JP2001026868A - Production of transparent conductive laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a producing method giving a transparent conductive laminate with reduced curling. SOLUTION: In a high polymer laminated film obtd. by successively laminating a hardening resin layer A and a metallic oxidizing layer on one side of a high polymer film and laminating a hardening resin layer B on the other side of the high polymer film, on the hardening resin layer B, by forming a transparent conductive thin film in which the partial pressure ratio between water and oxygen (H2O/O2) in a film forming atmosphere lies in the range of 0.04 to 2.0 by a sputtering method, a conductive laminated body small in curling, also good in specific resistance and heat resistance and suitable as an electrode substrate for a liq. crystal displaying device is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a transparent conductive laminate by a sputtering method, and more particularly, to a method in which a cured resin layer is provided in contact with both surfaces of a polymer film and one of the cured resin layers is formed on the cured resin layer. The present invention relates to a method for producing a transparent conductive laminate suitable for liquid crystal display applications, wherein a transparent conductive thin film mainly composed of indium oxide is formed on a cured resin layer of a polymer laminated film provided with a metal oxide layer.

[0002]

2. Description of the Related Art Conventionally, heavy, thick, and fragile glass substrates have been used as transparent electrode substrates for LCDs and touch panels. Recently, however, pagers, mobile phones, electronic organizers, personal digital assistants, and the like have become popular. In order to improve portability, information devices that can be carried around are required to be thinner, lighter, and more resistant to breakage.
As a material replacing the glass substrate, a transparent resin substrate is being adopted.

[0003] However, the transparent resin substrate is lightweight and excellent in flexibility, but is inferior in basic characteristics such as durability, solvent resistance, gas barrier property and the like to the glass substrate. For example, when a transparent resin substrate is used as an LCD electrode substrate, providing a metal oxide layer on the substrate provides gas barrier properties. However, since the metal oxide layer is exposed to an aqueous alkali solution during the resist stripping process after the transparent electrode patterning, there is a problem in that the metal oxide layer is dissolved, and in the process of forming the liquid crystal alignment film, a precursor material of the liquid crystal alignment film is used as a solvent such as N-methylpyrrolidone. When coating with a coating solution dissolved in water, there is a problem that the above-mentioned solvent causes damage such as whitening and swelling of the transparent resin substrate. In order to solve such a problem, it has been proposed to laminate a cured resin layer on a polymer film serving as a transparent resin substrate.

[0004] As the transparent conductive thin film, ITO is used.
(In-Sn-O) films are widely used as electrode materials for liquid crystal displays, touch panels and the like, utilizing their high conductivity and high transparency characteristics. In recent years,
The DC magnetron sputtering method is generally used from the viewpoint of controllability of a film forming rate, uniformity of a formed thin film, and the like. In particular, recent advances in thin film formation technology have been remarkable, and it has become possible to form a transparent conductive thin film even on a polymer film substrate having little heat resistance. Among them, the sputtering method has the advantages that (a) film formation can be performed for a long time, (b) composition does not shift even when the film is formed for a long time, and (c) widening is easy. This is one of the most used film forming technologies.

The present inventors have previously reported that a polymer laminated film in which a metal oxide layer and a cured resin layer are laminated on a polymer film is excellent in gas barrier properties, durability and handling strength, and is suitable for liquid crystal displays. They have found that they are suitable as a transparent resin substrate, and have studied the practical application of a transparent conductive laminate in which an ITO film is formed on this polymer laminated film using a sputtering method.

However, when a film is continuously formed on a polymer laminated film by a DC magnetron sputtering method using an ITM (In-Sn-Metal) or an ITO target, as the film forming time becomes longer, the produced transparent film becomes longer. It has been found that there is a problem that the conductive laminate is severely deformed.

That is, even when such a polymer laminated film itself is excellent in flatness and flat, there is a problem that when the ITO thin film is deposited on the polymer laminated film, the transparent conductive laminate itself is deformed. Do you get it. This deformation is generally called curl. When the curl becomes a certain size or more, in the process of forming the transparent conductive laminate into a panel, specifically, it becomes impossible to adsorb to the spinner head or the roll coater base at the time of resist application, and further, at the time of washing or drying Various problems arise, such as the inability to easily store in a substrate holder or carrier.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is to provide an IT
When a transparent conductive thin film is formed on a polymer laminated film by a sputtering method using an M or ITO target, the transparent conductive film is excellent in conductivity and transparency, and has small curl and good flatness (flatness). An object of the present invention is to provide a method capable of manufacturing a laminate.

