JP2002127294A - Gas barrier film and laminated sheet using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having extremely excellent gas barrier properties and a laminated sheet using the same. SOLUTION: In the gas barrier film having a base material, the silicon oxide film formed on the single surface or both surface of the base material by a plasma CVD method and the resin cured film covering the surface of the silicon oxide film, removal treatment for removing parts inferior in gas barrier properties is applied to the surface of the silicon oxide film coming into contact with the resin cured film to form a fine uneven structure to the surface of the silicon oxide film.

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 as a packaging material for foods and pharmaceuticals, a packaging material for electronic devices, and the like, and a laminated material using the same.

[0002]

2. Description of the Related Art Gas barrier films are mainly used as packaging materials for foods, pharmaceuticals, etc. in order to prevent the influence of oxygen, water vapor, etc., which may cause the quality of the contents to change, or to be used for liquid crystal display panels and EL displays. Elements formed on panels and the like are used as package materials for electronic devices and the like in order to avoid performance degradation due to contact with water vapor. In recent years, a gas barrier film is sometimes used for the purpose of giving flexibility to a portion where glass or the like is conventionally used.

[0003] Such a gas barrier film generally has a structure in which a gas barrier layer is formed on one or both sides of a plastic film as a base material. The gas barrier film is formed by CVD, PVD
It is formed by various methods such as a sputtering method and a sputtering method. Regardless of which method is used, the conventional gas barrier film has an oxygen transmission rate (OTR) of about ² cc / m ² / day, It has a water vapor transmission rate (WVTR) of only about ² g / m ² / day, and is still insufficient when used for applications requiring higher gas barrier properties.

Here, as a method for improving the barrier properties (gas permeability and water vapor permeability) of an inorganic oxide thin film such as a silicon oxide film as a barrier film, the present applicant has A barrier film combining the above-mentioned inorganic oxide thin film and a cured resin film containing an ethylene-vinyl alcohol copolymer as a main component is disclosed in
000-62078.

[0005] However, even with the barrier film disclosed by the present applicant, the performance is as follows: oxygen permeability is 0.5 cc / m ² / day or less, and water vapor permeability is 0.5 g / m ^2. / Day. This performance
It can be said that the performance is sufficiently superior compared to that of the conventional gas barrier film, but with the spread of computers in recent years, when a barrier film is used as a packaging material for precision electronic devices, further barrier properties are required. The required case has come out.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and a gas barrier film having extremely excellent gas barrier properties as compared with the prior art.
And a laminated material using the same.

[0007]

In order to achieve the above object, the present invention provides, in claim 1, a substrate, a silicon oxide film formed on both surfaces or one surface of the substrate by a plasma CVD method, A cured resin film covering the surface of the silicon oxide film, and a gas barrier film having a surface of the silicon oxide film in contact with the cured resin film, by performing a removal treatment to remove a portion having poor gas barrier properties. Provided is a gas barrier film, wherein the generated fine irregularities are formed.

On the surface of a silicon oxide film formed on a substrate by a plasma CVD method, a portion having high crystallinity and excellent gas barrier properties (grain) and a portion having low crystallinity and poor gas barrier properties (boundary) are provided. And exists. In the gas barrier film of the present invention, a removal treatment for removing the portion (boundary) having a poor gas barrier property is performed. As a result, the surface of the silicon oxide film has a portion having the excellent gas barrier property ( (Grain) is present.

According to the present invention, by combining a silicon oxide film having such fine irregularities and a cured resin film, a concave portion on the surface of the silicon oxide film, that is, a barrier in the conventional silicon oxide film is obtained. A portion having poor properties (not contributing to barrier properties) can be filled with a cured resin film having barrier properties, and a film having excellent gas barrier properties as a whole can be formed.

In the first aspect of the present invention, as described in the second aspect, it is preferable that the removal treatment is a removal treatment with a strong acid or a strong alkali.

A portion having poor barrier properties (boundary) existing on the surface of the silicon oxide film formed by the plasma CVD method is easily dissolved by a strong acid or a strong alkali.
This is because it can be removed.

Further, in the invention according to the second aspect, as described in the third aspect, the removal treatment is a removal treatment using hydrofluoric acid, an ammonium fluoride aqueous solution, or a mixed solution thereof. Is particularly preferred.

[0013] Hydrofluoric acid and aqueous ammonium fluoride are both types of strong acids, and they are relatively easily available and inexpensive.

In the invention according to any one of the first to third aspects, as described in the fourth aspect, the cured resin film contains an ethylene-vinyl alcohol copolymer as a main component. Further, it is preferable that the composition further contains at least a metal alkoxide compound.

This is because such a cured resin film has good adhesion to a silicon oxide film and also has excellent barrier properties.

In the invention according to the fourth aspect, as described in the fifth aspect, it is preferable that the ethylene-vinyl alcohol copolymer has an ethylene content of 25 to 50 mol%.

This is because, when the ethylene-vinyl alcohol copolymer is within the above range, a cured resin film having excellent barrier properties and flexibility can be obtained.

In the invention described in claim 4 or claim 5, as described in claim 6, the metal alkoxide compound is preferably an alkoxysilane compound.

By using an alkoxysilane compound, the crosslinked structure of the cured resin film can be made stronger, and the compound is commercially available and can be easily obtained.

In the invention according to any one of claims 1 to 6, it is preferable that the resin cured film contains a curing catalyst, as described in claim 7.

Further, in the invention described in any one of the first to seventh aspects, as described in the eighth aspect, the cured resin film may contain a silane coupling agent. preferable.

