TW201514333A - Moisture-proof substrate production method, moisture-proof substrate, polarizing plate using moisture-proof substrate, and liquid crystal display panel - Google Patents

Abstract

Provided is a method of producing a moisture-proof substrate which, even when thin, has sufficient moisture resistance and can significantly suppress warping and deformity caused by a hygroscopic substrate. This method is for producing a moisture-proof substrate provided with a hygroscopic substrate with moisture absorption rate of 1% or greater and with a moisture-proof film formed on at least one side of the hygroscopic substrate, and involves a process in which a 30nm or thicker moisture-proof film comprising a silicon oxide film or a silicon oxynitride film having a carbon component with a carbon content ratio of 2.0-20.0at% is formed with plasma-enhanced chemical vapor deposition on the at least one surface of the hygroscopic substrate.

Description

Method for producing moisture-proof substrate, moisture-proof substrate, and polarizing plate and liquid crystal display panel using moisture-proof substrate

The present invention relates to a moisture-proof substrate which is less likely to cause warpage and which has extremely low moisture permeability, which is used as a sealing material or a substrate material, such as an electronic device.

In various devices such as an optical element, a liquid crystal display panel, an organic electroluminescence (EL) electroluminescence (EL), a semiconductor device, and a solar cell module, many parts or parts are required to have moisture resistance. For example, in a polarizing plate used for a liquid crystal display panel, problems such as a change in polarization characteristics with humidity are known.

In order to solve these problems, it is known that a resin film formed by forming a film of a metal or an inorganic compound on a surface thereof is bonded as a moisture-proof substrate, and moisture-proof property is imparted to a portion or a part requiring moisture resistance. For example, it is known that a moisture-proof substrate as described above is bonded to a polarizing plate to impart moisture resistance.

In addition, the problem that the optical characteristics of the polarizing plate is lowered or the discoloration is caused by the interaction of heat and humidity is disclosed in Japanese Laid-Open Patent Publication No. Hei 03-148603 (hereinafter referred to as Patent Document 1). The transparent protective layer of the wet layer is disposed on one side or both sides of the polarizing film. Next, Patent Document 1 discloses that the transparent protective layer forming material is a polyester resin, a polyether oxime resin, a polycarbonate resin, a polyamide resin, a polyimide resin, or an acrylic resin. a resin or an acetate resin, and a compound such as cerium oxide, indium oxide, tin oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium fluoride or zinc oxide is described on at least one side of the transparent protective layer. The moisture-proof layer is formed by a vacuum vapor deposition method, a sputtering method, or an ion plating method.

Japanese Laid-Open Patent Publication No. 2001-235625 (hereinafter referred to as Patent Document 2) discloses a polarizing plate having a cellulose triacetate (TAC) film as a protective layer, and reduces protection for the purpose of reducing the thickness or weight of the polarizing plate. When the thickness of the layer is increased, the reliability of the humidification of the polarizing plate is deteriorated (that is, the amount of change in the light transmittance is increased, and the amount of change in the degree of polarization is increased) is proposed by making the temperature at 40 ° C × 90% RH. In the environment, the moisture permeability of the protective layer is 0.04 g/cm ² /24 h or less, and the moisture permeability reliability can be maintained. Further, Patent Document 2 describes that a vapor-deposited film such as a transparent film of various metals, an ITO film, or a transparent metal oxide film is formed by a vapor deposition method or a sputtering method, and the moisture permeability protection as described above can be obtained. Floor.

However, in recent years, display devices such as liquid crystal display panels have demanded further products to be lighter and thinner. As the glass substrate to be used, glass having a glass thickness of about 0.5 to 0.7 mm is used, but a thinner glass film having a glass thickness of 0.3 mm is required. Further, not only the glass substrate but also the thickness of each layer constituting the panel is attempted to be further thinned.

As the thickness of each layer is reduced, the panel rigidity is lowered. Therefore, not only the above-described problem of moisture-proof reliability is lowered, but also the panel is warped. For example, when the liquid crystal display panel is warped, the four corners of the panel become white and the display defective portion is generated, which may cause deterioration in display stability for a long period of time.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 03-148603

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-235625

A vapor deposited film comprising cerium oxide, indium oxide, tin oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium fluoride, or zinc oxide described in Patent Document 1, or a transparent film of various metals described in Patent Document 2, or ITO A thin film or a transparent metal oxide film can impart moisture resistance to the protective film. However, these moisture-proof films hardly expand/contract for moisture absorption/drying, so that the base film provided with the moisture-proof film expands/contracts due to moisture absorption/drying, and warpage occurs in the protective film. As a result, the warpage of the protective film remarkably causes the problem of warpage of the display panel itself which induces a decrease in rigidity due to the reduction in thickness.

Such moisture absorption caused by the warpage of the protective layer, in use three A hygroscopic substrate having a water absorption ratio of 1% or more such as a cellulose acetate (TAC) film is particularly remarkable as a base film provided with a moisture-proof film.

Further, the moisture-proof films described in Patent Document 1 and Patent Document 2 hardly expand and contract with respect to temperature changes, so that expansion/contraction due to temperature change of the base film causes warpage in the protective layer. Thus, the warpage caused by the temperature change is superimposed on the warpage caused by the moisture absorption/drying described above, which becomes a problem that cannot be ignored.

Further, the moisture-proof films described in Patent Document 1 and Patent Document 2 are formed on a base film by a vacuum deposition method, a sputtering method, or an ion plating method. In such a film formation method, high-temperature and high-energy vapor-deposited particles or sputtered particles come into contact with the base film, so that the base film is damaged. In particular, since the moisture-absorbing base film as described above has a low heat resistance, the flatness of the base film cannot be maintained after the film formation, and as a result, undulations, floating of the ends, curling, and the like occur on the surface of the protective layer. Shape deformation.

Further, when a moisture-proof film is provided on the moisture-absorbing base film, when a vacuum deposition method, a sputtering method, or an ion plating method is employed, high-temperature and high-energy vapor-deposited particles or sputtered particles reach the hygroscopic base film. On the surface, dehydration occurs on the surface of the hygroscopic substrate film. As a result, a dense film cannot be formed, and sufficient moisture-proof property cannot be obtained, and the adhesion between the moisture-absorbing base film and the moisture-proof film is also lowered, so that there is a problem that a protective film excellent in durability cannot be obtained.

The inventors of the present invention have obtained the following findings, that is, a moisture-proof substrate provided with a moisture-proof film on a moisture-absorbing substrate having a water absorption ratio of 1% or more, by using an oxidation including a specific carbon content. Bismuth film or oxynitridation The moisture-proof film of the enamel film can achieve sufficient moisture resistance even when it is thin, and can greatly suppress the moisture-proof substrate which is caused by warpage or deformation of the moisture-proof substrate. The present invention has been completed in accordance with the relevant findings.

That is, an object of the present invention is to provide a method for producing a moisture-proof substrate which can sufficiently suppress warpage or deformation of a hygroscopic substrate even if it is sufficiently thin and has sufficient moisture resistance.

Further, another object of the present invention is to provide a moisture-proof substrate obtained by the production method, a polarizing plate using a moisture-proof substrate, and a liquid crystal display panel.

