0.02 parts by weight of silicone oil (SH28PA, manufactured by Toray Dow Corning Corporation) as a leveling agent were mixed, and the mixture was diluted with 1-methoxy-2-propanol and methanol to a solids content of 35% by weight.
The thus-obtained roll of the laminate having the polyester film as the substrate was fixed with a sputtering apparatus evacuated to a pressure of 1.3 mPa. A mixed gas of Ar and O ₂ (O ₂ content: 1.4 vol%) was added and the temperature was adjusted to 9.27 Pa. DC sputtering was performed using an ITO target (SnO ₂ content 5 wt%) at an applied current density of 1 W / cm ₂ to attach a 130 탆 thick transparent conductive layer of ITO 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 procedure of Example 22 was repeated, 100 parts by weight of the silyl-containing polyvinyl alcohol polymer (R1130, manufactured by Kraray, less than 1% silyl content) (B3) was mixed with 1300 parts by weight of water and 600 parts by weight of n-propanol The mixture was thermally dissolved to form a homogeneous solution, cooled to room temperature, 0.1 part by weight of silicone oil (SH30PA, manufactured by Toray Dow Corning Silicone Corp.) as a leveling agent, and 124.8 parts by weight of acetic acid were added and then 3-aminopropyltrimethoxy 124.8 parts by weight of silane (B2) was added to the solution, stirred for 3 hours, and 171.6 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (B1) was further added thereto, 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 results are shown in Table 7.
(Example 24)
The procedure of Example 22 was repeated but the second coating solution was coated and heated at 180 캜 for 5 minutes and then heated at 130 캜 for 5 minutes to obtain a protective layer having a thickness of 5 탆. The second coating solution was prepared by mixing 20 parts by weight of a phenoxyester 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 addition of a polyfunctional isocyanate (Coronate L, Polyisocyanate) (20 parts) were added to the mixture.
The results are shown in Table 7.
Comparative Examples 11 and 12
(Comparative Example 11)
The procedure of Example 22 was repeated but no cured polymer layer made of the first coating solution was formed.
The results are shown in Table 7.
(Comparative Example 12)
The procedure of Example 22 was repeated but no cured polymer layer made of the first coating solution was formed.
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: High saponified polyvinyl alcohol (Gocenol NM-110, manufactured by Nippon Synthetic Chemical Industry)
E: Ethylene-vinyl alcohol copolymer (EVAL F104, Kraray)
ECHETMOS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
APTMOS: 3-aminopropyltrimethoxysilane
H (2): The B layer of Example 1
X (200): The SiO _X layer of Example 3
TF-PC: Polycarbonate membrane of Example 1
SX (70): The SiOx layer of Example 28
G: Filler included
Si content: " (B ₁ + B ₂ ) / (B ₁ + B ₂ + B ₃ )
B1 amount: "b ₁ / (b ₁ + b ₂ )] x 100 (mol)
[Table 7]
Examples 25 to 27
(Example 25)
The polycarbonate film having a 20 mu m-thick silicon oxide layer (layer A) was the same as in Example 3. [
A first coating solution for forming a cured polymer layer (layer B) was prepared. The coating solution was applied to both sides of the polycarbonate having the silicon oxide layer (A layer) by the Micro Gravia method and applied at 130 캜 for 2 minutes to obtain a cured polymer layer having a thickness of 2 탆.
The first coating solution was the same as that used to form the cured polymer layer (B layer) of Example 9.
An ITO layer was deposited on the cured polymer layer (layer B) formed on the silicon oxide layer in the same manner as in Example 22. [
The thus obtained laminate was evaluated, and the results are shown in Table 8.
(Example 26)
The procedure of Example 25 was repeated, but one of the cured polymer layers formed on the silicon oxide layer was prepared using the second coating solution, while the other cured polymer layer formed directly on the polycarbonate film was the first cured solution Lt; / RTI >
The second coating solution was prepared by thermally dissolving 100 parts of silyl-containing polyvinyl alcohol polymer (R1130, a product of Kraray, less than 1% silyl content) in a mixture of 1300 parts by weight of water and 600 parts by weight of n-propanol, cooling to room temperature, 0.1 parts by weight of silicone oil (SH30PA, manufactured by Toray Dow Corning Silicone Corp.), 124.8 parts by weight of acetic acid, and 171.6 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (B1) Min, and 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 thus obtained laminate 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 thus obtained laminate was evaluated, and the results are shown in Table 8.
Comparative Example 13
The procedure of Example 25 was repeated but the cured polymer layer formed consisted of a polyvinyl alcohol polymer (Gocenol NM-1Q, Nippon Synthetic Chemical).
The thus obtained laminate was evaluated, and the results are shown in Table 8.
[Table 8]
Examples 28 to 31
(Example 28)
The polycarbonate film used as the substrate was the same as Example 1, but had a film thickness of 100 mu m.
A first coating solution was coated on both sides of a polycarbonate film by a microgravure method and heated at 130 占 폚 for 2 minutes to obtain a laminated substrate having a cured polymer layer (B layer) on both sides.
The coating compositions used in this example were the same as in Example 9.
A mixed gas of Ar / O ₂ (O ₂ concentration: 12.0 vol%) was introduced into the sputtering chamber, and the pressure was adjusted to 0.27 Pa. DC magnetron sputtering was performed using a polycrystalline silicon Si metal target at an applied current density of 1 W / cm < ₂ > to form an SiO ₂ layer having a thickness of 7 μm on one surface of the cured polymer layer of the substrate.
