JP2014000812A - Transparent conductive laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive laminate film in which especially durability such as writability resistance is improved.SOLUTION: A transparent conductive laminate film comprises: a substrate layer (A) consisting of a transparent plastic film; a coating layer (B) formed by curing a polymerizable acrylic monomer or a mixture of the monomer and the oligomer (b), having a thickness of at least 0.1 μm and at most 20 μm, and laminated on the substrate layer (A); and a transparent conductive film layer (C) laminated on the coating layer (B), wherein a cure shrinkage of the polymerizable acrylic monomer or the mixture of the monomer and the oligomer (b) is at least 0.2% and at most 10%, the polymerizable acrylic monomer or the mixture of the monomer and the oligomer (b) has an acrylate having an acryloyl group of at least three functions, and a percentage content of the acrylate having the acryloyl group of at least three functions is less than 50% by weight.

Description

  The present invention relates to a transparent conductive laminated film used for a display element such as a liquid crystal display, a display input / output device such as a touch panel, a solar cell conversion element and the like.

  In recent years, transparent touch panels that allow input by simply touching a display screen with a finger or pressing with a pen have become widespread. A transparent conductive film is used for this touch panel. The touch panel voltage sensing method includes an analog type and a matrix type. In the former analog type, two transparent conductive bases having electrodes at both ends are arranged opposite to each other via a spacer, a voltage is applied to the upper and lower electrodes, and the voltage value at the pressed position is set as the position of the XY coordinate. Detect. In the latter matrix type, two transparent conductive substrates each having a conductive layer formed in a strip shape are arranged in a matrix shape, and the pressed position is detected by each electrode.

  A normal transparent conductive layer for a touch panel is used by being superimposed on the uppermost layer of a liquid crystal display element, and basically has a configuration in which a conductive layer (mainly ITO film) is laminated on glass or a polymer film. . In general, it is required that the visible light transmittance is at least 80%, the surface resistance is several kΩ to several hundred Ω / □, and the writing resistance is excellent.

  In Patent Document 1 (Japanese Patent Laid-Open No. 10-71667), it is excellent in chemical properties and rigidity, is lighter than that using a glass substrate, and can use a glass substrate process when manufacturing a liquid crystal display. For the purpose of providing a transparent conductive sheet excellent in impact resistance, a transparent conductive sheet having a transparent conductive film formed on the surface of a photocurable resin sheet is disclosed.

  By the way, as the conventional conductive film layer, there are indium oxide, tin oxide doped with silicon oxide, aluminum oxide or the like, indium oxide, tin oxide doped with nitrogen (Patent Document 2: JP-A-11-110110). Publication). However, simply forming a transparent conductive film layer on a transparent polymer substrate cannot withstand the 250 g load 100,000 character writing test required for analog use.

Japanese Patent Laid-Open No. 10-71667 JP 11-110110 A

  As described above, the conventional transparent conductive substrate basically has a layer structure of glass or polymer film / conductive layer (mainly ITO film). When a glass substrate is used, a chemically stable transparent conductive film layer is formed by heating the substrate to a high temperature and excellent in writing resistance and adhesion, but there are problems such as cracking, heavyness, and thickness. On the other hand, when a polymer substrate (polymer film) such as a plastic film is used, there is no problem as in a glass substrate. However, when an optically isotropic transparent polymer substrate is used, the temperature at which the transparent conductive film layer is formed is limited to the heat resistant temperature of the polymer substrate, and must be lowered.

  Therefore, it is not easy to form a transparent conductive film layer excellent in writing resistance and adhesion on a plastic film substrate. Further, when a conventionally proposed polymer substrate is used, it is difficult to satisfy all required performances such as optical isotropy, transparency, heat resistance, chemical resistance, and adhesion. In this invention, while providing the said required performance, provision of the transparent conductive laminated film which improved durability, such as writing resistance especially, is a subject.

