JP2000353426A - Transparent conductive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film excellent in bendability for use as a transparent conductive substrate for a liquid-crystal display element, by making up an organic layer on, at least, one surface of a polymeric film out of an acrylic polymer including units of a specific structure. SOLUTION: This transparent conductive film has organic layers on both surfaces of a transparent polymeric film, At least one of the organic layers is positioned between a transparent conductive layer and the transparent polymeric film, and is made up of an acrylic polymer including units expressed by a formula. Preferably, the structure of the units expressed by the formula is contained by 20 to 100% per total weight making up the organic layer. Preferably, the film thickness of the organic layer is 1 to 20 μm. From the viewpoint of transparency and adhesiveness to the organic layer, it is especially preferable to use a polycarbonate film as the transparent polymeric film, thereby sharply improving bending resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent conductive film, and more particularly, it has excellent flexibility and durability and can be preferably used as a transparent conductive electrode substrate of a liquid crystal display device. The present invention relates to a transparent conductive film that can be used also as an electrode substrate for an electrochromic device or the like.

[0002]

2. Description of the Related Art In recent years, as the use of portable devices such as pagers, cellular phones, electronic notebooks, and pen input devices has expanded, conventional glass substrates have been replaced with features such as light weight, improved impact resistance, and the ability to display curved surfaces. Liquid crystal display elements having a plastic substrate have been put into practical use.

A plastic substrate is disclosed in
86252, flat panel display 19
94 (Nikkei BP), pp. 123-131, on a polymer film, an organic layer exhibiting resistance to alkalis and organic solvents, and a layer having gas barrier properties for improving the reliability of the liquid crystal display device. It is described that the transparent conductive layer is laminated on the outermost layer. So far, studies have been made on polymer films, organic layers, gas barrier layers, and transparent conductive layers, and on layers and techniques for improving the interlayer adhesion.

[0004] For example, with respect to polymer films, from the viewpoints of optical characteristics, heat resistance, etc., amorphous polymers such as polycarbonate, polyethersulfone, polysulfone, amorphous polyolefin, heat-resistant acryl, polyester, and these polymers The metamorphic film is considered
Regarding a film forming method, a solution casting method, a melt extrusion method, and the like have been studied.

For the organic layer, various types of actinic ray (eg, ultraviolet) curable resins and thermosetting resins have been studied, and improvements in solvent resistance, adhesion to other layers, hard coat properties, and the like have been studied. Have been.

The gas barrier layer is made of an organic material such as polyvinyl alcohol, ethylene-vinyl alcohol, vinylidene chloride, polyacrylonitrile, polyamide or the like and a modified product thereof, or an inorganic material composed of silicon oxide, aluminum oxide or a modified product thereof. Layer considerations have been made.

[0007] Regarding the transparent conductive layer, studies have been made on its material and film forming method, for example, aiming at high transparency and low resistance.

[0008]

However, when used as an electrode substrate, none of the plastic substrates sufficiently satisfy the characteristic of flexibility. That is,
When the substrate is bent at the time of mounting, a crack occurs in the transparent conductive layer, and as a result, disconnection is caused, and a display failure may occur. Especially to lower the surface resistance
When the transparent conductive layer was made thicker, it was remarkable. An object of the present invention is to provide a transparent conductive film excellent in flexibility and particularly suitable as a transparent conductive substrate of a liquid crystal display device.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the organic layer provided between the transparent conductive layer and the polymer film is important for flexibility.

That is, the present invention provides (i) an organic layer on both surfaces of a polymer film, and (ii) at least one oxide selected from oxides of Si, Al and Mg on at least one surface. And (iii) a transparent conductive film having a transparent conductive layer containing indium oxide as a main component in at least one outermost layer,
The organic layer on at least one surface of the polymer film is a transparent conductive film comprising an acrylic polymer containing a unit represented by the following formula (1).

[0011]

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[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent conductive film of the present invention
The transparent polymer film has an organic layer on both sides and an inorganic layer and a transparent conductive layer on at least one side. Of the organic layers disposed on both sides of the polymer film, at least one of the organic layers is located between the transparent conductive layer and the polymer film, and has the following formula (1)

[0013]

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It is made of an acrylic polymer containing a unit represented by the formula: By providing such an organic layer made of an acrylic polymer between the transparent conductive layer and the polymer film, the bending resistance of the transparent conductive film is good, and the durability, transparency, gas barrier properties, retardation, etc. Thus, a transparent conductive film suitable for an electrode substrate of a liquid crystal display element, which is excellent in quality, is obtained. As such an acrylic polymer, the following formula (1-1)

[0015]

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The unit represented by the formula is preferred.

The organic layer composed of the acrylic polymer containing the unit represented by the above formula (1) is formed, for example, by using an acrylate monomer represented by the following formula (5) having the above structure,
After adding a reaction initiator as needed, it can be provided by irradiating with an actinic ray (for example, ultraviolet rays) or heating to polymerize and cure.

[0018]

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Here, R ⁹ and R ¹⁰ are each independently:
Shows a hydrogen atom or a methyl group.

Specific examples of the acrylate monomer include dimethylol tricyclodecane diacrylate.

The structure of the unit represented by the above formula (1) is preferably contained in an amount of 5 to 100% by weight, more preferably 20 to 100%, based on the total weight of the organic layer. If it is less than 5%, the desired flexibility and other properties (such as solvent resistance) may not be sufficiently exhibited. Specifically, the organic layer may contain 95 to 0% by weight of another unit derived from an acrylate monomer other than the acrylate monomer represented by the formula (5). As such another acrylate monomer, for example, urethane acrylate, ester acrylate, epoxy acrylate and other polyfunctional acrylates can be used.

