JPH1052876A - Transparent conductive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve solvent resistance, optical isotropy and adhesive properties between layers by forming a protective layer on a transparent resin board having a metal oxide layer having a barrier layer represented by a formula and formed in contact with the metal oxide layer, and forming a transparent conductive layer on the protective layer. SOLUTION: A barrier layer is a layer made of (partial) hydrolyzate of alkoxysilane represented by the formula (where R<1> is an organic group having one or more groups selected from the group consisting of an 1-4C alkyl group, vinyl group or methacryloxy group, amino group, epoxy group and mercapto group, R<2> is an 1-4C alkyl group, and n is integer of 0 to 2), its (partial) condensate or their mixture, a (partial) hydrolyzate of alkoxysilane represented by the formula, or a polyvinyl alcohol polymer crosslinked by its (partial) condensate or their mixture. As the metal oxide layer, a transparent insulating metal oxide layer of silicon, aluminum or magnesium is used. As the protective layer, a radiation curable resin or thermosetting resin is used. As the transparent conductive layer, metal oxides are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive laminate excellent in durability, solvent resistance and gas barrier properties.
More particularly, the present invention relates to a transparent conductive laminate suitable for a transparent electrode substrate such as a liquid crystal display (LCD), a touch panel, a photoconductive photoreceptor, a surface light emitter, and organic electroluminescence.

[0002]

2. Description of the Related Art In recent years, portable and mobile information devices such as pagers, mobile phones, electronic organizers, personal digital assistants, and the like have begun to spread, and the business or lifestyle is about to change.

[0003] In order to improve the portability of these information devices, further reduction in thickness, weight and breakage resistance are required. Conventionally, a heavy, thick, and fragile glass substrate has been used as a transparent conductive substrate for LCDs and touch panels, but a transparent resin substrate has been proposed as an alternative material. However, the resin substrate is inferior to the glass substrate in basic characteristics such as durability, solvent resistance, and gas barrier properties.

For example, when a transparent resin substrate is to be used as an LCD electrode substrate, a gas barrier property is imparted by providing a metal oxide layer. However, in the resist stripping process after the transparent electrode patterning, the metal oxide layer is dissolved due to exposure to an alkaline aqueous solution, and in the process of forming the liquid crystal alignment film, the precursor of the liquid crystal alignment film is changed to N.
When coating a coating solution dissolved in a solvent such as methylpyrrolidone, the above-mentioned solvent has a problem that the transparent resin substrate is damaged such as whitening and swelling. Therefore, several proposals have been made for laminating an agent having chemical resistance and gas barrier properties on a transparent resin substrate for the purpose of improving the above-mentioned disadvantages.

[0005] JP-B-5-52002 and JP-B-5-52002
Japanese Patent No. 52003 describes a transparent substrate having improved adhesion between a polymer film and an oxygen gas barrier layer made of a polyvinyl alcohol-based polymer resin, and further having a water vapor gas barrier property.

However, since the polyvinyl alcohol-based polymer is laminated on the outermost layer, these have insufficient chemical resistance and cause problems in the liquid crystal cell manufacturing process. In order to impart chemical resistance, it is necessary to further provide a layer having chemical resistance on the transparent substrate, which increases the cost.

[0007] JP-A-2-137922 and JP-A-Hei-5
JP-A-309794 describes a transparent substrate in which an anchor coat layer is formed on a transparent polymer film, an ethylene-vinyl alcohol copolymer layer is formed as a gas barrier layer, and a curable resin layer is further formed on both surfaces as a solvent-resistant layer. Have been. However, although these have satisfactory chemical resistance,
Due to the characteristics of the gas barrier agent, there is a problem that the gas barrier property at high humidity decreases. In addition, as many as six coatings are costly.

Further, in the transparent substrate of the liquid crystal display device, there are the following requirements or problems regarding the characteristics in addition to the above-mentioned requirements for the chemical resistance and gas barrier properties.

[0009] When the transparency of the substrate is low or when there is birefringence, problems such as coloring of display and lowering of contrast arise.

When the flatness is low, the gap of the liquid crystal layer becomes non-uniform, and the liquid crystal alignment becomes uneven.
Since the substrate itself also has optical unevenness, the display color also has unevenness.

Further, if the flatness, transparency, and gas barrier properties are easily deteriorated when exposed to mechanical or thermal influences or a solvent, it is called light and thin, free shape, and curved surface display. Practicality utilizing characteristics is reduced, and it is difficult to adapt to applications where external influences such as pagers, mobile phones, electronic organizers, and pen input devices are greatly affected.
In particular, in order to maintain such characteristics with respect to mechanical effects, good adhesion between the layers stacked for expressing the characteristics is also required.

[0012]

DISCLOSURE OF THE INVENTION The present invention is intended to solve such a problem and is excellent in solvent resistance and gas barrier properties, and has the above-mentioned transparency, optical isotropy, and flatness. It is an object of the present invention to provide a transparent gas-barrier laminate having excellent adhesiveness and good interlayer adhesion, and further to reduce the number of laminates and suppress the production cost.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a (partial) hydrolyzate of a specific alkoxysilane which is in contact with at least one side of a metal oxide layer of a transparent resin substrate having a metal oxide layer. A) forming a protective layer on at least one side of a substrate on which a barrier layer containing a condensate or a mixture thereof, or a polyvinyl alcohol-based polymer cross-linked by the condensate or a mixture thereof is formed, and forming a transparent conductive layer on the protective layer; The present invention has been accomplished by finding out that this can be achieved by the formed laminated film.