This SiO ₂ layer formed was an ITO layer. The process of forming the ITO layer was the same as that of Example 22.
The laminate thus obtained was evaluated, and the results are shown in Table 9. < tb > < TABLE >
(Example 29)
The procedure of Example 28 was repeated except that the first coating solution was replaced with the next solution and the coated 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. < tb > < TABLE >
(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. This first solution was coated on one side of the polycarbonate film by a microgravure method and heated at 130 캜 for 3 minutes to form a cured polymer layer (B layer) on one side thereof.
A second coating solution was prepared on the other side of the polycarbonate and the second coating solution was coated on the other side of the polycarbonate film by the microgravure method and preheated at 50 DEG C for 1 minute to form a coating film having a total exposure of 800 mJ / / Cm < / RTI > to UV radiation to form a cured protective layer having a thickness of 4 m to form a solvent-resistant protective layer.
100 parts by weight of trimethylolpropane triacrylate (Alonix M-309, manufactured by Toa Synthetic Chemical Corp.), 7 parts by weight of 1-hydroxycyclohexylketone (Irgacure 184, manufactured by Chiba Geigy Limited) And silicone oil (SH28PA, manufactured by Toray Dow Corning Silicone Corp.) as a leveling agent, and then diluted with 1-methoxy-2-propanol and methanol to a solids content of 35% by weight.
A silicon oxide layer similar to that of Example 28 was adhered to the cured polymer (B layer) of the laminated substrate in the same manner as in Example 28. [ Then, the ITO layer as in Example 28 was adhered 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. < tb > < TABLE >
(Example 31)
Although the procedure of Example 28 was repeated, an ITO layer was formed in 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 in the silicon oxide layer.
The laminate thus obtained was evaluated, and the results are shown in Table 9. < tb > < TABLE >
[Table 9]
Examples 32 to 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 (B layer) used in Example 9 was coated and cured.
The thus obtained laminate was fixed with a vapor deposition apparatus, and a SiOx layer (x: about 1.7) (thickness: 20 nm) having a thickness of 20 nm was vapor-deposited from a vapor source of a mixture of Si and SiO ₂ on a cured polymer layer . 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 캜 for 2 minutes to form a second cured polymer layer (B layer) having a thickness of 2 탆.
An ITO layer was formed in this second cured polymer layer in the same manner as in Example 22. [
Therefore, the first cured polymer layer (B layer) / the polycarbonate film (D layer) / the first cured polymer layer (B layer or anchor layer) / SiO x layer (A layer) / second cured polymer layer Thereby obtaining a laminated structure of the ITO layer (C layer).
The thus obtained laminate was evaluated, and the results are shown in Table 10.
(Example 33)
Example 32 Repeat the procedure but replacing the anchor layer of the silane coupler 1 is the cured polymer layer thickness 50㎚ (AP133, Nippon Unitaka claim) that the anchor layer serves for the SiOx layer, SiOx layer is Si, SiO ₂ And MgF ₂ were deposited to a 100 nm thick metal oxide layer composed mainly of SiOx and the MgF ₂ content in the SiOx layer was about 10 wt%.
The thus obtained laminate was evaluated, and the results are shown in Table 10.
(Example 34)
The procedure of Example 32 was repeated, except that the first cured polymer layer formed on both sides of the polycarbonate was replaced with a UV cured layer having a thickness of 4 占 퐉. In the same manner as in Example 30, a solvent-resistant coating layer ≪ RTI ID = 0.0 > propane triacrylate < / RTI > base).
The thus obtained laminate 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 replaced with a UV cured layer as used in Example 34. [
The thus obtained laminate 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 as the anchor layer under the metal oxide layer was changed to the solvent resistant protective layer and the cured layer of Example 24.
The thus obtained laminate was evaluated, and the results are shown in Table 10.
(Example 37)
The same procedure as in Example 32 was repeated, except that the fine particle-containing layer was further coated with a coating solution and heated at 130 캜 for 2 minutes to form a 2 탆 thick coating on the surface of the polycarbonate film opposite to the ITO layer. The coating solution was the same as the coating solution of Example 32, but the amount of silica powder having an average particle size of 2 탆 was added in an amount of 0.4 part, and the mixture was sufficiently stirred.
The thus obtained laminate was evaluated, and the results are shown in Table 10.
(Example 38)
The procedure of Example 37 was repeated, but the particulate containing layer was prepared from the coating solution basically the same as the UV curable solution of Example 34, to which 0.2 part of acrylic resin powder having an average particle size of 5 탆 was added.
The thus obtained laminate was evaluated, and the results are shown in Table 10.
[Table 10]
Examples 39 to 41
The procedure of Example 26 was repeated except for the following. Polyvinyl alcohol polymer (EVAL F104, manufactured by Kuraray Co., Ltd.) and the compounds shown in Table 11 were used in the amounts shown in Table 11 for the layer B in contact with the ITO layer. For the other B layer (B 'layer) in contact with the SiOx layer, the polyvinyl alcohol polymer EVAL F104 and the compounds shown in Table 11 were used in the amounts shown in Table 11.
Examples 42 to 46
The same procedure as in Example 9 was repeated, but the compounds as shown in Table 11 were used in the amounts shown 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
[Table 11]
No content.

