JP2008132643A - Substrate for liquid crystal cell and liquid crystal display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a substrate for a liquid crystal cell comprising a resin film having high gas barrier properties and suppressed color shift. <P>SOLUTION: In the substrate for the liquid crystal cell comprising the resin film, the substrate for the liquid crystal cell is a resin film having at least two layers of metal films selected from metal oxide films, metal nitride films or metal oxide nitride films on the resin film, and at least two layers of the metal films have the same composition, but have different shearing strengths. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid crystal cell substrate, and more particularly to a liquid crystal cell resin substrate made of a resin film.

  In recent years, electronic devices such as liquid crystal display devices have become heavy due to the addition of high demands such as long-term reliability and high degree of freedom in shape, and the ability to display curved surfaces in addition to the demands for weight reduction and size increase. Resin films such as transparent plastics have begun to be used in place of glass substrates that are easily broken and difficult to increase in area. For example, JP-A-2-251429 and JP-A-6-124785 disclose examples using a transparent resin film.

  However, there is a problem that the resin film is inferior in gas barrier properties to glass. For example, when a base material with inferior gas barrier properties is used when used as a substrate for a liquid crystal cell, the resin film deteriorates when the circuit is formed on the resin film, and the physical properties do not meet the requirements for the substrate. It had the disadvantage that it would end up.

  As a gas barrier film that solves such problems, for example, Japanese Patent Publication No. 53-12953 discloses a gas barrier film base material in which silicon oxide is deposited on a film substrate to form a transparent thin film, Japanese Patent Application Laid-Open No. 58-217344. In the publication, it is known that aluminum oxide is deposited on a film substrate to form a transparent thin film to form a gas barrier film substrate.

However, both have a water vapor barrier property of about 2 g / m ² / day and an oxygen permeability of about ² ml / m ² / day · atm, which is insufficient as a substrate for a liquid crystal cell. In addition, when trying to increase the thickness of silicon oxide or aluminum oxide, if these transparent inorganic films are set to a certain level or more from the viewpoint of flexibility and flexibility, cracks will occur and gas barrier properties will be reduced. Have the disadvantages.

Furthermore, in recent years, liquid crystal displays that require further gas barrier properties have been demanded to have a water vapor barrier performance of about 10 ⁻⁵ g / m ² / day for gas barrier performance due to the development of large-sized liquid crystal displays and high-definition displays. It is rising.

  In order to meet these requirements, many studies have been made on gas barrier materials using inorganic substances such as silicon oxide and aluminum oxide.

  For example, in JP-A-2006-44231, a barrier layer made of an inorganic oxide, an inorganic oxynitride, an inorganic oxycarbide, and an inorganic oxynitride carbide is laminated on a base film and a smoothing layer containing a cardo polymer. And gas barrier films with improved barrier properties are described.

  In JP-A-2005-289052, an organic layer and an inorganic layer are alternately laminated on a resin film as a gas barrier layer, and the back surface of the base film is an uneven surface to prevent cracking of the gas barrier layer. A gas barrier film is described.

  However, when these barrier layers are formed by laminating a combination of an organic layer and an inorganic layer, the physical properties of the organic layer and the inorganic layer are greatly different, so that cracks easily occur at the interface, and the gas barrier property is sufficient. Absent.

  Furthermore, in order to obtain a high gas barrier property, studies have been made to form the barrier layer as an inorganic layer / inorganic layer.

  For example, a laminated structure in which a first layer made of silicon oxide alone, a second layer made of silicon oxide containing carbon, and a third layer made of silicon oxide alone are sequentially formed on the base film as a barrier layer. A transparent gas barrier material characterized by the above is known (for example, see Patent Document 1).

  A gas barrier material in which silicon oxides having different carbon contents are laminated as a barrier layer on a base film is known (see, for example, Patent Document 2).

  However, the transparent gas barrier materials described in Patent Document 1 and Patent Document 2 exhibit high gas barrier properties under normal conditions. However, since the bending resistance is not sufficient, the barrier layer is liable to crack in the handling process and the gas barrier properties are reduced. Therefore, it is difficult to apply to a liquid crystal display or the like.

  A gas barrier film having a barrier layer in which a lower silicon nitride oxide layer is formed on a base film with a higher density than the upper silicon nitride oxide layer is known (see, for example, Patent Document 3). . However, the gas barrier film described in Patent Document 3 has a low transmittance and is difficult to apply to an organic EL display, a liquid crystal display, or the like.

As a barrier layer on a resin film, a gas barrier film having a high barrier property that compensates for defects generated in the SiO _x N _y layer by using a layer structure of SiO _x N _y / inorganic film / SiO _x N _y is known. (For example, refer to Patent Document 4).

  Certainly, the growth of cracks can be temporarily stopped by changing the composition, but the present inventors have confirmed that the gas barrier film described in Patent Document 4 has a laminated interface by having inorganic films having different compositions. Thus, it has been found that it has a defect that new cracks are easily generated.

  That is, it has been found that the introduction of a layer having a changed composition causes the crack growth to be suppressed and generated at the same time, and the cause of the deterioration of the barrier property due to the crack cannot be completely removed.

Furthermore, as an essential problem of liquid crystal display devices, when used as a substrate for a liquid crystal cell, it is required to display a liquid crystal display screen with an image quality equivalent to that of a glass cell, but a resin having a barrier film so far A substrate made of a film could not suppress a color shift level deterioration with respect to a glass substrate, which is estimated to be caused by a low elastic modulus with respect to glass or poor flatness (for example, see Patent Document 5). ).
JP-A-8-48369 JP 2003-257619 A JP 2003-206361 A JP 2003-21579 A JP 2002-221707 A

  The present invention has been made in view of the above situation, and an object of the present invention is to provide a liquid crystal cell substrate made of a resin film having high gas barrier properties and suppressed color shift.

The above object of the present invention has been achieved by the following constitution.
1. In the liquid crystal cell substrate comprising a resin film, the liquid crystal cell substrate is a resin film having at least two metal films selected from a metal oxide film, a metal nitride film, or a metal oxynitride film on the resin film, A substrate for a liquid crystal cell, wherein the at least two metal films have the same composition and different shear strengths;
2. 2. The liquid crystal cell substrate according to claim 1, wherein the two layers of metal films having different shear strengths are adjacent two layers of metal films,
3. 3. The liquid crystal cell substrate according to 1 or 2 above, wherein the density ratio Y of the two adjacent metal films is 1 ≧ Y ≧ 0.95,
4). The liquid crystal cell substrate according to any one of 1 to 3, wherein the at least two metal films are provided on both sides of a resin film,
5. The liquid crystal cell substrate according to any one of 1 to 4, wherein the metal film is formed by atmospheric pressure plasma CVD,
6). 6. A liquid crystal display device using the liquid crystal cell substrate according to any one of 1 to 5 above.

  According to the present invention, it is possible to provide a liquid crystal cell substrate made of a resin film having high gas barrier properties and suppressed color shift.

The best mode for carrying out the present invention will be described below with reference to FIGS. 1 to 7, but the present invention is not limited thereto.
<Layer structure and function of metal film produced on resin film>
FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the liquid crystal cell substrate of the present invention.

  FIG. 1A is a schematic cross-sectional view of a liquid crystal cell substrate having at least two adjacent metal films having different shear strengths.

  FIG. 1B is a schematic cross-sectional view of a liquid crystal cell substrate having two units of metal films when two adjacent metal films having different shear strengths are taken as one unit.

  FIG. 1C is a schematic sectional view of a liquid crystal cell substrate having one unit of metal film on each side of the resin film.

  FIG. 1D is a schematic cross-sectional view of a liquid crystal cell substrate having three adjacent metal film layers having different shear strengths as one unit.

  In the present invention, functions other than the gas barrier may be provided in addition to the metal film of the present invention, which are referred to as an adhesion layer and a protective layer. Although the composition is similar to that of the metal film of the present invention, the composition is adjusted in order to provide a function.