That is, the present invention provides a transparent conductive substrate comprising a transparent resin substrate and a metal oxide layer, a barrier layer, a protective layer having solvent resistance, and a transparent conductive layer provided on any surface thereof. In the functional laminate, the barrier layer has the following general formula (1)

[0015]

Embedded image R ¹ _n— Si (OR ² ) _4-n (1) wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, a methacryloxy group, an amino group, an epoxy An organic group having at least one group selected from the group consisting of a group and a mercapto group, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. (Partial) hydrolyzate of an alkoxysilane represented by the formula (1), a (partial) condensate thereof, or a mixture thereof; A transparent conductive laminate comprising a layer made of a polyvinyl alcohol-based polymer cross-linked by a product or a mixture thereof, wherein a transparent conductive layer is formed on a protective layer.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The material constituting the transparent resin substrate of the present invention is not particularly limited as long as it is a transparent resin having good transparency and heat resistance. When the transparent conductive laminate of the present invention is used as an electrode substrate of an LCD or as an electrode substrate of a touch panel installed between an LCD electrode substrate and a polarizing plate, a transparent resin substrate may be a known measuring device. The retardation value represented by the product of the refractive index difference Δn of the birefringence at the wavelength of 590 nm Δn and the film thickness d Δn · d is 30.
nm and an optical isotropy with a variation of the slow axis within ± 30 °, more preferably a retardation of 20 nm or less and a variation of the slow axis of ± 15.
Those having a high degree of optical isotropy within a degree are preferred. Such transparent resin substrates include polyester-based, polycarbonate-based, polyarylate-based, polysulfone-based resins such as polysulfone, polyethersulfone, and polyallylsulfone; polyolefin-based resins; acetate-based resins such as cellulose triacetate; and various thermosetting resins. And the like. Above all, a substrate containing a polycarbonate resin as a main component is more suitable from the viewpoint of the above-mentioned transparency and optical characteristics of low optical anisotropy. The thickness of the transparent resin substrate is usually 30 μm to 80 μm.
0 μm.

Examples of the metal oxide layer used in the present invention include transparent insulating metal oxide layers of silicon, aluminum, magnesium, zinc and the like. It is manufactured by an evaporation method, an ion plating method, a plasma CVD method, or the like.
Among them, silicon oxide is particularly preferred as the metal oxide of the water vapor barrier layer from the viewpoint of transparency, surface flatness, flexibility, film stress, cost, and the like.

The composition of the silicon oxide is analyzed and determined by X-ray photoelectron spectroscopy, X-ray microspectroscopy, Auger electron spectroscopy, Rutherford backscattering, etc., and the transmittance and the flexibility in the visible light region are determined. From the viewpoint of the average composition represented by SiOx, x is preferably in the range of 1.5 ≦ x ≦ 2. If the value x is smaller than 1.5, the flexibility and the transparency will be poor.

The thickness of the metal oxide layer is 2 nm to 2 nm.
A range of 00 nm is preferred. The thickness of the metal oxide layer is 2n
If it is less than m, it is difficult to form a film uniformly, and a portion where the film is not formed occurs, and gas penetrates from this portion, resulting in poor gas barrier properties. On the other hand, if the thickness is more than 200 nm, not only lacks transparency, but also has poor flexibility,
Cracks occur and impair gas barrier properties.

The barrier layer of the present invention comprises component (a) a polyvinyl alcohol-based polymer and / or component (b) a (partial) hydrolyzate of alkoxysilane, a partial condensate thereof or a mixture thereof, comprising component (c) ) It is obtained by applying a coating composition dissolved in a solvent containing a polyvinyl alcohol-based polymer-soluble solvent.

Here, as the (a) polyvinyl alcohol polymer, a known commercially available polymer can be used, and specifically, at least one selected from the group consisting of a vinyl alcohol component and a vinyl alcohol copolymer component. Is preferably a polymer resin containing 50% by mole or more. Examples of the vinyl alcohol copolymer include a vinyl alcohol-vinyl acetate copolymer, a vinyl alcohol vinyl butyral copolymer, an ethylene-vinyl alcohol copolymer, and a polyvinyl alcohol polymer having a silyl group in a molecule. Is mentioned. Above all, in terms of solvent resistance and adhesion,
An ethylene-vinyl alcohol copolymer and a polyvinyl alcohol polymer having a silyl group in the molecule are preferred. Here, the ethylene-vinyl alcohol copolymer preferably has an ethylene copolymerization ratio of 50 mol% or less. If the copolymerization ratio of ethylene exceeds 50 mol%, satisfactory gas barrier properties cannot be obtained when the composition is cured. The polyvinyl alcohol polymer having a silyl group in the molecule is a polymer having a reactive silyl group represented by the following formula (4).

[0023]

Embedded image Here, R ¹¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
Represents an acyl group or an alkali metal or an alkaline earth metal; R ¹² represents an alkyl group having 1 to 10 carbon atoms;
Represents an integer of 1 to 3.

The content of the silyl group is preferably at most 5 mol%, more preferably at most 1 mol%. When the content of the silyl group is large, the coating composition tends to thicken and gel easily, which is not preferable.

The polyvinyl alcohol polymer containing a silyl group in the molecule used in the present invention, wherein the term “molecular” includes the terminal of the polymer, and the silyl group and the polyvinyl alcohol polymer are hydrolyzed. There are no particular restrictions on the position, distribution state, etc., as long as it is bonded to the polyvinyl alcohol-based polymer through a non-ionic bond.