[0009]

Means for Solving the Problems The present inventors have studied the above problems, and as a result, in order to suppress the curl of the transparent conductive laminate, it is effective to reduce the stress of the deposited transparent conductive thin film. I found that.

As means for reducing the film stress of the transparent conductive thin film, which is considered to be the main cause of the curl, there is a method of increasing the film forming pressure as much as possible to decrease the density of the formed thin film. Since the formed thin film has a low density, the film stress is slightly lowered, and an effect is seen to some extent in suppressing the deformation of the transparent conductive laminate. However, it has been found that in this method, the effect may not be exhibited even if the pressure is increased depending on the film forming conditions.

Therefore, the present inventors have further studied and, in a method for producing a transparent conductive laminate by a sputtering method using an ITM or ITO target, taking into account a trace amount of water present in a polymer laminated film. ,
In addition to introducing an inert gas (mainly argon) during the sputtering, the partial pressures of water and oxygen present in the film formation atmosphere were measured by a quadrupole mass spectrometer, and the partial pressure ratio (H
₂ O / O ₂ ) is always adjusted to a specific range while controlling the amount of water and oxygen introduced.
An O thin film was obtained, and as a result, it was found that a good transparent conductive laminate having a small curl was obtained, and the present invention was completed.

That is, the present invention relates to a method for curing a polymer film laminate comprising a polymer film, in which a cured resin layer A and a metal oxide layer are laminated in this order on one side and a cured resin layer B is laminated on the other side. In manufacturing a transparent conductive thin film by forming a transparent conductive thin film on the resin layer B by a sputtering method, the partial pressure ratio of water and oxygen in the film formation atmosphere (H ₂ O / O ₂ )
Is in the range of 0.04 to 2.0 to form a transparent conductive thin film.

In the above method for producing a transparent conductive laminate, the transparent conductive thin film contains indium oxide as a main component,
In addition, it is preferable to contain a small amount of at least one oxide selected from tin, zinc and gallium. Further, in the method for producing a transparent conductive laminate described above, the polymer film is made of polycarbonate, the metal oxide layer is made of silicon oxide (SiOx), and the cured resin layers A and B
It is also preferable that each contains a reaction cured product of an alkoxysilane. Further, in the above-mentioned method for producing a transparent conductive laminate, the thickness of the transparent conductive thin film may be 300 to 30.
It is also preferable to set the thickness to 00 (30 to 300 nm), and these are all included in the present invention.

The transparent conductive laminate preferably has a specific resistance of the transparent conductive thin film of 1 × 10 ^-4 to 1 × 10 ^-3 Ω.
cm and a total light transmittance of 80 to 92%, and is excellent in transparency and conductivity.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing a transparent conductive laminate of the present invention will be described in detail. In the method of the present invention, a sputtering method is applied to the formation of the transparent conductive thin film. In a sputtering method for forming a transparent conductive thin film mainly containing indium oxide, an alloy mainly containing indium or a sintered body mainly containing indium oxide can be used as a target. When the former target is used, an inert gas such as argon and a reactive gas such as oxygen gas are introduced into a vacuum chamber (vacuum chamber) to perform reactive sputtering. In the latter case, sputtering is performed using an inert gas such as argon alone or a mixture of an inert gas such as argon and a small amount of a reactive gas such as oxygen gas. Known methods such as direct current or high frequency bipolar sputtering, direct current or high frequency magnetron sputtering, and ion beam sputtering can be applied to the sputtering method. Above all, the magnetron sputtering method is preferable because plasma impact on the polymer laminated film to be processed is small and high-speed film formation is possible.

As a sputtering apparatus, any of a batch type and a roll-to-roll type can be applied. Considering the productivity, the roll-to-roll system is particularly preferable.

In the present invention, the transparent conductive thin film formed by sputtering contains indium oxide as a main component. Indium oxide is originally a transparent electric insulator, but becomes a semiconductor when it contains a small amount of impurities, when it is slightly lacking in oxygen, or the like.
In particular, in order to form a transparent conductive film having good electric characteristics, it is recommended to use a transparent conductive layer of indium oxide containing 2 to 20% by weight of tin oxide.