The unit represented by the formula (1) preferably contains 5 to 100% by weight, more preferably 20 to 100% by weight, based on the total weight of the organic layer. It is even more preferred that the content is 20 to 90%. In particular, if it is less than 5%, the desired flexibility may not be sufficiently exhibited. By containing 20-90%,
Good adhesion when used in contact with the transparent conductive layer.

Specifically, the organic layer may contain 95 to 0% by weight of another unit derived from an acrylate monomer other than the acrylate monomer represented by the above formula (5). As another acrylate monomer for deriving such another unit, for example, urethane acrylate, ester acrylate, epoxy acrylate, or the like having two or more acrylic groups can be used. In particular, a polyfunctional acrylate monomer having three or more acrylic groups can be used as such another acrylate monomer in order to increase the organic solvent resistance of the organic layer.

In the organic layer, a catalyst for polymerization of the acrylic polymer, an additive for improving film forming property and functionality (leveling agent, fine particles such as silica, etc.) may be appropriately added. It is possible.

The quality of the bendability of the transparent conductive film of the present invention is determined by winding the transparent conductive film around round rods having different diameters, and determining the diameter at which a crack occurs in the transparent conductive layer. Considering mounting, etc., the diameter of the round bar where cracks occur is 14
mm or less, more preferably 10 mm or less. In addition, when wound around a round bar, two kinds of evaluations, that is, the case where the transparent conductive layer is set inside and the case where the transparent conductive layer is set outside are performed.

The flexibility also depends on the thickness of the transparent conductive layer,
In general, the greater the thickness, the worse the flexibility, and even when evaluated with a round bar having a large diameter, cracks easily occur. The transparent conductive layer of the transparent conductive film of the present invention has an excellent effect that it is hardly cracked even if the thickness is particularly 100 nm or more.

When the acrylic polymer containing the unit represented by the above formula (1) is used as the organic layer, it exhibits excellent bending resistance, that is, when the transparent conductive film is bent, cracks occur in the transparent conductive layer. It is not clear why it is unlikely to occur or the durability is excellent, but the organic layer has good adhesion to the transparent conductive layer or inorganic layer, or relieves the stress generated when the transparent conductive layer or inorganic layer is bent. It is estimated that there is work.

In order to form the organic layer, a lower layer (such as a polymer film) for forming the organic layer is coated with a coating solution containing the acrylate monomer and the initiator by, for example, wet coating. It can be formed by irradiating light rays (for example, ultraviolet rays), heating, or the like.

As such a wet coating method, various known methods such as microgravure and Meyer bar are used. At this time, it is also preferable to perform coating after dissolving the acrylate monomer in a solvent at an appropriate concentration, if necessary.

The thickness of the organic layer is preferably in the range of 1 to 20 μm. When the film thickness is 1 μm or less, sufficient solvent resistance may not be exhibited in some cases, and when the film thickness is 20 μm or more, physical properties such as poor adhesion of the layer may be reduced, which is not preferable.

The thickness of the organic layer is preferably in the range of 1 to 20 μm. If the film thickness is less than 1 μm, sufficient solvent resistance may not be exhibited in some cases, and if it exceeds 20 μm, physical properties such as poor adhesion of the layer are deteriorated, which is not preferable.
The thickness of the organic layer is more preferably 2 μm to 10 μm, since the problem that the film after forming the organic layer is warped due to curing shrinkage of the organic layer does not easily occur.

The organic layer provided on the opposite side of the transparent conductive layer of the polymer film may be the same as the above-mentioned organic layer between the high-definition film and the transparent conductive layer, or may be other curable. It may be a layer made of resin. Examples of such a curable resin include a thermosetting resin such as an epoxy resin and a urethane resin, and an actinic ray-curable resin such as an epoxy acrylate, a urethane acrylate, an ester acrylate, and other polyfunctional acrylates.

In the case where the transparent conductive film of the present invention is used as a substrate for a color display device, when the transparent conductive film of the present invention is used between a polymer film and a layer or between layers. May be provided with at least one colored layer. Here, the colored layer is, for example, R (red), B (blue), G (green) or M (magenta), C (cyan), and Y (yellow) in order to realize a color display element.
A colored layer having a primary color can be used. Further, a black matrix may be formed to improve contrast and prevent color mixing of the colored layer. The coloring layer is preferably formed by patterning a resin to which a pigment such as a pigment or a dye is added, that is, a so-called pigment dispersion method or a dye dispersion method. Further, the coloring layer may be formed by a conventional technique for forming a coloring layer such as a printing method, a dyeing method, and an electrodeposition method.

The transparent polymer film according to the present invention comprises:
There is no particular limitation, and thermoplastic polymers such as polyester, polycarbonate, polyarylate, and polyolefin, and those made of a thermosetting polymer can be used, and a film made of an amorphous thermoplastic polymer is particularly preferably used. Can be As such a polymer film, a polycarbonate film having particularly good transparency is excellent in adhesiveness to an organic layer made of an acrylic polymer containing a unit represented by the above formula (1), and when used in combination, a flex resistance is obtained. Very good properties.

The polycarbonate is, for example, represented by the following formula (2)

[0036]

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Containing a repeating unit represented by the formula (copolymerization)
Polycarbonate, the following formula (3)

[0038]

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(In the above formula (3), R _{1 to} R ₈ are each independently a hydrogen atom, a halogen atom and a carbon atom having 1 to 8 carbon atoms.
6 hydrocarbon groups. (Polycarbonate) containing a repeating unit represented by the following formula (4):

[0040]

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(In the above formula (4), R _{1 to} R ₈ are each independently a hydrogen atom, a halogen atom and a carbon atom having 1 to 8 carbon atoms.
6 hydrocarbon groups. ()) (Copolymerized) polycarbonate containing a repeating unit represented by the formula (1).

