JP3118339B2 - Gas barrier transparent conductive laminate and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a gas barrier conductive laminate based on a polymer film. More specifically, the present invention relates to a conductive film having transparency in a visible light region and having a small transmittance of a gas such as oxygen and water vapor, in which water vapor, oxygen, and other harmful gases must be avoided. The present invention relates to a gas barrier transparent conductive film suitable for application to liquid crystal display devices and the like.

[0002]

2. Description of the Related Art Conventionally, glass has been used as a base material of a transparent conductor for liquid crystal display. However, in recent years, it is lightweight, easy to enlarge, easy to break, and excellent in workability. It has been proposed to use a transparent conductive film having such a property as an electrode. However,
It has been found that when a conductive film is used, water vapor and oxygen passing through the film cause deterioration in the performance of the liquid crystal element. In order to solve such a problem, it has become clear that it is necessary to impart a gas barrier property to the film substrate. Research on transparent gas-barrier films has been conducted for some time, such as coating polypropylene or polyester films with a resin having excellent gas barrier properties such as vinylidene chloride or vinyl alcohol-based polymer (Japanese Patent Publication No. 50-28120). , Tokiko Sho 59-479
96), forming a thin film of silicon oxide or magnesium oxide on a polyester film by vacuum evaporation or sputtering (JP-B-51-4810, JP-B-53-1295)
30, JP-A-63-257630). Further, if necessary, a gas barrier layer provided with a protective layer or another polymer film is laminated with an adhesive for the purpose of further improving gas barrier properties.

[0003]

However, such a conventional transparent gas barrier film has the following problems. In the case of coating a resin, the temperature dependence of the transmittance of gas such as water vapor or oxygen is remarkable, and particularly, gas barrier properties are impaired at high temperatures. Due to the large interaction between the resin material and the gas molecules, the presence of one gas affects the permeability of another gas. For example, in polyvinylidene chloride or polyvinyl alcohol, the presence of water vapor has a significant effect on oxygen permeability. Insufficient heat resistance compared to inorganic substances. In the case of vacuum-depositing an inorganic substance such as silicon oxide, the transparency decreases when the gas barrier property is increased. If the coating film thickness is small, sufficient gas barrier properties cannot be obtained. If the coating film thickness is large, the adhesion to the base material is reduced, and the coating becomes brittle, loses flexibility and easily cracks during processing. The present inventors have conducted intensive studies to solve such a problem, and as a result, have found a transparent conductive laminate having a gas barrier layer having excellent adhesion to a polymer substrate, and have reached the present invention. .

[0004]

That is, the present invention provides a method in which a silicon oxide layer and a transparent conductive layer are laminated on a transparent polymer film substrate, wherein the silicon oxide layer is at least organic. A high gas barrier transparent conductive laminate, which is formed by a reduced pressure plasma enhanced chemical vapor deposition method using a silicon compound gas and oxygen, and preferably, the transparent polymer film substrate is a polyether. A gas-barrier transparent conductive laminate, which is a sulfone or a polyetherketone, and preferably also a gas-barrier transparent conductive laminate in which the layer of silicon oxide contains an organic substance derived from an organosilicon compound; Preferably, the silicon oxide layer is formed by a low pressure plasma chemical vapor deposition method using at least an organic silicon compound gas and oxygen gas, The transparent conductive layer is a gas barrier transparent conductive layer in which the light conductive layer is formed by a sputtering method. Preferably, at least a silicon oxide layer and a transparent conductive layer are appropriately formed on a transparent polymer film substrate. a laminate formed by the gas-barrier transparent conductive laminate permeability of oxygen gas of the laminate is less than 0.1cc / m ^2/24 hours / 1 atm, is preferably also oxidizing A gas barrier transparent conductive laminate in which a silicon layer (A) and a transparent conductive layer (B) are laminated on a polymer film substrate (C) in the order of ACB, CAB, or ACAB. Preferably, a method for producing a gas-barrier transparent conductive laminate pair in which a silicon oxide layer and a transparent conductive layer are laminated on a transparent polymer film substrate, wherein the silicon oxide layer is formed of at least an organic A gas-barrier transparent conductive laminate formed by a reduced-pressure plasma-enhanced chemical vapor deposition method using an elemental compound gas and oxygen, and preferably a gas-barrier property in which the transparent conductive layer is formed by a sputtering method. A method for producing a transparent conductive laminate is provided.

