JP6939968B2 - Barrier film, laminate using the barrier film, packaging product using the laminate - Google Patents

Description

The present invention relates to a barrier film, a laminate using the barrier film, and a packaged product using the laminate.

In the traffic, a long film such as plastic or a laminated film having a film formed on a base material of a sheet is used for various purposes. For example, a barrier laminated film in which a barrier layer made of a thin film such as aluminum oxide is provided on a plastic film to have a barrier function against oxygen and water vapor has also been developed.

As a method for producing a barrier film provided with an aluminum oxide thin film, for example, Patent Document 1 describes aluminum hydroxide by removing water contained in a reaction space in which an oxidation reaction between oxygen gas and evaporated aluminum occurs at the time of vapor deposition. It is disclosed that the formation of substances is suppressed and the heat resistance and water resistance are improved.

Japanese Unexamined Patent Publication No. 2016-203427

An object of the present invention is to provide a barrier film provided with an aluminum oxide vapor-deposited film, which has a higher barrier property, and a laminate using the barrier film.

As a result of diligent studies to solve the above problems, the present inventors have a higher barrier property by paying attention to the existence and position of the downwardly convex peak derived from the element bond OH in the TOF-SIMS analysis. We have found that it is possible to obtain a barrier film, and have completed the present invention.

Since aluminum hydroxide has a high affinity with water molecules, water molecules permeate into the film made of aluminum hydroxide, which lowers the barrier property against water vapor. Here, in the method of Patent Document 1, the number of hydroxyl groups (hydrogen atoms) in the entire aluminum oxide film is reduced.

However, according to the findings of the present inventors, the growth of the aluminum oxide vapor-deposited film on the surface of the aluminum hydroxide proceeds by two-dimensional growth, and a more dense aluminum oxide-deposited film is formed. That is, the aluminum oxide film deposited on the surface of the aluminum hydroxide has a characteristic of exhibiting an excellent barrier property against oxygen and water vapor as compared with aluminum oxide deposited directly on the surface of the plastic film.

Therefore, in order to realize a barrier film having high barrier performance, an alumina hydroxide region is formed in the vicinity of the plastic film and the aluminum vapor deposition interface, and the alumina hydroxide region is mainly oxidized. By forming the aluminum region, it is possible to provide a higher barrier property. The structure of such a thin-film deposition film is supported by the presence of a downwardly convex peak derived from the elemental bond OH by TOF-SIMS analysis and the depth position of the peak.

Specifically, the present invention provides the following.

(1) A barrier film in which a base material, an aluminum oxide vapor-deposited film, and an organic coating layer are laminated in this order.
When the aluminum oxide vapor-deposited film was etched from the surface side of the organic coating layer of the barrier film by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the strength derived from the element bond OH was detected.
The intensity derived from the elemental bond OH has a downwardly convex peak, and the downwardly convex peak is located at a depth of 10% or more and 60% or less from the surface side of the organic coating layer in the aluminum oxide vapor-deposited film. A barrier film that exists.

(2) The barrier film according to (1), wherein the organic coating layer is a cured product of a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin.

(3) The barrier film according to (2), wherein the resin composition further contains a silane coupling agent.

(4) A laminate comprising the barrier film according to any one of (1) to (3) and a sealant layer.

(5) A packaged product comprising the laminate according to (4).

The barrier film of the present invention has even higher barrier properties.

It is sectional drawing which shows an example of the barrier film which concerns on this embodiment. It is a figure which shows an example of the film forming apparatus which concerns on embodiment of this invention. It is sectional drawing which shows an example of the plasma pretreatment mechanism of a film forming apparatus. It is a top view which shows an example of the electrode part and the magnetic field formation part of the plasma pretreatment mechanism of a film forming apparatus. It is sectional drawing which shows an example of the electrode part and the magnetic field formation part of the plasma pretreatment mechanism of a film forming apparatus. It is sectional drawing which shows an example of the film forming mechanism of a film forming apparatus. It is sectional drawing which shows an example of the laminated body provided with the barrier film which concerns on embodiment of this invention. It is a graph analysis figure which shows the measurement result by TOF-SIMS of the barrier film of Example 1. It is a graph analysis figure which shows the measurement result by TOF-SIMS of the barrier film of Example 2. It is a graph analysis figure which shows the measurement result by TOF-SIMS of the barrier film of the comparative example 1. FIG. It is a graph analysis figure which shows the measurement result by TOF-SIMS of the barrier film of Example 3. FIG. It is a graph analysis figure which shows the measurement result by TOF-SIMS of the barrier film of Example 4. It is a graph analysis figure which shows the measurement result by TOF-SIMS of the barrier film of Example 5. It is a graph analysis figure which shows the measurement result by TOF-SIMS of the barrier film of the comparative example 2. It is a top view which shows an example of a loop stiffness measuring instrument. It is sectional drawing along the line VV of the loop stiffness measuring instrument of FIG. It is a figure for demonstrating the process of attaching a test piece to a loop stiffness measuring instrument. It is a figure for demonstrating the process of forming a loop part in a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece. It is a figure for demonstrating the process of applying a load to the loop part of a test piece.

Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and the present invention is carried out with appropriate modifications within the scope of the object of the present invention. can do. Further, in the present specification, the notation of "X to Y" (X and Y are arbitrary numerical values) means "X or more and Y or less".

FIG. 1 is a cross-sectional view showing an example of a barrier film according to the present embodiment. The barrier film produced by using the film forming apparatus according to the present embodiment includes a base material 1, a vapor-deposited film 2, and an organic coating layer 3, as in the barrier film A shown in FIG. 1, for example. In the example shown in FIG. 1, the vapor deposition film 2 is located on one surface of the base material 1. Further, in the example shown in FIG. 1, the barrier film A is laminated in the order of the base material 1, the vapor-deposited film 2, and the organic coating layer 3, and the organic coating layer 3 is located on the surface of the barrier film.

In the present specification, "laminated in this order" means that the base material, the aluminum oxide vapor-deposited film, and the organic coating layer are laminated in this order, and between these layers, For example, layers other than the primer may be laminated.

Hereinafter, each layer constituting the barrier film A will be described.

[Base material]
The base material 1 is a layer mainly containing a resin. The resin is not particularly limited, and a known resin film or sheet can be used. For example, polyester resins including polyethylene terephthalate resins, polybutylene terephthalate resins, polyethylene naphthalate resins, etc., and polyamide resins; polyolefin resins containing α-olefin polymers and copolymers such as polyethylene and polypropylene. A resin film containing a resin or the like can be used.

Among these resins, polyester-based resins are preferably used, and further, among polyester-based resins, polyethylene terephthalate-based resins and polybutylene terephthalate-based resins are preferably used. The polyester film used as the base material 1 may be stretched in a predetermined direction. In this case, the polyester film may be a uniaxially stretched film stretched in a predetermined unidirectional direction, or may be a biaxially stretched film stretched in a predetermined bidirectional direction. For example, when a film made of polyethylene terephthalate is used as the base material 1, a biaxially stretched polyethylene terephthalate film can be used.

The thickness of the polyester film used as the base material 1 as described above is not particularly limited, and it is possible to perform pretreatment or film formation treatment when the vapor deposition film 2 is formed by a film forming apparatus described later. It may be possible, but from the viewpoint of flexibility and shape retention, a range of 6 μm or more and 100 μm or less is preferable. When the thickness of the polyester film is within the above range, it is easy to bend and is not torn during transportation, and is easy to handle in a film forming apparatus used for manufacturing a barrier film having a vapor-deposited film 2 having improved adhesion. ..

As the polyethylene terephthalate film (PET film), in addition to the conventionally known PET film, a biomass PET film, a recycled PET film, or a high stiffness PET film (tough PET film) may be used as the base material 1.

<Biomass PET film>
The biomass PET film is a resin film containing a polyester derived from biomass, and the polyester derived from biomass is an ethylene glycol derived from biomass as a diol unit and a dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid unit.

Since ethylene glycol derived from biomass has the same chemical structure as ethylene glycol derived from conventional fossil fuel, the polyester film synthesized using ethylene glycol derived from biomass is the same as the polyester film derived from conventional fossil fuel. It is not inferior in terms of physical properties such as physical characteristics. Therefore, since the base material using the biomass-derived polyester film has a layer made of a carbon-neutral material, the amount of fossil fuel used is reduced as compared with the base material produced from the raw material obtained from the conventional fossil fuel. It can reduce the environmental load.

Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass such as sugar cane and corn. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a method of producing ethylene glycol via ethylene oxide by a conventionally known method. Further, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Co., Ltd. can be preferably used.

As the dicarboxylic acid unit of polyester, a fossil fuel-derived dicarboxylic acid is used. As the dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl esters of the aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl. Esters and the like can be mentioned. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid.

Biomass-derived polyester can be obtained by a conventionally known method of polycondensing a diol unit and a dicarboxylic acid unit. Specifically, a general method of melt polymerization such as an esterification reaction and / or a transesterification reaction between the above dicarboxylic acid component and a diol component and then a polycondensation reaction under reduced pressure, or an organic solvent. It can be produced by a known solution heating dehydration condensation method using.

The resin composition constituting the resin film containing the biomass-derived polyester may be composed of only the biomass-derived polyester, or may contain a fossil fuel-derived polyester in addition to the biomass-derived polyester. Polyester derived from fossil fuel is composed of a diol unit and a dicarboxylic acid unit, and is obtained by a polycondensation reaction using ethylene glycol of a diol derived from fossil fuel as a diol unit and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit. It is a thing.

The resin in the resin composition constituting the resin film containing the biomass-derived polyester may contain recycled polyester in addition to the biomass-derived polyester. The recycled polyester may be a recycled polyester derived from biomass or a recycled polyester derived from fossil fuel.

The resin composition constituting the resin film containing the biomass-derived polyester can contain various additives. Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, friction reducing agents, mold release agents, antioxidants, ion exchange. Agents, coloring pigments and the like can be mentioned. The additive is preferably contained in the entire resin composition containing PET in the range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less.

The resin film containing the biomass-derived polyester can be formed, for example, by forming a film by the T-die method. Specifically, after the above-mentioned PET is dried, it is supplied to a melt extruder heated to a temperature (Tm) to Tm + 70 ° C. above the melting point of the PET to melt the resin composition, for example, a T die. A film can be formed by extruding a sheet-like material from a die such as a die and quenching and solidifying the extruded sheet-like material with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder and the like can be used depending on the purpose. Hereinafter, the melting point may be referred to as Tm and the glass transition point may be referred to as Tg, if necessary.

Since 14C is contained in the carbon dioxide in the atmosphere at a constant ratio (105.5 pMC), the 14C content in a plant that grows by taking in the carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no 14C. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of 14C contained in all carbon atoms in polyester. In the present invention, the "biomass degree" indicates the mass ratio of the biomass-derived component. Taking PET (polyethylene terephthalate) as an example, PET is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1: 1 and is derived from biomass as ethylene glycol. When only is used, the mass ratio of the biomass-derived component in PET is 31.25%, so that the degree of biomass is 31.25% (molecular weight derived from ethylene glycol derived from biomass / molecular weight of 1 unit of polymerization of polyester). = 60 ÷ 192). Further, the mass ratio of the biomass-derived component of the fossil fuel-derived polyester is 0%, and the biomass degree of the fossil fuel-derived polyester is 0%. In the present invention, the degree of biomass in the resin film containing the polyester derived from biomass is preferably 5.0% or more, more preferably 10.0% or more, and preferably 30.0% or less.

The resin film containing the biomass-derived polyester is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the vertical direction to obtain a vertically stretched film. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually carried out in a temperature range of 50 to 100 ° C. Further, the magnification of longitudinal stretching depends on the required characteristics of the film application, but is preferably 2.5 times or more and 4.2 times or less. When the draw ratio is less than 2.5 times, the thickness unevenness of the polyester film becomes large, and it is difficult to obtain a good film.

The vertically stretched film is subsequently subjected to each of the treatment steps of transverse stretching, heat fixing, and heat relaxation to obtain a biaxially stretched film. The transverse stretching is usually carried out in a temperature range of 50 to 100 ° C. The lateral stretching ratio depends on the required characteristics of this application, but is preferably 2.5 times or more and 5.0 times or less. If it is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film formation.

After the transverse stretching, the heat fixing treatment is subsequently performed, and the preferable temperature range of the heat fixing is Tg + 70 to Tm-10 ° C. of polyester. The heat fixing time is preferably 1 to 60 seconds. Further, for applications that require a reduction in the heat shrinkage rate, heat relaxation treatment may be performed as necessary.

