JP2008179104A - Barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a barrier film having transparency, flexibility, stretchability, pliability, etc., having excellent gas barrier functionality, improved in tearability, having linear cutting performance and further excellent in various physical properties such as impact resistance, bendability, etc. <P>SOLUTION: The barrier film having linear cutting performance comprises a biaxially stretched polyamide film consisting of a mixed resin of a nylon resin and a nylon MXD6 resin, a barrier layer provided on one side of the biaxially stretched polyamide film, and a gas barrier coating film provide on the barrier layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a barrier film having a straight-cut property, and more specifically, it has transparency, flexibility, spreadability, flexibility, etc., has an excellent gas barrier property, and has a good tear property and a straight-cut. In addition, the present invention relates to a barrier film having a linear cut property that is excellent in various physical properties such as impact resistance and flexibility.

Conventionally, as a packaging material base having a gas barrier property, a packaging base material in which an aluminum foil or a vapor deposition film of aluminum is provided on a base film has been used.
However, the packaging base material having such a gas barrier property can provide a stable gas barrier property, but has an aluminum foil or an aluminum deposited film as a gas barrier layer, so that the incineration suitability is inferior. There is a problem that disposal is not easy.
Moreover, since the aluminum foil is provided, there is a problem that a packaging base material having transparency cannot be obtained.

In order to cope with this, for example, a packaging base material having a gas barrier layer made of polyvinylidene chloride resin (PVDC) or ethylene-vinyl alcohol copolymer (EVOH) has been developed.
However, since PVDC contains chlorine, incineration after use generates chlorine gas, which is not preferable for environmental hygiene.
On the other hand, although EVOH has the advantages of low oxygen permeability and low adsorption of flavor components, there is a problem in that the gas barrier property is remarkably lowered when it comes into contact with water vapor.
For this reason, in order to block EVOH which is a barrier layer from water vapor | steam, it is necessary to laminate | stack another packaging material base material and to make it a complicated laminated structure, and this has the problem that an increase in manufacturing cost will be brought about It is.

Thus, in recent years, a barrier layer made of a thin film of an inorganic oxide such as silicon oxide or aluminum oxide has been used as a packaging base material that stably exhibits high gas barrier properties and fragrance retention properties and has transparency. A gas barrier film provided has been developed.
This inorganic oxide thin film is formed by depositing the material inorganic oxide on the base film by vacuum deposition, and there is no environmental problem at the time of disposal, and the humidity dependence of the gas barrier property, etc. There is nothing.
However, in the barrier layer comprising a thin film of an inorganic oxide such as silicon oxide or aluminum oxide described above, since the inorganic oxide particles are deposited on the substrate, a crystal grain boundary is defined between the inorganic oxide particles. There are gaps, the gas barrier property is not sufficient, it is necessary to increase the film thickness (500 to 1000 mm), the smaller the oxygen atom ratio of the inorganic oxide, the better the gas barrier property, Since there is a need to increase the film thickness as described above, the transparency is lowered, and as a result, the spreadability is inferior and cracks are likely to occur, and the adhesion between the substrate and the inorganic oxide particles is weak. There is a problem of.

By the way, in recent years, the packaging material base having the above-mentioned gas barrier properties is also required to have functions such as easy-openability as its convenience as well as protection of contents.
In particular, as a performance that is strongly demanded for packaging materials in recent years, improvement of so-called usability performance such as global design is mentioned, and the cutting property at the time of opening the packaging material is one of them, It is desirable to have a straight-cut property (easy-opening property) that does not require an opening means such as a cutter or scissors, and can be easily and easily torn linearly.
Thus, various new techniques have been developed and proposed for methods, means, and the like for imparting linear cutability (easy opening).
For example, as an example, nylon 6 (Ny6) contains 40 to 85 parts by weight and metaxylylene adipamide (MXD6) 15 to 60 parts by weight (however, Ny6 + MXD6 = 100 parts by weight), MD direction ( The film has an easily tearable film whose stretching ratio in the TD direction (film width direction) is 2.8 times or more, and a vinylidene chloride resin layer formed on one side of the film. An easily tearable film has been proposed (see, for example, Patent Document 1).
As another example, at least one surface of a film (provided that PA + MXD6 = 100 parts by weight) containing 40 to 85 parts by weight of polyamide (PA) and 15 to 60 parts by weight of metaxylylene adipamide (MXD6), A packaging material in which an aluminum oxide layer is formed to a thickness of 100 to 4000 mm has also been proposed (see, for example, Patent Document 2).
JP 7-125152 A JP-A-7-125132

However, in the easily tearable film according to Patent Document 1 described above, since it has a vinylidene chloride-based resin layer as described above, it must be a laminated structure containing chlorine atoms. Incineration of packaging waste disposed of after use causes chlorine gas to be generated, which is not preferable for environmental hygiene.
Further, in the packaging material according to Patent Document 2, the aluminum oxide layer is formed by physical vapor deposition using a vacuum evaporation apparatus or the like, so that the aluminum oxide layer is formed on the base film. The particles are physically vaporized and adhered to form an aluminum oxide layer, which is simply composed of a deposited glassy film, and is flexible, flexible, spreadable, etc. For this reason, for example, it is difficult for the aluminum oxide layer to follow the elongation against the elongation of the film, and the aluminum oxide layer is cracked and the barrier property is deteriorated. It has a point.
Furthermore, in the packaging material according to Patent Document 2 described above, since the aluminum oxide particles are vaporized and adhered onto the base film, there is a gap called a grain boundary between the aluminum oxide particles as described above. However, the gas barrier property is not sufficient, and it is necessary to increase the film thickness (500 to 1000 mm). The smaller the oxygen atom ratio of aluminum oxide, the better the gas barrier property, but on the other hand, the transparency decreases. In addition, since there is a need to increase the film thickness as described above, as a result, various problems such as poor spreadability and easy cracking, weak adhesion between the base film and aluminum oxide particles, etc. There is something.
Therefore, the present invention has transparency, flexibility, spreadability, flexibility, etc., an excellent gas barrier property, a good tearing property and a linear cut property, and further, impact resistance, flexibility. It is providing the barrier film which has the linear cut property excellent in various physical properties, such as.

As a result of various studies to achieve the above object, the present inventor first made a nylon film obtained by forming a mixed resin of a nylon resin and a nylon MXD6 resin as a base film. Using a biaxially stretched polyamide film stretched in the direction, and when forming a barrier layer on one surface of the biaxially stretched polyamide film, use at least three film forming chambers; and For each chamber, the mixing ratio of each gas component of the film-forming mixed gas composition containing at least one kind of organic silicon compound, oxygen gas, and inert gas is changed. From the carbon-containing silicon oxide film formed by plasma chemical vapor deposition of three or more layers formed using the mixed gas composition for film formation prepared in the above, and using the mixed gas composition for film formation. And more Each of the carbon-containing silicon oxide films includes a carbon-containing silicon oxide film in which three or more layers containing carbon atoms in the film and having different carbon contents for each carbon-containing silicon oxide film are stacked. On the carbon-containing silicon oxide film, a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M is a metal N represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.) and polyvinyl alcohol A barrier film is produced by forming a gas barrier coating film by a gas barrier composition obtained by polycondensation by a sol-gel method, and containing a vinyl resin and / or an ethylene / vinyl alcohol copolymer. , Biaxially stretched polyamide film and carbon-containing oxidation The carbon-containing silicon oxide film is excellent in adhesion between the base film and the gas barrier coating film, and is excellent in flexibility, spreadability, flexibility, flexibility, etc., and has an extremely high barrier property from the first layer. An excellent film can be formed, and at least three layers of carbon-containing silicon oxide films are continuously stacked using a plasma chemical vapor deposition apparatus comprising at least three chambers. In addition, since each layer can form a film having a high barrier property, it is possible to obtain a gas barrier property higher than that of a single layer, and further, a continuous production that opens to the atmosphere. By forming a film, it is possible to prevent foreign matter, dust, and the like that cause cracks from entering between the film-forming layers, and no deterioration of the barrier property is observed. Further, each carbon-containing silicon oxide The film contains carbon atoms in the film. In addition, since each carbon-containing silicon oxide film is a discontinuous layer having a different carbon content, permeation of oxygen gas, water vapor, and the like can be completely prevented by a synergistic effect with the gas barrier coating film. The gas barrier property is extremely excellent, and further, the performance of the gas barrier property is not deteriorated. Further, the tearing property is good, the linear cutting property is excellent, and various physical properties such as impact resistance are excellent. The present invention has been completed by finding that a barrier film having a cutting property can be produced.

That is, the present invention is a nylon film made of a mixed resin of nylon resin and nylon MXD6 resin, and further, a biaxially stretched polyamide film stretched in the longitudinal and lateral directions, and one of the biaxially stretched polyamide films A barrier layer provided on the surface, and a gas barrier coating film provided on the barrier layer, and the barrier layer uses at least three film forming chambers, and For each chamber, the mixing ratio of each gas component of the film-forming mixed gas composition containing at least one kind of organic silicon compound, oxygen gas, and inert gas is changed. From the carbon-containing silicon oxide film formed by plasma chemical vapor deposition of three or more layers formed using the mixed gas composition for film formation prepared in the above, and using the mixed gas composition for film formation. And, Each carbon-containing silicon oxide film is composed of a carbon-containing silicon oxide film containing carbon atoms in the film and having a different carbon content for each silicon oxide film. Formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents an integer of 0 or more. M represents an integer of 1 or more, and n + m represents a valence of M.) and at least one alkoxide represented by polyvinyl alcohol resin and / or ethylene / vinyl alcohol. The present invention relates to a barrier film having a linear cut property, characterized by comprising a gas barrier coating film comprising a polymer and further comprising a gas barrier composition obtained by polycondensation by a sol-gel method.

The barrier film according to the present invention is a nylon film formed by forming a mixed resin of a nylon resin and a nylon MXD6 resin as a base film, and further biaxially stretched in the vertical and horizontal directions. Since a stretched polyamide film is used, it has a linear cut property (easy-opening property) that tears linearly very well.
In addition, the barrier film according to the present invention includes a base film, a carbon-containing silicon oxide film, and a gas barrier coating film by laminating a carbon-containing silicon oxide film and a gas barrier coating film by a plasma chemical vapor deposition method. The carbon-containing silicon oxide film is particularly excellent in flexibility, spreadability, flexibility, flexibility and the like.
Further, in the barrier film according to the present invention, the carbon-containing silicon oxide film can be formed into a film excellent in high barrier properties from the first layer, and can be manufactured in at least three chambers. Using a plasma chemical vapor deposition apparatus comprising a film chamber, three or more carbon-containing silicon oxide films are continuously stacked to form a film having a high barrier property for each layer. Therefore, a higher gas barrier property than that of a single layer can be obtained.
Furthermore, the barrier film according to the present invention can prevent foreign matter, dust, and the like causing cracks from being mixed between the film forming layers by continuously forming a film that opens to the atmosphere. And the fall of the barrier property is not recognized.
In the barrier film according to the present invention, each carbon-containing silicon oxide film is a discontinuous layer containing carbon atoms in the film and having a different carbon content for each carbon-containing silicon oxide film. Therefore, the permeation of oxygen gas, water vapor and the like can be completely prevented.
Thus, the barrier film according to the present invention has an extremely excellent gas barrier performance due to the synergistic effect of the carbon-containing silicon oxide film and the gas barrier coating film, for example, barrier properties used for packaging materials and the like. As a material, it has excellent gas barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and no deterioration in the performance of the gas barrier properties is observed. ) And a very useful barrier film.

The barrier film according to the present invention will be described below in more detail with reference to the drawings.
FIG. 1 is a schematic configuration diagram showing a schematic configuration of an example of a carbon-containing silicon oxide film-forming apparatus for a barrier film according to the present invention, and FIG. 2 shows the barrier film according to the present invention. It is a schematic sectional drawing which shows an example of a layer structure.

First, the production method of the barrier film according to the present invention will be described. The barrier film according to the present invention is produced, for example, by forming a carbon-containing silicon oxide film using a chemical vapor deposition method or the like. Specifically, for example, a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like is used. The carbon-containing silicon oxide film can be formed into a film, and among them, it is particularly desirable that the carbon-containing silicon oxide film is formed by using a low temperature plasma chemical vapor deposition method. is there.
In the present invention, specifically, on one surface of a biaxially stretched polyamide film as a base film, a monomer gas for film formation composed of one or more organic silicon compounds is used as a raw material, and as a carrier gas, Silicon oxide using low temperature plasma chemical vapor deposition using an inert gas such as argon gas or helium gas, oxygen gas as oxygen supply gas and low temperature plasma generator etc. By forming a carbon-containing silicon oxide film made of a material or the like, the barrier film according to the present invention can be manufactured.
In the above, for example, a high-frequency plasma, a pulse wave plasma, a microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, a highly active and stable plasma is obtained. For this purpose, it is desirable to use a high-frequency plasma generator.

Specifically, the manufacturing method of the barrier film according to the present invention will be described. FIG. 1 shows a low temperature plasma chemical vapor deposition apparatus that forms a carbon-containing silicon oxide film by plasma chemical vapor deposition. It is a schematic block diagram which shows the outline | summary about the plasma chemical vapor deposition apparatus which manufactures the barrier film based on this invention.
In the present invention, as shown in FIG. 1, the plasma chemical vapor deposition apparatus 11 includes a base film supply chamber 12, a first film formation chamber 13, a second film formation chamber 14, and a third film formation. The basic structure consists of a chamber 15 and a winding chamber 16 for winding up the barrier film according to the present invention in which a carbon-containing silicon oxide layer is formed and overlaid on the base film. .
Thus, in the present invention, first, the base film 1 wound on the unwinding roll 17 is fed out to the first film forming chamber 13, and further, the base film 1 is moved to the auxiliary roll. The drum 18 is conveyed onto the circumferential surface of the cooling / electrode drum 19 at a predetermined speed.
Next, in the present invention, a film-forming monomer gas, oxygen gas, inert gas, etc. composed of one or more organic silicon compounds are supplied from the raw material volatilization supply device 20 and the gas supply device 21 or the like. The film-forming mixed gas composition is introduced into the first film-forming chamber 13 through the raw material supply nozzle 22 while adjusting the film-forming mixed gas composition, and the cooling / electrode A plasma is generated by the glow discharge plasma 23 on the substrate film 1 conveyed on the peripheral surface of the drum 19 and irradiated therewith to form a first carbon-containing silicon oxide layer made of silicon oxide or the like. Form a film.