In the present invention, the transparent conductor formed on the polymer laminate film by magnetron sputtering contains indium oxide as a main component and at least one metal component selected from tin, zinc and gallium as an impurity. In order to form this film, an oxide sintered target containing indium oxide as a base material and containing one or more components selected from tin, zinc and gallium as impurities is used. Is appropriate. Further, a metal target containing at least one metal selected from tin, zinc and gallium as metal indium may be used. However, considering the control of various characteristics of the formed transparent conductive thin film, it is particularly preferable to use an oxide sintered target.

As a result of a study by the present inventors on a transparent conductive thin film, particularly an ITO film, formed by sputtering,
(1) The stress of the ITO thin film is governed not only by the deposition pressure but also by the ratio of moisture and oxygen in the deposition atmosphere, and (2) this moisture is mainly released from the polymer film or the cured resin layer during sputtering. Is estimated to be
It has been found that this variation in the amount of released water is the cause of the variation in curl characteristics.

Therefore, in the method of the present invention, a transparent conductive laminate formed mainly of a transparent conductive thin film composed of indium oxide is transported by a roll-to-roll method or a batch method while transporting a polymer laminated film having a structure described later. In manufacturing, in addition to an inert gas (mainly argon) conventionally used as a film formation atmosphere, the amount of water in the film formation atmosphere is monitored by, for example, a quadrupole mass spectrometer, and at least during the film formation, Is controlled by, for example, introducing or removing moisture from the outside so that the partial pressure ratio of water and oxygen (H ₂ O / O ₂ ) is maintained in the range of 0.04 to 2.0. Film formation.

In the sputtering of a polymer laminated film to which the method of the present invention is applied, the peak intensity ratio (ie, partial pressure ratio) of water (mass number 18) and oxygen (mass number 32) present in the film formation atmosphere is H ₂ O. When / O ₂ is less than 0.04, film growth occurs such that the stress of the ITO film becomes large from the initial stage of film formation, and the curl of the transparent conductive laminate increases due to the effect. On the other hand, when the above-mentioned H ₂ O / O ₂ is adjusted to 0.04 or more according to the present invention, the growth of the stress of the thin film is extremely small, so that the curl of the transparent conductive laminate becomes small.

According to the study of the present inventors, the stress of a thin film is closely related to the growth process of the film, and the ratio of oxygen and water present in the film formation atmosphere has a great influence on the film growth. . By controlling the amount ratio of oxygen and water present in the film formation atmosphere as described above, a transparent conductive film having a low film stress can be formed, and curling when forming a transparent conductive laminate can be reduced. it can.

In the structure of the polymer laminated film according to the present invention, since the metal oxide layer is formed on the surface opposite to the ITO film, the film stress of the metal oxide layer causes
The TO surface convex curl is slightly suppressed. Therefore, the curl can be suppressed even if the partial pressure ratio of H ₂ O / O ₂ is slightly lower than in the case of the laminated structure in which the ITO film is formed on the same surface as the metal oxide layer. Therefore, in this configuration, H ₂ O /
The O ₂ partial pressure ratio may be set to 0.04 or more.

On the other hand, when the H ₂ O / O ₂ partial pressure ratio in the atmosphere increases, curling is reduced, but there is a problem that the specific resistance increases and the heat resistance R / R ₀ deteriorates. Here, the heat resistance R / R ₀ is a value obtained by dividing the value of the surface resistance after the heat treatment at 130 ° C. for 4 hours by the value of the initial surface resistance, and 0.7 <R / R _0.
<1.5 is generally considered good. In the present invention, if the partial pressure ratio of H ₂ O / O ₂ is 2.0 or less, deterioration of specific resistance and heat resistance is hardly observed.

In the method of the present invention, as described above, the peak intensity ratio (partial pressure ratio) of moisture and oxygen present in the film formation atmosphere is such that H ₂ O / O ₂ is in the range of 0.04 to 2.0. , Curl is reduced, and
The specific resistance of the TO thin film is good. In particular, a better resistivity of the ITO film when H ₂ O / O ₂ is 0.05 to 1.5, ITO in the case of H ₂ O / O ₂ is 0.4 to 2.0
The heat resistance R / R ₀ of the thin film is better. Therefore, considering both of these factors, the range of H ₂ O / O ₂ in the range of 0.4 to 1.5 is optimal.