The thickness of the resin film containing the biomass-derived polyester is arbitrary depending on its use, but is usually about 5 to 500 μm. Breaking strength of a resin film comprising a polyester derived from biomass is a 5~35kgf / mm ² at 5~40kgf / ^mm 2, TD direction MD direction, elongation at break from 50 to 350% in MD direction, It is 50 to 300% in the TD direction. The shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1 to 5%.

The resin film containing biomass-derived polyester can be suitably used for applications such as packaging products such as bags, lid materials, and Lami tubes, various label materials, and sheet molded products. When a resin film containing recycled PET is used for packaging products, the thickness of the stretched film is preferably 5 to 30 μm.

<Recycled PET film>
The recycled PET film is a resin film containing recycled PET, and includes PET recycled by mechanical recycling. Specifically, it contains PET in which a PET bottle is recycled by mechanical recycling, and this PET contains ethylene glycol as a diol component and terephthalic acid and isophthalic acid as a dicarboxylic acid component.

Here, mechanical recycling generally refers to crushing a recovered polyethylene terephthalate resin product such as a PET bottle, cleaning it with an alkali to remove stains and foreign substances on the surface of the PET resin product, and then drying it under high temperature and reduced pressure for a certain period of time. This is a method in which the pollutants remaining inside the PET resin are diffused and decontaminated to remove stains on the resin product made of the PET resin, and the resin product is returned to the PET resin again.

Hereinafter, polyethylene terephthalate obtained by recycling PET bottles will be referred to as "recycled polyethylene terephthalate (hereinafter, also referred to as recycled PET)", and non-recycled polyethylene terephthalate shall be referred to as "virgin polyethylene terephthalate (hereinafter, also referred to as virgin PET)". ..

The content of the isophthalic acid component in the PET contained in the base material is preferably 0.5 mol% or more and 5 mol% or less, and 1.0 mol% or more, in the total dicarboxylic acid component constituting the PET. More preferably, it is 2.5 mol% or less. If the content of the isophthalic acid component is less than 0.5 mol%, the flexibility may not be improved, while if it exceeds 5 mol%, the melting point of PET may be lowered and the heat resistance may be insufficient.

The PET may be a biomass-derived PET as well as a normal fossil fuel-derived PET. This biomass-derived PET is a PET containing ethylene glycol derived from biomass as a diol component and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component.

The PET used in the PET bottle can be obtained by a conventionally known method of polycondensing the above-mentioned diol component and dicarboxylic acid component. Specifically, a general method of melt polymerization such as an esterification reaction and / or a transesterification reaction between the above diol component and a dicarboxylic acid component and then a polycondensation reaction under reduced pressure, or an organic solvent. It can be produced by a known solution heating dehydration condensation method or the like using the above. The amount of the diol component used in producing the PET is substantially equimolar with respect to 100 mol of the dicarboxylic acid or its derivative, but in general, esterification and / or transesterification reaction and / or condensation polymerization. Since there is distillation during the reaction, it is used in excess of 0.1 mol% or more and 20 mol% or less. Further, the polycondensation reaction is preferably carried out in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added at the time of raw material preparation or at the start of reduced pressure.

PET bottles made from recycled PET bottles are polymerized and solidified as described above, and then solid-phase polymerization is performed as necessary in order to further increase the degree of polymerization and remove oligomers such as cyclic trimers. You may go. Specifically, in solid phase polymerization, the PET is chipped and dried, and then heated at a temperature of 100 ° C. or higher and 180 ° C. or lower for about 1 to 8 hours to pre-crystallize the PET, followed by 190 ° C. It is carried out by heating at a temperature of 230 ° C. or lower for 1 hour to several tens of hours under an inert gas atmosphere or under reduced pressure.

The ultimate viscosity of PET contained in recycled PET is preferably 0.58 dl / g or more and 0.80 dl / g or less. If the ultimate viscosity is less than 0.58 dl / g, the mechanical properties required for the PET film as a resin base material may be insufficient. On the other hand, if the ultimate viscosity exceeds 0.80 dl / g, the productivity in the film forming process may be impaired. The ultimate viscosity is measured with an orthochlorophenol solution at 35 ° C.

The recycled PET preferably contains recycled PET in a proportion of 50% by mass or more and 95% by mass or less, and may contain virgin PET in addition to recycled PET. As the virgin PET, the diol component as described above may be ethylene glycol, the dicarboxylic acid component may be a PET containing terephthalic acid and isophthalic acid, and the dicarboxylic acid component may be a PET containing no isophthalic acid. May be good. For example, as the dicarboxylic acid component, an aliphatic dicarboxylic acid or the like may be contained in addition to the aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.

Specific examples of the aliphatic dicarboxylic acid include chains having 2 or more and 40 or less carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid and cyclohexanedicarboxylic acid. The shape or alicyclic dicarboxylic acid can be mentioned. Examples of the derivative of the aliphatic dicarboxylic acid include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of the aliphatic dicarboxylic acid, and cyclic acid anhydride of the aliphatic dicarboxylic acid such as succinic anhydride. .. Among these, as the aliphatic dicarboxylic acid, adipic acid, succinic acid, dimeric acid or a mixture thereof is preferable, and one containing succinic acid as a main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, a methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.

The resin in the resin composition constituting the resin film containing the recycled PET may be composed of only the recycled PET, or may contain a virgin PET in addition to the recycled PET. Further, the recycled PET film may be a single layer or a multilayer. When the resin film containing recycled PET has three layers of innermost layer / intermediate layer / outermost layer, the intermediate layer is a layer composed of only recycled PET or a mixed layer of recycled PET and virgin PET, and the innermost layers on both sides and the outermost layer. The outermost layer is preferably a layer composed of only virgin PET. As described above, by using only virgin PET for the innermost layer and the outermost layer, it is possible to prevent the recycled PET from being exposed from the front surface or the back surface of the resin film. Therefore, the hygiene of the laminated body can be ensured. When the resin film containing recycled PET is composed of two layers, one layer is a layer composed of only recycled PET or a mixed layer of recycled PET and virgin PET, and the other layer is composed of only virgin PET. It is preferable to use a layer. When a resin film containing recycled PET is formed by mixing recycled PET and virgin PET in a single layer, there are a method of separately supplying the resin film to a molding machine, a method of supplying the resin film after mixing with a dry blend or the like, and the like. Above all, the method of mixing by dry blend is preferable from the viewpoint of easy operation.

The resin composition constituting the resin film containing recycled polyethylene PET can contain various additives in the production process thereof or after the production thereof as long as the characteristics are not impaired. Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, friction reducing agents, mold release agents, antioxidants, ion exchange. Agents, coloring pigments and the like can be mentioned. The additive is preferably contained in the entire resin composition containing PET in the range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less.

The resin film containing recycled PET can be formed, for example, by forming a film by the T-die method. Specifically, after the above-mentioned PET is dried, it is supplied to a melt extruder heated to a temperature (Tm) to Tm + 70 ° C. above the melting point of the PET to melt the resin composition, for example, a T die. A film can be formed by extruding a sheet-like material from a die such as a die and quenching and solidifying the extruded sheet-like material with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder and the like can be used depending on the purpose.

The resin film containing recycled PET is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the vertical direction to obtain a vertically stretched film. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually carried out in a temperature range of 50 ° C. or higher and 100 ° C. or lower. Further, the magnification of longitudinal stretching depends on the required characteristics of the film application, but is preferably 2.5 times or more and 4.2 times or less. When the draw ratio is less than 2.5 times, the thickness unevenness of the PET film becomes large and it is difficult to obtain a good film. The vertically stretched film is subsequently subjected to each of the treatment steps of transverse stretching, heat fixing, and heat relaxation to obtain a biaxially stretched film. The transverse stretching is usually carried out in a temperature range of 50 ° C. or higher and 100 ° C. or lower. The lateral stretching ratio depends on the required characteristics of this application, but is preferably 2.5 times or more and 5.0 times or less. If it is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film formation. After the transverse stretching, a heat-fixing treatment is subsequently performed, and a preferable temperature range for heat-fixing is Tg + 70 to Tm-10 ° C. of PET. The heat fixing time is preferably 1 second or more and 60 seconds or less. Further, for applications that require a reduction in the heat shrinkage rate, heat relaxation treatment may be performed as necessary.

The thickness of the resin film containing recycled PET is arbitrary depending on its use, but is usually about 5 to 500 μm. Breaking strength of the resin film containing the recycled PET is a MD direction 5 kgf / mm ² or more 40 kgf / mm ² or less, at 35 kgf / mm ² or less 5 kgf / mm ² or more in the TD direction, elongation at break, MD direction Is 50% or more and 350% or less, and 50% or more and 300% or less in the TD direction. The shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1% or more and 5% or less.

The virgin PET may be fossil fuel polyethylene terephthalate (hereinafter, also referred to as fossil fuel PET) or biomass PET. Here, the "fossil fuel PET" has a diol derived from fossil fuel as a diol component and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component. Further, the recycled PET may be obtained by recycling a PET resin product formed by using fossil fuel PET, or may be obtained by recycling a PET resin product formed by using biomass PET. There may be.

The resin film containing recycled PET can be suitably used for applications such as packaging products such as bags, lid materials, and Lami tubes, various label materials, and sheet molded products. When a resin film containing recycled PET is used for packaging products, the thickness of the stretched film is preferably 5 to 30 μm.

<High stiffness PET film (tough PET film)>
The high-stiffness PET film contains polyester as a main component and has a loop stiffness of 0.0017 N / 15 mm or more in at least one direction. The high stiffness film has a loop stiffness of 0.0017 N or more in at least one of the flow direction (MD) and the vertical direction (TD), for example. The high stiffness film may have a loop stiffness of 0.0017 N or more in both the flow direction (MD) and the vertical direction (TD), for example.

Loop stiffness is a parameter that expresses the strength of the film. Hereinafter, a method for measuring loop stiffness will be described with reference to FIGS. 15 to 20. The measuring method described below can be used not only for a single-layer film such as a stretched plastic film but also for a film containing a plurality of layers such as a vapor-deposited film and a laminated film. The thin-film film is a film including a single-layer film such as a stretched plastic film and a thin-film film formed on the single-layer film. The laminated film is a film containing a plurality of laminated films.

FIG. 15 is a plan view showing the test piece 40 and the loop stiffness measuring instrument 45, and FIG. 16 is a cross-sectional view of the test piece 40 and the loop stiffness measuring instrument 45 of FIG. 15 along lines IV-IV. The test piece 40 is a rectangular film having a long side and a short side. In the present application, the length L1 of the long side of the test piece 40 is 150 mm, and the length L2 of the short side is 15 mm. As the loop stiffness measuring instrument 45, for example, No. 1 manufactured by Toyo Seiki Co., Ltd. 581 Loop STIFFNESS TESTER DA type can be used. The length L1 of the long side of the test piece 40 can be adjusted as long as the test piece 40 can be gripped by the pair of chuck portions 46 described later.

The loop stiffness measuring instrument 45 has a pair of chuck portions 46 for gripping a pair of end portions in the long side direction of the test piece 40, and a support member 47 for supporting the chuck portions 46. The chuck portion 46 includes a first chuck 461 and a second chuck 462. In the state shown in FIGS. 15 and 16, the test piece 40 is arranged on the pair of first chucks 461, and the second chuck 462 still grips the test piece 40 with the first chuck 461. Not. As will be described later, at the time of measurement, the test piece 40 is gripped between the first chuck 461 and the second chuck 462 of the chuck portion 46. The second chuck 462 may be connected to the first chuck 461 via a hinge mechanism.

When the film to be measured, such as a stretched plastic film, a vapor-deposited film, or a laminated film, is available in a state before the film is processed into a packaged product, the test piece 40 is manufactured by cutting the film to be measured. You may. Further, the test piece 40 may be manufactured by cutting a packaged product manufactured from a packaging material such as a packaging bag and taking out a film to be measured.

A method of measuring the loop stiffness of the test piece 40 using the loop stiffness measuring device 45 will be described. First, as shown in FIGS. 15 and 16, the test piece 40 is placed on the first chuck 461 of the pair of chuck portions 46 arranged at intervals L3. In the present application, the interval L3 is set so that the length of the loop portion 41 (hereinafter, also referred to as the loop length) described later is 60 mm. The test piece 40 includes an inner surface 40x located on the side of the first chuck 461 and an outer surface 40y located on the opposite side of the inner surface 40x. When the test piece 40 is made of a packaging material, the inner surface 40x and the outer surface 40y of the test piece 40 correspond to the inner surface and the outer surface of the packaging material. When the loop portion 41 described later is formed on the test piece 40, the inner surface 40x is located inside the loop portion 41 and the outer surface 40y is located outside the loop portion 41. Subsequently, as shown in FIG. 17, the second chuck 462 is arranged on the test piece 40 so as to grip the end portion of the test piece 40 in the long side direction with the first chuck 461.

