JP3294440B2 - Composite vapor-deposited film and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite vapor-deposited film, and more particularly to a composite vapor-deposited film having excellent gas barrier properties against oxygen, water vapor, helium and the like, and a method for producing the same. The composite vapor-deposited film of the present invention has excellent gas barrier properties and excellent bending fatigue resistance, and can be used as various packaging materials in the field of packaging of foods, pharmaceuticals, daily necessities and the like.

[0002]

2. Description of the Related Art In general, packaging materials are required to have a function of preventing quality deterioration of the contents. In particular, in the field of food packaging in which the contents are liable to be deteriorated or perishable, oxygen gas barrier properties and water vapor barrier properties are required. Is required to have excellent gas barrier properties. Conventionally, in a packaging material, in order to impart a gas barrier property, for example, a polyvinyl alcohol (PVA) film, a partially saponified ethylene-vinyl acetate copolymer (EVOH) film, a polyvinylidene chloride (PVDC) film, and aluminum vapor deposition Films, silicon oxide vapor-deposited films, and the like are used alone or in combination with various films.
These gas barrier films have both advantages and disadvantages, and improvements are being made.

[0005] In food packaging, factors that cause deterioration of the contents such as deterioration and decay of the contents are permeation of oxygen, moisture absorption of water vapor, and decomposition of the contents by various rays and heat. Among the various gas barrier films, a vapor-deposited film such as an aluminum vapor-deposited film has (1) good oxygen gas barrier properties and good water vapor barrier properties, and (2) excellent barrier properties against visible light and ultraviolet rays. (3) excellent gloss, (4) pinholes are less likely to be formed than aluminum foil, (5) printability on deposited films, (6) extrusion and dry lamination, etc. Therefore, it has many features such as that various films can be laminated on a vapor deposition film to form a composite vapor deposition film.

[0004] Evaporated films used in packaging materials are generally made of metals such as aluminum, metal oxides, inorganic substances,
An inorganic material such as an inorganic oxide is used as an evaporation source, and the inorganic material is deposited on a polymer film base material such as a polyethylene terephthalate (PET) film, an expanded polypropylene (OPP) film, an expanded nylon (ONY) film, etc. by various evaporation methods. Is formed. The vapor deposition method includes a chemical vapor deposition method and a physical vapor deposition method. In the field of packaging, a vacuum vapor deposition method, which is a physical vapor deposition method, is mainly used. According to the vacuum deposition method, it is possible to mass-produce a high-performance deposited film. Further, a composite vapor-deposited film obtained by laminating a heat-sealable polyethylene (PE) film or polypropylene (PP) film on a vapor-deposited film is widely used as a packaging material.

[0005] However, since the inorganic material vapor-deposited film is generally inferior in bending fatigue resistance, the vapor-deposited film may be damaged when subjected to secondary processing such as printing and bag making or used for applications subjected to bending. This is likely to occur and the original gas barrier properties may be impaired. In addition, when another thermoplastic resin film is laminated on a vapor-deposited film by melt extrusion, dry lamination, or the like, a crack (crack) is easily generated in the vapor-deposited film, and gas barrier properties may be significantly reduced. Further, the gas barrier property of the vapor-deposited film is still insufficient depending on the use, so that if the gas barrier property can be further improved, the use can be expanded.

On the other hand, PVDC films are widely used as food packaging materials such as ham / sausage packaging casings and household wraps because of their excellent oxygen gas barrier properties, water vapor barrier properties, chemical resistance and heat resistance. Have been. PVDC is also used as a barrier-imparting coating agent for films such as PET and OPP because PVDC can form a barrier thin film by coating and film formation. However, conventionally, vapor-deposited films and PVD
No proposal has been made for the formation of a composite with the C coating film.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer film substrate having a layer composed of a vapor-deposited film in which a vapor-deposited film of an inorganic material is formed on a polymer film substrate, and having excellent gas barrier properties and bending fatigue resistance. An object of the present invention is to provide a composite vapor-deposited film and a method for producing the same. The present inventor has conducted intensive studies to overcome the problems of the prior art, and as a result, formed a vapor-deposited film of an inorganic material on at least one surface of a polymer film substrate, and further formed PVDC on the vapor-deposited film. Is applied and dried to form a PVDC coating, surprisingly, the oxygen gas barrier property, water vapor barrier property, and helium gas barrier property of each layer of the deposited film and the PVDC coating. It has been found that these properties are synergistically improved by conjugation, more than would be expected from. This remarkable effect is obtained by directly combining the deposited film and the PVDC coating, and when the PVDC coating is formed on the surface of the polymer film base such as PET, the PVDC coating is formed. , Can not get.

