JPH08294991A - Barrier laminate - Google Patents

Abstract

PURPOSE: To obtain a barrier laminate having a good adhesiveness with resin and an evaporated thin film, and also having no possibility of barrier deterioration by laminating a hydrolyzate of a specific organic silicon compound, a conductive hydrolyzate layer consisting of conductive metal particles, and vapor deposited thin film on one or both surfaces of a resin film. CONSTITUTION: The barrier laminate 1 is formed of a resin film base material 2, a conductive hydrolyzate layer 3 consisting of hydrolyzate of a silicone compound or a alkoxide and a conductive metal particles, and vapor deposition thin film 4. The conductive hydrolyzate layer 3 is composed of a 1-99wt.% of hydrolyzate of an organic silicon compound represented by the formula of R-Si-(OR')3 (R represents an organic functional group, R' represents a hydrolytic group), and 1-99wt.% of conductive metal particles. Since the organic functional group has a strong bonding force and adhesiveness with resin of the resin film, the adhesiveness between the film and the vapor deposition thin film can be enhanced, and the lowering of a barrier property against gasses such as oxygen and steam can be prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can effectively prevent the permeation of gases such as oxygen and water vapor, which are used in the packaging field of foods, medical products and the like, and can be used in vapor deposition processing, printing processing, laminating processing and the like. The present invention relates to a laminate that prevents static electricity and has stable gas barrier performance.

[0002]

2. Description of the Related Art In recent years, packaging materials used for packaging foods, pharmaceuticals and the like have the purpose of suppressing deterioration of contents, particularly oxidation and deterioration of proteins and fats and oils in foods, and further maintaining taste and freshness. In addition, in the case of pharmaceuticals that require aseptic handling, the effects of oxygen, water vapor and other gases that permeate the packaging material are prevented in order to prevent deterioration of the active ingredient and maintain efficacy. Therefore, it is required to have a gas barrier property for blocking these gases.

For this reason, a polyvinyl alcohol film (P
VA), ethylene vinyl alcohol copolymer film (EVOH), polyacrylonitrile film (PAN), etc., and polypropylene film (OPP), polyethylene film (PE), etc. as gas barrier barrier films are laminated with gas barrier properties. It is used as a body as a packaging material, and a packaging film made of this packaging material has been generally used. However, these films alone do not have barrier properties against both oxygen and water vapor, and are generally laminated by laminating or coating other types of polymer resin compositions having different properties which are said to have relatively high gas barrier properties. Although it has been used as a film as a packaging material, it may not be able to exert a sufficient gas barrier property under the influence of temperature and humidity in storage and use environments.

Further, as a resin film having a gas barrier property against both oxygen and water vapor alone, polyvinylidene chloride film (PVDC), polyester film (PET), polypropylene film (OPP),
Also, there is a coat (K coat) film obtained by coating polyvinylidene chloride on a nylon film (Ny).
When such a resin film is discarded after use and incinerated, a toxic gas is generated, which may cause an environmental problem.

On the other hand, as a packaging material which requires a high gas barrier property, a conventional resin film (even a resin which does not have a high gas barrier property alone with an appropriate polymer resin composition) is used as a packaging material. Metal foils composed of metals or metal compounds such as Such metal foils contain oxygen,
Has excellent barrier properties against gases such as water vapor,
Since metal remains as a residue when it is incinerated as waste after use and it is difficult to reuse it, the disposal of this metal foil cannot avoid the environmental impact.

In order to solve the above problems, recently, silicon oxide (SiOx) such as silicon monoxide (SiO), aluminum oxide (AlxOy),
Vapor-deposited films have been developed in which a thin film of a metal such as aluminum (Al) or a metal oxide is formed on a resin film by means of vapor deposition or the like. These are superior to gas barrier materials made of polymer resin compositions. It also has excellent gas barrier properties and little deterioration under high humidity, and is beginning to be used for packaging materials.

The packaging material made of these vapor-deposited films is rarely used as a vapor-deposited film alone, and is processed into a packaging container, a packaging bag or the like as post-processing after vapor deposition. For example, a packaging bag is processed into a bag shape by a bag-making process in which a vapor-deposited film is further bonded to another base material.

[0008]

However, a vapor-deposited film in which the above metal or metal oxide is formed as a thin film on a resin film includes a resin film which is an organic compound and a vapor-deposited thin film which is an inorganic compound in contact with the resin film. Then
The physical properties of the two are very different, such as mechanical properties, chemical properties, thermal properties, and electrical properties.

Therefore, mechanical stress, thermal stress, etc. are added to the vapor-deposited thin film depending on the manufacturing process as a packaging material such as vapor deposition, printing, laminating, etc., the method of use as a packaging bag and the environment of use. Distortion occurs in the vapor-deposited thin film, damage and defects such as cracks and pinholes occur in the vapor-deposited film, and gases such as oxygen and water vapor permeate through these damaged and defective portions, which is a high level that conventional equipment should have. It has a problem that the barrier performance is lowered.

Further, it is difficult to obtain a strong chemical bond between the vapor-deposited thin film of the inorganic compound and the resin film which is the organic compound, and delamination occurs between the resin film, the ink, the adhesive, etc., resulting in sufficient adhesion. In addition to that, the vapor-deposited thin film is damaged and the barrier property is deteriorated.

In order to solve such problems, a method for improving the adhesion between the resin film as the vapor deposition base material and the vapor deposition film includes, for example, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, flame treatment of the surface of the resin film. In some cases, the surface is activated by a surface treatment with a chemical such as acid or alkali, and then the metal or metal oxide is vapor-deposited.
However, although improvement in adhesiveness can be expected by improving the secondary bonding force with the vapor-deposited thin film by improving the wettability of the resin film,
It has a problem that its activity ability decreases with time, and that a satisfactory adhesive force cannot be obtained even by this treatment, and it cannot be said to be sufficient.