权利要求:
Claims (44)
[1" claim-type="Currently amended] Wherein the liquid crystal layer comprises two electrode substrates disposed between and at least one of the following components:
A) a metal oxide layer,
B) adjacent to said metal oxide layer,
B1) a silicon compound having an epoxy and alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof; And
B3) a cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer;
C) a transparent whole layer; And
D) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm,
The transparent conductive layer (C) is formed on the liquid crystal layer of the transparent polymer substrate (D), and the combination of the metal oxide layer (A) and the cured polymer layer (B) D of the transparent polymer substrate (D) or on a surface facing the transparent conductive layer (C) of the transparent polymer substrate (D).
[2" claim-type="Currently amended] The liquid crystal display element according to claim 1, wherein the silicon compound having epoxy and alkoxysilyl groups is represented by Formula 6, and the silicon compound having amino and alkoxysilyl groups is represented by Formula 7:
(Formula 6)

And 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 7)

Wherein, R ⁴ is alkylene having 1 to 4 carbon atoms,
R ⁵ and R ⁶ are independently alkyl having from 1 to 4 carbon atoms,
Y is hydrogen or aminoalkyl,
m is 0 or 1;
[3" claim-type="Currently amended] The liquid crystal display element according to claim 1 or 2, wherein the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula:
1/9 (B3) / [(B1) + (B2)] 9/1, (by weight), and
1/9 (B ₁ ) / (b ₂ ) 9/1, (mol)
Wherein, B1 to B3 is the amount indicated by the weight of said compounds (B1) to (B3), respectively, b ₁ represents the amount of said compound (B1) which, based on the moles of its epoxy group, b ₂ is Refers to the amount of compound (B2) based on the total moles of its amino and imide groups.
[4" claim-type="Currently amended] 4. The method according to claim 2 or 3, wherein the silicon compound represented by the formula (6) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And the silicon compound represented by the general formula (7) is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N - (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
[5" claim-type="Currently amended] The polyvinyl alcohol composition according to any one of claims 1 to 4, wherein the polyvinyl alcohol polymer is a polyvinyl alcohol, an ethylene-vinyl alcohol copolymer having a degree of saponification of 80% or more, and a polyvinyl Wherein the liquid crystal display element is selected from the group consisting of an organic solvent and an alcohol.
[6" claim-type="Currently amended] 6. The liquid crystal display element according to any one of claims 1 to 5, wherein the metal oxide layer comprises SiOx (wherein x is 1.5 X 2.0).
[7" claim-type="Currently amended] 7. The method according to any one of claims 1 to 6, wherein the at least one electrode substrate comprises a component (C) / (B) / (A) / (D) / (B) (D) / (B) / (C) in this order.
[8" claim-type="Currently amended] The method according to any one of claims 1 to 6, wherein the at least one electrode substrate comprises a component (C) / (A) / (B) / (D) / (B) (D) / (B) / (C) in this order.
[9" claim-type="Currently amended] 7. The method according to any one of claims 1 to 6, wherein the at least one electrode substrate comprises a component (C) / (B) / (A) / (B) / (D) / (B) (A) / (B) / (D) / (B) / (C) in this order.