Next, the base film 1 obtained by forming the carbon-containing silicon oxide film of the first layer in the first film forming chamber 13 is transferred to the second film forming chamber 14 through the auxiliary rolls 24 and 25. Next, in the same manner as described above, the base film 1 obtained by forming the carbon-containing silicon oxide film of the first layer is transported onto the circumferential surface of the cooling / electrode drum 26 at a predetermined speed.
Thereafter, similarly to the above, in the present invention, the raw material volatilization supply device 27, the gas supply device 28, etc. are used to form a film-forming monomer gas, oxygen gas, inert gas, which is composed of one or more organic silicon compounds, While supplying the other, adjusting the film-forming mixed gas composition comprising them, introducing the film-forming mixed gas composition into the second film-forming chamber 14 through the raw material supply nozzle 29, and The glow discharge plasma is formed on the carbon-containing silicon oxide film of the first layer of the base film 1 obtained by forming the carbon-containing silicon oxide film of the first layer conveyed on the cooling / electrode drum 26 peripheral surface. Plasma is generated by 30 and irradiated to form a second layer carbon-containing silicon oxide film made of silicon oxide or the like.

Further, in the present invention, in the same manner as described above, the carbon-containing silicon oxide films of the first layer and the second layer are formed in the second film forming chamber 14 and the laminated base film 1 is supplemented by the auxiliary film. The substrate film 1 which is fed into the third film forming chamber 15 through the first and second layers 31, 32, etc. and then formed into the carbon-containing silicon oxide films of the first layer and the second layer is formed in the same manner as described above. At the speed of cooling / conveying on the circumferential surface of the electrode drum 33.
Thereafter, similarly to the above, in the present invention, the raw material volatilization supply device 34, the gas supply device 35 and the like are used to form a film-forming monomer gas, oxygen gas, inert gas, and the like. The above-mentioned mixed gas composition for film formation is introduced into the third film forming chamber 15 through the raw material supply nozzle 36 while supplying the other and the like, and adjusting the mixed gas composition for film formation made of them, and The carbon-containing silicon oxide film of the second layer of the base film 1 formed by laminating the carbon-containing silicon oxide films of the first layer and the second layer transported on the peripheral surface of the cooling / electrode drum 33 is formed. On top of this, plasma is generated by glow discharge plasma 37 and irradiated to form a third layer carbon-containing silicon oxide film made of silicon oxide or the like.
Next, in the present invention, the carbon-containing silicon oxide films of the first layer, the second layer, and the third layer are formed as described above, and the base film 1 in which the carbon-containing silicon oxide films are stacked is interposed through the auxiliary roll 38. Thus, the barrier property according to the present invention in which the carbon-containing silicon oxide films of the first layer, the second layer, and the third layer are overlaid by winding into the winding chamber 16 and then winding up on the winding roll 39. A film can be produced.

In the present invention, each of the cooling / electrode drums 19, 26, 33 disposed in each of the first, second, and third film forming chambers 13, 14, 15 is provided in each of the first, second, 2 and 3 and a predetermined power is applied from a power source 40 arranged outside the third film forming chambers 13, 14, 15, and in the vicinity of each cooling / electrode drum 19, 26, 33. The generation of plasma is promoted by arranging magnets 41, 42, and 43.
Although not shown, the plasma chemical vapor deposition apparatus is provided with a vacuum pump or the like, and it is needless to say that each film forming chamber can be prepared to be kept in vacuum.
The above exemplification is an example, and it is needless to say that the present invention is not limited thereby.
For example, in the above example, the barrier film according to the present invention in which the carbon-containing silicon oxide films of the first layer, the second layer, and the third layer are overlaid is manufactured. The film forming chamber can be arbitrarily prepared, and the carbon-containing silicon oxide film layer can be formed arbitrarily, such as four layers or more, and can be formed into a layered structure. The invention is not limited to the example of producing the barrier film according to the present invention in which the carbon-containing silicon oxide films of the first layer, the second layer, and the third layer are overlaid.

In the above, each film forming chamber is depressurized by a vacuum pump or the like, and the degree of vacuum is 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably the degree of vacuum is 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable to prepare it.
On the other hand, since a predetermined voltage is applied to each cooling / electrode drum from the power source, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in each film forming chamber and the cooling / electrode drum, The glow discharge plasma is derived from one or more gas components in the film-forming mixed gas composition. In this state, the base film is conveyed at a constant speed, and the glow discharge plasma is used. A carbon-containing silicon oxide film made of silicon oxide or the like can be formed on the base film on the cooling / electrode drum peripheral surface.
The degree of vacuum in each film forming chamber at this time is adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. In addition, it is desirable that the conveying speed of the base film is adjusted to about 10 to 300 m / min, preferably about 50 to 150 m / min.
In the present invention, the degree of vacuum in each film forming chamber may be the same or different in each chamber.

Further, in the raw material volatilization supply device, a film forming monomer gas composed of one or more organic silicon compounds as raw materials is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, The film-forming mixed gas composition is introduced into each film-forming chamber through a raw material supply nozzle while adjusting the film-forming mixed gas composition.
In this case, as the gas mixing ratio of each gas component of the mixed gas composition for film formation, the content of the monomer gas for film formation composed of one kind of organic silicon compound is about 1 to 40%, and the content of oxygen gas The amount is preferably 0.1 to 70%, and the inert gas content is preferably 1 to 60%.
Thus, in the present invention, for each film forming chamber, a film forming mixed gas composition prepared by changing the gas mixing ratio of each gas component of the film forming mixed gas composition introduced into each film forming chamber. A barrier film according to the present invention is manufactured by forming a film for each film forming chamber and overlaying a carbon-containing silicon oxide film made of silicon oxide or the like.
That is, in the present invention, the mixing ratio of each gas component of a film-forming mixed gas composition containing at least one monomer gas for forming a film, oxygen gas, and inert gas, which is composed of at least one organic silicon compound. 3 or more to prepare a mixed gas composition for film formation, and then use the mixed gas composition for film formation for each film forming chamber. The carbon-containing silicon oxide film by the plasma chemical vapor deposition method of three or more layers used can be formed into a film and can be stacked.

By the way, in the present invention, as the mixing ratio of each gas component of the above-mentioned mixed gas composition for film formation, for example, as the first mixed gas composition for film formation, film for monomer - when the volume ratio V _O / V _M of the gas (M) and oxygen gas (O) and R, the mixing film consisting of 0.1 ≦ R <2.5 range of the gas composition ratio of As the gas composition and the second mixed gas composition for film formation, the volume ratio V _O / M of the film forming monomer gas (M) and oxygen gas (O) in the mixed gas composition for film formation when the V _M and the R, 2.5 ≦ R <5.0 for film formation gas mixture composition consisting of gas composition ratio in the range of, further, a third film for mixed gas composition, film film for monomers of use mixed gas composition - the volume ratio V _O / V _M of the gas (M) and oxygen gas (O) can to have a R, range of 5.0 ≦ R <15.0 A mixed gas composition for forming a film having a gas composition ratio in the range can be used.
Thus, in the present invention, the mixed gas composition for film formation as described above is arbitrarily combined, and the mixed gas composition for film formation is placed in the first, second, or third film forming chamber. The film can be formed using a mixed gas composition for film formation in which the mixing ratio of each gas component is changed.

In addition, when forming into a film using the mixed gas composition for film forming which changed the mixing ratio of each gas component of said mixed gas composition for film forming, the 1st mixed gas composition for film forming is used. Then, the amount of carbon in the formed carbon-containing silicon oxide film tends to increase, and the C—C bond and the Si—CH ₃ bond tend to increase. A water-repellent carbon-containing silicon oxide film having high barrier properties can be formed.
In the present invention, when the second mixed gas composition for film formation is used, an appropriate amount of carbon can be contained in the formed carbon-containing silicon oxide layer, and Si—CH ₃ bonds are also present. The carbon-containing silicon oxide layer which can be contained appropriately and thereby has high flexibility and high barrier property against oxygen can be formed into a film.
Furthermore, in the present invention, when the third mixed gas composition for film formation is used, the carbon content in the formed carbon-containing silicon oxide layer tends to decrease, and Si—CH _{The number of three} bonds can also be reduced, whereby the flexibility is inferior, but a carbon-containing silicon oxide film having a high gas barrier property against oxygen or the like can be formed.
Thus, in the present invention, when the film-forming mixed gas composition as described above is used to form a film, the order in which the film-forming mixed gas composition is used is arbitrary. First, second and third film-forming mixed gas compositions, first, second and first film-forming mixed gas compositions, third, first and second film-forming compositions Each product is manufactured in the order of the mixed gas composition, the order of the third, first, and first mixed gas composition for film formation, or the order of the third, third, and first mixed gas composition for film formation. A mixed gas composition for a film can be introduced into each film forming chamber to form a film.
In the present invention, it is preferable to form a film in the order of the third, first and second mixed gas compositions for film formation.
In the above, by using the first film-forming mixed gas composition in two chambers, it is possible to form a carbon-containing silicon oxide film having high flexibility and high barrier property against water vapor. It is what has.

Further, in the above plasma chemical vapor deposition apparatus, the carbon-containing silicon oxide film made of silicon oxide or the like is formed in each film-forming chamber by using a plasma source gas as oxygen gas on the base film. Since the film is formed into a thin film in the form of SiO _x while being oxidized in, the carbon-containing silicon oxide film made of silicon oxide or the like formed into a film has a multi-layered structure. It is a thin film that is dense and has few gaps, and is rich in spreadability, flexibility, flexibility, etc. Therefore, the barrier property of the carbon-containing silicon oxide layer made of silicon oxide or the like is the conventional vacuum deposition method or the like It is much higher than a silicon oxide layer made of silicon oxide or the like formed by, and since it is made of a multilayered structure, an extremely high and sufficient barrier property can be obtained. is there.
Further, in the present invention, the surface of the base film is cleaned by SiO _X plasma, and polar groups, free radicals, etc. are generated on the surface. This has the advantage that the tight adhesion between the carbon-containing silicon oxide film and the substrate film is high.
Further, the degree of vacuum at the time of forming the carbon-containing silicon oxide film made of silicon oxide or the like as described above is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to Since the pressure is adjusted to 1 × 10 ⁻² Torr, the degree of vacuum when forming a carbon-containing silicon oxide film made of silicon oxide or the like by a conventional vacuum deposition method is 1 × 10 ⁻⁴ to 1 × 10 ^{−. 5 Since the} vacuum level is lower than that of the Torr position, it is possible to shorten the time for setting the vacuum state of the base film when replacing the original fabric, making it easy to stabilize the vacuum level and stabilizing the film forming process. is there.

Further, in the present invention, a carbon-containing silicon oxide film made of silicon oxide or the like formed using a vapor deposition monomer gas made of one or more kinds of organosilicon compounds formed into a film in each film forming chamber, A vapor-deposited monomer gas composed of one or more organic silicon compounds and oxygen gas react chemically, and the reaction product adheres tightly to the surface of the base film to form a dense, flexible thin film. Usually, it consists of a thin film of a continuous carbon-containing silicon oxide film mainly composed of silicon oxide represented by the general formula SiO _x (where X represents a number from 0 to 2). is there.
Thus, the carbon-containing silicon oxide film formed in each of the film forming chambers has a general formula SiO _X (where X is 1.3 to 1.. It is preferably a thin film of a carbon-containing silicon oxide layer mainly composed of silicon oxide represented by the number of 9. In the above, the value of X varies depending on the molar ratio between the vapor-deposited monomer gas and oxygen gas composed of one or more organic silicon compounds, the energy of the plasma, etc. Although the transmittance is small, the film itself is yellowish and the transparency is poor.

Further, in the present invention, the carbon-containing silicon oxide film made of silicon oxide or the like formed in each film forming chamber is mainly composed of silicon oxide, and further, carbon, hydrogen, silicon, or oxygen. It is characterized in that it contains at least one kind of compound composed of two or more kinds of elements by chemical bonding or the like, and in particular, the carbon atom component consists of a deposited film containing it as an essential component.
For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc. A derivative may be contained by a chemical bond or the like.
Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.
Other than the above, the type, amount, etc. of the compound contained in the carbon-containing silicon oxide layer formed in each film forming chamber can be changed by changing the conditions of the film forming process. It is.

Thus, the content of the compound contained in the carbon-containing silicon oxide film formed in each film forming chamber is about 0.1 to 50%, preferably about 5 to 20%. Is desirable.
In the above, if the content rate is less than 0.1%, the impact resistance, spreadability, flexibility, flexibility, flexibility, etc. of the carbon-containing silicon oxide film formed in each film forming chamber are improved. It becomes inadequate, and scratches, cracks, etc. are likely to occur due to bending, etc., and it becomes difficult to stably maintain a high barrier property. is there.
Furthermore, in the present invention, in the carbon-containing silicon oxide film formed in each film-forming chamber, the content of the above compound is increased from the surface of each carbon-containing silicon oxide film in the depth direction. It is preferable that, on the surface of each carbon-containing silicon oxide film, the impact resistance and the like are enhanced by the above-described compound and the like, and on the other hand, the content of the above-described compound is large at the interface with the base film. In addition, there is an advantage that the adhesion between the base film and the carbon-containing silicon oxide layer, the adhesion between the carbon-containing silicon oxide layers, or the like becomes strong.
Thus, in the present invention, the carbon-containing silicon oxide layer formed in each film forming chamber is, for example, an X-ray photoelectron spectrometer (Xray), a secondary ion mass spectrometer (Secondary). Using a surface analysis device such as Ion Mass Spectroscopy (SIMS), etc., and performing an elemental analysis of each carbon-containing silicon oxide layer using a method of analyzing by ion etching or the like in the depth direction, the above physical properties can be obtained. Can be confirmed.

