JP2002264246A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film which is light in weight and flexible, shows a small temperature dependence of a gas barrier property while showing the high gas barrier property and does not generate a toxic gas when the film is incinerated. SOLUTION: A gas barrier film has a gas barrier layer mounted on at least one surface of a substrate made of a plastic film wherein the gas barrier layer is made mainly of an oxide of indium and celium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier film used for packaging foods and medicines which require a barrier property against permeation of oxygen or water vapor, or used as a base material for liquid crystal display devices. . Further, the present invention relates to a gas barrier film having a gas barrier layer provided on at least one surface of a plastic film.

[0002]

2. Description of the Related Art A gas barrier film used for the above applications is required to have a high barrier property against permeation of oxygen and water vapor. That is, in food packaging, it is important to suppress the oxidation and deterioration of proteins and fats and oils to maintain taste and freshness, and in pharmaceutical packaging, it is important to suppress deterioration of active ingredients and maintain efficacy. In a liquid crystal display device, changing the substrate from glass to plastic is advantageous in terms of weight, impact resistance, and productivity, but for that purpose, the generation of display defects due to intrusion of air or the like into the liquid crystal cell. It is indispensable to prevent the liquid crystal cell from being damaged. In order to satisfy such requirements, polyvinyl alcohol (PVA) and ethylene vinyl alcohol copolymer (EV
OH) or a gas barrier polymer such as polyvinylidene chloride (PVDC) provided by lamination or coating, or a thin film of an inorganic compound such as silicon oxide (SiOx) formed by vapor deposition or sputtering. Used.

[0003] However, gas barrier films made of PVA or EVOH have a large dependence on the temperature and humidity of the gas barrier properties, and the gas barrier properties decrease at high temperatures or high humidity. In particular, the water vapor barrier property is remarkably reduced, and it is not suitable for use in boiling sterilization treatment or retort sterilization treatment or for food packaging with high water activity containing a large amount of water in the contents. In the case of a gas barrier film using PVDC, the humidity dependence is small, but it is difficult to obtain a high gas barrier property. In addition, since a large amount of chlorine is contained, waste gas treatment such as incineration and recycling is required. There is a problem in terms. On the other hand, a gas barrier film formed of a thin film of an inorganic compound such as SiOx has a better gas barrier property and a lower temperature / humidity dependency than those using a gas barrier polymer, but has a high gas barrier property such as a substrate for a liquid crystal display device. Is not enough to use for the applications where is needed. In addition, SiO
In many cases, the thin film of x is colored light yellow, which not only impairs the transparency but also has a problem that it is associated with the deterioration of the contents.

[0004] As a high gas barrier film for packaging, an aluminum foil or an aluminum vapor-deposited film is also used. However, these are opaque and the contents cannot be visually checked, and the foreign matter by a metal inspection machine after the contents are filled. (Metal pieces) Inability to inspect, content heating by microwave oven (microwave) not possible, aluminum melted in the incineration process after use and accumulated in the furnace bottom, damaging the incinerator Problem.

On the other hand, a glass substrate is used for a liquid crystal display element. However, the glass substrate is heavy and may be damaged during carrying with an electronic organizer or a mobile phone.
There are problems that it cannot be applied to a display having a curved surface, and that it is expensive because continuous production by winding is not possible.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and an object of the present invention is to make a glass base material by using a plastic film as a base material. Providing a gas barrier film that is lighter in weight, has excellent transparency and flexibility, has a high gas barrier property, has a small change in temperature and humidity, and does not generate toxic gas during incineration. Is to do.