  A description will be given of the liquid crystal cell substrate shown in FIG. In the figure, reference numeral 1a denotes a liquid crystal cell substrate. The liquid crystal cell substrate 1 a has the metal film 100 of the present invention on the resin film 101. The metal film 100 is composed of an adhesion layer 103 and a metal film 102 that is laminated on the adhesion layer 103 and has at least two layers of adjacent first metal film 102a and second metal film 102b having different shear strength. And a protective layer 104.

  The metal film 102 is composed of at least two layers of adjacent first metal film 102a and second metal film 102b having different shear strengths. However, the metal film can be increased as necessary. This figure shows a case where one unit of the metal film 102 is composed of two layers of an adjacent first metal film 102a and second metal film 102b.

  The liquid crystal cell substrate shown in FIG. In the figure, 1b represents a liquid crystal cell substrate. Other symbols are synonymous with the symbols in FIG. The liquid crystal cell substrate 1b has two units when the metal film having the first metal film 102a and the second metal film 102b adjacent to each other in two layers in the metal film 100-1 is one unit. The metal film 102 is laminated.

  The liquid crystal cell substrate shown in FIG. 1C will be described. In the figure, reference numeral 1c denotes a liquid crystal cell substrate. Other symbols are synonymous with the symbols in FIG. The liquid crystal cell substrate 1c has metal films 100 on both sides of the resin film 101, respectively. Each metal film 100 is the same as that shown in FIG.

  The liquid crystal cell substrate shown in FIG. In the figure, reference numeral 1d denotes a liquid crystal cell substrate. Other symbols are synonymous with the symbols in FIG. The liquid crystal cell substrate 1d has three layers of adjacent first metal film 102a, second metal film 102b, and third metal film 102c having different shear strengths in the metal film 100-2. The number of units of the metal film is preferably 2 to 10 units.

  By having a plurality of metal films, the gas barrier property is higher than that of the liquid crystal cell substrate 1a shown in FIG. Note that a transparent protective layer may be provided between the resin film 101 and the adhesion layer 103 as needed for protecting the resin film 101, maintaining flatness, and the like.

The substrate for a liquid crystal cell shown in this figure has a metal film 100 on a resin film, and the metal film 100 has at least two layers of adjacent first metal film 102a and second metal film 102b having different shear strengths. The metal film 102 has a layer structure in which an adhesion layer 103 is provided between the metal film and the resin film 101, and a protective layer 104 is laminated on the metal film. Of course, the metal film 100 may have other layers.
<Shear strength>
The shear strength of each of the adhesion layer 103, the metal film (first metal film 102a, second metal film 102b) and the protective layer 104 constituting the substrate for a liquid crystal cell of the present invention is as follows. It can be measured by a 04 type shear strength measuring instrument (referred to as cycus shear strength measurement in the present invention).

  In the present invention, the metal film a and the metal film b are adjacent to each other, but the difference in the shear strength can be detected by measuring the liquid crystal cell substrate shown in FIG.

  In the present invention, the metal film having different shear strength is a metal film in which the shear strength by this cycas shear strength measurement is composed of adjacent metal oxides, metal nitrides or metal oxynitrides having substantially the same composition. Means different. Specifically, one or more peaks obtained by the cycas shear strength measurement appear in the same range of the composition in the film thickness direction.

  The difference in shear strength between adjacent metal films is preferably 0.01 N or more and 1.0 N or less, more preferably 0.02 N or more and 0.8 N or less.

  The measurement conditions of the cycas shear strength are as follows: the sampling step is 0.2 sec / point, a diamond 1 mm wide blade is used, the shear angle is 45 °, the pressing load is 2 μN, the balance load is 1 μN, and the vertical speed is 1 nm / sec. Cutting was performed at a horizontal speed of 100 nm / sec, and horizontal and vertical forces were recorded.

  The substrate for a liquid crystal cell of the present invention is characterized in that a plurality of amplitudes of the horizontal force profile appear in a peak in recording under this condition. This is because, in the process of gradually applying a load from the surface of the film (that is, from the protective layer side), when the load is shifted from the metal film 102b (strong) to 102a (somewhat strong) to a region having different shear strength, It shows how the accumulated stress is relaxed.

  This mode of relaxation is detected as a peak, but the number of times of relaxation may be observed multiple times. On the other hand, in the barrier layer having no difference in shear strength, no peak is detected because stress relaxation due to load does not occur abruptly.

≪Other film properties: density ratio of metal film≫
In the present invention, the metal film formed on the resin film is a metal film formed by thermally oxidizing or thermally nitriding the base material so that the composition ratio is the same as that of the metal film when the density is ρf. When the density is ρb, the density ratio Y (= ρf / ρb) should be formed so that 1 ≧ Y> 0.95.

  In the present invention, the density of the metal film formed on the resin film can be determined using a known analysis means, but in the present invention, the value determined by the X-ray reflectance method is used.

  The outline of the X-ray reflectivity method is described in page 151 of the X-ray diffraction handbook (Science Electric Co., Ltd., 2000, International Literature Printing Co., Ltd.) 22 can be performed.

  Specific examples of measurement methods useful in the present invention are shown below.

  This is a method in which X-rays are incident on a material having a flat surface at a very shallow angle, and measurement is performed using MXP21 manufactured by Mac Science. Copper is used as the target of the X-ray source and it is operated at 42 kV and 500 mA. A multilayer parabolic mirror is used for the incident monochromator.

  The incident slit is 0.05 mm × 5 mm, and the light receiving slit is 0.03 mm × 20 mm. Measurement is performed by the FT method with a step width of 0.005 ° and a step of 10 seconds from 0 to 5 ° in the 2θ / θ scan method.

  With respect to the obtained reflectance curve, Reflectivity Analysis Program Ver. Curve fitting is performed using 1 and each parameter is obtained so that the residual sum of squares of the actually measured value and the footing curve is minimized.

  From each parameter, the thickness and density of the laminated film can be obtained. The film thickness evaluation of the laminated film in the present invention can also be obtained from the X-ray reflectivity measurement.

≪Other film properties: elastic modulus≫
The adhesion layer 103 is disposed between the resin film 101 and the first metal film 102a in order to prevent the first metal film 102a from peeling and cracking from the resin film when the liquid crystal cell substrates 1a to 1d are bent. The purpose is to provide adhesion of the first metal film 102a and to provide an action to relieve external stress.

  The protective layer 104 serves to protect the cracks and the second metal film 102b when the liquid crystal cell substrates 1a to 1d are bent, and to provide an effect of relieving external stress. The adhesion layer and the protective layer preferably have a lower elastic modulus than the metal film intended for the gas barrier of the present invention.

  The relationship between the elastic modulus of the adhesion layer 103, the metal film 102, and the protective layer 104 constituting the liquid crystal cell substrate shown in this figure is preferably the adhesion layer 103 <metal film 102> protective layer 104. .

  Further, the elastic modulus of the first metal film 102a and the second metal film 102b having different elastic moduli constituting the metal film preferably has a relationship of the first metal film 102a <the second metal film 102b. .

  The metal film 102 shown in this figure is sandwiched between an adhesive layer 103 and a protective layer 104 having a lower elastic modulus than the metal film 102 above and below.

  The elastic modulus of the adhesion layer 103 is preferably 5 GPa to 20 GPa. The elastic modulus of the protective layer 104 is preferably 5 GPa to 20 GPa. The elastic modulus of the barrier layer 102 is higher than that of the adhesion layer and the protective layer, and is preferably 20 GPa to 70 GPa, for example, and further has a laminated structure with different shear strengths.

  An elastic modulus shows the value measured using the nanoindentation measuring method. Specifically, as a device, a Triscope made by Hystron and SPI3800N made by SII were used, the indenter was 90 ° Cube corner tip, the maximum load was 20 μN, and the number of measurement n was n = 3.

≪Other film properties: residual stress≫
The residual stress of the metal film (the metal film having at least two layers of the first metal film and the second metal film having different shear strengths) of the substrate for the liquid crystal cell shown in this figure is the durability and gas barrier properties (water vapor) of the metal film. In consideration of the transmission rate and the oxygen transmission rate, etc., the compression stress is preferably 0.01 MPa to 20 MPa or less. More preferably, it is 0.1 MPa to 10 MPa or less, and the harder second metal film is preferably 0.1 to 3 MPa.