The thickness of the transparent conductive thin film containing indium oxide as a main component formed in the present invention is preferably 100 ° or more (10 nm or more) in order to obtain sufficient conductivity. The specific resistance of the transparent conductive thin film is 1 × 10 ^{−3 in} consideration of the response speed when a device is manufactured.
Ωcm or less, particularly preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻³ Ωcm. In order to maintain good visibility when a device is formed, the total light transmittance is 80% or more, particularly 80%.
It is preferably about 92%.

The force for deforming the transparent conductive laminate is greatly affected by the stress of the film and its thickness. In the present invention, in particular, the thickness of the transparent conductive thin film is 300 to 3000, because the larger the thickness of the transparent conductive thin film, the greater the deformation or curl when the transparent conductive thin film is formed.
The effect is remarkable in the case of Å (30 to 300 nm).

The polymer laminated film on which the transparent conductive thin film is formed by sputtering is formed on one surface of a transparent polymer film serving as a substrate by forming a cured resin layer A and a metal oxide layer from the film surface. A laminated structure in which a cured resin layer B is laminated on the other surface of the polymer film, and basically has a laminated structure of metal oxide layer / cured resin layer A / transparent polymer film / cured resin layer B Having. In the present invention, a transparent conductive thin film is formed on the cured resin layer B by sputtering under the above conditions.

Next, the structure of the polymer laminated film having the above structure to be sputtered according to the present invention, that is, the polymer laminated film to be sputtered on the cured resin layer B will be described in detail.

The polymer film is not particularly limited as long as it is made of a heat-resistant transparent organic polymer compound, and usually has a glass transition temperature (Tg) of 1%.
A film of a thermoplastic polymer compound having a temperature of 00 ° C or higher, preferably 130 ° C or higher is preferable. Examples of such a polymer compound include polyether sulfone, polycarbonate, polysulfone, polyarylate, polyester, polyamide, polyimide, and polyolefin. Of course, they can be used as homopolymers or copolymers and can be used alone or as a blend. Among them, polycarbonate from bisphenol A or 3,3,5-trimethyl-1,1
Polycarbonate obtained by copolymerizing -di (4-phenol) cyclohexylidene or fluorene-9,9-di (3-methyl-4-phenol) with bisphenol A is more preferable.

Since the transparent conductive thin film formed by the method of the present invention has a small film stress, it has a thickness of 0.025 as a substrate film.
The effect is particularly large when a thin polymer film of about 0.4 mm is used. Such a polymer film is prepared by a melting method,
It can be manufactured by a casting method, and is preferably obtained by a casting method in terms of surface flatness.

On the other hand, the cured resin layers A and B formed on the surface of the polymer film have good adhesion to the polymer film and the metal oxide layer, and have chemical resistance and bending resistance. Things are good. It is preferable that the cured resin layers A and B have substantially the same thickness on both surfaces of the polymer film in order to reduce the curl deformation of the polymer laminated film used in the present invention.

Specific examples of the resin constituting the cured resin layers A and B include, for example, an epoxy resin, an acrylic resin, an acrylic epoxy resin, a melamine resin, a phenol resin, a silicone resin, or a thermosetting resin. There are urethane resins and the like. In addition, examples of the photopolymerizable polymer include polyester acrylate, polyester urethane acrylate, epoxy acrylate, and polyol acrylate. Further, it is preferable to include an alkoxysilane in the cured resin in order to improve adhesion. Examples of such alkoxysilanes include tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N-
(2-aminoethyl) -3-aminopropylmethyldimethoxysilane can be mentioned. These can be used in combination of two or more. It is also possible to form a cured resin layer by combining such an alkoxysilane with a polymer having an OH group.

The cured resin layers A and B of the polymer laminated film are preferably made of the same resin. Further, two or more such cured resin layers may be provided.

The thickness of the cured resin layers A and B is not particularly limited, but is generally preferably 3 μm or more. If the thickness is smaller than 3 μm, the solvent resistance is generally insufficient. The upper limit of the film thickness is determined by the balance between film forming property, economic efficiency and solvent resistance. Preferably 20 μm or less,
More preferably, it is 10 μm or less.