Further, in the present invention, the carbon-containing silicon oxide layer formed by using the first mixed gas composition for film formation has 80 to 120 O atoms and 100 C atoms to 100 Si atoms. consist component ratio of 100 to 150, further, there is IR absorption based on Si-O-Si stretching vibration between 1030cm ^-1 ~1060cm ^-1, and the Si-CH ₃ stretching vibration 1274 ± 4 cm ^-1 It is characterized by IR absorption based on it.
Thus, the above is because the carbon-containing silicon oxide layer contains a carbon component and contains many C—C bonds and Si—CH ₃ bonds. This shows that the peak position of IR absorption based on vibration is shifted toward a decreasing direction.
That is, it can be confirmed that the film is highly water-repellent and has a high barrier property against water vapor.
Furthermore, in the present invention, the carbon-containing silicon oxide layer formed by using the second mixed gas composition for film formation has 100 to 150 O atoms and 100 C atoms to 100 Si atoms. 100 consists of the following component ratio, further, there is IR absorption based on Si-O-Si stretching vibration between 1045cm ^-1 ~1075cm ^-1, and, based on the Si-CH ₃ stretching vibration 1274 ± 4 cm ^-1 It is characterized by IR absorption.
Thus, the above-described phenomenon has a low carbon component in the carbon-containing silicon oxide layer and contains only Si—CH ₃ bonds. Therefore, the IR absorption peak based on the Si—O—Si stretching vibration is present. This indicates that the shift position does not shift.
That is, it can be confirmed that the film is highly flexible and has a high barrier property against oxygen.
In the present invention, the carbon-containing silicon oxide layer formed by using the third mixed gas composition for film formation has an oxygen atom number of 150 to 190 and a C atom number with respect to the Si atom number of 100. 80 consists of the following component ratio, further, there is IR absorption based on Si-O-Si stretching vibration between 1045cm ^-1 ~1075cm ^-1, and, based on the Si-CH ₃ stretching vibration 1274 ± 4 cm ^-1 It is characterized by IR absorption.
Thus, the above-described phenomenon has a low carbon component in the carbon-containing silicon oxide layer and contains only Si—CH ₃ bonds. Therefore, the IR absorption peak based on the Si—O—Si stretching vibration is present. This indicates that the center position does not shift, the degree of oxidation is higher, the film is denser, the flexibility is reduced, but it has a high barrier property against oxygen, and the base film It can be confirmed that the film has excellent adhesion.

Next, in the present invention, the total film thickness of the carbon-containing silicon oxide film formed in each film forming chamber constituting the barrier layer is preferably about 60 to 4000 mm. The film thickness is preferably about 100 to 1000 mm, and in the above, it is not preferable that the film is thicker than 1000 mm, more preferably 4000 mm, because cracks are easily generated in the film. Furthermore, if it is less than 60 mm, it is not preferable because it becomes difficult to achieve a barrier effect.
In the present invention, as the film thickness of each layer of the carbon-containing silicon oxide film formed in each film-forming chamber constituting the barrier layer, first, the film of the carbon-containing silicon oxide film constituting the first layer is used. The thickness is preferably 20 to 200 mm, preferably 30 to 100 mm, and the thickness of the carbon-containing silicon oxide film constituting the second layer is 20 to 200 mm, preferably 30 to 100 mm. Further, the film thickness of the carbon-containing silicon oxide film constituting the third layer is preferably about 20 to 200 mm, more preferably about 30 to 100 mm.
In the above, if it is 20 mm or less, its own barrier properties are not expressed, and if it exceeds 200 mm, cracks and the like are likely to occur in the film. In particular, the base film is wound during film formation. It is not preferable because cracks tend to occur during the process.
In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. Further, in the above, as a means for changing the film thickness of the carbon-containing silicon oxide layer, a method of increasing the volume velocity of the layer, that is, a method of increasing the amount of the monomer gas for film formation and the oxygen gas, It can be performed by a method of slowing the film forming speed.

Next, in the present invention, examples of the organosilicon compound constituting the monomer gas for film formation include 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, Hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octa Methylcyclotetrasiloxane, etc. can be used.
In the present invention, among the organic silicon compounds as described above, use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material.
Moreover, in this invention, argon gas, helium gas etc. can be used as inert gas, for example.

Next, in the present invention, the base film constituting the barrier film according to the present invention will be described. The base film is excellent in chemical or physical strength, and each carbon-containing silicon oxide film is formed into a film. Can be maintained well without damaging the film characteristics of the carbon-containing silicon oxide film, etc., and can be held linearly without using cutters, scissors, etc. It is possible to use a resin film or sheet having a straight cut property (easy-opening property).
Thus, in the present invention, specifically, for example, nylon 6 resin, nylon 11 resin, nylon 12 resin, nylon 66 resin, nylon 46 resin, nylon 610 resin, nylon 612 resin, and other nylon resins Furthermore, a mixed resin obtained by kneading two or more kinds and nylon MXD6 resin at a blending ratio of the former 30 to 85 parts by weight and the latter 15 to 70 parts by weight (however, 100 parts by weight) is used as a main component. A polyamide resin film or sheet of the resin composition can be used.
In the present invention, among the above-described polyamide resin films or sheets, polyamide resin films or sheets made of a resin composition obtained by kneading nylon 6 resin and nylon MXD6 resin can be used.
In the above, when the amount of nylon MXD6 resin is less than 15 parts by weight, it is not preferable because it tends to be inferior in easy tearability, linear cut property, etc., and when the amount of nylon MXD6 resin is more than 70 parts by weight This is not preferable because the impact strength is greatly lowered and the practicality becomes poor.

In the present invention, as the polyamide resin film or sheet, for example, a resin composition containing as a main component a mixed resin obtained by kneading one or more of the above nylon resins and nylon MXD6 resin is used. For example, a method for forming a film of the above-mentioned various resins alone by using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like, or two types By using the above-mentioned various resins to form a multilayer coextrusion film, and further using two or more kinds of resins and mixing them before forming a film, the polyamide resin can be formed. A film or sheet is manufactured and further stretched in a biaxial direction, for example, at least 2.5 times or more, preferably 3.0 times or more by using, for example, a tenter method or a tubular method. The film or sheet of the biaxially stretched polyamide resin as Te can be used.
In the present invention, when the draw ratio is less than 2.5, it is not preferable because it tends to be inferior in easy tearability, linear cut property, and the like, and it is not preferable because impact strength is reduced. Is.
In the present invention, the film thickness of the biaxially stretched polyamide resin film or sheet is preferably about 6 to 2000 μm, more preferably about 9 to 100 μm.

When forming the above-mentioned polyamide resin, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipping properties, mold release properties, flame retardancy, antifungal properties, etc. Various plastic compounding agents and additives can be added for the purpose of improving and modifying properties, electrical properties, strength, etc., and the addition amount is from a very small amount to several tens of percent. It can be arbitrarily added depending on the purpose.
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can be used.

In the present invention, the surface of the polyamide resin film or sheet may be provided with a desired surface treatment layer in advance, if necessary, in order to improve the tight adhesion with the carbon-containing silicon oxide film. Is.
In the present invention, as the surface treatment layer, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc. For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed and provided.
The surface pretreatment is carried out as a method for improving the close adhesion between various resin films or sheets and the carbon-containing silicon oxide film. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, an adhesive layer, or a deposition anchor coat agent layer is arbitrarily formed in advance on the surface of various resin films or sheets. Thus, a surface treatment layer can be formed.
Examples of the pretreatment coating agent layer include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyethylene, and polypropylene. A resin composition comprising a main component of a vehicle such as a polyolefin resin or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

Next, in the present invention, as described above, a nylon film made of a mixed resin of nylon resin and nylon MXD6 resin, and further, one surface of a biaxially stretched polyamide film formed by stretching in the longitudinal and lateral directions In addition, at least three or more film forming chambers are used, and each chamber contains at least one monomer gas for film formation, oxygen gas, and inert gas composed of one or more organic silicon compounds. Three or more film-forming mixed gas compositions prepared by changing the mixing ratio of each gas component of the film-forming mixed gas composition were used, and films were formed using each of the film-forming mixed gas compositions 3 Each of the carbon-containing silicon oxide films contains carbon atoms in the film, and the carbon content for each silicon oxide film. Different carbon-containing silicon oxide films After form, on the carbon-containing silicon oxide film of the general formula _{^{R 1 n M (OR 2)}} m ( where in the formula, R ^1, R ² represents an organic group having 1 to 8 carbon atoms, M Represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M), and at least one alkoxide represented by It contains a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, and further forms a gas barrier coating film by a gas barrier composition obtained by polycondensation by a sol-gel method. The barrier film which has such a linear cut property can be manufactured.

Thus, in the present invention, the above gas barrier coating film constituting the barrier film having a linear cut property according to the present invention will be described. As the gas barrier coating film, for example, a general formula R ¹ _n M ( OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents 1) And at least one alkoxide represented by the following formula: n + m represents the valence of M), and a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer. Furthermore, a step of preparing a gas barrier composition that undergoes polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent, a carbon-containing silicon oxide film provided on the surface of the biaxially stretched polyamide film On top of the , A step of applying a gas barrier composition that is polycondensed by the sol-gel method to provide a coating film, a biaxially stretched polyamide film having a coating film on the carbon-containing silicon oxide film, On the carbon-containing silicon oxide film provided on the surface of the biaxially stretched polyamide film by heating for 10 seconds to 10 minutes at a temperature not higher than the melting point of the biaxially stretched polyamide film at ˜250 ° C. It can be manufactured by a manufacturing process including a process of forming a gas barrier coating film from the above gas barrier composition.

In the present invention, the gas barrier coating film constituting the barrier film having a linear cut property according to the present invention has a general formula R ¹ _n M (OR ² ) _m (where R ¹ , R ² Represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. At least one alkoxide represented by formula (II)), a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel catalyst, an acid, water, and an organic solvent. A gas barrier composition that undergoes polycondensation by the above-mentioned sol-gel method on a carbon-containing silicon oxide film provided on the surface of the biaxially stretched polyamide film Coating And a biaxially stretched polyamide film provided with a coating film in which two or more layers are superimposed on the carbon-containing silicon oxide film, at a temperature of 50 ° C. to 250 ° C. The gas barrier composition is formed on the carbon-containing silicon oxide film provided on the surface of the biaxially stretched polyamide film by heat treatment for 10 seconds to 10 minutes at a temperature not higher than the melting point of the biaxially stretched polyamide film. It can be manufactured by a manufacturing process including a process of forming a composite polymer layer in which two or more gas barrier coating films are stacked.

In the above, the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m that forms the gas barrier coating film constituting the barrier film having linear cut property according to the present invention is a partial hydrolyzate of alkoxide. In addition, at least one of alkoxide hydrolysis condensates can be used, and the alkoxide partial hydrolyzate does not need to have all of the alkoxy groups hydrolyzed. It may be a hydrolyzed product or a mixture thereof. Further, the hydrolyzed condensate may be a dimer or more of a partially hydrolyzed alkoxide, specifically, a 2 to 6 mer. Used.

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum, and the like can be used as the metal atom represented by M.
Thus, in the present invention, examples of a preferable metal include silicon.
In the present invention, the alkoxide can be used alone or in combination of two or more different metal atom alkoxides in the same solution.

In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group, and the like.
In the present invention, these alkyl groups may be the same or different in the same molecule.

Thus, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, it is preferable to use an alkoxysilane in which M is Si.
The alkoxysilane is represented by the general formula Si (ORa) ₄ (wherein Ra represents a lower alkyl group).
In the above, Ra includes a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like.
As specific examples of the above alkoxysilane, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (0C ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, examples of the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m include, for example, the general formula Rb _n Si (ORc) _4-m (where n is 0 The above-mentioned integer is represented, m represents an integer of 1, 2, and 3, and Rb and Rc represent a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like. Alkoxysilanes can be used.
Specific examples of the above-mentioned alkylalkoxysilane include, for example, methyltrimethoxysilane CH ₃ Si (OCH ₃ ) ₃ , methyltriethoxysilane CH ₃ Si (OC ₂ H ₅ ) ₃ , dimethyldimethoxysilane (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , dimethyldiethoxysilane (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ , etc. can be used.
Said alkoxysilane, alkylalkoxysilane, etc. can be used individually or in mixture of 2 or more types.
In the present invention, a polycondensation product of the above alkoxysilane can also be used, and specifically, for example, polytetramethoxysilane, polytetraemethoxysilane, and the like can be used.

Next, in the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, a zirconium alkoxide in which M is Zr can be used.
Specific examples of the zirconium alkoxide include, for example, tetramethoxyzirconium Zr (OCH ₃ ) ₄ , tetraethoxyzirconium Zr (OC ₂ H ₅ ) ₄ , tetra ipropoxyzirconium Zr (is0-0C ₃ H ₇ ) ₄ , tetra n-Butoxyzirconium Zr (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, as the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , for example, a titanium alkoxide in which M is Ti can be used.
Specific examples of the titanium alkoxide include, for example, tetramethoxytitanium Ti (OCH ₃ ) ₄ , tetraethoxytitanium Ti (OC ₂ H ₅ ) ₄ , tetraisopropoxytitanium Ti (is0-0C ₃ H ₇ ) ₄ , tetra n-Butoxy titanium Ti (OC ₄ H ₉ ) ₄ , etc. can be used.

Furthermore, in the present invention, as the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , for example, an aluminum alkoxide in which M is Al can be used.
Specific examples of the aluminum alkoxide include, for example, tetramethoxyaluminum Al (OCH ₃ ) ₄ , tetraethoxyaluminum Al (OC ₂ H ₅ ) ₄ , tetraisopropoxyaluminum Al (is0-0C ₃ H ₇ ) ₄ , tetra nButoxyaluminum Al (OC ₄ H ₉ ) ₄ , etc. can be used.

In the present invention, the above alkoxides may be used as a mixture of two or more thereof.
Thus, in the present invention, in particular, by using a mixture of alkoxysilane and zirconium alkoxide, the toughness, heat resistance, etc. of the resulting barrier film can be improved, and the retort resistance of the film during stretching can be improved. Such as a decrease in sex is avoided.
The amount of the zirconium alkoxide used is in the range of 10 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, preferably about 5 parts by weight. In the above, if the amount exceeds 10 parts by weight, the formed gas barrier coating film tends to gel, the brittleness of the film increases, and the gas barrier coating film tends to peel easily. It is not preferable.

In the present invention, particularly, by using a mixture of alkoxysilane and titanium alkoxide, there is an advantage that the heat conductivity of the obtained gas barrier coating film is lowered and its heat resistance is remarkably improved.
In the above, the amount of titanium alkoxide used is in the range of 5 parts by weight or less with respect to 100 parts by weight of the alkoxysilane, and preferably about 3 parts by weight.
In the above, if it exceeds 5 parts by weight, the gas barrier coating film to be formed becomes more brittle, and the gas barrier coating film tends to peel off, which is not preferable.