The present invention will be described below with reference to the accompanying drawings. First, referring to the attached drawings, FIG. 1 is an explanatory view of an apparatus for carrying out the present invention, and FIGS. 2 to 5 show an example of a layer configuration of a high gas barrier transparent conductive laminate of the present invention. FIG. FIG. 2 illustrates a layer configuration including a transparent conductive layer / a transparent polymer film / a silicon oxide layer, and FIG. 3 illustrates a layer configuration including a transparent conductive layer / a silicon oxide layer / a transparent polymer film.
FIG. 4 shows a transparent conductive layer / silicon oxide layer / transparent polymer film /
FIG. 5 shows a layer configuration composed of a silicon oxide layer, and FIG. 5 shows a layer configuration composed of a transparent conductive layer / silicon oxide layer / transparent polymer film / silicon oxide layer / transparent conductive layer. Here, 1 is a supply roller, 2 is a transparent film, 3 is a vacuum container, 4 is a vacuum pump, 5 is a gas inlet, 6 is a high frequency electrode, 7 is a feed roller, 8 is a vacuum container, 9 is a target, 10 is Take-up roller, 11 denotes a transparent polymer film, 12 denotes a silicon oxide layer, and 13 denotes a transparent conductive layer.

In the present invention, the polymer film serving as the base material is not particularly limited, but those having transparency, high glass transition temperature and low hygroscopicity are desirable, and polyester, polyether sulfone, polyether ether ketone are preferable. , Polycarbonate, polyolefin film, etc., and particularly preferred are polyethersulfone and polyetheretherketone.

The silicon oxide layer to be laminated on the polymer film substrate used in the present invention is preferably formed by a low pressure plasma chemical vapor deposition method using at least an organic silicon compound and oxygen gas. Specific examples of the organic silicon compound used include acetoxytrimethylsilane, allyloxytrimethylsilane, allyltrimethylsilane, bistrimethylsilyl adipate, butoxytrimethylsilane, butyltrimethoxysilane, cyclohexyloxytrimethylsilane, and decamethylcyclopentasiloxane. , Decamethyltetrasiloxane, diacetoxydimethylsilane, diacetoxymethylvinylsilane, diethoxydimethylsilane, diethoxydiphenylsilane, diethoxy-3-glycidoxypropylmethylsilane, diethyl Cimethyloctadecylsilane, diethoxymethylsilane, diethoxymethylphenylsilane, diethoxymethylvinylsilane, dimethoxydimethylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, dimethylethoxyphenylsilane, dimethylethoxysilane, dimethylisopentyloxyvinylsilane, 1 , 3-Dimethyl-1,1,3,3
-Tetraphenyldisiloxane, diphenylethoxymethylsilane, diphenylsilanediol, 1,3-divinyl-1,1,3,3-tetramethyldisilane,
-(3,4-epoxycyclophenylethyl) trimethoxysilane, ethoxydimethylvinylsilane, ethoxytrimethylsilane, ethyltriacetoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethylsilane, 3-glycidoxypropyltrimethoxy Silane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, hexamethylcyclotrisiloxane, hexamethyldisiloxane, hexyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyl Trimethoxysilane,
Methoxytrimethylsilane, methyltriacetoxysilane, methyltriethoxysilane, methyltrimethoxysilane, methylisopropenoxysilane, methylpropoxysilane, octadecyltriethoxyethoxysilane,
Octamethylcyclotetrasiloxane, 1,1,1,
3,5,7,7,7-octamethyltetrasiloxane,
Octamethyltrisiloxane, octyltriethoxysilane, 1,3,5,7,9-pentamethylcyclopentasiloxane, pentamethyldisiloxane, 1,1,3,
5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, phenyltriethoxysilane, phenyltrimethoxysilane, phenyltrimethylsilane, propoxytrimethylsilane, propyltriethoxysilane,
Tetraacetoxysilane, tetrabutoxysilane, tetrateethoxysilane, tetraisopropoxysilane, tetramethoxysilane, 1,3,5,7-tetramethoxycyclotetrasiloxane, 1,1,3,3-tetramethyldiloxane, Tetramethylsilane, 1,3,3,5-
Tetramethyl-1,1,5,5-tetraphenyltrisiloxane, 1,3,5,7-tetramethyl-1,3,3
5,7-tetravinylcyclotetrasiloxane, tetrapropoxysilane, triacetoxyvinylsilane, triethoxyvinylsilane, triethylsilane, trihexylsilane, trimethoxysilane, trimethoxyvinylsilane, trimethylsilanol, 1,3,5-trimethyl-1, 3,5-trivinylcyclotrisiloxane, trimethylvinylsilane, triphenylsilanol, tris (2-methoxyethoxy) vinylsilane, and the like can be used, but are not limited to these, and aminosilane, silazane, or the like may be used. Can be To introduce these organic compound vapors into the reaction vessel, a rare gas such as helium or argon can be used as a carrier gas. Further, the gas of the organic silicon compound can be directly introduced by heating the organic silicon compound to increase the vapor pressure.

