JP2020189689A - Packaging bag - Google Patents

Abstract

To provide a packaging body capable of preventing metal products to be packaged from being rusted without requiring a multilayer structure of a conventional technique.SOLUTION: In the packaging body in which metal products rusted by oxidation are hermetically packed in a packaging bag 6, the packaging bag 6 is composed of a laminated film 1a prepared by laminating at least a barrier film 1 and a sealant layer 5; the opposite sealant layers 5 of the laminated film 1a are sealed and jointed at peripheries; in the barrier film 1, a base material layer 2, an aluminum oxide vapor deposition layer 3, and an organic coating layer 4 are laminated in this order; the aluminum oxide vapor deposition layer 3 has an element coupling structure part represented by Al2O3- structure part and Al3- structure part; and the barrier film 1 has a maximum intensity ratio (Al3-/Al2O3-×100) of 1 or more and 20 or less measured by flight time type secondary ion mass spectrometry from the organic coating layer 4.SELECTED DRAWING: Figure 1

Description

The present invention mainly relates to a packaging bag for packaging a metal product.

Packaging bags for packaging metal products have been developed for the purpose of transporting metal products. Such a packaging bag stably exhibits a higher barrier property that is not affected by temperature, humidity, etc., so as to prevent deterioration of the metal product as a content and maintain its function and properties. It is required to obtain.

For example, Patent Document 1 describes a technique relating to a packaging bag or the like formed by mixing a predetermined rust preventive composition with a thermoplastic resin. According to Patent Document 1, this packaging bag is described. , It is possible to prevent the occurrence of rust for a long period of time.

Further, Patent Document 2 includes a base material made of a thermoplastic resin, a first thin-film vapor-deposited thin film layer provided on the base material, and at least a water-soluble polymer provided on the first thin-film vapor-deposited thin film layer. A laminate composed of a gas barrier intermediate layer formed by applying a coating agent and a second thin-film vapor-deposited thin film layer provided on the intermediate layer, and further between the base material and the first thin-film vapor-deposited thin film layer. A gas-barrier laminate provided with a primer layer composed of a polyol, an isocyanate compound, and a silane coupling agent is disclosed.

Patent Document 3 discloses a barrier laminated film in which an aluminum oxide vapor deposition film is formed on the surface of a PET film, and a barrier coating layer is further laminated on the vapor deposition film. However, it is an invention relating to a plasma pretreatment apparatus, and there is no regulation on the amount of oxygen at the time of vapor deposition, and there is no disclosure about both high barrier property and appropriate transparency.

JP-A-2007-308726 WO2002 / 083408 WO 2013/100073

The packaging bag of Patent Document 1 cannot be said to have a sufficient barrier property because it imparts a barrier property by mixing the rust preventive agent composition with the thermoplastic resin.

Further, the barrier laminated film having a multilayer structure of Patent Document 2 has many steps as a manufacturing method. For this reason, not only cost increase such as raw material cost and equipment operating cost, but also complicated work such as quality check for each layer, quality control correction based on the quality control, and history management is required.

An object of the present invention is to provide a package having high barrier property and transparency and capable of preventing rust of a metal product to be packaged, without adopting a multi-layer structure as in the prior art.

As a result of diligent studies to solve the above problems, the present inventors have determined the ratio of the maximum strength of Al ₂ O ₃ ⁻ structural part to the strength of Al ₃ structural part ⁻ contained in the aluminum oxide vapor deposition layer of the barrier film. there, Al ₃ ^- maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) found that high barrier property and transparency by controlling are compatible, and have completed the present invention.

(1) A metal product that rusts due to oxidation is a packaging body sealed and packaged by a packaging bag, and the packaging bag is composed of a laminated film in which at least a barrier film and a sealant layer are laminated, and the laminated film. The periphery of the sealant layers facing each other is hermetically bonded, and in the barrier film, a base material layer, an aluminum oxide vapor deposition layer, and an organic coating layer are laminated in this order, and the organic coating layer is The aluminum oxide vapor-deposited layer is formed of a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin, and the aluminum oxide vapor-deposited layer is an element represented by an Al ₂ O ₃ ^- structured portion and an Al ₃ ^- structured portion. The barrier film has a bonded structure portion, and the barrier film is measured from the organic coating layer side by a flight time type secondary ion mass analysis method (TOF-SIMS), and the Al ₂ O ₃ ^- structure portion and the above. Al ₃ ^- maximum intensity ratio between the structural unit ^{_{(Al 3 - / Al 2 O}} 3 - × 100) is 1 or more and 20 or less, packaging.

(2) The maximum strength of the Al ₃ ^- structure portion exists at a depth position of 4% or more and 45% or less from the surface on the organic coating layer side in the film thickness direction of the aluminum oxide vapor deposition layer (1). Described packaging.

(3) The maximum strength of the Al ₃ ^- structure portion exists at a depth position of 10% or more and 25% or less from the surface on the organic coating layer side in the film thickness direction of the aluminum oxide vapor deposition layer (1) or. The package according to (2).