One embodiment of the present invention has a thickness of 0.1 μm obtained by curing a polymerizable acrylic monomer or a mixture of monomer and oligomer (b) on a base material layer (A) made of a transparent plastic film. The polymerizable acrylic monomer or the mixture of the monomer and the oligomer, wherein the film layer (B) having a thickness of 20 μm or less and the transparent conductive film layer (C) are laminated thereon to form the film layer (B). The cure shrinkage of (b) is 0.2% or more and 10% or less, and the polymerizable acrylic monomer or the mixture of the monomer and the oligomer (b) contains an acrylate having a trifunctional or higher acryloyl group. And the content rate of the acrylate which has the acryloyl group more than trifunctional is less than 50 weight%, It is a transparent conductive laminated film characterized by the above-mentioned.
In another embodiment of the present invention, a thickness of 0.1 μm obtained by curing a polymerizable acrylic monomer or a mixture of monomer and oligomer (b) on a base material layer (A) made of a transparent plastic film. The polymerizable acrylic monomer or the mixture of the monomer and the oligomer, wherein the film layer (B) having a thickness of 20 μm or less and the transparent conductive film layer (C) are laminated thereon to form the film layer (B). The transparent conductive laminated film, wherein the curing shrinkage of (b) is 0.2% or more and 10% or less, and the water vapor permeability (g / m ² · 24h) is 2 g / m ² · 24h or less. It is.
In another embodiment of the present invention, a thickness of 0.1 μm obtained by curing a polymerizable acrylic monomer or a mixture of monomer and oligomer (b) on a base material layer (A) made of a transparent plastic film. The polymerizable acrylic monomer or the mixture of the monomer and the oligomer, wherein the film layer (B) having a thickness of 20 μm or less and the transparent conductive film layer (C) are laminated thereon to form the film layer (B). The cure shrinkage of (b) is 0.2% or more and 10% or less, the resistance value (R) in a 23 ° C. environment after being immersed in a 3.5% KOH aqueous solution for 3 minutes, and the 23 ° C. environment before being immersed. Is a transparent conductive laminated film characterized by satisfying R / R0 <1.2.

  According to the present invention, a thickness of 0.1 μm or more and 20 μm obtained by curing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer (b) on a base material layer (A) made of a transparent plastic film. The following coating layer (B), a transparent conductive film layer (C) is laminated thereon, and the polymerizable acrylic monomer or mixture of monomer and oligomer (b) forming the coating layer (B) (b) ) Can be improved against external stress such as tension. For example, using a polyacetal pen with a diameter of 8 mm and performing 100,000 reciprocations (3 reciprocations / 1 second, one-way distance 35 mm) with a load of 250 g, the voltage is measured at equal intervals, and the deviation between the linearly approximated value and the measured value is It can be made 1.0% or less.

It is sectional drawing of the transparent conductive laminated film concerning this invention. It is sectional drawing of the transparent conductive laminated film concerning this invention. It is sectional drawing of the transparent conductive laminated film concerning this invention. It is a graph for demonstrating a linearity measuring method. It is typical sectional drawing which shows the state which performs a linearity measurement. It is a schematic plan view which shows the state which performs a linearity measurement.

Hereinafter, the best mode for carrying out the transparent conductive laminated film of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view of the transparent conductive laminated film of the present invention.
On the base material layer (A), a coating layer (B) and a transparent conductive film layer (C) are sequentially laminated.

  In the transparent conductive laminated film of the present invention, the base material layer (A) is made of a transparent plastic film. Examples of transparent plastic films include polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyolefin films such as polyethylene and polypropylene, polystyrene films, polyamide films, polyvinyl chloride films, polycarbonate films, polyacrylonitrile films, polyimide films, There are biodegradable plastic films such as polylactic acid. Other examples of the homopolymer include polyethersulfone, polyarylate, polyacrylate, polysulfone and the like, and a plastic film made of a copolymer of such a resin monomer and a copolymerizable monomer.