  For example, a resin film having a metal film formed by a vapor deposition method, a CVD method, a sol-gel method, or the like causes a positive curl and a negative curl due to the relationship between the resin film film and the film quality of the ceramic film when left under certain conditions. This curl is caused by the stress generated in the metal film, and it can be said that the larger the curl (plus curl), the greater the compressive stress.

  The internal stress in the metal film is measured by the following method. That is, a metal film having the same composition and thickness as the measurement film is formed on a quartz substrate having a width of 10 mm, a length of 50 mm, and a thickness of 0.1 mm so as to have a thickness of 1 μm by the same method. With the concave portion facing upward, it can be obtained by measurement with a thin film physical property evaluation apparatus MH4000 manufactured by NEC Saneisha.

  In general, a positive curl in which the film side contracts with respect to a resin film due to a compressive stress is expressed as a positive stress, and conversely, when a negative curl is generated due to a tensile stress, it is expressed as a negative stress.

  The residual stress of the resin film on which the silicon oxide film is formed can be adjusted by adjusting the degree of vacuum when the silicon oxide film is formed by, for example, a vacuum deposition method. A small residual stress means that the layer is less distorted, which means that it is smooth and, on average, is strong against deformation due to bending or the like.

  When the stress is too small, there may be a partial tensile stress, and the film is easily cracked or cracked, resulting in a non-durable film.

  To obtain a shear strength that requires the shear strength of each of the adhesion layer, the metal film (first metal film, second metal film) and the protective layer constituting the metal film of the liquid crystal cell substrate of the present invention. It is possible to adjust the deposition rate using a plasma CVD method at or near atmospheric pressure.

  For example, when an adhesion layer, a metal film (first metal film, second metal film), and a protective layer are laminated on a resin film using an atmospheric pressure plasma CVD method, the deposition rate (nm / sec) Examples include layers 20 to 70, first barrier layers 4 to 15, second barrier layers 0.1 to 1.0, and protective layers 50 to 150.

The lower the deposition rate (nm / sec) value, the denser and harder the layer is deposited. The adjustment of the deposition rate can be arbitrarily determined by factors such as the plasma density and the supply amount of the raw material. For example, when a dense and hard film is produced, it can be produced by putting a small amount of raw material supply into a discharge space having a high plasma density.
<Metal film with the same composition>
The first metal film 102a and the second metal film 102b constituting the metal film 102 of the liquid crystal cell substrate of the present invention are composed of metal oxide, metal nitride or metal oxynitride having substantially the same composition. Has been.

In the present invention, the same composition means that a metal oxide, metal nitride or metal oxynitride constituting a metal film is measured by XPS and expressed as M _x O _y N _z (M represents a metal atom). X, y, and z represent the composition ratio of M atom, O atom, and N atom, respectively), and the difference between the x, y, and z values of the adjacent first metal film and second metal film is 10%. Means less than. Preferably it is less than 5%, more preferably less than 2%, most preferably 0%.

In addition, since the metal film of this invention is comprised from the metal oxide, the metal nitride, or the metal oxynitride, impurities, such as carbon (C), are 0.5% or less in XPS measurement. Preferably it is below detection limit (0.1% or less). In the present invention, both the first metal film and the second metal film are preferably SiO ₂ .

  The thickness of the adhesion layer 103 is preferably 10 nm to 500 nm, more preferably 20 nm to 100 nm. The thickness of the first metal film 102a is preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm in consideration of gas barrier properties, flexibility, bending resistance, and the like.

  The thickness of the second metal film 102b is preferably 5 nm to 200 nm, more preferably 20 nm to 100 nm in consideration of gas barrier properties, flexibility, bending resistance, and the like. The thickness of the protective layer 104 is preferably 50 nm to 600 nm, more preferably 50 nm to 500 nm in consideration of protection of the barrier layer, flexibility, and the like.

  It is composed of a metal oxide film, metal nitride film or metal oxynitride film of the same composition shown in this figure, and has a metal film having at least two layers of adjacent metal films having different shear strengths, and is sheared more than this metal film. The following effects can be obtained by forming a layer structure sandwiched between an adhesive layer having a low strength and a protective layer.

  1) By dividing the metal film into a first metal film and a second metal film having different shear strengths, the stress applied to the metal film when bent can be relaxed even in the metal film, and in one layer It became possible to laminate a layer thicker than it was formed, and a metal film having a high gas barrier property could be formed.

2) Since the adhesion layer and the protective layer act as a stress relaxation layer when bent, it becomes possible to laminate a metal film having a dense hard structure thicker, and a liquid crystal cell substrate having a high gas barrier property. Fabrication is now possible.
<Composition of metal film, etc.>
≪Metal film≫
Next, the materials used for the metal film constituting the liquid crystal cell substrate of the present invention will be described. The first metal film and the second metal film constituting the metal film have the same composition. For example, metal carbide, metal nitride, metal oxide, metal sulfide, metal halide, or a mixture thereof (metal acid Nitride, metal oxyhalide, metal nitride carbide, etc.).

Among these, it is preferable that at least one layer of the first metal film and the second metal film is substantially made of a metal oxide, a metal nitride, or a composite compound thereof. Among these, silicon oxide (SiO _x ) which is a metal oxide is particularly preferable.

  The term “substantially” means that secondary components such as carbon may be contained in an atomic number concentration of 0 at% to 1 at%, preferably 0 at% to 0.5 at%.

≪Adhesion layer≫
The material used for the adhesion layer is preferably a metal oxide, a metal oxynitride, a metal nitride or a composite thereof, which are metal compounds having different carbon contents. Specifically, silicon oxide, aluminum oxide, silicon nitride, Preferable examples include silicon oxynitride, aluminum oxynitride, magnesium oxide, zinc oxide, indium oxide, and tin oxide.

More preferably, a metal oxide, a metal nitride or a composite compound thereof which is a metal compound having a carbon content of 1 at% to 30 at% is preferable. Among these, silicon oxide (SiO _x ) which is a metal oxide is particularly preferable.

≪Protective layer≫
The materials used for the protective layer are preferably metal oxides, metal oxynitrides, and metal nitrides having different carbon contents. Specifically, silicon oxide, aluminum oxide, silicon nitride, silicon oxynitride, aluminum oxynitride, Preferred examples include magnesium oxide, zinc oxide, indium oxide and tin oxide.

More preferably, a metal oxide, a metal nitride or a composite compound thereof which is a metal compound having a carbon content of 1 at% to 30 at% is preferable. Among these, silicon oxide (SiO _x ) which is a metal oxide is particularly preferable.

  Here, at% represents atomic concentration (atomic concentration). In the present invention, the carbon content is atomic number concentration% and can be determined using a known analysis means. In the present invention, the carbon content is calculated by the following XPS method and is defined below.

Atomic concentration% = number of carbon atoms / number of all atoms × 100
In the present invention, the XPS surface analyzer used ESCALAB-200R manufactured by VG Scientific. Specifically, Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 eV to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak.

  As a measurement, first, the range of the binding energy of 0 eV to 1100 eV was measured at a data acquisition interval of 1.0 eV to determine what elements were detected. Next, with respect to all the detected elements except for the etching ion species, the data capture interval was set to 0.2 eV, and the photoelectron peak giving the maximum intensity was subjected to narrow scan, and the spectrum of each element was measured.

  The obtained spectrum is COMMON DATA PROCESSING SYSTEM manufactured by VAMAS-SCA-JAPAN (preferably Ver. 2.3 or later) so as not to cause a difference in the content rate calculation result due to a difference in measuring apparatus or computer. After being transferred to the top, the processing was performed with the same software, and the content value of each analysis target element (carbon, oxygen, silicon, titanium, etc.) was determined as the atomic concentration (at%).

  Before performing the quantification process, calibration of the count scale was performed for each element, and a 5-point smoothing process was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used.