The cured resin layers A and B can be specifically formed as follows. That is, a reactive diluent, fine particles, various additives such as a leveling agent, a thermoplastic resin, and a modifier such as a plasticizer are added to a solution containing the thermosetting resin as needed to form a coating liquid. . Concentration of coating liquid,
It is diluted with an appropriate organic solvent as needed for viscosity adjustment. The coating liquid is coated on a substrate film 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 a temperature of 120 ° C. or more for 3 minutes or more. More preferably 1
It is formed by curing by heat treatment at a temperature of 30 ° C. or more for 5 minutes or more to form a cured layer. When a photopolymerizable polymer is used, the cured resin layer can be formed by irradiating a radiation such as an ultraviolet ray or an electron beam.

The metal oxide layer formed on one of the cured resin layers A is made of a thin metal oxide mainly composed of one or more metals selected from silicon, aluminum, magnesium and the like. Layers, which are known as materials having excellent gas barrier properties. These metal oxide layers are formed by a vapor deposition method, a sputtering method, an ion plating method, a plasma CVD method, or the like. Among them, silicon oxide (SiOx) whose ratio (x) of the number of oxygen atoms to the number of silicon atoms (x) is 1.5 to 2.0 is mainly used in terms of gas barrier properties, transparency, surface smoothness, flexibility and the like. The metal oxide as a component is good. The ratio of the number of oxygen atoms to silicon oxide is determined by X-ray electron spectroscopy, X-ray microspectroscopy,
It is analyzed and determined by Auger electron spectroscopy, Rutherford backscattering method and the like. If this ratio is smaller than 1.5, the transparency becomes poor.

The thickness of the metal oxide layer is 5 to 20.
A range of 0 nm is preferred. If the thickness is less than 5 nm, it is difficult to form a uniform film, and a portion where the film is not formed occurs, and gas permeates from this portion, and the gas barrier property tends to deteriorate. On the other hand, when the thickness is more than 200 nm, not only lack of transparency but also poor flexibility, cracks are often generated and gas barrier properties are often impaired. For higher transparency requirements, the above silicon oxide containing 5 to 30% by weight of magnesium fluoride based on the total weight is preferred.

In the present invention, since the metal oxide layer is provided on the cured resin layer A formed on one side of the polymer film, the metal oxide layer has excellent gas barrier properties,
It can be preferably used as a liquid crystal display substrate.

The transparent conductive laminate according to the method of the present invention as described above contains a polymer film, a metal oxide layer, cured resin layers A and B, and a transparent conductive thin film as constituent components.
A cured resin layer A and a metal oxide layer are laminated in this order on one surface of the polymer film from the film surface side, and a cured resin layer B is formed on the other surface of the film. A transparent conductive thin film is formed on B by the above-described sputtering. That is, as a specific configuration, a metal oxide layer / cured resin layer A / polymer film /
It is a laminate composed of the cured resin layer B / the transparent conductive thin film.

In this laminate, between the polymer film and the cured resin layer B, between the polymer film and the cured resin layer A, between the cured resin layer A and the metal oxide layer, or between the cured resin layer B and the cured resin layer B. Improve the adhesion between transparent conductive thin films,
In order to further enhance chemical resistance, bending resistance, wear resistance, etc.,
A layer that functions as an adhesive layer or a chemical resistant layer may be present.

Next, the sputtering will be described with reference to the drawings. FIG. 1 is a configuration diagram showing an example of a sputtering apparatus for performing the film forming method of the present invention. In the figure, 1 is a vacuum chamber (vacuum chamber), 2 is a long roll-shaped polymer laminated film, 3 is a target, 4 is an unwinding shaft, 5 is a main roll, 6 is a sub roll, and 7 is a winding shaft. These are provided in a vacuum chamber (vacuum chamber). 8 is an Ar gas introduction system (O ₂ / Ar mixed gas), 9 is an oxygen gas introduction system, 10 is a moisture introduction system,
1 is a microminiature pressure gauge MPA, 12 is a computer,
Reference numeral 13 denotes a mass flow controller.

In FIG. 1, the roll 2 of the polymer laminated film is set on the unwinding shaft 4, and the film is unwound, and is placed on the cured resin layer B surface of the polymer laminated film along the illustrated film forming path. After performing sputtering, it is set so as to be wound on a winding core set on a winding shaft 7. During film formation, water and oxygen are introduced or removed while monitoring the water pressure and the oxygen partial pressure during film formation with the ultra-compact partial pressure vacuum gauge MPA11 to adjust to a predetermined H ₂ O / O ₂ partial pressure ratio. Water can be introduced using the mass flow controller 13 or a variable leak valve (not shown).