  These transparent plastic films may be either stretched or unstretched, but those having excellent mechanical strength and dimensional stability are preferred. In particular, polyethylene terephthalate stretched in the biaxial direction is preferably used from the viewpoints of heat resistance and dimensional stability. In addition, an antistatic agent, an ultraviolet ray inhibitor, a plasticizer, a lubricant, etc., a curing agent, a hard coat agent, a moisture-proof coat agent, a gas barrier coat agent, a corrosive agent, etc. are added or laminated on or inside the transparent plastic film. May be. Furthermore, in a transparent plastic film, the surface on the side where other layers are laminated is subjected to corona treatment, low-temperature plasma treatment, ion bombard treatment, chemical treatment, solvent treatment, etc., or an anchor coat to improve adhesion. You may perform well-known surface treatments, such as. Although there is no restriction | limiting in particular in the thickness of a base material layer (A), When a touch-panel use is considered, about 10-250 micrometers is preferable.

The coating layer (B) is formed by curing a polymerizable acrylic monomer or a mixture (b) of a monomer and an oligomer. In order to improve the durability of the transparent conductive film layer (C) described later, the curing shrinkage rate may be 0.2% or more and 10% or less, and it may be either dry coating or wet coating, and is particularly limited. It is not a thing.
The curing shrinkage is measured by {(density after curing−density before curing) / density after curing} × 100.
However, a method of vaporizing a polymerizable acrylic monomer or a mixture of a monomer and an oligomer (b) from a nozzle inserted in a high-temperature evaporation source in a vacuum vapor deposition apparatus (flash vapor deposition method) Is laminated on the base material layer (A) as an uncured coating layer and cured by irradiating with ultraviolet rays or an electron beam, and then on the base material layer (A) in a vacuum deposition apparatus in a vacuum. Since the coating layer (B) and the transparent conductive film layer (C) or the inorganic oxide vapor-deposited thin film layer (D) to be described later can be laminated continuously, the production cost can be reduced efficiently. Then, it is desirable to use the above method.

When the uncured coating layer is cured by irradiating with ultraviolet rays, a photopolymerization initiator is mixed with a polymerizable acrylic monomer or a mixture of monomer and oligomer (b). Specific examples of the photopolymerization initiator include benzoin ethers, benzophenones, xanthones, and acetophenone derivatives. These photopolymerization initiators are mixed in a proportion of 0.01 to 10% by weight, preferably 0.1 to 2% by weight.
When the uncured coating layer is cured by irradiation with an electron beam, the balance between the thickness of the deposited coating layer, the energy condition of the electron beam, the processing speed, and the charge removal becomes important. This is because if excessive electron beam energy is supplied, the deposited coating layer is charged, and as a result, the adjacent layer may be damaged by the peeling discharge.

The role of the coating layer (B) in the transparent conductive laminated film of the present invention is that external stress such as bending or pulling is applied to the adjacent transparent conductive film layer (C) or inorganic oxide vapor-deposited thin film layer (D). A protective function in the case of normal processing, and a protective function in the case of performing normal processing such as laminating. Thereby, durability, such as writing resistance, improves.
Furthermore, when there is an inorganic oxide vapor-deposited thin film layer (D) having a gas barrier property adjacent to the coating layer (B), the gas barrier property is improved by internal stress due to curing shrinkage during the formation of the coating layer (B), Durability such as writing resistance is improved. The curing shrinkage of the polymerizable acrylic monomer or the mixture of monomer and oligomer (b) forming the coating layer (B) is preferably 0.2% or more and 10% or less, and the curing shrinkage is 0. If it is less than 2%, only a slight internal stress is generated due to curing shrinkage during the formation of the coating layer (B), and a sufficient protective function cannot be obtained. On the other hand, if the cure shrinkage rate exceeds 10%, the internal stress due to cure shrinkage during the formation of the coating layer (B) is excessively acted, and the possibility that the adhesion with the adjacent layer is lowered is increased.
The thickness of the coating layer (B) is preferably 0.1 μm or more and 20 μm or less. If the film thickness is less than 0.1 μm, it is difficult to form a uniform coating layer, and only a slight internal stress due to curing shrinkage during the formation of the coating layer (B) is produced, so that a sufficient protective function cannot be exhibited. On the other hand, when the film thickness exceeds 20 μm, internal stress due to curing shrinkage during the formation of the coating layer (B) is excessively acted, and the possibility that the adhesiveness with the adjacent layer is lowered is increased.
When there is an inorganic oxide vapor-deposited thin film layer (D) having a gas barrier property adjacent to the coating layer (B), the polymerization for forming the coating layer (B) is performed to improve the gas barrier property and increase the durability. The curing shrinkage of the possible acrylic monomer or monomer-oligomer mixture (b) is preferably 0.2% or more and 10% or less, and the thickness is preferably 0.1 μm or more and 20 μm or less. .