[0008] Instead of oxygen gas, a gas having an oxidizing effect, for example, ozone, water vapor, laughing gas or the like may be used. The ratio of the flow rates of the organic silicon compound gas and the oxygen gas to be introduced depends on the type of the organic silicon compound, but is preferably in the range of the flow ratio of oxygen gas / organic silicon compound gas = 0.2 to 1.2. . When a rare gas such as helium is used as the carrier gas, the range of the flow rate of the organic silicon compound gas and the flow rate of the oxygen gas in helium is 0.2 to 1.
A range of 2 is preferred. If the oxygen flow is too low,
The light transmittance and gas barrier properties of the formed film decrease, and conversely, when the oxygen flow rate is too large, the adhesion and gas barrier properties of the film decrease.

The pressure during the reaction may be within a range in which plasma discharge occurs. In the case of forming a film by a general parallel plate type high frequency plasma apparatus, the pressure is 0.05 to 2.5 Torr.
And more preferably 0.1 to 1.5 Torr.
It is. If the pressure is too low, it becomes difficult to maintain the plasma discharge, and if the pressure is too high, the adhesion of the film tends to decrease. However, when using electron cyclotron resonance discharge, helicon wave discharge, or magnetron discharge that can be discharged at a lower pressure, the pressure range is not limited to the above range. For the measurement and control of the flow rate, a mass flow controller, a float type flow meter, a bubble meter and the like can be used. For measuring the pressure, a Pirani vacuum gauge, a diaphragm vacuum gauge, a spinning rotor vacuum gauge, a heat conduction vacuum gauge, an ionization vacuum gauge, or the like can be used, but a diaphragm vacuum gauge is preferably used. The thickness of the silicon oxide layer is not particularly limited, but may be any thickness as long as the transparency is not impaired, the gas barrier property is maintained, and the adhesion to the polymer substrate is ensured. Specifically, 2
0 nm to 550 nm, preferably 20 nm to 50
It is preferably 0 nm or less, more preferably 20 nm or more and 300 nm or less. If the thickness is less than this, it is difficult to form a uniform and continuous film. If the thickness exceeds this, the adhesion to the polymer substrate and the transparency to visible light decrease. To measure the film thickness, there are a stylus roughness meter, a repetitive reflection interferometer, a microbalance, a crystal oscillator method, and the like. It is suitable for obtaining a desired film thickness while monitoring with. Also,
It is also possible to adopt a method in which film formation conditions are determined in advance, a film is formed on a test substrate, the relationship between the film formation time and the film thickness is examined, and the film thickness is controlled by the film formation time.

