JP3605908B2 - Barrier laminate and method for producing the same - Google Patents

Description

【００４４】
表１から考察すると、酸素、水蒸気に対するバリアー性は、実施例１、４、５は非常に良好な結果が得られ、比較例１、２はやや良好なバリア性が得られた。比較例３、４はやや不良あるいは不良であった。
積層体のプラズマＣＶＤ膜および蒸着膜の密着性を示す剥離強度は、実施例１、４、５は非常に良好な密着性が得られ、比較例３、４はやや良好な結果が得られ、比較例１、２はやや不良あるいは不良であった。
【００４５】
【発明の効果】
以上述べたように本発明によれば、樹脂フィルム上で金属、金属化合物蒸着膜間、または金属、金属化合物蒸着膜上に、低温プラズマＣＶＤ法によるシリコン化合物薄膜を設けることにより、積層体のガスバリアー性および積層体の密着性が向上する。
また、低温プラズマＣＶＤ法によるシリコン化合物薄膜層は耐熱性、熱寸法安定性、硬度に優れることから、蒸着、印刷、ラミネート、製袋等の積層体製造工程における機械的ストレス、熱的ストレスからくる歪みによるクラック、ピンホールが発生しにくく、バリアー性劣化が起き難い。
さらに、ウェットコーティング膜程厚みを必要とせず、しかも膜厚制御性も良好であるため、加工性、生産性に非常に有利である。
【図面の簡単な説明】
【図１】（ａ）本発明のバリアー性積層体の一実施例を示す断面図である。
（ｂ）本発明のバリアー性積層体の別の実施例を示す断面図である。
（ｃ）本発明のバリアー性積層体のさらに別の実施例を示す断面図である。
【図２】本発明のバリアー性積層体を製造する装置を説明する模式説明図である。
【符号の説明】
１‥‥樹脂フィルム
２‥‥低温プラズマＣＶＤシリコン化合物薄膜、ＣＶＤ−ＳｉＯ_２
３‥‥金属または金属化合物蒸着薄膜、ＳｉＯ
４‥‥バリアー性積層体
５‥‥バリアー性積層体
６‥‥バリアー性積層体
１０‥‥真空蒸着兼低温プラズマＣＶＤ発生装置
１１‥‥巻出しロール
１２‥‥ガイドロール
１３‥‥冷却ドラム
１４‥‥蒸着源
１５‥‥巻取りロール
１６−１、１６−２‥‥原料ガス源
１７−１、１７−２‥‥高電圧源
１８−１、１８−２‥‥プラズマ発生電源
２１‥‥ロール室
２２−１、２２−２‥‥低温プラズマＣＶＤ発生室
２３‥‥蒸着室[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is a barrier having excellent gas barrier properties against oxygen, water vapor, etc., and having a performance of preventing a thin film from being peeled off in a vapor deposition process, a printing process, a laminating process, a bag making process, etc., and a thin film when used in a packaging form. The present invention relates to a functional laminate and a method for producing the same.
[0002]
[Prior art]
In recent years, packaging materials used for packaging of foods, medical products, etc. are used to suppress deterioration of contents, especially oxidation and deterioration of proteins and oils and fats in foods, and to maintain taste and freshness. For medical products that need to be handled in a state, prevent the effects of oxygen, water vapor, and other gas that alters the contents of the packaging material to prevent deterioration of the active ingredient and maintain the efficacy, in order to maintain the efficacy. It is necessary to provide a gas barrier property for blocking these gases.
[0003]
Therefore, as a barrier film that conventionally blocks oxygen, a polyvinyl alcohol film, an ethylene vinyl alcohol copolymer film, a polyacrylonitrile film, and the like, and as a barrier film that blocks water vapor, a polypropylene film, a polyethylene film, and the like are gas barrier laminates. And a packaging film made of the packaging material has been generally used.
[0004]
However, these films alone do not have sufficient gas barrier properties against both oxygen and water vapor, and are generally laminated or coated with polymer resin compositions having different properties, which are said to have relatively high gas barrier properties. Although it has been used as a laminated film for packaging materials, there have been cases where sufficient gas barrier properties cannot be exhibited due to the effects of temperature and humidity in storage and use environments.
[0005]
In addition, as a resin film alone having both oxygen and water vapor barrier properties, a polyvinylidene chloride film, or a polyester film coated with a vinylidene chloride copolymer resin, and a polypropylene film coated with a vinylidene chloride copolymer resin. Films and films obtained by coating a vinylidene chloride copolymer resin on a nylon film are available. Such a resin film is discarded after use and, when incinerated, generates toxic gas, which may cause environmental problems.