  In the transparent conductive laminated film of the present invention, the polymerizable acrylic monomer or mixture of monomer and oligomer (b), which is a raw material for the coating layer (B), is at least one of monoacrylate and diacrylate. It is preferable that the content rate which combined the said monoacrylate and the said diacrylate is 50 weight% or more. That is, when the content ratio of the acrylate having a trifunctional or higher acryloyl group is 50% by weight or more, it is difficult to suppress the curing shrinkage rate at the time of forming the coating layer (B) to 10% or less. This is because the stress works excessively, and the possibility that the adhesion between the adjacent layer and the coating layer (B) is lowered is increased. However, since an acrylate having a tri- or higher functional acryloyl group has an effect of improving the crosslinking degree, it is preferable to use a small amount when forming a strong coating layer (B). If present, about 10% by weight is desirable.

As these acrylates, polyester monomers, polyether acrylates, acrylic acrylates, urethane acrylates, epoxy acrylates, silicone acrylates, polyacetal acrylates, polybutadiene acrylates, melamine acrylates and other highly polymerizable acrylic monomers or oligomers are appropriately selected. Can be used.
There are various types of monoacrylates, diacrylates and triacrylates, which are not particularly limited, but have good adhesion to the transparent conductive film layer (A) and the inorganic oxide vapor-deposited thin film layer (D), and are efficient. It is preferable that an uncured vapor-deposited coating layer can be formed. If necessary, it is preferable to select one having excellent hygiene. Specific examples of the monoacrylate include 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-succinic acid, methoxy-polyethylene glycol acrylate, and phenoxy-polyethylene glycol acrylate. Examples of the diacrylate include triethylene glycol diacrylate, tripropylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, and 1,9-nonanediol diacrylate. Examples of the triacrylate include trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate. These ratios are desirably set to, for example, monoacrylate / diacrylate / triacrylate = 60/30/10 (% by weight).

  The viscosity of the polymerizable acrylic monomer or the mixture (b) of this monomer and oligomer is preferably 200 mPa · s / 25 ° C. or less, more preferably 100 mPa · s / 25 ° C. or less. This is because a polymerizable acrylic monomer or a mixture of monomer and oligomer (b) is dropped from a nozzle inserted in a high-temperature evaporation source in a vacuum deposition apparatus and vaporized instantaneously. This is because, when the uncured vapor-deposited coating layer is formed, if its viscosity is too high, it is difficult to drop it at a constant rate little by little from a nozzle or the like inserted into a high-temperature evaporation source.

  The transparent conductive laminated film of the present invention is a packaging material in the field of electronic devices such as display elements such as liquid crystal displays, display input / output devices such as touch panels and solar cell conversion elements, and packaging fields such as foods, daily necessities, and pharmaceuticals. Therefore, the polymerizable acrylic monomer or the mixture of monomer and oligomer (b) preferably has a PII (Primary Irritation Index) of 2.0 or less. In addition, PII shows the degree of skin disorder of chemicals, and the smaller the value, the lower the irritation.