The above-mentioned polycarbonate is substantially composed of the repeating units represented by the above formula (3), a copolymer composed of the repeating units represented by the above formulas (2) and (3), ) And a copolymer comprising the repeating units represented by (3) are preferred.

In the above formulas (2) and (4), R _{1 to} R ₈
Is independently selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, and an iodine atom. Examples of the hydrocarbon group having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a cyclohexyl group.

As specific examples of the repeating unit represented by the above formula (2), 3,3,5-trimethyl-1,1-di (4-phenol) cyclohexylidene type polycarbonate and the above formula (4) Preferred examples of the above include fluorene-9,9-di (4-phenol) type polycarbonate and fluorene-9,9-di (3-methyl-4-phenol) type polycarbonate.

As the polycarbonate containing the repeating unit represented by the above formula (2), in addition to the homopolycarbonate comprising the repeating unit represented by the above formula (2),
Copolymerized polycarbonate comprising a repeating unit represented by the above formula (2) and a repeating unit represented by the above formula (3) can be exemplified. The composition ratio of the copolymer may be any composition ratio, but as the composition ratio of the repeating unit represented by the above formula (2) increases, the heat resistance (glass transition temperature) increases and the photoelastic system number decreases. On the other hand, since the price is high, the composition is determined by the balance. Specifically, the repeating unit represented by the above formula (2) is preferably from 1 to 70 mol%, more preferably from 30 to 70 mol% from the viewpoint of heat resistance, and from 1 to 50 mol% from the viewpoint of price. preferable. These may be used in combination of two or more kinds. For example, a blend of a polycarbonate composed of the repeating unit represented by the above formula (2) and a polycarbonate composed of the repeating unit represented by the above formula (3) can be used. .

As the (copolymer) polycarbonate containing a repeating unit represented by the above formula (4),
In addition to the homopolycarbonate composed of the repeating unit represented by the formula, a copolymerized polycarbonate composed of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (4) is preferable. The composition ratio of such a copolymer is:
Although any composition ratio may be used, as the composition ratio of the repeating unit represented by the above formula (4) increases, heat resistance (glass transition temperature) increases and the number of photoelastic systems decreases. Therefore, the composition is determined by the balance. Specifically, the repeating unit represented by the above formula (4) is preferably 1 to 60 mol%, more preferably 20 to 60 mol% from the viewpoint of heat resistance, and 1 to 40 mol% from the viewpoint of price. preferable. These may be used in combination of two or more kinds. For example, a blend of a polycarbonate composed of a repeating unit represented by the above formula (2) and a polycarbonate composed of a repeating unit represented by the above formula (4) can be used. .

The polymer film preferably has a retardation of 30 nm or less. If it exceeds 30 nm, problems such as a decrease in contrast when a panel is formed may occur.

The above polymer film has a total light transmittance of 7
It is preferably 0% or more. If it is less than 70%, problems such as a decrease in visibility may occur.

The method for forming the polymer film is as follows.
For example, a known method such as solution film formation and melt extrusion film formation can be used, but from the viewpoint of film smoothness, a solution film formation method is more preferable.

The thickness of the polymer film is 30 to 700 μm
Is preferred. When the thickness is less than 30 μm, there is a problem that handling becomes difficult in the process of manufacturing the base material. When the thickness is larger than 700 μm, not only the characteristic of the polymer film, which is lightweight, is lost, but also the display quality is deteriorated due to an increase in parallax, which is not preferable. The thickness of the polymer film is more preferably 70 to 500 μm
It is.

The inorganic layer in the present invention is mainly for exhibiting gas barrier properties. As such an inorganic layer, for example, Si, Al, Mg, Zn, Zr, Ti, Y,
Examples thereof include a metal oxide containing one or more metals selected from the group consisting of Ta, In, and Sn, a metal nitride of silicon, aluminum, and boron, or a mixture thereof. Among them, at least one oxide selected from oxides of Si, Al, and Mg is preferable.

This inorganic layer can be formed by, for example, a known sputtering method, ion plating method, vapor deposition method, CVD method or the like, but the sputtering method is preferable from the viewpoint of chemical resistance.

The thickness of the inorganic layer is preferably in the range of 5 to 300 nm. If it is less than 5 nm, it is difficult to stably obtain gas barrier properties, and if it exceeds 300 nm, it takes an extremely long time to form a layer, which is not preferable.

The film on which the inorganic layer was formed (the transparent conductive film having no transparent conductive layer) was obtained at 40 ° C. and 90% RH.
Oxygen permeability and water vapor permeability under environment are 3c each
It is preferably c / m ² / day / atm or less, and 3 g / m ² / day or less.

Further, in order to achieve a very high gas barrier property, the inorganic layer is made of a metal oxide mainly composed of silicon oxide in which the ratio of the number of oxygen atoms to the number of silicon atoms is 1.5 to 2.0. It is preferable to use the product (X) and provide the cured resin layers (B) and (C) containing silicon on both surfaces of (X). As the silicon-containing cured resin layer, a vinyl alcohol-containing polysiloxane resin (P) or an organic polysiloxane resin (Q) is preferable, and at least one of the cured resin layers (B) and (C) is (P). More preferably, there is. With such a layer structure, the gas permeability of the substrate can be reduced even when a metal oxide having a thin film thickness as a main component is used, and in particular, the water vapor permeability is reduced to 0.1 g / m ^2. / Day (provided that there is no transparent conductive layer). For example, when used as a substrate for a liquid crystal display device, it is electro-optically stable even when exposed to a high temperature and high humidity environment for a long time. An element having excellent properties can be obtained.