Further, the composite vapor-deposited film of the present invention has a P
To prevent the VDC coating from cracking the deposited film,
It has excellent bending fatigue resistance, and suppresses the destruction of the inorganic material vapor-deposited film and the decrease in gas barrier properties. Moreover, the composite vapor-deposited film of the present invention has excellent helium gas barrier properties, and thus can be applied to new uses such as balloon materials. The composite vapor-deposited film of the present invention may be provided with an additional layer for the purpose of imparting heat sealability and the like. The present invention has been completed based on these findings.

[0009]

Thus, according to the present invention, a vapor-deposited film (B) of an inorganic material is formed on at least one surface of the polymer film substrate (A), and the vapor-deposited film (B) Film of polyvinylidene chloride (C)
Is laminated, wherein the composite vapor-deposited film is formed in a 35-60 ° C. oven for 12-100 hours after a polyvinylidene chloride coating film (C) is formed.
Are those heat-treated Gana between, and oxygen permeability of the composite deposited film measured at a temperature 30 ° C. and a relative humidity of 80% ^{[ml (STP) / m 2 ·} day · atm {Pa} ]
Is Z, a vapor-deposited film [polymer film substrate (A) /
When the oxygen permeability of the vapor-deposited film (B)] is X and the oxygen permeability of the polyvinylidene chloride coating (C) layer is Y, the following relational expression (1 / Z)> (1 / X) + ( 1 / Y), and the same relational expression holds for the water vapor permeability measured at a temperature of 40 ° C. and a relative humidity of 90% and the helium permeability measured at a temperature of 30 ° C. and a relative humidity of 0%. A composite vapor-deposited film is provided. Further, according to the present invention, a vapor-deposited film (B) of an inorganic material is formed on at least one surface of the polymer film substrate (A), and a solution of polyvinylidene chloride is further formed on the vapor-deposited film (B). Alternatively, the dispersion is applied and dried to form a coating film (C) of polyvinylidene chloride, and then the coating film (C) of polyvinylidene chloride is heated in an oven at 35 to 60 ° C. for 12 to 10 minutes.
Oxygen permeability [ml (STP) / m ² · day · atm {Pa}] of the composite vapor-deposited film measured at a temperature of 30 ° C. and a relative humidity of 80%, characterized by performing a heat treatment for 0 hour.
Is Z, a vapor-deposited film [polymer film substrate (A) /
When the oxygen permeability of the vapor-deposited film (B)] is X and the oxygen permeability of the polyvinylidene chloride coating (C) layer is Y, the following relational expression (1 / Z)> (1 / X) + ( 1 / Y), and the same relational expression holds for the water vapor permeability measured at a temperature of 40 ° C. and a relative humidity of 90% and the helium permeability measured at a temperature of 30 ° C. and a relative humidity of 0%. A manufacturing method is provided.

Hereinafter, the present invention will be described in detail. Examples of the vapor-deposited film polymer film substrate (A) include polyamides such as nylon 6, nylon 66, nylon 12, nylon 6.66 copolymer, and nylon 6.12 copolymer;
Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycarbonate, polyurethane, poly 4
-Methylpentene-1, polyphenylene sulfide,
A film formed from a polymer material such as polypropylene (PP) and polyethylene can be given. These films are unstretched films or stretched films, and include sheet materials.