As another method, there is a method of using a copolymerized resin film obtained by copolymerizing a resin film with other resin components or the like, and a coextruded multilayer resin film obtained by coextruding another resin at the time of forming the resin film. . Although the adhesion is improved, the heat resistance is inferior, so the thermal dimensional stability is poor, and the vapor-deposited thin film is subjected to mechanical stress during heat load in each process such as vapor deposition, printing, laminating, etc. Holes are generated and the barrier properties deteriorate, so it cannot be said to be sufficient.

A method of applying a coating material such as ethyleneimine-based, amine-based, epoxy-based, urethane-based, or polyester-based on the surface of the resin film, which is the vapor deposition substrate, at the time of forming the resin film, offline or inline. There is. Although the adhesion is improved, the heat resistance is inferior, so the thermal dimensional stability is poor, and the vapor-deposited thin film is subjected to mechanical stress during heat load in each process such as vapor deposition, printing, laminating, etc. Holes are generated and the barrier properties deteriorate, so it cannot be said to be sufficient.

Further, the adhesion between the vapor-deposited thin film formed on the resin film and the inks, adhesives, etc. added in the printing and laminating processes has been improved, and ethyleneimine type, amine type, epoxy type, There is a method of applying a urethane-based or polyester-based coating material. Depending on the resin component of the coating agent, the adhesiveness may be deteriorated or the barrier property may be deteriorated, and both the adhesiveness and the barrier property are not satisfied. According to this, since the thermal dimensional stability of the coating layer is poor, the vapor-deposited thin film undergoes mechanical stress due to volume expansion or volume contraction due to the heat load applied at the time of diameter or during the bag making process or the molding process, and the vapor-deposited thin film becomes The barrier properties deteriorated due to cracks, pinholes, delamination from ink, adhesive, etc.

A major cause of impairing the barrier property is the charging of the resin film and the vapor deposition film. Vapor deposition processing,
Since the manufacturing process such as printing process and laminating process is a web winding process, electrostatic charge is apt to occur, and ink is likely to fall off and adhesion failure is likely to occur in a portion where dust is caught by the charge. In addition, in the vapor deposition by the electron beam (EB) heating method, in addition to being in a dry state which is easily charged by static electricity because of the vacuum, the vapor deposition is caused by secondary electrons emitted from the vapor deposition material irradiated with the electron beam. The film becomes excessively charged. Such a charged vapor deposition film causes an arcing phenomenon during the web winding process and causes defects such as cracks in the vapor deposition thin film.Thus, gas such as oxygen and water vapor permeates from the damaged portion and the defective portion, It has a problem that the high barrier performance which should be possessed conventionally is deteriorated.

To solve such problems, there are a method of kneading an antistatic agent into a resin film and a method of coating an antistatic paint on the resin film. However, conventional kneading of antistatic agents and coating types of antistatic paints have a large humidity dependency, and there is a drawback that the effect is not exerted in a low humidity atmosphere, particularly metal or metal oxide on a resin film. In the vapor deposition step, since it is a vacuum, it is in an extremely low humidity atmosphere, and the effect is hardly exhibited. Therefore, dust adheres to the resin film before forming the vapor-deposited thin film, and the vapor-deposited thin film formed on the dust is easily peeled off to form a pinhole, which deteriorates the barrier property. For secondary electron charging from the vapor deposition material during vapor deposition, it is usually necessary to neutralize and remove the charged electrons by plasma discharge treatment on the surface of the vapor deposited film immediately after vapor deposition. Since the sufficient static elimination effect against charging is not exhibited, the static elimination conditions by the plasma discharge treatment immediately after vapor deposition are not stable. That is, the adjustment becomes extremely difficult, the static elimination effect varies, and it is difficult to obtain a vapor-deposited thin film having a stable barrier property.

Further, depending on the type of the antistatic agent, there is a drawback that it reacts with oxygen in the air and its effect decreases with time.

Further, there are methods of kneading and coating an antistatic filler in the resin film, but there is a method of coating, but the particle size of the filler is large and the surface of the resin film on which the vapor-deposited thin film is formed becomes rough, and pinholes and cracks are formed in the vapor-deposited thin film. There is a drawback that it tends to occur.

Therefore, the present invention is excellent in the adhesion between the resin film and the vapor-deposited thin film, the adhesion between the ink and the adhesive, and oxygen,
Without lowering the barrier property against gases such as water vapor, further, in processing such as vapor deposition, printing, laminating, etc.
We provide a highly practical barrier laminate that can remove electrostatic charges due to static electricity satisfactorily without depending on humidity, and prevents the deposition of vapor-deposited thin films, inks, adhesives, etc., and the adhesion of dust that causes pinholes. The purpose is to do.

[0020]

The invention according to claim 1 is characterized in that 1 to 99 parts by weight of a hydrolyzate of an organosilicon compound represented by the chemical formula (I) according to claim 1 is provided on one side or both sides of a resin film. %, A conductive hydrolyzate layer composed of 1 to 99% by weight of conductive metal particles, and a vapor-deposited thin film layer composed of a metal or a metal compound, which are sequentially stacked, which is a barrier laminate.

The invention according to claim 2 is characterized in that 1 to 99% by weight of the hydrolyzate of the alkoxide represented by the chemical formula (II) according to claim 2 and the conductive metal particles 1 are provided on one side or both sides of the resin film. The barrier laminate is characterized in that a conductive hydrolyzate layer of about 99 wt% and a vapor-deposited thin film layer of a metal or a metal compound are sequentially laminated.

The present invention according to claim 3 further comprises the vapor-deposited thin film layer comprising the metal or metal compound according to claim 1, further comprising:
A barrier property comprising a coating film layer comprising 1 to 99% by weight of the organosilicon compound according to claim 1, 1 to 99% by weight of conductive metal particles, and 1 to 99% by weight of a binder. It is a laminated body.