The vinyl alcohol-containing polysiloxane resin (P) is obtained by applying a coating composition containing a vinyl alcohol-based polymer, a silicon compound containing an epoxy group and a silicon compound containing an amino group, and curing by heating or the like. Can be

As the vinyl alcohol-based polymer, a known commercially available polymer can be used. For example, a polymer containing at least one selected from the group consisting of a vinyl alcohol component and a vinyl alcohol copolymer component in an amount of 50 mol% or more is used. Is applied. Examples of the vinyl alcohol copolymer include a vinyl alcohol-vinyl acetate copolymer, a vinyl alcohol vinyl butyral copolymer, an ethylene-vinyl alcohol copolymer, and a polyvinyl alcohol having a silyl group in a molecule. . Among them, when an ethylene-vinyl alcohol copolymer is used, a vinyl alcohol-containing polysiloxane resin (P) having further excellent chemical resistance, water resistance and durability can be obtained.

The vinyl alcohol polymer can be dissolved in water, dimethylimidazoline or the like to be used as a component of the coating composition. The ethylene-vinyl alcohol copolymer can be dissolved in a mixed solvent containing water / propanol as a main component and used as a component of the coating composition.

The silicon compound containing an epoxy group is selected from the group consisting of a silicon compound having an epoxy group and an alkoxysilyl group, a (partly) hydrolyzate thereof, a (partly) condensate thereof, and a mixture thereof. 11).

[0060]

X-R ₁₁ -Si (R ₁₂ ) _n (OR ₁₃ ) _3-n (11) where R ₁₁ is an alkylene group having 1 to 4 carbon atoms, and R ₁₂ and R ₁₃ are 1 to 3 carbon atoms. And X is a glycidoxy group or an epoxycyclohexyl group, and n is 0 or 1.

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

The amino group-containing silicon compound is selected from the group consisting of a silicon compound having an amino group and an alkoxysilyl group, a (partial) hydrolyzate thereof, a (partial) condensate thereof, and a mixture thereof. It is represented by (2).

[0063]

Y—HN—R ₁₄ —Si (R ₁₅ ) _m (OR ₁₆ ) _3-m (12) where R ₁₄ is an alkylene group having 1 to 4 carbon atoms, and R ₁₅ and R ₁₆ are carbon atoms. 1-4 alkyl groups, Y is a hydrogen atom or an aminoalkyl group, and m is 0 or 1.

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

The epoxy group-containing silicon according to the present invention
(Partial) Hydrolysis of Compounds and Amino Group-Containing Silicon Compounds
The decomposition product and its (partial) condensate are
Some silicon-containing compounds and some amino-containing silicon compounds
Or all hydrolyzed, a part of the hydrolyzate or
A condensate that is entirely condensed, and hydrolyzed with the condensate
Raw material epoxy group-containing silicon compound and
Are condensed with a silicon group-containing silicon compound.
What is obtained by the so-called sol-gel reaction
is there. Here, the hydrolyzate is, for example, an inorganic acid such as hydrochloric acid, vinegar.
Mix with an acidic aqueous solution such as an organic acid such as an acid, or pure.
And is obtained by In addition, the coating liquid is storage-stable
Alcohol, S
Various types such as ter, ether, ketone, and cellosolve
It is preferably diluted with an organic solvent. Epoxy group
Mixing ratio of silicon compound containing amino and silicon compound containing amino group
Are the epoxy equivalent molar equivalents Ep and the amino group equivalents
Range of 1/6 <Ep / Ap <6/1 in the ratio of the conversion amount Ap
Is preferred. If the mixing ratio is out of this range, close contact
, Heat resistance, solvent resistance, water resistance, and durability decrease. This
Group containing epoxy group and amino group containing silicon
Compound mixture into polyvinyl alcohol polymer
In doing so, the weight ratio after curing is 20% by weight or more, 95% or more.
Mix so as to be less than wt%. Less than 20 parts by weight
If not, the water resistance and chemical resistance tend to be inferior.
When the content is more than the weight percentage, the gas barrier property tends to decrease.
Here, the epoxy group-containing silicon compound and the amino group-containing silicon compound
The weight of the mixture with the compound after curing is XR₁₁-Si
(R₁₂)_nO_{(3-n) / 2}And Y-HN-R₁₄-Si (R₁₅)_m
O_{(3- m) / 2}It is a weight standard shown by. Here this weight
The conversion formula is the conversion of the alkoxysilyl group in each silicon compound.
Assuming that all have undergone hydrolysis and condensation reactions
Defined as described. In particular, the polyvinyl alcohol containing
Polysiloxane resin with the above-mentioned silicon oxide as the main component
At least one of the gas barrier layers composed of a metal oxide
Gas barrier properties can be further improved by stacking in contact with
To improve.

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

The organic polysiloxane resin (Q) is preferably obtained by subjecting an organosilicon compound represented by the following formula (13) or a hydrolyzate thereof to a so-called sol-gel reaction.