By including a curing catalyst or a silane coupling agent in the cured resin film, the formation time of the layer can be shortened, the structure of the layer can be strengthened, and the curing catalyst or the silane coupling agent can be further improved. The ring agent can be suitably used because it does not affect the barrier properties of the layer.

Further, according to the present invention, as described in claim 9, at least the gas barrier film according to any one of claims 1 to 8 and a surface of a cured resin film in the gas barrier film. And a heat seal layer provided on the laminate.

By forming a laminated material by laminating a heat seal layer or the like on the surface of the gas barrier film of the present invention described above (the surface opposite to the substrate), it is suitable as a packaging material for food and electronic parts. It is because it can be used for.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the gas barrier film of the present invention will be specifically described with reference to the drawings.

FIG. 1 is a schematic sectional view showing an example of the configuration of the gas barrier film of the present invention. As shown in FIG.
The gas barrier film 1 of the present invention includes a substrate 2, a silicon oxide film 3 formed on both sides or one side of the substrate 2, and a cured resin film 4 covering the surface of the silicon oxide film 3. .

Hereinafter, [1] a silicon oxide film, [2] a cured resin film, and [3] a substrate will be described in detail.

[1] Silicon Oxide Film First, the silicon oxide film 3 constituting the gas barrier film 1 of the present invention will be described.

The silicon oxide film 3 in the gas barrier film 1 of the present invention is formed on both sides or one side of the substrate 2 by a plasma CVD method, and the surface of the silicon oxide film 3 (opposite to the surface in contact with the substrate) (Surface on the side) is characterized in that fine irregularities generated by a removal treatment for removing a portion having poor gas barrier properties are formed.

First, the irregularities formed on the surface of the silicon oxide film 3 will be described.

The irregularities are formed by removing the surface of the silicon oxide film formed by the plasma CVD method. When a silicon oxide film is formed by a plasma CVD method, the surface of the silicon oxide film includes
There are a portion (grain) having high crystallinity of silicon atoms (Si) and oxygen atoms (O), and a portion (boundary) having low crystallinity. The portion having high crystallinity (grain) is a portion having excellent gas barrier properties, and the portion having low crystallinity (boundary) is a portion having poor gas barrier properties.

By removing the low crystallinity portion (boundary) by the removal treatment, on the contrary, only the portion not removed by the removal treatment, that is, only the high crystallinity portion (grain) remains on the surface of the silicon oxide film. As a result, irregularities are formed on the silicon oxide film.

As described above, by providing irregularities on the surface of the silicon oxide film, that is, by removing portions having low crystallinity and poor gas barrier properties, the resin hardening provided over the surface of the silicon oxide film can be cured. The film 4 can have a structure in which the concave portions on the surface of the silicon oxide film are clogged, whereby the gas barrier film 1 can exhibit excellent gas barrier properties as a whole.

Here, when the silicon oxide film is formed by the normal plasma CVD method (when the boundary is not removed), the surface of the film is in a smooth state. In the present invention, the fine unevenness refers to the unevenness formed by removing the boundary by performing a removing treatment on the smooth film surface, formed by a plasma CVD method,
The level difference of the unevenness of the smooth surface formed without the removal treatment is usually 2 to 3 nm, so that the fine unevenness in the present invention may be more than this. Further, the height difference of the unevenness is preferably such that unevenness of 5 to 60 nm is formed, most preferably 5 to 40 nm.

If the irregularities in the above range are formed, a portion having low crystallinity and not contributing to the barrier property (boundary)
Is considered to be sufficiently removed.

The silicon oxide film 3 in the present invention is formed by the plasma CVD method as described above. In the plasma CVD method, a silicon oxide film can be formed at a low temperature (in a range of about −10 to 150 ° C.) at which thermal damage is not applied to a polymer resin. It is preferably applied to Further, the plasma CVD method is a method in which a source gas at a constant pressure is discharged into a plasma state, and a chemical reaction is promoted and formed on a substrate surface by active particles generated in the plasma. There is an advantage that the type and physical properties (film quality) of the obtained film can be controlled by the type / flow rate, film forming pressure, input power and the like. Furthermore, when a silicon oxide film is formed by a plasma CVD method, the silicon oxide film and the substrate are chemically bonded at the interface, so that the adhesion between the two can be sufficiently increased.

According to the present invention, a silicon oxide film is formed by plasma C
When formed by the VD method, a mixed gas of an organosilicon compound gas and oxygen gas is supplied at a predetermined flow rate into a reaction chamber of a plasma CVD apparatus, and DC power or a low-frequency to high-frequency voltage is applied to the electrode. Is generated by applying electric power having a constant frequency of, and a reaction between the organic silicon compound gas and the oxygen gas in the plasma forms a silicon oxide film on the substrate. The type of plasma CVD apparatus used is not particularly limited, and various types of plasma CVD apparatuses can be used.

As a mixed gas for forming a silicon oxide film, (I) hexamethyldisiloxane (HMDS)
O), 1,1,3,3-tetramethyldisiloxane (T
An organic silicon compound gas such as MDSO), vinyltrimethoxysilane, vinyltrimethylsilane, tetramethoxysilane (TMOS), methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, or hexamethyldisilazane is mixed with oxygen gas. Or a mixture of (II) silane-based gas and oxygen gas or oxide gas, for example, SiH ₄ gas, N ₂ O
Gas, NO gas, CO gas, CO ₂ gas, O ₂ gas, Ar
A gas in which a gas or the like is mixed can be preferably used.

In the film formed as described above,
A component derived from a mixed gas as a raw material, for example, when an organosilicon compound gas is used, may contain a carbon atom or the like.