[0006]
On the other hand, packaging materials that require high gas barrier properties include resin films (even if the resin alone does not have high gas barrier properties with a suitable polymer resin composition) and a metal such as aluminum or the like. A laminated film with a metal foil made of a metal compound has been used. However, metal foils such as aluminum foil used here have excellent barrier properties against gases such as oxygen and water vapor, but when incinerated as waste after use, the metal remains as residues and is difficult to reuse. Therefore, disposal of this metal foil cannot avoid the influence on the environment.
[0007]
In order to solve the above problems, recently, silicon oxide (SiO _x ) such as silicon monoxide (SiO), aluminum oxide (Al _x O _y ), metal such as aluminum (Al), and metal oxide Vapor deposition films have been developed in which a thin film of a product is formed on a resin film by a forming means such as vapor deposition, and these have better gas barrier properties than a gas barrier material composed of a polymer resin composition. It has started to be used for packaging materials with little deterioration under high humidity.
A 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 through a bag-making process by attaching a vapor-deposited film to another base material.
[0008]
However, a vapor-deposited film in which the above-mentioned metal and metal oxide are formed as a thin film on a resin film is a resin film that is an organic compound, and a vapor-deposited thin film that is an inorganic compound in contact with the resin film, the mechanical properties of both, Various physical properties such as chemical properties, thermal properties, and electrical properties are very different.
Therefore, 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 usage environment, mechanical stress, thermal stress, etc. are applied to the vapor deposited thin film, and the vapor deposited thin film is damaged. This causes problems such as cracks, pinholes, and other damages and defects, and the passage of gases such as oxygen and water vapor from those damaged and defective portions, which lowers the high barrier performance that should be originally possessed. are doing.
In addition, it is difficult to obtain a strong bond between the vapor-deposited thin film of the inorganic compound and the resin film that is an organic compound, and peeling occurs between the resin film, the ink, the adhesive, and the like, and sufficient adhesion cannot be obtained. The vapor-deposited thin film also has a problem that the barrier property deteriorates due to damage.
[0009]
In order to solve such a problem, methods for improving the adhesion between the resin film serving as the deposition base material and the deposition film include, for example, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, flame treatment, or heat treatment on the surface of the resin film. In some cases, a metal or a metal compound is deposited after activating the surface by a surface treatment with a chemical such as alkali or alkali. However, the improvement of the wettability of the resin film can be expected to improve the adhesiveness by increasing or decreasing the secondary bonding force with the deposited thin film. However, the activity ability decreases with time, and even with this treatment method, a satisfactory adhesive force is not necessarily obtained. And it is not sufficient.
[0010]
As another method, a method using a co-extruded multilayer resin film obtained by co-extrusion of another resin at the time of forming a resin film, a copolymer resin film obtained by copolymerizing a resin film with other resin components, or a vapor-deposited base material There is a method of applying an ethyleneimine-based, amine-based, epoxy-based, urethane-based or polyester-based coating agent on the surface of the resin film to be formed off-line or in-line during the formation of the resin film. Although the heat resistance is poor, the thermal dimensional stability is poor because the heat resistance is inferior, and the deposited thin film is subjected to mechanical stress at the time of heat load in each step such as vapor deposition, printing, lamination, etc., so that cracks, pinholes, etc. Occurs, and the barrier property is lowered, which is not sufficient.
[0011]
Furthermore, the adhesion between the deposited thin film formed on the resin film, the ink added by the printing and laminating processes, the adhesive, and the like has also been improved, and ethyleneimine-based, amine-based, epoxy-based, urethane-based or There is a method of applying a coating agent such as polyester. Depending on the resin component of the coating agent, the adhesiveness is deteriorated or the barrier property is lowered, and both the adhesiveness and the barrier property are not satisfied. According to this method, the thermal dimensional stability during coating is poor, and the volume expansion or volume contraction occurs due to aging or the thermal load applied during the bag making process or the molding process, and the deposited thin film receives mechanical stress, thereby cracking the deposited thin film. Then, pinholes and the like were generated, and peeling from the ink, the adhesive and the like occurred, and the barrier property was lowered.
[0012]
In addition to the problem of performance as a packaging material, the coating process of the coating layer interposed between the resin film and the vapor-deposited thin film, and the coating process of the coating layer interposed between the vapor-deposited film and the printed layer or adhesive layer, Except for providing a coating layer in-line at the time of film production, that is, in most cases, since each layer is a separate step, there is a problem that the production cost is extremely high.