Subsequently, as shown in FIG. 18, at least one of the pair of chuck portions 46 is slid on the support member 47 in the direction in which the distance between the pair of chuck portions 46 is reduced. As a result, the loop portion 41 can be formed on the test piece 40. The test piece 40 shown in FIG. 18 has a loop portion 41, a pair of intermediate portions 42, and a pair of fixing portions 43. The pair of fixing portions 43 are portions of the test piece 40 that are gripped by the pair of chuck portions 46. The pair of intermediate portions 42 are portions of the test piece 40 located between the loop portion 41 and the pair of intermediate portions 42. As shown in FIG. 18, the chuck portion 46 is slid on the support member 47 until the inner surfaces 40x of the pair of intermediate portions 42 come into contact with each other. As a result, the loop portion 41 having a loop length of 60 mm can be formed. The loop length of the loop portion 41 is the position P1 at which the surface of one second chuck 462 on the loop portion 41 side and the test piece 40 intersect, and the surface of the other second chuck 462 on the loop portion 41 side and the test piece 40. It is the length of the test piece 40 with respect to the position P2 where the two intersect. The above-mentioned interval L3 is a value obtained by adding 2 × t to the length of the loop portion 41 when the thickness of the test piece 40 is ignored. t is the thickness of the second chuck 462 of the chuck portion 46.

After that, as shown in FIG. 19, the posture of the chuck portion 46 is adjusted so that the protruding direction Y of the loop portion 41 with respect to the chuck portion 46 is in the horizontal direction. For example, the posture of the chuck portion 46 supported by the support member 47 is adjusted by moving the support member 47 so that the normal direction of the support member 47 faces the horizontal direction. In the example shown in FIG. 19, the protruding direction Y of the loop portion 41 coincides with the thickness direction of the chuck portion. Further, the load cell 48 is prepared at a position separated from the second chuck 462 by a distance Z1 in the protruding direction Y of the loop portion 41. In the present application, the distance Z1 is set to 50 mm. Subsequently, the load cell 48 is moved toward the loop portion 41 of the test piece 40 at a speed V by the distance Z2 shown in FIG. The distance Z2 is set so that the load cell 48 comes into contact with the loop portion 41 and then the load cell 48 pushes the loop portion 41 toward the chuck portion 46, as shown in FIGS. 19 and 20. In the present application, the distance Z2 is set to 40 mm. In this case, the distance Z3 between the load cell 48 and the second chuck 462 of the chuck portion 46 in the state where the load cell 48 is pushing the loop portion 41 toward the chuck portion 46 is 10 mm. The speed V for moving the load cell 48 was set to 3.3 mm / sec.

Subsequently, as shown in FIG. 20, the load cell 48 is moved toward the chuck portion 46 by a distance Z2, and is added to the load cell 48 from the loop portion 41 in a state where the load cell 48 is pushing the loop portion 41 of the test piece 40. After the load value stabilizes, record the load value. The value of the load thus obtained is adopted as the loop stiffness of the film constituting the test piece 40. In the present application, unless otherwise specified, the environment at the time of measuring the loop stiffness is a temperature of 23 ° C. and a relative humidity of 50%.

By using a high stiffness film having a loop stiffness of 0.0017 N or more in at least one direction as the stretched plastic film, the puncture strength of the stretched plastic film can be increased. Thereby, in the laminated film provided with the high stiffness film, the puncture strength of the laminated film can be made, for example, 13 N or more, more preferably 14 N or more, and further preferably 15 N or more or 16 N or more. can.

Examples of the high-stiffness film include a high-stiffness PET film containing 51% by mass or more of PET. The content of PET in the high-stiffness PET film may be 80% by mass or more, 90% by mass or more, or 95% by mass or more. The thickness of the high stiffness film is preferably 5 μm or more, more preferably 7 μm or more. The thickness of the high stiffness film may be 10 μm or more, or 14 μm or more. The thickness of the high stiffness film is preferably 30 μm or less, 25 μm or less, or 20 μm or less.

The preferred mechanical properties of the high stiffness film will be further described. The piercing strength of the high stiffness film is preferably 10 N or more, more preferably 11 N or more. The tensile strength of the high stiffness film in at least one direction is preferably 250 MPa or more, more preferably 280 MPa or more. For example, the tensile strength of the high stiffness film in the flow direction is preferably 250 MPa or more, more preferably 280 MPa or more. The tensile strength of the high stiffness film in the vertical direction is preferably 250 MPa or more, more preferably 280 MPa or more. The tensile elongation of the high stiffness film in at least one direction is preferably 130% or less, more preferably 120% or less. For example, the tensile elongation of the high stiffness film in the flow direction is preferably 130% or less, more preferably 120% or less. The tensile elongation of the high stiffness film in the vertical direction is preferably 120% or less, more preferably 110% or less. Preferably, in at least one direction, the value obtained by dividing the tensile strength of the high stiffness film by the tensile elongation is 2.0 [MPa /%] or more. For example, the value obtained by dividing the tensile strength of the high stiffness film in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa /%] or more, and more preferably 2.2 [MPa /%] or more. Is. The value obtained by dividing the tensile strength of the high stiffness film in the flow direction (MD) by the tensile elongation is preferably 1.8 [MPa /%] or more, and more preferably 2.0 [MPa /%] or more. ..

The heat shrinkage of the high stiffness film in at least one direction is preferably 0.7% or less, more preferably 0.5% or less. For example, the heat shrinkage rate of the high stiffness film in the flow direction is preferably 0.7% or less, and more preferably 0.5% or less. The heat shrinkage of the high stiffness film in the vertical direction is preferably 0.7% or less, more preferably 0.5% or less. The heating temperature when measuring the heat shrinkage rate is 100 ° C., and the heating time is 40 minutes.

The Young's modulus of the high stiffness film in at least one direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more. For example, the Young's modulus of a high-stiffness film in the flow direction is preferably 4.0 GPa or more, and more preferably 4.5 GPa or more. The Young's modulus of the high stiffness film in the vertical direction is preferably 4.0 GPa or more, and more preferably 4.5 GPa or more.

Young's modulus can be measured according to JIS K7127 as well as tensile strength and tensile elongation. As the measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used. As the test piece, a high-stiffness film cut out into a rectangular film having a width of 15 mm and a length of 150 mm can be used. The distance at the start of measurement between the pair of chucks holding the test piece is 100 mm, and the tensile speed is 300 mm / min. The length of the test piece can be adjusted as long as the test piece can be gripped by a pair of chucks. In the present application, unless otherwise specified, the environment at the time of measuring Young's modulus is a temperature of 25 ° C. and a relative humidity of 50%.

The high-stiffness film has the same mechanical properties as a single high-stiffness film even when a vapor-deposited film is provided. For example, a high-stiffness film provided with the aluminum oxide vapor-deposited film 3 has a loop stiffness of 0.0017 N or more in at least one direction. Further, even when the organic coating layer is further provided on the vapor-deposited film, it has the same mechanical properties as a single high-stiffness film. For example, a high-stiffness film provided with an aluminum oxide vapor-deposited film and an organic coating layer has a loop stiffness of 0.0017 N or more in at least one direction.

In the process of manufacturing a high-stiffness film, for example, first, a plastic film obtained by melting and molding polyester is tripled to 4.5 times at 90 ° C. to 145 ° C. in the flow direction and the vertical direction, respectively. The first stretching step of stretching is carried out. Subsequently, a second stretching step of stretching the plastic film 1.1 to 3.0 times at 100 ° C. to 145 ° C. in the flow direction and the vertical direction is carried out. Then, heat fixing is performed at a temperature of 190 ° C. to 220 ° C. Subsequently, in the flow direction and the vertical direction, a relaxation treatment (a treatment for reducing the film width) of about 0.2% to 2.5% is carried out at a temperature of 100 ° C. to 190 ° C. By adjusting the stretching ratio, stretching temperature, heat fixing temperature, and relaxation treatment rate in these steps, a high stiffness film having the above-mentioned mechanical properties can be obtained.

As a specific example of the high stiffness film, XP-55 manufactured by Toray Industries, Inc. can be used. This high stiffness film is biaxially stretched, contains 90% by mass or more of PET, and has a thickness of 16 μm. The measured value of the loop stiffness of this high-stiffness PET film was 0.0021N in both the flow direction and the vertical direction. The Young's modulus of the high-stiffness PET film in the flow direction was 4.8 GPa, and the Young's modulus of the high-stiffness PET film in the vertical direction was 4.7 GPa. The tensile strength of the high-stiffness PET film in the flow direction was 292 MPa, and the tensile strength of the high-stiffness PET film in the vertical direction was 257 MPa. The tensile elongation of the high-stiffness PET film in the flow direction was 107%, and the tensile elongation of the high-stiffness PET film in the vertical direction was 102%. In this case, the value obtained by dividing the tensile strength of the high-stiffness PET film in the flow direction by the tensile elongation is 2.73 [MPa /%], and the tensile strength of the high-stiffness PET film in the vertical direction is divided by the tensile elongation. The value is 2.52 [MPa /%]. The heat shrinkage of the high-stiffness PET film in the flow direction and the vertical direction was 0.4%.

The base material 1 may have a single layer or a multi-layered structure of two or more layers, and in the case of a multi-layered structure, it may be a layer having the same composition or a layer having a different composition. Further, in the case of a multi-layer structure, each layer may be bonded with an adhesive layer or the like interposed therebetween.

[Aluminum oxide vapor deposition film]
Next, the vapor deposition film 2 will be described. The vapor-deposited film 2 contains aluminum oxide. Aluminum exists in the vapor-deposited film 2 in a state where, for example, an element bond Al ₂ O _{3 is formed.} The vapor deposition film 2 further includes metal oxides such as silicon oxide, silicon nitride, silicon oxide nitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, and zirconium oxide, or metals thereof. It may contain nitrides and carbides. The thickness of the vapor-deposited film 2 is preferably 3 nm or more and 100 nm or less, more preferably 5 nm or more and 50 nm or less, and particularly preferably 5 nm or more and 15 nm or less. The "aluminum oxide vapor-deposited film" in the present invention means "aluminum oxide-containing vapor-deposited film" as described above, and in _{addition to aluminum oxide Al 2} O ₃ , aluminum hydroxide Al ₂ O ₄ H and the like are used. It may be included.

(TOF-SIMS analysis)
The composition of the barrier film according to this embodiment will be described in detail with reference to FIG. 9 of Example 2 described later. FIG. 9 shows the elements contained in the barrier film A obtained by etching the barrier film A shown in FIG. 1 from the surface side of the organic coating layer 3 using a time-of-flight secondary ion mass spectrometry (TOF-SIMS). It is an example of a graph analysis diagram showing the strength of an element and an element bond when the element bond is measured. The unit (intensity) on the vertical axis of the graph is the common logarithm of the ion intensity. The unit (Et times) on the horizontal axis of the graph is the etching time.

TOF-SIMS (Time-of-Flight Secondary Ion Mass Spectrometry) irradiates the surface of a solid sample to be analyzed with a primary ion beam from a primary ion gun and is sputtered from the surface of the sample. This is a method of mass spectrometry of released secondary ions by mass separation using the difference in flight time (flight time is proportional to the square root of weight).

Here, by detecting the secondary ion intensity while proceeding with sputtering, the transition time with respect to the data of the time transition of the ion intensity of the secondary ion, that is, the element to be detected or the molecular ion bonded to the element to be detected. Is converted into the depth, so that the concentration distribution of the element to be detected in the depth direction of the sample surface can be known.

Then, the depth of the dent formed on the sample surface by the irradiation of the primary ion is measured in advance using a surface roughness meter, and the average sputter rate is calculated from the depth of the dent and the transition time. It is possible to calculate the depth (spatter amount) from the irradiation time (that is, transition time) or the number of irradiation cycles under the assumption that the sputter rate is constant.

Specifically, the vapor deposition film 2 and the base material 1 are used by using a flight time type secondary ion mass spectrometer while repeating soft etching from the outermost surface of the organic coating layer 3 with a Cs (cesium) ion gun at a constant speed. By measuring the elements and elemental bonds at the interface with and the elements and elemental bonds of the vapor deposition film 2, each graph can be obtained for the measured elements and elemental bonds. As a specific example, as shown in FIG. 9, from the barrier film according to the present embodiment, the strength derived from OH, the strength derived from Si, the strength derived from Al ₂ O ₃ , and AL ₂ O are shown. _At least the intensity derived from 4H and the intensity derived from C6 are detected. In the example shown in FIG. 9, an example in which the strength of these five types of elemental bonds is measured is shown.