For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).
<Resin film>
As the resin film, a sheet-like sheet-like or strip-like resin film is exemplified, and can be selected as necessary. Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polysulfones, polyetherketone imide, polyester Amide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylates, and cycloolefin resins such as ARTON (trade name JSR Corp.) or APEL (trade name Mitsui Chemicals, Inc.).
<Production method of metal film, adhesion layer, protective layer>
The adhesion layer, metal film (at least two first metal films having different shear strength, metal film having a second metal film) and protective layer according to the present invention are placed in the discharge space under atmospheric pressure or pressure near atmospheric pressure. A thin film is formed on a resin film by supplying a gas containing a thin film forming gas and a discharge gas, exciting the gas by applying a high-frequency electric field to the discharge space, and exposing the resin film to the excited gas. It is preferable to form by using the atmospheric pressure plasma CVD method.

  The vicinity of atmospheric pressure represents a pressure of 20 kPa to 110 kPa, but 93 kPa to 104 kPa is preferable in order to obtain a good effect described in the present invention.

≪Atmospheric pressure plasma CVD method≫
In the thin film formation by the atmospheric pressure plasma CVD method of the present invention, the thin film forming gas mainly includes a raw material gas for forming a thin film, a decomposition gas and a plasma state for decomposing the raw material gas to obtain a thin film forming compound And a discharge gas.

  In the thin film formation by the atmospheric pressure plasma CVD method, it is preferable to use a thin film forming gas for forming a thin film composed of the same composition, respectively, which makes it possible to produce a very stable production without contamination with impurities. Even when stored in a rough environment, a liquid crystal cell substrate having good transparency and gas barrier resistance can be obtained without deterioration of adhesion.

  In the liquid crystal cell substrate of the present invention, the method for forming the adhesion layer, the metal film, and the protective layer having a desired configuration is not particularly limited, but an optimum raw material is selected, and a raw material gas, a decomposition gas, and a discharge are selected. It is preferable to appropriately select the gas composition ratio, the supply rate of the thin film forming gas to the plasma discharge generator, the output conditions during the plasma discharge process, and the like.

  Subsequently, the raw material used for manufacture of the contact | adherence layer based on this invention, a metal film, and a protective layer is demonstrated. For the adhesion layer, metal film and protective layer according to the present invention, conditions such as organometallic compound, decomposition gas, decomposition temperature, and input power as raw materials (also referred to as raw materials) are selected in the plasma CVD method and atmospheric pressure plasma CVD method. Thus, the composition of the metal compound, such as a metal oxide, a metal nitride, or a composite compound thereof, can be made differently.

  For example, when a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

  As such an inorganic material, as long as it contains a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation.

  Moreover, you may dilute and use with a solvent and can use organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  As such an organometallic compound, as a silicon compound, silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis ( Dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbonate Bodiimide, diethylaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldi Silazane, tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltri Tylsilane, propargyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetra Examples include methylcyclotetrasiloxane, hexamethylcyclotetrasiloxane, and M silicate 51.

  Examples of the titanium compound include titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium tetraisoporooxide, titanium n-butoxide, titanium diisopropoxide (bis-2,4-pentanedionate), titanium. Examples thereof include diisopropoxide (bis-2,4-ethylacetoacetate), titanium di-n-butoxide (bis-2,4-pentanedionate), titanium acetylacetonate, and butyl titanate dimer.

  Zirconium compounds include zirconium n-propoxide, zirconium n-butoxide, zirconium t-butoxide, zirconium tri-n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetylacetonate, zirconium acetate, Zirconium hexafluoropentanedioate and the like can be mentioned.

  Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t-butoxide, aluminum acetylacetonate, and triethyl dialumonium tri-s-butoxide. Can be mentioned.

  The boron compounds include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-diethyl ether complex, borane-THF complex, borane-dimethyl sulfide complex, boron trifluoride diethyl ether complex, triethylborane, trimethoxy. Examples include borane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylborazole, triethylborazole, triisopropylborazole, and the like.

  Examples of tin compounds include tetraethyltin, tetramethyltin, di-n-butyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, Dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diisopropoxytin, dibutoxytin, tin dibutyrate, tin diacetoacetonate, ethyltin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate Examples of tin halides such as tin hydrogen compounds include tin dichloride and tin tetrachloride.

  Other organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, barium 2,2,6,6-tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoropentanedionate, dimethylcadmium, calcium 2,2,6,6-tetramethylheptanedionate, chromium trifluoropentanedionate, cobalt acetylacetonate, copper hexafluoropentanedionate, magnesium hexafluoropentanedionate-dimethyl ether complex, gallium ethoxide, tetraethoxygermane Tetramethoxygermane, hafnium t-butoxide, hafnium ethoxide, indium acetylacetonate, indium 2,6-dimethylaminoheptanedionate, Erocene, lanthanum isopropoxide, lead acetate, tetraethyl lead, neodymium acetylacetonate, platinum hexafluoropentanedionate, trimethylcyclopentadienylplatinum, rhodium dicarbonylacetylacetonate, strontium 2,2,6,6-tetramethyl Examples include heptanedionate, tantalum methoxide, tantalum trifluoroethoxide, tellurium ethoxide, tungsten ethoxide, vanadium triisopropoxide oxide, magnesium hexafluoroacetylacetonate, zinc acetylacetonate, and diethylzinc.

  In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  The discharge gas and the reactive gas are mixed and supplied to a plasma discharge generator (plasma generator) as a thin film forming (mixed) gas to form a film. Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

  The adhesion layer is made of a metal oxide, metal nitride or a composite compound thereof, which is a metal compound having a carbon content of 1 at% to 30 at%, and the protective layer is a metal oxide which is a metal compound having a carbon content of 1 at% to 30 at%. It is preferable that it is comprised from the thing, the metal nitride, or its complex compound.

In particular, from the viewpoint of gas barrier properties such as water vapor and oxygen, light transmittance, and suitability for atmospheric pressure plasma CVD described later, metal oxide silicon oxide (SiO _x ) is preferable.

  The inorganic compound according to the present invention, for example, obtains a film containing at least one of O atoms and N atoms, and Si atoms and C atoms by further combining oxygen gas and nitrogen gas in a predetermined ratio with the above organic silicon compound. I can do it.

  Next, the atmospheric pressure plasma discharge treatment apparatus used in the present invention will be described. The atmospheric pressure plasma discharge treatment apparatus discharges between the counter electrodes, puts the gas introduced between the counter electrodes into a plasma state, and exposes the resin film that is placed between the counter electrodes or transferred between the electrodes to the plasma state gas Thus, a thin film is formed on the resin film. As another method, the atmospheric pressure plasma discharge processing apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes or puts it in a plasma state, and excites or plasmas it in a jet form outside the counter electrode. There is a jet type apparatus in which a thin film is formed on a resin film by blowing out the gas and exposing a resin film (which may be left still or transferred) in the vicinity of the counter electrode.

  FIG. 2 is a schematic view showing an example of a jet-type atmospheric pressure plasma discharge treatment apparatus useful for the present invention.

  In addition to the plasma discharge processing apparatus and the electric field applying means having two power sources, the jet type atmospheric pressure plasma discharge processing apparatus includes a gas supply means 9 (see FIG. 3) and an electrode temperature adjusting means 10 (see FIG. 3). It is the device which has.

  The plasma discharge treatment apparatus 2 has a counter electrode composed of a first electrode 2a and a second electrode 2b. Between the counter electrodes, a frequency ω1 from the first power source 3a and an electric field are provided from the first electrode 2a. A first high-frequency electric field having intensity V1 and current I1 is applied, and a second high-frequency electric field having frequency ω2, electric field intensity V2, and current I2 from the second power source 3b is applied from the second electrode 2b. ing. The first power source 3a applies a higher high-frequency electric field strength (V1> V2) than the second power source 3b, and the first frequency ω1 of the first power source 3a applies a frequency lower than the second frequency ω2 of the second power source 3b. To do.

  A first filter 4a is installed between the first electrode 2a and the first power source 3a, and it is easy to pass a current from the first power source 3a to the first electrode 2a, and a current from the second power source 3b. Is designed so that the current from the second power source 3b to the first power source 3a does not easily pass.