The film forming conditions of the silicon oxide film thus formed are set in consideration of the removal treatment described later, and the film quality is controlled. Usually, the thickness is 5 to 200 nm.
Is preferably formed in the range described above. If the thickness is less than 5 nm, a sufficient film that covers the surface of the substrate may not be formed. On the other hand, there is no particular problem if the thickness exceeds 200 nm, but it is preferably 200 nm or less in consideration of production efficiency.

Next, the above-described removal treatment performed on the surface of the silicon oxide film will be described.

The removal treatment in the present invention, as described above, removes a portion having low crystallinity (boundary), in other words, a portion having poor gas barrier properties, on the surface of the silicon oxide film to cause irregularities on the surface. Processing.

Therefore, the removal processing in the present invention is as follows:
Any processing may be used as long as the above-mentioned object can be achieved. For example, a chemical processing method or a physical processing may be used.

Among the above chemical treatments, it is preferable to use a strong acid or strong alkali, and particularly preferable to use hydrofluoric acid, an aqueous solution of ammonium fluoride, or a mixed solution thereof. On the surface of the silicon oxide film, portions to be removed (portions having low crystallinity and poor gas barrier properties) have a property of dissolving in strong acids and strong alkalis. Because it is possible.

The concentration of the solution in the case of performing the removal treatment using hydrofluoric acid is not particularly limited in the present invention, and can be arbitrarily determined depending on the quality of the silicon oxide film. For example, when a silicon oxide film is formed by a plasma CVD method using tetramethoxysilane as a raw material, the concentration of hydrofluoric acid used for the removal treatment is about 0.5 mol / l (in the case of a removal treatment for 30 seconds). .

As the physical processing, an ultrasonic wave can be used. This is because the portion to be removed by the removal treatment is a portion having low crystallinity, so that the crystal state can be physically destroyed by the vibration by the ultrasonic wave.

Further, the chemical treatment (for example, hydrofluoric acid) and the physical treatment (for example, ultrasonic wave) can be used in combination. This is because the dissolution and removal by the solution can be supplemented by ultrasonic waves.

[2] Cured Resin Film Next, the cured resin film constituting the gas barrier film 1 of the present invention will be described.

As the cured resin film 4 constituting the gas barrier film 1 of the present invention, for example, one or more ethylene-vinyl alcohol copolymers are used as a main component of a vehicle, and at least a metal alkoxide compound One or more of the following, and further, if necessary, for example, a light stabilizer such as a filler, a stabilizer, a plasticizer, an antioxidant, an ultraviolet absorber, a dispersant, a thickener, a drying agent, Lubricant, antistatic agent, cross-linking agent, optionally add other additives such as,
Solvent type, aqueous type, sufficiently kneaded with solvent, diluent, etc.
Alternatively, a resin composition composed of an emulsion type or the like is prepared, or the resin composition is used, for example, a roll coat method, a gravure roll coat method, a kiss roll coat method, a squeeze roll. A coating amount, for example, from 0.1 g / m ² to 0.1 g / m ² , by a coating method such as a roll coating method, a reverse roll coating method, a curtain flow coating method, etc.
About 10 g / m ² (dry state), preferably 0.5 g / m ²
forming a cured resin film 4 according to the present invention by coating so as to be about m ^{2 to 5} g / m ² (dry state), and then performing heat drying and further aging treatment. Can be.

In the above, as the resin composition, an ethylene-vinyl alcohol copolymer, a metal alkoxide compound or the like is dissolved or kneaded, and further these are cured. It is preferable to use a resin composition prepared and used. Further, examples of the alcohol component include, for example, n-propyl alcohol, isopropyl alcohol, n-butanol, and t-butanol. , Ethyl alcohol, methyl alcohol and the like.
In the aqueous solution, the mixing ratio of alcohol and water is, for example, 50 to 70 parts by weight of alcohol and 50 to 30 parts by weight of water. It is desirable to adjust.

In the above description, the ethylene-vinyl alcohol copolymer may be, for example, an ethylene-vinyl acetate copolymer having a vinyl acetate content of about 79 to 92% by weight, which is completely saponified. ５０50 mol% of ethylene-vinyl alcohol copolymer can be used. The above-mentioned ethylene-vinyl alcohol copolymer has high gas barrier properties, and is further excellent in fragrance retention, transparency and the like. In the above description, those having an ethylene content of 50 mol% or more are not preferred because the gas barrier properties are rapidly lowered and the transparency is deteriorated, and those having 25 mol% or less have a brittle thin film. In addition, the gas barrier property deteriorates under high humidity, which is not preferable.