[0068]

(R ₁₇ ) _a (R ₁₈ ) _b SiX _4-ab (13)

Here, R ₁₇ is an organic group having 1 to 10 carbon atoms, R ₁₈ is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 6 carbon atoms, X is a hydrolyzable group, a and b are 0 or 1. Examples of the organosilicon compound represented by the above formula (13) include, for example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, (3,4-epoxycyclohexyl) ethyltriethoxysilane, aminomethyltriethoxysilane, 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, N-aminomethyl-3-aminopropyltrimethoxysilane, N-
(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and the like can be mentioned. These compounds can be used alone or in combination of two or more. Among them, it is preferable to use a mixture of the epoxy group-containing silicon compound of the formula (1) and the amino group-containing silicon compound of the formula (2) as a main component. Here, the mixing ratio of the epoxy group-containing silicon compound and the amino group-containing silicon compound is
It is preferable in terms of chemical resistance and interlayer adhesion that the ratio of the epoxy group molar equivalent conversion amount Eq and the amino group molar equivalent conversion amount Aq be within the range of 5/95 <Eq / Aq <95/5. In particular, by forming a gas barrier layer made of a metal oxide containing silicon oxide as a main component on the organic polysiloxane-based resin layer, the gas barrier property is further improved.

The thickness of the organic polysiloxane resin (Q) can be appropriately selected generally from the range of 0.01 to 20 μm.

The transparent conductive layer in the present invention is located at the outermost layer and contains indium oxide as a main component (preferably 80% by weight or more) and one or more oxides selected from tin or zinc (preferably). 20% by weight or less). Such a transparent conductive layer preferably contains indium oxide as a main component, and contains 2 to 20% by weight of tin oxide and / or 2 to 20% by weight of zinc oxide. The method for forming such a transparent conductive layer is not particularly limited, but is preferably a sputtering method, and a DC sputtering method, a high-frequency magnetron sputtering method, an ion beam sputtering method, or the like can be applied. The method is preferred.

The thickness of the transparent conductive layer is preferably at least 10 nm in order to obtain sufficient conductivity.

The transparent conductive film of the present invention preferably has a total light transmittance of 70% or more. If it is less than 70%, problems such as a decrease in visibility may occur.

The transparent conductive film of the present invention preferably has a retardation of 30 nm or less. 30n
If it exceeds m, problems such as a decrease in contrast when a panel is formed may occur.

As described above, the transparent conductive film of the present invention comprises the above-mentioned polymer film, an organic layer, an inorganic layer and a transparent conductive layer.
At least one of the surfaces includes a unit represented by the above formula (1) (sometimes referred to as a specific organic layer), and the specific organic layer exists between the transparent conductive layer and the polymer film. Specific examples of such a transparent conductive film include: a transparent conductive layer / an inorganic layer / a specific organic layer / a polymer film /
Specific organic layer, transparent conductive layer / specific organic layer / polymer film / specific organic layer / inorganic layer, transparent conductive layer / inorganic layer / specific organic layer / polymer film /
Specific organic layer / inorganic layer, transparent conductive layer / inorganic layer / colored layer / specific organic layer / polymer film / specific organic layer, transparent conductive layer / specific organic layer / colored layer / polymer film /
Specific organic layer / inorganic layer, transparent conductive layer / specific organic layer / colored layer / specific organic layer / polymer film / specific organic layer / inorganic layer, transparent conductive layer / inorganic layer / specific organic layer / polymer film /
Organic layer ・ Transparent conductive layer / Specific organic layer / Polymer film / Organic layer /
Inorganic layer, transparent conductive layer / inorganic layer / specific organic layer / polymer film /
Organic layer / inorganic layer, transparent conductive layer / inorganic layer / colored layer / specific organic layer / polymer film / organic layer, transparent conductive layer / specific organic layer / colored layer / polymer film /
Organic layer / inorganic layer, transparent conductive layer / specific organic layer / color layer / specific organic layer / polymer film / organic layer / inorganic layer, transparent conductive layer / specific organic layer / color layer / organic layer / polymer film / Organic layer / inorganic layer, transparent conductive layer / organic layer / colored layer / specific organic layer / polymer film / organic layer / inorganic layer, transparent conductive layer / specific organic layer / polymer film / organic polysiloxane resin ( Q) / metal oxide layer (X) / vinyl alcohol-containing polysiloxane resin (P), transparent conductive layer / specific organic layer / polymer film / vinyl alcohol-containing polysiloxane resin (P) / metal oxide layer (X ) / Organic polysiloxane resin (Q), transparent conductive layer / specific organic layer / polymer film / vinyl alcohol-containing polysiloxane resin (P) / metal oxide layer (X) / vinyl alcohol-containing polysiloxane resin (P), · transparent conductive layer / colored layer / specific organic layer / polymer film /
Vinyl alcohol-containing polysiloxane resin (P) / metal oxide layer (X) / vinyl alcohol-containing polysiloxane resin (P), transparent conductive layer / specific organic layer / colored layer / polymer film /
Vinyl alcohol-containing polysiloxane resin (P) / metal oxide layer (X) / vinyl alcohol-containing polysiloxane resin (P), transparent conductive layer / specific organic layer / colored layer / organic layer / polymer film / vinyl alcohol-containing Polysiloxane resin (P) / metal oxide layer (X) / vinyl alcohol-containing polysiloxane resin (P), transparent conductive layer / organic layer / colored layer / specific organic layer / polymer film / vinyl alcohol-containing polysiloxane resin (P) / metal oxide layer (X) / vinyl alcohol-containing polysiloxane resin (P).

In the above, the specific organic layer is a transparent conductive layer,
Although it may be in contact with any of the inorganic layer and the polymer film,
By being in contact with the transparent conductive layer or being in contact with the inorganic layer, the adhesiveness is particularly excellent, and the flexibility, durability, and the like are good. More preferably, the specific organic layer is on the same side as the transparent conductive layer, and is in contact with the transparent conductive layer, or the transparent conductive layer and the polymer film.