According to the method for producing a moisture-proof substrate according to the first aspect of the invention, the method for producing a moisture-proof substrate is included in at least one side of a hygroscopic substrate having a water absorption ratio of 1% or more, by plasma chemical vapor phase. The deposition method forms a moisture-proof film having a film thickness of 30 nm or more including a ruthenium oxide film or a yttrium oxynitride film containing a carbon component having a carbon content of 2.0 at% or more and 20.0 at% or less.

In the first invention, the film formation is preferably carried out by a plasma chemical vapor deposition method using a film-forming material gas containing an organic germanium monomer.

The moisture-proof substrate according to the second aspect of the invention includes a moisture-absorbing substrate having a water absorption ratio of 1% or more, and a moisture-proof base of the moisture-proof film formed on at least one side of the moisture-absorbing substrate. The moisture-proof film includes a carbon content of 2.0 at% or more, 20.0 at% or less of a cerium oxide film or a yttrium oxynitride film having a carbon thickness of 30 nm or more.

According to the moisture-proof substrate of the second aspect of the invention, the moisture permeability in an environment of 25° C. and 90% RH is preferably 6.0 g/(m ² .24 h) or less.

The present invention also provides a polarizing plate comprising the moisture-proof substrate according to the second aspect of the invention, and a liquid crystal display panel including the polarizing plate.

According to the present invention, since the moisture-proof film is formed by the plasma chemical vapor deposition method, damage to the moisture-absorbing substrate caused by heat or particle collision energy can be greatly reduced. Therefore, even if the film thickness of the moisture-proof substrate is reduced, a moisture-proof substrate which can greatly reduce deformation or bending of the substrate can be realized.

Further, according to the present invention, the moisture-proof film is formed of a ruthenium oxide film or a yttrium oxynitride film containing a carbon component having a carbon content of 2.0 at% or more and 20.0 at% or less, so that the water absorption rate is 1% or more. When the moisture-proof film is provided on the moisture-absorbing substrate, it is possible to achieve a moisture-proof substrate which is sufficiently thin and has a large moisture-proof property and can suppress the warpage or deformation of the moisture-proof substrate.

1‧‧‧Moisture-proof substrate

2‧‧‧Hygroscopic substrate

3‧‧‧Dampproof film

4‧‧‧ hard coating

5‧‧‧Optical adjustment layer

6‧‧‧Anti-fouling layer

10‧‧‧Polar plate

11‧‧‧Polar photons

20‧‧‧LCD panel

21‧‧‧ liquid crystal cell

22‧‧‧ glass substrate

23‧‧‧Adhesive layer

31‧‧‧ Plasma CVD device

32‧‧‧vacuum room

33‧‧‧lower electrode

34‧‧‧Upper electrode

35‧‧‧ Plasma generating device

36‧‧‧Exhaust valve

37‧‧‧Exhaust device

38‧‧‧ gas inlet

39a, 39b, 39c‧‧‧Adding gas supply device

39d, 39e‧‧‧ film forming material supply device

40a, 40b, 40c, 40d, 40e‧‧‧ flowmeter

41d, 41e‧‧‧ gasifier

50‧‧‧vacuum room

51‧‧‧Feed rolls

52‧‧‧Winding roller

53‧‧‧lower electrode

54‧‧‧ Coating roller (upper electrode)

55a, 55b‧‧‧ exhaust valve

56a, 56b‧‧‧ exhaust

57a, 57b, 57c‧‧‧ gas inlet

58a, 58b, 58c‧‧‧Adding gas supply

59a, 59b‧‧‧ filming material supply source

60a, 60b‧‧‧ flowmeter

61‧‧‧ Guide roller

62a, 62b‧‧‧ gasifier

63a, 63b, 63c‧‧‧ flowmeter

71‧‧‧Stainless steel substrate

72‧‧‧Moisture-proof substrate sample

Fig. 1 is a schematic cross-sectional view showing a first embodiment of a moisture-proof substrate according to the present invention.

Fig. 2 is a schematic cross-sectional view showing a second embodiment of the moisture-proof substrate according to the present invention.

Fig. 3 is a schematic cross-sectional view showing an application form of a moisture-proof substrate according to the present invention. (a) shows the first application type, and (b) shows the second application type.

Fig. 4 is a schematic cross-sectional view showing an application form of a moisture-proof substrate according to the present invention. (a) shows the third application type, and (b) shows the fourth application type.

Fig. 5 is a schematic cross-sectional view showing an application form of a polarizing plate according to the present invention. (a) shows the first application type, and (b) shows the second application type.

Fig. 6 is a schematic cross-sectional view showing an application form of a liquid crystal display panel according to the present invention.

Fig. 7 is a schematic view showing a first example of a plasma CVD apparatus used for the production of the present invention.

Fig. 8 is a schematic view showing a second example of a plasma CVD apparatus used for the production of the present invention.

Fig. 9 is a schematic view showing a warpage evaluation method of the present invention.

Hereinafter, specific embodiments of the present invention will be described in detail below using the drawings and the like. Further, the present invention is not limited to any of the following embodiments, and can be implemented by applying appropriate modifications within the scope of the object of the present invention.

[definition]

In the present specification, the term "permeability" means a value measured under the conditions of 25 ° C and 90% RH in accordance with Japanese Industrial Standard JIS Z 0208 "Test method for moisture permeability of moisture-proof packaging materials".

In the present specification, the term "at%" refers to a unit indicating the atomic composition percentage of the ratio of the number of atoms, and is also referred to as "atom% (atomic percent)". The atomic composition percentage, as described later, is a value measured by X-ray photoelectron spectroscopy. X-ray photoelectron spectroscopy, also known as XPS (X-ray Photoelectron Spectroscopy) or ESCA (Electron Spectroscopy for Chemical Analysis). As a specific example, the atomic composition percentage is measured by an X-ray photoelectron spectroscopy apparatus (ESCA LAB220i-XL manufactured by VG Scientific), but is not limited to this measuring apparatus.

In the present specification, the term "water absorption rate" means a value measured according to Japanese Industrial Standard JIS K7209 (water absorption rate of plastic and boiling water absorption rate test method), and is expressed as the original mass of the test piece and the mass increase amount before and after water absorption. ratio. Specifically, the water absorption rate was measured as follows.

(1) In principle, the test piece is a circular plate having a diameter of 50 ± 1 mm, or a square plate having a side of 50 ± 1 mm, and a thickness of 3 ± 0.2 mm.

(2) The test piece was dried in a thermostat kept at 50 ± 2 ° C for 24 ± 1 hour, and placed in a desiccator to cool.

(3) Next, the mass of the test piece was measured to a unit of 0.1 mg, and the measured value was M1.

(4) Thereafter, the test piece was placed in a container to which water of 23 ± 2 ° C was added, and after 24 ± 1 hour, the test piece was taken out from the water and measured to a unit of 0.1 mg, and the measured value was M2.

(5) From the measured M1 and M2, the water absorption rate was determined according to the following formula.

Water absorption rate = (M2-M1) / M1 × 100

In the present specification, "(meth) acrylate" means both acrylate and methacrylate.

[moisture resistant substrate]

As shown in FIGS. 1 to 2, the moisture-proof substrate 1 of the present invention comprises an absorbent substrate 2 having a water absorption ratio of 1% or more and at least one side formed on the moisture-absorbing substrate 2. The moisture-proof film 3 on the side. Further, the moisture-proof substrate 1 according to the present invention is provided before the object of the present invention is not impaired, as shown in Figs. 3 to 4, and further includes a hard coating layer 4, an optical adjustment layer 5, and the like. The functional layer such as the stain layer 6 can also be used. Each layer constituting the moisture-proof substrate according to the present invention will be described below.