Further, as the metal alkoxide compound,
For example, an alkoxysilane compound, a zirconium alkoxide compound, a titanium alkoxide compound, and the like can be used. Specifically, for example, tetramethoxysilane [Si (O-CH _{3) 4],} tetraethoxysilane _{[Si (O-C 2 H 5} ) 4 ], tetraisopropoxysilane [Si (O-iso-C ₃ H _{7) 4],} tetrabutoxysilane _{[Si (0-C 4 H 9} ) 4 ], dimethyldimethoxysilane _{[(H 3 C) 2 Si (} O-CH 3) 2 ],
Trimethoxymethylsilane [H ₃ CSi (OC
H ₃ ) ₃ ], dimethyldiethoxysilane [(H ₃ C) ₂ Si
_{(O-C 2 H 5)} 2 ] alkoxysilane compounds such as tetramethoxysilane zirconium [Zr (O-CH _{3) 4],} tetraethoxy zirconium _{[Zr (O-C 2 H 5} ) 4 ], tetraisopropoxy zirconium [Zr (O-iso-
C ₃ H ₇ ) ₄ ], tetrabutoxyzirconium [Zr (O
-C ₄ H ₉ ) ₄ ], a zirconium alkoxide compound,
Tetramethoxy titanium [Ti (O-CH _{3) 4],} tetraethoxy titanium _{[Ti (O-C 2 H 5} ) 4 ], tetraisopropoxy titanium [Ti (O-iso-C
₃ H _{7) 4],} tetrabutoxy titanium [Ti (0-C ₄
H ₉ ) ₄ ] and the like. As the above-mentioned metal alkoxide compound, it is particularly preferable to use an alkoxysilane compound from the viewpoints of handleability, curing reactivity, economy, and the like. In the resin composition according to the present invention, the mixing ratio of the above-mentioned ethylene-vinyl alcohol copolymer and the above-mentioned metal alkoxide compound is such that the ethylene-vinyl alcohol-copolymer is mixed with 10 parts by weight of the metal alkoxide compound. A compounding ratio of 0.1 to 20 parts by weight is preferable.

Next, in the resin composition according to the present invention, a silane coupling agent having dual reactivity can be added as a crosslinking agent or the like. Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ
-Mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β -Hydroxyethyl) -γ-aminopropyltriethoxysilane, one or more of γ-aminopropylsilicone can be used.
As the amount of use, only a small amount may be added.

In the resin composition according to the present invention, the above-mentioned ethylene-vinyl alcohol copolymer, metal alkoxide compound, silane coupling agent and the like are cured individually or by reacting with each other. A curing catalyst can be added. Examples of the above-mentioned curing catalyst include, for example, tertiary amines which are substantially insoluble in water and soluble in an organic solvent. N-dimethylbenzylamine, tripropylamine, tributylamine,
Examples of the acids include tripentylamine and the like, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid. It is sufficient to add a small amount as the amount used.

In the present invention, the above-mentioned ethylene-vinyl alcohol copolymer is used as a main component of the vehicle, and at least the above-mentioned metal alkoxide compound is added thereto. And, if necessary, other additives are optionally added, and a resin composition which is sufficiently kneaded with an alcohol-water-based solvent, a diluent, or the like is prepared, and the resin composition is mixed with a normal core. The resin cured film can be formed by coating by a coating method, followed by heat drying and further aging treatment.

The above cured resin film has excellent barrier properties against oxygen gas, water vapor gas and the like, and further has transparency, heat resistance,
It is excellent in hot water resistance, other properties, etc., and is also excellent in close adhesion to a silicon oxide film. In the present invention, the reaction mechanism is not clear, but first, the metal alkoxide compound is hydrolyzed with water or the like to generate a hydroxyl group (eg, a silanol group). Hydrolysis produces hydroxyl groups (eg, silanol groups) and the like, and these hydroxyl groups and the hydroxyl groups of the ethylene-vinyl alcohol copolymer cause a dehydration polycondensation reaction individually or mutually. It is presumed that a cured resin film having a crosslinked structure or a three-dimensional network structure can be formed. Furthermore, the above-mentioned hydroxyl group, and further, the other reactive group of the silane coupling agent or the like reacts with a metal constituting the silicon oxide film or an active group on the surface of the silicon oxide film by some action, for example, a dehydration condensation reaction. It is presumed that such a reaction occurs to modify the silicon oxide film surface with a covalent bond or the like, and further form a hardened resin cured film that is firmly bonded to the surface of the silicon oxide film of the hydroxyl group itself by adsorption or hydrogen bonding. You.

[3] Substrate Next, the substrate 2 constituting the gas barrier film 1 of the present invention
Will be described.

The substrate 2 in the gas barrier film 1 of the present invention is not particularly limited as long as it can hold the silicon oxide film 3 having the above-mentioned barrier properties, and any film can be used. it can.

Specifically, ethylene, polypropylene,
Polyolefin (PO) resin such as homopolymer or copolymer or copolymer such as butene, amorphous polyolefin resin (APO) such as cyclic polyolefin, polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN) Polyester-based resins such as nylon 6, nylon 12, polyamide nylon (PA) resin such as copolymerized nylon, polyvinyl alcohol (PVA) resin,
Polyvinyl alcohol resin such as ethylene-vinyl alcohol copolymer (EVOH), polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin,
Polyetheretherketone (PEEK) resin, polycarbonate (PC) resin, polyvinylbutyrate (PV
B) Resin, polyarylate (PAR) resin, ethylene-
Ethylene tetrafluoride copolymer (ETFE), ethylene trifluoride chloride (PFA), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer (FEP), vinylidene fluoride (PVDF), vinyl fluoride (PVF), Fluorinated resins such as perfluoroethylene-perfluoropropylene-perfluorovinylether-copolymer (EPA) can be used.

In addition to the above resins, a resin composition comprising an acrylate compound having a radically reactive unsaturated compound, a resin composition comprising the acrylate compound and a mercapto compound having a thiol group,
It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as epoxy acrylate, urethane acrylate, polyester acrylate, or polyether acrylate is dissolved in a polyfunctional acrylate monomer, or a mixture thereof. Further, a resin film obtained by laminating one or more of these resins by means such as lamination and coating can be used as the base film.

The substrate 2 of the present invention using the above-mentioned resins and the like may be an unstretched film or a stretched film.

The substrate 2 of the present invention can be manufactured by a conventionally known general method. For example, a resin as a material is melted by an extruder, extruded by an annular die or a T die, and quenched, whereby a substantially amorphous, unoriented, unstretched substrate can be produced.
In addition, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, or the like, in the flow direction (vertical axis) of the base material, or A stretched base material can be manufactured by stretching in a direction (horizontal axis) perpendicular to the flow direction of the base material. The stretching ratio in this case can be appropriately selected according to the resin used as the raw material of the base material, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.