The transparent conductive film used in the present invention includes: 1) a single metal or alloy thin film layer of gold, silver, copper, aluminum, palladium, etc. 2) a compound semiconductor such as tin oxide, indium oxide, copper iodide, zinc oxide, etc. 3) A known film such as a laminated film combining the above 1) and 2) can be applied. The transparent conductive film can be formed by a physical vapor deposition method or a wet film forming method. As the physical vapor deposition method, a vacuum vapor deposition method, a sputtering method, an ion plating method, an activated reactive vapor deposition method, or the like can be used. A sol-gel method or the like is known as a wet film forming method. However, since the silicon oxide layer is formed by a vacuum process, the transparent conductive film is preferably formed by a physical vapor deposition method which is a vacuum process. The barrier properties are further improved. The thickness of the transparent conductive layer may be in a range where sufficient conductivity can be obtained as long as transparency is not impaired, and is preferably in a range of 30 nm to 500 nm, and more preferably in a range of 50 to 300 nm.

The silicon oxide may contain trace amounts of iron, nickel, chromium, titanium, magnesium, aluminum, indium, zinc, tin, antimony, tungsten, molybdenum, copper and the like. For the purpose of improving the flexibility of the film, carbon or fluorine may be appropriately contained.

The compositions of the silicon oxide layer and the transparent conductive film layer are as follows:
It can be analyzed using X-ray photoelectron spectroscopy, X-ray microanalysis, Auger electron spectroscopy, Rutherford backscattering, or the like. For example, when using the Rutherford backscattering method, a test sample film is placed in a vacuum vessel, and α-particles accelerated to 1 to 4 MeV are irradiated from the test sample surface to analyze the energy of ions backscattered. This makes it possible to investigate the composition of the film in the depth direction and the uniformity of the composition. Gold or the like may be appropriately deposited on the surface to prevent charging of the surface layer. In addition, when performing analysis by Auger electron spectroscopy, place the specimen in an ultra-high vacuum container,
The composition can be examined by irradiating the surface of the specimen with an electron beam accelerated to 1 to 10 keV and detecting Auger electrons emitted at that time. In this case, since the electrical resistance of the specimen may be high, it is preferable to suppress the current of the primary electron beam to 10 pA or less and further to reduce the energy to 2 keV or less so as to prevent the influence of charging. Photoelectron spectroscopy using X-rays instead of electron beams is advantageous over Auger electron spectroscopy in that it is less affected by charging.

When a silicon oxide layer or a transparent conductive layer is formed on a polymer film substrate, corona discharge treatment, plasma treatment, glow discharge treatment,
A reverse sputtering treatment, a surface roughening treatment, a chemical treatment or the like can be performed, or a known undercoat can be applied. In addition, a protective layer can be formed on the layer as required. The protective layer may be a transparent plastic, and examples thereof include polyester resin, acrylic resin, vinyl resin, and polycarbonate.

Here, a method for producing the transparent conductive laminate of the present invention will be described with reference to the accompanying drawings. As shown in FIG. 1, a transparent polymer film 2 is introduced from a supply roller 1 into a vacuum container. The vacuum container is evacuated using a vacuum pump 4 to maintain a desired degree of vacuum. For vacuum pumps,
An oil rotary pump, a roots pump, a diaphragm pump, an oil diffusion pump, a turbo molecular pump, a cryopump, and the like are used in appropriate combination. Gas inlet 5 to vacuum vessel
A raw material gas for forming a thin film is introduced from. The gases introduced here are at least an organic silicon compound gas and an oxygen gas. Examples of the organic silicon gas include various siloxanes, various silanes, various aromatic silanes, and various silanols described above. In particular, hexamethyldisiloxane,
Tetramethyldisiloxane is preferably used. As described above, a compound having a low vapor pressure at room temperature is introduced into a vacuum vessel by bubbling a rare gas such as helium or argon as a carrier gas. Alternatively, the gas is introduced into the vacuum vessel by heating it until it has a sufficient vapor pressure. Instead of oxygen gas, steam, ozone, and laughing gas may be used. Further, a nitrogen gas or a carbon fluoride gas may be introduced for improving the performance. While introducing the above reaction gas, a high frequency is introduced from the high frequency electrode 6 to generate plasma, and preferably on a film,
A film is formed at 100 ° C. or lower. Either capacitive coupling or inductive coupling can be used to introduce a high frequency.