(hygroscopic substrate)

In the present embodiment, the moisture-absorbing base material 2 serves as a base material that functions as a base film of the moisture-proof base material 1. It is necessary to maintain the film of the moisture-proof film 3, but what kind of film to use, as long as the moisture-proof substrate 1 is used You can choose if you want to use it.

For example, when the moisture-proof substrate 1 is used as a protective layer of a polarizing plate of a liquid crystal display panel, it is preferable that the light transmittance is 70% or more, and it is preferable that the moisture-proof substrate 1 has no polarizing characteristics. Further, in the case of an electronic component, if the laminated film for a display is exposed to a temperature of 150 ° C or more, the linear expansion coefficient is 15 ppm/K to 100 ppm/K, and the glass transition point Tg is preferably 150 ° C to 300 ° C. In the present embodiment, the glass transition point is measured by Japanese Industrial Standard JIS K 7121 "Method for Measuring Transfer Temperature of Plastics".

The hygroscopic substrate 2 is not limited to a material which can select a low water absorption rate, depending on the performance thus pursued. As a result, as the thickness of the display panel or the like is reduced, the warpage of the panel which absorbs moisture/drys with the moisture absorbent substrate 1 becomes a problem when a panel or the like is produced. As a result of the moisture absorption/drying warpage of the moisture absorbent base material 1 itself, when the water absorption rate of the material of the moisture absorbent base material 2 is 1% or more, it cannot be ignored. In the present embodiment, the hygroscopic substrate having a water absorption ratio of 1% or more is targeted. The upper limit of the water absorption rate is not particularly limited, and a general plastic material is preferably 10% or less, preferably 5% or less.

Examples of the material used for the hygroscopic substrate 2 include a cellulose triacetate (TAC) film, a polyamide film, a polyarylamine film, a polyvinyl alcohol (PVA) film, and an ethylene-vinyl alcohol copolymer resin film. A polyethylene glycol (PEG) film, a polyimide film (PI) film, a polyurethane resin film, a polyether oxime (PES) resin, or the like.

Further, the thickness of the hygroscopic substrate 2 is 5 μm to 220 μm. The degree is preferably from 10 μm to 50 μm. If it is less than this range, the occurrence of pinholes may be caused by the discharge of static electricity, and the barrier property may be deteriorated. If the range is exceeded, even if the same performance can be maintained, the throughput of one lot will be small, which is not preferable.

The surface of the hygroscopic substrate 2 may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, heat treatment, and drug treatment. A specific method of such surface treatment can be suitably used in a conventionally known method. Further, on the surface of the absorbent substrate 2, an anchor coating film may be formed for the purpose of improving the adhesion to the moisture-proof film 3 or the like. As such an anchor coating film, it is sufficient to use a previously known one. Further, a barrier layer may be provided between the moisture absorbent substrate 2 and the moistureproof film 3 for the purpose of improving gas barrier properties. The material for forming the barrier layer and the method of forming the same may be used as long as it is appropriately used.

(moisture proof film)

The moisture-proof film 3 formed on at least one side of the moisture-absorbing substrate 2 is a carbon component containing a carbon content of 2.0 at% or more and 20.0 at% or less formed by a plasma chemical vapor deposition method. A hafnium oxide film or a hafnium oxynitride film. Hereinafter, a film forming method of the moisture proof film will be described.

Plasma chemical vapor deposition, also known as plasma CVD (plasma-enhanced chemical vapor deposition, PECVD), is a chemical vapor deposition method. In the plasma chemical vapor deposition method, the film forming raw material is vaporized in the plasma discharge It is necessary to add an additive gas as necessary to cause the gases in the system to be activated by radical reaction or ionization by collision, so that the reaction can be carried out at a low temperature at which the reaction is impossible only by thermal excitation. The moisture-absorbing substrate 2 is formed into a moisture-proof film 3 by a reaction in discharge between electrodes. As the frequency of occurrence of plasma is different, it is classified into low frequency (LF, tens to hundreds of kHz), high frequency (RF, 13.56 MHz), and microwave (2.45 GHz). When microwaves are used, they can be roughly classified into a method of exciting a reaction gas, forming a film in afterglow, and introducing an ECR plasma CVD method in which a microwave is introduced in a magnetic field (875 Gauss) satisfying ECR conditions. In addition, if it is classified by the plasma generation method, it can be classified into a capacitive coupling method (parallel flat type) and an inductive coupling method (coil method). In addition, a magnetron structure according to a magnet may be provided in the reaction system as needed, and a space having a high density such as ions or electrons may be appropriately provided. With the arrangement position of the magnetron, it is possible to reduce the damage to the film-formed substrate or, conversely, to enhance the damage to the film-formed substrate to improve the adhesion to the film-formed substrate.

Fig. 7 is a structural view showing an example of a plasma CVD apparatus formed by plasma chemical vapor deposition used in the present aspect. In FIG. 7, the plasma CVD apparatus 31 includes a vacuum chamber 32, a lower electrode 33 disposed in the vacuum chamber 32, an upper electrode 34, and a plasma generating device (power source) 35 connected to the lower electrode 33, An oil-type rotary pump connected to the vacuum chamber 32 through the exhaust valve 36, an exhaust device 37 such as a turbo molecular pump, and a gas introduction port 38 for introducing the film-forming material gas into the vacuum chamber 32. The gas introduction port 38 is connected to the additive gas supply sources 39a, 39b, 39c and Individual gas flow meters 40a, 40b, 40c. Further, the film forming material supply sources 39d and 39e and the individual flow meters 40d and 40e are connected, and the respective vaporizers 41d and 41e are necessary.

Next, a method of manufacturing the moisture-proof substrate 1 using such a plasma CVD apparatus will be described. After the film formation surface of the moisture absorbent substrate 2 is placed on the lower electrode 33 on the upper side, the inside of the vacuum chamber 32 is depressurized to a specific degree of vacuum by the exhaust device 37. Then, in order to introduce the film forming material gas into the vacuum chamber 32, first, the flow rate is adjusted by the flow meters 40d and 40e, and the film forming raw material supply source 39d, 39e is supplied to all the film forming raw materials containing the organic germanium monomer, and the vaporizer 41d is used. After 41e, the film-forming raw material is vaporized, and then supplied to the gas introduction port 38 in a gaseous state. At the same time, the additive gas is supplied to the gas introduction port 38 by adjusting the flow rate by the flow meters 40a, 40b, and 40c by the additive gas supply sources 39a, 39b, and 39c. These gases may be uniformly mixed after the gas introduction port 38 and then supplied to the vacuum chamber 2, and may be supplied from the gas introduction port 38 depending on the type of gas. Next, the inside of the vacuum chamber 32 is set to a specific pressure by controlling the degree of opening and closing of the exhaust valve 36 between the exhaust device 37 and the vacuum chamber 32. In a state where the flow of the gas inside the vacuum chamber 32 is stable, when the lower electrode 33 is supplied with electric power having a specific frequency using the power source 35, a plasma discharge is formed between the lower electrode 33 and the upper electrode 34, by absorbing moisture. The moisture-repellent film 3 is deposited on the substrate 2 to form a film.