[0007]

SUMMARY OF THE INVENTION The present invention has the above object.
The invention according to claim 1 for achieving
Is at least one piece of a substrate made of a plastic film
Gas barrier film with a gas barrier layer on the surface
The gas barrier layer is mainly composed of indium cerium
Gas barrier film characterized by being composed of a base oxide
It provides a system. The invention described in claim 2 is a
On at least one side of a substrate made of a plastic film
Gas barrier mainly composed of indium cerium oxide
Layer is formed, and a protective layer is further provided thereon.
To provide a gas barrier film characterized by
It is. The invention described in claim 3 is also applicable to claim 1.
Alternatively, based on the premise of the invention described in 2, the gas barrier
The surface of the film on the gas barrier layer and protective layer side is 1 × 1
0 ⁸It has a sheet resistance value of Ω / □ or more.
And a gas barrier film. Claim
The invention described in Item 4 is based on the invention described in Claims 1 to 3.
And the gas barrier layer is made of indium-cerium-based oxide.
As a main component, one or both of tin and titanium
Gas barrier filter comprising an oxide containing
It provides lum.

[0008] According to a fifth aspect of the present invention, the gas barrier layer comprises a first layer mainly composed of an indium-cerium-based oxide;
A water-soluble polymer and a second layer comprising at least one of (a) one or more metal alkoxides and hydrolysates thereof, and (b) tin chloride, are laminated. It is intended to provide a gas barrier film. The invention according to claim 6 is based on the invention according to claim 2, wherein the protective layer contains at least one of (a) one or more metal alkoxides and a hydrolyzate thereof, or (b) tin chloride. The gas barrier film according to claim 2, comprising a second layer made of a material. According to a seventh aspect of the present invention, there is provided a gas barrier film according to the fifth or sixth aspect, wherein the inorganic compound forming the first layer comprises only indium-cerium-based oxide. To provide. The invention according to claim 8 is based on the premise of claim 5 or 6, wherein the inorganic compound forming the first layer is mainly composed of indium-cerium-based oxide, and one of tin and titanium; Another object of the present invention is to provide a gas barrier film comprising an oxide containing both of them. According to a ninth aspect of the present invention, there is provided a gas-barrier film characterized in that the water-soluble polymer is polyvinyl alcohol, based on the premise of the fifth, sixth, seventh or eighth aspect. It is. According to a tenth aspect of the present invention, there is provided a gas barrier film according to the fifth or sixth aspect, wherein the metal alkoxide is tetraethoxysilane or triisopropoxyaluminum, or a mixture thereof. To provide.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, plastic films used as substrates include polyolefins (polyethylene, polypropylene, etc.) and polyesters (polyethylene terephthalate, polybutylene terephthalate).
, Polyethylene naphthalate, etc.), polyamide, polyimide, polyacrylate, polycarbonate, polyethersulfone, and the like, and non-stretched or stretched films of copolymers thereof. Selected. Especially for liquid crystal display devices, in addition to transparency and gas barrier properties, it has good heat resistance due to the application of heat in the process of forming a transparent electrode film and alignment film, because it is used in a deflection film It is required that the optical anisotropy (retardation) is small. Therefore, polyacrylate, polycarbonate, polyethersulfone,
A plastic film substrate is preferably used such as an amorphous polyolefin.

[0010] Such a plastic film may contain additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant and the like, if necessary. It may be modified by a system treatment, a chemical treatment, an anchor coat treatment or the like.

In the present invention, at least one surface of the plastic film as described above is provided with indium-cerium-based oxide or an oxide containing indium-cerium-based oxide as a main component and containing either or both of tin and titanium. A gas barrier layer of an inorganic compound layer made of is formed. Note that the gas barrier layer may be formed using only an inorganic compound layer, or may be formed as a gas barrier layer by adding another layer. In particular, the inorganic compound layer alone is weak in rubbing and bending due to lack of flexibility, cracks are generated during post-processing as a packaging material or a substrate for a liquid crystal display element, and gas barrier properties are reduced, or when used in portable applications. When a certain degree of flexibility is required, the water-soluble polymer and (a) 1
It is more effective to add a second layer comprising at least one of at least one of metal alkoxides and hydrolysates thereof, and (b) tin chloride. In addition, in order to aim for another effect or to express further high gas barrier properties,
It is also possible to replace or add the second layer to another gas barrier layer.