Next, the transparent conductive layer is fed to another vacuum vessel by a feed roller 7 for laminating the transparent conductive layer, and a transparent conductive layer is formed from a polymer film by a sputtering method using a target 9 mainly composed of indium oxide or metal indium. Is done. When sputtering indium oxide, argon is used as a working gas. When sputtering metal indium, sputtering is performed with a mixed gas of argon and oxygen, and the ratio of the introduced amounts of oxygen and argon is preferably in a range of oxygen / argon = 0.1 to 0.5, more preferably 0/0. 0.2 to 0.3. However, since this value changes depending on the performance of the device, the above value is not necessarily limited. If necessary, before forming a film, a pretreatment for improving adhesion or the like can be appropriately performed inside or outside the vacuum container. Also,
It is of course possible to form the silicon oxide layer and the transparent conductive film in separate vacuum vessels. Hereinafter, an example of an embodiment of the present invention will be described with reference to examples.

[0016]

EXAMPLES In Examples and Comparative Examples, a test for gas permeability was performed in accordance with ASTM 1434-75. Examples 1 to 7 On a polyethersulfone (hereinafter abbreviated as PES) film having a thickness of 50 μm, 4
Tetramethyldisiloxane vaporized at 0 ° C. (hereinafter TM
DSO) and introduced into the vacuum vessel at a flow rate ratio of TMDSO / oxygen = 0.5, and while maintaining a degree of vacuum of 0.1 Torr, a high frequency of 13.56 MHz was introduced into the parallel plate electrode to generate plasma. Discharge was performed, and silicon oxide layers having different thicknesses were formed by a reduced pressure plasma enhanced chemical vapor deposition method. Furthermore, in some samples, 10 wt.
A transparent conductive layer having a thickness of 50 nm was formed by a sputtering method using a target containing% tin oxide. Table 1 shows the structure of the above sample, the oxygen gas transmittance, and the light transmittance at λ = 550 nm.

Comparative Example 1 A transparent conductive layer having a thickness of 50 nm was formed on a PES film by a sputtering method using a target containing 10 wt% tin oxide in indium oxide. Table 1 also shows the configuration of the above sample, the oxygen gas transmittance, and the light transmittance at λ = 550 nm.

[0018]

[Table 1]

Comparative Examples 2 to 8 Silicon oxide layers having different thicknesses were formed on a PES film having a thickness of 50 μm using SiO ₂ as a raw material by a vacuum evaporation method. Furthermore, in some samples, 1
Transparent conductive layers having different thicknesses were formed by a sputtering method using a target containing 0 wt% tin oxide. Table 2 shows the structure of the above sample and the oxygen gas permeability.

[0020]

[Table 2]

Comparative Examples 9 to 15 Silicon oxide layers having different thicknesses were formed on a 50 μm-thick PES film by sputtering using SiO ₂ as a target. Further, in some samples, transparent conductive layers having different thicknesses were formed by a sputtering method using a target containing 10 wt% tin oxide in indium oxide. Table 3 shows the structure of the above sample and the oxygen gas permeability.

[0022]

[Table 3] From the examples and comparative examples shown in Tables 1, 2 and 3, it can be seen that the laminate of the present invention has extremely excellent gas barrier properties.

Examples 8 to 14 Polyetheretherketone (hereinafter referred to as PE) having a thickness of 50 μm
EK) on the film as organic silicon gas
Using TMDSO vaporized at 0 ° C., introduced into a vacuum vessel at a flow rate ratio of TMDSO / oxygen = 0.5, and 0.1 Torr
While maintaining the degree of vacuum of r, a high frequency of 13.56 MHz was introduced into the parallel plate electrodes to cause plasma discharge, and silicon oxide layers having different thicknesses were formed by reduced pressure plasma enhanced chemical vapor deposition. Further, in some samples, transparent conductive layers having different thicknesses were formed by a sputtering method using a target containing 10 wt% tin oxide in indium oxide. Table 4 shows the structure of the above sample and the oxygen gas permeability.

[0024]

[Table 4]

Comparative Examples 16 to 22 Silicon oxide layers having different thicknesses were formed on a 50 μm-thick PEEK film by sputtering using SiO ₂ as a target. Further, in some samples, transparent conductive layers having different thicknesses were formed by a sputtering method using a target containing 10 wt% tin oxide in indium oxide. Table 5 shows the structure of the above sample and the oxygen gas permeability.