[0044]

The present invention will be described more specifically below with reference to examples and comparative examples. In addition, each measured value in the present invention is measured by the following method.

(1) Measurement of Moisture / Oxygen Partial Pressure Ratio in Film Forming Atmosphere Using Quadrupole Mass Spectrometer The quadrupole mass spectrometer used in the present invention is mainly composed of the types of elements existing in the vacuum chamber. And an apparatus for evaluating the abundance thereof. In order to measure gas components in the film formation atmosphere using this quadrupole mass spectrometer, a pressure lower than the actual film formation pressure (1 × 1
0 ^-4 Torr or less). An example of a quadrupole mass spectrometer is MASS MATE manufactured by Nippon Vacuum Engineering Co., Ltd.
There are 100. In the present invention, the product is manufactured by MC Electronics Co., Ltd. (released by Ferran Scientific. I).
nc) Micropole Analyzer micro-partial pressure gauge system MPA was used. Model number MPA-CF-21 whose MPA sensor has a maximum operating pressure of 5 mTorr and an analysis chamber volume range of 2 to 100 AMU this time.
5 was used. This MPA is a mass spectrometer that can measure at a film forming pressure (1 × 10 ⁻² to 1 × 10 ⁻⁴ Torr) without using a differential pumping system.

(2) Measurement of total light transmittance Measurement was performed using COH-300A manufactured by Nippon Denshoku Industries Co., Ltd.

(3) Measurement of curl A method for measuring the amount of deformation of the transparent conductive laminate for liquid crystal display due to the stress of the thin film of the present invention is described below. Here, this measurement method is described as a curl measurement method, and the deformation amount is described as a curl. The transparent conductive laminate for liquid crystal display is cut into a square of 10 cm square, and left for 24 hours under constant humidity and normal temperature (25 ° C., 50% RH environment). Thereafter, the laminate is placed on a horizontal support plate such that the surface on which the transparent conductive layer is provided faces down,
Average value of the heights of the four corners of the laminate from the support plate (curl)
Are within the range of 0 to 20 mm as good characteristics.

(4) Measurement of specific resistance The surface resistance of the ITO thin film was measured by Mitsubishi Chemical Corporation Lores.
The thickness of the ITO thin film was measured with a fluorescent X-ray analyzer manufactured by Rigaku Denki Kogyo Co., Ltd. using a Ta MP MCP-T350. The specific resistance was determined from the product of the surface resistance and the film thickness.

(5) Evaluation of heat resistance Surface resistance (Ω / cm ² ) of film with ITO immediately after film formation
R ₀ is measured, and then heat treatment is performed at 130 ° C. for 4 hours, and the surface resistance (Ω / cm ² ) R is measured in the same manner. The _value obtained by dividing the surface resistance R after the heat treatment by the surface resistance R ₀ before the heat treatment is referred to as R / R ₀ heat resistance. R / _R0 = 0.7-1.
Those in the range of 5 have good characteristics.

Example 1 As a polymer film, DS
A 100 μm thick film made of a transparent bisphenol A-based polycarbonate having a glass transition temperature (Tg) of 150 ° C. measured in C was used.

First, the following cured resin layer A was laminated on one surface of the polycarbonate film. That is, vinylmethoxysilane (KBM1003 manufactured by Shin-Etsu Silicone Co., Ltd.) 148 is placed in a stirring vessel whose outside is cooled with water.
Parts by weight were added, 54 parts of 0.01 N hydrochloric acid solution was gradually added while stirring vigorously, and the mixture was further stirred slowly for 3 hours to obtain a hydrolyzed liquid of vinylmethoxysilane. Next, 50 parts by weight of the acrylic resin, 50 parts by weight of the above hydrolyzate of vinylmethoxysilane,
10 parts by weight of unhydrolyzed vinyltrimethoxysilane and photoinitiator 2-hydroxy-2-methyl-1-phenylpropan-1-one ("Dulcure" 117 manufactured by Merck & Co.)
3) 5 parts by weight and silicone oil as a leveling agent (SH28PA manufactured by Toray Dow Corning Silicone Co., Ltd.)
0.02 parts by weight were mixed to obtain a coating liquid (a). This coating liquid (a) is coated on the magnesium fluoride-containing silicon oxide layer subjected to the corona discharge treatment by using a microgravure roll coating method, and heated at 60 ° C. for 1 minute to remove the residual solvent in the coating film by exhaustion. After that, the coating was cured by irradiating ultraviolet rays using a 120 W / cm high-pressure mercury lamp under the condition of an integrated light quantity of 800 mJ / cm ² , thereby forming a cured resin layer A having a thickness of 4 μm.