In the transparent conductive film of the present invention, an intermediate layer for further improving the adhesion or the like is interposed between the above-mentioned layers or between the polymer film and the layer immediately above the polymer film. Can be.

[0078]

The transparent conductive film of the present invention has good flexibility, excellent resistance to bending during mounting, and has excellent heat resistance and transparency when used as a liquid crystal display element, and is useful as a substitute for a glass substrate. is there.

[0079]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. In addition,
Various evaluations of each of the following Examples and Comparative Examples were performed in the following manner.

<Flexibility> The transparent conductive film was
Cut out to × 16cm, heat treated at 150 ° C for 2 hours,
Two kinds of metal rods having a diameter of 8 mmφ and 10 mmφ were wound in close contact with each other, left standing for 30 seconds, then returned again, and observed for occurrence of cracks in the transparent conductive layer with an optical microscope. In addition, two kinds of evaluations, that is, the case where the transparent conductive layer is set inside and the case where the transparent conductive layer is set outside, were performed. In the evaluation of the diameter of 8 mmφ, the case where no cracking of the transparent conductive layer occurs was excellent, and the diameter was 8 mm.
In the evaluation of φ, a crack occurs in the transparent conductive layer.
Good at 0 mmφ with no cracks, diameter 10
In the evaluation of mmφ, those which cracked were not considered. However, only in Example 8, heat treatment at 150 ° C. for 2 hours was performed at 130 ° C.
Changed to 2 hours.

<Durability> The transparent conductive film was heated at 60 ° C.
The transparent conductive layer was allowed to stand for 250 hours in an environment of 90% RH for 250 hours, and the presence or absence of cracks in the transparent conductive layer was observed with an optical microscope. The case where cracks did not occur was evaluated as excellent, and the case where cracks occurred did not.

<Organic solvent resistance>
Place on a hot plate at 0 ° C. and place n-
One drop of methylpyrrolidone was dropped, wiped off after 3 minutes, and the appearance change was visually observed. Those with no change in appearance were rated as excellent, and those with change were rated as unacceptable.

<Alkali Resistance> The transparent conductive film
It was immersed in a 3.5 wt% NaOH aqueous solution at 0 ° C. for 10 minutes, and the appearance change was observed with an optical microscope. Those with no change in appearance were rated as excellent, and those with change were rated as unacceptable.

<Total light transmittance> COH manufactured by Nippon Denshoku Industries Co., Ltd.
It measured using -300A.

<Retardation> M-1 manufactured by JASCO Corporation
It was measured using a 50-type ellipsometer.

<Oxygen Permeability> The oxygen permeability was measured for a polymer film on which an organic layer and an inorganic layer were laminated before laminating a transparent conductive layer. The measurement was carried out under the environment of 40 ° C. and 90% RH using Oxytran 2/20 manufactured by MOCON.

<Water Vapor Permeability> The water vapor permeability was measured for a polymer film having an organic layer and an inorganic layer laminated before a transparent conductive layer was laminated. The measurement was carried out under the environment of 40 ° C. and 90% RH using Permatran Model W1A manufactured by MOCON.

Example 1 3,3,5-Trimethyl-
1,1-di (4-phenol) cyclohexylidene is 5
8 mol%, 42 mol% of bisphenol A copolymerized polycarbonate (APEC-HT937 manufactured by Bayer AG)
1, a glass transition temperature of 205 ° C.) was dissolved in methylene chloride to a concentration of 27% by weight, cast on a glass plate using an applicator, allowed to stand at room temperature for 20 minutes, and then peeled from the glass plate. After drying at 130 ° C. for 2 hours, a polymer film having a thickness of 100 μm was obtained.

An organic layer was formed on each side of the obtained polymer film as follows. 50 parts by weight of dimethylol tricyclodecane diacrylate (light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.) and 50 parts by weight of urethane acrylate (TPH19 manufactured by Jujo Chemical Co., Ltd.) SH-manufactured by Dow Corning Toray as a leveling agent
After drying, a coating liquid comprising 0.05 parts by weight of 28PA and 180 parts by weight of 1-methoxy-2-propanol as a diluting solvent was roll-coated so as to have a film thickness of 5 μm, dried at 60 ° C. for 30 seconds, and then subjected to a high pressure of 160 W / cm strength The organic layer was formed by irradiating an ultraviolet ray with an integrated light amount of 700 mJ / cm ² by a mercury lamp.

Subsequently, an inorganic layer was formed on the organic layer on one side as follows. After arranging the film in a take-up type magnetron sputtering apparatus provided with a Si target and exhausting the film, a mixed gas of Ar: O ₂ = 7: 3 was introduced, and the pressure was adjusted to 8 × 10 ⁻⁴ Torr. did.
Under this atmosphere, reactive sputtering was performed at an input power density of 1 W / cm ² and a film speed of 1 m / min to form an inorganic layer made of silicon oxide having a thickness of about 30 nm.

Subsequently, a transparent conductive layer was formed on the inorganic layer as follows. After arranging and evacuating the film in a take-up type magnetron sputtering apparatus provided with an oxide target having a weight ratio of In: Sn = 9: 1, mixing of Ar: O ₂ = 98.8: 1.2. Gas was introduced and the pressure was adjusted to 1 × 10 ⁻³ Torr.
In this atmosphere, reactive sputtering was performed at a power density of 1 W / cm 2 and a film speed of 0.1 m / min to form a 130 nm thick transparent conductive layer. The surface resistance of this transparent conductive layer was 45 ohms.

The structure of the thus formed transparent conductive film is transparent conductive layer / inorganic layer / specific organic layer / polymer film / specific organic layer. Table 1 shows the properties of the transparent conductive film. It was a transparent conductive film having excellent flexibility, durability and other properties.