[0013]
[Problems to be solved by the invention]
The present invention has been made in order to eliminate the above-described problems relating to the barrier laminate, has good adhesion between the resin film and the metal-deposited thin film, and has excellent gas barrier properties and a barrier laminate having excellent gas barrier properties. The aim is to provide a method.
[0014]
[Means for Solving the Problems]
According to a first aspect of the present invention, a thin film of a silicon compound is formed on one side of a resin film by a low-temperature plasma CVD method, and a thin film of a metal or a metal compound is laminated on the thin film by a physical vapor deposition method. This is a barrier laminate obtained by laminating silicon compound thin films by a method.
[0018]
[Action]
As described above, according to the present invention, the action of the silicon compound thin film formed on the resin film by the low-temperature plasma CVD method causes a strong -O-Si-O-Si- bond inside the thin film, A strong chemical bond is formed even with the resin film serving as the substrate, and sufficient adhesion is exhibited. In addition, a strong chemical bond such as -O-Si-OM (metal) is sufficiently formed between a silicon compound thin film formed by low-temperature plasma CVD and a metal or metal compound thin film formed by physical vapor deposition. Demonstrate good adhesion. Since a thin film of a plasma CVD silicon compound is similar to a thin film of a metal or a metal compound formed by physical vapor deposition in terms of internal stress, thermal expansion coefficient, and the like, strong adhesion can be obtained because distortion generated between the two layers is small.
[0019]
Furthermore, the plasma CVD silicon compound has a dense film quality and the cross-linking is advanced. Since it is a dry process, there is little foreign matter such as dust, and the number of pinholes is very small. At the same time, the number of film formation points when forming a metal or metal compound thin film by physical vapor deposition on the thin film becomes extremely large, there is no residual solvent and degassing, and it hinders the adhesion of evaporated particles. Since it is not provided, the film quality of the metal or metal compound thin film is also made dense, and the barrier performance is improved. A metal or metal compound thin film formed by a physical vapor deposition method has a relatively large number of pinholes. However, when a plasma CVD silicon compound film is formed on the film, the pinholes are covered because of good step coverage. It can be concealed, and the gas barrier property becomes good.
[0020]
The plasma CVD silicon compound film has strong hardness, good heat resistance, does not require a thickness as much as a wet coating film, and has good film thickness controllability. This is very advantageous for workability and productivity.
Therefore, the plasma CVD silicon compound film is much more effective as an anchor coat layer and a top coat layer for a metal or metal compound thin film formed by physical vapor deposition than a conventional wet coat layer.
[0021]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
1 (a), 1 (b) and 1 (c) are cross-sectional views illustrating the configuration of the barrier laminate of the present invention, respectively, and FIG. 2 is a schematic explanatory view of an apparatus for producing the barrier laminate of the present invention. It is.
1 (a), 1 (b) and 1 (c), 4, 5 and 6 denote barrier laminates, 1 is a resin film, 2 is a low-temperature plasma CVD silicon compound thin film, and 3 is a metal or metal compound deposited thin film. It is.
[0022]
The resin film (1) is in the form of a sheet or a film, and includes polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene terephthalate, polyethylene 2,4-naphthate, etc.), polyamide (nylon 6, nylon 12, etc.), Polyvinyl chloride, polyvinyl alcohol, aromatic polyamide, polyamide imide, polyether imide polysulfone, polyether sulfone, polyether ketone, polyarylate, polyphenylene sulfide, polyphenylene oxide, tetrafluoroethylene, ethylene trifluoride, ethylene fluoride Those usually used as packaging materials such as ethylene propylene copolymer and polyimide can be used. These resin films (1) are appropriately selected from the above materials depending on the application. If necessary, a biaxially stretched film can be used.
In addition, known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a coloring agent can be added to these resin films, and are appropriately added as necessary.
[0023]
Further, the surface of the resin film (1) is a known surface such as a corona discharge treatment, a plasma activation treatment, a glow discharge treatment, a reverse sputtering treatment, a surface activation treatment such as a roughening treatment, a cleaning treatment, and a charge removal treatment. Processing, or applying a coating agent such as ethyleneimine, amine, epoxy, urethane, polyester, etc., off-line or in-line, resin film (1) and low-temperature plasma CVD silicon compound thin film (2) Alternatively, it is also possible to improve the adhesion to the metal or metal compound vapor-deposited thin film (3).