Further, the plasma CVD apparatus shown in Fig. 7 is formed by forming a sheet-shaped hygroscopic base material 2, but a coil type plasma CVD apparatus may be used.

Fig. 8 is a view showing the configuration of another example of a plasma CVD apparatus which is formed by plasma chemical vapor deposition in the present embodiment. In FIG. 8, the plasma CVD apparatus includes a vacuum chamber 50 having a film formation region, and a delivery roller 51, a take-up roller 52, and a guide roller 61 for transporting the moisture-absorbing substrate 2 in the vacuum chamber 50. The transport system that constitutes it. In the film formation region, the lower electrode 53 and the coating drum (upper electrode) 54 which also serves as the upper electrode are connected to a power source. Further, the vacuum chamber 50 is provided with an oil rotary pump such as an oil rotary pump or a turbo molecular pump connected to the exhaust valve 55b, and an oil rotary pump connected to the exhaust valve 55a in the film formation region. An exhaust device 56a such as a turbo molecular pump and gas introduction ports 57a, 57b, and 57c for introducing a material gas into the film formation region. The gas introduction ports 57a, 57b, and 57c are connected to the additive gas supply sources 58a, 58b, and 58c, and are connected to the film formation material supply sources 59a and 59b through the flow meters 60a and 60b and the vaporizers 61a and 61b.

Next, a method of manufacturing the moisture-proof substrate 1 using such a plasma CVD apparatus will be described. First, the moisture-absorbing base material 2 is attached to the transport system of the plasma CVD apparatus so that the film formation surface becomes the outer side of the coating drum 54. Next, the inside of the vacuum chamber 50 is depressurized to a specific degree of vacuum by the exhaust devices 56 and 56 ' . Then, the gas supply sources 58a, 58b, and 58c are used to adjust the flow rate by flow meters such as 62a, 62b, and 62c, and then oxygen gas, carbon monoxide, carbon dioxide, methane, ethylene, or the like is supplied, and the flow rate of the film forming material supply sources 59a and 59b is used as a flow meter. The flow rate of the flowmeters 60a and 60b is adjusted, and the film-forming raw material containing the organic fluorene monomer is supplied as a gas by the gasifiers 61a and 61b, and introduced through the gas introduction ports 57a, 57b, and 57c, and the exhaust device 56a is controlled. The degree of opening and closing of the exhaust valves 55a and 55b between the 56b and the film forming zone maintains the film forming zone at a specific pressure. Then, the hygroscopic substrate 2 is transported in a desired direction, and electric power having a specific frequency is applied to the coating drum (upper electrode) 54 and the lower electrode 53 of the film formation region by the power source. Thereby, the film formation source gas and the additive gas are introduced into the film formation region, and plasma discharge is formed between the lower electrode 53 and the coating drum (upper electrode) 54. Next, the moisture-proof film 3 is formed on the absorbent substrate 2 to be conveyed.

In any of the plasma CVD apparatuses, the film formation of the moisture-proof film 3 is preferably such that the discharge frequency is 10 Hz or more and 300 kHz or less in such a manner that excellent adhesion can be obtained by the effect of inserting ions into the moisture-absorbing substrate 2.

Further, in the vicinity of the surface on which the moisture-proof film 3 of the absorbent substrate 2 is formed, a magnetron mechanism is provided to form a plasma discharge, and it is preferable to improve the productivity and reduce the production cost. That is, by forming a magnetron discharge mechanism to form a plasma discharge, the plasma density is increased to increase the film formation speed. Further, with the arrangement position of the magnetron, it is possible to reduce the damage to the film-formed substrate, and conversely, it is possible to enhance the damage to the film-formed substrate to improve the adhesion to the film-formed substrate. .

Further, when the moisture-proof film 3 is formed, it is preferable that the upper electrode 34 of FIG. 7 in contact with the moisture-absorbing substrate 2 and the coating roller 54 of FIG. 8 are cooled by providing a cooling mechanism. By simultaneously forming the moisture-proof film 3 by the lower electrode 33 of FIG. 7 in contact with the moisture-absorbing substrate 2 and the coating roller 54 of FIG. 8, the heat damage to the moisture-absorbing substrate 2 can be further reduced, and the prevention can be reduced. Deformation or undulation of the wet substrate 1.

An organic tantalum compound is used as a film-forming raw material used for forming a moisture-proof film by a plasma chemical vapor deposition method. In particular, it is easy to introduce the carbon content of the moisture-proof film 3, so that it is suitable for the organic fluorene monomer. As the organic ruthenium compound constituting the monomer gas for film formation, for example, 1.1.3.3-tetramethyldioxane, hexamethyldioxane (HMDSO) or vinyltrimethylnonane can be used alone or in combination. , methyltrimethylnonane, hexamethyldioxane, methyl decane, dimethyl decane, trimethyl decane, diethyl decane, propyl decane, phenyl decane, vinyl triethoxy decane, ethylene Trimethoxy decane, tetramethoxy decane, tetraethoxy decane, phenyl trimethoxy decane, methyl triethoxy decane, octamethylcyclotetraoxane, hexamethyldioxane, etc. .

In the present embodiment, 1.1.3.3-tetramethyldioxane or hexamethyldioxane is used in the above organic ruthenium compound because of its handleability or characteristics of a continuous film formed, etc. Excellent raw materials. Further, in the present embodiment, as the inert gas, for example, argon gas, helium gas or the like can be used. Further, as the additive gas, oxygen, carbon monoxide, carbon dioxide, water, methane, ethylene or the like can be used.

Further, in the present embodiment, in order to adjust the carbon content of the moisture-proof film, oxygen, carbon monoxide, carbon dioxide, methane, ethylene or the like may be added as an additive gas to the film-forming material gas at the time of film formation. The type of the organic fluorene monomer contained in the film-forming material gas for forming the moisture-proof film is appropriately selected, and an appropriate amount of an additive gas such as oxygen, carbon monoxide, carbon dioxide, methane or ethylene can be added to form a film suitable for moisture-proof film. Carbon content Moisture proof film. In the moisture-proof substrate 3, the moisture-proof substrate 1 exhibits a function of lowering the moisture permeability (water vapor transmission rate) of the moisture-proof substrate 1 itself. In addition, in order to prevent intrusion of moisture into the hygroscopic base material 2, the function of reducing the warpage of the moisture-proof substrate caused by moisture absorption/drying of the moisture-absorbing base material 1 is exhibited.

The yttrium oxide film formed as described above is mainly detected by X-ray photoelectron spectroscopy, and is mainly detected as a film of yttrium, oxygen, and carbon, and Si-O- which is generally detected as an infrared absorption spectrum. The absorption peak caused by the stretching vibration of Si is 1045 to 1060 cm ^-1 , and the absorption peak caused by the stretching vibration of Si-CH ₃ is 1274 ± 8 cm ^-1 . The cerium oxide film containing a carbon component of the present embodiment has a carbon content of 2.0 at% or more and 20.0 at% or less as measured by X-ray photoelectron spectroscopy, and carbon is present in a form of Si-CH ₃ bonding.