_{In FIG. 9, the position of Et time T 1} at which the intensity of strength derived from C6 is halved (the strongest strength) is defined as the interface between the plastic base material and aluminum oxide. _{Next, the position of Et time T 2} at which the intensity of Si-derived strength constituting the organic coating layer is halved (the strongest strength) is defined as the interface between the organic coating film and aluminum oxide. Then, T ₁ to T ₂ are formed as an aluminum oxide vapor-deposited film (X in FIG. 9).

In FIG. 9, the intensity derived from OH exists in the aluminum oxide vapor deposition film, that is, within the range of X in FIG. 9, and the intensity derived from OH is mainly present in the region of the organic coating layer on the left side of X in the figure. It is the strength derived from the organic coating layer, and in the region of the base material on the right side of X in the figure, it is the strength mainly derived from the base material (moisture). In the region X in the figure, the intensity derived from OH is a peak mainly derived from aluminum hydroxide. That is, in the region of X, the change in strength derived from OH reflects the change in the abundance of aluminum hydroxide. Then, according to FIG. 9, there is a downwardly convex peak Tp in the region of X.

Further, in FIG. 9, the peak (Tp) depth position (corresponding to Y / X in FIG. 9) at X is preferably 10% or more and 60% or less from the surface side (organic coating layer side) of the vapor-deposited film. Is present in 10% or more and 50% or less, more preferably 10% or more and 40% or less. This means that Tp is present on the organic coating layer side of the vapor deposition film. _{That is, while the main region of Al 2} O ₄ H exists on the substrate side of _{the vapor deposition film, the ratio of Al 2} O ₄ H is small in the region on the organic coating side of the vapor deposition film, and mainly of Al ₂ O ₃ It means that there is a region of state. Thereby, the barrier performance can be improved.

The presence of the downwardly convex peak Tp derived from OH and the depth position of Tp are determined by the conditions of pretreatment, especially oxygen plasma treatment, plasma assist treatment during vapor deposition, and the formation of an aluminum oxide vapor deposition film. It can be adjusted by controlling the combination of the oxygen concentration at the time of vapor deposition in.

_{The intensity derived from Al 2} O ₄ H (mass number 118.93) in FIG. 9 has two peaks in the vicinity of 3100 cycles and in the vicinity of 3600 cycles. _{Since the former peak is the intensity that may contain the derivative AlSiO 4} generated at the interface between the organic coating layer and the aluminum oxide layer, the intensity of Al2O4H can be determined by separating the two from each other and observing only the latter peak. Although it can be directly supplemented, according to the present invention, the distribution of the intensity of _{Al 2} O _{4 H in the vapor-deposited film can be known by measuring the intensity derived from OH regardless of this.}

For waveform separation, for example, a profile with a mass number of 118.93 obtained by TOF-SIMS is subjected to non-linear curve fitting using a Gaussian function, and overlapping peaks are separated using a least squares Levenberg-Marquardt algorithm. Just do.

(Organic coating layer)
The organic coating layer 3 laminated on the surface of the aluminum oxide vapor-deposited film 2 mechanically and chemically protects the aluminum oxide-deposited film and improves the barrier performance of the laminated film having a barrier property. Hereinafter, the organic coating layer 3 coated to form a barrier laminated film having retort resistance having excellent barrier properties will be described.

The organic coating layer 3 is formed by applying a barrier coating agent on an aluminum oxide vapor-deposited film and solidifying it. The barrier coating agent is composed of a metal alkoxide, a water-soluble polymer, a silane coupling agent added as needed, a sol-gel method catalyst, an acid and the like.

As the metal alkoxide, the general formula R1 _n M (OR ² ) _m (where R ₁ and R ₂ represent organic groups having 1 to 8 carbon atoms, M represents a metal atom, and n represents a metal atom. Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents the valence of M.) At least one kind of metal alkoxide, a metal atom represented by M of the metal alkoxide. Examples thereof include silicon, zirconium, titanium, aluminum, and the like. For example, it is preferable to use alkoxide silane in which M is Si.

The above alkoxysilane is represented by, for example, the general formula Si (ORa) ₄ (where Ra represents a lower alkyl group in the formula). In the above, as Ra, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc. are used. Specific examples of the above alkoxysilane include, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) 4, and tetrabutoxysilane Si. (OC ₄ H ₉ ) ₄ , etc. can be used. Two or more kinds of the above alkoxides may be used in combination.

As the silane coupling agent, one having a reactive group such as a vinyl group, an epoxy group, a methacryl group and an amino group can be used. In particular, organoalkoxysilane having an epoxy group is preferable, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxy. Propyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be used. The above-mentioned silane coupling agent may be used alone or in combination of two or more.

Among them, the cross-linking density of the cured film of the organic coating layer using bifunctionality such as γ-glycidoxypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane was determined in the system using trialkoxysilane. It is lower than the crosslink density. Therefore, while being excellent as a film having gas barrier properties and heat-resistant water treatment properties, it becomes a flexible cured film and also has excellent bending resistance. Therefore, the packaging material using the barrier film has gas barrier properties even after the Gelboflex test. Hard to deteriorate.

As the water-soluble polymer, a polyvinyl alcohol-based resin or an ethylene / vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer can be used in combination. can do. In the organic coating layer 3 according to the present embodiment, a polyvinyl alcohol-based resin is suitable.

As the polyvinyl alcohol-based resin, generally, one obtained by saponifying polyvinyl acetate can be used. The polyvinyl alcohol-based resin may be a partially saponified polyvinyl alcohol-based resin in which several tens of percent of acetic acid groups remain, a completely saponified polyvinyl alcohol in which no acetic acid groups remain, or a modified polyvinyl alcohol-based resin in which OH groups are modified. good. As for the saponification degree, it is necessary to use at least a polyvinyl alcohol-based resin that is crystallized to improve the film hardness of the gas barrier coating film, and the saponification degree is preferably 70% or more. Further, the degree of polymerization can be used as long as it is in the range (about 100 to 5000) used in the conventional sol-gel method. Examples of such polyvinyl alcohol-based resins include "RS-110 (degree of polymerization = 99%, degree of polymerization = 1,000)", which is an RS resin manufactured by Kuraray Co., Ltd., and "Gosenol" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. NM-14 (degree of saponification = 99%, degree of polymerization = 1,400) ”and the like can be mentioned.

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 can be used. For example, it includes, and is not particularly limited, from a partially saponified product in which several tens of mol% of acetic acid groups remain to a completely saponified product in which only a few mol% of acetic acid groups remain or no acetic acid groups remain. However, from the viewpoint of barrier properties, the degree of saponification preferably is 80% or more, more preferably 90% or more, further preferably 95% or more and 100% or less, and particularly preferably 99% or more and 100% or less. It is preferable to do so.

As the sol-gel method catalyst, an acid or amine compound is suitable.

As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid can be used.

The acid content is preferably 0.001 to 0.05 mol%, more preferably 0.01 to 0.03 mol%, based on the total molar amount of the alkoxy groups of the metal alkoxide. If it is less than 0.001% mol, the catalytic effect is too small, and if it is more than 0.05 mol%, the catalytic effect is too strong and the reaction rate becomes too fast, which tends to cause non-uniformity.

As the amine compound, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is preferable. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. In particular, N, N-dimethylbenzylamine is preferable.

The content of the amine compound is preferably 0.01 to 1.0 parts by mass, particularly 0.03 to 0.3 parts by mass, per 100 parts by mass of the metal alkoxide. If it is less than 0.01 part by mass, the catalytic effect is too small, and if it is more than 1.0 part by mass, the catalytic effect is too strong and the reaction rate becomes too fast, which tends to cause non-uniformity.

As the solvent, it is preferable to use water, alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropanol and n-butanol.

The barrier coating layer formed as described above has a layer thickness of 100 to 500 nm. This range is preferable because the coating film does not crack and sufficiently covers the surface of the vapor-deposited film.

When the silane coupling agent is contained, the composition of the barrier coating agent is 5 to 10 parts by mass of a water-soluble polymer such as a polyvinyl alcohol resin and 1 part by mass of the silane coupling agent with respect to 100 parts by mass of alkoxysilane. It can be used within the range of 10 to 10 mass parts. As a result, the flexibility of the film can be maintained and the retort resistance can be enhanced. In the above, when the silane coupling agent is used in an amount of more than 20 parts by mass, the rigidity and brittleness of the formed barrier coating film are increased, which is not preferable.

When the silane coupling agent is not contained, the amount ratio of the metal alkoxide is lowered by using 10 to 20 parts by mass of a water-soluble polymer such as a polyvinyl alcohol resin with respect to 100 parts by mass of the alkoxysilane. Therefore, the barrier property can be enhanced.

(Film formation equipment)
Next, an example of the film forming apparatus 10 used in the method for producing a barrier film will be described. As shown in FIG. 2, the film forming apparatus 10 includes a base material transport mechanism 11A for transporting the base material 1, a plasma pretreatment mechanism 11B for performing plasma pretreatment on the surface of the base material 1, and a thin-film deposition film 2. A film forming mechanism 11C for forming a film is provided. In the example shown in FIG. 5, the film forming apparatus 10 further includes a pressure reducing chamber 12. The decompression chamber 12 has a decompression mechanism that adjusts the atmosphere of at least a part of the space inside the decompression chamber 12 to atmospheric pressure or less, such as a vacuum pump described later.

In the example shown in FIG. 2, the decompression chamber 12 is composed of a base material transfer chamber 12A in which the base material transfer mechanism 11A is located, a plasma pretreatment chamber 12B in which the plasma pretreatment mechanism 11B is located, and a film forming mechanism 11C. Membrane chamber 12C and. The decompression chamber 12 is preferably configured to prevent the atmosphere inside each chamber from mixing with each other. For example, as shown in FIG. 2, the decompression chamber 12 is formed between the base material transfer chamber 12A and the plasma pretreatment chamber 12B, between the plasma pretreatment chamber 12B and the film formation chamber 12C, and between the base material transfer chamber 12A and the film formation. It may have partition walls 35a to 35c that are located between the chambers 12C and separate the chambers.

The base material transfer chamber 12A, the plasma pretreatment chamber 12B, and the film formation chamber 12C will be described. The plasma pretreatment chamber 12B and the film forming chamber 12C are each provided in contact with the base material transfer chamber 12A, and each has a portion connected to the base material transfer chamber 12A. As a result, the base material 1 can be transported between the base material transport chamber 12A and the plasma pretreatment chamber 12B and between the base material transport chamber 12A and the film forming chamber 12C without being exposed to the atmosphere. For example, between the base material transport chamber 12A and the plasma pretreatment chamber 12B, the base material 1 can be transported through the opening provided in the partition wall 35a. The base material transport chamber 12A and the film forming chamber 12C have the same structure, and the base material 1 can be transported between the base material transport chamber 12A and the film forming chamber 12C.

The function of the decompression mechanism of the decompression chamber 12 will be described. The decompression mechanism of the decompression chamber 12 is configured so that the atmosphere of the space in which at least the plasma pretreatment mechanism 11B or the film forming mechanism 11C of the film forming apparatus 10 is arranged can be depressurized to atmospheric pressure or less. The depressurizing mechanism may be configured so that each of the base material transport chamber 12A, the plasma pretreatment chamber 12B, and the film forming chamber 12C, which are partitioned by the partition walls 35a to 35c, can be depressurized to atmospheric pressure or lower.

The configuration of the decompression mechanism of the decompression chamber 12 will be described. The decompression chamber 12 may have, for example, a vacuum pump connected to the plasma pretreatment chamber 12B. By adjusting the vacuum pump, the pressure in the plasma pretreatment chamber 12B when performing the plasma pretreatment described later can be appropriately controlled. Further, it is possible to prevent the plasma supplied into the plasma pretreatment chamber 12B from diffusing into another chamber by the method described later. The decompression mechanism of the decompression chamber 12 may have a vacuum pump connected to the film forming chamber 12C as well as a vacuum pump connected to the plasma pretreatment chamber 12B. As the vacuum pump, a dry pump, a turbo molecular pump, a cryopump, a rotary pump, a diffusion pump and the like can be used.

The base material transport mechanism 11A of the base material 1 of the film forming apparatus 10 according to the present embodiment will be described together with the transport path of the base material 1. The base material transport mechanism 11A is a mechanism for transporting the base material 1 arranged in the base material transport chamber 12A. In the example shown in FIG. 2, the base material transport mechanism 11A includes a winding roller 13 to which the roll-shaped raw fabric of the base material 1 is attached, a winding roller 15 for winding the base material 1, and guide rolls 14a to 14d. Have. The base material 1 sent out from the base material transfer mechanism 11A is then subjected to a pretreatment roller 20 described later arranged in the plasma pretreatment chamber 12B and a film forming roller 25 described later arranged in the film forming chamber 12C. , Transported by.