Next, as a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer forming a gas barrier coating film constituting the barrier film having a straight-cut property according to the present invention, a polyvinyl alcohol-based resin is used. A resin or an ethylene / vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer can be used in combination. In the present invention, by using a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, the physical properties such as gas barrier properties, water resistance, weather resistance, and the like of the gas barrier coating film are remarkably increased. It can be improved.
In particular, in the present invention, by using a combination of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, in addition to the above physical properties such as gas barrier properties, water resistance, and weather resistance, hot water resistance and hot water The first and second gas barrier coating films that are remarkably excellent in gas barrier properties after the treatment can be formed.

  In the present invention, when a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer are used in combination, the blending ratio of each is polyvinyl alcohol resin: ethylene / vinyl alcohol by weight ratio. The copolymer is preferably in the 10: 0.05 to 10: 6 position, and more preferably in a blending ratio of about 10: 1.

In the present invention, the content of the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is in the range of 5 to 500 parts by weight with respect to 100 parts by weight of the total amount of the alkoxide, Preferably, it is preferable to prepare the gas barrier composition at a blending ratio of about 20 to 200 parts by weight.
In the above, if it exceeds 500 parts by weight, the brittleness of the gas barrier coating film increases, and its water resistance and weather resistance tend to decrease. Therefore, it is not preferable.

In the present invention, as the polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, first, as the polyvinyl alcohol resin, generally obtained by saponifying polyvinyl acetate is used. be able to.
As the above-mentioned polyvinyl alcohol-based resin, partially saponified polyvinyl alcohol resin in which several tens of percent of acetic acid groups remain, or completely saponified polyvinyl alcohol in which acetic acid groups do not remain, or OH groups have been modified. A modified polyvinyl alcohol resin may be used and is not particularly limited.
Specific examples of the polyvinyl alcohol-based resin include RS-110 (saponification degree = 99%, polymerization degree = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (saponification) manufactured by Kuraray Co., Ltd. Degree = 40%, degree of polymerization = 2,000), Gohsenol NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can be used.

In the present invention, as the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer should be used. Can do.
Specific examples include partial saponification products in which several tens mol% of acetic acid groups remain to complete saponification products in which acetic acid groups remain only a few mol% or no acetic acid groups remain. However, it is desirable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. Is preferably used.
Specific examples of the ethylene / vinyl alcohol copolymer include Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content: 29 mol%). ) Etc. can be used.

Next, in the present invention, the gas barrier composition for forming the gas barrier coating film constituting the barrier film having the linear cut property according to the present invention will be described. Formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents an integer of 0 or more. M represents an integer of 1 or more, and n + m represents a valence of M.), a polyvinyl alcohol-based resin and / or ethylene. A gas barrier composition containing a vinyl alcohol copolymer and further polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent is prepared.

In preparing the gas barrier composition, for example, a silane coupling agent or the like can be added.
Thus, as the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used.
In the present invention, an organoalkoxysilane having an epoxy group is particularly suitable. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, or β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane or the like can be used.
The above silane coupling agents may be used alone or in combination of two or more. In this invention, the usage-amount of the above silane coupling agents can be used within the range of 1-20 weight part with respect to 100 weight part of said alkoxysilane.
In the above, use of 20 parts by weight or more is not preferable because the gas barrier coating film to be formed has increased rigidity and brittleness, and the insulating property and workability of the gas barrier coating film tend to be lowered. It is.

Next, as a sol-gel method catalyst, mainly a polycondensation catalyst, used in the gas barrier composition, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used.
Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, and the like can be used.
In the present invention, N, N-dimethylbenzylamine is particularly preferable.
The amount used is 0.01 to 1.0 part by weight, preferably about 0.03 parts by weight per 100 parts by weight of the total amount of alkoxide and silane coupling agent.
The acid used in the gas barrier composition is used as a catalyst for the sol-gel method, mainly as a catalyst for hydrolysis of an alkoxide, a silane coupling agent, or the like.
Examples of the acid include mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid and tartaric acid, and the like.
The amount of the acid used is about 0.001 to 0.05 mol, preferably about 0.01 mol, relative to the total molar amount of the alkoxide and the alkoxide content of the silane coupling agent (for example, silicate moiety). Is preferred.

Furthermore, in the gas barrier composition, water can be used in a proportion of 0.1 to 100 mol, preferably 0.8 to 2 mol, relative to 1 mol of the total molar amount of the alkoxide.
When the amount of the water exceeds 2 mol, the polymer obtained from the alkoxysilane and the metal alkoxide becomes spherical particles, and the spherical particles are three-dimensionally cross-linked to form a porous material having a low density. Therefore, such a porous polymer is not preferable because the gas barrier property of the gas barrier coating film cannot be improved.
Moreover, when the amount of the water is less than 0.8 mol, it is not preferable because the hydrolysis reaction tends to hardly proceed.

Furthermore, as the organic solvent used in the gas barrier composition, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol, and the like can be used.
Furthermore, in the gas barrier composition, the polyvinyl alcohol-based resin and / or the ethylene / vinyl alcohol copolymer is in a state of being dissolved in a coating solution containing the alkoxide or the silane coupling agent. Therefore, the type of the organic solvent is appropriately selected.
In the case of using a combination of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, it is preferable to use n-butanol.
In the present invention, as the ethylene / vinyl alcohol copolymer solubilized in a solvent, for example, those commercially available as Soarnol (trade name) can be used.
The amount of the organic solvent used is usually 30 per 100 parts by weight of the total amount of the alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, acid and sol-gel catalyst. ~ 500 parts by weight.

In the present invention, when preparing the above gas barrier composition, for example, scale-shaped silicon dioxide fine particles can be added.
Thus, in the present invention, the scaly silicon dioxide fine particles forming the gas barrier coating film are high-purity scaly silica fine particles (SiO ₂ : 98% or more), which are chemically stable. Unlike ordinary spherical silica fine particles, they are of a scale shape, specifically, nonporous scale-shaped particles having a thickness of 0.01 to 1 μm and a surface diameter of 0.1 to 5 μm, and high What has transparency can be used.
Thus, the scale-shaped silicon dioxide fine particles have a large specific surface area (50 to 300 m ² / g), and further have high density Si—OH groups that are active and highly functional on the surface and between the layers. Yes, for example, by adding and blending in an organic coating agent, the film is oriented and laminated in a film, and the effects of gas barrier properties, strength, surface hydrophilicity, heat resistance and flame retardancy are imparted. It plays.
As the above scale-shaped silicon dioxide fine particles, specifically, “San Lovely Series” product (powder product, product name, sun love product, slurry product, Product name, Sun Lovely-LFS, etc.) can be used. In the present invention, the proportion of the scale-shaped silicon dioxide fine particles is preferably about 0.1 to 20% by weight of the scale-shaped silicon dioxide fine particles relative to the alkoxide.
In the above, if it is less than 0.1% by weight, it is not preferable because the barrier property is not effective, and if it exceeds 20% by weight, it is not preferable because the barrier property is deteriorated.

Next, in the present invention, the gas barrier coating film according to the present invention is specifically manufactured as follows, for example.
First, alkoxide such as alkoxysilane, scale-shaped silicon dioxide fine particles, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer, sol-gel method catalyst, acid, water, organic solvent, and If necessary, a metal barrier alkoxide or the like is mixed to prepare a gas barrier composition (coating liquid).
Next, a polycondensation reaction gradually proceeds in the gas barrier composition (coating liquid).
Next, on the carbon-containing silicon oxide film formed on the surface of the biaxially stretched polyamide film, the above gas barrier composition (coating liquid) is applied by a usual method and dried.
Thus, by the above drying, polycondensation of the alkoxide such as alkoxysilane, metal alkoxide, silane coupling agent, polyvinyl alcohol resin and / or ethylene / vinyl alcohol copolymer proceeds, and the coating film Is formed.
Further, preferably, the above coating operation is repeated to laminate a plurality of coating films composed of two or more layers.
Finally, the biaxially stretched polyamide film coated with the above coating solution is at a temperature of about 50 ° C. to 250 ° C. and below the melting point of the biaxially stretched polyamide film, preferably in the range of about 50 ° C. to 160 ° C. A gas barrier coating film made of the above gas barrier composition (coating liquid) is formed on the carbon-containing silicon oxide film formed on the surface of the biaxially stretched polyamide film by heating at a temperature of 10 seconds to 10 minutes. The gas barrier coating film according to the present invention can be produced by forming one or more layers.
The gas barrier coating film according to the present invention thus obtained is excellent in gas barrier properties.

  In the present invention, in place of the polyvinyl alcohol resin, an ethylene / vinyl alcohol copolymer, or both a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer are used in the same manner as described above. The gas barrier coating film according to the present invention produced by performing drying and heat treatment has an advantage that the gas barrier property after hot water treatment such as boil treatment and retort treatment is further improved.

  Furthermore, in the present invention, as described above, when ethylene vinyl alcohol copolymer or polyvinyl alcohol resin and ethylene vinyl alcohol copolymer are not used in combination, that is, only polyvinyl alcohol resin is used. In the case of producing a gas barrier coating film according to the present invention, in order to improve the gas barrier property after the hot water treatment, for example, a gas barrier composition using a polyvinyl alcohol resin is applied in advance. Then, a first coating layer is formed, and then a gas barrier composition containing an ethylene / vinyl alcohol copolymer is coated on the coating layer to form a second coating layer. By forming these composite layers, it is possible to improve the gas barrier properties of the gas barrier coating film according to the present invention.

  Furthermore, the coating layer formed by the gas barrier composition containing the above-mentioned ethylene / vinyl alcohol copolymer, or the gas barrier composition containing a combination of a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer. Forming a plurality of coating layers formed of an object as a plurality of layers is also an effective means for improving the gas barrier property of the gas barrier coating film according to the present invention.

Next, the operation of the method for producing a gas barrier coating film according to the present invention will be described by using an alkoxysilane as an alkoxide as an example. First, an alkoxysilane and a metal alkoxide are hydrolyzed by added water. Is done.
At that time, the acid serves as a catalyst for hydrolysis.
Next, protons are taken from the generated hydroxyl groups by the action of the sol-gel method catalyst, and hydrolyzed products undergo dehydration polycondensation.
At this time, the silane coupling agent is simultaneously hydrolyzed by the acid catalyst, and the alkoxy group becomes a hydroxyl group.
In addition, due to the action of the base catalyst, ring opening of the epoxy group also occurs and a hydroxyl group is generated.
A polycondensation reaction between the hydrolyzed silane coupling agent and the hydrolyzed alkoxide also proceeds.
Furthermore, since the reaction system contains a polyvinyl alcohol resin, an ethylene / vinyl alcohol copolymer, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer, the polyvinyl alcohol resin and the ethylene / vinyl alcohol Reaction with the hydroxyl group of the copolymer also occurs.
The resulting polycondensate contains, for example, an inorganic part composed of bonds such as Si—O—Si, Si—O—Zr, Si—O—Ti, and the like, and an organic part derived from the silane coupling agent. In the above reaction constituting the composite polymer, for example, a linear polymer having a partial structural formula represented by the following formula (III) and further having a portion derived from the silane coupling agent is first formed. .
This polymer has an OR group (an alkoxy group such as an ethoxy group) branched from a linear polymer.
This OR group is hydrolyzed to become an OH group using an existing acid as a catalyst, and the OH group is first deprotonated by the action of a sol-gel method catalyst (base catalyst), and then polycondensation proceeds.
That is, this OH group undergoes a polycondensation reaction with a polyvinyl alcohol-based resin represented by the following formula (I) or an ethylene / vinyl alcohol copolymer represented by the following formula (II)), and Si—O— For example, it is considered that a composite polymer represented by the following formula (IV) or a copolymerized composite polymer represented by the following formulas (V) and (VI) having Si bonds is formed.

The above reaction proceeds at room temperature, and the viscosity of the gas barrier composition (coating liquid) increases during preparation.
When this gas barrier composition (coating solution) is applied onto a carbon-containing silicon oxide film provided on the surface of a biaxially stretched polyamide film and heated to remove the solvent and the alcohol produced by the polycondensation reaction, The condensation reaction is completed, and a transparent coating layer is formed on the carbon-containing silicon oxide film provided on the surface of the biaxially stretched polyamide film.
In the case of laminating a plurality of the above-mentioned coating layers, the composite polymers in the coating layers between layers are also condensed, and the layers are firmly bonded to each other.
Furthermore, since the organic reactive group of the silane coupling agent and the hydroxyl group generated by hydrolysis are bonded to the hydroxyl group on the surface of the carbon-containing silicon oxide film provided on the surface of the biaxially stretched polyamide film, the biaxially stretched polyamide film The adhesion between the surface of the carbon-containing silicon oxide film provided on this surface and the coating layer, adhesion, and the like are also good.

In the method of the present invention, the amount of water added is adjusted to 0.8 to 2 mol, preferably 1.5 mol, relative to 1 mol of alkoxides. Is formed.
Such a linear polymer has crystallinity and has a structure in which a large number of minute crystals are embedded in an amorphous part.
Such a crystal structure is the same as that of a crystalline organic polymer (for example, vinylidene chloride or polyvinyl alcohol). Furthermore, a polar group (OH group) is partially present in the molecule, and the molecular aggregation energy is high. Excellent gas barrier properties due to high rigidity.

Furthermore, in the present invention, when silicon dioxide fine particles are added in the shape of a scale, the reaction process and the like will be described in more detail. As shown in the following formula (VII), together with the reaction between a polymer and an alkoxide, carbon-containing The reaction between the silicon oxide film and the polymer via the alkoxide also proceeds.
In particular, in the water vapor barrier property, the contribution of the reaction at the interface of the carbon-containing silicon oxide film is large, and the water vapor barrier property is improved by promoting the interface reaction by high-temperature heating after drying.
Further, the hydroxyl group of the surface of the carbon-containing silicon oxide film reacts with the hydroxyl group of the hydrolyzed alkoxide, and the hydroxyl group of the other alkoxide and the hydroxyl group of the polymer are bonded, so that the carbon-containing silicon oxide film and the polymer are bonded via the alkoxide. In addition, the adhesion between the carbon-containing silicon oxide film and the gas barrier coating film is improved, and the synergistic effect of the two layers and its multilayering can provide a better gas barrier effect. It is.
The polymer is hydrophilic and when water vapor reaches it, water molecules are likely to intervene between the molecules and the water vapor barrier property deteriorates.However, as described above, the intermolecular bonds become stronger due to chemical bonding at the interface, and the water vapor barrier property is reduced. It will improve.