[Example 2] In Example 1, the coating liquid for forming the organic layer was prepared by using 50 parts by weight of dimethylol tricyclodecane diacrylate and 50 parts by weight of urethane acrylate to obtain dimethylol tricyclodecane diacrylate 8
0 parts by weight, changed to 20 parts by weight of urethane acrylate,
Otherwise, a transparent conductive film was obtained in the same manner. The properties of the transparent conductive film thus produced are described in Table 1. The film was excellent in flexibility, durability and other properties.

Example 3 In Example 1, the coating liquid for forming the organic layer was prepared by adding 50 parts by weight of dimethylol tricyclodecane diacrylate and 50 parts by weight of urethane acrylate to dimethylol tricyclodecane diacrylate 2
0 parts by weight, changed to 80 parts by weight of urethane acrylate,
Otherwise, a transparent conductive film was obtained in the same manner. The properties of the transparent conductive film thus produced are described in Table 1. The film was excellent in flexibility, durability and other properties.

Example 4 In Example 1, the coating liquid for forming the organic layer was changed from 50 parts by weight of urethane acrylate to 50 parts by weight of ester acrylate (Aronix M9050 manufactured by Toagosei Co., Ltd.), and the other conditions were the same. Thus, a transparent conductive film was obtained. The properties of the transparent conductive film thus produced are described in Table 1. The film was excellent in flexibility, durability and other properties.

Example 5 In Example 1, dimethylol tricyclodecane diacrylate was prepared from 50 parts by weight of dimethylol tricyclodecane diacrylate and 50 parts by weight of urethane acrylate.
A transparent conductive film was obtained in the same manner except that the amount was changed to 0 parts by weight. The properties of the transparent conductive film thus produced are described in Table 1. The film was excellent in flexibility, durability and other properties.

Example 6 Example 1 was the same as Example 2 except that the transparent conductive layer was formed on the organic layer opposite to the inorganic layer.
Each layer was formed in the same manner as described above. The structure of the transparent conductive film was transparent conductive layer / specific organic layer / polymer film / specific organic layer / inorganic layer. The properties of the transparent conductive film thus produced are described in Table 1. The film was excellent in flexibility, durability and other properties.

Example 7 In Example 1, the polymer film was changed as follows. As the polymer of the polymer film, a polycarbonate obtained by copolymerizing fluorene-9,9-di (3-methyl-4-phenol) as a bisphenol component at 30 mol% and bisphenol A at 70 mol% was used. This polymer is prepared by adding fluorene-9,9-di (3-methyl-4-phenol) and bisphenol A to the above composition in an aqueous sodium hydroxide solution, adding a small amount of hydrosulfite, and subsequently adding methylene chloride. After blowing phosgene at about 20 ° C. over about 60 minutes, p-tert-butylphenol was further added to emulsify, and triethylamine was added, followed by stirring at 30 ° C. for about 3 hours. The glass transition temperature of the obtained polymer was 195 ° C. Using this polymer, a film having a thickness of 100 μm was formed in the same manner as in Example 1, and a specific organic layer, an inorganic layer, and a transparent conductive layer were formed to obtain a transparent conductive film. The properties of the transparent conductive film thus produced are described in Table 1. The film was excellent in flexibility, durability and other properties.

Example 8 In Example 1, the polymer film was changed as follows. The polymer film is a polycarbonate film using only bisphenol A as a bisphenol component (Pure Ace manufactured by Teijin, thickness 100 μm).
m, glass transition temperature 155 ° C.). Table 1 shows the properties of the transparent conductive film. The film was excellent in flexibility, durability and other properties.

Example 9 In Example 1, an inorganic layer was formed on both sides of the organic layer. That is, the configuration of the transparent conductive film is: transparent conductive layer / inorganic layer / specific organic layer / polymer film / specific organic layer / inorganic layer. Table 1 shows the properties of the transparent conductive film. The film was excellent in flexibility and durability, and also very excellent in gas barrier properties.

Example 10 In Example 6, a vinyl alcohol-containing polysiloxane resin (P) was further laminated on the inorganic layer as follows.

Component (P1) 100 parts of ethylene vinyl alcohol copolymer was mixed with 720 parts of water and 10 parts of n-propanol 10
The mixture was heated and dissolved in 80 parts of a mixed solvent to obtain a homogeneous solution. To this solution was added a leveling agent (“SH” manufactured by Dow Corning Toray).
30PA "and 0.1 part of acetic acid, and then the component (P
2) 211 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane were added and stirred for 10 minutes. Further, 77 parts of the component (P3) 3-aminopropyltrimethoxysilane was added to this solution and stirred for 3 hours to obtain a coating composition.

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

That is, the structure of the transparent conductive film is as follows:
Transparent conductive layer / specific organic layer / polymer film / specific organic layer / inorganic layer / vinyl alcohol-containing polysiloxane resin layer. Table 1 shows the properties of the transparent conductive film. The film was excellent in flexibility and durability, and also very excellent in gas barrier properties.

[Example 11] In Example 10, an organic polysiloxane resin (Q) was laminated in the following manner, instead of the specific organic layer laminated under the inorganic layer.

720 parts by weight of water, 2-propanol 108
After adding 88 parts by weight of acetic acid to 0 parts by weight of the mixed solvent,
(Q1) 640 parts by weight of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane and 154 parts by weight of (Q2) 3-aminopropyltrimethoxysilane were sequentially added and stirred for 3 hours to obtain a coating composition. The composition of the coating composition is (Q1) / (Q2) = 3/1.
This coating composition was coated on one side of a polymer film and heat-treated at 130 ° C. for 3 minutes to form a (Q) layer having a thickness of 0.05 μm.