Although not shown, the base material transport mechanism 11A may further include a tension pickup roller. Since the base material transport mechanism 11A has the tension pickup roller, the base material 1 can be transported while adjusting the tension applied to the base material 1.

(Plasma pretreatment mechanism)
The plasma pretreatment mechanism 11B will be described. The plasma pretreatment mechanism 11B is a mechanism for applying plasma pretreatment to the surface of the base material 1. The plasma pretreatment mechanism 11B shown in FIG. 2 generates plasma P, and uses the generated plasma P to perform plasma pretreatment on the surface of the base material 1. The plasma pretreatment activates the surface of the base material 1 so that the nitrogen contained inside the base material 1 easily collects on the surface of the base material 1, or the nitrogen contained in the environment surrounding the base material 1 is the base material. It can be easily taken into the surface of 1. Therefore, when the vapor-deposited film 2 is formed on the surface of the base material 1 subjected to the plasma pretreatment, the peak of the element-bonded CN can be formed at the interface between the base material 1 and the vapor-deposited film 2. The plasma pretreatment mechanism 11B shown in FIG. 2 is between the pretreatment roller 20 arranged in the plasma pretreatment chamber 12B, the electrode portion 21 facing the pretreatment roller 20, and the pretreatment roller 20 and the electrode portion 21. It has a magnetic field forming unit 23 that forms a magnetic field in the.

The pretreatment roller 20 will be described. FIG. 3 is an enlarged view of the portion surrounded by the alternate long and short dash line in FIG. In FIG. 3, the description of the power supply wiring 31 connecting the power supply 32 shown in FIG. 2 and the electrode portion 21 described later and the plasma P generated by the plasma pretreatment mechanism 11B is omitted. The pretreatment roller 20 has a rotation axis X. The pretreatment roller 20 is provided so that at least the rotation axis X is located in the plasma pretreatment chamber 12B partitioned by the partition walls 35a and 35b. A base material 1 having dimensions in the direction of the rotation axis X is wound around the pretreatment roller 20. In the following description, the dimension of the base material 1 in the direction of the rotation axis X is also referred to as the width of the base material 1. Further, the direction of the rotation axis X is also referred to as the width direction of the base material 1.

As shown in FIG. 2, the pretreatment roller 20 may be provided so that a part thereof is exposed on the base material transport chamber 12A side. In the example shown in FIG. 2, the plasma pretreatment chamber 12B and the base material transfer chamber 12A are connected via an opening provided in the partition wall 35a, and a part of the pretreatment roller 20 is connected through the opening. Is exposed on the base material transport chamber 12A side. There is a gap between the partition wall 35a between the base material transfer chamber 12A and the plasma pretreatment chamber 12B and the pretreatment roller 20, and through the gap, from the base material transfer chamber 12A to the plasma pretreatment chamber 12B. And, the base material 1 can be conveyed. Although not shown, the pretreatment roller 20 may be provided so that the entire pretreatment roller 20 is located in the plasma pretreatment chamber 12B.

Although not shown, the pretreatment roller 20 may have a temperature adjusting mechanism for adjusting the temperature of the surface of the pretreatment roller 20. For example, the pretreatment roller 20 may have a temperature adjustment mechanism inside the pretreatment roller 20 including a pipe for circulating a temperature adjustment medium such as a refrigerant or a heat medium. The temperature adjusting mechanism adjusts the surface temperature of the pretreatment roller 20 to a target temperature in the range of, for example, −20 ° C. or higher and 100 ° C. or lower.

Since the pretreatment roller 20 has a temperature adjusting mechanism, it is possible to suppress shrinkage or breakage of the base material 1 due to heat during plasma pretreatment.

The pretreatment roller 20 is made of a material containing at least one or more of stainless steel, iron, copper and chromium. The surface of the pretreatment roller 20 may be subjected to a hard chrome hard coat treatment or the like in order to prevent scratches. These materials are easy to process. Further, by using the above-mentioned material as the material of the pretreatment roller 20, the thermal conductivity of the pretreatment roller 20 itself is increased, so that the temperature of the pretreatment roller 20 can be easily controlled.

The electrode portion 21 will be described. In the examples shown in FIGS. 2 and 3, the electrode portion 21 has a first surface 21c facing the pretreatment roller 20 and a second surface 21d located on the opposite side of the first surface 21c. In the examples shown in FIGS. 2 and 3, the electrode portion 21 is a plate-shaped member, and both the first surface 21c and the second surface 21d are flat surfaces. The electrode portion 21 generates plasma with the pretreatment roller 20 by applying an AC voltage with the pretreatment roller 20. The electrode portion 21 preferably creates an electric field with the pretreatment roller 20 so that the generated plasma moves in a direction perpendicular to the surface of the base material 1 so as to be directed toward the surface of the base material 1. Form. Thereby, the base material 1 can be efficiently pretreated. Therefore, when the vapor-deposited film 2 is formed on the surface of the plasma-pretreated base material 1, the peak intensity H1 of the peak of the element-bonded CN formed at the interface between the base material 1 and the vapor-deposited film 2 is increased. It can be made larger.

The number of electrode portions 21 is preferably 2 or more. The two or more electrode portions 21 are preferably arranged along the transport direction of the base material 1. In the examples shown in FIGS. 2 and 3, an example in which the film forming apparatus 10 has two electrode portions 21 is shown. The number of electrode portions 21 is, for example, 12 or less.

The effect of arranging two or more electrode portions 21 along the transport direction of the base material 1 will be described. As described above, plasma is generated between the electrode portion 21 and the pretreatment roller 20. The region where plasma is generated expands as the size of the electrode portion 21 in the transport direction increases. On the other hand, when the electrode portion 21 is a flat plate-shaped member, the larger the dimension of the electrode portion 21 in the transport direction, the more the first surface 21c of the electrode portion 21 in the transport direction faces the pretreatment roller 20. The distance from the end of the pretreatment roller 20 to the pretreatment roller 20 becomes large, and the processing capacity by plasma decreases.

In the film forming apparatus 10, two or more electrode portions 21 are arranged along the transport direction of the base material 1. Therefore, even when the size of the electrode portion 21 in the transport direction of the base material 1 is small, plasma can be generated over a wide range in the transport direction. Further, by reducing the size of the electrode portion 21, the distance from the end of the first surface 21c of the electrode portion 21 to the pretreatment roller 20 in the transport direction can be reduced, and plasma is uniformly generated in the transport direction. Can be made to.

As shown in FIGS. 2 and 3, the electrode portion 21 has a first end portion 21e and a second end portion 21f located on the first surface 21c of the electrode portion 21. The first end portion 21e is the end portion on the upstream side in the transport direction of the base material 1, and the second end portion 21f is the end portion on the downstream side in the transport direction of the base material 1. As described above, by reducing the size of the electrode portion 21 in the transport direction of the base material 1, the distance from the first end portion 21e and the second end portion 21f of the electrode portion 21 in the transport direction to the pretreatment roller 20 can be increased. It can be made smaller. The dimensions of the electrode portion 21 in the transport direction of the base material 1 correspond to the angle θ shown in FIG. The angle θ is an angle formed by a straight line passing through the first end portion 21e and the rotation axis X and a straight line passing through the second end portion 21f and the rotation axis X. The angle θ is preferably 20 ° or more and 90 ° or less, more preferably 60 ° or less, and further preferably 45 ° or less. By setting the angle θ within the above range, when the first surface 21c of the electrode portion 21 is flat, plasma can be uniformly generated between the electrode portion 21 and the pretreatment roller 20 in the transport direction. can.

The material of the electrode portion 21 is not particularly limited as long as it has conductivity. Specifically, aluminum, copper, and stainless steel are preferably used as the material of the electrode portion 21.

The thickness L3 of the electrode portion 21 when viewed in a direction perpendicular to the first surface 21c of the electrode portion 21 is not particularly limited, but is, for example, 15 mm or less. When the thickness of the electrode portion 21 is the above value, the magnetic field forming portion 23 can effectively form a magnetic field between the pretreatment roller 20 and the electrode portion 21. The thickness L3 of the electrode portion 21 is, for example, 3 mm or more.

The magnetic field forming unit 23 will be described. As shown in FIGS. 2 and 3, the magnetic field forming portion 23 is provided on the side of the electrode portion 21 opposite to the side facing the pretreatment roller 20. The magnetic field forming portion 23 is a member that forms a magnetic field between the pretreatment roller 20 and the electrode portion 21. The magnetic field between the pretreatment roller 20 and the electrode portion 21 contributes to the generation of higher density plasma when, for example, plasma is generated using the plasma pretreatment mechanism 11B. The magnetic field forming portion 23 shown in FIGS. 2 and 3 has a first magnet 231 and a second magnet 232 provided on the second surface 21d of the electrode portion 21.

The number of magnetic field forming portions 23 is preferably 2 or more. When the plasma pretreatment mechanism 11B has two or more electrode portions 21 and two or more magnetic field forming portions 23, each of the two or more magnetic field forming portions 23 is a respective of the two or more electrode portions 21. , It is preferable that the pretreatment roller 20 is provided on the side opposite to the side facing the pretreatment roller 20. In the examples shown in FIGS. 2 and 3, each of the two magnetic field forming portions 23 is provided on the second surface 21d of each of the two electrode portions 21.

The structures of the first magnet 231 and the second magnet 232 in the normal direction of the second surface 21d of the electrode portion 21 will be described. As shown in FIGS. 2 and 3, the first magnet 231 and the second magnet 232 have an north pole and an south pole, respectively. Reference numeral N shown in FIGS. 2 and 3 indicates the north pole of the first magnet 231 or the second magnet 232. Further, reference numeral S shown in FIGS. 2 and 3 indicates an S pole of the first magnet 231 or the second magnet 232. One of the north pole or the south pole of the first magnet 231 is located closer to the base material 1 than the other. Further, the other of the north pole or the south pole of the second magnet 232 is located closer to the base material 1 than one. In the examples shown in FIGS. 2 and 3, the north pole of the first magnet 231 is located closer to the base material 1 than the south pole of the first magnet 231 and the south pole of the second magnet 232 is the second magnet. It is located on the base material 1 side of the north pole. Although not shown, the S pole of the first magnet 231 is located closer to the base material 1 than the N pole of the first magnet 231 and the N pole of the second magnet 232 is based on the S pole of the second magnet 232. It may be located on the material 1 side.

Subsequently, the structures of the first magnet 231 and the second magnet 232 in the plane direction of the second surface 21d of the electrode portion 21 will be described. FIG. 4 is a plan view of the electrode portion 21 and the magnetic field forming portion 23 shown in FIG. 2 as viewed from the magnetic field forming portion 23 side. FIG. 5 is a cross-sectional view showing a cross section taken along the line VIII-VIII of FIG. Further, in FIG. 4, the direction D1 is the direction in which the rotation axis X of the pretreatment roller 20 extends.

As shown in FIGS. 4 and 5, the first magnet 231 has a first axial portion 231c. As shown in FIG. 4, the first axial portion 231c extends along the direction D1, that is, along the rotation axis X of the pretreatment roller 20. The first magnet 231 provided on one electrode portion 21 may have one first axial portion 231c or may have two or more first axial portions 231c. In the example shown in FIG. 4, the first magnet 231 provided on one electrode portion 21 has one first axial direction portion 231c.

Further, as shown in FIGS. 4 and 5, the second magnet 232 has a second axial portion 232c. As shown in FIG. 4, the second axial portion 232c also extends along the direction D1, that is, along the rotation axis X, like the first axial portion 231c.

By including a portion in which both the first magnet 231 and the second magnet 232 extend along the rotation axis X, the uniformity of the strength of the magnetic field formed around the base material 1 in the width direction of the base material 1 is enhanced. be able to. Thereby, the uniformity of the distribution density of the plasma formed around the base material 1 in the width direction of the base material 1 can be enhanced.

The second magnet 232 provided on one electrode portion 21 may have one second axial portion 232c or may have two or more second axial portions 232c. In the examples shown in FIGS. 4 and 5, the second magnet 232 provided on one electrode portion 21 has two second axial portions 232c. The two second axial portions 232c may be positioned so as to sandwich the first axial portion 231c in the direction D2 orthogonal to the rotation axis X in the surface direction of the second surface 21d of the electrode portion 21.