The invention according to claim 4 is such that 1 to 99% by weight of the alkoxide according to claim 2 and 1 to 99% by weight of conductive metal particles are formed on the vapor-deposited thin film layer comprising the metal or metal compound according to claim 2. %, And a coating layer composed of 1 to 99% by weight of a binder are laminated, which is a barrier laminate.

The invention according to claim 5 is formed by laminating the organic silicon compound represented by the chemical formula (I) according to claim 1 on the vapor-deposited thin film layer comprising the metal or metal compound according to claim 1. It is a barrier layered product characterized by the above.

According to a sixth aspect of the present invention, the alkoxide represented by the chemical formula (II) according to the second aspect is laminated on the vapor-deposited thin film layer comprising the metal or the metal compound according to the second aspect. It is a characteristic barrier laminate.

The invention according to claim 7 is a vapor-deposited thin film layer comprising the metal or metal compound according to claim 1, which is provided in the outermost layer, a coating layer according to claim 3, or an organosilicon compound according to claim 5. A barrier laminate comprising a heat-adhesive resin layer laminated on the layer via an adhesive layer.

The invention according to claim 8 is a vapor-deposited thin film layer comprising the metal or metal compound according to claim 2, which is provided as an outermost layer, a coating layer according to claim 4, or an alkoxide coating layer according to claim 6. And a heat-adhesive resin layer laminated via an adhesive layer, which is a barrier laminate.

[0028]

According to the present invention, the function of the organosilicon compound in the conductive hydrolyzate layer is that the organic functional group has a strong bonding force with the resin of the resin film and a strong adhesion. In addition, when the organosilicon compound is dissolved in water or a mixed solution of water and alcohol during coating, the hydrolyzable group of the organosilicon compound is hydrolyzed to generate a hydroxyl group (-OH), which is active.
A Si-OH bond is formed, and the active -Si-OH bond is formed by the thermal decomposition reaction in the drying step, whereby a strong -O-Si-O-Si layer of the conductive hydrolyzate layer made of an organosilicon compound is formed.
-Create a bond.

Since this active --Si--OH bond forms a strong bond --O--Si--OM--O-- in the presence of the metal element (M), the metal element (M ') of the vapor-deposited thin film, or Metal element (M ') in metal compound and -Si-OM'
A strong —O— bond is formed, and the adhesion between the organosilicon compound and the deposited thin film layer is improved.

The action of the alkoxide in the conductive hydrolyzate layer is that the alkoxide is hydrolyzed when the alkoxide is dissolved in water or a mixed solution of water and alcohol at the time of coating the alkoxide. (-O
H) is produced to form an active -M-OH bond, and this active -M-OH bond forms a strong -OMOMOM bond of an alkoxide by a thermal decomposition reaction in the drying step. To generate.

Since this active --M--OH bond forms a strong bond --O--M--O--M--O-- in the presence of the metal element (M), the metal element (M ') in the deposited thin film, or The metal element (M ') in the metal compound, and further the oxygen element (O') in the vapor-deposited thin film are also entangled, and -O-M-O'-M'-O.
A strong bond of-is formed, and the adhesion between the alkoxide and the vapor-deposited thin film layer is improved.

Such an organosilicon compound or alkoxide is excellent in heat resistance, thermal dimensional stability and hardness, and the vapor deposition thin film layer can be protected from mechanical stress and strain due to thermal stress due to the structure sandwiching the vapor deposition thin film layer. it can.

The action of the conductive metal particles in the conductive hydrolyzate layer consisting of the organic silicon compound or alkoxide formed on the resin film, and the conductive metal particles and the binder is due to the action inside the thin coating layer or the organic silicon layer. Since the compound or the alkoxide is uniformly dispersed or bonded in the network, the conductive hydrolyzate layer itself can be provided with conductivity, and constant static charge removal can be performed without depending on humidity. Furthermore, as for the charging by the secondary electrons from the deposition material during deposition, a sufficient charge-eliminating effect is exhibited against the charging by the static electricity before deposition. It can be easily adjusted by the neutralization method of neutralization of charged electrons by discharge treatment.
It tends to be a vapor-deposited thin film that can exhibit stable barrier properties.

[0034]

【Example】

A detailed description will be given based on an embodiment of the present invention.
FIG. 1 is a cross-sectional view for explaining the constitution of the barrier laminate of the present invention, and FIGS. 2, 3, 4, 5, and 6 respectively show other constitutions of the barrier laminate of the present invention. FIG.

In FIG. 1, 1 is a barrier laminate, which is a resin film substrate 2, a hydrolyzate of an organic silicon compound or an alkoxide, and a conductive hydrolyzate layer 3 composed of conductive metal particles, and a vapor-deposited thin film layer. It is 4. The resin film substrate 2 is in the form of a sheet or a film, and is made of polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polyethylene 2,4-naphthalate, etc.), polyamide (nylon-6, nylon-12, etc.). ), Polyvinyl chloride, polyvinyl alcohol, aromatic polyamide, polyamideimide, polyetherimide polysulfone, polyether sulfone, polyether ketone, polyarylate,
Polyphenylene sulfide, polyphenylene oxide, tetrafluoroethylene, trifluoroethylene monochloride, fluorinated ethylene-propylene copolymer, polyimide and the like which are usually used as packaging materials can be used. These resin film base materials 2 are appropriately selected from the above materials according to the application. A biaxially stretched resin film can be used if necessary. Known additives such as an antistatic agent, an ultraviolet absorber, a reversible agent, a lubricant, and a coloring agent can be added to these resin film base materials 2, and they are appropriately added as necessary.

Furthermore, the surface of the resin film substrate 2 on which the conductive hydrolyzate layer 3 composed of the organosilicon compound or alkoxide and the conductive metal particles and the binder is subjected to corona discharge treatment, plasma activation treatment, glow discharge treatment, and reverse. Performing a known surface activation treatment such as sputtering treatment or surface roughening treatment, or applying an ethyleneimine-based, amine-based, epoxy-based, urethane-based, or polyester-based coating agent offline or in-line, Resin film substrate 2 and an organic silicon compound or alkoxide,
It is also possible to improve the adhesion of the conductive hydrolyzate layer 3 made of conductive metal particles.