The substrate of the present invention may be subjected to a surface treatment such as a corona treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment, a chemical treatment, etc., before forming the silicon oxide film. .

Further, the surface of the substrate of the present invention may be coated with an anchor coat for the purpose of improving the adhesion to the silicon oxide film. As the anchor coating agent used in this case, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicone resin, alkyl titanate, etc. Two or more can be used in combination. Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and the solvent, diluent and the like are dried and removed to perform anchor coating. be able to. The amount of the anchor coating agent applied is 0.1
About 5 g / m ² (dry state) is preferred.

The gas barrier film 1 having the structure described above can exhibit excellent gas barrier properties.

Next, a laminated material using the above-described gas barrier film 1 of the present invention will be described.

FIG. 2 is a schematic sectional view showing an example of a laminated material 20 using the gas barrier film of the present invention. As shown in FIG. 2, the laminated material of the present invention includes a heat-sealing layer 5 and a printed pattern layer 6 on the surface of the resin cured film 4 in the gas barrier film 1 shown in FIG. Are laminated.

In the laminated material 20 of the present invention, the layer laminated on the surface of the resin cured film 4 only needs to include at least a heat seal layer, and can be arbitrarily selected depending on the purpose and use of the laminated material. is there.

First, the heat seal layer 5 will be described.

The heat sheath constituting the laminated material 20 of the present invention
The metal layer 5 may be any material that can be melted and fused to each other by heat, such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, and ethylene. -Vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene or Acid-modified polyolefin-based resins, poly (vinyl acetate) -based resins obtained by modifying polyolefin-based resins such as polypropylene with acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and other unsaturated carboxylic acids. 1 of polyester resin, polystyrene resin, and other resins Or it may be a resin composed of more.

Further, a resin film or sheet formed by using one or more of the above-mentioned resins by a method such as an inflation method, a T-die method, or the like, or It can be used as a coating film made of a resin composition containing one or more of the above resins as a main component of the vehicle.
The thickness is about 5 to 100 μm, preferably 1 to 100 μm.
About 0 to 50 μm is desirable.

In the present invention, among the resins forming the heat seal layer as described above, it is particularly preferable to use a linear (linear) low-density polyethylene. The above-mentioned linear low-density polyethylene has the advantage of having a small amount of propagation of rupture due to its tackiness and improving impact resistance. It is also effective for preventing deterioration of environmental stress cracking properties.

In the present invention, other resins can be blended with the linear low-density polyethylene. For example, by blending an ethylene-butene copolymer or the like, the heat-resistance is slightly lower than that of the high-temperature environment. Although the seal stability tends to be deteriorated under the following conditions, there is an advantage that the tearability is improved and contributes to easy opening. Further, in the present invention, as the linear low-density polyethylene as the heat-sealing resin, specifically, an ethylene-α-olefin copolymer polymerized using a metallocene catalyst is used. be able to. Specifically, the product name "Kernel" manufactured by Mitsubishi Chemical Corporation, the product name "Evolu" manufactured by Mitsui Petrochemical Industry Co., Ltd., the product name "EXACT" manufactured by EXXON CHEMICAL, USA (EXACT) ", Dow Chemical, USA (DO
W CHEMICAL) brand name “Affinity-
(AFFINITY), brand name "ENGAGE (ENGA
GE) ”and the like, and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst can be used. In the present invention, when an ethylene-α-olefin copolymer polymerized by using the above-mentioned metallocene catalyst is used, an advantage that a low-temperature heat-sealing property can be obtained at the time of producing a bag is provided. Have

Next, the printed picture layer 6 constituting the laminated material 20 of the present invention will be described. The print pattern layer 6
Is a layer that is not an essential component of the laminated material of the present invention but can be arbitrarily provided.

As such a printed picture layer 6, for example, a usual gravure ink composition, offset ink composition, letterpress ink composition, screen ink composition, or the like may be formed on the above-mentioned coated cured film. Using ink compositions such as gravure printing, offset printing, letterpress printing, silk screen printing, etc., for example, characters, graphics, pictures, symbols, etc. It can be constituted by forming a desired print pattern composed of the above. In the above, various ink compositions include, for example, vehicles constituting the ink composition include, for example, polyethylene resins, polyolefin resins such as chlorinated polypropylene resins, poly (meth) acrylic resins, and polyvinyl chloride. Resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer,
Polystyrene resin, styrene-butadiene copolymer,
Vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral
Resin, polybutadiene resin, polyester resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, melamine resin, urea resin, polyurethane Resin, phenolic resin, xylene resin, maleic resin, cellulose resin such as nitrocellulose, ethylcellulose, acetylbutylcellulose, ethyloxyethylcellulose, chloride rubber, and cyclized rubber Resin such as rubber-based resin, petroleum-based resin, rosin, casein, etc., linseed oil, soybean oil, etc., and other resins
A mixture of species or two or more species can be used. Thus, in the present invention, one or more of the above-mentioned vehicles are used as a main component, and one or more of colorants such as dyes and pigments are added thereto. ,
For example, fillers, stabilizers, plasticizers, antioxidants, light stabilizers such as ultraviolet absorbers, dispersants, thickeners, drying agents, lubricants,
It is possible to use ink compositions of various forms obtained by arbitrarily adding additives such as an antistatic agent, a cross-linking agent, and the like, and kneading them sufficiently with a solvent, a diluent, or the like.