Next, a cured resin layer B having the same composition and the same thickness as the above-mentioned cured resin layer A was formed on the opposite surface of the polycarbonate film. The curl deformation of the polymer laminated film itself was 0 mm.

The polymer laminate film thus obtained was set in a take-up type magnetron sputtering apparatus, and the inside was evacuated to 3 × 10 ^-6 Torr. Subsequently, the film was rewound and sufficiently degassed. Then, it was confirmed that there was no change in water pressure even when the film was conveyed. The target is B-doped S
An i target was used. Thereafter, an O ₂ / Ar mixed gas (O ₂ : Ar = 30: 70) was introduced into the tank at 100 sccm, and the pressure was adjusted to 1.0 × 10 ⁻³ Torr. Was set to 4 W / cm ² and the film speed was set to Vf = 1.0 m / min, and sputtering was performed on the cured resin layer A surface of the polymer film. The thickness of the formed SiOx thin film was 280 °.

Next, the Si target was replaced with an ITO target, and the gas was exhausted to 1.5 × 10 ⁻⁵ Torr. Thereafter, an O ₂ / Ar mixed gas (O ₂ /Ar=1.2%) was introduced into the tank at 150 sccm, and the pressure in the tank was set at 3.0 × 10 3.
^-3 Torr, the main roll temperature was room temperature, the film speed was Vf = 0.1 m / min, and the input power density was 1
An ITO film having a thickness shown in Table 1 was continuously formed on the cured resin layer B surface of the polymer laminated film at a setting of W / cm ² . Moisture present in the deposition atmosphere at that time (mass number 18)
And oxygen (mass nunmer 32) quadrupole mass spectrometer (MP
A) Peak intensity ratio (partial pressure ratio) H ₂ O / O ₂ = 1.7
It was introduced while adjusting the water content so that The evaluation results of this transparent conductive laminate are shown in the column of Example 1 in Table 1 below. As is clear from Table 1, good results were obtained in all the evaluations.

Example 2 The polymer laminated film described in Example 1 was set in a roll-up type magnetron sputtering apparatus, and the inside of the tank was evacuated to 2 × 10 ⁻⁵ Torr. Thereafter, an Ar / O ₂ mixed gas (Ar / O ₂ = 9)
8.8 / 1.2) was introduced into the tank at 150 sccm, the pressure was adjusted to 3.0 × 10 ⁻³ Torr, the temperature of the main roll was room temperature, the film speed was Vf = 0.1 m / min, and the input power was An ITO film having the thickness shown in Table 1 was continuously formed on the cured resin layer B of the polymer laminated film while setting the density to 1 W / cm ² . At this time, the moisture (mass
number 18) and oxygen (mass number 32) peak intensity ratio (partial pressure ratio) H ₂ O by quadrupole mass spectrometer (MPA)
Water was replenished so that / O ₂ = 0.9. The evaluation results of the transparent conductive laminate manufactured in this manner are shown in the column of Example 2 in Table 1 below. As is clear from Table 1, good results were obtained in all the evaluations.

[Comparative Example 1] The polymer laminated film described in Example 1 was set in a roll-up type magnetron sputtering apparatus, and the inside of the tank was evacuated to 2 × 10 ^-6 Torr. Thereafter, an Ar / O ₂ mixed gas (Ar / O ₂ = 9)
8.8 / 1.2) was introduced into the tank at 150 sccm, the internal pressure was adjusted to 3.0 × 10 ⁻³ Torr, the temperature of the main roll was set to room temperature, and the film speed was set to Vf = 0.1 m / mi.
n, the input power density was set to 1 W / cm ² , and an ITO film having a film thickness shown in Table 1 was continuously formed on the cured resin layer B of the polymer laminated film. Peak intensity ratio (partial pressure ratio) of water (mass number 18) and oxygen (mass number 32) present in the film formation atmosphere at that time by a quadrupole mass spectrometer (MPA)
It was _{H 2 O / O 2 = 0.03} . As shown in Table 1, this transparent conductive laminate had a large curling problem.