In addition, in the present embodiment, the yttrium oxynitride film is mainly detected by X-ray photoelectron spectroscopy, and a film of ruthenium, oxygen, nitrogen, and carbon is mainly detected, which is generally detected according to infrared absorption measurement. The absorption peak due to Si-O and Si-N stretching vibration of the infrared absorption spectrum is in the range of 830 to 1060 cm ^-1 , and the absorption peak due to the stretching vibration of Si-CH ₃ is 1274 ± 8 cm ^-1 . The carbon oxynitride film of the present embodiment has a carbon content of 2.0 at% or more and 20.0 at% or less as measured by X-ray photoelectron spectroscopy, and carbon is present in a form of Si-CH ₃ bonding.

The carbon contained is in the form of Si-CH ₃ bonding, and is also characterized by plasma chemical vapor deposition. That is, when a film of yttrium oxide or yttrium oxynitride is formed, a carbon atom contained in a film-forming source gas or an additive gas, or a decomposition product such as an ion species formed by a plasma at the time of film formation is etched to etch a substrate surface. The carbon atoms are taken into the film to form a Si-CH ₃ bond. According to this feature, the water repellency of the Si-CH ₃ bond formed on the surface of the film reduces the adsorption of water vapor on the surface of the moisture-proof film, thereby greatly reducing the water molecules diffused into the moisture-proof film. In other words, since the intrusion of moisture into the moisture-absorbing substrate 2 is greatly reduced, the warpage of the moisture-proof substrate caused by moisture absorption/drying of the moisture-proof substrate 1 can be reduced to such an extent that it does not cause a problem.

Further, the ruthenium oxide film or the yttrium oxynitride film contains carbon in a form in which Si-CH _{3 is} bonded, and is considered to be tempered and absorbed as compared with the case where a film composed only of an inorganic compound is used as the moisture-proof film 3 . The difference in heat shrinkage ratio (thermal expansion coefficient) of the wet substrate 2 also exhibits an effect of alleviating warpage due to a temperature difference.

When the carbon content ratio is less than 2.0 at% by the X-ray photoelectron spectroscopy, the adsorption of moisture to the surface of the moisture-proof film 3 cannot be sufficiently reduced, so that the moisture permeability is high. In addition, the organic component in the moisture-proof film 3 is reduced, so that the flexibility of the moisture-proof film 3 is lowered, and the moisture-proof film 3 is easily cracked, which causes a problem that barrier properties such as an increase in moisture permeability are lowered. In other words, it becomes difficult to sufficiently reduce the warpage caused by moisture absorption/drying of the moisture-proof substrate 1 . The carbon content is preferably 2.4 at% or more.

When the carbon content ratio measured by the X-ray photoelectron spectroscopy method is larger than 20.0 at%, the organic film property of the moisture proof film becomes strong, the denseness of the film is lowered, and the moisture permeability is increased, thereby causing a problem that the gas barrier property is lowered. So not good. The carbon content is preferably 18.0 at% or less.

Whether or not the moisture-proof film 3 has a specific carbon content can be confirmed by determining the ratio of the atomic numbers of Si, O, C, and N. As a method of obtaining the atomic ratio in this manner, a previously known method can be used, and this embodiment can be used. The state is evaluated by the results obtained by an analytical device such as an X-ray photoelectron analyzer (XPS). In the present embodiment, the measurement of XPS was carried out by XPS (ESCA LAB220i-XL manufactured by VG Scientific). As the X-ray source, a MgKα line of an X-ray source having an Ag-3d-5/2 peak intensity of 300 Kcps to 1 Mcps was used, and a slit having a diameter of about 1 mm was used. The measurement is performed in a state where the detector is placed on the normal line of the sample surface to be measured, and appropriate charging correction is performed. The analysis after the measurement was carried out using a software Eclipse version 2.1 attached to the XPS device, using a peak corresponding to the binding energy of Si: 2p, C: 1s, N: 1s, and O: 1s. At this time, among the peaks of C:1s, the peak shifts are corrected based on the peak corresponding to the hydrocarbon, and the combined states of the peaks are assigned. Next, the background of Shirley was removed for each peak, and the sensitivity coefficient of each element was corrected for the peak area (Si = 1.07, N = 1.77, O = 2.85 with respect to C = 1.0), and the atomic ratio was obtained. With respect to the obtained atomic ratio, the atomic number of Si, C, N, and O was 100, and the atomic composition percentage of C was determined.

The thickness of the moisture-proof film 3 of the present embodiment can be measured by a contact type step meter, and specifically, a step meter (DEKTAK IIA manufactured by Ulvac Co., Ltd.) is used for measurement. Next, the scanning range was set to 2 mm, and the scanning speed was set to low speed (Low). In the present embodiment, the film thickness of the moisture proof film is required to be 30 nm or more. When the film thickness of the moisture-proof film 3 is thinner than 30 nm, sufficient moisture resistance cannot be obtained. On the other hand, when the film thickness of the moisture-proof film 3 is 500 nm or more, productivity may be remarkably lowered. The film thickness of the moisture proof film 3 is 100 nm or more Very good below 300nm.

(hard layer)

The hard coating layer 4 may be arbitrarily provided on the moisture-proof substrate 1 according to the present invention in order to prevent the surface of the polarizing plate from being damaged or the like. The hard coat layer 4 is provided on at least one side of the moisture-proof substrate 1. More specifically, the hard coat layer 4 may be provided on the surface of the moisture absorbent base material 2 on which the moisture proof film 3 is formed. Thereby, the moisture-proof substrate 1 is protected by the hard coating 4, and as a result, the moisture-proof substrate 1 which is not easily damaged can be provided.

For example, the hard coating layer 4 can be formed by adding a hardened film having excellent hardness or slidability such as a suitable ionizing radiation-curable resin to the surface of the transparent protective film. As the hard coat layer 4, those known in the past can be used as appropriate. Specifically, as the material of the hard coat layer 4, those having an acrylate-based functional group of the ionizing radiation-curable resin, that is, those having an acrylic skeleton, and having an epoxy skeleton are preferable, and the hard coat layer 4 is considered. In the case of hardness, heat resistance, solvent resistance, and scratch resistance, a structure having a high bridging density is preferred. Examples of the material for obtaining such a structure include ethylene glycol di(meth)acrylate, 1,6-hexanediol diacrylate, and trimethylolpropane tri(meth)acrylate. An acrylate monomer having two or more functional groups such as Pentaerythritol tri(metha)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

As the material of the hard coat layer 4, the aforementioned ionizing radiation is used. In the case of a wire-curable resin, a known photopolymerization initiator or a photosensitizer can be used in combination. Such a photopolymerization initiator or a photosensitizer is suitably used in the case where ultraviolet rays are irradiated to cure the ionizing radiation-curable resin. When the electron beam is irradiated, the ionizing radiation-curable resin tends to be sufficiently hardened. The addition amount of the photopolymerization initiator or the photosensitizer is generally 0.1 parts by weight or more and 10 parts by weight or less based on 100 parts by weight of the ionizing radiation-curable resin. In addition to such a material, various inorganic or organic additives such as a solvent, a curing catalyst, a wettability improver, a plasticizer, an antifoaming agent, and a tackifier may be added as necessary.

The hard coat layer 4 can be formed by applying the above-mentioned material as a coating liquid to the moisture-proof substrate 1 to be cured. The coating amount of the coating liquid is usually preferably 0.5 g/m ² or more and 15.0 g/m ² or less in terms of the solid content. Moreover, as an ultraviolet source used for hardening, an ultrahigh pressure mercury lamp etc. are mentioned, for example. For the wavelength of the ultraviolet light, a wavelength region of 190 nm or more and 380 nm or less can be used. For example, various electron beam accelerators such as a Cockcroft-Walton type can be used as the electron beam source.