Thus, in the present invention, the scale-like silicon dioxide fine particles were laminated in the coating film, whereby this effect was further promoted and an excellent water vapor barrier property could be obtained.
That is, as shown in the following formula (VIII), the hydroxyl group present on the surface of the scale-shaped silicon dioxide fine particles reacts with the hydroxyl group of the alkoxide, and further reacts with the hydroxyl group of the polymer. Is in an intimate state and is effective in improving the water vapor barrier property.
The barrier property is improved by increasing the interface reaction.
Therefore, as shown in the following formula (IX), in the present invention, by laminating scale-shaped silicon dioxide fine particles in the coating film, the cross-linking density at the interface between the polymer and the scale-shaped silicon dioxide fine particles in the entire coating film is increased. It is estimated that the water vapor barrier was improved as a result.

In the present invention, the carbon-containing silicon oxide film and the gas barrier coating film form, for example, a chemical bond, a hydrogen bond, or a coordination bond by a hydrolysis / co-condensation reaction. Adhesiveness with the adhesive coating film is improved, and a better gas barrier property effect can be exhibited by the synergistic effect of the multilayer lamination.
As a method for applying the gas barrier composition of the present invention, for example, a roll coating such as a gravure roll coater, a spray coating, a spin coating, a date coating, a brush, a barcode, an applicator, etc. Alternatively, a coating film having a dry film thickness of 0.01 to 30 μm, preferably about 0.1 to 10 μm, can be formed by applying a plurality of times, and further, under a normal environment, 50 to 250 ° C., Preferably, condensation is performed by heating and drying at a temperature of 70 to 200 ° C. for 0.005 to 60 minutes, preferably 0.01 to 10 minutes, and the gas barrier coating film of the present invention is formed. can do.
If necessary, when applying the gas barrier composition of the present invention, a primer agent or the like can be applied on the carbon-containing silicon oxide film in advance, and corona discharge treatment or plasma can be applied. Preprocessing such as processing and others can be arbitrarily performed.

As apparent from the above description, the barrier film according to the present invention produced by forming the film as described above is a nylon made of a mixed resin of a nylon resin and a nylon MXD6 resin as shown in FIG. A biaxially stretched polyamide film 1 that is stretched in the longitudinal and lateral directions, a barrier layer 2 provided on one surface of the biaxially stretched polyamide film 1, and a barrier layer 2 Further, the barrier layer 2 uses at least three film forming chambers, and at least one kind of organosilicon compound for each chamber. Three or more film-forming mixed gas compositions prepared by changing the mixing ratio of each gas component of the film-forming mixed gas composition containing the above-described monomer gas for film-forming, oxygen gas, and inert gas For each film formation Each of the carbon-containing silicon oxide films 2a, 2b, and 2c is formed by a plasma chemical vapor deposition method of three or more layers formed by using a mixed gas composition, and the carbon-containing silicon oxide films 2a, 2b, and 2c are further formed. Consists of carbon-containing silicon oxide films 2a, 2b and 2c containing carbon atoms in the film and having different carbon contents for each silicon oxide film, and the gas barrier coating film 3 is General formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents an integer of 0 or more) M represents an integer of 1 or more, and n + m represents the valence of M.) and at least one alkoxide represented by the formula: Copolymer, and further obtained by polycondensation by a sol-gel method. That is intended according to the barrier film A having a linear cutting properties, characterized in that it consists of a gas barrier coating film 3a by the gas barrier composition.

Thus, the barrier film having a linear cut property according to the present invention has excellent characteristics and is useful as a packaging material. In particular, gas barrier properties (O ₂ , N ₂ , H ₂ O, CO ₂ , Therefore, it is suitably used as a gas barrier substrate constituting a food packaging film.
In particular, when used in so-called gas-filled packaging filled with N ₂ or CO ₂ gas, the excellent gas barrier property is extremely effective for holding the filled gas.
Furthermore, the gas barrier coating film according to the present invention is excellent in hot water treatment, particularly high-pressure hot water treatment (retort treatment), and exhibits extremely excellent gas barrier properties.
In addition, the barrier film having a linear cut property according to the present invention has a good tear property and a linear cut property, and is excellent in various physical properties such as impact resistance, and is extremely useful.

  Thus, the barrier film having a linear cut property according to the present invention has a good tight adhesion between the biaxially stretched polyamide film, the carbon-containing silicon oxide film, and the gas barrier coating film, In addition, it stably maintains high gas barrier properties and has good transparency, hot water resistance, impact resistance, etc., and is less dependent on temperature and humidity, and has good tearability and linear cut performance. It is extremely useful as a gas barrier material constituting a packaging bag, etc., and includes, for example, a substrate such as a surface base material layer, a heat-sealable resin layer, a plastic intermediate base material film, and the like. Laminate materials are optionally laminated to produce laminated materials as packaging materials composed of various layers, and then used to form bags to produce packaging bags and packaging products of various forms. It is possible.

That is, in the present invention, the barrier film according to the present invention produced as described above uses this as a barrier material, and other plastic film, paper base material, metal foil, cellophane, woven fabric or non-woven fabric. 1 and 2 or more kinds of various base materials such as glass plates, etc., to produce laminated materials having various forms, and thus the laminated materials are used as packaging materials and optical members. Protective sheet for solar cell module, protective film for organic EL display, protective film for film liquid crystal display, packaging material for polymer battery, aluminum packaging material, etc. Is.
As an example of the method for producing the laminated material, for example, first, a primer agent layer is formed on the surface of the gas barrier coating film forming the barrier layer constituting the barrier film according to the present invention, Next, a laminating adhesive layer is formed on the surface of the primer layer, and then a substrate such as a plastic film is provided via the primer layer and the laminating adhesive layer. By laminating the layers using the dry lamination method, laminated materials having various forms can be produced.
Alternatively, in the present invention, for example, first, a primer agent layer is formed on the surface of the gas barrier coating film that forms the barrier layer constituting the barrier film according to the present invention, and then the primer agent layer is formed. An anchor coat agent layer is formed on the surface, and then various resins are melt extruded through the primer agent layer and the anchor coat agent layer to laminate a desired base material. By laminating using the extrusion laminating method, laminated materials having various forms can be produced.
In the present invention, in the same manner as described above, another base material can be arbitrarily inserted and laminated between the above layers, and the biaxially stretched polyamide constituting the barrier film according to the present invention. Similarly to the above, other desired base materials can be arbitrarily laminated on the surface of the film to produce laminated materials having various forms. In the present invention, the purpose of use and the form of use Depending on the application, etc., other substrates can be arbitrarily laminated, and various forms of laminated materials can be designed and manufactured.

Next, in the present invention, a packaging container will be described as an example of use of the above laminated material. In the present invention, for example, two sheets of the above laminated material are prepared as packaging containers. Then, the surfaces of the heat-sealable resin layer located in the innermost layer are made to face each other, and thereafter, the seal part is formed by heat-sealing the three ends of the outer periphery. In addition, a three-sided seal type soft packaging container can be manufactured by providing an opening on the upper side.
Thus, in the present invention, although not shown, from the opening of the three-sided seal type soft packaging container manufactured above, for example, the contents such as food and drink, etc. are filled, and then the upper Heat seal the opening to form an upper seal, etc., and, if necessary, for example, boil treatment, retort treatment, etc., to produce packaged products of various forms It is something that can be done.
In the present invention, it goes without saying that the present invention is not limited to the illustrated packaging containers shown above, and depending on the purpose, use, etc., a flexible packaging bag, a liquid paper container, a paper can, It goes without saying that various types of packaging containers such as others can be manufactured.

Next, in the present invention, the primer agent layer constituting the laminated material will be described. First, as the primer agent layer, a polyurethane resin or a polyester resin is used as a main component of the vehicle, and the polyurethane agent layer The silane coupling agent is about 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, and the filler is 0.1 to 20% by weight with respect to 1 to 30% by weight of the resin or polyester resin. , Preferably in a proportion of about 1 to 10% by weight, and if necessary, additives such as stabilizers, curing agents, crosslinking agents, lubricants, ultraviolet absorbers, etc. are optionally added, and solvent Then, a diluent or the like is added and mixed well to prepare a polyurethane-based or polyester-based resin composition, and thus the polyurethane-based or polyester-based resin composition is used. For example, the barrier layer constituting the barrier film according to the present invention is formed by a roll coat, a gravure coat, a knife coat, a dip coat, a spray coat, or other coating methods. After coating on the surface of the gas barrier coating film to be formed, the coating film is dried to remove the solvent, diluent, etc., and if necessary, an aging treatment or the like is performed. A primer layer according to the invention can be formed. In the present invention, the film thickness of the primer layer is preferably, for example, about 0.1 g / m ^{2 to} 1.0 g / m ² (dry state).
Thus, in the present invention, a gas barrier coating film for forming a barrier layer constituting the barrier film according to the present invention by the primer layer as described above, a heat seal resin layer, The barrier layer according to the present invention at the time of post-processing is improved, for example, by improving the close adhesion of the film and improving the degree of elongation of the primer layer, for example, improving the post-processing suitability such as laminating or bag making. The generation of cracks and the like of the carbon-containing silicon oxide film constituting the conductive film is prevented.

In the above, as a polyurethane-type resin which comprises a polyurethane-type resin composition, the polyurethane-type resin obtained by reaction of a polyfunctional isocyanate and a hydroxyl-group containing compound can be used, for example.
Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, hexamethylene diisocyanate, xylylene diisocyanate One obtained by reacting a polyfunctional isocyanate such as an aliphatic polyisocyanate such as a salt with a hydroxyl group-containing compound such as a polyether polyol, a polyester polyol, a polyacrylate polyol, or the like. A liquid or two-component curable polyurethane resin can be used.
Thus, in the present invention, by using the polyurethane resin as described above, the tight adhesion between the gas barrier coating film and the heat seal resin layer is improved and the primer agent layer is elongated. For example, the suitability of post-processing such as laminating or bag-making processing is improved, and the occurrence of cracks or the like of the carbon-containing silicon oxide film during post-processing is prevented.

In the above, the polyester resin constituting the polyester resin composition is, for example, one or more aromatic saturated dicarboxylic acids having a benzene nucleus such as terephthalic acid as a basic skeleton, and saturated dicarboxylic acid. Thermoplastic polyester resins produced by polycondensation with one or more valent alcohols can be used. In the above, examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4, 4-dicarboxylic acid, and the like.
In the above, saturated divalent alcohols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, aliphatic glycols such as neopentyl glycol, alicyclic glycols such as cyclohexanedimethanol, 2.2- Bis (4'-β-hydroxyethoxyphenyl) propane, naphthalene diol, other aromatic geo- and the like can be used.

In the present invention, specific examples of the polyester resin include thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, terephthalic acid and tetramethylene glycol. Polybutylene terephthalate resin produced by polycondensation with styrene, thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, terephthalic acid Polyethylene terephthalate resin produced by copolycondensation of phthalic acid, isophthalic acid and ethylene glycol, produced by copolycondensation of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol Thermoplastic polyethylene terephthalate resin, terephthalic acid and isophthalic acid And ethylene glycol - le and propylene glycol - thermoplastic polyethylene terephthalate produced by co-polycondensation of Le - DOO resins, polyester polyol - can be used Le resin, other like.
In the present invention, the saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton as described above, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, One or more aliphatic saturated dicarboxylic acids such as sebacic acid and dodecanoic acid can be added and copolycondensed, and the amount used is an aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, It is preferable to add 1 to 10% by weight.
Thus, in the present invention, by using the polyester resin as described above, the tight adhesion and the like are improved and the elongation of the primer layer is improved, for example, laminating or This improves the suitability for post-processing such as bag making and prevents the occurrence of cracks and the like in the carbon-containing silicon oxide film during post-processing.

  Next, in the above, as the silane coupling agent constituting the polyurethane-based or polyester-based resin composition, organic functional silane monomers having binary reactivity can be used, for example, γ-chloropropyl Trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyl Dimethoxysilane, γ One or more of ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, an aqueous solution of γ-aminopropylsilicone, and the like can be used.

In the silane coupling agent as described above, a functional group at one end of the molecule, usually, chloro, alkoxy, or acetoxy group is hydrolyzed to form a silanol group (SiOH), which is a gas barrier property. A gas barrier coating film is caused by a reaction such as a dehydration condensation reaction by some action with a metal constituting the coating film or an active group on the film surface of the gas barrier coating film, for example, a functional group such as a hydroxyl group. A silane coupling agent is modified with a covalent bond or the like on the surface of the film, and further, a strong bond is formed on the film surface of the gas barrier coating film of the silanol group itself by adsorption or hydrogen bond.
On the other hand, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on the thin film of the silane coupling agent. -React with substances constituting the adhesive layer, anchor coating layer, other layers, etc. to form a strong bond, and further, the printed pattern layer, the laminating adhesive layer, The heat-sealable resin layer is firmly and tightly bonded through the anchor coating agent layer and the like to increase its laminating strength. Thus, in the present invention, the laminating strength is increased. It is possible to form a high-strength laminated structure.
In the present invention, the inorganic property and organic property of the silane coupling agent are utilized, and the heat-resistant property is obtained through the carbon-containing silicon oxide film and the printed pattern layer, the adhesive layer or the anchor coating agent layer. -Improving the tight adhesion with the rusty resin layer, thereby increasing the laminating strength and the like.

Next, in the present invention, examples of the filler constituting the polyurethane-based or polyester-based resin composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like. Can be used.
Thus, the above-mentioned filler adjusts the viscosity of the polyurethane-based or polyester-based resin composition liquid, improves its coating suitability, and is a silane coupling with a polyurethane-based or polyester-based resin as a binder resin. It binds via an agent to improve the cohesive strength of the coating film.