[0026]

[Table 5] From the examples and comparative examples shown in Tables 4 and 5,
It can be seen that the laminate of the present invention using PEEK exhibits extremely excellent gas barrier properties.

Comparative Examples 23 to 25 On a PES film having a thickness of 50 μm, TMDSO vaporized at 40 ° C. as an organic silicon gas was used.
Oxygen is introduced into the vacuum vessel at a flow ratio of 0.5, and 0.1T
While maintaining a vacuum degree of orr, a high frequency of 13.56 MHz was introduced into the parallel plate electrode to cause plasma discharge,
Silicon oxide layers having different thicknesses were formed by a low pressure plasma chemical vapor deposition method. In addition, 10 wt.
Transparent conductive layers having different thicknesses were formed by a sputtering method using a target containing% tin oxide. Table 6 shows the structure of the sample and the oxygen gas permeability.

[0028]

[Table 6] Table 6 shows that the silicon oxide layer is too thick, for example, 10 nm, so that sufficient gas barrier properties cannot be obtained.

Examples 15 to 18 On a PES and PEEK film having a thickness of 50 μm, TMDSO vaporized at 40 ° C. as an organic silicon gas was introduced into a vacuum vessel at a flow ratio of TMDSO / oxygen = 0.5. While maintaining a vacuum of 0.1 Torr.
A high frequency of 3.56 MHz was introduced into the parallel plate electrode to cause plasma discharge, and silicon oxide layers having different thicknesses were formed in a thickness range of 500 nm or less by a reduced pressure chemical vapor deposition method. In addition, 10
Transparent conductive layers having different thicknesses were formed by a sputtering method using a target containing wt% tin oxide. Table 7 shows the structure of the above sample and the results of an adhesion test performed by the Scotch tape test.

[0030]

[Table 7]

Comparative Examples 26 to 29 On a PES and PEEK film having a thickness of 50 μm, TMDSO vaporized at 40 ° C. as an organosilicon gas was introduced into a vacuum vessel at a flow ratio of TMDSO / oxygen = 0.5. While maintaining a vacuum of 0.1 Torr.
A high frequency of 3.56 MHz was introduced into the parallel plate electrodes to generate plasma discharge, and silicon oxide layers having different thicknesses were formed in a thickness range of 600 nm or less by reduced pressure plasma enhanced chemical vapor deposition. In addition, 10
Transparent conductive layers having different thicknesses were formed by a sputtering method using a target containing wt% tin oxide. Table 8 shows the structure of the sample and the results of an adhesion test performed by the Scotch tape test.

[0032]

[Table 8] From the examples and comparative examples shown in Tables 7 and 8, it can be seen that in the laminate of the present invention, when the silicon oxide layer has a thickness of, for example, 500 nm or less, extremely excellent adhesion strength is exhibited.

Comparative Examples 30 to 32 On a 50 μm thick PES film, TMDSO vaporized at 40 ° C. as an organosilicon compound gas was used.
SO / oxygen is introduced into the vacuum vessel at a flow rate of 0.1,
13.56M while maintaining a vacuum of 0.1 Torr
Hz high frequency is introduced into the parallel plate electrode to cause plasma discharge, and 500 nm
Silicon oxide layers having different thicknesses were formed in the following thickness ranges. Table 9 shows the structure of the above sample and the results of the gas transmittance test and the light transmittance test.

[0034]

[Table 9] As shown in Examples and Comparative Examples in Tables 1 and 9, the flow rate ratio between TMDSO and oxygen, TMDSO / oxygen, is too low, not more than 0.2, especially 0.1, for example. It turns out that it is not enough.