The degree of polymerization and the degree of saponification of the polyvinyl alcohol polymer used in the present invention are not particularly limited, but the average degree of polymerization is preferably 100 to 5,000 and the degree of saponification is preferably 70% or more. If the degree of polymerization is too low, the adhesion will be reduced and the coating film will be brittle. Conversely, if it is too high, the viscosity will be too high and the coatability will deteriorate. If the saponification degree is too low, sufficient gas barrier properties cannot be obtained.

Component (b) The alkoxysilane which gives a (partial) hydrolyzate of an alkoxysilane, a partial condensate thereof or a mixture thereof is represented by the general formula (1)

[0028]

Embedded image It is preferable to use a tetra, tri or dialkoxysilane represented by R ¹ _n— Si (OR ² ) _4-n (1). In the formula, R ¹ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, or an organic group having at least one group selected from the group consisting of a methacryloxy group, an amino group, an imino group, an epoxy group, and a mercapto group; ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. Such an organic group is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that can include a cyclic structure, and the hydrocarbon group has a part of its carbon atoms converted to a hetero atom such as an oxygen atom or a nitrogen atom. It may be replaced.

Examples of such alkoxysilanes include, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropyloxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxy Silane, glycidoxymethyltripropoxysilane, glycidoxymethyltributoxysilane, 2-glycidoxyethyltrimethoxysilane, 2 Glycidoxy triethoxysilane, 2- glycidoxyethyl tripropoxysilane,
2-glycidoxyethyltributoxysilane, N-glycidoxyethyltrimethoxysilane, N-glycidoxyethyltriethoxysilane, N-glycidoxyethyltripropoxysilane, N-glycidoxyethyltributoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane,
3-glycidoxypropyltripropoxysilane, 3-
Glycidoxypropyltributoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltripropoxysilane, 2-glycidoxypropyltributoxysilane, N- Glycidoxypropyltrimethoxysilane, N-glycidoxypropyltriethoxysilane, N-glycidoxypropyltripropoxysilane, N-glycidoxypropyltributoxysilane,
(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, (3,4-epoxycyclohexyl) methyltripropoxysilane, (3,4-epoxycyclohexyl) methyltributoxy Silane, (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltriethoxysilane, (3,4-epoxycyclohexyl) ethyltripropoxysilane, (3,4-epoxycyclohexyl) ethyltributoxysilane, (3 , 4-epoxycyclohexyl) propyltrimethoxysilane,
(3,4-epoxycyclohexyl) propyltriethoxysilane, (3,4-epoxycyclohexyl) propyltripropoxysilane, (3,4-epoxycyclohexyl) propyltributoxysilane, (3,4-epoxycyclohexyl) butyltrimethoxy Silane,
(3,4-epoxycyclohexyl) butyltriethoxysilane, (3,4-epoxycyclohexyl) butyltripropoxysilane, (3,4-epoxycyclohexyl) butyltributoxysilane, aminomethyltriethoxysilane, 2-aminoethyltrisilane Methoxysilane,
2-aminoethyltriethoxysilane, 2-aminoethyltripropoxysilane, 2-aminoethyltributoxysilane, N-aminoethyltrimethoxysilane, N-
Aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3
-Aminopropyltributoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 2-aminopropyltripropoxysilane, 2-aminopropyltributoxysilane, N-aminopropyltrimethoxysilane, N-amino Propyltriethoxysilane, N-aminopropyltripropoxysilane, N-aminopropyltributoxysilane, N-
Aminomethylaminoethyltrimethoxysilane, N-aminomethylaminomethyltripropoxysilane, N-aminomethyl-2-aminoethyltrimethoxysilane, N
-Aminomethyl-2-aminoethyltriethoxysilane, N-aminomethyl-2-aminoethyltripropoxysilane, N-aminomethyl-3-aminopropyltrimethoxysilane, N-aminomethyl-3-aminopropyltriethoxysilane N-aminomethyl-3-aminopropyltripropoxysilane, N-aminomethyl-2
-Aminopropyltrimethoxysilane, N-aminomethyl-2-aminopropyltriethoxysilane, N-aminomethyl-2-aminopropyltripropoxysilane,
N-aminopropyltrimethoxysilane, N-aminopropyltriethoxysilane, N- (2-aminoethyl)
-2-aminoethyltrimethoxysilane, N- (2-aminoethyl) -2-aminoethyltriethoxysilane,
N- (2-aminoethyl) -2-aminoethyltripropoxysilane, N- (2-aminoethyl) -N-aminoethyltrimethoxysilane, N- (2-aminoethyl)
-N-aminoethyltriethoxysilane, N- (2-aminoethyl) -N-aminoethyltripropoxysilane, N- (2-aminoethyl) -2-aminoethyltrimethoxysilane, N- (2-aminoethyl ) -2-Aminoethyltriethoxysilane, N- (2-aminoethyl) -2-aminoethyltripropoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl)-
3-aminopropyltripropoxysilane, N- (3
-Aminoethyl) -2-aminoethyltrimethoxysilane, N- (3-aminoethyl) -2-aminoethyltriethoxysilane, N- (3-aminoethyl) -2-aminoethyltripropoxysilane, N-methyl Examples include aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-diethylenetriaminepropyltriethoxysilane.
These compounds can be used alone or in combination of two or more.

Of these, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane are preferable in terms of gas barrier properties and durability of the obtained coating film.

In addition, the alkoxysilane having an epoxy group and the alkoxysilane having an amino group are used in combination in that the obtained coating film has further improved solvent resistance and adhesion to a transparent resin substrate. Is more preferable. Here, particularly preferred alkoxysilanes having an epoxy group are 3-glycidoxypropyltrimethoxysilane and (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Particularly preferred alkoxysilanes having an amino group and / or imino group are 3-aminopropyltrimethoxysilane,
Aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl)
-3-aminopropyltrimethoxysilane, N- (2-
Aminoethyl) -3-aminopropylmethyldimethoxysilane. These compounds can be used alone or in combination of two or more.