In the transparent conductive laminated film of the present invention, it is desirable that the surface of the coating layer (B) is subjected to plasma treatment including corona discharge and glow discharge. By doing so, the adhesiveness with an adjacent layer can be improved. Moreover, it is also for removing the uncured component of the polymerizable acrylic monomer or the mixture of monomer and oligomer (b) used as a raw material and improving the degree of curing. When used as a packaging material in the packaging field of foods, daily necessities, pharmaceuticals, etc., it is also possible to cope with problems such as food hygiene by improving the degree of curing.
When this coating layer (B) is subjected to plasma treatment, a DC power source or an RF power source is used to generate plasma continuously and stably, and a polymerizable acrylic monomer or a mixture of a monomer and an oligomer (b) In order to efficiently remove the uncured component, a mixed gas for plasma treatment containing a normal gas such as hydrogen, oxygen, nitrogen, carbon dioxide and at least one inert gas such as helium or argon is used. It is desirable to use it.

The transparent conductive film layer (C) may be made of indium tin oxide (ITO). Considering specific resistance and visible light transmittance, the content of tin is preferably 3 to 50% by weight. Since the thickness affects the surface resistance and visible light transmittance, the thickness may be appropriately determined according to the required surface resistance and visible light transmittance. Usually, about 10-50 nm is preferable. In addition, zinc oxide (ZnO) or the like may be used as a material.
The surface resistance value of the transparent conductive film layer (C) is usually about several hundred Ω / □.

  As a method for forming the transparent conductive film layer (C), any of the conventional known techniques such as vacuum deposition, sputtering, and ion plating can be employed. In the sputtering method, indium tin oxide (ITO) or an indium tin alloy may be used for the target.

In the transparent conductive laminated film of the present invention, there is an inorganic oxide vapor-deposited thin film layer (D) between the base material layer (A) and the coating layer (B), or the base material layer (A) and the coating layer (B ), An inorganic oxide vapor-deposited thin film layer (D) and a coating layer (B) are alternately laminated, that is, “C / (B / D) × n / B / A” or “C / (B / D) × n / A ”(n is an integer of 1 or more) (FIGS. 2 and 3) is preferable because the gas barrier property of the transparent conductive laminated film is improved and the durability is improved accordingly.
As the inorganic oxide vapor-deposited thin film layer (D), a silicon oxide (SiOx) vapor-deposited thin film (x is preferably closer to 2), an aluminum oxide vapor-deposited thin film, a magnesium oxide vapor-deposited thin film, or the like is used. Of these, silicon oxide (SiOx) is preferable from the viewpoints of transparency, gas barrier properties that block oxygen and water vapor, and durability associated therewith.

  Although the formation method of an inorganic oxide vapor deposition thin film layer (D) is not specifically limited, The inorganic oxide vapor deposition thin film layer (D) of a silicon oxide (SiOx) vapor deposition thin film is formed on the surface of a base material layer (A). At the present time, vacuum deposition is the best method for stacking at a higher rate in vacuum. In the current vacuum vapor deposition method, the electron source heating method, the resistance heating method, the induction heating method, or the like is preferable as the heating means for the evaporation source material in the vacuum vapor deposition apparatus. Moreover, in order to improve adhesiveness with a base material layer (A) and a film layer (B), it is also possible to use a plasma assist method, an ion beam assist method, etc. Further, in order to increase the transparency of the deposited thin film layer, reactive deposition may be performed by blowing oxygen gas or the like.