When the laminate according to the present invention is used as a packaging container, the packaging container is usually subjected to severe physical and chemical conditions. Strict packaging suitability is required, and various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing, quality maintenance, workability, hygiene, etc. are required, For this purpose, in the present invention, a material that satisfies the above conditions is arbitrarily selected and used,
These can be laminated in addition to the above-mentioned materials constituting the laminated material according to the present invention to form a desired laminated material.

Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene -Ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-chloride Vinylidene copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester Resin, polyamide resin , Polycarbonate - Bonnet - Doo-based resin,
Films or sheets of known resins such as polyvinyl alcohol-based resins, saponified ethylene-vinyl acetate copolymers, fluorine-based resins, diene-based resins, polyacetal-based resins, polyurethane-based resins, nitrocellulose, etc. -Can be arbitrarily selected and used. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used. In the present invention, the above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but can be selected from a range of several μm to about 300 μm. Further, in the present invention, as the film or sheet, extrusion film formation,
Any film such as an inflation film or a coating film may be used.

The method for producing the laminated material of the present invention using the gas barrier film, printed picture layer, heat seal layer, and other materials of the present invention includes the following.
Dry lamination using a laminating adhesive via a laminating adhesive layer, or extruding laminating using a melt-extruding adhesive resin via a melt-extruded resin layer. Can be. In the above, the laminating adhesive may be, for example, a one-part or two-part curing or non-curing type vinyl, (meth) acrylic, polyamide, polyester, polyether or polyurethane. System, epoxy, rubber, etc. solvent type, aqueous type, or
An adhesive for a laminate such as an emulsion type can be used. Examples of the coating method of the adhesive for laminating include direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating and the like. Method, Fonten method, transfer
It can be applied by a roll coating method or other methods, and the coating amount is 0.1 to 10 g / m 2.
² (dry state), more preferably 1 to 5 g / m ² (dry state). In the present invention, for example, an adhesion promoter such as a silane coupling agent can be optionally added to the adhesive for laminating. Next, in the above, as the melt-extruded adhesive resin, the above-mentioned heat-sealing resin forming the heat-sealing layer can be similarly used. Thus, in the present invention, it is preferable to use a low-density polyethylene, particularly a linear low-density polyethylene, and an acid-modified polyethylene as the melt-extruded adhesive resin. The thickness of the melt-extruded resin layer of the melt-extruded adhesive resin is about 5 to 100 μm, more preferably,
About 10 to 50 μm is desirable. In the present invention,
If it is necessary to obtain a stronger adhesive strength when performing the above-mentioned lamination, if necessary, for example, an adhesive improver such as an anchor coat agent may be coated. Specific examples of the above-mentioned anchor coating agent include organic titanium-based anchor coating agents such as alkyl titanate, isocyanate-based anchor coating agents, and polyethyleneimine-based anchor coating agents. Various aqueous or oil-based anchor coating agents, such as a coating agent, a polybutadiene-based anchor coating agent, and the like, can be used. Thus, in the present invention, the above-mentioned anchor coating agent is, for example, roll-coated.
Coating, gravure coating, knife coating, dip coating, spray coating, and other coating methods, and drying the solvent, diluent, etc. to form an anchor coating agent layer. can do. In the above, the coating amount of the anchor coating agent is 0.1 to 5 g / m ² (dry state).
Position is desirable.

The laminate of the present invention described above has excellent gas barrier properties and can be suitably used as a packaging material.

[0080]

The present invention will be described more specifically with reference to the following examples and comparative examples. (Example 1) (1) Formation of a silicon oxide film A roll-shaped biaxially stretched polyester film (made by Unitika, PET, 12 μm thick, 700 mm wide, 5 mm long as a substrate)
000m) is prepared, and is supplied to the chamber 10 of the plasma-enhanced chemical vapor deposition apparatus 101 equipped with the winding mechanism shown in FIG.
2. Next, the inside of the chamber 102 of the chemical vapor deposition apparatus 101 is filled with an oil rotary pump and an oil diffusion pump 10.
3, the ultimate vacuum degree is 3.0 × 10 ⁻⁵ Torr (4.0).
× 10 ⁻³ Pa).

As the source gas 104, tetramethoxysilane (TMOS, Shin-Etsu Chemical Co., Ltd., KBM-0)
4) and oxygen gas (Taiyo Oriental Oxygen Co., Ltd., purity 9)
9.9999% or more) and helium gas (Taiyo Toyo Oxygen Co., Ltd., purity 99.9999% or more) were prepared.

Next, in the vicinity of the coating drum 105,
The electrode 106 is opposed to the coating drum 105.
And the coating drum 105 and the electrode 106
Between the high frequency power of 40 kHz (input power:
3.0 kW).

Then, a TMOS gas 3 is supplied through a gas inlet 107 provided near the electrode 106 in the chamber 102.
00 sccm, oxygen gas 50 sccm, helium gas 1
2,000 sccm is introduced, and the degree of opening and closing of the valve 108 between the vacuum pump 103 and the chamber 102 is controlled, so that the inside of the film formation chamber is 5 × 10 ⁻² Torr.
(6.7 Pa), and a silicon oxide film was formed on the substrate film. The running speed of the base film 200 was set so that the thickness of the silicon oxide film was 100 nm, and the transparent gas barrier film of Example 1 was obtained.

(2) Removal Treatment Using Hydrofluoric Acid As shown in FIG. 4, the gas barrier film on which the silicon oxide film has been formed is set in the raw fabric processing apparatus 400 and
The substrate was treated with a 0.5% hydrofluoric acid solution 401 at 5 ° C. for 5 seconds, washed with water 402 for 60 seconds, and then dried by a drying device 403.