The dimension L4 of the first axial portion 231c and the dimension L5 of the second axial portion 232c in the transport direction of the base material 1 shown in FIG. 5 are not particularly limited. Further, the ratio of the dimension L4 of the first axial portion 231c and the dimension L5 of the second axial portion 232c in the transport direction of the base material 1 is not particularly limited. The dimension L4 of the first axial portion 231c and the dimension L5 of the second axial portion 232c may be equal, and the dimension L4 of the first axial portion 231c may be larger than the dimension L5 of the second axial portion 232c. ..

The distance L6 between the first axial portion 231c and the second axial portion 232c in the direction D2 is such that the magnetic field generated by the first axial portion 231c and the second axial portion 232c is between the pretreatment roller 20 and the electrode portion 21. Is set to be formed in.

The second magnet 232 may surround the first magnet 231 when the magnetic field forming portion 23 is viewed along the normal direction of the second surface 21d of the electrode portion 21. For example, as shown in FIG. 4, the second magnet 232 has two second axial portions 232c and two connecting portions 232d provided to connect the two second axial portions 232c. May be good.

Examples of the types of magnets used as the magnetic field forming unit 23, such as the first magnet 231 and the second magnet 232, include a ferrite magnet and a permanent magnet such as a rare earth magnet such as neodium and samarium-cobalt (samarium-cobalt). .. Further, an electromagnet can also be used as the magnetic field forming unit 23.

The magnetic flux density of the magnets of the magnetic field forming unit 23 such as the first magnet 231 and the second magnet 232 is, for example, 100 gauss or more and 10,000 gauss or less. When the magnetic flux density is 100 gauss or more, a sufficiently high density plasma can be generated by forming a sufficiently strong magnetic field between the pretreatment roller 20 and the electrode portion 21, and a good pretreatment surface can be generated. Can be formed at high speed. On the other hand, in order to increase the magnetic flux density on the surface of the base material 1 to more than 10,000 gauss, an expensive magnet or a magnetic field generation mechanism is required.

Although not shown, the plasma pretreatment mechanism 11B may have a plasma raw material gas supply unit. The plasma raw material gas supply unit supplies the plasma raw material gas into the plasma pretreatment chamber 12B. The configuration of the plasma raw material gas supply unit is not particularly limited. For example, the plasma raw material gas supply unit is provided on the wall surface of the plasma pretreatment chamber 12B and includes a hole for ejecting a gas as a raw material for plasma. Further, the plasma raw material gas supply unit may have a nozzle for discharging the plasma raw material gas at a position closer to the base material 1 than the wall surface of the plasma pretreatment chamber 12B. As the plasma raw material gas supplied by the plasma raw material gas supply unit, for example, an inert gas such as argon, an active gas such as oxygen, nitrogen, carbon dioxide gas, or ethylene, or a mixed gas of these gases is supplied. As the plasma raw material gas, regardless of whether one of the inert gases is used alone or one of the active gases is used alone, the inert gas or two or more kinds of gases contained in the active gas You may use the mixed gas of. As the plasma raw material gas, it is preferable to use a mixed gas of an inert gas such as argon and an active gas. As an example, the plasma raw material gas supply unit supplies a mixed gas of _{argon (Ar) and oxygen (O 2).}

Plasma pretreatment mechanism 11B is, for example, supplied between the pretreatment roller 20 and the electrode portion 21 of the plasma density 100W · sec / ^{m 2} or more 8000W · sec / ^{m 2} or less of the plasma.

In the example shown in FIG. 2, the plasma pretreatment mechanism 11B includes the base material transfer chamber 12A and the film formation chamber 1.
It is arranged in the plasma pretreatment chamber 12B separated from 2C by a partition wall. By separating the plasma pretreatment chamber 12B from other regions such as the base material transfer chamber 12A and the film formation chamber 12C, the atmosphere of the plasma pretreatment chamber 12B can be easily adjusted independently. This allows, for example,
It becomes easy to control the plasma raw material gas concentration in the space where the pretreatment roller 20 and the electrode portion 21 face each other, and the productivity of the laminated film is improved.

In the present embodiment, the voltage applied between the pretreatment roller 20 of the plasma pretreatment mechanism 11B and the electrode portion 21 is an AC voltage. By applying an AC voltage, plasma is generated between the pretreatment roller 20 and the electrode portion 21. Preferably, by applying an AC voltage, an electric field is formed so that the generated plasma moves toward the surface of the base material 1 in a direction perpendicular to the surface of the base material 1.

The value of the AC voltage applied between the pretreatment roller 20 and the electrode portion 21 is preferably 250 V or more and 1000 V or less. When the AC voltage has the above values, plasma having a sufficient plasma density can be generated between the pretreatment roller 20 and the electrode portion 21. Here, the value of the AC voltage means the effective value Ve. The effective value Ve of the AC voltage is calculated by the following formula when the maximum value of the AC voltage is Vm.

The AC voltage applied between the pretreatment roller 20 and the electrode portion 21 has, for example, a frequency of 20 kHz or more and 500 kHz or less.

(Film formation mechanism)
Next, the film forming mechanism 11C will be described. In the example shown in FIG. 2, the film forming mechanism 11C has a film forming roller 25 arranged in the film forming chamber 12C and an evaporation mechanism 24.

The film forming roller 25 will be described. The film forming roller 25 is a roller that winds and conveys the base material 1 with the treatment surface of the base material 1 pretreated by the plasma pretreatment mechanism 11B on the outside.

The material of the film forming roller 25 will be described. The film forming roller 25 is preferably formed of a material containing at least one or more of stainless steel, iron, copper and chromium. The surface of the film forming roller 25 may be subjected to a hard chrome hard coat treatment or the like in order to prevent scratches. These materials are easy to process. Further, by using the above-mentioned material as the material of the film forming roller 25, the thermal conductivity of the film forming roller 25 itself is increased, so that the temperature controllability is excellent when the temperature is controlled. The surface average roughness Ra of the surface of the film forming roller 25 is, for example, 0.1 μm or more and 10 μm or less.

Further, although not shown, the film forming roller 25 may have a temperature adjusting mechanism for adjusting the temperature of the surface of the film forming roller 25. The temperature adjusting mechanism has, for example, a circulation path for circulating a cooling medium or a heat source medium inside the film forming roller 25. The cooling medium (refrigerant) is, for example, an ethylene glycol aqueous solution, and the heat source medium (heat medium) is, for example, silicon oil. The temperature adjusting mechanism may have a heater installed at a position facing the film forming roller 25. When the film forming mechanism 11C forms a film by a thin film deposition method, the temperature adjusting mechanism preferably sets the temperature of the surface of the film forming roller 25 to −20 from the viewpoint of heat resistance restrictions and versatility of related mechanical parts. Adjust to the target temperature within the range of ° C or higher and 200 ° C or lower. Since the film forming roller 25 has a temperature adjusting mechanism, it is possible to suppress fluctuations in the temperature of the base material 1 due to heat generated during film formation.

The evaporation mechanism 24 will be described. FIG. 6 is an enlargement of the portion surrounded by the alternate long and short dash line in FIG. 2, showing a specific form of the evaporation mechanism 24 which was omitted in FIG. 5, and was omitted in FIG. It is a figure which showed the vapor deposition material supply part 61 which supplies the vapor deposition material. In FIG. 6, the description of the decompression chamber 12 and the partition walls 35b and 35c is omitted. The evaporation mechanism 24 is a mechanism for evaporating a vaporized material containing aluminum. When the evaporated vaporized material adheres to the base material 1, a thin-film vapor-deposited film containing aluminum is formed on the surface of the base material 1. The evaporation mechanism 24 in this embodiment adopts a resistance heating type. In the example shown in FIG. 6, the evaporation mechanism 24 has a boat 24b. In this embodiment, the boat 24b has a power supply (not shown) and a resistor (not shown) electrically connected to the power supply. A plurality of boats 24b may be arranged in the width direction of the base material 1.

As shown in FIG. 6, the film forming mechanism 11C may have a vapor deposition material supply unit 61 that supplies the vapor deposition material to the evaporation mechanism 24. FIG. 6 shows an example in which the thin-film deposition material supply unit 61 continuously sends out a metal wire rod made of aluminum.

Although not shown, the film forming mechanism 11C has a gas supply mechanism. The gas supply mechanism is a mechanism for supplying gas between the evaporation mechanism 24 and the film forming roller 25. The gas supply mechanism supplies at least oxygen gas. The oxygen gas evaporates from the evaporation mechanism 24 and reacts with or combines with an evaporative material such as aluminum heading toward the base material 1 on the film forming roller 25. As a result, a vapor-deposited film containing aluminum oxide can be formed on the surface of the base material 1.

Further, the film forming mechanism 11C includes a plasma supply mechanism 50 that supplies plasma between the surface of the base material 1 and the evaporation mechanism 24. In the examples shown in FIGS. 2 and 6, the plasma supply mechanism 50 has a hollow cathode 51. In the present embodiment, the hollow cathode 51 is a cathode having a hollow portion that is partially open. The hollow cathode 51 can generate plasma in the cavity. In the example shown in FIG. 6, the hollow cathode 51 is provided so that the opening of the cavity of the hollow cathode 51 is located obliquely above the boat 24b. Although not shown, the plasma supply mechanism 50 according to the present embodiment has an anode facing the opening that draws plasma from the opening of the cavity of the hollow cathode 51. The plasma supply mechanism 50 according to the present embodiment generates plasma in the cavity of the hollow cathode 51, and pulls the plasma between the surface of the base material 1 and the evaporation mechanism 24 by an anode facing the base material. A strong plasma can be generated between the surface of 1 and the evaporation mechanism 24. The position of the facing anode is not particularly limited as long as the facing anode can draw plasma from the opening of the cavity of the hollow cathode 51 and supply the plasma between the surface of the base material 1 and the evaporation mechanism 24. .. In the present embodiment, the case where the opposing anodes are arranged on both sides of the boat 24b in the width direction of the base material 1 will be described. In this case, the film forming mechanism 11C has a plurality of boats 24b and a plurality of opposing anodes, and even if the plurality of boats 24b and the plurality of facing anodes are alternately arranged in the width direction of the base material 1. good. Although not shown, the plasma supply mechanism 50 may have a raw material supply device that supplies plasma raw material gas at least in the cavity of the hollow cathode 51. As the plasma raw material gas supplied by the raw material supply device, for example, a gas similar to the gas that can be used as the plasma raw material gas supplied by the plasma raw material gas supply unit of the plasma pretreatment mechanism 11B can be used.

The plasma supply mechanism 50 supplies plasma between the surface of the base material 1 and the evaporation mechanism 24. By performing plasma assist at the time of vaporization, the aluminum and oxygen gas evaporated in the evaporation mechanism 24 are activated. The reaction or bond between aluminum and oxygen gas can be promoted. As a result, the ratio of aluminum present as aluminum oxide in the vapor-deposited film 2 formed on the surface of the base material 1 can be increased, and the characteristics of the vapor-deposited film 2 can be stabilized.

Although not shown, the film forming apparatus 10 is caused by the film formation by the film forming mechanism 11C in the portion of the base material conveying chamber 12A located on the downstream side in the conveying direction of the base material 1 with respect to the film forming chamber 12C. A base material charge removing portion for performing post-treatment for removing the charge generated on the base material 1 may be provided. The base material charge removing portion may be provided so as to remove the charge on one side of the base material 1, or may be provided so as to remove the charge on both sides of the base material 1.

The device used as the base material charge removing unit for post-treating the base material 1 is not particularly limited, and examples thereof include a plasma discharge device, an electron beam irradiation device, an ultraviolet irradiation device, a static elimination bar, a glow discharge device, and a corona treatment device. Can be used.

When post-treatment is performed by forming a discharge using a plasma treatment device or a glow discharge device, a single discharge gas such as argon, oxygen, nitrogen, or helium, or a mixed gas thereof is supplied in the vicinity of the base material 1. However, post-processing can be performed using any discharge method such as AC (AC) plasma, DC (DC) plasma, arc discharge, microwave, and surface wave plasma. In a reduced pressure environment, it is most preferable to perform post-treatment using a plasma discharge device.

The base material charge removing portion is installed in a portion of the base material transport chamber 12A located downstream of the film forming chamber 12C in the transport direction of the base material 1, and the base material 1 is removed from the charge. The material 1 can be quickly separated from the film forming roller 25 at a predetermined position and conveyed. Therefore, stable transfer of the base material is possible, damage to the base material 1 and deterioration of quality due to charging can be prevented, and the wettability of the front and back surfaces of the base material can be improved to improve post-processing suitability.