[10" claim-type="Currently amended] 10. The liquid crystal display element according to any one of claims 1 to 9, wherein the transparent polymer substrate is selected from the group consisting of polycarbonate, polyarylate, polysulfone and polyethersulfone.
[11" claim-type="Currently amended] 11. The method according to any one of claims 1 to 10,
I) The cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula:
1/9 (B3) / [(B1) + (B2)] 9/1, (by weight), and
1/9 (B ₁ ) / (b ₂ ) 9/1, (mol)
Wherein, B1 to B3 is the amount indicated by the weight of said compounds (B1) to (B3), respectively, b ₁ represents the amount of said compound (B1) which, based on the moles of its epoxy group, b ₂ is The amount of compound (B2) based on the total moles of its amino and imide groups;
ii) the silicon compound represented by the formula (6) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane;
iii) the silicon compound represented by the general formula (7) is at least one selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane;
iv) the polyvinyl alcohol-based polymer is an ethyl-polyvinyl alcohol copolymer having an ethylene content of 10 to 50 mol%;
v) said metal oxide layer comprises SiOx (x is 1.5 x 2.0);
vi) the liquid crystal display element is characterized in that the transparent polymer substrate is selected from the group consisting of polycarbonate, polyarylate, polysulfone and polyethersulfone.
[12" claim-type="Currently amended] 12. The method according to any one of claims 1 to 11, wherein the transparent electrode substrate
I) the change in haze value is 1% or less when the N-methylpyrrolidone is brought into contact with the side of the cured polymer layer of the electrode substrate after being washed at 25 ° C for 10 minutes;
ii) the liquid does not deteriorate when the 3.5% NaOH aqueous solution comes into contact with the cured polymer layer side of the electrode substrate after being washed at 25 캜 for 10 minutes.
[13" claim-type="Currently amended] Wherein at least one of the electrode substrates comprises the following components:
A) a metal oxide layer,
B) a cured polymer layer adjacent the metal oxide layer;
C) a transparent whole layer; And
D) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm,
The transparent conductive layer (C) is formed on the liquid crystal layer side of the transparent polymer substrate (D), and the combination of the metal oxide layer (A) and the cured polymer layer (B) (D) or on a surface of the transparent polymer substrate (D) opposite to the transparent conductive layer (C)
Wherein the cured polymer layer comprises a cross-linked polyvinyl alcohol-based polymer and a unit represented by formula (1): < EMI ID =
(Formula 1)

Wherein p is an integer from 0 to 5,
q is an integer of 0 to 5,
A is a group represented by the following formula,
(2)

(Formula 3)

Wherein R ⁷ and R ⁸ are independently hydrogen, methyl, ethyl or phenyl and l is 0 or 1,
B is a group of formula
(Formula 4)

(Wherein r is an integer of 0 to 5 and s is an integer of 0 to 2), wherein * 2 and * 3 are bonded to each other.
[14" claim-type="Currently amended] 14. The method according to claim 13, wherein the cured polymer layer is obtained by a cross-linking reaction between a silicon compound having an epoxy and alkoxysilyl groups represented by the formula (6) and a silicon compound having an amino and alkoxysilyl group represented by the formula Liquid crystal display element:
(Formula 6)

And 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 7)