[Comparative Example 2] The polymer laminated film described in Example 1 was set in a roll-up type magnetron sputtering apparatus, and the inside of the tank was evacuated to 4 × 10 ^-6 Torr. Thereafter, an Ar / O ₂ mixed gas (Ar / O ₂ = 9)
8.8 / 1.2) was introduced into the tank at 150 sccm, the pressure was adjusted to 3.0 × 10 ⁻³ Torr, the temperature of the main roll was room temperature, the film speed was Vf = 0.1 m / min, and the input power was The density was set to 1 W / cm ² , and a 1300 ° thick ITO (In-Sn-
O) A film was continuously formed. Moisture (mass number 18) and oxygen (mass number 32) present in the film formation atmosphere at that time
Water was replenished so that the peak intensity ratio (partial pressure ratio) H ₂ O / O ₂ = 5.0 by a quadrupole mass spectrometer (MPA) was obtained. As shown in Table 1, the curling of this transparent conductive laminate was suppressed, but the specific resistance was high and the heat resistance was poor.

[0058]

[Table 1]

[0059]

According to the method of the present invention, water (mass number 18) and oxygen (mass number) existing in the film formation atmosphere by sputtering are used regardless of the batch system or the roll-to-roll system.
s number 32) By controlling the peak intensity ratio (partial pressure ratio) with a quadrupole mass spectrometer (MPA) within an appropriate range, a transparent conductive thin film is formed on the polymer laminated film to achieve durability, A transparent conductive laminate having good curl characteristics in addition to properties such as processability and gas barrier properties can be provided.

The transparent conductive laminate can be effectively used for a transparent electrode substrate for a liquid crystal display device, a touch panel, etc. by utilizing its characteristics.

[Brief description of the drawings]

FIG. 1 is a simplified cross-sectional view of a manufacturing apparatus showing an example of a general roll-to-roll type film forming method that can be employed in the method of the present invention.

[Explanation of symbols]

1. 1. Vacuum chamber (vacuum chamber) 2. Long roll polymer film Target 4. Unwind shaft 5. Main roll 6. Sub-roll 7. Winding shaft 8. Ar gas introduction system (O ₂ / Ar mixed gas) 9. Oxygen gas introduction system 10. Moisture introduction system 11. Ultra-compact partial pressure gauge MPA 12. Computer 13. Mass flow controller

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroshi Hara 4-3-2 Asahigaoka, Hino City, Tokyo Teijin Limited, Tokyo Research Center F-term (reference) 4F100 AA17C AA20C AA25E AA28E AA40E AH06B AH06D AK01A AK01B AK01D AK25 AK45A AT00A BA05 BA07 BA10E CA02 CA18 EH66E EJ54 GB41 JB12B JB12D JG01 JG01E JL04 JM02E JN01 JN01E 4K029 AA11 AA25 BA45 BC09 BD00 EA01 EA03 EA05 5G323 BA02 BB05

Claims (4)

[Claims] 1. A polymer film laminate in which a cured resin layer A and a metal oxide layer are laminated in this order on one surface of a polymer film, and a cured resin layer B is laminated on the opposite surface of the polymer film. When a transparent conductive thin film is formed on the cured resin layer B by a sputtering method to produce a transparent conductive laminate, the partial pressure ratio of water and oxygen in the film formation atmosphere (H ₂
O / O ₂ ) is maintained at 0.04 to 2.0 to form a transparent conductive thin film. 2. The transparent conductive film according to claim 1, wherein the transparent conductive thin film contains indium oxide as a main component and at least one oxide selected from tin, zinc and gallium. A method for manufacturing a laminate. 3. The polymer film is made of polycarbonate, the metal oxide layer is made of silicon oxide, and the cured resin layer A and the cured resin layer B each contain a reaction cured product of alkoxysilane. The method for producing a transparent conductive laminate according to claim 1 or 2. 4. The transparent conductive thin film has a thickness of 300 to 3000.
The method for producing a transparent conductive laminate according to any one of claims 1 to 3, wherein Å.