The inorganic compound layer in such a gas barrier layer may be any layer as long as it contains indium-cerium-based oxide as a main component and exerts the function and effect of the present invention. Therefore,
In general, the indium-cerium-based oxide is made of an oxide containing one or both of tin and titanium, and further contains a material such as another metal. At this time, when the material contained is intentionally mixed for the purpose of conductivity, gas barrier property, transparency, adhesion, etc., or even if it is not intended, the indium-cerium-based oxide An object is a main component and is included in the present invention. The composition of the inorganic compound layer has sufficient gas barrier properties so that the atomic ratio of indium and cerium in the content of all metal elements contained in the layer is in the range of 70 to 98 at% and 2 to 30 at%, respectively. Which are desired in the description, and are preferably 85 to 95 at% and 5 to 15 a, respectively.
t%, most preferably 87-92%, respectively 8-13
%. When one or both of the contents of indium and cerium deviate from this range, the gas barrier properties gradually decrease. In this case, the indium-cerium-based oxide is in an indium-cerium composite oxide state, but a mixture of indium oxide and cerium, a mixture of indium and cerium oxide,
A mixture formed by oxidizing a mixture of indium and cerium may be used, but a mixture of indium oxide and cerium oxide is preferable for obtaining uniform performance. When one or both of tin and titanium are contained in the layer, the content thereof is 7 at% of the total metal element.
Less than 3 at%, preferably 5 at% each.
%, Less than 1 at%. In any case, elements other than indium, cerium, tin, titanium, and oxygen may be contained as long as the gas barrier properties and the transparency are not impaired.

The method of forming such a gas barrier layer is not particularly limited, but includes indium-cerium-based oxide or one or both of tin and titanium with indium-cerium-based oxide as a main component. Film formation by direct current (DC) sputtering, alternating current (AC) sputtering, radio frequency (RF) sputtering, or the like using a target made of an oxide is also required in view of film quality such as gas barrier properties and transparency. This is also a suitable method from the viewpoint of. Since such an indium-cerium-based oxide target has conductivity, DC
Is also possible. In order to obtain a completely colorless and transparent film, supplying an oxidizing gas such as oxygen gas during sputtering is also an effective method. The thickness of such an inorganic compound layer is from 5 nm to 50 nm.
It is desirable that the thickness be within the range of 0 nm, but if it is less than 10 nm, it may become an island and not a continuous film. Since it may not be obtained, the thickness is preferably 10 nm to 300 nm.
When the second layer is provided on the inorganic compound layer, the second layer contains a water-soluble polymer and at least one of (a) one or more metal alkoxides and a hydrolyzate thereof, and (b) tin chloride.

A solution obtained by dissolving a water-soluble polymer and tin chloride in an aqueous (water or water / alcohol mixture) solvent, or a solution prepared by directly or preliminarily hydrolyzing a metal alkoxide. Is coated on an inorganic compound layer on a plastic film substrate, dried by heating and formed. Each component contained in the coating agent will be described in detail below.

The water-soluble polymer used in the coating agent includes polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. In particular, when polyvinyl alcohol (hereinafter, referred to as PVA) is used for the coating agent for the gas barrier film of the present invention, the gas barrier properties are most excellent. PVA here
Is generally obtained by saponifying polyvinyl acetate, and includes so-called partially saponified PVA in which acetic acid groups remain in several tens percent, to completely saponified PVA in which only a few percent of acetic acid groups remain, and is particularly limited. It is not something to be done. The tin chloride may be stannous chloride (SnCl ₂ ), stannic chloride (SnCl ₄ ), or a mixture thereof, and may be used as an anhydride or a hydrate.

The metal alkoxide is a general formula such as tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxy aluminum [Al (O-2′-C ₃ H ₇ ) ₃ ], M (OR) n (M: metal such as Si, Ti, Ai, Zr, R: alkyl group such as CH ₃ , C ₂ H ₅ ). Among them, tetraethoxysilane and triisopropoxyaluminum are preferable since they are relatively stable in an aqueous solvent after hydrolysis. Each of the above-described components can be added to the coating agent alone or in a combination of some, and as long as the gas barrier property of the coating agent is not impaired, an isocyanate compound, a silane coupling agent, or a dispersant, a stabilizer, Known additives such as a viscosity modifier and a coloring agent can be added.