Wherein, R ⁴ is alkylene having 1 to 4 carbon atoms,
R ⁵ and R ⁶ are independently alkyl having from 1 to 4 carbon atoms,
Y is hydrogen or aminoalkyl,
m is 0 or 1;
[15" claim-type="Currently amended] The following ingredients:
A) a metal oxide layer,
B) adjacent to said metal oxide layer,
B1) a silicon compound having an epoxy and alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof; And
B3) a cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer;
C) a transparent whole layer; And
D) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm,
The combination of the metal oxide layer (A) and the cured polymer layer (B) may be disposed between the transparent conductive layer (C) and the transparent polymer substrate (D) Wherein the transparent electrode substrate is disposed on a surface opposite to the transparent electrode substrate.
[16" claim-type="Currently amended] The transparent electrode substrate according to claim 15, wherein the silicon compound having epoxy and alkoxysilyl groups is represented by Chemical Formula 6 and the silicon compound having amino and alkoxysilyl groups is represented by Chemical Formula 7:
(Formula 6)

And 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 7)

Wherein, R ⁴ is alkylene having 1 to 4 carbon atoms,
R ⁵ and R ⁶ are independently alkyl having from 1 to 4 carbon atoms,
Y is hydrogen or aminoalkyl,
m is 0 or 1;
[17" claim-type="Currently amended] The transparent electrode substrate according to claim 15 or 16, wherein the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula:
1/9 (B3) / [(B1) + (B2)] 9/1, (by weight), and
1/9 (B ₁ ) / (b ₂ ) 9/1, (mol)
Wherein, B1 to B3 is the amount indicated by the weight of said compounds (B1) to (B3), respectively, b ₁ represents the amount of said compound (B1) which, based on the moles of its epoxy group, b ₂ is Refers to the amount of compound (B2) based on the total moles of its amino and imide groups.
[18" claim-type="Currently amended] The method according to claim 16 or 17, wherein the silicon compound represented by the formula (6) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And the silicon compound represented by the formula (6) is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N - (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.
[19" claim-type="Currently amended] The polyvinyl alcohol composition according to any one of claims 15 to 18, wherein the polyvinyl alcohol polymer is a polyvinyl alcohol, an ethylene-vinyl alcohol copolymer having a saponification degree of 80% or more, and a polyvinyl Wherein the transparent electrode substrate is made of a material selected from the group consisting of silicon, aluminum, and aluminum.
[20" claim-type="Currently amended] The transparent electrode substrate according to any one of claims 15 to 19, wherein the polyvinyl alcohol polymer is an ethylene-vinyl alcohol copolymer having an ethylene content of 10 to 50 mol%.
[21" claim-type="Currently amended] 21. The transparent electrode substrate according to any one of claims 15 to 20, wherein the metal oxide layer comprises SiOx (x is 1.5 X 2.0).
[22" claim-type="Currently amended] 22. The transparent electrode substrate according to any one of claims 15 to 21, wherein the transparent polymer substrate is selected from the group consisting of polycarbonate, polyarylate, polysulfone, and polyethersulfone.
[23" claim-type="Currently amended] The composition according to any one of claims 15 to 22, wherein component (C) / (B) / (A) / (D) / (B) or (B) / (A) / (D) / / (C) in this order.
[24" claim-type="Currently amended] The composition according to any one of claims 15 to 22, wherein component (C) / (A) / (B) / (D) / (B) or (A) / (B) / (D) / / (C) in this order.
[25" claim-type="Currently amended] The composition according to any one of claims 15 to 22, wherein component (C) / (B) / (A) / (B) / (D) / (B) / (D) / (B) / (C) in this order.
[26" claim-type="Currently amended] 26. The transparent polymer substrate according to any one of claims 15 to 25, wherein one of the metal oxide layer (A), the cured polymer layer (B) and the transparent conductive layer (C) Wherein an anchor layer ( ) Selected from the group consisting of a silane coupler, a thermoplastic resin, a radiation-curable resin, and a heat-curable resin is disposed between them.
[27" claim-type="Currently amended] 11. The method according to any one of claims 1 to 10,
i) the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula:
1/9 (B3) / [(B1) + (B2)] 9/1, (by weight), and
1/9 (B ₁ ) / (b ₂ ) 9/1, (mol)
(Wherein, B1 to B3 is the amount indicated by the weight of said compounds (B1) to (B3), respectively, b ₁ represents the amount of said compound (B1) which, based on the moles of its epoxy group, b ₂ Represents the amount of compound (B2) based on the total moles of its amino and imide groups;
ii) the silicon compound represented by the formula (6) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane;
iii) the silicon compound represented by the general formula (7) is at least one selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane;
iv) the polyvinyl alcohol-based polymer is an ethyl-polyvinyl alcohol copolymer having an ethylene content of 10 to 50 mol%;
v) said metal oxide layer comprises SiOx (x is 1.5 x 2.0);
vi) The transparent electrode substrate is characterized in that the transparent polymer substrate is selected from the group consisting of polycarbonate, polyarylate, polysulfone and polyethersulfone.
[28" claim-type="Currently amended] 28. The method according to any one of claims 15 to 27,
I) the change in haze value is 1% or less when the N-methylpyrrolidone is brought into contact with the side of the cured polymer layer of the electrode substrate after being washed at 25 ° C for 10 minutes;
and ii) the aqueous solution of 3.5% of NaOH is not deteriorated when brought into contact with the side of the cured polymer layer of the electrode substrate after being washed at 25 캜 for 10 minutes.
[29" claim-type="Currently amended] The following ingredients:
A) a metal oxide layer,
B) a cured polymer layer adjacent the metal oxide layer;
C) a transparent whole layer; And
D) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm,
The combination of the metal oxide layer (A) and the cured polymer layer (B) may be disposed between the transparent conductive layer (C) and the transparent polymer substrate (D) Are arranged on opposite surfaces with respect to each other,
Wherein the cured polymer layer comprises a cross-linked polyvinyl alcohol-based polymer and a unit represented by Formula (1)
(Formula 1)