The (partial) hydrolyzate of alkoxysilane and its partial condensate include those obtained by partially or entirely hydrolyzing the alkoxysilane, condensates obtained by subjecting part or all of the hydrolyzate to a condensation reaction, and The condensate and a non-hydrolyzed raw material alkoxysilane are condensed,
These are obtained by a so-called sol-gel reaction.

When the alkoxysilane is used, it can be added as a component as it is, or after hydrolysis in advance, a (partial) hydrolyzate of the alkoxysilane and a partial condensate thereof are added and used. It is also possible.

For the hydrolysis, a usual method, for example, a method of hydrolysis with an inorganic acid such as hydrochloric acid, an organic acid such as acetic acid, or an alkali such as caustic soda, or using only water can be used. It is also possible to carry out hydrolysis after mixing the alkoxysilane and the alkoxysilane-soluble solvent for the purpose of performing the hydrolysis uniformly. Depending on the purpose, cooling or heating can be performed during the hydrolysis. Further, after the hydrolysis, an alcohol or the like generated by the reaction can be removed by heating and / or an appropriate amount under reduced pressure before use, or an appropriate solvent can be added thereafter.

It is also possible to add a curing catalyst as required. As the curing catalyst, for example, aluminum acetylacetonate, aluminum ethyl acetoacetate bisacetylacetonate, aluminum bisacetoacetate acetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i-propoxide monomethylacetoacetate and the like Aluminum chelate compounds, alkali metal salts of carboxylic acids such as sodium acetate, potassium acetate, potassium formate, amine carboxylates such as dimethylamine acetate, ethanol acetoate, dimethylaniline formate, benzyltrimethylammonium hydroxide, tetramethylammonium acetate Quaternary ammonium salts such as benzyltrimethylammonium acetate, metal carboxylic acids such as tin octoate , And triethylamine, triethanolamine, amine such as pyridine, 1,8-diazabicyclo [5,4,0] -7-undecene is used. These compounds can be used alone or
More than one species can be used together.

The solvent of the component (c) is a solvent containing a polyvinyl alcohol polymer soluble solvent. Here, examples of the polyvinyl alcohol-based polymer-soluble solvent include water and dimethylimidazoline. Also,
When an ethylene-vinyl alcohol copolymer is used as the polyvinyl alcohol-based polymer, examples of the soluble solvent include a mixed solvent of water / propanol. The mixing ratio of water and propanol is preferably water / propanol = 3/7 to 7/3 by weight. As a solvent that can be used in combination, a solvent can be used as long as it is uniformly mixed with a polyvinyl alcohol-based polymer-soluble solvent and the component (a) and / or component (b) can be uniformly dissolved. , Ketones, amides and the like. Among these solvents which can be used in combination, alcohol solvents such as butanol, cellosolve solvents such as 1-methoxy-2-propanol, and ketone solvents such as cyclohexanone are preferable for improving the smoothness of the barrier layer. Used. These solvents that can be used together can be used alone or in combination of two or more.

The components (a) to (c) are preferably used in the following proportions. That is, the weight ratio (a) / (b) of the component (a) and the component (b) is used in the range of 9/1 to 1/9. Here, the component (b) is based on weight based on R ¹ _n- SiO _{(4-n) / 2} . If (a) / (b) is more than 9/1, the water resistance and chemical resistance tend to be inferior, and if it is less than 1/9, the storage stability of the coating composition tends to deteriorate. A more preferred range of (a) / (b) is 4/1 to 1
/ 4.

As component (a), a silyl group-containing polyvinyl alcohol is used. As component (b), an alkoxysilane having an epoxy group and a (partial) hydrolyzate of an alkoxysilane having an amino group and / or an imino group, When the partial condensate or a mixture thereof is used, the weight ratio (a) / (b) can be used in the range of 2/1 to 0/1. Further, an ethylene-vinyl alcohol copolymer as the component (a), an alkoxysilane having an epoxy group, and a (partial) hydrolyzate of an alkoxysilane having an amino group and / or an imino group as the component (b), and partial condensation thereof When using a product or a mixture thereof, the weight ratio (a) / (b) is 9/1 to 0 /
1 can be used. Here, when an alkoxysilane having an epoxy group and a (partial) hydrolyzate of an aminosilane and / or an alkoxysilane having an imino group, a partial condensate thereof, or a mixture thereof are used, the (epoxy) group / (amino group) And the sum of imino groups) affect the performance of the resulting coating film, and when the molar equivalent is 6/1 to 1/6, the adhesion, heat resistance, chemical resistance, water resistance, and durability A coating film with excellent quality can be obtained. Either the epoxy group or the amino group component becomes excessive relative to the other, and the performance of the coating film decreases as the content deviates from the above range.

The amino group and / or imino group is a condensation catalyst for a hydrolyzate of an alkoxysilane having an epoxy group, and simultaneously reacts with the epoxy group. When an alkoxysilane having the formula (1) is added, the reaction occurs rapidly, and the coating composition tends to gel. Therefore, when an alkoxysilane having an amino group and / or an imino group is used, it is preferable to use a carboxylic acid to make a weakly acidic organic acid salt and adjust the pot life. Here, the carboxylic acid includes, for example, formic acid, acetic acid, propionic acid, butyric acid, etc., and acetic acid is most preferable in view of its acidity and volatility.