  In the transparent conductive laminated film of the present invention, the inorganic oxide vapor-deposited thin film layer (D) is transparent and has an excellent gas barrier property that blocks a gas that alters the contents such as oxygen and water vapor. The thickness of this inorganic oxide vapor-deposited thin film layer (D) is 5 to 200 nm, more preferably 5 to 100 nm. Here, when the film thickness is less than 5 nm, a uniform vapor-deposited thin film layer may not be obtained, gas barrier properties do not appear, and the function of improving durability cannot be sufficiently achieved. On the other hand, when the film thickness exceeds 200 nm, when an external stress such as bending or pulling is applied to the vapor-deposited thin film layer, the vapor-deposited thin film layer is cracked, and the durability may be deteriorated.

  The transparent conductive laminated film of the present invention uses a polyacetal pen having a diameter of 8 mm (the whole pen is made of polyacetal, the pen tip has a cylindrical shape, and the diameter of the cylinder is 8 mm) at a load of 250 g and 100,000. After reciprocating (3 reciprocations / 1 second, one-way distance 35 mm), voltage measurement is performed at equal intervals, and the deviation (linearity) between the linearly approximated value and the measured value is 1.0% or less. Hereinafter, this linearity measurement method (writing characteristic evaluation method) will be described with reference to the drawings.

First, linearity will be described.
FIG. 4 is a graph for explaining a linearity measurement method. When the relationship between the distance from the reference electrode to the measurement point and the voltage is measured, it should be ideally a straight line (ideal voltage) as shown by the chain line in FIG. However, in reality, the relationship between the distance and the voltage is a curve (measured voltage) as shown by the solid line in FIG. Here, the linearity is calculated from the following equation using the maximum deviation (ΔVmax) from the ideal voltage value and the ideal voltage value (V) at that distance.
Linearity [%] = (ΔVmax / V) × 100

  FIG. 5 is a schematic cross-sectional view showing a state in which the linearity of the touch panel sample of the present invention is measured. In this figure, in the touch panel sample, a transparent conductive laminated film 3 is laminated on a glass 1 with a conductive film via a spacer 2, and a polarizing film 5 with a hard coat is further laminated thereon via an adhesive layer 4. Being done. When measuring the linearity of the transparent conductive laminated film 3 used as a transparent electrode of this touch panel, as shown in FIG. 1, 100,000 round trips (speed: 3 round trips / 1 second, one way distance 35mm).

  FIG. 6 is a schematic plan view showing a state in which the linearity of the touch panel sample of the present invention is measured. When the polyacetal pen 6 is slid, as shown in FIG. 6, the electrode 7 (sliding portion 8) is slid back and forth. Specifically, as shown in FIG. 6, a voltage of 5 V is applied in the 9 cm direction of a sample cut into a 5 cm × 9 cm square, the voltage is measured at 1 cm intervals, and the deviation (ΔVmax) from the ideal value is measured. calculate.

<Example 1>
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 100 μm is prepared as a base material layer (A), and 2-hydroxy-3-phenoxypropyl acrylate, propoxylated neopentyl glycol diacrylate, and ethoxylated trichloride are prepared under atmospheric pressure. A base layer of a diluted liquid mixture of 50% by weight of acrylic solid content obtained by diluting a 60/30/10 (% by weight) mixture with methylolpropane triacrylate (b) (curing shrinkage: 6.3%) with methyl ethyl ketone After coating on (A) and sufficiently evaporating methyl ethyl ketone by drying at 70 ° C., it was cured by irradiation with an electron beam to form a coating layer (B) having a thickness of 0.5 μm. Thereafter, in a vacuum vapor deposition apparatus, a film thickness (about 20 nm) of indium tin oxide (ITO) with a surface resistance value of 500Ω / □ is formed by DC magnetron sputtering to form a transparent conductive film layer (C). did.