The polymer film substrate may contain various additives for imparting surface smoothness and stability.
When they bleed on the surface during vacuum deposition, the adhesion between the substrate and the deposited film is reduced. Therefore, it is preferable that the content of the additive is as small as possible. Further, the polymer film substrate preferably has heat resistance enough to withstand the drying conditions and, if necessary, the subsequent heat treatment conditions when a PVDC solution or emulsion is applied and formed. A polymer film having poor heat resistance, such as softening during heat drying or heat treatment or loss of dimensional stability, is not preferred as a substrate. Such a polymer film substrate preferably has a Vicat softening point of 100 to 380 ° C. The Vicat softening point temperature can be measured according to JIS K7206. Among the polymer films, films of polypropylene, polyamide, PET, PEN and the like are particularly preferable.

Although the thickness of the polymer film substrate is not particularly limited, it is usually 5 to 5 from the viewpoint of flexibility and economy.
It is 1000 μm, preferably 10 to 100 μm. As the inorganic material used as the vapor deposition source, metals, metal oxides, inorganic substances, and inorganic oxides commonly used for producing a vapor deposition film can be used. Specifically, aluminum (Al), aluminum oxide (Al
₂ O ₃ ), silicon oxide (SiO _x , x = 1 to 2), silicon oxynitride (SiO _x N _y , x = 0.6 to 0.8, y = 0.
7 to 0.9).

The thickness of the inorganic material-deposited film (B) can be arbitrarily determined depending on desired transparency or opacity, color tone, gloss, flexibility, and the like.
m, preferably 10 to 300 nm, more preferably 10
１５０150 nm. If the thickness of the vapor-deposited film is too thin, the gas barrier property will be reduced, and it will be easy to peel off from the polymer film substrate. If it is too thick, the handleability will be poor. The vapor deposition method includes a chemical vapor deposition method and a physical vapor deposition method.
It is preferable to perform evaporation using a vacuum evaporation method which is a physical evaporation method. In the vacuum deposition method, generally, a polymer film serving as a substrate is placed in a vacuum deposition apparatus, and the inside of the
A method is preferably used in which a vacuum of about ^-4 Pa is applied, and a vapor deposition source such as aluminum is heated and evaporated to continuously form the same vapor deposited film on the polymer film. .

In the present invention, a vapor-deposited film (B) of an inorganic material is formed on at least one surface of the polymer film substrate (A), and a PVDC coating is further performed on the vapor-deposited film (B). A film (C) is formed. The PVDC used in the present invention is vinylidene chloride 6
It refers to a copolymer of 0 to 98% by weight and 2 to 40% by weight of at least one other monomer copolymerizable therewith. Examples of the copolymerizable monomer include, for example, vinyl chloride (V
C), acrylonitrile, acrylic acid, alkyl acrylate (alkyl having 1 to 18 carbon atoms), methacrylic acid, alkyl methacrylate (alkyl having 1 to 18 carbon atoms), maleic anhydride, itaconic acid, itaconic acid Examples thereof include alkyl esters, vinyl acetate, ethylene, propylene, isobutylene, and butadiene. These monomers can be used alone or in combination of two or more.

Among PVDC, vinylidene chloride (V
D) A vinylidene chloride-vinyl chloride copolymer (VD / VC) having a content of 65 to 98% by weight, and a vinylidene chloride-methyl acrylate copolymer (V) having a VD content of 85 to 98% by weight
D / MA), and a vinylidene chloride-methyl methacrylate copolymer (VD / MMA) having a VD content of 85 to 98% by weight. PVDC is used as a solution dissolved in an organic solvent or a dispersion such as an emulsion. From the viewpoint of gas barrier properties, a solution using a solution dissolved in an organic solvent is more convenient. As the organic solvent, a mixed solvent of tetrahydrofuran (THF) and cyclohexanone is preferable. In the case of a dispersion, an aqueous medium is preferred. However, the solvent or the dispersion medium is not limited as long as the coating film forming method is applied.