The thickness of the resin film (1) is not particularly limited, but is preferably in the range of 2 to 400 μm in consideration of the suitability for processing in the vapor deposition step.
[0024]
The low-temperature plasma CVD silicon compound thin film (2) is, for example, a silicon oxide film (SiO _x ) such as SiO, SiO ₂ , a silicon nitride film (SiN _y ) such as Si ₃ N _4, or a silicon oxynitride film such as SiO _x N _y. .
The forming method is a low-temperature plasma generator such as direct current (DC) plasma, low frequency plasma, high frequency (RF) plasma, pulse wave plasma, triode structure plasma, microwave plasma, downstream plasma, columnar plasma, plasma assisted epitaxy, etc. Is used. From the viewpoint of plasma stability, a radio frequency (RF) plasma method is more preferable.
As a raw material gas, a mixed gas of SiH ₄ , Si ₂ H ₆ , SiH _x F _y , TEOS and the like, and O ₂ , N ₂ O, H ₂ O, NH ₃ , N ₂ , PSG and the like is used. These source gases are turned into plasma by the above-mentioned method and deposited on the resin film.
[0025]
The thickness of the low-temperature plasma CVD silicon compound thin film (2) may be in the range of 10 to 5000 °, preferably in the range of 50 to 500 °. This is because if the film thickness is less than 10 °, the film is liable to escape, and if it exceeds 5000 °, the flexibility of the deposited thin film is impaired, and cracks and pinholes are liable to occur. The CVD silicon compound thin film (2) may be not only a single component but also a multi-component, or may be a multi-layer film instead of a single-layer film.
[0026]
Metals or metal compound deposited thin films (3) include metals such as aluminum, silica, titanium, zinc, zirconium, magnesium, tin, copper and iron, and oxides, nitrides, sulfides and fluorides of these metals. For example, aluminum oxide (Al ₂ O ₃ ) silicon monoxide (SiO), silicon dioxide (SiO ₂ ), titanium oxide (TiO ₂ ), zinc oxide (ZnS), zirconium oxide (ZrO ₂ ), magnesium oxide (MgO), fluorine oxide Magnesium oxide (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, and sputtering can be used, but vacuum evaporation and ion plating are preferable in terms of productivity. As a heating method of the vapor deposition apparatus, resistance heating, electron beam (EB) heating, high-frequency induction heating, or the like is used.
[0027]
The thickness of the metal or metal compound deposited thin film (3) may be in the range of 50 to 5000 °, preferably in the range of 200 to 1500 °. This is because if the film thickness is less than 50 °, the vapor-deposited thin film tends to fall out and the barrier property tends to vary, and if it exceeds 5000 °, the flexibility of the vapor-deposited thin film is impaired, and cracks and pinholes are easily generated. The barrier properties decrease. The deposited thin film is not limited to a single layer of a single component, and may be a deposited thin film made of a mixture of the above-described deposition materials, or may be a multilayer film having two or more layers.
[0028]
The low-temperature plasma CVD silicon compound thin film (2) and the metal or metal compound vapor-deposited thin film (3) are respectively separated into separate chambers (22-1, 22) in the same vacuum deposition and low-temperature plasma CVD generator (10) shown in FIG. -2 and 23), and are sequentially and sequentially laminated.
The vacuum deposition and low-temperature plasma CVD generator (10) is evacuated to 2 × 10 ⁻⁶ to 8 × 10 ⁻³ Torr, preferably 8 × 10 ⁻⁶ to 8 × 10 ⁻⁵ Torr, and then the low-temperature plasma is generated. Perform CVD and vapor deposition processing.
[0029]
【Example】
Hereinafter, a specific embodiment of the present invention will be described in detail with reference to FIG.
<Example 1>
An unwinding roll (11) of, for example, a biaxially stretched polyethylene terephthalate film (hereinafter abbreviated as PET) having a thickness of 12 μm, which is a resin film (1), is provided in a roll chamber (21) in a vacuum deposition / low-temperature plasma CVD generator (10). ).
This PET film (1) passes through a guide roll (12) and is held by a metal cooling drum (13) while being held in a low-temperature plasma CVD generation chamber (22-1), and then a vapor deposition chamber (23) having a vapor deposition source (14). ), A low-temperature plasma CVD generation chamber (22-2), and finally a take-up roll (15) installed in a roll chamber (21) via a guide roll (12) apart from the cooling drum (13). ).