The thickness of the hard coat layer 4 is usually 1 μm or more, preferably 3 μm or more, or usually 10 μm or less, and preferably 8 μm or less. When it is in this range, the transparency of the moisture-proof substrate 1 is not easily impaired, and the scratch resistance is also likely to be good.

(optical adjustment layer)

Further, in the moisture-proof substrate 1 according to the present invention, anti-reflection is provided The optical adjustment layer 5 such as a film or an anti-glare film may be used. The optical adjustment layer 5 is provided for the purpose of preventing reflection of external light, and is realized by the formation of the optical adjustment layer 5 in the past. For example, the anti-glare layer of one of the anti-glare films is provided for the purpose of preventing external light from being reflected on the surface of the polarizing plate and obstructing the identification of the transmitted light of the polarizing plate. The anti-glare layer can be formed, for example, by applying a fine uneven structure to the surface of the transparent protective film by a smoothing method or a method of blending transparent fine particles by a sandblasting method or a press working method.

Examples of the transparent fine particles include cerium oxide or aluminum oxide having an average particle diameter of 0.5 μm to 20.0 μm, titanium oxide or zirconium oxide, tin oxide or indium oxide, cadmium oxide or cerium oxide, and the like. Inorganic fine particles may be used, and organic fine particles such as bridged or unbridged polymer particles may be used. The amount of the transparent fine particles to be used is generally from 2 parts by mass to 70 parts by mass, and more preferably from 5 parts by mass to 50 parts by mass per 100 parts by mass of the transparent resin.

The anti-glare layer to which the transparent fine particles are blended may be provided as a layer which also serves as a hard coat layer, or as a coat layer on the surface of the moisture-proof base material 1. The anti-glare layer can also serve as a diffusion layer (viewing angle compensation function, etc.) for diffusing the viewing angle of the diffusing polarizing plate through the light. Further, the antireflection layer, the anti-sticking layer, the diffusion layer, the anti-glare layer, or the like may be an individual different from the transparent protective layer as an optical layer composed of a sheet or the like provided with these layers.

(other film)

Other than the hard coat layer 4 and the optical adjustment layer 5 described above, other films may be used as necessary. Examples of such a film include an antifouling film 6, an antistatic film, and a smoothing film. These antifouling film 6 and antistatic film can also be bonded to the moisture-proof substrate 1 of the present embodiment by an optical adhesive to obtain a desired function.

Such other films may be formed on the surface of the hard coat layer 4 as long as they are appropriately used. However, it is also possible to attach an anti-reflection function or a viewing angle control function or the like to the hard coat layer 4.

The antireflection film has a function of suppressing the reflection of external light, and the antistatic film has a function of preventing adhesion of dust or the like, and the antifouling film is resistant to an adhesive such as a fingerprint, and is generally known to be used as it is, and most of them are formed. On the surface of the hard coating 4. However, an anti-reflection function, a transparent conductive function, or the like may be attached to the hard coat layer 4. The smoothing film is used to flatten the surface, and is formed, for example, on the surface of the moisture-proof film 3.

[Polarizer]

In the present embodiment, as illustrated in FIG. 5, the polarizing plate 10 includes a polarizer 11 having a polarizing function capable of passing only polarized light in a specific direction or a polarized light, and moisture shielding applied to the polarizer 11. Substrate 1. The moisture-proof substrate 1 is used for the purpose of protecting the polarizer 11 from moisture and making the polarizing plate 10 rigid. Generally, as the polarizer 11, a uniaxially stretched polyvinyl alcohol or the like is generally used. Such a polarizer has disadvantages such as easy cracking in the direction of the extension axis and poor water resistance, and is thin and weak on the strength surface. In the present invention, in order to compensate for these disadvantages, the moisture-proof substrate 1 is used. Both sides of the sandwiched polarizer 11 are used as the polarizing plate 10. The hygroscopic base material 2 which is a base film of the moisture-proof base material 1 is made of cellulose triacetate (hereinafter also referred to as TAC) from the viewpoints of transparency, adhesion, moisture impermeability and the like.

As the polarizer 11, for example, an iodine or a dichroic dye is applied in an appropriate order or manner using a film composed of a suitable vinyl alcohol polymer such as polyvinyl alcohol or partially formalized polyvinyl alcohol. An appropriate treatment such as a dyeing treatment, an extension treatment, or a bridging treatment by the dichroic material is performed, and an appropriate material that transmits linearly polarized light when natural light is incident. In particular, it is preferred that the light transmittance or the degree of polarization is excellent.

The thickness of the polarizer 11 and the moisture-proof substrate 1 provided on one or both sides thereof is preferably 135 μm or less. Although the polarizer 11 is preferably a thickness of about 15 to 30 μm, the thickness of the moisture-proof substrate 1 is preferably 60 to 25 μm, and more preferably 50 to 25 μm. When the moisture-proof substrate 1 is formed on both sides of the polarizer 11, the thickness of the moisture-proof substrate 1 is almost twice the total value of the front and back, and the polarizer is considered in consideration of the thickness of the adhesive layer. In the state where the moisture-proof substrate 1 is formed on both sides of the eleventh, the thickness of the polarizer 11 or the moisture-proof substrate 1 is appropriately selected so that the total thickness of the obtained polarizing plate 10 is 135 μm or less. When the thickness of the moisture-proof substrate 1 is too small, the production becomes difficult, and the handleability is deteriorated. Therefore, it is usually preferable to be thinner than 25 μm.

As the hygroscopic substrate 2 such as the base film of the moisture-proof substrate 1 provided on one side or both sides of the polarizer 11, an appropriate transparent film should be used. As an example of the polymer, an acetate system such as cellulose triacetate is generally used. Resin, but not limited to this.

Only subtly controlling the birefringence of the photon is required to have no birefringence for the TAC film. When the film is formed by extrusion molding by a general method of polymer film, the molecules of the resin are aligned in a certain direction, and birefringence occurs. Here, as a method for producing a TAC film, a solution casting film forming method in which a polymer is dissolved in a solvent and spread thinly on a wide plate to volatilize a solvent to form a film is generally used.

The polarizer 11 and the moisture-proof substrate 1 are in particular a polyvinyl alcohol-based adhesive or an urethane-based adhesive, followed by a moisture-proof substrate 1 composed of a cellulose triacetate film.

The polarizing plate 10 according to the present embodiment can be used as an optical member laminated with other optical layers at the time of application. The optical layer is not particularly limited, and for example, a reflector or a semi-transmissive reflector, a phase difference plate (including a λ plate such as a 1⁄2 wavelength plate or a 1⁄4 wavelength plate), a visual compensation film, or a brightness enhancement plate can be used. For example, a suitable optical layer 1 or more layers for forming a liquid crystal display panel or the like, in particular, the polarizing plate 10 composed of the polarizer 11 and the moisture-proof substrate 1 of the present embodiment described above, Further, a reflective polarizing plate or a transflective polarizing plate which is formed by laminating a reflecting plate or a semi-transmissive semi-reflecting plate, and polarizing light composed of the polarizer 11 and the moisture-proof substrate 1 of the present embodiment described above are polarized. On the plate 10, an elliptical or circular polarizing plate in which a phase difference plate is laminated is further laminated on the polarizing plate 10 composed of the polarizing plate 11 of the present embodiment and the moisture-proof substrate 1 to be laminated. The polarizing plate 10 is formed on the polarizing plate 10 composed of the polarizer 11 and the moisture-proof substrate 1 of the present embodiment. Further, the polarizing plate 10 in which the brightness enhancement film is laminated is preferable.