The amount of the carboxylic acid to be added is 0.1 to 1 per mole of the total of the amino groups and imino groups of the component (b).
The amount is in the range of 0 mol, preferably in the range of 0.5 to 5.0 mol. When the amount is less than 0.5 mol, the pot life of the coating composition to be adjusted from this becomes short, and the composition is easily gelled. Become. On the other hand, when the amount is more than 10 mol, the curing of the coating composition becomes insufficient.

Further, component (c) comprises component (a) and / or
Or 200 parts by weight with respect to 100 parts by weight of the total solid content of (b).
A range of not less than 99 parts by weight and not more than 99900 parts by weight is preferably used. When the amount is less than 200 parts by weight, the storage stability of the composition is deteriorated. On the other hand, when the amount is more than 99900 parts by weight, the storage stability of the composition itself is improved, but the solid content in the composition is reduced and the composition is obtained by coating. The thickness of the applied coating film is limited.

As the additive, various surfactants can be used for the purpose of improving the surface smoothness, and examples thereof include silicone compounds, fluorine surfactants, and organic surfactants. Further, as a modifier, various epoxy resins compatible with the coating composition,
Melamine resins, amide resins, colloidal silica, and the like may be added. Such additional components other than the components (a), (b) and (c) are characteristics of the cured resin layer of the present invention, for example, heat resistance, weather resistance, water resistance, durability, adhesion, or chemical resistance. Various practical characteristics can be improved depending on the application to which the laminated film of the present invention is applied.

In the present invention, when a transparent polymer film has a metal oxide layer on at least one surface, the coating composition for providing a barrier layer is laminated so as to be in contact with at least the metal oxide layer. As the method, a commonly used coating method such as dip coating, spray coating, flow coating, roll coating, bar coating, and spin coating is used. The thickness of the barrier layer having barrier properties is preferably from 0.01 to 100 μm. If it exceeds 100 μm, it takes time to cure the film, which is not economically preferable.

In the applied polymer film, the solvent is usually removed by evaporation at a temperature from room temperature to a temperature not higher than the heat deformation temperature of the film. Next, it is heated and cured at a temperature of 50 to 150 ° C. for 1 minute or more. In this step, the barrier layer is cured, and the coating composition for providing the barrier layer is a (partial) hydrolyzate of an alkoxysilane represented by the general formula (1), a (partial) condensate thereof, or a mixture thereof, and a polyvinyl alcohol-based polymer. In the case of containing, a barrier layer which is a cured film of a polyvinyl alcohol-based polymer crosslinked by a (partial) hydrolyzate of an alkoxysilane, a (partial) condensate thereof, or a mixture thereof is formed.

The barrier layer adheres well to the surface of the substrate provided with the SiOx (1.5 ≦ x ≦ 2) thin film, particularly as a metal oxide layer. Can be subjected to surface modification such as corona treatment and anchor coat treatment to further improve the adhesion between layers.

In the present invention, the protective layer having solvent resistance must be selected in consideration of the adhesion between the transparent conductive layer and the substrate. Examples of such a protective layer include a radiation-curable resin and a thermosetting resin. The radiation-curable resin refers to a resin that cures when irradiated with radiation such as ultraviolet rays or electron beams. For example, a resin containing an unsaturated double bond such as an acryloyl group, a methacryloyl group, or a vinyl group in a molecule or a unit structure can be used. Above all, a resin containing an acryloyl group is preferred from the viewpoint of reactivity.

These radiation-curable resins may be of a single composition or a mixture of several kinds, but from the viewpoint of solvent resistance, a polyfunctional acrylate component having two or more acryloyl groups in the molecule or unit structure. Is preferably contained in the resin component. Examples of the polyfunctional acrylate component include acrylate monomers such as dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, petaerythritol triacrylate, and trimethylolpropane triacrylate, and polyester-modified or urethane-modified polyacrylates. Functional acrylate oligomers include, but are not limited to.

Among these, polyester-modified acrylate oligomers are preferred from the viewpoint of the mechanical properties of the transparent conductive film and the resistance to alkali aqueous solution. Particularly, the compound represented by the following general formula (2) is preferably 50% by weight in terms of solid content. % Is preferable.

[0049]

Embedded image

Here, R ³ is a hydrogen atom, a halogen atom,
Shows a methyl group or an ethyl group. m is an average value,
It is a number in the range of 0.5 to 2.

These radiation-curable resin compositions may be modified, if necessary, with a photoinitiator, various additives such as a polymerization inhibitor, a leveling agent and an ultraviolet absorber, a thermoplastic resin and a plasticizer. An agent is added to make a coating liquid. It is diluted with an appropriate organic solvent as needed to adjust the concentration and viscosity of the coating liquid. The coating liquid is coated on a substrate or a barrier layer having a barrier property by a known coating method, for example, dip coating, spray coating, flow coating, roll coating, bar coating, spin coating, and the like, if necessary. After pre-drying, it is cured by irradiation with radiation.

When curing by irradiation with ultraviolet light, a photoinitiator is an essential component. Such initiators include, for example, diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,
2-hydroxy-2-methyl-1-phenylpropane-
Examples include acetophenone compounds such as 1-one and 1-hydroxycyclohexyl phenyl ketone; benzoin compounds such as benzoin and benzyldimethyl ketal; and thioxane compounds such as thioxanthone and 2,4-dichlorothioxanthone.

In order to further improve the curability, triethanolamine, methyldiethanolamine, 4-
It is also effective to add an appropriate amount of a known photoinitiating aid such as ethyl dimethylamine benzoate. The thickness of the protective layer of the radiation-curable resin composition is preferably from 2 to 8 μm, particularly preferably 2 to 8 μm.
〜6 μm is preferred. If it is less than 2 μm, the solvent resistance is insufficient, and if it exceeds 8 μm, curling due to curing shrinkage occurs, which is not preferable.