To produce the composite vapor-deposited film of the present invention, first, a vapor-deposited film of an inorganic material is formed on at least one surface of a polymer film substrate using an inorganic material as a vapor deposition source.
Next, PVDC was deposited on the deposited film of the obtained deposited film.
Is applied and dried to form a PVDC coating. In order to form a PVDC coating on the deposited film of the deposited film, for example, an air knife coater,
Using a device such as a kiss roll coater, a metering bar coater, a gravure roll coater, a reverse roll coater, a dip coater, a die coater, or a combination thereof, a PVDC solution or dispersion is deposited on the deposited film of the deposited film. Apply to desired thickness, then arch dryer, straight bath dryer,
Using a device such as a tower drier or a drum drier, or a device combining them, the solvent or moisture is evaporated and dried by blowing hot air or irradiating infrared rays. Drying is usually performed in a dry heat atmosphere at 50 to 200 mm.
° C, preferably 80-150 ° C, more preferably 100
Temperature in the range of １３０130 ° C., and 0.5-90 minutes, preferably 0.5-60 minutes, more preferably 0.5-3
From the time in the range of 0 minutes, conditions may be appropriately selected such that the PVDC coating does not become sticky.

[0017] After drying, it performs more coating of heat treatment on the Orb down. For example, after drying, the composite vapor-deposited film having the PVDC coating formed thereon is heated in an oven at 35 to 60 ° C, preferably 40 to 50 ° C for 12 to 100 hours, preferably 25 to 5 hours.
About 0 hours heat treatment. By such heat treatment, PV
The crystallization of DC is promoted, and the gas barrier property of the PVDC coating is further improved. By coating film forming method, P
By forming a VDC coating, unlike a conventional thermoplastic resin film by melt extrusion lamination or dry lamination, cracking does not occur in the deposited film, and the resulting composite deposited film has bending fatigue resistance. The performance is improved. The thickness of the PVDC coating film can be appropriately determined according to the purpose of use, and is not particularly limited. The thickness after drying is usually 0.5 to 100 μm, preferably 0.5 to 50 μm, more preferably 0.1 to 50 μm. It is about 5 to 25 μm. In the composite vapor-deposited film of the present invention, the thickness of the PVDC coating is 0.5 to 15 μm, and further 0.5 to 5 μm.
Excellent effects can be obtained even with the order of m.

Composite vapor-deposited film The composite vapor-deposited film of the present invention has a laminated constitution of a polymer film substrate (A) / vapor-deposited film (B) / PVDC coating (C) as an essential layer constitution. It is necessary that the deposited film of the inorganic material and the PVDC coating layer are adjacent to each other. When the vapor-deposited film and the PVDC coating layer are not provided adjacent to each other, a synergistic improvement effect on gas barrier properties cannot be obtained, and an improvement effect on bending fatigue resistance cannot be obtained.

The composite vapor-deposited film of the present invention has excellent oxygen gas barrier properties. For example, when the thickness of the polymer film substrate is 12 μm, the thickness of the deposited film is 50 to 80 nm, and the thickness of the PVDC coating layer in contact with the deposited film is 1 to 3 μm,
Oxygen permeability of composite deposited film (temperature 30 ° C, 80% R
H) is usually 5 ml (STP) / m ² · day
・ Atm {Pa} or less, preferably 3 ml (STP) /
m ² · day · atm {Pa} or less, more preferably 2
ml (STP) / m ² · day · atm {Pa} or less.

The composite vapor-deposited film of the present invention has excellent water vapor barrier properties. For example, when the thickness of the polymer film substrate is 12 μm, the thickness of the vapor-deposited film is 50 to 80 nm, and the thickness of the PVDC coating layer in contact with the vapor-deposited film is 1 to 3 μm, the water vapor permeability of the composite vapor-deposited film (temperature 40 ° C., (Measured at a relative humidity of 90%) is usually 5 g / m ² · day or less, preferably 3 g / m ² · day or less, more preferably ² g / m ² · day or less.
/ M ² · day or less.