In the polarizing plate 10 according to this embodiment, an adhesive layer for use in connection with other members such as the liquid crystal cell 21 may be provided. The adhesive layer can be formed by an appropriate adhesive such as acrylic or the like. In particular, it is possible to prevent a foaming phenomenon or a peeling phenomenon caused by moisture absorption, and to prevent deterioration of optical characteristics or warpage of liquid crystal cells due to poor thermal expansion or the like, and even formation of liquid crystal display panel 20 having high quality and excellent durability. In view of the above, an adhesive layer having a low moisture absorption rate and excellent heat resistance is preferred. Further, it may be an adhesive layer containing fine particles exhibiting light diffusibility. The adhesive layer can be placed on the necessary surface as long as necessary.

When the adhesive layer provided on the polarizing plate 10 is exposed on the surface, it is preferable to temporarily cover the partition plate for the purpose of preventing contamination during the period in which the adhesive layer is supplied for practical use. The separator may be provided by a suitable release sheet according to the transparent protective film or the like, if necessary, by a polyether or a long-chain alkyl group, a fluorine-based or molybdenum sulfide, or the like according to a suitable release agent. The way to wait to form.

Further, each of the polarizing plate 10, the polarizer 11 forming the optical member, the moisture-proof substrate 1, the optical layer, and the adhesive layer is, for example, a salicylate-based compound, an benzophenone-based compound, or a benzotriazole-based compound. The compound, the cyanoacrylate compound, the nickel complex salt compound, or the like may be subjected to ultraviolet absorbing energy or the like by an appropriate method such as treatment with an ultraviolet absorber.

According to the polarizing plate 10 of the present embodiment, it can be suitably used for formation of various devices such as the liquid crystal display panel 20 and the like.

[Liquid Crystal Display Panel]

As shown in FIG. 6, the liquid crystal display panel 20 of the present embodiment can be formed by arranging the polarizing plate 10 according to the present embodiment on one side or both sides of the liquid crystal cell 21, or through transmission or reflection. The /reflective dual-purpose type or the like has an appropriate constructor according to the former method. In other words, the liquid crystal cell 21 forming the liquid crystal display panel 20 is arbitrary. For example, an active matrix driving type represented by a thin film transistor type or a simple one represented by a twisted nematic or super twisted nematic type may be used. A liquid crystal cell 21 of a suitable form such as a matrix-driven type.

Further, in the case where the polarizing plate 10 is provided on both sides of the liquid crystal cell 21, those may be the same or different. Further, at the time of forming the liquid crystal display panel 20, for example, one or two or more layers of appropriate components such as a ruthenium array sheet, a lens array sheet, a light diffusion plate, or a backlight may be disposed at appropriate positions.

The use of the moisture-proof substrate according to the present invention is not particularly limited. However, it is suitable for use in a thin and lightweight type, and it is required to have high moisture resistance and does not cause deformation such as warpage. In addition to the liquid crystal display panel described above, for example, it is widely applicable to an electronic display such as an organic EL.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples and the like, but the invention is not limited to the following examples.

[Example 1]

As the hygroscopic substrate, a cellulose triacetate (TAC) film having a thickness of 40 μm was used. On the hygroscopic substrate, a ruthenium oxide film is formed as a moisture-proof film by plasma chemical vapor deposition. The plasma chemical vapor deposition method uses a parallel plate type plasma CVD apparatus as shown in Fig. 7, so that the distance between the electrode plates is 25 mm. The hygroscopic substrate is placed on the lower electrode, and the vacuum chamber is evacuated by a vacuum pump to a degree of vacuum of 1 × 10 ^-2 Pa or less. Thereafter, hexamethyldioxane 2 sccm was used as a film forming material gas, and 10 sccm of argon gas and 30 sccm of oxygen gas were introduced into the electrodes from the gas introduction port 38 as an additive gas, and the opening degree of the exhaust valve of the vacuum chamber was adjusted. The pressure in the vacuum chamber was set to 7 Pa. Then, a plasma discharge device was formed under the conditions of a frequency of 40 kHz and an input power of 200 W, and a ruthenium oxide film having a film thickness of 102 nm was formed as a moisture-proof film to prepare a moisture-proof substrate 1 .

[Embodiment 2]

In Example 1, a ruthenium oxide film having a thickness of 103 nm was formed on one surface of the hygroscopic substrate (described as the surface in Table 1), and a film thickness of 102 nm was formed on the other surface (described as the back surface in Table 1). A moisture-proof substrate 2 was produced in the same manner as in Example 1 except for the ruthenium oxide film.

[Example 3]

In the same manner as in Example 1, except that the film forming material gas was changed to hexamethyldioxane 2 sccm, and the moisture absorbing film was formed to have a film thickness of 100 nm. Substrate 3.

[Example 4]

In Example 3, a yttrium oxynitride film having a film thickness of 105 nm was formed on one surface of the moisture absorbing substrate (described as the surface in Table 1), and a film thickness was formed on the other surface (described as the back surface in Table 1). A moisture-proof substrate 4 was produced in the same manner as in Example 3 except for a 101 nm yttrium oxide film.

[Example 5]

In Example 1, except that the amount of oxygen added when the ruthenium oxide film was formed was increased to 75 sccm, and the moisture-proof film having a film thickness of 103 nm having a carbon content of 2.4 at% as described below was used, and Examples 1 was carried out in the same manner to prepare a moisture-proof substrate 5.

[Embodiment 6]

In Example 1, except that the amount of oxygen added when the ruthenium oxide film was formed was increased to 35 sccm, and the moisture-proof film having a film thickness of 78 nm having a carbon content of 12.3% as described below was used, and Example 1 In the same manner, the moisture-proof substrate 6 was produced.

[Embodiment 7]

In Example 1, except that the amount of oxygen added when the ruthenium oxide film was formed was increased to 40 sccm, and the moisture-proof film having a film thickness of 50 nm having a carbon content of 7.8% as measured below was used, and Example 1 In the same manner, the moisture-proof substrate 7 was produced.

[Embodiment 8]

In the same manner as in Example 1, except that the moisture-proof film was formed so that the film thickness of the yttrium oxide film was 195 nm, the moisture-proof substrate 8 was produced.

[Embodiment 9]

In the same manner as in Example 1, except that the moisture-proof film was formed so that the film thickness of the yttrium oxide film was 308 nm, the moisture-proof substrate 9 was produced.

[Comparative Example 1]

In the same manner as in Example 1, except that the moisture-proof film was formed so that the film thickness of the yttrium oxide film was 25 nm, the moisture-proof substrate 10 was produced.

[Comparative Example 2]

In Example 1, except that the amount of oxygen added when the ruthenium oxide film was formed was reduced to 6 sccm, and the moisture-proof film having a film thickness of 102 nm having a carbon content of 25.2 at% as measured below was used, and Examples 1 was carried out in the same manner, and the moisture-proof substrate 11 was produced.