Next, in the present invention, the laminating adhesive layer constituting the laminated material will be described. Examples of the laminating adhesive layer constituting the laminating adhesive layer include a polyvinyl acetate adhesive and acrylic acid. Homopolymers such as ethyl, butyl, 2-ethylhexyl ester, etc., or polyacrylate adhesives comprising these and copolymers of methyl methacrylate, acrylonitrile, styrene, etc., cyanoacrylate adhesives, ethylene Ethylene copolymer adhesives, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimides, and the like, and copolymers of vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid and other monomers -Based adhesives, amino resin-based adhesives made of urea resin or melamine resin, and phenolic resin-based adhesives Epoxy adhesives, polyurethane adhesives, reactive (meth) acrylic adhesives, rubber adhesives such as chloroprene rubber, nitrile rubber, styrene-butadiene rubber, silicone adhesives, alkali metal silicates It is possible to use an inorganic adhesive made of low-melting glass or the like, and other adhesives.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof are film / sheet type, powder type, solid type, etc. Any form may be used, and the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
Thus, the above adhesive can be applied by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method or the like, or a printing method. The coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, in the present invention, the anchor coat agent layer constituting the laminated material will be described. As the anchor coat agent constituting the anchor coat agent layer, for example, alkyl titanate or the like is used. Various aqueous or oil-based anchor coating agents such as organic titanium, isocyanate, polyethyleneimine, polyptadiene, etc. can be used.
The above-mentioned anchor coating agent can be coated using a coating method such as a roll coat, a gravure roll coat, a kiss coat, and the like. The amount is preferably 0.1 to 5 g / m ² (dry state).

Examples of the melt-extruded resin layer in the melt-extrusion laminating method include, for example, polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers, saps. 1 of thermoplastic resins such as phosphorus resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin, etc. A seed | species thru | or 2 or more types can be used.
In the melt extrusion lamination method, in order to obtain stronger adhesive strength, for example, lamination can be performed via an anchor coating agent layer such as the above-described anchor coating agent.

Next, in the present invention, as a base material such as a plastic film for forming the innermost layer of the laminated material, for example, a heat-seal resin film or sheet that can be melted by heat and fused to each other is used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, ethylene-α-olefin polymerized using a metallocene catalyst Copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer Polymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene Polyolefin resins such as pyrene modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meta ) A film or sheet of a resin such as an acrylic resin, a polyvinyl chloride resin, or the like can be used.
Thus, the above film or sheet can be used in the state of a coating film made of a composition containing the resin.
The thickness of the film or film or sheet is preferably about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

Furthermore, in the present invention, as a base material such as a plastic film constituting the above laminated material, for example, as a basic material of the laminated material, excellent properties in mechanical, physical, chemical, etc. In particular, a resin film or sheet having strength and toughness and heat resistance can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid Films, sheets, etc. of tough resins such as resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin, etc. can be used. .
Thus, as the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used.
The thickness of the film is about 5 μm to 100 μm, preferably about 10 μm to 50 μm.
In the present invention, the base film as described above is subjected to surface printing or back printing by a normal printing method with a desired printing pattern such as letters, figures, symbols, patterns, patterns, etc., for example. May be.

Next, in the present invention, as the base material constituting the laminated material, for example, various paper base materials constituting the paper layer can be used. Specifically, in the present invention, Materials include formability, bending resistance, rigidity, etc., for example, strong sized bleached or unbleached paper base, or pure white roll paper, kraft paper, paperboard, processed paper Paper base materials such as, etc., etc. can be used.
In the above, as the paper substrate constituting the paper layer, it is desirable to use a material having a basis weight of about 80 to 600 g / m ² , preferably a basis weight of about 100 to 450 g / m ² .
Of course, in the present invention, the paper base material constituting the paper layer and various resin films or sheets as the base film mentioned above can be used in combination.

Furthermore, in the present invention, as a material constituting the above laminated material, for example, low density polyethylene having a barrier property such as water vapor, water, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene -Resin film or sheet such as propylene copolymer, or polyvinylidene chloride, polyvinyl alcohol, saponified ethylene-vinyl acetate copolymer, nylon MXD6 resin having barrier properties against oxygen, water vapor, etc. Various resin films or sheets having light-shielding properties obtained by adding a colorant such as a pigment to the resin and kneading the resin with a desired additive and kneading into a film. Can be used.
These materials can be used alone or in combination.
The thickness of the film or sheet is arbitrary, but is usually about 5 μm to 300 μm, more preferably about 10 μm to 100 μm.

In the present invention, when the above laminated material is usually applied to various conditions, it is subjected to severe conditions both physically and chemically. Various requirements such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Can be used by arbitrarily selecting a material that satisfies the above-mentioned conditions. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene , Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methyl Pentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene Resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol Resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. You can select and use.
In addition, for example, a film such as cellophane, synthetic paper, and the like can be used.
In the present invention, the above-described film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Further, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

  Thus, in the present invention, when performing the above-mentioned lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the film, and for example, isocyanate (urethane) Type), polyethyleneimine type, polybutadiene type, organic titanium type anchor coating agent, or polyurethane type, polyacrylic type, polyester type, epoxy type, polyvinyl acetate type, cellulose type, etc. -Known pretreatments such as adhesives for coating, anchor coating agents, adhesives and the like can be used.

In the present invention, a desired printed pattern layer can be formed between any of the layers constituting the laminated material.
Thus, the printed pattern layer is mainly composed of one or more ordinary ink vehicles, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet ray, and the like. One or more additives such as an absorbent, a curing agent, a crosslinking agent, a lubricant, an antistatic agent, a filler, and the like are arbitrarily added, and a colorant such as a dye / pigment is added, and a solvent is added. The ink composition is prepared by sufficiently kneading with a diluent, and then the ink composition is used. For example, gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc. The printing pattern layer according to the present invention can be formed by printing a desired printing pattern composed of characters, figures, symbols, patterns, etc. on the above-described coating thin film using a printing method such as .

In the present invention, as the primer layer provided on the surface of the gas barrier coating film, in addition to the primer layer formed of the polyurethane-based or polyester-based resin composition, for example, a polyamide-based resin is used. , Epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, polyolefin resins such as polyethylene aly polypropylene, or copolymers or modified resins thereof, cellulose resins, etc. The primer agent layer can be formed using a resin composition containing as a main component of the vehicle.
In the present invention, for example, a primer coating layer is formed by coating using a coating method such as a roll coat, a gravure roll coat, a kiss coat, or the like. Therefore, the coating amount is preferably about 0.1 to 10 g / m ² (dry state).

Next, in the present invention, a description will be given of a bag making or box making method for manufacturing a packaging container using the above-described laminated material. For example, when the packaging container is a flexible packaging bag made of a plastic film or the like Using the laminated material manufactured by the method as described above, facing the heat-sealable film of the inner layer facing each other, folding them up or stacking the two sheets, The bag body can be configured by heat sealing the portion to provide a seal portion.
Thus, as a bag-making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side sheet. Seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope-sealed seal type, jointed seal type (pillar seal type), pleated seal type The various types of packaging containers according to the present invention can be manufactured by heat sealing in the form of a heat sealing such as a flat bottom sealing type, a square bottom sealing type, or the like.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-described laminated material.
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.
In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.

Next, in the case of a liquid-filled paper container including a paper base material as a packaging container, for example, as a laminated material, a laminated material in which a paper base material is laminated is manufactured, and a blank plate for manufacturing a desired paper container is prepared from this After that, the body, bottom, head, etc. can be boxed by using the blank plate, and for example, a brick type, flat type or gable top type liquid paper container can be manufactured. .
Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.

In the present invention, the packaging container produced as described above can be used for filling and packaging various foods, chemicals such as adhesives and adhesives, cosmetics, pharmaceuticals, miscellaneous goods such as chemical warmers, and other items. It is what is used.
Thus, in the present invention, in particular, for example, a liquid sachet for filling and packaging soy sauce, sauce, soup, etc., a sachet for filling and packaging rice cake, a soft packaging bag for filling and packaging fresh confectionery, etc. It is useful as a packaging container for filling and packaging foods and beverages such as soft packaging bags for filling and packaging boiled or retort foods.
In the present invention, after filling and packaging the contents in the packaging container described above, when opening the contents, it has functions such as easy opening as convenience as well as the protection performance of the contents.
That is, in the present invention, the cutting property at the time of opening the packaging material as one of the improvement of usability-performance such as the global design as the performance strongly demanded for the packaging material. -It does not require an opening means such as scissors, and has a straight cut property (easy opening property) that can be easily and easily torn linearly.
Hereinafter, the present invention will be described in more detail with reference to examples.

(1). Prepare a biaxially stretched nylon film (trade name, Emblem NC # 15, a film made of a mixed resin of nylon 6 resin and nylon MXD6 resin) with a thickness of 15 μm as a base film. The apparatus was installed in a plasma chemical vapor deposition apparatus having a three-chamber configuration as shown in FIG.
Next, a film was formed under the film forming conditions shown in Table 1 below.
(Film forming conditions)
(Table 1)
┌───┬────┬─────┬─────┬─────┬─────┬────┐ │ │ Output │ He │HMDSO│ O ₂ │ Ar │Pressure │ │ │ [kW] │ [slm] │ [slm] │ [slm] │ [slm] │ [mTo│ │ │ │ │ │ │ rr] │ ────┼─────┼─────┼─────┼────┤ │Room 1│10.0│ 0.5 │ 1.0 │ 0.5 │ 0 │50.0│ ├───┼────┼─────┼─────┼─────┼─────┼────┤ │ Room 2 │10.0│ 0.5 │ 1.0 │ 0.5 │ 0.5 │50.0│ ├───┼────┼─────┼─────┼─── ──┼─────┼────┤ │Room 3│10.0│ 0.5 │ 1.0 │ 0.5 │ 0.5 │50 0│ └───┴────┴─────┴─────┴─────┴─────┴────┘ First of all, plasma chemical vapor deposition equipment The inside of the chamber was depressurized.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device, and is an oxygen gas (O ₂ ) and an inert gas supplied from the gas supply device. The raw material gas was mixed with helium (He), argon (Ar), or the like.
Regarding the raw material gas used in the first film forming chamber, the raw material gas used in the second film forming chamber, and the raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases shown in Table 1 above It was.
In the table, the unit; slm means stander-driter-minit.
Using the raw material gas as described above, the raw material gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively. While the biaxially stretched nylon film is conveyed at a line speed of 150 m / min, a power of 10 kW is applied to form a film, and the film thickness of the first layer is 3 nm on one corona-treated surface of the biaxially stretched nylon film. A three-layer carbon-containing silicon oxide film having a thickness of 3 nm for the second layer, a thickness of 3 nm for the third layer, and a total thickness of 9 nm was formed.
Next, a glow discharge plasma generator is used on the surface of the carbon-containing silicon oxide film formed as described above, and the power is 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2 .5 (unit: slm) is used, and the oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr and a processing speed of 420 m / min. A plasma-treated surface having a surface tension of 54 dyne / cm or more was formed.
(2). On the other hand, a composition prepared according to the composition shown in Table 2 below. A pre-prepared composition b. In a mixed solution comprising an aqueous solution of polyvinyl alcohol, acetic acid, isopropyl alcohol and ion-exchanged water. A hydrolyzed solution composed of ethyl silicate 40, scale-shaped silicon dioxide particle solution, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 2)
a Polyvinyl alcohol 1.235 (wt%)
Water 58.866
Isopropyl alcohol 5.139
Acetic acid 0.104
b Ethyl silicate 40 9.259
Scale-shaped silicon dioxide particle solution 5.000
Water 16.491
Isopropyl alcohol 3.888
Acetylacetone aluminum 0.018
Total 100,000
Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat-treated at 150 ° C. for 30 seconds. Thus, a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) was formed.
Next, an epoxy silane coupling agent (8.0 wt%) and an antiblocking agent (1.0 wt%) are added to the polyurethane resin initial condensate on the gas barrier coating film formed as described above. The primer composition is added and kneaded sufficiently, and this is coated by the gravure roll coating method so that the film thickness becomes 0.4 g / m ² (dry state). -The agent layer was formed and the barrier film based on this invention was manufactured.
It was.
(3). Next, a two-component curable polyurethane laminating adhesive is used on the surface of the primer layer formed as described above, and this is applied to a film thickness of 4.0 g / m ² by a gravure roll coating method. An adhesive layer for laminating was formed by coating so as to be (dry state).
Next, on the surface of the laminating adhesive layer formed as described above, a linear low density polyethylene film having a thickness of 50 μm is overlapped with its corona-treated surface facing each other, and then both are laminated with dry laminating. The laminated material was manufactured by laminating.
Next, two sheets of the laminated material produced above are prepared, the surfaces of the linear low-density polyethylene film are overlapped with each other, and then the outer peripheral edge is three-sided. Thus, a three-sided seal type flexible packaging bag having a seal part and an opening on the upper side was manufactured.
In the three-sided seal type soft packaging bag manufactured above, the candy is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. Thus, a confectionery packaged food according to the present invention was produced.