Wherein p is an integer from 0 to 5,
q is an integer of 0 to 5,
A is a group represented by formulas 2 and 3,
(2)

(Formula 3)

Wherein R ⁷ and R ⁸ are independently hydrogen, methyl, ethyl or phenyl and l is 0 or 1,
B is a group represented by the formula
(Formula 4)

(Wherein r is an integer of 0 to 5 and s is an integer of 0 to 2), wherein * 2 and * 3 are bonded to each other.
[30" claim-type="Currently amended] 29. The transparent conductive film according to claim 29, wherein the cured polymer layer is obtained by a cross-linking reaction between a silicon compound having epoxy and alkoxysilyl groups represented by the formula (6) and a silicon compound having an amino and alkoxysilyl group represented by the formula Electrode substrate:
(Formula 6)

And 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 7)

Wherein, R ⁴ is alkylene having 1 to 4 carbon atoms,
R ⁵ and R ⁶ are independently alkyl having from 1 to 4 carbon atoms,
Y is hydrogen or aminoalkyl,
m is 0 or 1;
[31" claim-type="Currently amended] D) a substrate; And
B) formed on the substrate surface,
B1) a silicon compound having an epoxy and alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof; And
B3) An article comprising a cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer.
[32" claim-type="Currently amended] 32. The article of claim 31, further comprising: A) a metal oxide layer adjacent the cured polymer layer.
[33" claim-type="Currently amended] 33. An article according to claim 31 or 32, characterized in that the substrate is made of resin.
[34" claim-type="Currently amended] 33. The epoxy resin composition according to claim 31, 32 or 33, wherein the silicon compound having epoxy and alkoxysilyl groups is represented by the formula (6), and the silicon compound having amino and alkoxysilyl groups is represented by the formula Goods:
(Formula 6)

And 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 7)