The thickness of the resin film substrate 2 is not particularly limited, but if the processability of the vapor deposition process is taken into consideration, it is 2-4.
The range of 00 μm is preferable.

The conductive hydrolyzate layer 3 is an organosilicon compound.
And organosilicon compounds consisting of conductive particles
The product is an organic silica represented by the chemical formula (I) according to claim 1.
In an elementary compound, for example, the organic functional group (R) is —CH═CH
₂ -, -CH_2,-CH₂ -CH₂ -NH₂ -,-CH
₂ -NH₂ -,-CH₂ -NHCONH₂ -,-CH₂
-NH-CH₂ -CH₂ -NH₂ -,-CH₂ -OC
H₂ − (C₂ H₃ O) and the like, and a hydrolyzable group (R ')
Is -Cl, -CH₃ , -CH₂ -CH₃ , -CH ₂ -C
H₂ -O-CH₃ Etc., epoxy group, amino group, urine
Acid groups and the like are preferred. Further, a hydrolyzable group (R ')-Cl,-
CH₃ , -CH₂ -CH₃ , -CH₂ -CH₂ -OC
H₃ Etc. The above organosilicon compound is replaced with water, or
Applying an aqueous solution dissolved in a mixed solution of water and alcohol
I do.

When the conductive hydrolyzate layer 3 is composed of alkoxide and conductive metal particles, the alkoxide is composed of the alkoxide represented by the chemical formula (II), and the metal element (M) is aluminum ( Al), silicon (Si), titanium (Ti), zirconium (Zr), etc., and the alkyl group (R) is tetraethyl orthosilicate [Si (OC ₂ H ₅ ) ₄ ], triisopropoxy aluminum [Al (O -iC a ₃ H _{7) 3]} and the like. These are preferable because they are relatively stable in an aqueous solution, and the metal element (M) is preferably aluminum (Al), silicon (Si), and titanium (Ti), which have low reactivity with water. Especially, considering the cost. Silicon is preferred. An aqueous solution in which the above alkoxide is dissolved in water or a mixed solution of water and alcohol is applied.

This aqueous solution does not cause a significant chemical reaction with known silicon compounds, silane coupling agents, general dispersants, stabilizers, viscosity modifiers, colorants, surfactants and other organosilicon compounds. If so, it can be added if necessary.

In the conductive hydrolyzate layer 3, the conductive metal particles are titanium, aluminum, manganese, magnesium, chromium, nickel, iron, vanadium, cobalt,
Copper, scandium, zirconium, silver, palladium, zinc, yttrium, ruthenium, molybdenum, gallium, niobium, rhodium, indium, tin, technetium, gold, tantalum, platinum, thallium, osmium,
Tungsten, lanthanoids, rhenium, lead, bismuth, hafnium, iridium, etc. Further, any conductive alloy containing at least one of the above metals can be used. Conductive metal particles, conductive alloy particles 1
The particle size of the secondary particles is preferably 10 to 1000Å, and these particles further aggregate to form secondary particles of 20 to 3000Å.

These conductive metal particles and conductive alloy particles are prepared by first treating the salt of the above metal or alloy with polyvinyl alcohol, polyvinylpyrrolidone, water-soluble acrylic resin,
Water-soluble polymer such as water-soluble urethane resin, methanol,
Ethanol, butanol, in a mixed solution of alcohols such as isopropyl alcohol and water, or in a mixed solution of water-soluble organic solvents such as tetrahydrofuran, methyl ethyl ketone, acetone and the like, or the above alcohols and aqueous organic solvents and water Of the conductive metal particles, obtained as a dispersion of conductive alloy particles, obtained by boiling above the boiling point of the water-soluble organic solvent, below the boiling point of water,
A dispersion aqueous solution of conductive metal particles or conductive alloy particles or a dispersion mixed solution of alcohol and water is applied.

When the conductive hydrolyzate layer 3 is applied, a binder is used. The binder is, in addition to the above water-soluble polymer, a water-soluble acrylic resin, a water-acid urethane resin, a phenoxy resin, a water-dispersible polyester resin,
Examples thereof include vinyl chloride resin, vinyl acetate resin, and isocyanate resin. Even after the hydrolysis reaction, the shape of the conductive hydrolyzate layer 3 is generally changed or left as it is by performing or not performing the hydrolysis or condensation reaction.

The coating solution for forming a coating layer comprising an organosilicon compound or alkoxide, and conductive metal particles and a binder may be a known lubricant, antistatic agent, crosslinking agent, catalyst,
Additives such as an isocyanate compound, a silane coupling agent, a general dispersant, a stabilizer, a viscosity modifier, a colorant, and a surfactant can be added as necessary.

The mixing ratio of the organosilicon compound or alkoxide, the conductive metal particles and the binder in the coating layer comprising the organosilicon compound or alkoxide and the conductive metal particles and the binder is 1 to 99% by weight: 1 to 99% by weight. : 1 to 99% by weight.

As a method for forming a coating film layer comprising an organic silicon compound or alkoxide, and conductive metal particles and a binder, an in-line method of applying at the time of producing a resin film, or a step different from that at the time of producing a resin film is applied. There are two types of offline method, but the inline method has the advantages that it has fewer steps and less dust is mixed in the manufacturing process compared to the offline method, and that the inline method has a large adhesion to the resin film substrate 1. preferable.