(1). Prepare a biaxially stretched nylon film (trade name, Emblem NC # 15, a film made of a mixed resin of nylon 6 resin and nylon MXD6 resin) with a thickness of 15 μm as a base film. The apparatus was installed in a plasma chemical vapor deposition apparatus having a three-chamber configuration as shown in FIG.
Next, a film was formed under the film forming conditions shown in Table 3 below.
(Film forming conditions)
(Table 3)
┌───┬────┬─────┬─────┬─────┬─────┬────┐ │ │ Output │ He │HMDSO│ O ₂ │ Ar │Pressure │ │ │ [kW] │ [slm] │ [slm] │ [slm] │ [slm] │ [mTo│ │ │ │ │ │ │ rr] │ ────┼─────┼─────┼─────┼────┤ │Room 1│10.0│ 0.5 │ 1.0 │ 3.5 │ 0 .5 │50.0│ ├───┼────┼─────┼─────┼─────┼─────┼────┤ │ Room 2 │10.0│ 0.5 │ 1.0 │ 3.5 │ 0.5 │50.0│ ├───┼────┼─────┼─────┼─── ──┼─────┼────┤ │Room 3│10.0│ 0.5 │ 1.0 │ 3.5 │ 0.5 │50 0│ └───┴────┴─────┴─────┴─────┴─────┴────┘ First of all, plasma chemical vapor deposition equipment The inside of the chamber was depressurized.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device, and is an oxygen gas (O ₂ ) and an inert gas supplied from the gas supply device. The raw material gas was mixed with helium (He), argon (Ar), or the like.
Regarding the raw material gas used in the first film forming chamber, the raw material gas used in the second film forming chamber, and the raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases shown in Table 1 above It was.
In the table, the unit; slm means stander-driter-minit.
Using the raw material gas as described above, the raw material gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively. While the biaxially stretched nylon film is conveyed at a line speed of 150 m / min, a power of 10 kW is applied to form a film, and the film thickness of the first layer is 3 nm on one corona-treated surface of the biaxially stretched nylon film. A three-layer carbon-containing silicon oxide film having a thickness of 3 nm for the second layer, a thickness of 3 nm for the third layer, and a total thickness of 9 nm was formed.
Next, immediately after forming the carbon-containing silicon oxide film as described above, a glow discharge plasma generator is used on the surface of the carbon-containing silicon oxide film, and the power is 9 kW, oxygen gas (O ₂ ): argon gas (Ar ) = 7.0: 2.5 (unit: Slm), a mixed gas pressure of 6 × 10 ⁻² mbar, a processing speed of 200 m / min, oxygen / argon mixed gas plasma treatment is performed, and carbon A plasma-treated surface in which the surface tension of the silicon oxide film surface was improved by 54 dyne / cm or more was formed.
(2). On the other hand, a composition prepared according to the composition shown in Table 4 below b. Composition prepared in advance in a mixture of polyvinyl alcohol, flaky silicon dioxide particle dispersion, N, N-dimethylbenzylamine 32 wt% ethanol solution and ion-exchanged water. A hydrolyzed solution composed of ethyl silicate (tetraethoxysilane), ethanol, 2N hydrochloric acid, ion-exchanged water and a silane coupling agent (epoxysilica SH6040) was added and stirred to obtain a colorless and transparent barrier coating solution. .
(Table 4)
a Ethyl silicate 34.074 (wt%)
Water 34.074
2N hydrochloric acid 2.535
Ethanol 2.058
Silane coupling agent 3.407
b Polyvinyl alcohol 2.372
Scale-shaped silicon dioxide particle dispersion 3.200
Wed 18.144
NN dimethylbenzylamine ethanol solution (32 wt%)
0.136
Total 100,000
Next, the gas barrier composition produced above is used for one plasma-treated surface formed in the above (1), and this is coated by a gravure roll coating method, and then heated at 100 ° C. for 30 seconds. The gas barrier coating film having a thickness of 0.4 g / m ² (dry operation state) was formed by processing.
Furthermore, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (1.0% by weight) are added to the polyurethane resin initial condensate on the gas barrier coating film formed as described above. Then, a primer resin composition obtained by sufficiently kneading is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.5 g / m ² (dry state). An agent layer was formed to produce a barrier film according to the present invention.
(3). About the barrier film manufactured above, the confectionery foodstuff which concerns on this invention was manufactured like the said Example 1 like the said Example 1.

(1). Prepare a biaxially stretched nylon film (trade name, Emblem NC # 15, a film made of a mixed resin of nylon 6 resin and nylon MXD6 resin) with a thickness of 15 μm as a base film. The apparatus was installed in a plasma chemical vapor deposition apparatus having a three-chamber configuration as shown in FIG.
Next, a film was formed under the film forming conditions shown in Table 5 below.
(Film forming conditions)
(Table 5)
┌───┬────┬─────┬─────┬─────┬─────┬────┐ │ │ Output │ He │HMDSO│ O ₂ │ Ar │Pressure │ │ │ [kW] │ [slm] │ [slm] │ [slm] │ [slm] │ [mTo│ │ │ │ │ │ │ rr] │ ────┼─────┼─────┼─────┼────┤ │Room 1│10.0│ 0.5 │ 1.0 │ 6.0 │ 0 .5 │50.0│ ├───┼────┼─────┼─────┼─────┼─────┼────┤ │ Room 2 │10.0│ 0.5 │ 1.0 │ 6.0 │ 0.5 │50.0│ ├───┼────┼─────┼─────┼─── ──┼─────┼────┤ │Room 3│10.0│ 0.5 │ 1.0 │ 6.0 │ 0.5 │50 0│ └───┴────┴─────┴─────┴─────┴─────┴────┘ First of all, plasma chemical vapor deposition equipment The inside of the chamber was depressurized.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device, and is an oxygen gas (O ₂ ) and an inert gas supplied from the gas supply device. The raw material gas was mixed with helium (He), argon (Ar), or the like.
Regarding the raw material gas used in the first film forming chamber, the raw material gas used in the second film forming chamber, and the raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases shown in Table 1 above It was.
In the table, the unit; slm means stander-driter-minit.
Using the raw material gas as described above, the raw material gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively. While the biaxially stretched nylon film is conveyed at a line speed of 150 m / min, a power of 10 kW is applied to form a film, and the film thickness of the first layer is 3 nm on one corona-treated surface of the biaxially stretched nylon film. A three-layer carbon-containing silicon oxide film having a thickness of 3 nm for the second layer, a thickness of 3 nm for the third layer, and a total thickness of 9 nm was formed.
Next, immediately after the carbon-containing silicon oxide film is formed as described above, a glow discharge plasma generator is used on the surface of the carbon-containing silicon oxide film, and the power is 9 kW, oxygen gas (O ₂ ): argon gas (Ar ) = 7.0: 2.5 (unit: Slm), a mixed gas pressure of 6 × 10 ⁻² mbar, a processing speed of 200 m / min, oxygen / argon mixed gas plasma treatment is performed, and carbon A plasma-treated surface in which the surface tension of the silicon oxide film surface was improved by 54 dyne / cm or more was formed.
(2). On the other hand, according to the composition shown in Table 6 below, the composition a. Composition prepared in advance in EVOH solution in which EVOH (ethylene copolymerization ratio 29%) was dissolved in a mixed solvent of isopropyl alcohol and ion-exchanged water b. A hydrolyzate composed of ethyl silicate 40 (manufactured by Colcoat Co.), acetylacetone aluminum, ion-exchanged water and isopropyl alcohol was added, stirred, and further prepared in advance c. A mixture of a polyvinyl alcohol aqueous solution, a scale-shaped silicon dioxide particle dispersion, a silane coupling agent (epoxysilica SH6040), acetic acid, isopropyl alcohol, and ion-exchanged water was added and stirred to obtain a barrier coating solution.
(Table 6) a EVOH (ethylene copolymerization ratio 29%) 0.610 (wt%)
Water 3.294
Isopropyl alcohol 2.196
b Ethylsilicate 40 11.460
Water 2.752
Isopropyl alcohol 10.662
Aluminum acetylacetone 0.020
c Polyvinyl alcohol 1.520
Scale-shaped silicon dioxide particle dispersion 3.500
Silane coupling agent 0.050
Water 35.462
Isopropyl alcohol 10.344
Acetic acid 0.130
Total 100,000
Next, the plasma-treated surface formed in the above (2) is coated with the gas barrier composition produced above by the gravure roll coat method, and then heat-treated at 100 ° C. for 30 seconds. Thus, a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) was formed.
Furthermore, an epoxy-based silane coupling agent (8.0% by weight) and an anti-blocking agent (1.0% by weight) are added to the polyester resin initial condensate on the surface of the gas barrier coating film formed above. Then, a primer resin composition obtained by sufficiently kneading is used, and this is coated by a gravure roll coating method so that the film thickness becomes 0.2 g / m ² (dry state). An agent layer was formed to produce a barrier film according to the present invention.
(3). About the barrier film manufactured above, the confectionery foodstuff which concerns on this invention was manufactured like the said Example 1 like the said Example 1.

(1). Prepare a biaxially stretched nylon film (trade name, Emblem NC # 15, a film made of a mixed resin of nylon 6 resin and nylon MXD6 resin) with a thickness of 15 μm as a base film. The apparatus was installed in a plasma chemical vapor deposition apparatus having a three-chamber configuration as shown in FIG.
Next, a film was formed under the film forming conditions shown in Table 7 below.
(Film forming conditions)
(Table 7)
┌───┬────┬─────┬─────┬─────┬─────┬────┐ │ │ Output │ He │HMDSO│ O ₂ │ Ar │Pressure │ │ │ [kW] │ [slm] │ [slm] │ [slm] │ [slm] │ [mTo│ │ │ │ │ │ │ rr] │ ────┼─────┼─────┼─────┼────┤ │Room 1│10.0│ 0.5 │ 1.0 │ 6.0 │ 0 .5 │50.0│ ├───┼────┼─────┼─────┼─────┼─────┼────┤ │ Room 2 │10.0│ 0.5 │ 1.0 │ 0.5 │ 0.5 │50.0│ ├───┼────┼─────┼─────┼─── ──┼─────┼────┤ │Room 3│10.0│ 0.5 │ 1.0 │ 3.0 │ 0.5 │50 0│ └───┴────┴─────┴─────┴─────┴─────┴────┘ First of all, plasma chemical vapor deposition equipment The inside of the chamber was depressurized.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device, and is an oxygen gas (O ₂ ) and an inert gas supplied from the gas supply device. The raw material gas was mixed with helium (He), argon (Ar), or the like.
Regarding the raw material gas used in the first film forming chamber, the raw material gas used in the second film forming chamber, and the raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases shown in Table 1 above It was.
In the table, the unit; slm means stander-driter-minit.
Using the raw material gas as described above, the raw material gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively. While conveying the biaxially stretched nylon film at a line speed of 150 m / min, a power of 10 kW is applied to form a film, and the first layer has a thickness of 3 nm on one of the corona-treated surfaces of the biaxially stretched nylon film. A three-layer carbon-containing silicon oxide layer having a thickness of 3 nm for the second layer, a thickness of 3 nm for the third layer, and a total thickness of 9 nm was formed.
(2). On the other hand, a composition prepared according to the composition shown in Table 2 below. A pre-prepared composition b. In a mixed solution comprising an aqueous solution of polyvinyl alcohol, acetic acid, isopropyl alcohol and ion-exchanged water. A hydrolyzed solution composed of ethyl silicate 40, scale-shaped silicon dioxide particle solution, isopropyl alcohol, acetylacetone aluminum, and ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
(Table 2)
a Polyvinyl alcohol 1.235 (wt%)
Water 58.866
Isopropyl alcohol 5.139
Acetic acid 0.104
b Ethyl silicate 40 9.259
Scale-shaped silicon dioxide particle solution 5.000
Water 16.491
Isopropyl alcohol 3.888
Acetylacetone aluminum 0.018
Total 100,000
Next, the plasma-treated surface formed in the above (1) is coated with the gas barrier composition produced above by the gravure roll coating method, and then heat-treated at 150 ° C. for 30 seconds. Thus, a gas barrier coating film having a thickness of 0.4 g / m ² (in a dry operation state) was formed.
Next, an epoxy silane coupling agent (8.0 wt%) and an antiblocking agent (1.0 wt%) are added to the polyurethane resin initial condensate on the gas barrier coating film formed as described above. The primer composition is added and kneaded sufficiently, and this is coated by the gravure roll coating method so that the film thickness becomes 0.4 g / m ² (dry state). -The agent layer was formed and the barrier film based on this invention was manufactured.
It was.
(3). About the barrier film manufactured above, the confectionery foodstuff which concerns on this invention was manufactured like the said Example 1 like the said Example 1.

(Comparative Example 1)
(1). A biaxially stretched nylon 6 film (trade name, Emblem ON, manufactured by Unitika Ltd.) having a thickness of 15 μm is prepared as a base film, and this is a three-chamber configuration as shown in FIG. It was equipped with a plasma chemical vapor deposition apparatus.
Next, a film was formed under the film forming conditions shown in Table 7 below.
(Film forming conditions)
(Table 7)
┌───┬────┬─────┬─────┬─────┬─────┬────┐ │ │ Output │ He │HMDSO│ O ₂ │ Ar │Pressure │ │ │ [kW] │ [slm] │ [slm] │ [slm] │ [slm] │ [mTo│ │ │ │ │ │ │ rr] │ ────┼─────┼─────┼─────┼────┤ │Room 1│10.0│ 0.5 │ 1.0 │ 6.0 │ 0 .5 │50.0│ ├───┼────┼─────┼─────┼─────┼─────┼────┤ │ Room 2 │10.0│ 0.5 │ 1.0 │ 0.5 │ 0.5 │50.0│ ├───┼────┼─────┼─────┼─── ──┼─────┼────┤ │Room 3│10.0│ 0.5 │ 1.0 │ 3.0 │ 0.5 │50 0│ └───┴────┴─────┴─────┴─────┴─────┴────┘ First of all, plasma chemical vapor deposition equipment The inside of the chamber was depressurized.
On the other hand, hexamethyldisiloxane (hereinafter referred to as HMDSO), which is an organic silicon compound as a raw material, is volatilized in a raw material volatilization supply device, and is an oxygen gas (O ₂ ) and an inert gas supplied from the gas supply device. The raw material gas was mixed with helium (He), argon (Ar), or the like.
Regarding the raw material gas used in the first film forming chamber, the raw material gas used in the second film forming chamber, and the raw material gas used in the third film forming chamber, the mixing ratio of the raw material gases shown in Table 1 above It was.
In the table, the unit; slm means stander-driter-minit.
Using the raw material gas as described above, the raw material gas is introduced into the first film forming chamber, the second film forming chamber, and the third film forming chamber, respectively. While conveying the biaxially stretched nylon 6 film at a line speed of 150 m / min, a power of 10 kW is applied to form a film on the first layer on one corona-treated surface of the above biaxially stretched nylon 6 film. A three-layer carbon-containing silicon oxide layer having a thickness of 3 nm, a second layer thickness of 3 nm, a third layer thickness of 3 nm, and a total thickness of 9 nm was formed.
(2). Thereafter, a confectionery packaged food was produced in the same manner as in Example 1 above, as in Example 1 above.

(Experimental example 1)
The barrier films and laminates produced in Examples 1 to 4 and Comparative Example 1 were measured for oxygen permeability, water vapor permeability, peel strength, and linear cut property.
(1). Measurement of Oxygen Permeability This is for a barrier film under the conditions of a temperature of 23 ° C. and a humidity of 90% RH on a measuring instrument manufactured by Mocon, USA [model name, OX-TRAN 2/20]. Measured.
(2). Measurement of water vapor permeability This is for a barrier film under the conditions of a temperature of 40 ° C. and a humidity of 100% RH on a measuring machine manufactured by MOCON, USA [model name, PERMATRAN 3/31]. Measured.
(3). Measurement of peel strength (laminate strength) This was measured using a Tensilon measuring instrument under the conditions of a test piece 15 mm wide, T-shaped peel, and a peel rate of 50 mm / min.
(4). Measurement of linear cutability This uses a Tensilon measuring instrument to tear both ends of a notch portion of a 30 mm wide test piece with a notch in the center as a notch in the MD direction with a peel strength of 1000 mm / min, and the tear resistance is 100 gf or less And what was cut in a straight line of 50 mm or less was regarded as a good product.
The measurement results are shown in Table 8 below.