Wherein, R ⁴ is alkylene having 1 to 4 carbon atoms,
R ⁵ and R ⁶ are independently alkyl having from 1 to 4 carbon atoms,
Y is hydrogen or aminoalkyl,
m is 0 or 1;
[35" claim-type="Currently amended] 36. The method according to any one of claims 31 to 35,
i) the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula:
1/9 (B3) / [(B1) + (B2)] 9/1, (by weight), and
1/9 (B ₁ ) / (b ₂ ) 9/1, (mol)
(Wherein, B1 to B3 is the amount indicated by the weight of said compounds (B1) to (B3), respectively, b ₁ represents the amount of said compound (B1) which, based on the moles of its epoxy group, b ₂ Represents the amount of compound (B2) based on the total moles of its amino and imide groups;
ii) the silicon compound represented by the formula (6) is selected from the group consisting of 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane;
iii) the silicon compound represented by the general formula (7) is at least one selected from the group consisting of 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) said article further comprises a continuous metal oxide layer in said cured polymer layer, said metal oxide layer comprising SiOx (x is 1.5 x 2.0).
[36" claim-type="Currently amended] 36. The method according to any one of claims 31 to 35,
i) the change in haze value is 1% or less when N-methylpyrrolidone comes in contact with said cured polymer layer side of said article after being washed for 10 minutes at 25 占 폚;
ii) the 3.5% NaOH aqueous solution does not deteriorate when coming into contact with the side of the cured polymer layer of the article after being washed for 10 minutes at 25 占 폚;
and iii) the 5.0% aqueous HCl solution does not deteriorate when brought into contact with the side of the cured polymer layer of the article after being washed for 10 minutes at 25 ° C.
[37" claim-type="Currently amended] A) a metal oxide layer,
B) B1) a silicon compound having an epoxy and alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof; And
B3) a cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer; And
D) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm,
Wherein the metal oxide layer (A) and the cured polymer layer (B) are adjacent to each other.
[38" claim-type="Currently amended] 39. The method of claim 37,
I) the oxygen permeability is less than 10 cm ³ / m ² / day / atmospheric pressure at 40 ° C and 90% RH;
ii) when the N-methylpyrrolidone is brought into contact with the side of the cured polymer layer of the polymer substrate after being washed at 25 占 폚 for 10 minutes, the change in haze value is 1% or less;
iii) when the 3.5% NaOH aqueous solution is contacted with the cured polymer layer side of the polymer substrate after being washed at 25 占 폚 for 10 minutes;
iv) a 5.0% HCl aqueous solution is not deteriorated when brought into contact with the side of the cured polymer layer of the polymer substrate after being washed for 10 minutes at 25 ° C.
[39" claim-type="Currently amended] D) a transparent polymer substrate having a retardation of 30 nm or less with respect to a wavelength of 590 nm;
A) a metal oxide layer formed on the first side of the transparent polymer substrate;
B-1) adjacent to the metal oxide layer,
B1) a silicon compound having an epoxy and alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof; And
B3) a first cured polymer layer obtained from a crosslinking reaction of a polyvinyl alcohol polymer; And
B-2) a second transparent substrate disposed on a second side of the transparent polymer substrate opposite to the first substrate,
B1) a silicon compound having an epoxy and alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof; And
B3) A second cured polymer layer obtained from the crosslinking reaction of the polyvinyl alcohol polymer
≪ / RTI >
[40" claim-type="Currently amended] a) B1) a silicon compound having an epoxy and alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof; And
B3) Polyvinyl alcohol polymer
B4) carboxylic acid;
B5) organic solvent; And
B6) water
≪ / RTI >
b) coating the substrate with the coating composition; And
c) curing the coating composition by a cross-linking reaction between the compounds B1) to B3) to form a cured polymer layer on the substrate.
[41" claim-type="Currently amended] 41. The method of claim 40, further comprising forming a metal oxide layer.
[42" claim-type="Currently amended] 42. The method according to claim 40 or 41, further comprising the step of forming a transparent conductive layer.
[43" claim-type="Currently amended] B1) a silicon compound having an epoxy and alkoxysilyl group, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof;
B2) a silicon compound having amino and alkoxysilyl groups, a complete or partial hydrolysis product thereof, a complete or partial condensation product thereof, or a mixture thereof; And
B3) Polyvinyl alcohol polymer
B4) carboxylic acid;
B5) organic solvent; And
B6) water
≪ / RTI >
[44" claim-type="Currently amended] The coating composition according to claim 43, wherein the cured polymer layer (B) is obtained from the compounds (B1) to (B3) in an amount satisfying the following formula:
1/9 (B3) / [(B1) + (B2)] 9/1, (by weight), and
1/9 (B ₁ ) / (b ₂ ) 9/1, (mol)
Wherein, B1 to B3 is the amount indicated by the weight of said compounds (B1) to (B3), respectively, b ₁ represents the amount of said compound (B1) which, based on the moles of its epoxy group, b ₂ is Refers to the amount of compound (B2) based on the total moles of its amino and imide groups.

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同族专利:

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公开号 | 公开日

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KR100475418B1|2005-05-16|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
1996-03-25|Priority to JP6813596

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1996-03-25|Priority to JP96-68135

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1996-04-25|Priority to JP96-105142

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1996-08-09|Priority to JP21107596

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1996-08-09|Priority to JP96-211075

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1997-03-25|Application filed by 이타가키 히로시, 데이진 가부시키가이샤

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1998-06-05|Publication of KR19980018054A

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2005-05-16|Application granted

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2005-05-16|Publication of KR100475418B1

优先权:

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申请号 | 申请日 | 专利标题

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JP6813596|1996-03-25|

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JP96-68135|1996-03-25|

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JP96-105142|1996-04-25|

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JP96-211075|1996-08-09|

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JP21107596|1996-08-09|