[0030]
First, the entire vacuum vapor deposition / low-temperature plasma CVD generator (10) is set to a degree of vacuum of 1.5 × 10 ⁻⁵ Torr, and then is run on the cooling drum (13) in the low-temperature plasma CVD generation chamber (22-1). To the PET film (1), a mixed gas of TEOS and oxygen gas (25%) whose flow rate was adjusted was supplied from the raw material gas source (16-1). 0 Torr. At the same time, a frequency (RF) of 13.56 MHz was applied to the plasma generation power supply (cathode, 18-1) from the high voltage source (17-1), and the supply gas was excited with 500 W power to generate plasma. A plasma CVD film (2) of SiO ₂ (H) having a thickness of 100 ° was deposited on the surface of a PET film (1) running on a cooling drum (13) serving as an anode.
[0031]
Further, the low-temperature plasma CVD silicon compound thin film (2) of the PET film (1) on which the low-temperature plasma CVD silicon compound thin film (2) is deposited, running while holding the cooling drum (13) of the vapor deposition chamber (23). On top, silicon oxide SiO was vapor deposited and laminated to a film thickness of 500 ° under the conditions of EB-Power 30KV-0.75A and pressure of 2 × 10 ⁻⁴ Torr, and PET (1) / CVD silicon compound thin film (2) / SiO (3 ).
[0032]
In addition, the PET (1) / CVD silicon compound thin film (2) / SiO vapor deposition of the SiO vapor deposition film (3) running so as to hold the cooling drum (13) serving as the anode of the low temperature plasma CVD generation chamber (22-2). A mixed gas of TEOS and oxygen gas (25%) whose flow rate was adjusted was supplied from the source gas source (16-2) to the thin film, and the pressure was set to 1.0 Torr. At the same time, a 13.56 MHz frequency (RF) is applied from a high voltage source (17-2) to a plasma generation power supply (cathode, 18-2) to excite the supply gas with a power of 500 W to generate plasma, A plasma CVD film (2) of composition SiO ₂ (H) having a thickness of 100 ° is deposited, and then this PET film leaves the cooling drum (13), passes through a guide roll (12) and is continuously fed to a winding roll (15). wound taken, barrier laminate of the present invention _{(5), PET (1)} / CVD-SiO 2 (2) / SiO (3) / CVD-SiO 2 (2) is produced (see FIG. 1 (b) reference).
[0033]
An unstretched polypropylene film having a thickness of 30 μm was bonded as a heat-adhesive resin to the outermost layer plasma CVD film surface of the obtained barrier laminate (5) by a dry lamination method.
[0034]
Reference Example 2 A barrier laminate (4) was produced in the same manner as in Example 1, except that the plasma CVD-SiO2 film was not laminated in the low-temperature plasma CVD generation chamber (22-2). That is, it is a laminate (4) having a PET (1) / CVD-SiO ₂ (2) / SiO (3) configuration (see FIG. 1A).
[0035]
Reference Example 3 A barrier laminate (6) was produced in the same manner as in Example 1, except that the plasma CVD-SiO ₂ film was not laminated in the low-temperature plasma CVD chamber (22-1). That is, it is a laminate (6) having a PET (1) / SiO (3) / CVD-SiO ₂ (2) configuration (see FIG. 1C).
[0036]
<Example 4>
A barrier laminate was produced in the same manner as in Example 1, except that the deposition material was aluminum oxide (purity 99.99%) and the deposition conditions were EB-Power 30KV-0.75A. That _is, a laminate of _{PET / CVD-SiO 2 / Al} 2 O 3 / CVD-SiO 2 configuration.
[0037]
<Example 5>
In two low-temperature plasma CVD generation chambers (22-1, 22-2), a mixture of SiH ₄ and NH ₃ (25%) is mixed with a mixed gas whose flow rate has been adjusted from source gas sources (16-1, 16-2). using a gas, other than depositing a silicon nitride film SiN _x was prepared barrier laminate in the same manner as in example 1. That is, it is a laminate having a PET / SiN _x / SiO / SiN _x configuration.
[0038]
<Comparative Example 1>
A laminated body was produced in the same manner as in Example 1 except that the plasma CVD-SiO ₂ film was not laminated in the two low-temperature plasma CVD generation chambers (22-1, 22-2). That is, it is a laminate having a PET / SiO structure.