<Example 2>
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 100 μm is prepared as the base material layer (A), and 2-hydroxy-3-phenoxypropyl acrylate and propoxylated neopentyl glycol diacrylate are formed thereon by flash vapor deposition. A 60/30/10 (% by weight) mixture (b) (curing shrinkage: 6.3%) with ethoxylated trimethylolpropane triacrylate was dropped into a high-temperature evaporation source to evaporate, and a thickness of 0. A 5 μm uncured vapor-deposited coating layer was laminated. This deposited coating layer was cured by irradiation with an electron beam to form a coating layer (B). Thereafter, in a vacuum vapor deposition apparatus, a film thickness (about 20 nm) of indium tin oxide (ITO) with a surface resistance value of 500Ω / □ is formed by DC magnetron sputtering to form a transparent conductive film layer (C). did.

<Example 3>
In the same manner as in Example 2, an inorganic oxide thin film layer (D) made of a silicon oxide (SiOx) vapor-deposited thin film and a coating layer (B) were sequentially laminated on the base material layer (A), and then a DC power source was used. A 1/1 mixed gas of nitrogen and argon was converted into plasma, and the surface of the coating layer (B) was subjected to plasma treatment. Thereafter, in a vacuum vapor deposition apparatus, a film thickness (about 20 nm) of indium tin oxide (ITO) with a surface resistance value of 500Ω / □ is formed by DC magnetron sputtering to form a transparent conductive film layer (C). did.

<Example 4>
A biaxially stretched polyethylene terephthalate (PET) film having a thickness of 100 μm was prepared as the base material layer (A) and installed in a vacuum deposition apparatus. Silicon oxide was evaporated by an electron beam heating method, and an inorganic oxide thin film layer (D) composed of a 20 nm thick silicon oxide (SiOx) vapor-deposited thin film was laminated on the base material layer (A). Thereafter, in the same manner as in Example 2, a coating layer (B) and a transparent conductive film layer (C) were formed.

<Example 5>
Similarly to Example 2, the coating layer (B) is formed on the base material layer (A), and thereafter, in the same manner as in Example 4, the inorganic oxide thin film layer (D) and the coating layer (B ) And a transparent conductive film layer (C) were formed in this order.

<Comparative Example 1>
In the transparent conductive laminated film of Example 1, the coating layer (B) was not laminated on the base material layer (A), and a transparent conductive film layer (C) was formed.

<Comparative example 2>
In the transparent conductive laminated film of Example 1, a 60/30/10 (% by weight) mixture of 2-hydroxy-3-phenoxypropyl acrylate, propoxylated neopentyl glycol diacrylate, and ethoxylated trimethylolpropane triacrylate ( b) Instead of (curing shrinkage: 6.3%), tripropylene glycol diacrylate (curing shrinkage: 11.5%) was used. Other conditions were the same as in Example 1.

<Comparative Example 3>
In the transparent conductive laminated film of Example 2, a 60/30/10 (% by weight) mixture of 2-hydroxy-3-phenoxypropyl acrylate, propoxylated neopentyl glycol diacrylate, and ethoxylated trimethylolpropane triacrylate ( b) Instead of (curing shrinkage: 6.3%), tripropylene glycol diacrylate (curing shrinkage: 11.5%) was used. Other conditions were the same as in Example 2.

<Comparative Example 4>
In the transparent conductive laminated film of Example 2, the thickness of the coating layer was 25 μm. Other conditions were the same as in Example 2.

<Comparative Example 5>
In the transparent conductive laminated film of Example 2, the thickness of the coating layer was 0.08 μm. Other conditions were the same as in Example 2.