Comparative Examples 33 to 34 On a PES film having a thickness of 50 μm, TMDSO vaporized at 40 ° C. as an organic silicon gas was used.
Oxygen was introduced into the vacuum vessel at a flow ratio of 1.3, and 0.1 T
While maintaining a vacuum degree of orr, a high frequency of 13.56 MHz was introduced into the parallel plate electrode to cause plasma discharge,
Silicon oxide layers having different thicknesses were formed in a thickness range of 500 nm or less by low-pressure plasma enhanced chemical vapor deposition. Further, Table 10 shows the structure of the transparent conductive film, the oxygen gas permeability test, and the results of the Scotch tape test performed by the vacuum deposition method.

[0036]

[Table 10] As can be seen from the examples and comparative examples in Tables 1, 7, and 10, when the flow rate ratio between TMDSO and oxygen, TMDSO / oxygen is 1.2 or more, for example, 1.3, oxygen gas permeability and adhesion are not sufficient. I understand.

COMPARATIVE EXAMPLES 35-38 On a PES and PEEK film having a thickness of 50 μm, TMDSO vaporized at 40 ° C. as an organosilicon gas was introduced into a vacuum vessel at a flow ratio of TMDSO / oxygen = 0.5. While maintaining a vacuum of 0.1 Torr.
A plasma discharge was generated by introducing a high frequency of 3.56 MHz to the parallel plate electrodes, and a 200 nm-thick silicon oxide layer was formed by a reduced pressure plasma enhanced chemical vapor deposition method. further,
A transparent conductive layer having a film thickness of 50 nm was formed by a vacuum deposition method using a target having 10 wt% tin oxide contained in indium oxide as a deposition source by pulverizing a target having a size of about 1 to 3 mm. For deposition, oxygen was introduced and oxygen partial pressure was set to 1x
The test was performed while maintaining the pressure at 10 ^-4 Torr. Table 11 shows the structure of the sample, the measurement results of the oxygen gas permeability, and the results of the adhesion test performed by the Scotch tape test.

[0038]

[Table 11] According to the examples and comparative examples shown in Tables 1 and 11, it is found that when the transparent conductive layer is formed by the vacuum evaporation method, the oxygen gas permeability becomes larger than that when the transparent conductive layer is formed by the sputtering method.

Examples 19 to 25 TMDSO was bubbled on a 50 μm thick PES film at room temperature (23 ° C.) using helium at 1.5 atm, and oxygen was introduced into a vacuum vessel at 5 sccm, and bubbled helium was introduced at 10 sccm. Then, while maintaining a degree of vacuum of 0.07 Torr, a high frequency of 13.56 MHz was introduced into the parallel plate electrodes to cause plasma discharge, and silicon oxide layers having different thicknesses were formed by reduced pressure plasma enhanced chemical vapor deposition. . Furthermore, in some samples, 10 wt.
A transparent conductive layer having a thickness of 50 nm was formed by a sputtering method using a target containing% tin oxide. Table 12 shows the structure of the above sample, the oxygen gas transmittance, and the light transmittance at λ = 550 nm.

[0040]

[Table 12] From the examples shown in Table 12, it can be seen that desired performance can be obtained even when TMDSO is introduced into a vacuum vessel by bubbling with helium.

Examples 26 to 27 Hexamethyldisiloxane (hereinafter abbreviated as HMDSO) was bubbled on a 50 μm-thick PES film at room temperature (23 ° C.) using helium at 1.5 atm. 5 sccm, bubbling helium 15 sc
cm, and while maintaining a vacuum degree of 0.05 Torr, a high frequency of 13.56 MHz was introduced into the parallel plate electrodes to cause plasma discharge, and silicon oxide layers having different thicknesses were formed by a reduced-pressure plasma-enhanced chemical vapor deposition method. It was created. further,
In some samples, a film thickness of 50 n was formed by a sputtering method using a target containing 10 wt% tin oxide in indium oxide.
m transparent conductive layers were formed. Table 13 shows the structure of the above sample, the oxygen gas transmittance, and the light transmittance at λ = 550 nm.

[0042]

[Table 13] From the examples shown in Table 13, helium-bubbled H
Even with MDSO, desired performance can be obtained.