  In addition, a second filter 4b is installed between the second electrode 2b and the second power source 3b to facilitate passage of current from the second power source 3b to the second electrode 2b, and from the first power source 3a. Is designed so that the current from the first power source 3a to the second power source 3b is difficult to pass.

  The thin film forming gas G is introduced from the gas supply means as shown in FIG. 3 into the space (discharge space) 2c between the opposing electrodes of the first electrode 2a and the second electrode 2b, and the first power source 3a and the second power source A high frequency electric field is applied between the first electrode 2a and the second electrode 2b by 3b to generate a discharge, and the thin film forming gas G is jetted to the lower side of the counter electrode (the lower side of the paper) in a plasma state. Then, the processing space formed by the lower surface of the counter electrode and the resin film F is filled with the gas G ° in the plasma state, and is unwound from the original winding (unwinder) of the resin film (not shown) and conveyed. A thin film is formed near the processing position 5 on the resin film F conveyed from the process.

  During the thin film formation, the medium heats or cools the electrode through the pipe from the electrode temperature adjusting means as shown in FIG. Depending on the temperature of the resin film during the plasma discharge treatment, the properties, composition, etc. of the thin film obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used.

  During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that temperature unevenness in the width direction or longitudinal direction of the resin film does not occur as much as possible.

  FIG. 2 shows a measuring instrument used for measuring the applied electric field strength and the discharge starting electric field strength and the measurement position. 6a and 6b are high-frequency voltage probes, and 6c and 6d are oscilloscopes.

  By arranging a plurality of jet-type atmospheric pressure plasma discharge treatment devices in parallel with the direction of transport of the resin film F, and simultaneously discharging gas in the same plasma state, it becomes possible to form a plurality of thin films at the same position, and for a short time. Thus, a desired film thickness can be formed. If a plurality of units are arranged in parallel with the transport direction of the resin film F, different thin film forming gases are supplied to each apparatus and different plasma states of the gas are jetted, it is possible to form laminated thin films having different layers.

  FIG. 3 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus of a method for treating a resin film between counter electrodes useful for the present invention.

  The atmospheric pressure plasma discharge treatment apparatus of the present invention is an apparatus having at least a plasma discharge treatment apparatus 7, electric field application means 8 a and 8 b having two power supplies, a gas supply means 9, and an electrode temperature adjustment means 10.

  11c between the opposing electrodes of the roll rotating electrode (first electrode) 11a and the square tube type fixed electrode group (second electrode) (hereinafter, the square tube type fixed electrode group is referred to as a fixed electrode group) 11b In the space 11c), the resin film F is subjected to plasma discharge treatment to form a thin film.

  In the discharge space 11c formed between the roll rotating electrode 11a and the fixed electrode group 11b, the roll rotating electrode 11a receives the first high frequency electric field of the frequency ω1, the electric field strength V1, and the current I1 from the first power supply 8b1. The fixed electrode group 11b is applied with a second high-frequency electric field of frequency ω2, electric field strength V2, and current I2 from the second power source 8a1.

  A first filter 8b2 is installed between the roll rotation electrode 11a and the first power supply 8b1, and the first filter 8b2 passes a current from the first power supply 8b1 to the roll rotation electrode (first electrode) 11a. It is designed so that the current from the second power source 8a1 is grounded and the current from the second power source 8a1 to the first power source 8b1 is not easily passed.

  A second filter 8a2 is installed between the fixed electrode group 11b and the second power supply 8a1, and the second filter 8a2 is a current from the second power supply 8a1 to the fixed electrode group (second electrode 11b). Is designed so that the current from the first power supply 8b1 is grounded and the current from the first power supply 8b1 to the second power supply 8a1 is difficult to pass.

  In the present invention, the roll rotating electrode 11a may be the second electrode, and the rectangular tube fixed electrode group 11b may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. The first power source preferably applies a higher high-frequency electric field strength (V1> V2) than the second power source. Further, the frequency has the ability to satisfy ω1 <ω2.

The current is preferably I1 <I2. Current I1 of the first high-frequency electric field is preferably ^{0.3mA / cm 2 ~20mA / cm 2} , more preferably at ^{1.0mA / cm 2 ~20mA / cm 2} . The current I2 of the second high-frequency electric field is preferably ^{10mA / cm 2 ~100mA / cm 2} , more preferably ^{20mA / cm 2 ~100mA / cm 2} .

  The thin film forming gas G generated by the gas generator 9a of the gas supply means 9 is introduced into the plasma discharge processing vessel 7a from the air supply port 7b while the flow rate is controlled by a gas flow rate adjusting means (not shown).

  The resin film F is unwound from an original winding (not shown) and is conveyed or is conveyed in the direction of the arrow from the previous process, and is accompanied by the resin film by the nip roll 12b through the guide roll 12a. Etc., and is transferred to and from the rectangular tube fixed electrode group 11b while being wound while being in contact with the roll rotating electrode 11a.

  During transfer, an electric field is applied from both the roll rotating electrode 11a and the rectangular tube fixed electrode group 11b, and discharge plasma is generated between the counter electrodes (discharge space) 11c. The resin film F forms a thin film with a gas in a plasma state while being wound while being in contact with the roll rotating electrode 11a.

  In addition, the number of the rectangular tube-shaped fixed electrodes 11b1 is set in plural along the circumference larger than the circumference of the roll electrode, and the discharge area of the electrodes is all the surfaces facing the roll rotating electrode 11a. It is represented by the sum of the areas of the surfaces of the rectangular tube-shaped fixed electrode facing the roll rotating electrode 11a.

  The resin film F passes through the nip roll 12c and the guide roll 12d, and is taken up by a winder (not shown) or transferred to the next step. Discharged treated exhaust gas G ′ is discharged from the exhaust port 7c.

  During the thin film formation, in order to heat or cool the roll rotating electrode 11a and the rectangular tube-shaped fixed electrode group 11b, the medium whose temperature is adjusted by the electrode temperature adjusting means 10 is sent to both electrodes via the pipe 10a by the liquid feed pump P. Adjust the temperature from inside the electrode. Reference numerals 7d and 7e denote partition plates that partition the plasma discharge processing vessel 7a from the outside.

  FIG. 4 is a perspective view showing an example of the structure of the conductive metallic base material of the roll rotating electrode shown in FIG. 3 and the dielectric material coated thereon.

  The roll rotating electrode 11a is formed by covering a conductive metallic base material 11a1 and a dielectric 11a2 thereon. In order to control the electrode surface temperature during the plasma discharge treatment and to keep the surface temperature of the resin film F at a predetermined value, a temperature adjusting medium (such as water or silicon oil) can be circulated.

  FIG. 5 is a perspective view showing an example of the structure of the conductive metallic base material of the rectangular tube electrode shown in FIG. 3 and the dielectric material coated thereon.

  The rectangular tube electrode 11b1 has a coating of a dielectric 11b11 with respect to the conductive metallic base material 11b12, and the structure of the electrode is a metallic pipe, which becomes a jacket and is being discharged. The temperature can be adjusted. The rectangular tube electrode 11b1 shown in the figure may be a cylindrical electrode. However, the rectangular tube electrode has an effect of expanding the discharge range (discharge area) as compared with the cylindrical electrode, and thus is preferably used in the present invention. .

  4 and 5, a roll rotating electrode 11a and a rectangular tube electrode 11b1 are formed by spraying ceramics as dielectrics 11a2 and 11b11 on conductive metallic base materials 11a1 and 11b12, respectively, and then sealing the inorganic compound. Is subjected to a sealing treatment.

  The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed.

  The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  Examples of the conductive metallic base materials 11a1 and 11b12 include titanium metal, titanium alloy, silver, platinum, stainless steel, aluminum, iron, and other metals, a composite material of iron and ceramics, or a composite material of aluminum and ceramics. Although titanium metal or a titanium alloy is particularly preferable for the reasons described later.

  The distance between the opposing first electrode and second electrode is the shortest distance between the surface of the dielectric and the surface of the conductive metallic base material of the other electrode when a dielectric is provided on one of the electrodes. Say that. When a dielectric is provided on both electrodes, it means the shortest distance between the dielectric surfaces.