[Comparative Example 3]

As the hygroscopic substrate, a cellulose triacetate film having a thickness of 40 μm was used. On the hygroscopic substrate, a ruthenium oxide film was formed as a moisture-proof film by a vacuum deposition method. The hygroscopic substrate was placed in a film forming vacuum chamber, and SiO was used as a film forming material of the moisture proof film, and oxygen was simultaneously added to form a film. At this time, the distance between the hygroscopic substrate and the film forming material was set to 500 mm. A hygroscopic substrate and a vapor deposition material are placed in a vacuum chamber, and evacuated to a temperature of 1×10 ⁻³ Pa or less, and then the vapor deposition material is heated by an EB (electron beam) gun to evaporate, and 20 sccm of oxygen is introduced. Reactive vapor deposition was carried out to form a ruthenium oxide film having a film thickness of 105 nm as a moisture-proof film, and a moisture-proof substrate 12 was produced.

[Comparative Example 4]

In Comparative Example 3, a ruthenium oxide film having a thickness of 103 nm was formed on one surface of the hygroscopic substrate (described as the surface in Table 1), and a film thickness of 103 nm was formed on the other surface (described as the back surface in Table 1). A moisture-proof substrate 13 was produced in the same manner as in Comparative Example 3 except for the ruthenium oxide film.

[Comparative Example 5]

As the hygroscopic substrate, a cellulose triacetate film having a thickness of 40 μm was used. On the hygroscopic substrate, a ruthenium oxide film is formed as a moisture proof film by a sputtering method. The hygroscopic substrate is placed in a film forming vacuum chamber, and the vacuum chamber is evacuated to 1 × 10 ^-3 Pa or less, and ruthenium is introduced as a film forming target material, and argon gas and oxygen as a reaction gas are introduced to form a film. The pressure was 0.3 Pa, and the input electric power was 2 kW. A ruthenium oxide film having a film thickness of 105 nm was formed as a moisture-proof film by a double magnetron sputtering method (frequency: 40 kHz), and a moisture-proof substrate 14 was produced.

[Comparative Example 6]

In Comparative Example 5, a ruthenium oxide film having a thickness of 105 nm was formed on one surface of the hygroscopic substrate (described as the surface in Table 1), and a film thickness of 105 nm was formed on the other surface (described as the back surface in Table 1). A moisture-proof substrate 15 was produced in the same manner as in Comparative Example 5 except for the ruthenium oxide film.

[Measurement of film thickness of moisture proof film]

For the hygroscopic substrates 1 to 15 obtained as described above, a step difference meter (DEKTAK IIA manufactured by Ulvac) was used, and the scanning range was set to 2 mm, and the scanning speed was set to a low speed (Low). The film thickness of the moisture proof film. The film thickness measured is shown in the column of "film thickness" in Table 1.

[Evaluation of flatness after film formation]

The flatness was evaluated for the hygroscopic substrates 1 to 15 as described above. First, the moisture-proof substrate was cut out to 15 cm × 15 cm to obtain a moisture-proof substrate sample 72 shown in Fig. 9 . Next, as shown in the figure, the moisture-proof substrate sample 72 was placed on a stainless steel substrate 71, and the orthogonal distance between the vertex 8 of the moisture-proof substrate sample 72 and the stainless steel substrate 71 was measured. In addition, the undulations were observed visually. Next, in accordance with the magnitude of the orthogonal distance L and the state of the undulation, the degree of occurrence of curl of the hygroscopic substrate was evaluated in accordance with the following evaluation criteria.

Good: The orthogonal distance L is 1 mm or less and no undulations are observed.

Bad: The orthogonal distance L is larger than 1mm, or it is seen to be undulating.

The evaluation results are shown in the column of "post-filming flatness" in Table 1.

[Moisture resistance evaluation]

For the hygroscopic substrates 1 to 15 as shown in the above, the moisture permeability was measured in accordance with Japanese Industrial Standard JIS Z 0208 "Test method for moisture permeability of moisture-proof packaging materials" at 25 ° C and 90% RH, and evaluated. Moisture resistance. The results of the evaluation are shown in the column of "Trans-humidity" in Table 1.

[Measurement of carbon content]

The moisture-absorbing substrate 1 to 15 obtained as described above is subjected to argon gas to remove the contaminant adsorbed on the surface of the moisture-proof film, and then the composition of the moisture-proof film is analyzed by an X-ray photoelectron spectroscopy apparatus to determine the content. Carbon rate. The measurement of the carbon content was carried out by using XPS (ESCA LAB220i-XL manufactured by VG Scientific). As the X-ray source, a MgKα line of an X-ray source having an Ag-3d-5/2 peak intensity of 300 Kcps to 1 Mcps was used, and a slit having a diameter of about 1 mm was used. The measurement is performed in a state where the detector is placed on the normal line of the sample surface to be measured, and appropriate charging correction is performed. The analysis after the measurement was carried out using a software Eclipse version 2.1 attached to the XPS device, using a peak corresponding to the binding energy of Si: 2p, C: 1s, N: 1s, and O: 1s. Among the peaks of C:1s, the peak displacement is corrected based on the peak corresponding to the hydrocarbon, and the combined state of the peaks is assigned. Next, for each peak, the background of Shirley is removed, and the sensitivity coefficient of each element is performed on the peak area. Correction (with respect to C = 1.0, using Si = 0.87, N = 1.77, and O = 2.85), the atomic ratio was obtained. With respect to the obtained atomic ratio, the atomic number of Si, C, N, and O was 100, and the atomic composition percentage of C was determined. The carbon content (at%) of the moisture-proof film calculated by the analysis is shown in Table 1.

[Panel Evaluation]

The liquid crystal display panel shown in Fig. 6 was produced using the hygroscopic substrate obtained as described above, and stored in an environmental tester at 60 ° C and 90% RH for one week. Thereafter, the panel display state was visually confirmed, and it was evaluated whether or not the display portion was whitened. The evaluation criteria are as follows.

Good: no whitening was seen on the display.

Bad: The display is visible and whitened.

The results of the assessment are shown in the column of “Panel Evaluation” in Table 1.

1‧‧‧Moisture-proof substrate

2‧‧‧Hygroscopic substrate

3‧‧‧Dampproof film

Claims (6)

A method for producing a moisture-proof substrate, comprising: comprising at least one side of a hygroscopic substrate having a water absorption ratio of 1% or more, formed by a plasma chemical vapor deposition method comprising a carbon content including 2.0 A moisture-proof film having a thickness of 30 nm or more of a cerium oxide film or a yttrium oxynitride film of a carbon component of at% or more and 20.0 at% or less. The method for producing a moisture-proof substrate according to the first aspect of the invention, wherein the film formation is carried out by a plasma chemical vapor deposition method using a film-forming material gas containing an organic germanium monomer. A moisture-proof substrate comprising: a moisture-absorbing substrate having a water absorption ratio of 1% or more; and a moisture-proof film formed on at least one side of the moisture-absorbing substrate; and the moisture-proof film The ruthenium oxide film or the yttrium oxynitride film containing a carbon component having a carbon content of 2.0 at% or more and 20.0 at% or less is included, and the film thickness is 30 nm or more. A moisture-proof substrate according to claim 3, wherein the moisture permeability in an environment of 25 ° C and 90% RH is 6.0 g / (m ² .24 h) or less. A polarizing plate characterized by having a moisture-proof substrate of claim 3 or 4. A liquid crystal display panel characterized by having a polarizing plate of claim 5th.