[0039]
<Comparative Example 2>
A laminated body was produced in the same manner as in Example 4, except that the plasma CVD-SiO ₂ film was not laminated in the two low-temperature plasma CVD generation chambers (22-1, 22-2). That is, it is a laminate having a PET / Al ₂ O ₃ configuration.
[0040]
<Comparative Example 3>
Comparative Example 1 was repeated except that a 12 μm-thick PET film was coated with a TEOS aqueous solution by a gravure coating method and dried to form a 0.1 μm-thick coating film. A laminate was produced in the same manner. That is, the laminate has a PET / coating layer / SiO structure.
[0041]
<Comparative Example 4>
Comparative Example 3 was performed except that a TEOS aqueous solution was applied and dried by a gravure coating method on the silicon oxide SiO deposited film surface of the laminate obtained in Comparative Example 3, and a coated PET having a 0.1 μm thick coating film was used. A laminate was produced in the same manner as in Example 1. That is, it is a laminate having a structure of PET / coating layer / SiO / coating layer.
[0042]
The oxygen permeability and the moisture permeability indicating the barrier properties of the laminated body of the examples and the comparative examples, which are manufactured as described above, and the peel strength indicating the adhesion properties of the plasma CVD film and the deposited film of the laminated body are shown. Each physical property of the peel strength was measured according to the following measurement conditions. Table 1 shows the results.
Oxygen transmission rate ‥‥ Mocon method (MOCON OXTRAN-10 / 50A), 25 ° C-100% RH, samples are vapor deposition film and laminate film.
Moisture permeability ‥‥ MOCON PERMATRAN-W6, 40 ° C-90% RH, sample is vapor deposition film and laminate film.
Peel strength: Instron type tensile tester, sample 15 mm width, peel angle 90 °, peel speed 300 mm / min. The sample is a laminated film.
[0043]
[Table 1]

[0044]
Considering from Table 1, as for the barrier properties against oxygen and water vapor, Examples 1, 4, and 5 obtained very good results, and Comparative Examples 1 and 2 obtained somewhat good barrier properties. Comparative Examples 3 and 4 were slightly defective or defective.
With respect to the peel strength indicating the adhesion between the plasma CVD film and the deposited film of the laminate, Examples 1, 4, and 5 obtained very good adhesion, and Comparative Examples 3 and 4 obtained somewhat good results. Comparative Examples 1 and 2 were slightly defective or defective.
[0045]
【The invention's effect】
As described above, according to the present invention, by providing a silicon compound thin film by a low-temperature plasma CVD method between a metal and a metal compound vapor-deposited film on a resin film, or on a metal and a metal compound vapor-deposited film, The barrier properties and the adhesion of the laminate are improved.
In addition, since the silicon compound thin film layer formed by the low-temperature plasma CVD method has excellent heat resistance, thermal dimensional stability, and hardness, it comes from mechanical stress and thermal stress in a laminate manufacturing process such as vapor deposition, printing, lamination, and bag making. Cracks and pinholes due to distortion are not easily generated, and barrier property deterioration is unlikely to occur.
Furthermore, since the thickness is not required as much as the wet coating film and the controllability of the film thickness is good, it is very advantageous in workability and productivity.
[Brief description of the drawings]
FIG. 1A is a cross-sectional view showing one embodiment of a barrier laminate of the present invention.
(B) It is sectional drawing which shows another Example of the barrier laminated body of this invention.
(C) It is sectional drawing which shows another Example of the barrier laminated body of this invention.
FIG. 2 is a schematic explanatory view illustrating an apparatus for producing a barrier laminate of the present invention.
[Explanation of symbols]
1 {resin film 2} low temperature plasma CVD silicon compound thin film, CVD-SiO ₂
3) Metal or metal compound deposited thin film, SiO
4 Barrier laminate 5 Barrier laminate 6 Barrier laminate 10 Vacuum evaporation and low-temperature plasma CVD generator 11 Unwinding roll 12 Guide roll 13 Cooling drum 14 {Evaporation source 15} Take-up roll 16-1, 16-2 {Source gas source 17-1, 17-2} High voltage source 18-1, 18-2} Plasma generation power supply 21} Roll chamber 22-1, 22-2 {low temperature plasma CVD generation chamber 23} evaporation chamber

Claims (1)

Thin on one surface of the resin film to form a thin film of silicon compounds by a low-temperature plasma CVD method, the by physical vapor deposition on the thin film by laminating a thin film of metal or metal compound Ri Na, silicon compound further the low temperature plasma CVD method And a laminate having a barrier property.

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