  The distance between the electrodes is determined in consideration of the thickness of the dielectric provided on the conductive metal base material, the magnitude of the applied electric field strength, the purpose of using the plasma, etc. From the viewpoint of performing, it is preferably 0.1 mm to 20 mm, particularly preferably 0.5 mm to 2 mm.

  Details of the conductive metallic base material and dielectric useful in the present invention will be described later.

  As the plasma discharge treatment vessel 7a (see FIG. 3), a treatment vessel made of Pyrex (registered trademark) glass or the like is preferably used.

  For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation. In FIG. 2, it is preferable to cover both side surfaces of the parallel electrodes (up to the vicinity of the resin film surface) with the above-described material.

As the first power source (high frequency power source) 8b1 (see FIG. 3) installed in the atmospheric pressure plasma discharge processing apparatus of the present invention,
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

As the second power source (high frequency power source) 8a1 (see FIG. 3),
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power sources, the symbol * indicates a HEIDEN Laboratory impulse high-frequency power source (100 kHz in continuous mode). Other than that, it is a high frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the electric power applied between the electrodes facing each other supplies power (power density) of 1 W / cm ² or more to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film.

The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to the area in which discharge occurs between the electrodes.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it.

Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  Here, the waveform of the high-frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  An electrode used in such a method for forming a thin film by atmospheric pressure plasma must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

In the dielectric-coated electrode used in the present invention, it is preferable that the characteristics match between various metallic base materials and dielectrics. One of the characteristics is linear thermal expansion between the metallic base material and the dielectric. The combination is such that the difference in coefficient is 10 × 10 ⁻⁶ / ° C. or less.

It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

As a combination of a conductive metallic base material and a dielectric whose difference in linear thermal expansion coefficient is within this range,
1: Metal base material is pure titanium or titanium alloy, dielectric is ceramic sprayed coating 2: Metal base material is pure titanium or titanium alloy, dielectric is glass lining 3: Metal base material is stainless steel, Dielectric is ceramic spray coating 4: Metal base material is stainless steel, Dielectric is glass lining 5: Metal base material is a composite material of ceramics and iron, Dielectric is ceramic spray coating 6: Metal base material Ceramic and iron composite material, dielectric is glass lining 7: Metal base material is ceramic and aluminum composite material, dielectric is ceramic spray coating 8: Metal base material is ceramic and aluminum composite material, dielectric The body has glass lining. From the viewpoint of difference in linear thermal expansion coefficient, the above 1 or 2 and 5 to 8 are preferable, and 1 is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or titanium alloy as the metal base material, the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.

  The metallic base material of the electrode useful for the present invention is a titanium alloy or titanium metal containing 70% by mass or more of titanium. In the present invention, if the titanium content in the titanium alloy or titanium metal is 70% by mass or more, it can be used without any problem, but preferably contains 80% by mass or more of titanium.

  As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very few iron atoms, carbon atoms, nitrogen atoms, oxygen atoms, hydrogen atoms, etc. As content, it has 99 mass% or more.

  As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-mentioned atoms, and the titanium content is 98% by mass or more.

  Further, as the titanium alloy, T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin in addition to the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more.

  These titanium alloys or titanium metals have a thermal expansion coefficient that is about 1/2 smaller than that of stainless steel, such as AISI 316, and are combined with dielectrics described later applied on titanium alloys or titanium metals as a metallic base material. It can withstand the use at high temperature for a long time.

  On the other hand, as the required characteristics of the dielectric, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferable, and examples of such a dielectric include ceramics such as alumina and silicon nitride, Alternatively, there are glass lining materials such as silicate glass and borate glass.

  In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable. In particular, a dielectric provided by spraying alumina is preferable.

  Alternatively, as one of the specifications that can withstand high power as described above, the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, preferably more than 0% by volume and 5% by volume or less. It is.

  The porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment covered with a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation.

  High durability is achieved because the dielectric has a low porosity. Examples of the dielectric having such a void and having a low void ratio include a high-density, high-adhesion ceramic sprayed coating by the atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform a sealing treatment.

  The above-mentioned atmospheric plasma spraying method is a technique in which fine powder such as ceramics, wire or the like is put into a plasma heat source and sprayed onto a metallic base material to be coated as fine particles in a molten or semi-molten state to form a coating. A plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and further given energy to release electrons.

  The plasma gas injection speed is high, and since the sprayed material collides with the metallic base material at a higher speed than conventional arc spraying or flame spraying, high adhesion strength and high density coating can be obtained. For details, a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A No. 2000-301655 can be referred to.

  By this method, the porosity of the dielectric (ceramic sprayed film) to be coated can be obtained.

  Another preferred specification that can withstand high power is that the dielectric thickness is 0.5 mm to 2 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

In order to further reduce the porosity of the dielectric, it is preferable to further perform a sealing treatment with an inorganic compound on the sprayed film such as ceramics as described above. As the inorganic compound, metal oxides are preferable, and those containing silicon oxide (SiO _x ) as a main component are particularly preferable.

  The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. When the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

  Here, it is preferable to use energy treatment for promoting the sol-gel reaction. Examples of the energy treatment include thermal curing (preferably 200 ° C. or less) and ultraviolet irradiation. Furthermore, as a method of sealing treatment, when the sealing liquid is diluted and coating and curing are sequentially repeated several times, the mineralization is further improved and a dense electrode without deterioration can be formed.

  In the case of performing a sealing treatment that cures by a sol-gel reaction after coating a ceramic sprayed film using the metal alkoxide or the like of the dielectric-coated electrode according to the present invention as a sealing liquid, the content of the metal oxide after curing is 60 It is preferably at least mol%.

When alkoxysilane is used as the metal alkoxide of the sealing liquid, the content of SiO _x (x is 2 or less) after curing is preferably 60 mol% or more. The cured SiO _x content is measured by analyzing a tomographic layer of the dielectric layer by XPS (X-ray photoelectron spectroscopy).

  In the electrode according to the thin film forming method of the present invention, adjusting the maximum height (Rmax) of the surface roughness defined by JIS B 0601 on the side in contact with at least the resin film of the electrode to be 10 μm or less, Although it is preferable from the viewpoint of obtaining the effects described in the present invention, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably 7 μm or less.

  In this way, by polishing the dielectric surface of the dielectric-coated electrode, the thickness of the dielectric and the gap between the electrodes can be kept constant, the discharge state can be stabilized, the heat shrinkage difference and Distortion and cracking due to residual stress can be eliminated, and durability can be greatly improved with high accuracy.

  The polishing finish on the dielectric surface is preferably performed at least on the dielectric in contact with the resin film. Furthermore, the centerline average surface roughness (Ra) defined by JIS B 0601 is preferably 0.5 μm or less, more preferably 0.1 μm or less.

  In the dielectric-coated electrode used in the present invention, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The upper limit is 500 ° C.

The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without causing dielectric breakdown at the voltage used in the atmospheric pressure plasma treatment. Such a heat-resistant temperature is within the range of the difference between the linear thermal expansion coefficient of the above-mentioned metallic base material and the dielectric by applying the dielectric material provided by the above-mentioned ceramic spraying or layered glass lining with different amounts of bubbles mixed in. This can be achieved by appropriately combining means for appropriately selecting the materials.
<Production of substrate for liquid crystal cell>
A circuit for liquid crystal display and the like can be provided by a usual method on the resin film provided with the metal film of the present invention.

  A liquid crystal cell substrate made of a resin film according to an embodiment of the present invention will be described with reference to FIG.

  First, a metal film 100-1 according to the present invention is formed on one surface of a resin film substrate 101 made of polyethylene naphthalate (PEN).

  Next, the metal film 100 is formed on the other surface of the resin film substrate 101 on which the metal film 100-1 is formed.

  Next, a Ta thin film is formed on the metal film 100-1 by a sputtering apparatus, and a gate electrode 50 and a scanning wiring (not shown) are formed from the Ta film by photolithography. Further, a gate insulating film 52 made of a silicon nitride film (SiNx), an intrinsic amorphous silicon film, and an n + amorphous silicon film are sequentially stacked using a plasma CVD apparatus.