(3) Formation and Printing of Resin Cured Film A gravure coating roll was set on the surface of the hydrofluoric acid-treated silicon oxide film on the surface of the silicon oxide film using a gravure printing machine. 10 parts by weight of an alcohol copolymer (ethylene content 32 mol%), 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of isopropyl alcohol, 0.17 parts by weight of a tertiary amine catalyst,
In addition, an aqueous resin composition consisting of 3.4 parts by weight of epoxysilane was used, and this was coated by a gravure roll coating method to form a cured resin film having a thickness of 1.1 g / m ² (dry state). Next, a gas barrier film according to the present invention was manufactured by curing the cured resin film by heating at 120 ° C. for 2 minutes.

Next, on the cured resin film of the gas barrier film, using the gravure printing machine described above, a gravure ink composition was used to form a multicolor printing pattern layer using the gas barrier film of the present invention. .

(4) Lamination (dry lamination; D
L) Next, the biaxially stretched polyethylene terephthalate film having the printed pattern layer formed thereon was dried by a first laminating machine.
Attached to a delivery roll, a two-component curable polyurethane-based laminating adhesive is applied to the printed pattern layer surface at a rate of 4.5 g / m ² (dry weight) using a gravure roll coating method, and is used for lamination. An adhesive layer was formed, and a low-density polyethylene film having a thickness of 70 μm was dry-laminated on the surface of the adhesive layer for lamination to produce a laminate according to Example 1 of the present invention.

Example 2 (1) Formation of Silicon Oxide Film Instead of a roll-form biaxially stretched polyester film (made by Unitika, PET, 12 μm thick), a biaxially stretched polypropylene film (Fujimura Chemical) A film was formed in the same manner as in Example 1 except that a silicon oxide film was deposited on the corona-treated surface of the substrate using GH-I (trade name, manufactured by Kogyo Co., Ltd., trade name: single-sided corona treated product, thickness: 20 μm).

(2) Removal treatment using hydrofluoric acid The same treatment as in Example 1 was performed.

(3) Formation and Printing of Resin Cured Film A gravure printing machine was used on the surface of the above-mentioned hydrofluoric acid-treated silicon oxide film, and a gravure coating roll was set for the first color, and ethylene 10 parts by weight of a vinyl alcohol copolymer (ethylene content 29 mol%), 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of isopropyl alcohol, 0.17 parts by weight of a tertiary amine catalyst, and epoxy silane 3 An aqueous resin composition consisting of 0.4 parts by weight was coated by a gravure roll coating method to form a cured resin film having a thickness of 0.9 g / m ² (dry state). For 3 minutes to cure the resin cured film, thereby producing a gas barrier film according to the present invention.

Next, a multicolor printing pattern layer using the gas barrier film of the present invention was formed on the cured resin film of the gas barrier film using the gravure ink composition using the gravure printing machine described above. .

(4) Lamination (dry lamination; D
L) Next, the biaxially stretched polypropylene film on which the printed picture layer was formed was mounted on a first delivery roll of a dry laminator, and a two-component curable polyurethane-based laminate was applied to the printed picture layer using a gravure roll coating method. Apply the adhesive at a rate of 4.5 g / m ² (dry weight),
An adhesive layer for lamination was formed, and an unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the adhesive layer for lamination to produce a laminate according to Example 2 of the present invention.

Example 3 (1) Formation of Silicon Oxide Film Instead of a roll-form biaxially stretched polyester film (made by Unitika, PET, 12 μm thick), a biaxially stretched polypropylene film (Toyobo) Product name
N1102, single-sided corona-treated product, thickness 15 μm), and a film was formed in the same manner as in Example 1 except that a silicon oxide film was deposited on the corona-treated surface of the substrate.

(2) Removal treatment using hydrofluoric acid The same treatment as in Example 1 was performed.

(3) Formation and Printing of Resin Cured Film A gravure printing machine was used on the surface of the hydrofluoric acid-treated silicon oxide film, and a gravure coating roll was set for the first color. 10 parts by weight of a vinyl alcohol copolymer (ethylene content 32 mol%), 34 parts by weight of tetraethoxysilane, 15 parts by weight of water, 10 parts by weight of isopropyl alcohol, 0.17 parts by weight of a tertiary amine catalyst, and epoxy silane 3 An aqueous resin composition consisting of 0.4 parts by weight was used and coated by a gravure roll coating method to form a cured resin film having a thickness of 1.2 g / m ² (dry state). The gas barrier film according to the present invention was produced by curing the cured resin film by heating for 1 minute.

Next, a multicolor printing pattern layer using the gas barrier film of the present invention was formed on the cured resin film of the gas barrier film using the gravure ink composition using the gravure printing machine described above. .

(4) Lamination (dry lamination; D
L) Next, the biaxially-stretched polypropylene film having the printed pattern layer formed thereon was mounted on a first delivery roll of a dry laminator, and a two-component curable polyurethane-based laminate was applied to the printed pattern layer surface using a gravure roll coating method. Apply the adhesive at a rate of 4.5 g / m ² (dry weight),
An adhesive layer for lamination was formed, and an unstretched polypropylene film having a thickness of 70 μm was dry-laminated on the surface of the adhesive layer for lamination to produce a laminate according to Example 3 of the present invention.