That is, the structure of the transparent conductive film is as follows:
Transparent conductive layer / specific organic layer / polymer film / organic polysiloxane resin layer / inorganic layer / vinyl alcohol-containing polysiloxane resin layer. Table 1 shows the properties of the transparent conductive film. The film was excellent in flexibility and durability, and also very excellent in gas barrier properties.

Comparative Example 1 In Example 1, 50 parts by weight of dimethylol tricyclodecane diacrylate forming an organic layer and 50 parts by weight of urethane acrylate were changed to 100 parts by weight of urethane acrylate. Table 1 shows the properties of the obtained transparent conductive film. The film was inferior in flexibility and durability.

Comparative Example 2 In Example 4, 50 parts by weight of dimethylol tricyclodecane diacrylate and 50 parts by weight of ester acrylate forming an organic layer were changed to 100 parts by weight of ester acrylate. Table 1 shows the properties of the obtained transparent conductive film. The film was inferior in flexibility, durability and alkali resistance.

[0110]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/30 102 B32B 27/30 102 27/36 102 27/36 102 C08F 20/20 C08F 20/20 C08G 64/00 C08G 64/00 77/00 77/00 C08J 7/04 C08J 7/04 PCFD CFDZ 7/06 CEY 7/06 CEYB G02F 1/1333 500 G02F 1/1333 500 (72) Inventor Naoya Saito Tokyo 4-3-2 Asahigaoka, Hino-shi, Tokyo Teijin Co., Ltd., Tokyo Research Center (72) Inventor Shin Shinichiro 4-4-2-3 Asahigaoka, Hino-shi, Tokyo Teijin, Tokyo Research Center Co., Ltd. (72) Inventor Toru Hanada Tokyo Research Center, Teijin Limited 4-3-2 Asahigaoka, Hino-shi, Tokyo

Claims (14)

[Claims] 1. A polymer film comprising (i) an organic layer on both surfaces, (ii) an inorganic layer on at least one surface, and (iii) an indium oxide on the outermost layer on at least one surface. A transparent conductive film having a transparent conductive layer as a main component, wherein the organic layer on at least one surface of the polymer film is made of an acrylic polymer containing a unit represented by the following formula (1). Transparent conductive film. Embedded image 2. The transparent conductive film according to claim 1, wherein the organic layer comprising the acrylic polymer containing the unit represented by the formula (1) is located between the transparent conductive layer and the polymer film. 3. The transparent conductive substrate according to claim 1, wherein an organic layer made of an acrylic polymer containing the unit represented by the formula (1) is in contact with the transparent conductive layer. 4. The transparent conductive film according to claim 1, wherein an organic layer comprising an acrylic polymer containing the unit represented by the formula (1) is in contact with the polymer film. 5. The transparent conductive substrate according to claim 1, wherein an organic layer comprising an acrylic polymer containing the unit represented by the formula (1) is in contact with the inorganic layer. 6. The silicon-containing cured resin layer (B) on the surface of the polymer film opposite to the surface having the transparent conductive layer, and the ratio of the number of oxygen atoms to the number of silicon atoms of the inorganic layer is 1.5
To 2.0, a metal oxide layer (X) containing silicon oxide as a main component and a cured resin layer containing silicon (C) are laminated in this order, and a cured resin layer (B) and / or a cured resin layer (C) is a vinyl alcohol-containing polysiloxane resin (P) or an epoxy group-containing silicon compound and an amino group-containing silicon compound which can be obtained by a curing reaction of a vinyl alcohol polymer, an epoxy group-containing silicon compound and an amino group-containing silicon compound. The transparent conductive film according to any one of claims 1 to 5, comprising an organic polysiloxane resin (Q) obtainable by a reaction with: 7. The transparent conductive film according to claim 1, wherein the polymer film contains polycarbonate as a main component. 8. The transparent conductive film according to claim 7, wherein the polycarbonate is a polycarbonate containing a repeating unit represented by the following formula (2). Embedded image (In the above formula (2), R _{1 to} R ₈ are each independently
It is at least one selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms. ) 9. The polycarbonate is a copolymerized polycarbonate comprising a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3), and is a copolymer of the repeating unit represented by the following formula (2). The transparent conductive film according to claim 8, wherein the proportion is 1 to 70 mol% of the entire repeating unit. Embedded image (In the above formula (2), R _{1 to} R ₈ are each independently
It is at least one selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms. ) 10. The transparent conductive film according to claim 9, wherein the polycarbonate is a polycarbonate containing a repeating unit represented by the following formula (4). Embedded image (In the above formula (4), R _{1 to} R ₈ are each independently:
It is at least one selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms. ) 11. The polycarbonate is a copolymerized polycarbonate composed of a repeating unit represented by the following formula (3) and a repeating unit represented by the following formula (4), and is a copolymer of the repeating unit represented by the following formula (4). The transparent conductive film according to claim 10, wherein the proportion is 1 to 60 mol% of the entire repeating unit. Embedded image (In the above formula (4), R _{1 to} R ₈ are each independently:
It is at least one selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms. ) 12. The transparent conductive film according to claim 1, wherein the transparent conductive layer contains indium oxide as a main component and at least one oxide selected from tin and zinc. 13. The unit represented by the above formula (1) is 20 to
The transparent conductive film according to any one of claims 1 to 12, which is an organic layer made of an acrylic polymer containing 100% by weight. 14. The transparent conductive film according to claim 1, wherein the inorganic layer contains at least one oxide selected from the group consisting of Si, Al and Mg.