  The formed intrinsic amorphous silicon film and n + amorphous silicon film are patterned into an island-like intrinsic amorphous silicon layer 53 and n + amorphous silicon film by photolithography.

  Next, a Ti thin film is formed on the n + amorphous silicon film patterned in an island shape by using a sputtering apparatus, and the source electrode 56, the signal wiring 60, and the drain are formed by photolithography similarly to the gate electrode 50 and the scanning wiring. The electrode 57 is patterned.

  Using the patterned source electrode 56 and drain electrode 57 as a mask, the n + amorphous silicon film patterned in an island shape is electrically separated on the gate electrode 50 by dry etching, thereby forming an n + amorphous silicon layer 55.

  Next, ITO, which is a transparent conductive film, is formed on the gate insulating film 52 using a sputtering apparatus, and the pixel electrode 58 is formed so as to be electrically connected to the drain electrode 57 by photolithography.

  Finally, a protective film 59 made of a silicon nitride film is formed using a CVD apparatus so as to cover all the thin films formed on the metal film 100-1.

  Through the above-described steps, a substrate-attached thin film laminated device as shown in FIG. 6, that is, a liquid crystal cell substrate made of an active matrix resin film using TFTs is formed.

Next, a method of manufacturing the liquid crystal display device according to the embodiment will be briefly described with reference to FIG.
<Creation of liquid crystal display device>
On one substrate, that is, the protective film 59 of the active matrix substrate manufactured as described above, an alignment material to be the alignment film 70 is applied and an alignment process is performed by a rubbing method.

  Next, a color filter 74 is formed on the other substrate, that is, the counter substrate 75 by a normal method, and a counter electrode 73 that is a transparent electrode is patterned on the color filter 74.

  On the counter substrate 75, the metal film (100) of the present invention is provided on both surfaces in advance.

  On the counter electrode 73 of the counter substrate 75, an alignment film 72 subjected to an alignment process is disposed by performing an alignment process in the same manner as the active matrix substrate.

  Next, the active matrix substrate having the alignment film 70 and the counter substrate 75 on which the alignment film 72 is disposed are sealed so that the alignment film 70 and the alignment film 72 face each other to form a gap having a constant thickness. Bonding is performed via a material 76. A liquid crystal display device is manufactured by injecting a liquid crystal material between the bonded substrates to form a liquid crystal layer 71.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

(Example 1)
<Evaluation of substrate for liquid crystal cell>
(Preparation of resin film with active ray curable resin layer)
On the PEN (polyethylene naphthalate) film G01S (thickness 125 μm) manufactured by Kimoto Co., Ltd., a coating solution for actinic radiation curable resin layer having the following composition was prepared, using a micro gravure coater so that the film thickness after curing was 6 μm. After applying and evaporating and drying the solvent, an actinic radiation curable resin layer made of an acrylic cured layer was laminated by curing with 0.2 J / cm ² ultraviolet irradiation using a high pressure mercury lamp to obtain a resin film with an actinic radiation curable resin layer.

(Coating liquid for active ray curable resin layer)
Dipentaerythritol hexaacrylate monomer 60 parts by mass Dipentaerythritol hexaacrylate dimer 20 parts by mass Dipentaerythritol hexaacrylate trimer component 20 parts by mass Dimethoxybenzophenone photoinitiator 4 parts by mass Methyl ethyl ketone 75 parts by mass Propylene Glycol monomethyl ether 75 parts by mass The centerline average roughness (Ra) of the surface of the actinic radiation curable resin layer (polymer layer) was 5 nm or less and was smooth. The center line average roughness (Ra) was determined for an area of 1.2 mm × 0.9 mm using an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO) according to JIS B 0601. .
(Preparation of liquid crystal cell substrate)
[Sample No. Production of 101]
On the prepared resin film with an actinic radiation curable resin layer, as a metal film, under the conditions shown below, from the resin film side, an adhesion layer, a metal film (metal film a (20 nm), metal film b (30 nm)), A protective layer (400 nm) was sequentially formed into a thin film under the conditions described below to produce a liquid crystal cell substrate. 101.

(Preparation of adhesion layer)
<A mixed gas composition for the adhesion layer>
Discharge gas: Nitrogen gas 94.85% by volume
Thin film forming gas: Hexamethyldisiloxane 0.20% by volume
Additive gas: Oxygen gas 5.0% by volume
<Filming conditions for adhesion layer>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 12 W / cm ² (the voltage Vp at this time was 8 kV)
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
(Preparation of metal film a)
<Mixed gas composition for metal film a>
Discharge gas: Nitrogen gas 79.2% by volume
Thin film forming gas: 15.8% by volume of tetraethoxysilane
Additive gas: Oxygen gas 5.0% by volume
<Deposition conditions for metal film a>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (Voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (Voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
(Preparation of metal film b)
<Mixed gas composition for metal film b>
Discharge gas: Nitrogen gas 94.5% by volume
Thin film forming gas: Tetraethoxysilane 0.5% by volume
Additive gas: Oxygen gas 5.0% by volume
<Film forming conditions for metal film b>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 13 W / cm ² (the voltage Vp at this time was 8.5 kV)
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (Voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
(Preparation of protective layer)
<Combination gas composition for protective layer>
Discharge gas: Nitrogen gas 91.4% by volume
Thin film forming gas: hexamethyldisiloxane 3.6% by volume
Additive gas: Oxygen gas 5.0% by volume
<Filming conditions for protective layer>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 12 W / cm ² (the voltage Vp at this time was 8 kV)
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 5 W / cm ² (the voltage Vp at this time was 1 kV)
Electrode temperature 90 ° C
The adhesion layer, the metal film, and the protective layer were all laminated using the atmospheric pressure plasma discharge processing apparatus shown in FIG. The residual stress of the metal film was 1.0 MPa in terms of compressive stress. Residual stress was measured by a thin film physical property evaluation apparatus MH4000 manufactured by NEC Sanei Co., Ltd.

  The carbon content of the adhesion layer was 7 at%, the carbon content of each of the metal films a and b was 0.1 at% or less of the detection limit, and the carbon content of the protective layer was 18 at%. The carbon content was measured using ESCALAB-200R (XPS surface analyzer) manufactured by VG Scientific. The SiOxCy composition of each layer was as follows.

The adhesion layer was SiO _1.9 C _0.2 , the metal film a was SiO ₂ , the metal film b was SiO ₂ , and the protective layer was SiO _1.9 C _0.7 .

  The elastic modulus of the adhesion layer was 12 GPa, the elastic modulus of the protective layer was 15 GPa, and the elastic modulus of all metal films including the metal film a and the metal film b was 50 GPa. The elastic modulus was measured using a nanoindentation measurement method.

[Sample No. Production of 102]
Sample No. The resin film with an actinic radiation curable resin layer same as 101 is used, and the structure of the metal film is changed from the resin film side to metal film a (20 nm) / metal film b (30 nm) / metal film a (20 nm) / metal film b. Sample No. 2 except that two units (30 nm) were laminated. A liquid crystal cell substrate was prepared under the same conditions as in Example 1. 102. The residual stress of all metal films was 0.8 MPa in terms of compressive stress.

[Sample No. 103)
Sample No. A resin film in which the same actinic radiation curable resin layer was laminated on the back side of the resin film with an actinic radiation curable resin layer used for the production of No. 101 was used. A metal film having the same configuration as that of 102 (adhesion layer from the resin film side, 2 units of metal film, protective layer) was laminated. 103. The residual stress of the sub-metal film of 2 units on each side of the resin film was 1.0 MPa in terms of compressive stress.

[Sample No. Preparation of 104]
Sample No. The resin film with an actinic radiation curable resin layer same as 101 is used, and the structure of the metal film is changed from the resin film side to metal film a (20 nm) / metal film b (30 nm) / metal film a (20 nm) / metal film b. A liquid crystal cell substrate was prepared under the same conditions except that three units of (30 nm) / metal film a (20 nm) / metal film b (30 nm) were laminated. 104. The residual stress of all metal films was 0.9 MPa in terms of compressive stress.