(Example 4) In (4) of Example 1 described above, a low-density 70 μm thick film was placed on the printed pattern layer surface of a biaxially stretched polyethylene terephthalate film having a printed pattern layer formed thereon via a laminating adhesive. Instead of dry laminating a polyethylene film to produce a laminate,
The biaxially stretched polyethylene terephthalate film on which the printed picture layer is formed is mounted on the first delivery roll of an extruder, and the printed picture layer surface is melt-extruded to a thickness of 20 μm using low-density polyethylene for melt extrusion. Extrusion and lamination of a low-density polyethylene film having a thickness of 70 μm.
A laminate according to Example 4 of the present invention was manufactured in exactly the same manner as in Example 1.

(Example 5) [0099] In Example 2 (4), the thickness of the biaxially stretched polypropylene film on which the print pattern layer was formed was applied to the print pattern layer surface via a laminating adhesive.
Instead of dry laminating a 0 μm low-density polyethylene film to produce a laminated material, a biaxially stretched polypropylene film having a printed pattern layer formed thereon is mounted on a first delivery roll of an extruder and melted on the printed pattern layer surface. Using a low-density polyethylene for extrusion, while extruding this to a thickness of 20 μm, an unstretched polypropylene film having a thickness of 70 μm was extruded and laminated. 5 were manufactured.

(Example 6) In Example 3 (4),
The thickness of the biaxially stretched polyamide film having the printed pattern layer formed on the surface of the printed pattern layer is reduced to 70 by a laminating adhesive.
Instead of dry laminating a low-density polyethylene film of μm to produce a laminated material, a biaxially stretched polyamide film having a printed picture layer is mounted on the first delivery roll of an extrusion laminating machine and melted on the printed picture layer surface. Use low density polyethylene for extrusion, thickness 20μ
m, while extruding a 70 μm-thick unstretched polypropylene film while extruding the same, and laminating the same.
Was manufactured.

(Comparative Examples 1 to 6) In Examples 1 to 6,
In each case, those without the hydrofluoric acid treatment after the deposition of the silicon oxide film were used as comparative examples. (Evaluation method) The gas permeability was measured under the following conditions. The evaluation results are shown in Table 1 below.

Oxygen gas permeability measurement: Oxygen gas permeability measurement device (OX-TRAN 2/2, manufactured by MOCON)
0), Measurement conditions: temperature 23 ° C., humidity 90% Rh.

Water vapor transmission rate measurement: Water vapor transmission rate measuring apparatus (PERCONTRAN-W 3/3 manufactured by MOCON)
1), Measurement conditions: 37.8 ° C, 100% Rh.

[0104]

[Table 1] As is clear from Table 1 above, it was found that the laminated material of the present invention had excellent gas barrier properties.

[0105]

As described above, by removing the surface of the silicon oxide film, a fine uneven structure is formed on the surface, and the silicon oxide film and the resin cured film having such fine unevenness are formed. By combining with the above, a concave portion on the surface of the silicon oxide film, that is, a portion of the conventional silicon oxide film that has poor barrier properties (does not contribute to barrier properties),
It can be filled with a cured resin film having a barrier property, and a film having excellent gas barrier properties as a whole can be formed.

By forming a laminate using the gas barrier film, the laminate can be suitably used as a packaging material.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of the configuration of a gas barrier film of the present invention.

FIG. 2 is a schematic cross-sectional view showing one example of a laminate of the present invention using the gas barrier film of the present invention shown in FIG.

FIG. 3 is a configuration diagram illustrating an example of a plasma CVD apparatus.

FIG. 4 is a configuration diagram illustrating an example of a web drying device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Gas barrier film 2 ... Substrate 3 ... Silicon oxide film 4 ... Resin cured film 5 ... Heat seal layer 6 ... Printed pattern layer

Front page of the continued F-term (reference) 4F100 AA20B AA20D AH06C AH06E AH06H AH08C AH08E AH08H AK01C AK01E AK41A AK69C AK69E AK69K AT00A BA05 BA06 BA10C BA10E CA02C CA02E CA30C CA30E DD07B EH46 EH66B EH66D EJ15B EJ38A EJ59 EJ61B EJ61D GB15 GB41 JB12C JB12E JD02 JL12E JM02B JM02D 4K030 BA44 CA07 CA12 DA08 LA01 LA11

Claims (9)

[Claims] 1. A gas barrier film comprising: a substrate; a silicon oxide film formed on both surfaces or one surface of the substrate by a plasma CVD method; and a resin cured film covering a surface of the silicon oxide film. A gas barrier film having fine irregularities formed by performing a removal treatment for removing a portion having poor gas barrier properties on a surface of a silicon oxide film in contact with the resin cured film. 2. The gas barrier film according to claim 1, wherein the removal treatment is a removal treatment with a strong acid or a strong alkali. 3. The gas barrier film according to claim 2, wherein the removal treatment is a removal treatment using hydrofluoric acid, an aqueous solution of ammonium fluoride, or a mixed solution thereof. 4. The resin cured film according to claim 1, wherein the resin-cured film has an ethylene-vinyl alcohol copolymer as a main component and further contains at least a metal alkoxide compound. The gas barrier film according to the above. 5. The gas barrier film according to claim 4, wherein the ethylene-vinyl alcohol copolymer has an ethylene content of 25 to 50 mol%. 6. The gas barrier film according to claim 4, wherein the metal alkoxide compound is an alkoxysilane compound. 7. The gas barrier film according to claim 1, wherein the cured resin film contains a curing catalyst. 8. The gas barrier film according to claim 1, wherein the cured resin film contains a silane coupling agent. 9. At least the claims 1 to 8
A gas barrier film according to any one of claims,
A laminated material comprising a gas barrier film and a heat sealing layer provided on a surface of a cured resin film of the gas barrier film.