In the in-line method, an unstretched resin obtained by heat-melting a polymer of a resin film and extruding the polymer as it is, or a resin in a state of being stretched uniaxially in either a longitudinal direction or a transverse direction before completion of crystal orientation On the film surface, an aqueous solution prepared by dissolving the above organosilicon compound or alkoxide in water or a mixed solution of water and alcohol (aqueous solution, mixed solution of water and alcohol, hydrolyzate of organic silicon compound or alkoxide, thermal decomposition product). (Including also)), a conductive metal particle, a conductive alloy particle dispersion aqueous solution or an alcohol / water dispersion mixed solution, and a binder, and a coating liquid is stirred. Surface treatment such as corona discharge treatment or plasma activation treatment may be performed before coating. The applied resin film undergoes the steps of biaxial stretching and heat setting to complete the transfer of crystals, whereby the coating layer becomes the conductive hydrolyzate layer 3. The conductive hydrolyzate layer 3 is dried by using the heat fixing step of the resin film, but it is preferable to provide the drying step immediately before that.

As the off-line method, a known coating method can be used. Examples include roll coating, roll brushing, spray coating, air knife coating, gravure coating, impregnation and curtain coating.

The layer thickness of the conductive hydrolyzate layer 3 is not particularly limited, but the layer thickness after drying is 0.01 to.
The thickness may be in the range of 50 μm, and the range of 0.05 to 5 μm is preferable in order to shorten the reaction rate and the drying rate.

The deposited thin film layer 4 includes aluminum, silica, titanium, zinc, zirconium, magnesium,
Metals such as tin, copper and iron and oxides, nitrides, sulfides and fluorides of these metals such as aluminum oxide (Al ₂ O ₃ ), silicon monoxide (SiO), silicon dioxide (SiO ₂ ), Titanium oxide (TiO ₂ ), zinc oxide (ZnO), zinc sulfide (ZnS), zirconium oxide (ZrO ₂ ), magnesium oxide (MgO), magnesium fluoride (MgF ₂ ), tin oxide (SnO ₂ ), copper oxide ( CuO), iron oxide (Fe ₂ O ₃ ) and the like are used.
As a forming method, an evaporation method such as vacuum evaporation, ion plating, or sputtering can be used, and vacuum evaporation and ion plating are preferable from the viewpoint of productivity.
Resistance heating, electron beam (EB) heating, high frequency induction heating, or the like is used as a heating method of the vapor deposition apparatus.

The inside of the vapor deposition apparatus is 2 × 10 ⁻⁶ to 8 × 10 ^−3.
Torr, preferably 8 × 10 ⁻⁶ to 8 × 10 ⁻⁵ Torr
After evacuation to, vacuum evaporation is performed. The vapor-deposited metal thin film or metal compound thin film has a barrier property against oxygen and water vapor, but the barrier property varies depending on the material and film thickness of the vapor-deposited thin film. Particularly, aluminum, silicon oxide, aluminum oxide and the like have excellent barrier properties.

The thickness of the vapor-deposited thin film layer 4 may be in the range of 50 to 5000Å, preferably 300 to 1500Å. This is because when the film thickness is less than 50Å, the vapor-deposited thin film is likely to come off, and the barrier property tends to vary.
When it exceeds 00Å, the flexibility of the vapor-deposited thin film is impaired, cracks and pinholes are easily generated, and the barrier properties are deteriorated. The vapor-deposited thin film is not limited to a single layer of a single component, and may be a vapor-deposited thin film made of a mixture of the above vapor deposition materials or a multi-layer film having two or more layers.

Further, in FIG. 2, the coating layer 6 composed of the organosilicon compound or alkoxide, and the conductive metal particles and the binder is the same as the coating layer used for forming the conductive hydrolyzate layer 3, The forming method is an off-line method.

In FIG. 3, the coating layer 8 made of an organosilicon compound or an alkoxide is the coating layer used to form the conductive hydrolyzate layer 3 or the organosilicon compound in the coating layer 6. Alternatively, it is the same as the alkoxide component and is formed by an off-line method.

The vapor-deposited thin film layer 4 located at the outermost layer of the barrier laminates 1, 5, 7 of the present invention shown in FIGS. 1, 2 and 3.
A heat-adhesive resin layer 11 is laminated on a coating layer 6 made of an organosilicon compound or alkoxide, and conductive metal particles and a binder, and a coating layer 8 made of an organosilicon compound or alkoxide via an adhesive layer 10, respectively. Figure 4,
The barrier laminates 9 and 12 of the present invention shown in FIGS.
13 is obtained. The heat-adhesive resin layer 11 is processed into a packaging form such as a bag or a container.

The heat-adhesive resin layer 11 is a resin layer that is easily heat-bonded by heating and pressing, and is made of, for example, polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, polyester, polyamide, ionomer, ethylene-vinyl acetate copolymer. Examples thereof include acrylic resins such as acrylic acid esters and methacrylic acid esters, polyvinyl acetals, phenol resins, modified epoxy resins and copolymers and mixtures thereof, but are not limited to these as long as the above conditions are satisfied. Not a thing.
In particular, polyolefin, polyester, polyamide, ethylene vinyl acetate copolymer and the like are preferable.

The layer thickness of the heat-adhesive resin 11 varies depending on the application, but is in the range of 1 to 200 μm, preferably 10 to 100 μm. As a forming method, a general processing method such as a dry laminating method, a solventless laminating method or an extrusion laminating method can be used.

Specific examples of the present invention will be described below in detail. <Example 1> Polyethylene terephthalate having a heat of fusion of crystal of 9.7 cal / g was extruded from a die by an extrusion device,
While electrostatically applying on a drum cooled to 40 ° C, the film thickness is 15
An unstretched resin film of 3 μm was prepared. After stretching this film 3.6 times in the flow direction on a metal roll heated to 95 ° C., an organosilicon compound is used as a coating liquid for forming a coating layer composed of an organosilicon compound and conductive metal particles and a binder. An aqueous solution of N- (β-aminoethyl) -γ-amino-propylmethoxysilane and a dispersion liquid of conductive metal particles were obtained by refluxing aluminum (III) chloride hexahydrate, polyvinyl alcohol, ethanol, and water. A coating solution having a solid content of 2 wt% obtained by mixing and stirring an aluminum dispersion aqueous solution and a water-dispersible acrylic resin is applied to one surface of the film by a gravure coating method, passes through a preheating zone of 95 ° C., and is 3.85 in the width direction at 102 ° C. It was stretched twice. 20 more
A heat treatment was performed at 0 to 230 ° C. for 4.0 seconds to prepare a 12 μm biaxially stretched ethylene terephthalate film having a coating film having a thickness of 0.2 μm formed on one surface of the film.