The composite vapor-deposited film of the present invention has excellent helium gas barrier properties. For example, the thickness of the polymer film substrate is 12 μm, the thickness of the deposited film is 50 to 80 nm,
When the thickness of the PVDC coating layer in contact with the deposited film is 1 to 3 μm, the helium permeability of the composite deposited film (temperature 30 ° C.,
(Measured at 0% relative humidity) is usually 200 ml (STP)
/ M ² · day · atm {Pa} or less, preferably 18
0 ml (STP) / m ² · day · atm {Pa} or less, more preferably 170 ml (STP) / m ² · da
y · atm {Pa} or less. In particular, when a vapor deposition film having an aluminum vapor deposition film is used, the helium permeability can be significantly reduced. In the composite vapor-deposited film of the present invention, the gas barrier properties are synergistically improved more than expected from the gas barrier properties of the vapor-deposited film (polymer film substrate / vapor-deposited film) and each layer of the PVDC coating film.

Specifically, a certain temperature (for example, 30
° C) and relative humidity (for example, 80%), the oxygen permeability of the composite vapor-deposited film [ml (STP) / m ² · day ·
atm {Pa}] is Z, the oxygen permeability of the vapor-deposited film (polymer film substrate / vapor-deposited film) is X, and the oxygen permeability of the PVDC coating layer is Y, the following relational expression holds. (1 / Z)> (1 / X) + (1 / Y) The same relational expression holds for the water vapor permeability and the helium permeability. Therefore, the composite vapor-deposited film of the present invention has a synergistic effect on gas barrier properties. The composite vapor-deposited film of the present invention is excellent in bending fatigue resistance, and retains a high gas barrier property even after a bending fatigue test using a gelbo flex tester.

The composite vapor-deposited film of the present invention is not limited to a laminated structure of a polymer film substrate (A) / a vapor-deposited film (B) / a PVDC coating (C), and if desired, may additionally have another layer. May be laminated. For example, when the heat-sealing property of the composite vapor-deposited film is insufficient, a heat-sealable layer can be laminated on at least one of the surfaces. As the heat seal layer, for example, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, polypropylene, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, Examples of the layer include a layer formed from a polyolefin such as an ethylene / ethyl acrylate copolymer, a nylon copolymer such as a nylon 6.66 copolymer, or a nylon 6.12 copolymer.

By laminating a thermoplastic resin layer on the PVDC coating layer, the mechanical strength and the like can be improved. Various films, coating layers, and the like may be provided to impart functions such as gloss, anti-fogging property, and ultraviolet blocking property. When various layers are additionally provided, and the adhesiveness between the layers is insufficient, an adhesive layer may be provided. As an adhesive therefor, urethane-based, which is generally used for dry lamination of various films,
Various adhesives such as acrylic and polyester can be used. In each layer of the composite vapor deposition film of the present invention,
If desired, antioxidants, lubricants, UV absorbers, pigments,
Various additives such as a filler and an antistatic agent can be added.

[0025]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the measuring method of physical properties is as follows. (1) Oxygen permeability According to ASTM D-3985, Modern Conn.
OX-TRAN 2/2 oxygen transmission tester manufactured by trol
The measurement was performed using Type 0 under conditions of 30 ° C. and 80% RH. (2) Water vapor permeability Measured under the conditions of 40 ° C. and 90% RH according to JIS Z-0208. (3) Helium permeability Yanaco's Yanagimoto gas permeability measuring device GTR-1
0A and GAS CHROMATOGRAPH G3
The measurement was carried out under the conditions of 30 ° C. and 0% RH using 800. (4) Flex fatigue resistance (oxygen permeability after gelbo test) Using a gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd.
The bending fatigue resistance was evaluated. According to MIL-B131C,
A 30 cm × 20 cm (12 inch × 8 inch) sample piece was formed into a cylindrical shape having a diameter of 9 cm (3.5 inch), both ends were held, an initial gripping interval was 18 cm (7 inch), and a stroke of 9 cm (3.5 inch) was used. ), A total of 15 cm (6 inches) consisting of a step (test operation A) of linearly compressing at 6 cm (2.5 inches) as it is after adding a twist of 440 degrees
Oxygen permeability (30 ° C., 80% RH) of each film after bending 5 times at 25 ° C., 50% RH at a speed of 40 reciprocating motions (cycles) per minute by repeating the above operation. .