Typical examples of the thermosetting resin include an epoxy resin and an isocyanate-crosslinked urethane resin. Among them, a phenoxy resin, a phenoxy ether resin and a phenoxy ester resin represented by the following general formula (3) are used. Phenoxy resin cured products, phenoxy ether resin cured products, and phenoxy ester resin cured products cured with compounds are preferred.

[0055]

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Here, R ⁴ to R ⁹ are the same or different hydrogen or an alkyl group having 1 to 3 carbon atoms, R ¹⁰ is an alkylene group having 2 to 5 carbon atoms, Y is an ether group, an ester group, and p is 0 to An integer of 3 and q mean an integer of 20 to 300, respectively.

The thickness of the protective layer of the thermosetting resin is not particularly limited, but if it is less than 3 μm, the solvent resistance is insufficient. The upper limit of the film thickness is determined by the balance between film forming property, economic efficiency and solvent resistance. Preferably it is 20 μm or less, more preferably 10 μm or less.

These thermosetting resin compositions are coated with various additives such as reactive diluents, fine particles and leveling agents, and modifiers such as thermoplastic resins and plasticizers, if necessary. It will be a working fluid. It is diluted with an appropriate organic solvent as needed to adjust the concentration and viscosity of the coating liquid. The coating liquid is coated on a substrate or a barrier layer having a barrier property by a known coating method, for example, dip coating, spray coating, flow coating, roll coating, bar coating, spin coating, or the like, and is applied at 120 ° C. or higher. At a temperature of 3 minutes or more, more preferably at 130 ° C. or more for 5 minutes or more.

The transparent conductive layer of the present invention is preferably a metal oxide film from the viewpoint of transparency, conductivity and mechanical properties.
For example, metal oxide thin film layers such as indium oxide, cadmium oxide, and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, and the like are added as impurities, zinc oxide, and titanium oxide to which aluminum is added as impurities are given. In particular, a thin film layer of indium oxide (ITO) containing 2 to 15% by weight of tin oxide is excellent in transparency and conductivity, and is preferably used.

Examples of the method for forming the transparent conductive layer include a vacuum deposition method, a sputtering method, an ion beam sputtering method, and an ion plating method.

The thickness of the transparent conductive layer is preferably 15 to 180 nm. If it is less than 15 nm, the film becomes a discontinuous film and the conductivity becomes insufficient. On the other hand, if it exceeds 180 nm, the transparency is lowered or the bending resistance is deteriorated.

In the transparent conductive laminate of the present invention, a protective layer having solvent resistance is laminated on both sides of the transparent resin substrate,
The protective layer can be provided on one side and a metal oxide layer and a barrier layer can be provided on the other side. Further, the transparent conductive layer is preferably formed by lamination on the surface of one of the solvent-resistant protective layers.

As a preferred layer structure of the transparent conductive laminate of the present invention, a metal oxide layer and a barrier layer are laminated in this order on one surface of a transparent resin substrate, and the other surface has a solvent resistance. Having a protective layer, a configuration in which a transparent conductive layer is laminated in this order, a metal oxide layer on one surface of a transparent resin substrate,
A structure in which a barrier layer, a protective layer having solvent resistance is laminated in this order, and a protective layer having solvent resistance on the other surface, a transparent conductive layer is laminated in this order, on one surface of the transparent resin substrate. A structure in which a metal oxide layer, a barrier layer, a protective layer having solvent resistance and a transparent conductive layer are laminated in this order, and a protective layer having solvent resistance is laminated on the other surface; On the surface, a metal oxide layer, a barrier layer, a protective layer having solvent resistance and a transparent conductive layer are laminated in this order, and on the other surface, a protective layer having solvent resistance and a transparent conductive layer are laminated in this order. The laminated structure, on one surface of the transparent resin substrate, a metal oxide layer, a barrier layer, a protective layer having solvent resistance, a transparent conductive layer is laminated in this order, a metal oxide layer on the other surface,
A structure in which a barrier layer is laminated in this order, a metal oxide layer, a barrier layer, and a protective layer having solvent resistance are laminated in this order on both surfaces of the transparent resin substrate. A structure in which a metal oxide layer, a barrier layer, a protective layer having solvent resistance, and a transparent conductive layer are laminated in this order on both surfaces of a transparent resin substrate. .

It is also possible to improve the adhesion reliability between each layer and between the substrate and each layer by adding a silane coupling agent or using an adhesive layer serving as a primer or a corona treatment.

[0065]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but it should not be construed that the invention is limited thereto.
In the examples, parts and% are by weight unless otherwise specified. Various measurements in the examples were performed as follows.

Transparency: Wavelength 55 using an ordinary spectrophotometer
The light transmittance of a parallel light of 0 nm was measured. Further, the haze value (ΔH%) was measured using COH-300A manufactured by Nippon Denshoku. Optical isotropy: Multi-wavelength birefringence index measuring device M- manufactured by JASCO
Using 150, the retardation value for light having a wavelength of 590 nm was measured. Solvent resistance: immersed in a 3.0% NaOH aqueous solution at 25 ° C. for 10 minutes, sufficiently washed with running water, dried, and visually observed. Solvent resistance: immersed in a 5.0% HCl aqueous solution at 25 ° C. for 10 minutes, sufficiently washed with running water, dried, and visually observed for appearance. Solvent resistance: A few drops of N-methylpyrrolidone at 80 ° C. were dropped on the transparent conductive layer, left standing for 5 minutes, washed sufficiently with running water, and visually observed for appearance.