This biaxially stretched terephthalate film was wound up, loaded into an EB heating vacuum vapor deposition apparatus, and the degree of vacuum was set to 1.5 × 10 ^-5 Torr, and then an organosilicon compound,
Further, silicon monoxide (purity 99.99%) is applied to the surface of the coating layer composed of the conductive metal particles and the binder with EB-Power30.
kV-0.75 A, winding speed 1.5 m / sec. ,
A barrier laminate of the present invention having a silicon oxide vapor-deposited layer was prepared by vapor deposition at a pressure of 2 × 10 ⁻⁴ Torr to a film thickness of 1000Å.

Further, an unstretched polypropylene film having a thickness of 30 μm was bonded as a heat-adhesive resin to the outermost silicon oxide vapor-deposited layer surface of the produced barrier laminate by a dry laminating method to obtain the barrier laminate of Example 1. It was made.

Example 2 Among the coating liquids for forming the coating layer consisting of the organosilicon compound and the conductive metal particles and the binder, the organosilicon compound aqueous solution was γ-aminopropyltriethoxysilane. In the same manner as in Example 1, a barrier laminate was prepared.

Example 3 Among the coating liquids for forming the coating layer consisting of the organic silicon compound and the conductive metal particles and the binder, the dispersion liquid of the conductive metal particles was manganese (II) chloride.
Other than tetrahydrate, polyvinyl alcohol, ethanol, aluminum dispersion aqueous solution obtained by refluxing water,
A barrier laminate was prepared in the same manner as in Example 1.

Example 4 Aluminum oxide (purity 99.99%) was used as the vapor deposition material, and EB-Power3 was used as the vapor deposition conditions.
A barrier laminate was produced in the same manner as in Example 1 except that the voltage was 0 kV-0.75A.

Example 5 On the silicon oxide vapor deposition layer, a winding speed of 40 m / min. , The drying condition is 95 ~ 110 ℃,
A coating solution for forming a coating layer composed of the organosilicon compound used in Example 1 and the conductive metal particles and a binder under the condition of a coating amount of 0.15 g / m ² (the organosilicon compound is N-
An aluminum dispersion obtained by refluxing an aqueous solution of (β-aminoethyl) -γ-amino-propylmethoxysilane and a conductive metal particle dispersion of aluminum (III) chloride hexahydrate, polyvinyl alcohol, ethanol, and water. Solid content obtained by mixing and stirring an aqueous solution and a water-dispersible acrylic resin
wt% coating liquid) was applied by a gravure coating method and dried to form a coating layer, to prepare a barrier laminate in the same manner as in Example 1.

Example 6 A winding speed of 40 m / min. , The drying condition is 95 ~ 110 ℃,
The organosilicon compound was coated with an aqueous solution of N- (β-aminoethyl) -γ-amino-propylmethoxysilane by a gravure coating method under the condition of a coating amount of 0.15 g / m ² .
A barrier laminate was prepared in the same manner as in Example 1 except that the coating layer was formed by drying.

Example 7 Heat of fusion of crystal 9.7 cal / g
Polyethylene terephthalate of was extruded from the die with an extruding device and electrostatically applied on a drum cooled to 40 ° C. to prepare an unstretched resin film having a thickness of 153 μm.
This film was stretched 3.6 times in the direction of flow on a metal roll heated to 95 ° C., and the alkoxide was tetraethyl orthosilicate as a coating liquid for forming a coating layer consisting of the conductive metal particles and a binder. [S
i (OC ₂ H ₅ ) ₄ ] 1 part, 8.6 parts of 0.1N hydrochloric acid was added, and the mixture was stirred and hydrolyzed to give a solid content of 3 wt% (SiO 2
₂ conversion) Aqueous solution, dispersion liquid of conductive metal particles is aluminum chloride (III) hexahydrate, polyvinyl alcohol, ethanol, aluminum dispersion aqueous solution obtained by refluxing water, water-dispersible acrylic resin mixed and stirred solid Minute 2wt
% Aqueous solution was applied to one side of the film by the gravure coating method, and then, the film was passed through a preheating zone of 95 ° C. and stretched 3.85 times in the width direction at 102 ° C. Further, it was heat-treated at 200 to 230 ° C. for 4.0 seconds to prepare a 12 μm biaxially stretched ethylene terephthalate film having a 0.2 μm thick coating film formed on one surface of the film.

This biaxially stretched terephthalate film was wound up, loaded into an EB heating vacuum vapor deposition apparatus, and the degree of vacuum was adjusted to 1.5 × 10 ^-5 Torr.
Further, silicon monoxide (purity 99.99%) is applied to the surface of the coating layer composed of the conductive metal particles and the binder with EB-Power30.
kV-0.75 A, winding speed 1.5 m / sec. ,
A barrier laminate of the present invention having a silicon oxide vapor-deposited layer was prepared by vapor deposition at a pressure of 2 × 10 ⁻⁴ Torr to a film thickness of 1000Å.

Further, an unstretched polypropylene film having a thickness of 30 μm was bonded as a heat-adhesive resin to the outermost silicon oxide vapor-deposited layer surface of the produced barrier laminate by a dry laminating method to obtain the barrier laminate of Example 1. It was made.

[0070] <Example 8> alkoxides, and of a coating liquid for forming a coating layer made of a conductive metal particles and a binder, alkoxide hydrolysis solution triisopropoxyaluminum _{[Al (O-iC 3 H 7} ) 3 ] 1.5, 8
A barrier laminate was prepared in the same manner as in Example 7, except that the solution was dissolved in 22.5 parts of hot water at 0 ° C. and then an aqueous solution of ₃ wt% (Al ₂ O ₃ ) having a solid content of 5 N was added. Was produced.