Example 1 A vinylidene chloride-vinyl chloride copolymer (hereinafter referred to as PVDC-1) having a VD / VC composition ratio (weight%) of 79/21 was mixed with THF and cyclohexanone (mixed solvent). (Weight ratio: 80:20) to prepare a solution having a concentration of 10% by weight. 12 μm thick
The above solution was coated on a tabletop coater (RK Print-Coat Instrument) on a vapor-deposited film in which a 50-nm-thick aluminum (Al) vapor-deposited film was formed on a polyethylene terephthalate (PET) film.
Co., Ltd. K303 PROOFER), coated with a Mayer bar, and then dried with a drier for 110
Drying was performed at 1 ° C. for 1 minute to obtain a dry coating film having a thickness of 1 μm. The vapor-deposited film on which the dried coating film was formed was heat-treated in an oven at 40 ° C. for 48 hours.

Example 2 In Example 1, an 80 nm thick SiO _x evaporated PET was used in place of the Al evaporated film.
Except having used the film, it processed similarly to Example 1 and obtained the composite vapor deposition film.

Example 3 An emulsion of a vinylidene chloride-methyl acrylate copolymer (hereinafter referred to as PVDC-2) having a VD / MA composition ratio (% by weight) of 90/10 [Kureha Chemical Co., Ltd. Kurehalon latex DO-8
33S: solid content 50% by weight], and a PET having a thickness of 12 μm.
A 50-nm thick Al vapor-deposited film was formed on the film and applied on the vapor-deposited film, and dried at 110 ° C. for 1 minute to obtain a dry film having a thickness of 1 μm. The vapor-deposited film on which the dried coating film was formed was heat-treated in an oven at 40 ° C. for 48 hours.

[0029] In Example 4 Example 3, in place of the Al deposition film, having a thickness of 80 nm SiO _x deposited PET
Except having used the film, it processed similarly to Example 3 and obtained the composite vapor deposition film.

Example 5 A vinylidene chloride-methyl acrylate copolymer (hereinafter referred to as PVDC-3) having a VD / MA composition ratio (% by weight) of 96/4 was mixed with THF and cyclohexanone. (Mixing weight ratio 80:20)
And a solution having a concentration of 10% by weight was prepared. This solution was applied on a vapor-deposited film in which a 50-nm-thick Al vapor-deposited film was formed on a 12-μm-thick PET film, and dried at 110 ° C. for 1 minute to obtain a dry film having a thickness of 1 μm. 40 ° C.
In the oven for 48 hours.

[0031] In Example 6 Example 5, instead of the Al deposition film, having a thickness of 80 nm SiO _x deposited PET
Except having used the film, it processed similarly to Example 5 and obtained the composite vapor deposition film.

Example 7 A vinylidene chloride-methyl methacrylate copolymer (hereinafter referred to as PVDC-4) having a VD / MMA composition ratio (% by weight) of 98/2 was mixed with THF and cyclohexanone ( Mixing weight ratio 80: 2
0) to prepare a solution having a concentration of 10% by weight. This solution was spread on a PET film having a thickness of 12 μm to a thickness of 50 n.
m was deposited on the deposited film of the deposited film on which an Al deposited film was formed, and dried at 110 ° C. for 1 minute to obtain a dry coating film having a thickness of 1 μm. The deposited film on which the dried coating film was formed
Heat treatment was performed in an oven at 0 ° C. for 48 hours.

Example 8 In Example 7, an 80 nm thick SiO _x evaporated PET was used instead of the Al evaporated film.
Except having used the film, it processed similarly to Example 7 and obtained the composite vapor deposition film.

[Embodiment 9] In Embodiment 7, PVDC
Except that the thickness of the coating after drying was 3 μm, the same treatment as in Example 7 was performed to obtain a composite vapor-deposited film.

[Embodiment 10] In Embodiment 8, PVD
Except that the thickness of the C coating after drying was 3 μm, the same treatment as in Example 8 was performed to obtain a composite vapor-deposited film. Table 1 shows the laminated structure of the composite vapor-deposited films obtained in each of the above examples and the measurement results of gas barrier properties (oxygen permeability, water vapor permeability, helium permeability).