For example, an isocyanate compound added to a coating agent has two or more isocyanate groups (NCO groups) in its molecule. For example, tolylene diisocyanate (hereinafter referred to as TDI), triphenylmethane triisocyanate (Hereinafter, referred to as TTI), tetramethylxylene diisocyanate (hereinafter, referred to as TTI)
TMXDI), and polymers and derivatives thereof.

As a method for applying the coating agent, conventionally known means such as a dipping method, a roll coating method, a screen printing method, and a spray method, which are usually used, are used. Although the thickness of the coating varies depending on the type of the coating agent, the thickness after drying may be in the range of about 0.01 to 100 μm. When the thickness is 50 μm or more, cracks are easily generated in the film. It is desirable that the thickness be 50 μm.

Although the details are not clear in many places, any reaction layer (interaction layer) is formed between the inorganic compound layer and the second layer, or a pin formed on the inorganic compound layer is formed on the inorganic compound layer. Filling and reinforcing defects, such as holes, cracks, grain boundaries, or micropores, forms a dense structure,
This also plays a role of improving the gas barrier properties and as a protective layer of the inorganic compound layer which is the inorganic compound layer.

Further, since the composition of the coating agent is mainly composed of an inorganic component such as metal alkoxide or tin chloride and a water-soluble polymer such as PVA, gas barrier properties can be improved. In other words, the inorganic component consisting of metal alkoxide or tin chloride undergoes hydrolysis and polycondensation reaction in a solution to form a chain or three-dimensional dendritic polymer, and the polymerization proceeds further by evaporation of the solvent accompanying drying and heating. It is an inorganic component rich in properties, and is considered to form a complex at the molecular level with a water-soluble polymer. Therefore, they are different from fine particles such as silica (SiO ₂ ) having a specific particle diameter or silica sol (colloidal silica) obtained from sodium silicate (water glass) in which fine particles are simply dispersed.

In particular, a gas barrier film used for a liquid crystal display device is required to have a large surface resistance and to be substantially insulating since a patterning layer of a transparent conductive film is provided thereon as an electrode. Indium cerium-based oxide in the present invention, or based on indium cerium-based oxide, any one of tin and titanium,
Or, the gas barrier layer made of an oxide containing both, the surface resistance can be easily controlled by the film forming conditions,
A film having a surface resistance of 1.0 × 10 ⁸ Ω / □ or more and exhibiting substantially electrical insulation can be obtained. Specific conditions vary depending on the film forming method, film forming apparatus, type of base material, etc., but generally when the film forming speed is low, when the surface temperature of the base material is low, and when the gas partial pressure during film forming is high. For example, a high-resistance film is easily obtained. However, the transparent conductive film patterned as an electrode is often a composite oxide (ITO) of indium and tin, and even if the gas barrier layer in the present invention has a large surface resistance, its main component is Since it is indium oxide, it may be etched together in a patterning (etching) step of the transparent conductive film. Therefore, when the gas barrier film of the present invention is used for such a purpose, it is necessary to provide a protective layer on the gas barrier layer even if the formation of the second layer is not necessary, since the gas barrier layer is physically and chemically formed. This is effective not only for protecting the film, but also for increasing the surface resistance to obtain a film having substantially electric insulation. Of course, a configuration in which a protective layer is further provided on the above-described second layer may be employed.

The components, compositions, manufacturing methods, thicknesses, and the like of such a protective layer are not limited as long as the above objects are satisfied.
There is no particular limitation. For example, an organic polymer layer made of an ultraviolet ray or an electron beam curable resin of an ultraviolet curable or electron beam curable resin, or a thermosetting layer of an urethane-based, epoxy-based, acrylic-based organic polymer, or the above-described second layer And inorganic compound layers such as silicon oxide and aluminum oxide obtained by hydrolysis and polymerization of other metal alkoxides (so-called sol-gel method).