Example 9 Among the coating liquids for forming the coating layer consisting of the alkoxide and the conductive metal particles and the binder, the dispersion liquid of the conductive metal particles was manganese (II) chloride tetrahydrate or polyvinyl alcohol. A barrier laminate was prepared in the same manner as in Example 7, except that the aqueous aluminum dispersion solution was obtained by refluxing ethanol, water.

Example 10 Aluminum oxide (purity: 99.99%) was used as the vapor deposition material, and EB-Power was used as the vapor deposition conditions.
A barrier laminate was prepared in the same manner as in Example 7, except that the voltage was 30 kV-0.75A.

<Embodiment 11> A winding speed of 40 m / min. , The drying condition is 95 ~ 110
A coating solution for forming a coating layer composed of the alkoxide used in Example 1 and the conductive metal particles and a binder under the conditions of ℃ and a coating amount of 0.15 g / m ² (the alkoxide is tetraethyl orthosilicate [Si (OC ₂ H ₅ ) ₄ ] Part 1,
8.6 parts of 0.1 N hydrochloric acid was added, and the mixture was stirred and hydrolyzed to obtain a solid content 3 wt% (SiO ₂ equivalent) aqueous solution, and a dispersion liquid of conductive metal particles was aluminum (III) chloride hexahydrate, polyvinyl alcohol, Except that an aluminum dispersion aqueous solution obtained by refluxing ethanol and water, and a solid content 2 wt% aqueous solution obtained by mixing and stirring a water-dispersible acrylic resin) were applied by a gravure coating method and dried to form a coating layer. A barrier laminate was prepared in the same manner as in Example 7.

<Embodiment 12> A winding speed of 40 m / min. , The drying condition is 95 ~ 110
The alkoxide is tetraethyl orthosilicate [Si (OC ₂ H ₅ )] under the conditions of ℃ and coating amount of 0.15 g / m ^2.
₄ ] To 1 part, 8.6 parts of 0.1N hydrochloric acid was added, and an aqueous solution having a solid content of 3 wt% (SiO ₂ conversion) which was stirred and hydrolyzed was applied by a gravure coating method and dried to form a coating layer. A barrier laminate was produced in the same manner as in Example 7 except that the barrier laminate was formed.

Comparative Example 1 A silicon oxide vapor-deposited layer was formed directly on a plain 12 μm biaxially stretched ethylene terephthalate film without forming a coating layer consisting of an organosilicon compound, conductive metal particles and a binder. A barrier laminate was prepared in the same manner as in Examples 1 and 7 except for the above.

Comparative Example 2 Instead of the coating liquid for forming the coating layer consisting of the organic silicon compound, the conductive metal particles and the binder, the solid content of the polyurethane coating agent is 20 wt.
%, A barrier laminate was prepared in the same manner as in Example 1 except that the solution was used.

<Comparative Example 3> In the coating liquid for forming a coating layer comprising an organosilicon compound and conductive metal particles and a binder, a polyurethane coating agent having a solid content of 20 wt% was used in place of the organosilicon compound aqueous solution. Except that it was a solution
A barrier laminate was prepared in the same manner as in Example 1.

<Comparative Example 4> Example 4 except that the aluminum-dispersed aqueous solution and the water-dispersible acrylic resin were removed from the coating liquid for forming the coating layer consisting of the organosilicon compound and the conductive metal particles and the binder. A barrier laminate was prepared in the same manner as in 1.

Comparative Example 5 Instead of a coating liquid for forming a coating layer comprising alkoxide, conductive metal particles and a binder, a copolymer polyester, 1 mol of trimethylolpropane and 3 mol of toluylene diisocyanate are used. Is mixed with the isocyanate compound to which is added in a mixing ratio of 90:10 by weight ratio to adjust the adhesive, and further to add ethyl acetate /
Toluene / methyl ethyl ketone mixed solvent (weight ratio 1 /
Barrier properties were obtained in the same manner as in Example 7, except that the solution was dissolved in 1/1) and diluted with an ethyl acetate / butyl acetate / methyl isobutyl ketone mixed material (weight ratio 1/1/1) to give a solution having a solid content of 25 wt%. A laminated body was produced.

Comparative Example 6 Copolymerized polyester was used in place of the alkoxide in the coating liquid for forming the coating layer consisting of the alkoxide and the conductive metal particles and the binder.
1 mol of trimethylolpropane and 3 mol of toluylene diisocyanate are added to the isocyanate compound in a mixing ratio of 90:10 by weight ratio to adjust the adhesive, and further, ethyl acetate / toluene / methyl ethyl ketone mixed solvent Example 7 except that it was dissolved in (weight ratio 1/1/1) and diluted with an ethyl acetate / butyl acetate / methyl isobutyl ketone mixed material (weight ratio 1/1/1) to give a solution having a solid content of 25 wt%. A barrier laminate was prepared in the same manner.

Comparative Example 7 Example 7 was repeated except that the aluminum-dispersed aqueous solution and the water-dispersible acrylic resin were removed from the coating liquid for forming the coating layer consisting of the alkoxide and the conductive metal particles and the binder. A barrier laminate was prepared in the same manner.

Examples 1 to 6 and Comparative Examples 1 to 4
And Examples 7 to 12, Comparative Example 1 and Comparative Example 5
-The barrier laminate of Comparative Example 7 was comparatively evaluated as follows. Oxygen permeability, which shows barrier properties, and moisture permeability,
Peel strength showing adhesion characteristics between the vapor-deposited thin film layer and the adjacent layer,
Measure the surface specific resistance value, which shows the charging characteristics, and
The results are shown in Tables 1 and 2.