[0036]

[Table 1]

[Comparative Example 1] The Al deposited film used in Example 1 was used as Comparative Example 1.

Comparative Example 2 The SiO _x deposited film used in Example 2 was used as Comparative Example 2.

Comparative Example 3 A 12 μm thick PET film was used as Comparative Example 3.

[Comparative Example 4] The solution of PVDC-1 prepared in Example 1 was applied on a PET film, and the thickness was 1 μm.
A dried coating film was obtained. The dried coating film was heat-treated in the same manner as in Example 1 to form a laminate. Using this laminate, the oxygen permeability of the PVDC-1 coating film was measured by the following method.

<Calculation Method of Oxygen Permeability of PVDC Coating>
oxygen control tester OX manufactured by Odern Control
Using a TRAN 2/20 type, the oxygen permeability (30%) of the laminate on which the PET film and the PVDC coating were formed
° C, 80% RH), and PVD is calculated by the following formula.
The oxygen permeability P _coat of the C coating was calculated. 1 / P _total = 1 / P _coat + 1 / P _PET P _total : oxygen permeability of laminate P _coat : oxygen permeability of PVDC coating P _PET : oxygen permeability of PET film

Comparative Example 5 A laminate was prepared in the same manner as in Comparative Example 4, except that the emulsion of PVDC-2 used in Example 3 was used instead of the solution of PVDC-1. PV
The oxygen permeability of the DC-2 coating was measured.

Comparative Example 6 A laminate was prepared in the same manner as in Comparative Example 4, except that the solution of PVDC-3 used in Example 5 was used instead of the solution of PVDC-1.
The oxygen permeability of the C-3 coating was measured.

Comparative Example 7 A laminate was prepared in the same manner as in Comparative Example 4, except that the solution of PVDC-4 used in Example 7 was used instead of the solution of PVDC-1.
The oxygen permeability of the C-4 coating was measured.

Comparative Example 8 A laminate was prepared in the same manner as in Comparative Example 7, except that the thickness of PVDC-4 after drying was 3 μm, and the oxygen permeability of the PVDC-4 coating film was measured. Table 2 shows the laminated structure of the composite vapor-deposited films obtained in each of the above comparative examples and the measurement results of gas barrier properties (oxygen permeability, water vapor permeability, helium permeability).

[0046]

[Table 2]

From the results shown in Tables 1 and 2, the composite vapor-deposited films (Examples 1 to 10) of the present invention were obtained by using Al vapor-deposited films (Comparative Example 1), SiO _x vapor-deposited films (Comparative Example 2), and PVDC coating films. Compared with (Comparative Examples 4 to 8), the oxygen permeability, the water vapor permeability, and the helium permeability are all significantly improved. These gas barrier property improving effects are all synergistic.

Example 11 The composite deposited film prepared in Example 5 was subjected to a bending fatigue resistance test (Gelbo test).
The oxygen permeability before and after was measured.

Example 12 The oxygen permeability of the composite vapor-deposited film prepared in Example 6 was measured before and after the bending fatigue test.

[Comparative Example 9] With respect to the Al vapor-deposited film used in Example 1, the oxygen permeability before and after the bending fatigue test was measured.

Comparative Example 10 SiO _x used in Example 2
The oxygen permeability of the deposited film was measured before and after the bending fatigue test.

Comparative Example 11 The oxygen permeability of a PET film having a thickness of 12 μm before and after the bending fatigue test was measured. Table 3 shows the results of these examples and comparative examples.

[0053]

[Table 3] From the results in Table 3, the composite vapor-deposited film of the present invention (Example 1)
1 to 12) have excellent bending fatigue resistance.

Example 13 A 30 μm-thick linear low-density polyethylene (LLDPE) film was dry-laminated on the composite vapor-deposited film obtained in Example 1 according to a conventional method. The adhesive used was Toyo Morton's main agent: Adcoat 335A and curing agent: CAT-10. The LLDPE layer of the laminated film was heat-sealed to form a spherical balloon having a diameter of 50 cm, and helium was injected. Balloon aptitude is 23
Floating in a room at 50 ° C and 50% RH, the number of days from when the floating height reaches 1 meter until it falls to the floor (number of floating days)
Was evaluated by measuring.