[0023]

Next, the gas barrier film of the present invention will be described in more detail with reference to specific examples.

Example 1 A polyethylene terephthalate (PET) film having a thickness of 100 μm was used as a base material, and the following target of a composite oxide of indium and cerium was used on the upper surface thereof. 300 sccm) and an oxygen gas (10 sccm) as a reaction gas are supplied, and DC magnetron sputtering (DC output: 3.0 kW, film formation speed: 6.0 n)
m / min) to form a gas barrier layer composed of an inorganic compound layer having a thickness of about 50 nm to obtain a gas barrier film.

(Ratio of Each Metal Element in Oxide Target) Indium (In) / Cerium (Ce) = 90/10
(At%) The gas barrier properties of the obtained gas barrier film were evaluated by measuring oxygen permeability and water vapor permeability. The oxygen barrier property is measured under an atmosphere of 30 ° C.-70% RH under an atmosphere of oxygen permeability (MOCON OX manufactured by Modern Control Co., Ltd.).
TRAN 10 / 50A), and the water vapor barrier property was measured under a 40 ° C.-90 RH atmosphere using a water vapor permeability measuring device (PERMATRAN manufactured by Modern Control Co., Ltd.).
W6). Table 1 shows the results. Table 1 shows an X-ray photoelectron spectrometer (manufactured by Shimadzu Corporation).
Average metal element content (at%) in the inorganic compound layer obtained from the depth profile analyzed by using ESCA 3200) and a four-terminal method resistance device (Lore manufactured by Mitsubishi Chemical Corporation)
sta HP) was also described.

[0026]

[Table 1]

Example 2 A PET film having a thickness of 100 μm was used as a base material, and the following target of a composite oxide of indium, cerium, tin and titanium was used on the upper surface thereof, and argon gas (300 scc) was used as a sputtering gas.
m) and oxygen gas (10 sccm) as a reaction gas, and DC magnetron sputtering (DC output 3.
An inorganic compound layer having a thickness of about 50 nm was formed at 0 kW at a film formation rate of 6.5 nm / min) to obtain a gas barrier film.

(Ratio of Each Metal Element in Oxide Target) Indium (In) / Cerium (Ce) / Tin (Sn)
/ Titanium (Ti) = 88 / 8.5 / 3 / 0.5 (at
%)

The gas barrier properties of the obtained gas barrier film, the average metal element content in the inorganic compound layer, and the surface sheet resistance were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 A PET film having a thickness of 100 μm was used as a base material, and the following target of a composite oxide of indium, cerium and tin was used on the upper surface thereof, and reacted with argon gas (300 sccm) as a sputtering gas. Oxygen gas (10 sccm) is supplied as a gas, and DC
Approximately 50 nm in film thickness by magnetron sputtering (DC output: 3.0 kW, film formation speed: 5.0 nm / min)
To form a gas barrier film.

(Ratio of Each Metal Element in Oxide Target) Indium (In) / Cerium (Ce) / Tin (Sn)
= 89/9/2 (at%) The gas barrier properties of the obtained gas barrier film, the average metal element content in the inorganic compound layer, and the surface sheet resistance were measured in the same manner as in Example 1. The results were as follows. Are shown in Table 1.

Example 4 A PET film having a thickness of 100 μm was used as a base material, and the following target of a composite oxide of indium, cerium and tin was used on the upper surface thereof, and reacted with argon gas (300 sccm) as a sputtering gas. Oxygen gas (10 sccm) is supplied as a gas, and DC
Approximately 50 nm in film thickness by magnetron sputtering (DC output: 3.0 kW, film formation speed: 3.5 nm / min)
To form a gas barrier film.

(Ratio of Each Metal Element in Oxide Target) Indium (In) / Cerium (Ce) / Titanium (S
n) = 90 / 9.5 / 0.5 (at%) The gas barrier properties of the obtained gas barrier film, the average metal element content in the inorganic compound layer and the surface sheet resistance were the same as in Example 1. And the results are shown in Table 1.