[0083]

[Table 1]

[0084]

[Table 2]

The measurement conditions are: oxygen transmission rate: MOCON OXTRAN
-10 / 50A) 25 ° C-100% RH Sample ... Vapor-deposited film, laminated film Moisture vapor transmission rate: MOCON PERMAT
RAN-W6) 40 ° C.-90% RH sample ... Evaporated film, laminated film Peel strength: Instron type tensile tester sample 15 mm width, peel angle 90 degrees, peel speed 300 mm
/ Min Sample ... Laminated film Surface resistivity: Surface resistance measuring device (Loresta A
PMCP-T400) 25 ° C.-50% RH sample ... Vapor deposited film.

From Table 1, it can be seen that the barrier properties against oxygen and water vapor were good in Example 1, Example 2, Example 3, Example 4, Example 5, and Example 6, but
Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were somewhat defective or defective. Regarding the peel strength indicating the adhesion between the vapor-deposited thin film layer and the adjacent layer, good results were obtained in Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, and Comparative Example 4. However, Comparative Example 1, Comparative Example 2, and Comparative Example 3
Was a little bad. Regarding the surface specific resistance value showing the charging characteristic, good results were obtained in Example 1, Example 2, Example 3, Example 4, Example 5, Example 6 and Comparative Example 3, but comparison was made. Example 1, Comparative Example 2, and Comparative Example 4 were somewhat defective.

From Table 2, as for the barrier property against oxygen and water vapor, good barrier properties were obtained in Example 7, Example 8, Example 9, Example 10, Example 11 and Example 12, Comparative Example 1, Comparative Example 5, Comparative Example 6, and Comparative Example 7 were somewhat defective or defective. As for the peel strength indicating the adhesion between the vapor-deposited thin film layer and the adjacent layer, good results were obtained in Example 7, Example 8, Example 9, Example 10, Example 11, Example 12, and Comparative Example 7. However, Comparative Examples 1, 5, and 6 were somewhat defective. Regarding the surface specific resistance value showing the charging characteristic, good results were obtained in Example 7, Example 8, Example 9, Example 10, Example 11, Example 12, and Comparative Example 6, but comparison was made. Example 1, Comparative Example 5, and Comparative Example 7 were somewhat defective.

[0088]

As described above, according to the present invention, the bonding strength with the resin of the resin film and the vapor-deposited thin film is strong, and the adhesion is improved. In addition, since the conductive hydrolyzate layer has excellent heat resistance, thermal dimensional stability, and hardness, cracks due to strain caused by mechanical stress and thermal stress in the laminate manufacturing process such as vapor deposition, printing, laminating, and bag making. , Pinholes are less likely to occur, and barrier deterioration is less likely to occur. Furthermore,
Since the conductive metal particles are dispersed in the conductive hydrolyzate layer, an effective charge removal effect is exhibited even in a low humidity atmosphere, and stable secondary electron charge removal during vapor deposition can be performed.

[0089]

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a barrier laminate of the present invention.

FIG. 2 is a cross-sectional view showing an example of the barrier laminate of the present invention.

FIG. 3 is a cross-sectional view showing an example of the barrier laminate of the present invention.

FIG. 4 is a cross-sectional view showing an example of the barrier laminate of the present invention.

FIG. 5 is a cross-sectional view showing an example of the barrier laminate of the present invention.

FIG. 6 is a cross-sectional view showing an example of the barrier laminate of the present invention.

[Explanation of symbols]

 1, 5, 7, 9, 12, 13 Barrier Laminate 2 Resin Film Base Material 3 Conductive Hydrolyzate Layer 6 Coating Layer 4 Vapor Deposition Thin Film Layer 8 Coating Layer 10 Adhesive Layer 11 Thermal Adhesive Resin Layer

Claims (8)

[Claims] 1. The following chemical formula (I), R—Si— (OR ′) _{3 is formed on} one or both sides of a resin film. (I) (wherein R is an organic functional group and R ′ is a hydrolyzable group): 1 to 99% by weight of a hydrolyzate of an organosilicon compound represented by: and conductive metal particles 1 to 99. A barrier laminate, comprising a conductive hydrolyzate layer consisting of 1 wt% and a vapor-deposited thin film layer consisting of a metal or a metal compound, which are sequentially laminated. 2. The following chemical formulas (II) and M (OR) _n are provided on one side or both sides of the resin film. (II) (wherein M is a metal element, R is an alkyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 4). %
And a conductive hydrolyzate layer composed of 1 to 99% by weight of conductive metal particles, and a vapor-deposited thin film layer composed of a metal or a metal compound, which are sequentially stacked. 3. On the vapor-deposited thin film layer comprising the metal or metal compound according to claim 1, 1 to 99% by weight of the organosilicon compound according to claim 1 and 1 to 99% by weight of conductive metal particles, A barrier laminate comprising a coating layer comprising 1 to 99% by weight of a binder. 4. The alkoxide 1 to 2 according to claim 2 on the vapor-deposited thin film layer comprising the metal or metal compound according to claim 2.
A barrier laminate comprising a coating film layer comprising 99% by weight, 1 to 99% by weight of conductive metal particles, and 1 to 99% by weight of a binder. 5. A barrier property, characterized in that the organosilicon compound represented by the chemical formula (I) according to claim 1 is laminated on the vapor-deposited thin film layer comprising the metal or metal compound according to claim 1. Laminate. 6. A barrier laminate comprising the vapor-deposited thin film layer comprising the metal or metal compound according to claim 2 and the alkoxide represented by the chemical formula (II) according to claim 2 laminated thereon. . 7. A vapor-deposited thin film layer comprising the metal or metal compound according to claim 1, which is provided on the outermost layer, a coating layer according to claim 3, or an organosilicon compound layer according to claim 5,
A barrier laminate comprising a thermoadhesive resin layer laminated via an adhesive layer. 8. An evaporated thin film layer comprising the metal or metal compound according to claim 2, which is provided on the outermost layer, the coating layer according to claim 4, or the alkoxide coating layer according to claim 6,
A barrier laminate comprising a thermoadhesive resin layer laminated via an adhesive layer.