Comparative Example 12 A 30 μm-thick LL was applied to the Al-deposited film of Comparative Example 1 in the same manner as in Example 13.
The DPE film was dry-laminated according to a standard method to form a balloon. As is clear from Table 4, the composite vapor deposition film of the present invention has excellent suitability as a balloon.

[0056]

[Table 4]

[0057]

According to the present invention, oxygen gas barrier properties,
A composite vapor-deposited film having remarkably excellent water vapor barrier properties and helium gas barrier properties is provided. In the present invention,
Since a PVDC coating or film is formed by applying a PVDC solution or a dispersion on the deposited film of the deposited film having a deposited film of an inorganic material such as aluminum or silicon oxide, cracks on the deposited film surface And a composite vapor-deposited film in which the bending fatigue resistance of the vapor-deposited film is improved. The gas barrier property of the composite vapor-deposited film of the present invention shows a synergistic improvement effect far exceeding the level expected from the gas barrier property of each layer. Further, in the composite vapor-deposited film of the present invention, since the vapor-deposited film is protected by the PVDC coating layer, gas barrier properties are not impaired by secondary processing such as printing and lamination. Therefore, the composite vapor-deposited film of the present invention is suitable as a packaging material for foods, medicines, daily necessities and the like. Further, the composite vapor-deposited film of the present invention has excellent helium gas barrier properties, and thus is useful as a balloon material and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-139446 (JP, A) JP-A-60-250041 (JP, A) JP-A-4-77531 (JP, A) JP-A-7-1995 285191 (JP, A) Actually open 1-141024 (JP, U) Actually open 63-6378 (JP, U) Actually open 62-123920 (JP, U) Actually open 55-8113 (JP, U) (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (2)

(57) [Claims] An inorganic material vapor-deposited film (B) is formed on at least one surface of a polymer film substrate (A).
A composite vapor-deposited film in which a coating film (C) of polyvinylidene chloride is laminated adjacent to the vapor-deposited film (B),
After the polyvinylidene chloride coating film (C) was formed, the composite vapor-deposited film was placed in an oven at 35 to 60 ° C. for 1 hour.
Is intended is Gana heat treatment 2-100 hours, and,
Oxygen permeability of the composite vapor-deposited film measured at a temperature of 30 ° C. and a relative humidity of 80% [ml (STP) / m ² · day · at
m {Pa}] is Z, the oxygen permeability of the vapor-deposited film [polymer film substrate (A) / vapor-deposited film (B)] is X, and the oxygen permeability of the polyvinylidene chloride coating (C) layer is Y. The following relational expression (1 / Z)> (1 / X) + (1 / Y) holds, and the water vapor permeability measured at a temperature of 40 ° C. and a relative humidity of 90%, and a temperature of 30 ° C. and a relative humidity A composite vapor-deposited film characterized in that the same relational expression holds for the helium permeability measured at 0%. 2. A vapor-deposited film (B) of an inorganic material is formed on at least one surface of a polymer film substrate (A), and a solution or dispersion of polyvinylidene chloride is formed on the vapor-deposited film (B). To form a polyvinylidene chloride coating film (C), and then heat-treating the polyvinylidene chloride coating film (C) in an oven at 35 to 60 ° C. for 12 to 100 hours. The oxygen permeability [ml (STP) / m ² · day · atm {Pa}] of the composite vapor-deposited film measured at a temperature of 30 ° C. and a relative humidity of 80% is defined as Z, and the vapor-deposited film [polymer film base X is the oxygen permeability of the material (A) / deposited film (B)] and Y is the oxygen permeability of the polyvinylidene chloride coating (C) layer, and the following relational expression (1 / Z)> (1 / X) + (1 / Y) holds, the temperature is 40 ° C. and the relative humidity is 90. In the manufacturing method of the composite deposited film similar relations with regard measured water vapor permeability and the temperature 30 ° C. and a relative humidity of helium permeability measured at 0% is established.