Example 5 An acrylate monomer [triethylene glycol] was formed on the gas barrier layer comprising the inorganic compound layer of the gas barrier film obtained in Example 1 so that the thickness after polymerization and curing was about 2 μm. -Mixture of ethylene glycol-diglycidyl ether / methacrylic acid adduct at a molar ratio of 8: 2], and irradiating with an electron beam having an acceleration voltage of 120 kV and an irradiation dose of 0.1 kGy. Form a protective layer by curing,
A gas barrier film was obtained. The gas barrier properties, average metal element content in the inorganic compound layer, and surface sheet resistance of the obtained gas barrier film were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 6 An acrylate monomer [triethylene glycol diacrylate] was formed on the inorganic compound layer of the gas barrier film obtained in Example 2 so that the thickness after polymerization and curing was about 2 μm. And a mixture of ethylene glycol diglycidyl ether and methacrylic acid in a molar ratio of 8: 2], and the accelerating voltage is 120 k.
V, an electron beam having an irradiation dose of 0.1 kGy was irradiated to cure the film, thereby forming a protective layer to obtain a gas barrier film. The gas barrier properties, average metal element content in the inorganic compound layer, and surface sheet resistance of the obtained gas barrier film were measured in the same manner as in Example 1. The results are shown in Table 1.

[Example 7] An acrylate monomer [triethylene glycol diacrylate] was formed on the inorganic compound layer of the gas barrier film obtained in Example 3 so that the thickness after polymerization was about 2 µm. And a mixture of ethylene glycol diglycidyl ether and methacrylic acid in a molar ratio of 8: 2], and the accelerating voltage is 120 k.
V, an electron beam having an irradiation dose of 0.1 kGy was irradiated to cure the film, thereby forming a protective layer to obtain a gas barrier film. The gas barrier properties, average metal element content in the inorganic compound layer, and surface sheet resistance of the obtained gas barrier film were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 8 An acrylate monomer [triethylene glycol diacrylate] was applied on the inorganic compound layer of the gas barrier film obtained in Example 4 so that the thickness after polymerization and curing was about 2 μm. And a mixture of ethylene glycol diglycidyl ether and methacrylic acid in a molar ratio of 8: 2], and the accelerating voltage is 120 k.
V, an electron beam having an irradiation dose of 0.1 kGy was irradiated to cure the film, thereby forming a protective layer to obtain a gas barrier film. The gas barrier properties, average metal element content in the inorganic compound layer, and surface sheet resistance of the obtained gas barrier film were measured in the same manner as in Example 1. The results are shown in Table 1.

COMPARATIVE EXAMPLE 1 An indium oxide (In 2 O 3) target was used on a PET film having a thickness of 100 μm, and argon gas (3) was used as a sputtering gas.
00 sccm) and oxygen gas (10 sccm) as a reaction gas.
cm) and RF magnetron sputtering (R
At an F output of 3.0 kW and a film formation rate of 2.5 nm / min), an inorganic compound layer having a thickness of about 50 nm was formed to obtain a gas barrier film. The gas barrier properties of the obtained gas barrier film, the average metal element content in the inorganic compound layer and the surface sheet resistance were measured in the same manner as in Example 1.
The results are shown in Table 1.

[Comparative Example 2] A reactive evaporation of about 20 nm in thickness was performed on a PET film having a thickness of 100 μm by using an electron beam heating vacuum evaporation apparatus to evaporate metallic aluminum and supply oxygen gas to oxidize. An aluminum oxide film was formed to obtain a gas barrier film. The gas barrier properties, average metal element content in the inorganic compound layer, and surface sheet resistance of the obtained gas barrier film were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 A silicon oxide film having a thickness of about 40 nm was formed by evaporating and condensing silicon monoxide on a PET film having a thickness of 100 μm by using an electron beam heating type vacuum evaporation apparatus. A functional film was obtained. The gas barrier properties, average metal element content in the inorganic compound layer, and surface sheet resistance of the obtained gas barrier film were measured in the same manner as in Example 1. The results are shown in Table 1.