(Power supply)
In the example shown in FIG. 2, the film forming apparatus 10 further includes a power supply 32 electrically connected to the pretreatment roller 20 and the electrode portion 21. In the example shown in FIG. 5, the power supply 32 is electrically connected to the pretreatment roller 20 and the electrode portion 21 via the power supply wiring 31. The power supply 32 is, for example, an AC power supply. When the power supply 32 is an AC power supply, the power supply 32 can apply an AC voltage having a frequency of, for example, 20 kHz or more and 500 kHz or less between the pretreatment roller 20 and the electrode portion 21. The input power that can be applied by the power source 32 (the power that can be applied per 1 m width of the electrode portion 21 in the width direction of the base material 1) is not particularly limited, but is, for example, 0.5 kW / m or more and 20 kW / m or less. be. The pretreatment roller 20 may be electrically installed at the ground level or electrically at the floating level.

(Manufacturing method of barrier film)
Next, a method for producing the barrier film shown in FIG. 1 will be described using the film forming apparatus 10 described above. First, a film forming method for forming the vapor deposition film 2 on the surface of the base material 1 will be described. In the film formation using the film forming apparatus 10, the substrate 1 is transported along the above-mentioned transport path of the base material 1, and the surface of the base material 1 is subjected to plasma pretreatment using the plasma pretreatment mechanism 11B. A plasma pretreatment step and a film forming step of forming a vapor-deposited film on the surface of the base material 1 by using the film-forming mechanism 11C are performed. The transport speed of the base material 1 is preferably 200 m / min or more, more preferably 400 m / min or more and 1000 m / min or less.

(Plasma pretreatment process)
The plasma pretreatment step is performed by, for example, the following method. First, the plasma raw material gas is supplied into the plasma pretreatment chamber 12B. Next, the above-mentioned AC voltage is applied between the pretreatment roller 20 and the electrode portion 21. When applying the AC voltage, input power control, impedance control, or the like may be performed.

As the plasma raw material gas supplied in the pretreatment, oxygen alone or a mixed gas of oxygen gas and an inert gas is supplied from the gas storage unit via a flow rate controller while measuring the gas flow rate. Examples of the inert gas include one or more mixed gases selected from the group of argon, helium, and nitrogen.

As the plasma treatment, the mixing ratio of the oxygen gas and the inert gas and the oxygen gas / inert gas are preferably 6/1 to 1/1, more preferably 5/2 to 3 / 2.5.

By setting the mixing ratio to 6/1 to 1/1, the film forming energy of the vapor-deposited aluminum on the resin substrate increases, and by further setting it to 5/2 to 3/2, the oxide of the aluminum oxide-deposited film is oxidized. It is possible to increase the degree and secure the adhesion between the aluminum oxide vapor deposition film and the base material.

By applying an AC voltage, plasma is generated at the same time as glow discharge, and the plasma P becomes denser between the pretreatment roller 20 and the magnetic field forming portion 23. In this way, the plasma P can be supplied between the pretreatment roller 20 and the magnetic field forming unit 23. With this plasma P, the surface of the base material 1 can be subjected to plasma (ion) pretreatment.

And 8000W · sec / ^{m 2} or less 50 W · sec / ^{m 2} or more as the plasma intensity per unit area in the plasma processing, the 50 W · sec / ^{m 2} or less, without the effect of the plasma pretreatment was observed, also, 8000W · At sec / m ² or more, the resin base material tends to deteriorate due to plasma such as wear, damage coloring, and firing of the resin base material. In particular, the plasma intensity of the plasma pretreatment is preferably ^{100 W · sec / m 2} or more and 1000 W · sec / m ^{2 or less in order to form an aluminum oxide layer.}

The pressure in the plasma pretreatment chamber 12B when an AC voltage is applied between the pretreatment roller 20 and the electrode portion 21 is reduced to atmospheric pressure or less by the pressure reducing chamber 12. In this case, the atmospheric pressure in the plasma pretreatment chamber 12B is adjusted so that a glow discharge can be generated between the pretreatment roller 20 and the electrode portion 21 by applying an AC voltage, for example. The degree of vacuum in the plasma pretreatment chamber 12B when an AC voltage is applied between the pretreatment roller 20 and the electrode portion 21 can be set and maintained at about 0.1 Pa or more and 100 Pa or less, and in particular, 1 Pa or more. 20 Pa or less is preferable.

The operation of the magnetic field forming unit 23 in the plasma pretreatment step will be described. The magnetic field forming portion 23 forms a magnetic field between the pretreatment roller 20 and the electrode portion 21. The magnetic field can act to capture and accelerate the electrons present between the pretreatment roller 20 and the electrode section 21. Therefore, in the region where the magnetic field is formed, the frequency of collision between the electrons and the plasma raw material gas can be increased, the density of the plasma can be increased, and the plasma can be localized, so that the efficiency of the plasma pretreatment can be improved. can.

(Film formation process)
In the film forming step, the film forming mechanism 11C is used to form a film on the surface of the base material 1. As an example of the film forming process, a case where the aluminum oxide vapor deposition film is formed by using the film forming mechanism 11C having the evaporation mechanism 24 shown in FIG. 6 will be described.

First, a vapor deposition material containing aluminum is supplied into the boat 24b of the evaporation mechanism 24 so as to face the film forming roller 25. As the vapor deposition material, an aluminum metal wire can be used. In the example shown in FIG. 6, the vapor deposition material is supplied to the boat 24b by continuously sending the aluminum metal wire into the boat 24b by the vapor deposition material supply unit 61.

The heating evaporates the aluminum in the boat 24b. FIG. 6 illustrates the evaporated aluminum vapor 63 for convenience. The oxygen gas that oxidizes aluminum may be supplied as a simple substance of oxygen or a mixed gas with an inert gas such as argon, but by controlling the amount of oxygen, both barrier property and transparency can be achieved. The degree of vacuum at this time is preferably 0.05 Pa or more and 8.00 Pa or less.

Further, a method of supplying plasma between the surface of the base material 1 and the evaporation mechanism 24 by the plasma supply mechanism 50, that is, plasma assist at the time of vapor deposition will be described. In the present embodiment, plasma is generated in the cavity of the hollow cathode 51 of the plasma supply mechanism 50. Next, a discharge is generated between the hollow cathode 51 and the anode facing the hollow cathode 51, and the plasma in the cavity of the hollow cathode 51 is drawn out between the surface of the base material 1 and the evaporation mechanism 24.

In the present embodiment, the discharge generated between the hollow cathode 51 and the anode facing the hollow cathode 51 is an arc discharge. The arc discharge means, for example, a discharge in which the value of the current is 10 A or more.

Plasma is supplied to the aluminum vapor 63 by evaporating aluminum while supplying plasma between the surface of the base material 1 and the evaporation mechanism 24. The supply of plasma can promote the reaction or bond between the aluminum vapor 63 and the oxygen gas. Thereby, the aluminum vapor 63 can be oxidized before reaching the surface of the base material 1. By adhering the evaporated and oxidized aluminum to the base material 1, an aluminum oxide vapor-deposited film can be formed on the surface of the base material 1 to produce the barrier film shown in FIG.

The plasma raw material gas supplied by the plasma supply mechanism 50 is preferably oxygen alone or a mixed gas of oxygen gas and an inert gas.

In the present embodiment, a plasma pretreatment step of supplying plasma to the surface of the base material 1 is carried out before the film forming step. In the plasma pretreatment step, an AC voltage is applied between the electrode portion 21 and the pretreatment roller 20. Further, the space between the electrode portion 21 and the pretreatment roller 20 is utilized by using the magnetic field forming portion 23 located on the side of the surface of the electrode portion 21 opposite to the surface facing the pretreatment roller 20. Generates a magnetic field in. Therefore, plasma can be efficiently generated in the space between the electrode portion 21 and the pretreatment roller 20, or the plasma can be made to enter perpendicularly to the surface of the base material 1 wound around the pretreatment roller 20. can do. Therefore, it is possible to improve the adhesion between the film formed by the film forming step and the base material 1.

(Organic coating layer forming process)
The organic coating layer 3 can be produced by the following method. First, the above metal alkoxide, a water-soluble polymer, a silane coupling agent added as necessary, a sol-gel method catalyst, an acid, and an organic solvent such as water as a solvent and alcohols such as methyl alcohol, ethyl alcohol, and isopropanol are mixed. And prepare a barrier coating agent. Next, the above barrier coating agent is applied onto the aluminum oxide vapor-deposited film by a conventional method and dried. By this drying step, polycondensation of the metal alkoxide, the silane coupling agent and the water-soluble polymer further proceeds, and a coating film is formed. On the first coating film, the above coating operation may be repeated to form a plurality of coating films composed of two or more layers. Further, the heat treatment is carried out at a temperature of 20 to 200 ° C. and lower than the melting point of the plastic substrate, preferably a temperature in the range of 50 to 180 ° C. for 3 seconds to 10 minutes. As a result, the organic coating layer 3 made of the barrier coating agent can be formed on the aluminum oxide vapor-deposited film.

(Laminated body)
An example of a laminated body formed by using the barrier film according to the present embodiment will be described. FIG. 7 is a diagram showing an example of a laminated body 40 formed by using the barrier film according to the present embodiment. The laminate 40 includes the barrier film shown in FIG. 1 and the sealant layer 7. Specifically, the laminate 40 is formed on the organic coating layer of the barrier film shown in FIG. 1, an adhesive layer 4, a second base material 5 composed of polyamide or the like, an adhesive layer 6, and a sealant. Layers 7 are provided in this order. The laminate of the present invention is obtained by laminating at least one heat-sealable layer on a barrier film, and a heat-sealable thermoplastic resin is used as the innermost layer with or without an adhesive layer. It is laminated and has a sealing property such as a heat seal.

Examples of the thermoplastic resin constituting the sealant layer 7 include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, polypropylene, polymethylpentene, polystyrene, and ethylene-vinyl acetate. Contains one or more resins such as polymers, ionomer resins, ethylene-acrylic acid copolymers, ethyl ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, and elastomers. A film can be exemplified. The thickness of the sealant layer 7 is preferably 3 to 100 μm, more preferably 15 to 70 μm.

(Packaging material)
The above-mentioned laminate is useful when used as a packaging material for producing a packaging bag for containing contents such as food. In particular, a barrier film that maintains high adhesion even after heat treatment can be suitably used as a material for packaging bags. The above-mentioned barrier film can suppress peeling of the layers constituting the barrier film in the packaged product when the packaged product is produced using the barrier film as a material. For example, when a packaging bag made of a barrier film is subjected to a heat sterilization treatment using hot water, for example, a retort treatment or a boil treatment, the layers constituting the barrier film are peeled off, particularly the vapor deposition film 2. The peeling from the base material 1 can be suppressed.

The retort treatment is a treatment in which the contents are filled in the packaging bag, the packaging bag is sealed, and then the packaging bag is heated in a pressurized state using steam or heated hot water. The temperature of the retort treatment is, for example, 120 ° C. or higher. The boil treatment is a treatment in which the contents are filled in a packaging bag, the packaging bag is sealed, and then the packaging bag is boiled in hot water under atmospheric pressure. The temperature of the boiling treatment is, for example, 90 ° C. or higher and 100 ° C. or lower.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these descriptions. First, the barrier films according to Examples 1 and 2, Reference Examples 1 and 2, and Comparative Example 1 were produced by using the film forming apparatus 1 which is the film forming apparatus according to the present embodiment and the film forming method. .. Table 1 summarizes the pretreatment conditions, vapor deposition conditions, and the like. In the following table, "○" in the evaluation of "presence or absence of plasma pretreatment" means that plasma pretreatment is present, and "x" means that there is no plasma pretreatment. Further, "○" in the evaluation of "presence or absence of plasma assist during vapor deposition" means that plasma assist is present during vapor deposition, and "x" means that there is no plasma assist during vapor deposition.

(Example 1)
A biaxially stretched polyethylene terephthalate film (PET film) having a thickness of 12 μm was used as the base material 1, and a plasma pretreatment step and a film forming step were performed using the film forming apparatus 10 shown in FIG.

In the pretreatment step, the surface of the base material 1 was subjected to plasma pretreatment using the plasma pretreatment mechanism 11B shown in FIGS. 2 and 3. _{Specifically, first, a mixed gas (O 2} : Ar = 2.5: 1) of _{oxygen (O 2} ): argon (Ar) is supplied to the plasma pretreatment chamber 12B using the plasma raw material gas supply unit. While doing so, the pressure in the plasma pretreatment chamber 12B was adjusted using the decompression chamber 12. Next, a voltage was applied between the pretreatment roller 20 and the electrode portion 21 to generate plasma, and the surface of the base material 1 was subjected to plasma pretreatment. The atmospheric pressure in the plasma pretreatment chamber 12B was 6.2 Pa, and a permanent magnet of 1000 gauss was used as the magnetic field forming portion 23. The plasma density was 417 W · sec / m ² .