<Comparison evaluation>
1. Written tolerance (linearity evaluation)
About Examples 1-5 and Comparative Examples 1-5, the writing tolerance was evaluated by the linearity measurement. The conductive film of the glass with conductive film 1 is a SnO2 film, the material of the spacer 2 is an acrylic resin, the width is 100 μm, the height is 200 μm, the thickness of the adhesive 4 is 20 μm, the hardness of the polarizing film 5 with hard coat is 2H or more, A thickness of 180 μm was used. For the linearity value [%], 1.0 or less was evaluated as “◯”, 1.0 to 1.2 as “Δ”, and over 1.2 as “×”.
In the state before the reciprocation of the polyacetal pen sliding 100,000 times, the linearity of each sample was 1.0% or less.
2. Oxygen permeability About Examples 1-5 and Comparative Examples 1-5, oxygen permeability in a 30 ° C-70% RH atmosphere was measured with an oxygen permeability meter (MOCON OX-TRAN 2/21) manufactured by Modern Control. (Cc / m ² · 24 h · MPa) was measured.
20cc / m ² · 24h · MPa or less was rated as ◯, more than 20 to 100cc / m ² · 24h · MPa as Δ, and more than 100cc / m ² · 24h · MPa as x.
3. Water Vapor Permeability For Examples 1 to 5 and Comparative Examples 1 to 5, the water vapor permeability in a 40 ° C.-90% RH atmosphere was measured with a water vapor permeability meter (MOCON PERMATRAN-W 3/31) manufactured by Modern Control. (G / m ² · 24 h) was measured.
2 g ^/ m 2 · 24h or less ○, 2 super ~4g ^/ m 2 · 24h △, and as × 4g ^/ m 2 · 24h greater.
4). Alkali resistance About Examples 1-5 and Comparative Examples 1-5, the resistance value (R) after 3-minute immersion in 3.5% KOH aqueous solution was measured (under 23 degreeC environment). The resistance value before immersion is R0.
R / R0 ≦ 1.1 was evaluated as “◯”, 1.1 <R / R0 <1.2 as Δ, and 1.2 <R / R0 as “×”.

  These measurement results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 ... Glass with conductive film 2 ... Spacer 3 ... Transparent conductive laminated film 4 ... Adhesion layer 5 ... Polarizing film 6 with hard coat ... Polyacetal pen 7 ... Electrode 8 ..Sliding part

Claims (3)

  A coating layer (B) having a thickness of 0.1 μm or more and 20 μm or less formed by curing a polymerizable acrylic monomer or a mixture (b) of a monomer and an oligomer on a base material layer (A) made of a transparent plastic film. ), A transparent conductive film layer (C) is laminated thereon, and the curing shrinkage ratio of the polymerizable acrylic monomer or mixture of monomer and oligomer (b) forming the coating layer (B) is 0.2% or more and 10% or less, and the polymerizable acrylic monomer or the mixture of monomer and oligomer (b) contains an acrylate having a trifunctional or higher acryloyl group, and the trifunctional or higher acryloyl A transparent conductive laminated film, wherein the content of the acrylate having a group is less than 50% by weight. A coating layer (B) having a thickness of 0.1 μm or more and 20 μm or less formed by curing a polymerizable acrylic monomer or a mixture (b) of a monomer and an oligomer on a base material layer (A) made of a transparent plastic film. ), A transparent conductive film layer (C) is laminated thereon, and the curing shrinkage ratio of the polymerizable acrylic monomer or mixture of monomer and oligomer (b) forming the coating layer (B) is A transparent conductive laminated film having a water vapor transmission rate (g / m ² · 24h) of 2 g / m ² · 24 h or less, being 0.2% or more and 10% or less.   A coating layer (B) having a thickness of 0.1 μm or more and 20 μm or less formed by curing a polymerizable acrylic monomer or a mixture (b) of a monomer and an oligomer on a base material layer (A) made of a transparent plastic film. ), A transparent conductive film layer (C) is laminated thereon, and the curing shrinkage ratio of the polymerizable acrylic monomer or mixture of monomer and oligomer (b) forming the coating layer (B) is The resistance value (R) in a 23 ° C. environment after immersion in a 3.5% KOH aqueous solution for 3 minutes and the resistance value (R0) in a 23 ° C. environment before immersion are 0.2% or more and 10% or less. R / R0 <1.2 is satisfied, The transparent conductive laminated film characterized by the above-mentioned.

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