[Examples 9 to 13] A polyethylene terephthalate (PET) film having a thickness of 12 μm was used as a base material, the following target of indium / cerium oxide was used on the upper surface, and argon gas was used as a sputtering gas. Supplying oxygen gas as a reaction gas, DC
Approximately 30 nm in film thickness by magnetron sputtering
An inorganic compound layer is formed, and the following composition is further combined, and a coating agent obtained by mixing in a predetermined ratio is applied by a bar coater, and dried at 120 ° C. for 1 minute by a drier to obtain a coating layer having a thickness of about 0.3 μm. Was formed to obtain a gas barrier film.

(Target Composition) Indium oxide (In ₂ O ₃ ) / cerium oxide (Ce)
O ₂ ) = 90/10 (wt%)

(Components of Coating Agent) (A) Tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ : hereinafter referred to as TEOS] 10.4 g of hydrochloric acid (0.1N) 8
9.6 g was added thereto, and the mixture was stirred for 30 minutes and hydrolyzed to obtain a hydrolysis solution having a solid content of 3 wt% (in terms of SiO ₂ ). (B) Triisopropoxy aluminum [Al (O-
2′-C ₃ H ₇ ) ₃ : hereinafter referred to as TPOA] after dissolving 6.0 g in 90 g of hot water at 80 ° C., and then adding 4 g of hydrochloric acid (5N).
3 wt% of water / ethanol solution of hydrolyzed solution of the added solids 3 wt% obtained by peptizing a (Al ₂ O ₃ in terms of) (C) stannous chloride (anhydrous) (water: ethanol weight ratio of 50: 50) (D) 3 wt% aqueous solution of stannic chloride (anhydride) (E) 3.0 wt% water / isopropyl alcohol solution of polyvinyl alcohol (90:10 by weight of water: isopropyl alcohol)

(Composition of Coating Agent) Example 9 (A) / (E) Compounding Ratio (wt%) 60/40 Example 10 (B) / (E) Compounding Ratio (wt%) 50/10/40 Example 11 (C) / (E) Mixing ratio (wt%) 60/40 Example 12 (A) / (C) / (E) Mixing ratio (wt%) 40/30/30 Example 13 (A) / (D) / (E) Compounding ratio (wt%) 40/30/30

The obtained gas barrier film was heated at 40 ° C.
The gas barrier property of 90% RH was evaluated by measuring oxygen permeability and water vapor permeability.

The oxygen barrier property was measured in an atmosphere of 25 ° C.-70% RH using an oxygen permeability measuring apparatus (MOCON OXTRAN 10 / 50A manufactured by Modern Control), and the water vapor barrier property was measured as in Example 1. Performed under conditions.

Table 1 shows that the inorganic compound layer-formed film was coated with a coating agent (Examples 9 to 13).
Showed higher gas barrier properties in both oxygen barrier property and water vapor barrier property.

[Examples 14-18] A polyethersulfone (hereinafter referred to as PES) film having a thickness of 200 µm was used as a base material, and the following targets of alloy oxides containing tin and titanium in addition to indium and cerium on the upper surface thereof Using
An argon gas as a sputtering gas and an oxygen gas as a reaction gas are supplied, an inorganic compound layer having a thickness of about 30 nm is formed by DC magnetron sputtering, and the same coating agent as in Examples 9 to 13 is further coated with a bar coater. It was applied and dried at 120 ° C. for 1 minute with a drier to form a coating layer having a thickness of about 0.3 μm to obtain a gas barrier film.