[Comparative Sample No. Production of 105]
Sample No. A liquid crystal cell substrate was prepared under the same conditions except that a resin film with an actinic radiation curable resin layer same as 101 was used, and the metal film was laminated with one metal film b (film thickness 50 nm). No. 105. The residual stress of the metal film was 3.0 MPa as a compressive stress.

[Comparative Sample No. 106)
Sample No. In Sample No. 102, all samples except for the metal film c (film thickness 1 μm) shown below instead of the metal film a were sample Nos. A liquid crystal cell substrate was prepared under the same conditions as in No. 102. 106. The residual stress of all metal films was 2.3 MPa in terms of compressive stress.

(Lamination of metal film c)
8 g of Soarnol D2908 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., ethylene-vinyl alcohol copolymer) was dissolved in a mixed solvent of 118.8 g of 1-propanol and 73.2 g of water at 80 ° C. To 10.72 g of this solution, 2.4 ml of 2M (2N) hydrochloric acid was added and mixed.

  While stirring this solution, 1 g of tetraethoxysilane was added dropwise and stirring was continued for 30 minutes. Next, dimethylbenzylamine was added as a pH adjuster immediately before application of the obtained coating solution, and this solution was applied with a wire bar. Then, after irradiating the whole surface with a microwave, the metal film c was laminated | stacked by drying at 120 degreeC.

[Comparative Sample No. 107)
Sample No. In Sample No. 102, Sample No. 10 was used except that instead of the metal film a, a metal film d (film thickness 10 nm) was used. A liquid crystal cell substrate was prepared under the same conditions as in Sample No. 102. 107. The residual stress of all metal films was 6.2 MPa in terms of compressive stress.

(Lamination of metal film d)
A metal film d of a chromium oxide layer (film thickness: 10 nm) is formed by sputtering (for details, see Example 1 of Japanese Patent Laid-Open No. 2003-21579) under the conditions of an oxygen partial pressure of 0.009 Pa and an overall system pressure of 0.13 Pa. Were laminated.

[Comparative Sample No. 108 production)
Sample No. In Sample No. 102, except that the metal film e shown below was used instead of the metal film a, Sample No. A liquid crystal cell substrate was prepared under the same conditions as in Sample No. 102. 108. In addition to silicon and oxygen, 3% of carbon was detected from the metal film e. The residual stress of all metal films was 1.8 MPa in terms of compressive stress.

(Production of metal film e)
<Mixed gas composition for metal film e>
Discharge gas: Nitrogen gas 79.2% by volume
Thin film forming gas: 15.8% by volume of tetraethoxysilane
Additive gas: Oxygen gas 5.0% by volume
<Film forming conditions for metal film e>
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 7.5 W / cm ² (Voltage Vp at this time was 6 kV)
Electrode temperature 120 ° C
2nd electrode side power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (Voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
The composition of the metal film e was SiO _1.9 C _0.2 .

Evaluation Each sample No. Table 1 shows the results of the tests on gas barrier properties and shear strength given in 101 to 108 and evaluated according to the following evaluation ranks.

≪Evaluation of gas barrier properties≫
As a gas barrier property, the water vapor transmission rate was tested by the following method. Each prepared sample was spread by winding the membrane surface side around a 100 mmφ cylinder 20 times (winding the membrane surface side around the cylinder 20 times), and then spread by the calcium corrosion method described in JP-A-2005-283561. Using a film water vapor permeability measuring device, the water vapor transmission rate was measured using the calcium corrosion method evaluation method described in the publication.

Evaluation rank of water vapor transmission rate ○: No deterioration of water vapor transmission performance △: Slightly deteriorated ×: Largely deteriorated << Evaluation of shear strength >>
It was measured with a shear strength measuring instrument of the type of CYCUS NN-04 manufactured by Daipla Intes and used as the CYCUS shear strength. As measurement conditions, the sampling step was 0.2 sec / point, a diamond 1 mm wide blade was used, the shear angle was 45 °, the pressing load was 2 μN, the balance load was 1 μN, the vertical speed was 1 nm / sec, and the horizontal speed was 100 nm. Cutting was performed at / sec, and horizontal and vertical forces were recorded to obtain shear strength.

(Example 2)
<Evaluation of liquid crystal display device using liquid crystal cell substrate>
A VA circuit and an alignment film were formed on the samples 101 to 108, and the color shift amount was evaluated as a VA liquid crystal display device.

  Note that the optical film such as a polarizing plate and a retardation plate and a basic liquid crystal display device were used by disassembling the configuration of AQUAS-LC37GX1W.

≪Measurement method of color shift amount of liquid crystal display device≫
A black image was displayed on the liquid crystal display device, and the hue, x value, and y value in all directions (360 °) in the polar angle 60 ° direction were measured using a product name “EZ Contrast 160D” manufactured by ELDIM.

Further, in the x value and y value calculated by EZ Contrast at a polar angle of 60 ° and an azimuth angle of 45 °, the difference Δxy between the maximum value and the minimum value of the x and y values in all directions is expressed by the formula: {(x (maximum) -X (minimum)) ² + (y (maximum)-y (minimum)) ² } ^1/2 .

  Note that the azimuth angle 45 ° represents an azimuth rotated 45 ° counterclockwise when the long side of the panel is 0 °. Further, the polar angle of 60 ° represents an orientation viewed obliquely by 60 ° when the vertical direction is 0 ° with respect to the panel.

  The effectiveness of the present invention was confirmed.

It is a schematic sectional drawing which shows an example of the layer structure of the board | substrate for liquid crystal cells of this invention. It is the schematic which showed an example of the atmospheric pressure plasma discharge processing apparatus of the jet system useful for this invention. It is the schematic which shows an example of the atmospheric pressure plasma discharge processing apparatus of the system which processes a resin film between counter electrodes useful for this invention. It is a perspective view which shows an example of the structure of the electroconductive metal base material of the roll rotating electrode shown in FIG. 3, and the dielectric material coat | covered on it. FIG. 4 is a perspective view showing an example of a structure of a conductive metal base material of the rectangular tube electrode shown in FIG. 3 and a dielectric material coated thereon. 1 is a liquid crystal cell substrate made of a resin film according to an embodiment of the present invention. It is sectional drawing of the liquid crystal display device by one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a, 1b Liquid crystal cell board | substrate 100 The structure of the metal film which consists of two layers 100-1 The structure of the metal film of 2 units 100-2 The structure of the metal film which consists of three layers 101 Resin film 102 Metal film 102a First metal film 102b First 2 Metal film 103 Adhesion layer 104 Protective layer 2, 7 Plasma discharge treatment apparatus 2 a First electrode 2 b Second electrode 2 c, 11 c Between counter electrodes (discharge space)
8a, 8b Electric field application means 9 Gas supply means 11a Roll rotating electrode 11b Square tube fixed electrode group 19 Glass sealing can 50 Gate electrode 52 Gate insulating film 53 Semiconductor layer 55 n + semiconductor layer 56 Source electrode 57 Drain electrode 58 Pixel electrode 59 Protective film 60 Signal wiring

Claims (6)

A liquid crystal cell substrate comprising a resin film, wherein the liquid crystal cell substrate has a metal film having at least two layers selected from a metal oxide film, a metal nitride film, or a metal oxynitride film on the resin film, A substrate for a liquid crystal cell, wherein the at least two metal films have the same composition and different shear strengths. 2. The substrate for a liquid crystal cell according to claim 1, wherein the two metal films having different shear strengths are adjacent two metal films. 3. The liquid crystal cell substrate according to claim 1, wherein the density ratio Y of the two adjacent metal films is 1 ≧ Y ≧ 0.95. The liquid crystal cell substrate according to claim 1, wherein the at least two metal films are provided on both sides of the resin film. 5. The liquid crystal cell substrate according to claim 1, wherein the metal film is formed by atmospheric pressure plasma CVD. A liquid crystal display device using the liquid crystal cell substrate according to claim 1.

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