(Table 8)
┌────┬────────────────┬───────────────┐ │ │ Barrier film │ Laminate │ │ ├ ───────┬────────┼───────┬───────┤ │ │ Oxygen permeability │ Water vapor permeability │ Oxygen permeability │ Water vapor permeability │ ├────┼───────┼────────┼───────┼───────┤ │Example 1│ 0.5 │ 2 0 │ 0.5 │ 0.5 │ ├────┼───────┼────────┼───────┼───────┤ │Example 2│ 0.3 │ 3.5 │ 0.2 │ 1.5 │ ├────┼───────┼────────┼─────── ─┼───────┤ │Example 3│ 0.2 │ 8.9 │ 0.2 │ 2.0 │ ├────┼───────┼─── ────┼───────┼───────┤ │Example 4│ 0.4 │ 2.5 │ 0.3 │ 0.5 │ ├────┼── ─────┼────────┼───────┼───────┤ │Comparative Example 1│ 0.2 │ 2.0 │ 0.2 │ 0. 5 │ └ ────┴───────┴────────┴───────┴───────┘
┌─────┬──────────┬────────┐ │ │ Peel strength [gf] │ Straight cut │ ├─────┼──── ──────┼────────┤ │Example 1 │ 335 │ Good │ ├─────┼──────────┼──────── ─┤ │Example 2 │ 360 │ Good │ ├─────┼──────────┼────────┤ │Example 3 │ 385 │ Good │ ├── ───┼──────────┼────────┤ │Example 4 │ 385 │ Good │ ├────┼────────── │────────┤ │Comparative Example 1 │ 335 │ Impossible │ └────┴┴──────────┴────────┘ Table 8 above The unit of oxygen permeability is [cc / m ² / day · 23 ° C. · 90% RH], and water vapor permeability The unit of [g / m ² / day · 40 ° C. · 100% RH].

As is clear from the results shown in Table 8 above, the barrier film according to the present invention was excellent in oxygen permeability, water vapor permeability, peel strength, linear cut property and the like.
In particular, as shown in Table 8 above, Example 1, which has a small amount of oxygen relative to HMDSO, has good water vapor permeability but poor oxygen permeability and a slightly low peel strength.
Further, in Example 2 where the amount of oxygen was medium with respect to HMDSO, both oxygen and water vapor permeability showed intermediate values, and the peel strength was the best.
Furthermore, although Example 3 with a large amount of oxygen compared to HMDSO had a poor water vapor permeability, the oxygen permeability was good.
Next, Example 4 which has the form which employ | adopted each condition of each film | membrane of Examples 1-3 had the barrier property and the tight adhesiveness which were balanced in the highest dimension.
In addition, the linear cut property was good when a biaxially stretched nylon film having a thickness of 15 μm (trade name, Emblem NC # 15, manufactured by Unitika Co., Ltd.) was used as the base film, The one using a biaxially stretched nylon 6 film having a thickness of 15 μm simply had a poor linear cut property.

(Experimental example 2)
The barrier films according to the present invention produced in Examples 1 to 4 and Comparative Example 1 were subjected to a bending test using a gelbo flex tester, and then subjected to oxygen permeation in the same manner as in Experimental Example 1 above. And water vapor permeability were measured.
For the barrier film according to the present invention, the biaxially stretched polyamide film as a base film was pulled 2%, and the oxygen permeability and water vapor permeability were measured in the same manner as described above.
(1). Measurement of Oxygen Permeability This is for a laminated material under the conditions of a temperature of 23 ° C. and a humidity of 90% RH, using a measuring instrument manufactured by Mocon, USA (model name: OX-TRAN 2/20). It was measured.
(2). Measurement of water vapor transmission rate This is for a laminated material under the conditions of a temperature of 40 ° C. and a humidity of 100% RH, using a measuring instrument manufactured by Mocon, USA [model name, Permatran 3/31]. It was measured.
The measurement results are shown in Table 9 below.

(Table 9)
┌─────┬────────────────────────┐ │ │ Barrier film │ │ ├ ─────────── ──┬───────────┤ │ │ Oxygen permeability │ Water vapor permeability │ │ ├─────┬──────┼─────┬──── ─┤ │ │Gelbo 0 times │Gelbo 50 times │Gelbo 0 times │Lubo 50 times │ ├────┼┼────┼──────┼─────┼──── ─┤ │Example 1 │ 0.5 │ 0.9 │ 0.5 │ 1.2 │ ├─────┼─────┼──────┼─────┼─ ────┤ │Example 2 │ 0.2 │ 1.2 │ 1.5 │ 1.7 │ ├─────┼─────┼──────┼──── ─┼─────┤ │Example 3 │ 0.2 │ 1.5 │ 2.0 │ 3.2 │ ├─────┼─────┼── ───┼─────┼ ─────┤ │Example 4 │ 0.3 │ 1.0 │ 0.5 │ 1.5 │ ├─────┼─────┼ ──────┼─────┼─────┤ │Comparative Example 1 │ 0.2 │ 0.9 │ 0.5 │ 1.2 │ └ ──────┴─── ──┴──────┴─────┴─────┘
┌─────┬────────────────────────┐ │ │ Barrier film (2% pull) │ │ ├───── ───────┬───────────┤ │ │ Oxygen permeability │ Water vapor permeability │ │ ├─────┬──────┼───── ┬─────┤ │ │ 0% │ 2% │ 0% │ 2% │ ├─────┼─────┼──────┼─────┼─── ──┤ │Example 1 │ 0.5 │ 0.8 │ 0.5 │ 0.6 │ ├────┼─────┼──────┼─────┼ ─────┤ │Example 2 │ 0.2 │ 0.7 │ 1.5 │ 1.5 │ ├─────┼─────┼──────┼─── ──┼─────┤ │Example 3 │ 0.2 │ 1.0 │ 2.0 │ 2.2 │ ├─────┼─────┼───── ─┼─────┼─────┤ │Example 4 │ 0.3 │ 0.4 │ 0.5 │ 0.6 │ ├─────┼─────┼── ────┼─────┼─────┤ │Comparative Example 1 │ 0.5 │ 0.8 │ 0.5 │ 0.6 │ └─────┴───── ┴──────┴─────┴─────┘ In Table 9 above, the unit of oxygen permeability is [cc / m ² / day ・ 23 ℃ ・ 90% RH] The unit of water vapor permeability is [g / m ² / day · 40 ° C. · 90% RH].

  As is clear from the results shown in Table 9 above, the barrier film according to the present invention showed excellent resistance to flexibility and tension.

  The barrier film according to the present invention is excellent in adhesion between the biaxially stretched polyamide film, the carbon-containing silicon oxide film, and the gas barrier coating film. In particular, the carbon-containing silicon oxide film is flexible and spreadable. High barrier properties that are excellent in flexibility, flexibility, etc., do not generate cracks, and can completely block the transmission of oxygen gas, water vapor, etc. due to the synergistic effect with the gas barrier coating film Furthermore, it is excellent in straight-cut property (easy-opening property), and relates to a very useful barrier film as a barrier material used for, for example, packaging materials.

It is a schematic block diagram which shows the schematic structure of an example of the manufacturing apparatus about the barrier film which concerns on this invention. It is a schematic sectional drawing which shows an example of the layer structure about the barrier film which concerns on this invention.

Explanation of symbols

A barrier film 1 biaxially stretched polyamide film 2 barrier layer 2a carbon-containing silicon oxide film 2b carbon-containing silicon oxide film 2c carbon-containing silicon oxide film 3 gas barrier coating film 3a gas barrier coating film

Claims (24)

A nylon film comprising a mixed resin of a nylon resin and a nylon MXD6 resin, and further a biaxially stretched polyamide film stretched in the longitudinal and lateral directions, and a barrier provided on one surface of the biaxially stretched polyamide film And a gas barrier coating film provided on the barrier layer, and the barrier layer uses at least three film forming chambers, and each chamber has at least 3 or more prepared by changing the mixing ratio of each gas component of the mixed gas composition for film formation containing a monomer gas for film formation, oxygen gas, and inert gas composed of one or more organic silicon compounds Using a mixed gas composition for film formation, comprising a carbon-containing silicon oxide film by plasma chemical vapor deposition of three or more layers formed using each mixed gas composition for film formation, Carbon-containing silicon oxide Contains carbon atoms in its film, and becomes carbon content for each oxide silicon film from different carbon-containing silicon oxide film, and the above-mentioned gas barrier coating film of the general formula R ¹ _n M ( OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, and m represents 1) And at least one alkoxide represented by the following formula: n + m represents the valence of M), and a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer. Furthermore, it comprises a gas barrier coating film of a gas barrier composition obtained by polycondensation by a sol-gel method. The biaxially stretched polyamide film is a nylon film composed of a mixed resin of nylon 6 resin and nylon MXD6 resin, and further composed of a biaxially stretched polyamide film stretched in the longitudinal and lateral directions. A barrier film having a linear cut property according to claim 1. Organosilicon compounds are 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenyl The above-mentioned, characterized by comprising one or more of silane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, or octamethylcyclotetrasiloxane The barrier film which has the linear cut property described in any one of Claims 1-2. The barrier film having a linear cut property according to any one of claims 1 to 3, wherein the inert gas is composed of argon gas or helium gas. Film mixed gas composition 1, a film for the monomer in the mixed gas composition for the first film - the volume ratio V _O / V _M of the gas (M) and oxygen gas (O) and the R When it is 0.1 <= R <2.5, The barrier property film which has the linear cut property described in any one of Claims 1-4 characterized by the above-mentioned. Film mixed gas composition of 2, film for monomer in the mixed gas composition for the second film - the volume ratio V _O / V _M of the gas (M) and oxygen gas (O) and the R When it is 2.5 <= R <5.0, The barrier film which has the linear cut property as described in any one of the said Claims 1-5 characterized by the above-mentioned. Film mixed gas composition of 3, a film for the monomer in the mixed gas composition for the second film - the volume ratio V _O / V _M of the gas (M) and oxygen gas (O) and the R When it is 5.0 <= R <15.0, The barrier film which has the linear cut property of any one of said Claims 1-6 characterized by the above-mentioned. The carbon-containing silicon oxide film has a component ratio of 80 to 120 O atoms and 100 to 150 C atoms with respect to 100 Si atoms, and further Si—O—Si between 1030 cm ^{−1 to} 1060 cm ^−1. 6. The barrier film having linear cut property according to claim 5, wherein the film has IR absorption based on stretching vibration and has IR absorption based on Si—CH ₃ stretching vibration at 1274 ± 4 cm ^−1. . The carbon-containing silicon oxide film has a component ratio of 100 to 150 O atoms and 100 or less C atoms with respect to 100 Si atoms, and further Si—O—Si stretch between 1045 cm ^{−1 to} 1075 cm ^−1. The barrier film having a linear cut property according to claim 6, wherein the film has IR absorption based on vibration and has IR absorption based on Si—CH ₃ stretching vibration at 1274 ± 4 cm ⁻¹ . The carbon-containing silicon oxide film has a component ratio of 150 to 190 O atoms and 80 or less C atoms with respect to 100 Si atoms, and further Si—O—Si stretch between 1045 cm ^{−1 to} 1075 cm ^−1. 8. The barrier film having a linear cut property according to claim 7, wherein the film has IR absorption based on vibration and has IR absorption based on Si—CH ₃ stretching vibration at 1274 ± 4 cm ⁻¹ . The carbon-containing silicon oxide film is composed of a carbon-containing silicon oxide film formed by preparing a first layer with a thickness of 20 to 200 mm, a second layer with a thickness of 20 to 200 mm, and a third layer with a thickness of 20 to 200 mm. The barrier film having a linear cut property according to any one of claims 1 to 10. The carbon-containing silicon oxide film contains carbon atoms in the film, and the carbon content in the film increases in the depth direction from the film surface. The barrier film which has the linear cut property described in any one of -11. The barrier film having a linear cut property according to any one of claims 1 to 12, wherein the plasma chemical vapor deposition method comprises a low temperature plasma chemical vapor deposition method. The straight-cut property according to any one of claims 1 to 13, wherein M in the general formula R ¹ _n M (OR ² ) _m is composed of silicon, zirconium, titanium, or aluminum. A barrier film. The barrier film having a linear cut property according to any one of claims 1 to 14, wherein the alkoxide is an alkoxysilane. The barrier film having linear cut property according to any one of claims 1 to 15, wherein the alkoxide comprises a hydrolyzate of alkoxide or a hydrolyzed condensate of alkoxide. The straight-cut property according to any one of claims 1 to 16, wherein the gas barrier composition contains scale-shaped silicon dioxide fine particles having a thickness of 0.5 µm or less and a surface diameter of 5 µm or less. A barrier film. The gas barrier composition contains a silane coupling agent, The barrier film having linear cut property according to any one of claims 1 to 17, wherein the gas barrier composition contains a silane coupling agent. The gas barrier composition has the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), a polyvinyl alcohol-based resin, and / or Or an ethylene-vinyl alcohol copolymer, and further comprising a gas barrier composition that undergoes polycondensation by the sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent. The barrier film having a linear cut property according to any one of claims 1 to 18. 20. The sol-gel method catalyst in the gas barrier composition comprises a tertiary amine that is substantially insoluble in water and soluble in an organic solvent. A barrier film having a linear cut property described in 1. The tertiary amine in a gas barrier composition consists of N, N-dimethylbenzylamine, The barrier film having a linear cut property according to any one of claims 1 to 13, wherein the tertiary amine is N, N-dimethylbenzylamine. The water in the gas barrier composition is used at a ratio of 0.1 to 100 mol with respect to 1 mol of alkoxide, and the linear cut property according to any one of claims 1 to 21, A barrier film. 23. The barrier film having a linear cut property according to any one of claims 1 to 22, wherein the gas barrier coating film is composed of a composite polymer layer in which one layer or two or more layers are laminated. The gas barrier coating film is a base film provided with a coating film by applying a gas barrier composition at a temperature of 50 ° C. to 250 ° C. and a temperature not higher than the melting point of the above base film for 30 seconds to 10 seconds. It consists of a cured film heat-processed for minutes, The barrier film which has the linear cut property of any one of said Claims 1-23 characterized by the above-mentioned.

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