(Composition of target) Indium oxide (In 2 O 3) was added to the following elements at the following ratio to form an alloy oxide. Cerium (Ce) 8.5 (at%) Tin (Sn) 3.0 (At%) Titanium (Ti) 0.5 (at%)

(Components of Coating Agent) Examples 9 to 13
Same as

(Composition of Coating Agent) Example 14 (A) / (E) Compounding Ratio (wt%) 60/40 Example 15 (B) / (E) Compounding Ratio (wt%) 50/10/40 Example 16 (C) / (E) Mixing ratio (wt%) 60/40 Example 17 (A) / (C) / (E) Mixing ratio (wt%) 40/30/30 Example 18 (A) / (D) / (E) Compounding ratio (wt%) 40/30/30

The obtained gas barrier film was used in Example 9.
The evaluation was performed in exactly the same manner as in Examples 13 to 13.

Table 1 shows that the inorganic compound layer formed film was coated with a coating agent (Examples 14 to 1).
8) showed higher gas barrier properties than Examples 1 to 8 in both oxygen barrier properties and water vapor barrier properties.

[0054]

According to the present invention, as a gas barrier layer, a composite oxide of indium and cerium, or a composite oxide containing indium and cerium as a main component and containing either or both of tin and titanium is formed of a plastic film. By providing the gas barrier film on a substrate, it is possible to provide a gas barrier film capable of extremely suppressing the permeation rate of oxygen or water vapor. Further, in the invention in which a protective layer such as an organic polymer layer is provided on such a composite oxide layer, the sheet resistance of the surface can be easily reduced to 1 × 10 5
It is possible to provide a gas barrier film which can be set to ⁸ Ω / □ or more and can be applied to a substrate of a liquid crystal display device and the like. Moreover, according to the addition of the second layer, the change in temperature and humidity is small while having excellent transparency and flexibility and high gas barrier properties, and furthermore, toxic gas is generated during incineration treatment. It is possible to provide a gas barrier film having no gas barrier.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Haruo Uyama, Inventor, 1-5-1, Taito, Taito-ku, Tokyo Inside Toppan Printing Co., Ltd. (72) Ryuyoshi Matsuo 1-1-1, Taito, Taito-ku, Tokyo Letterpress F-term (Reference) in Printing Co., Ltd. JB09C JB09E JD02B JG04B JM02B YY00B 4K029 AA11 AA25 BA50 BC05 BD00 CA05 CA06 DC05 DC34 DC39 GA03

Claims (10)

[Claims] 1. A gas barrier film having a gas barrier layer provided on at least one surface of a substrate made of a plastic film, wherein the gas barrier layer is mainly composed of a layer containing an indium-cerium-based oxide. Film. 2. A gas barrier property comprising: a gas barrier layer mainly composed of indium-cerium-based oxide formed on at least one surface of a substrate composed of a plastic film, and a protective layer further provided thereon. the film. 3. The gas barrier film having a surface of 1 × 1
0 ⁸ Ω / □ or more sheet - gas barrier film according to claim 1 or claim 2, characterized in that it has a sheet resistance value. 4. The gas barrier according to claim 1, wherein the gas barrier layer comprises an oxide containing indium cerium-based oxide as a main component and either or both of tin and titanium. Film. 5. The gas barrier layer according to claim 1, wherein the first layer comprises a layer mainly containing an indium-cerium-based oxide, and a water-soluble polymer; and (a) one or more metal alkoxides and hydrolysates thereof; A) a gas barrier film, wherein a second layer comprising at least one of tin chloride is laminated. 6. The protective layer comprises a second layer comprising at least one of (a) at least one metal alkoxide and a hydrolyzate thereof, and (b) tin chloride. Item 3. A gas barrier film according to Item 2. 7. The gas barrier film according to claim 5, wherein the inorganic compound forming the first layer comprises only an indium-cerium-based oxide. 8. The method according to claim 5, wherein the inorganic compound forming the first layer comprises an oxide containing indium cerium-based oxide as a main component and one or both of tin and titanium. 7. The gas barrier film according to any one of claims 6 and 7. 9. The gas barrier film according to claim 5, wherein the water-soluble polymer of the second layer is polyvinyl alcohol. 10. The method according to claim 10, wherein the metal alkoxide of the second layer is tetraethoxysilane or triisopropoxyaluminum.
Alternatively, the gas barrier film according to claim 5 or 6, which is a mixture thereof.