Gas Barrier Property: The gas barrier property was evaluated without providing a transparent conductive layer. The oxygen permeability is Oxytran 2/2 manufactured by Modern Control (MOCON).
Using 0ML, the measurement was performed in a low humidity environment of 30 ° C. and 50% RH and in a high humidity environment of 30 ° C. and 90% RH.
In addition, the water vapor permeability is Percontran W1 manufactured by MOCON.
Using A, the water vapor permeability under an atmosphere of 40 ° C. and 90% RH was measured. Adhesion: The adhesion of the coating film was evaluated according to JIS K5400 8.5.2. Flex resistance: 10 m in diameter so that the transparent conductive layer is on the inside
m, deformed along the periphery of the glass tube, held for 1 minute, returned, and observed for cracks in the transparent conductive layer. Length 5
The case where there is a crack of not less than mm is regarded as defective.

Example 1 A roll of a polycarbonate film having a thickness of 100 μm was set at a predetermined position of a vacuum evaporation apparatus, and then evacuated to a pressure of 1.3 mPa. A vapor deposition material composed of a mixture of Si and SiO ₂ was evaporated by electron beam heating to form a 20 nm thick SiOx film (x value was about 1.7) on one surface of the polycarbonate film.

Next, a coating composition A for providing a barrier layer of the present invention was prepared, and the coating composition A was applied on a SiOx layer of a polycarbonate film on which SiOx was laminated by a microgravure method.
The resultant was dried by heating at 0 ° C. for 3 minutes to form a barrier layer having a thickness of 2 μm. Here, in preparing the coating composition A, a solution of 5 parts of a polyvinyl alcohol-based polymer (manufactured by Nippon Synthetic Chemical Co., Ltd., Gohsenol NM-11Q, (a)) and 95 parts of distilled water was mixed with tetramethoxy. After 6.3 parts of silane (b) were mixed and the solution became uniform,
0.5 parts of a 0% aqueous benzyltrimethylammonium hydroxide solution was added, and the mixture was aged for 24 hours. In the coating composition A, (a) / (b) = 2/1.

Further, the coating composition B for providing the solvent-resistant protective layer of the present invention was prepared, and the coating composition B was applied to both sides of the laminate having the polycarbonate film formed with the SiOx layer and the barrier layer. Coated by gravure method, pre-dried at 50 ° C for 1 minute,
Next, by using a 160 W / cm high-pressure mercury lamp and irradiating ultraviolet rays under the condition of an integrated light quantity of 800 mJ / cm ² , the coating film was cured to form a 4 μm-thick protective layer. Here, in preparing the coating composition B, 100 parts of trimethylolpropane triacrylate (Aronix M-309, manufactured by Toa Gosei Chemical Co., Ltd.)
After mixing 7 parts of photoinitiator 1-hydroxycyclohexyl phenyl ketone (Irgacure-184, manufactured by Ciba Geigy) and 0.02 parts of silicon oil (SH28PA, manufactured by Dow Corning Toray) as a leveling agent, 1
-Methoxy-2-propanol and methanol to 35 wt% solids.

Next, the roll of the laminate having the polycarbonate film obtained as a substrate as a substrate was set in a sputtering apparatus and then evacuated to a pressure of 1.3 mPa. Subsequently, an Ar.O ₂ mixed gas (O ₂ concentration 1.4)
vol%), and the pressure was adjusted to 0.27 Pa. ITO target (SnO ₂ concentration 5wt%)
By performing DC sputtering under the condition of an input power density of 1 W / cm ² and providing a transparent conductive layer made of an ITO film having a thickness of 130 nm on a solvent-resistant protective layer in contact with the polycarbonate film. A laminate was obtained. Table 1 shows the evaluation results of the obtained transparent conductive laminate.

Example 2 A coating composition C was used in place of the coating composition A for providing a barrier layer, and a protective layer having solvent resistance was opposite to the surface of the polycarbonate film on which the SiOx layer and the barrier layer were formed. A transparent conductive laminate was obtained in the same manner as in Example 1, except that only the surface was laminated. Table 1 shows the obtained results. Here, in adjusting the coating composition C, ethylene-
Vinyl alcohol copolymer (EVAL- manufactured by Kuraray Co., Ltd.)
F (ethylene copolymerization ratio 32%), (a)) 100 parts,
After heating and dissolving in a mixed solution of 720 parts of water, 1080 parts of n-propanol, and 100 parts of n-butanol to form a uniform solution and allowing it to cool to room temperature, 0.1 part of SH30PA manufactured by Toray Dow Corning Co., Ltd. was added as a leveling agent. Acetic acid 6
2.4 parts were added, followed by 85.8 of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (b).
Was added and stirred for 10 minutes. 62.4 parts of 3-aminopropyltrimethoxysilane (b) was further added to this solution to give 3 parts.
Stirred for hours. In the coating composition C, (a)
/ (B) = 1/1, and (epoxy) group / (sum of amino group and imino group) = 1/1.

Example 3 A transparent conductive laminate was obtained in the same manner as in Example 2 except that the coating composition C for providing a barrier layer was replaced with the coating composition D. Table 1 shows the obtained results. Here, in preparing the coating composition D, a mixed solution of 100 parts of a silyl group-containing polyvinyl alcohol polymer (Kuraray R1130 (silyl group content less than 1%)), 1300 parts of water, and 600 parts of n-propanol was used. After heating and dissolving the mixture in a homogeneous solution, the mixture was allowed to cool to room temperature, and 0.1 parts of SH30PA manufactured by Toray Dow Corning Co., Ltd. and 124.8 parts of acetic acid were added thereto as a leveling agent, and then 3-aminopropyltrimethoxysilane was added. 124.8 parts were added and the mixture was stirred for 3 hours. Further, 2- (3,4-epoxycyclohexyl) was added to the solution.
171.6 parts of ethyltrimethoxysilane was added and stirred for 3 hours. In the coating composition D, (a) /
(B) = 1/2, and (epoxy) group / (sum of amino group and imino group) = 1/1.