Examples 28 to 29 Methyltritetoxysilane (hereinafter abbreviated as MTMOS) was bubbled on a 50 μm thick PES film at room temperature (23 ° C.) using helium at 1.5 atm. 5 sccm, bubbling helium 24 sc
cm, and while maintaining a vacuum degree of 0.05 Torr, a high frequency of 13.56 MHz was introduced into the parallel plate electrodes to cause plasma discharge, and silicon oxide layers having different thicknesses were formed by a reduced-pressure plasma-enhanced chemical vapor deposition method. It was created. further,
In some samples, a film thickness of 50 n was formed by a sputtering method using a target containing 10 wt% tin oxide in indium oxide.
m transparent conductive layers were formed. Table 14 shows the structure of the above sample, the oxygen gas transmittance, and the light transmittance at λ = 550 nm.

[0044]

[Table 14] According to the examples shown in Table 14, M bubbled with helium.
Even if TMOS is used, desired performance can be obtained.

[0045]

According to the present invention, a silicon oxide layer is provided on the surface of a transparent polymer film substrate by a plasma enhanced chemical vapor deposition method using at least an organic silicon compound gas and an oxygen gas, and a transparent conductive layer is provided as appropriate. It is possible to efficiently obtain a gas barrier transparent conductive laminate which is extremely excellent in transparency and gas barrier properties and which can be suitably used for a liquid crystal display element or the like without impairing adhesion, by using a vacuum integrated process. it can.

[Brief description of the drawings]

FIG. 1 is an explanatory view of an apparatus for carrying out the present invention.

FIG. 2 is a view showing a layer structure of a transparent conductive laminate having a high gas barrier property of the present invention.

FIG. 3 is a diagram showing a layer structure of a transparent conductive laminate having a high gas barrier property of the present invention.

FIG. 4 is a view showing a layer structure of a transparent conductive laminate having a high gas barrier property of the present invention.

FIG. 5 is a view showing a layer structure of a transparent conductive laminate having a high gas barrier property of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Supply roller 2 Transparent film 3 Vacuum container 4 Vacuum pump 5 Gas inlet 6 High frequency electrode 7 Feed roller 8 Vacuum container 9 Target 10 Winding roller 11 Transparent polymer film 12 Silicon oxide layer 13 Transparent conductive layer

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C23C 14/06 H01B 13/00 503

Claims (8)

(57) [Claims] 1. A transparent polymer film substrate comprising a silicon oxide layer and a transparent conductive layer laminated on a transparent polymer film substrate, wherein the silicon oxide layer is formed by a pressure reduction using at least an organic silicon compound gas and oxygen. High-gas-barrier transparent conductive laminate formed by plasma enhanced chemical vapor deposition. 2. The transparent polymer film substrate is polyether sulfone or polyether ketone.
The transparent conductive laminate having gas barrier properties described in the above. 3. The gas-barrier transparent conductive laminate according to claim 1, wherein the silicon oxide layer contains an organic substance derived from an organic silicon compound. 4. The method according to claim 1, wherein the silicon oxide layer is formed by a low pressure plasma chemical vapor deposition method using at least an organic silicon compound gas and an oxygen gas, and the transparent conductive layer is formed by a sputtering method. Certain claims 1
4. The gas-barrier transparent conductive laminate according to any one of 3. 5. A laminate in which at least a layer of silicon oxide and a transparent conductive layer are appropriately formed on a transparent polymer film substrate, and the laminate has an oxygen gas transmittance of 0.1 cc.
/ M ^2/24 hours / 1 atm or less is gas-barrier transparent conductive multilayer body according to any one of claims 1 to 4. 6. A layer of silicon oxide (A) and a transparent conductive layer (B)
Is a polymer film substrate (C), ACB, CA
B or ACAB is laminated in this order.
5. The gas-barrier transparent conductive laminate according to any one of the above items 5. 7. A method for producing a gas-barrier transparent conductive laminate pair comprising laminating a silicon oxide layer and a transparent conductive layer on a transparent polymer film substrate, wherein the silicon oxide layer comprises at least an organic A method for producing a gas-barrier transparent conductive laminate formed by a reduced pressure plasma enhanced chemical vapor deposition method using a silicon compound gas and oxygen. 8. The method for producing a gas-barrier transparent conductive laminate according to claim 7, wherein the transparent conductive layer is formed by a sputtering method.