In the film forming step, the vapor deposition film 2 containing aluminum oxide was deposited by the vacuum vapor deposition method using the evaporation mechanism 24 as shown in FIG. Specifically, after adjusting the degree of vacuum in the film forming chamber 12C to 1.5 Pa, the boat uses a resistance heating type evaporation mechanism 24 while supplying an aluminum metal wire as a vapor deposition material into the boat 24b. The vapor-deposited material in 24b was heated to evaporate the aluminum so as to reach the surface of the base material 1, and the vapor-deposited film 2 was formed on the surface of the base material 1 while supplying oxygen at 12500 sccm.

Further, as the plasma supply mechanism 50, a hollow cathode 51 shown in FIG. 6 and an anode (not shown) facing the opening of the cavity of the hollow cathode 51 arranged on both sides in the width direction of the base material 1 as viewed from the boat 24b. , using a form having a hollow cathode 51 cavity to the plasma source gas _{(O 2: Ar = 35:} 1) to supply, to discharge to excite a plasma, the plasma, by opposing the anode, substrate It was pulled out between the surface of No. 1 and the evaporation mechanism 24 to perform plasma assist during vapor deposition.

The thin-film deposition film 2 was laminated on the base material 1 by the above method. At this time, the transport speed was 600 m / min, and the thickness of the vapor-deposited film 2 was 8 nm.

Further, the organic coating layer 3 (organic coating layer A in Tables 1 and 2) was laminated on the vapor-deposited film 2. 307 g of water, 147 g of isopropyl alcohol and 7.3 g of 0.5N hydrochloric acid were mixed, and 175 g of tetraethoxysilane as a metal alkoxide and glycidoxypropyltrimethoxysilane as a silane coupling agent were added to a solution adjusted to pH 2.2. Solution A was prepared by mixing 7 g while cooling to 10 ° C. As a water-soluble polymer, a solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of polymerization of 2400 with a degree of polymerization of 99% or more, 324 g of water, and 17 g of isopropyl alcohol. The solution obtained by mixing the solution A and the solution B so as to have a mass ratio of 6.5: 3.5 was used as a barrier coating agent. The barrier coating agent prepared above was coated on the aluminum oxide vapor deposition film of the PET film by a spin coating method. Then, it was heat-treated in an oven at 180 ° C. for 60 seconds to form a barrier coating layer having a thickness of about 400 nm on an aluminum oxide vapor-deposited film to form an organic coating layer A, and the barrier film of Example 1 was formed. Manufactured.

(Example 2)
In Example 1, the barrier film of Example 2 was produced in the same manner as in Example 1 except that the transport speed was 480 m / min and the thickness of the vapor-deposited film 2 was 13 nm.

(Reference example 1)
As shown in Table 1, in Example 1, EB (electron beam) type evaporation mechanism (not shown) was used instead of the resistance heating type evaporation mechanism 24 without performing plasma pretreatment, and plasma during vapor deposition was used. The barrier film of Reference Example 1 was produced in the same manner as in Example 1 except that the oxygen supply amount was 8500 sccm and the vacuum degree at the time of vaporization was 0.15 Pa without performing the assist treatment.

(Reference example 2)
As shown in Table 1, in Example 1, the air pressure in the plasma pretreatment chamber 12B was 3.5 Pa, the plasma assist treatment during vapor deposition was not performed, the oxygen supply amount was 10000 sccm, and the degree of vacuum during vapor deposition was 0. The barrier film of Reference Example 2 was produced in the same manner as in Example 1 except that it was set to .02 Pa.

(Comparative Example 1)
As shown in Table 1, the barrier film of Comparative Example 1 was produced in the same manner as in Reference Example 2 except that the transport speed was 480 m / min and the thickness of the vapor-deposited film 2 was 13 nm in Reference Example 3.

(Examples 3 to 5, Comparative Example 2)
Barrier films of Examples 3 to 5 and Comparative Example 2 were produced under the film-forming conditions shown in Table 2 using a film-forming device 2 different from the above-mentioned film-forming device 1.

In the organic coating layer B, 197 g of water, 34 g of isopropyl alcohol and 4.7 g of 0.5N hydrochloric acid were mixed, and 145 g of tetraethoxysilane as a metal alkoxide was cooled to 15 ° C. in a solution adjusted to pH 2.2. Solution A was prepared by mixing with each other. As a water-soluble polymer, a solution B was prepared by mixing 8.3 g of polyvinyl alcohol having a degree of polymerization of 99% or more, 182 g of water, and 9.6 g of isopropyl alcohol. The solution obtained by mixing the solution A and the solution B so as to have a mass ratio of 4.0: 6.0 was used as a barrier coating agent. The barrier coating agent prepared above was coated on the aluminum oxide vapor deposition film of the PET film by a spin coating method. Then, it was heat-treated in an oven at 180 ° C. for 60 seconds to form a barrier coating layer having a thickness of about 400 nm on an aluminum oxide vapor-deposited film to form an organic coating layer B.

[TOF-SIMS analysis]
For the barrier films of Examples 1 to 5 and Comparative Examples 1 and 2, the surface of the vapor-deposited film of the barrier film was subjected to the following measurement conditions using a time-of-flight secondary ion mass spectrometer (TOF.SIMS5, manufactured by ION TOF). From the side, while repeating soft etching at a constant speed with a Cs (cesium) ion gun, C _{6 derived from a resin substrate (mass number 72.00) and Al 2} O ₃ derived from an aluminum oxide vapor deposition film (mass number 101. _{94), mass spectrometry of Al 2} O ₄ H (mass number 118.93) derived from aluminum oxide vapor deposition film, Si (mass number 27.97) derived from organic coating layer, and OH (mass number 17.00) was performed. .. Graph analysis diagrams of the measurement results of the film forming apparatus 1 are shown in FIGS. 8 to 10. FIG. 8 is the measurement result of Example 1, FIG. 9 is the measurement result of Example 2, and FIG. 10 is the measurement result of Comparative Example 1. Graph analysis diagrams of the measurement results of the film forming apparatus 2 are shown in FIGS. 11 to 14. 11 is a measurement result of Example 3, FIG. 12 is a measurement result of Example 4, FIG. 13 is a measurement result of Example 5, and FIG. 14 is a measurement result of Comparative Example 2. In the figure, the unit on the vertical axis (intensity) is the common logarithm of the intensity of ions, and the unit on the horizontal axis (Ettimes (s)) is the number of seconds after etching.

TOF-SIMS measurement conditions-Primary ion type: Bi ^{3 ++} (0.2 pA, 100 μs)
-Measurement area: 150 x 150 μm ²
・ Etching gun type: Cs (1keV, 60nA)
・ Etching area: 600 × 600 μm ²
・ Etching rate: 10 sec / Cycle

Further, the position representing the intensity peak of the measured elemental bond OH (mass number 17.00) is determined by the number of etching seconds (peak position Y), and the depth position from the surface of the vapor-film deposition film on the organic coating layer side at that position (peak position Y). The peak position Y / X in FIG. 9 (unit:%) was determined. These results are summarized in Tables 3 and 4.

(Evaluation of barrier property)
The values of water vapor permeability and oxygen permeability were measured for each of the barrier films of Examples 1 to 5, Reference Examples 1 and 2, and Comparative Examples 1 and 2 produced by the above method.

The water vapor transmittance was measured using a water vapor transmittance measuring device (manufactured by Mocon Co., Ltd., product name "Permatlan") under the measurement conditions of 40 ° C. and 100% RH in accordance with the JIS K 7129B method. In addition, the oxygen permeability is based on JIS K 7126-2 under the measurement conditions of 23 ° C and 90% RH using an oxygen permeability measuring device (manufactured by Mocon, product name "OXTRAN"). It was measured. The results are shown in Tables 5 and 6.

(Evaluation of adhesion)
A two-component curable polyurethane-based laminating adhesive is applied onto the organic coating layer 3 of the barrier film of Examples 1, 2, Reference Examples 1 to 3, and Comparative Example 1 produced by the above method, and a gravure roll coating method is applied. It was used to coat a thickness of 4.0 g / m ² (dry state) to form an adhesive layer 4, and then on the surface of the adhesive layer 4, a biaxially stretched nylon having a thickness of 15 μm as a second base material 5. The 6 films were opposed to each other, dry-laminated and laminated. Next, the adhesive layer 6 for laminating is formed on the surface of the second base material 5 in the same manner as the adhesive layer 4 described above, and then the thickness of the sealant layer 7 is formed on the surface of the adhesive layer 6. A 70 μm unstretched polypropylene film was dry-laminated and laminated to produce a laminated body having a layer structure as shown in FIG. 7.

Next, the laminated body having this layer structure was formed into a pouch by facing the sealant layers so as to face each other and heat-sealing them. After filling the pouch with water, it was retorted at 135 ° C. for 40 minutes. The value of the watering peel strength was measured for each of the laminated bodies in the state after the retort treatment. The results are summarized in Tables 5 and 6.

The watering peel strength was measured by the following method. First, each of the laminated bodies in the state after the retort treatment was cut into strips to obtain a rectangular test piece having a width of 15 mm. Next, the vapor-deposited film of the test piece and the base material were partially peeled off in the longitudinal direction of the test piece (the direction orthogonal to the width direction of the test piece). The peeling of the vapor-deposited film and the base material was performed so that the vapor-deposited film and the base material maintained a bond in part. Next, using a Tensilon universal material tester, the peel strength at the interface between the vapor-deposited film and the substrate was measured under the conditions of a peeling angle of 180 ° and a peeling speed of 50 mm / min in accordance with JIS Z6854-2. In the measurement of the watering peel strength, the portion where the vapor-deposited film and the base material maintain the bond and the portion where the vapor-deposited film and the base material are peeled off when viewed along the longitudinal direction of the test piece. With water dropped on the boundary portion with a dropper, the tensile force required to proceed the peeling over 30 mm was measured, and the average value of the tensile force was calculated. For each of Examples 1 to 5, Reference Examples 1 and 2, and Comparative Examples 1 and 2, the average value of the tensile strength was calculated for each of the six test pieces, and the average value was calculated from Examples 1 to 5 and Reference Example. The water peeling strength in each of 1 and 2 and Comparative Examples 1 and 2 was used. The results are shown in Tables 5 and 6.

From Tables 5 and 6, the strength derived from the elemental bond OH has a downwardly convex peak, and the downwardly convex peak is located at a depth of 10% or more and 60% or less from the surface side of the organic coating layer in the vapor deposition film. In the existing Examples 1 to 5, the barrier property is higher than that of the comparative example.

1 Base material 2 Vapor deposition film 3 Organic coating layer 4 Adhesive layer 5 Second base material 6 Adhesive layer 7 Sealant layer 10 Film formation device P Plasma X Rotating shaft 11A Base material transfer mechanism 11B Plasma pretreatment mechanism 11C Film formation mechanism 12 Decompression chamber 12A Substrate transfer chamber 12B Plasma pretreatment chamber 12C Film formation chamber 13 Unwinding roller 14a to d Guide roll 15 Winding roller 20 Pretreatment roller 21 Electrode portion 23 Magnetic field forming portion 23a First surface 23b Second surface 231 First 1 Magnet 231c 1st axial part 232 2nd magnet 232c 2nd axial part 232d Connection part 24 Evaporation mechanism 24b Boat 25 Film formation roller 31 Power supply wiring 32 Power supply 35a to 35c Partition 50 Plasma supply mechanism 51 Hollow cathode 61 Vapor deposition material Supply part 63 Aluminum steam

Claims (3)

A method for producing a barrier film in which a base material, an aluminum oxide vapor-deposited film, and an organic coating layer are laminated in this order.
When laminating the aluminum oxide vapor deposition film, plasma assist during vapor deposition is performed.
When the aluminum oxide vapor-deposited film was etched from the surface side of the organic coating layer of the barrier film by time-of-flight secondary ion mass spectrometry (TOF-SIMS), the strength derived from the element bond OH was detected.
The strength derived from the elemental bond OH has a downward convex peak continuous from the baseline on the organic coating layer side, and the downward convex peak is the surface side of the organic coating layer in the aluminum oxide vapor-deposited film. A method for producing a barrier film, which is present at a depth of 10% or more and 60% or less. The method for producing a barrier film according to claim 1, wherein the organic coating layer is a cured product of a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin. The method for producing a barrier film according to claim 2, wherein the resin composition further contains a silane coupling agent.

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