Example 4 A coating composition E was used in place of the coating composition B to provide a protective layer having solvent resistance. The coating composition E was heat-treated at 80 ° C. for 5 minutes and at 130 ° C. for 5 minutes to form a 5 μm protective layer. Except for forming, a transparent conductive laminate was obtained in the same manner as in Example 2. Table 1 shows the obtained results. Here, in preparing the coating composition E, as a phenoxy ester resin, 20 parts of PKHM-30 manufactured by Union Carbide Corporation, 40 parts of methyl ethyl ketone, and 2-ethoxyethyl acetate 2
To the mixture obtained by mixing 0 parts, 20 parts of Coronate L manufactured by Nippon Polyurethane Co., Ltd. was further mixed as a polyfunctional isocyanate.

Example 5 A transparent conductive laminate was obtained in the same manner as in Example 2, except that the coating composition F for providing a barrier layer was replaced with the coating composition F. Table 1 shows the obtained results. Here, in adjusting the coating composition F, 0.2 part of Toray Dow Corning SH30PA as a leveling agent and 230 parts of acetic acid were added to a mixed solution of 1300 parts of water and 650 parts of n-propanol. 233 parts of 3-aminopropyltrimethoxysilane was added and stirred for 3 hours, and 640 parts of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was further added to this solution and stirred for 24 hours. In the coating composition F, the (epoxy) group /
(Sum of amino group and imino group) = 2/1.

Comparative Example 1 A transparent conductive laminate was obtained in the same manner as in Example 2 except that the barrier layer was not laminated. Table 1 shows the obtained results.

Comparative Example 2 A transparent conductive film was formed in the same manner as in Example 1 except that a 2 μm-thick polyvinyl alcohol-based polymer (Gohsenol NM-11Q, manufactured by Nippon Synthetic Chemical Co., Ltd.) was laminated instead of the barrier layer. The obtained laminate was obtained. Table 1 shows the obtained results.

[0078]

[Table 1]

[0079]

According to the present invention, there is provided a gas barrier laminate having excellent solvent resistance and gas barrier properties, as well as excellent transparency, optical isotropy and flatness, and excellent adhesion between layers.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C23C 14/08 C23C 14/08 D

Claims (8)

[Claims] 1. A transparent conductive laminate comprising a transparent resin substrate and a metal oxide layer, a barrier layer, a protective layer having solvent resistance, and a transparent conductive layer provided on any surface thereof. The barrier layer is made of the following general formula (1): R ¹ _n —Si (OR ² ) _4-n (1) [where R ¹ is an alkyl group having 1 to 4 carbon atoms. , A vinyl group, or an organic group having at least one group selected from the group consisting of a methacryloxy group, an amino group, an epoxy group and a mercapto group; R ² is an alkyl group having 1 to 4 carbon atoms;整数 2. (Partial) hydrolyzate of alkoxysilane represented by the formula (1), (partial) condensate thereof or a mixture thereof, or (partial) hydrolyzate of alkoxysilane represented by the above general formula (1), (partial) condensation thereof A transparent conductive laminate comprising a layer made of a polyvinyl alcohol-based polymer crosslinked by a product or a mixture thereof, wherein a transparent conductive layer is formed on a protective layer. 2. The transparent resin substrate according to claim 1, wherein the protective layer and the transparent conductive layer are laminated in this order on one surface of the transparent resin substrate, and a metal oxide layer and a barrier layer are laminated in this order on the other surface. 2. The transparent conductive laminate according to 1. 3. The method according to claim 1, wherein the metal oxide layer has a thickness of 2 nm to 200 nm.
The transparent conductive laminate according to claim 1, comprising a silicon oxide having an average composition represented by SiOx of nm (where 1.5 ≦ x ≦ 2). 4. The transparent conductive laminate according to claim 1, wherein the alkoxysilane is an alkoxysilane having an epoxy group and an alkoxysilane having an amino group and / or an imino group. 5. The polyvinyl alcohol-based polymer according to claim 1,
The transparent conductive laminate according to any one of claims 1 to 4, which is a silyl group-containing polyvinyl alcohol and / or an ethylene-vinyl alcohol copolymer. 6. The transparent conductive laminate according to claim 1, wherein the transparent resin substrate mainly comprises a polycarbonate resin. 7. The protective layer having solvent resistance is represented by the following general formula (2): (Where, R ³ represents a hydrogen atom, a halogen atom, a methyl group or an ethyl group. M is a number in the range of 0.5 to 2 as an average value). The transparent conductive laminate according to any one of claims 1 to 6, which is a cured product of a radiation-curable resin containing at least 50% by weight of the radiation-curable resin. 8. The protective layer having solvent resistance, which is represented by the following general formula (3): (Where R ⁴ to R ⁹ are the same or different hydrogen or an alkyl group having 1 to 3 carbon atoms, R ¹⁰ is an alkylene group having 2 to 5 carbon atoms, Y is an ether group, an ester group, and p is 0 to 3 Phenoxy resin, phenoxy ether resin, phenoxy ester resin cured with a polyfunctional isocyanate compound, phenoxy resin cured product, phenoxy ether resin cured product, phenoxy ester The transparent conductive laminate according to any one of claims 1 to 6, which is a cured resin.