(4) the barrier film, the oxygen permeability by JIS K 7126 B method is not more than 0.15cc / m2 / day / atm, the water vapor permeability is less than ^{0.2g / m 2 / day, (} 1) The package according to any one of (3).

(5) The package according to any one of (1) to (4), further sealed and packaged with a hygroscopic agent.

The packaging body of the present invention is a packaging body capable of achieving both high barrier properties and transparency and preventing rusting of the metal product to be packaged, without adopting a multi-layer structure as in the prior art.

It is sectional drawing which shows an example of the barrier film which comprises the package body which concerns on this embodiment. It is a perspective view which shows the structure of the packaging bag which comprises the package body which concerns on this embodiment. It is a top view which shows an example of the vapor deposition apparatus which forms the aluminum oxide vapor deposition layer. It is a graph analysis figure of the measurement result by TOF-SIMS of the barrier film in Example 1. 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. It is a graph analysis figure which shows the measurement result by TOF-SIMS of the barrier film in another example.

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".

<< Packaging >>
The package according to the present embodiment is a package in which a metal product that rusts due to oxidation is hermetically packaged in a packaging bag. The packaging bag constituting the packaging body according to the present embodiment makes it possible to prevent rusting of metal products. Hereinafter, the packaging bag constituting the packaging body according to the present embodiment will be described.

<Packaging bag>
This packaging bag is composed of a laminated film in which at least a barrier film and a sealant layer are laminated. As shown in FIG. 1, the barrier film 1 constituting the laminated film 1a has a base material layer 2, an aluminum oxide vapor deposition layer 3, and an organic coating layer 4 laminated in this order. In the laminated film 1a, the sealant layer 5 is further laminated on the surface of the organic coating layer 4 of the barrier film 1. As shown in FIG. 2, the packaging bag 6 is formed by sealing and joining the periphery of the two opposing sealant layers of the laminated films.

In the present specification, "laminated in this order" may mean that the base material layer, the aluminum oxide vapor deposition layer, and the coating layer are laminated in this order, and other layers may be laminated between these layers. The layers may be laminated.

The aluminum oxide vapor deposition layer 3 constituting the packaging bag 6 has an element-bonded structural portion represented by an Al ₂ O ₃ ^- structure portion and an Al ₃ ^- structural portion. The Al ₂ O ₃ ^- structure part and the Al ₃ ^- structure part are the above-mentioned with respect to the strength of the Al ₂ O ₃ ^- structure part measured by the flight time type secondary ion mass spectrometry (TOF-SIMS). Al ₃ structure ^- is the ratio of the maximum intensity of the "Al ₃ ^- maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) " (hereinafter, simply referred to as the maximum intensity ratio) is 1 to 20 It is characterized by being.

According to the views of the present inventors, the barrier property of the barrier film can be improved by controlling the maximum strength ratio of the Al ₃ ^- structure portion. As a result, it is possible to sufficiently impart barrier properties to the barrier film without forming a barrier film having a multi-layer structure, and it is possible to prevent rusting of the metal product to be packaged. The packaging bag and the barrier film on which the aluminum oxide vapor deposition layer in which the maximum strength ratio of the Al ₃ ^- structure is specified is laminated is at least used only for the production of the packaging of the present invention, and the packaging of the present invention. It is indispensable for solving the problems caused by.

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 sample surface. This is a method of mass spectrometry of released secondary ions by mass separation using the time difference in flight time (the 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 ionic strength of the secondary ion, that is, the element to be detected or the molecular ion bonded to the element to be detected. Is converted to depth, 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 sputtering rate is calculated from the depth of the dent and the transition time, and sputtering is performed. It is possible to calculate the depth (sputter amount) from the irradiation time (that is, transition time) or the number of irradiation cycles under the assumption that the speed is constant.

Derived from the aluminum oxide vapor deposition layer of the barrier film, preferably using a Cs (cesium) ion gun to measure to a deep region while repeating soft etching at a constant speed as described above. The intensity ratio of each ion can be calculated by measuring the ions of Al ₃ ⁻ and Al ₂ O ₃ ⁻ and the C ₆ ion derived from the base material layer or the organic coating layer.

For example, if it is an Al ion having a mass number of 27, it will be detected from both the Al ₃ ⁻ structural part and the Al ₂ O ₃ ⁻ structural part. Therefore, the Al ₃ ⁻ structural part and the Al ₂ O ₃ ⁻ structural part It is not suitable as a guideline for quantifying the ratio. In the present invention, Al ₃ having a mass number of 80.94 ^- by calculating the ions, the intensity ratio, Al ₃ ^{- -} and ion mass number 101.94Al ₂ O ₃ structure and the _Al 2 _{O 3} ^- It is possible to quantify the ratio with the structural part.

Further, by specifying the interface between the aluminum oxide vapor deposition layer and the base material layer, it is possible to know at what depth the maximum value of the detected ions exists from the interface. That is, the position where the intensity of the ion of C ₆ becomes half of the maximum value, that is defined as a interface between the base layer and the aluminum oxide vapor deposition layer, the maximum value of the intensity of the detected ions, aluminum oxide It is possible to know the position of the vapor deposition layer at what depth.

The measurement result can be obtained, for example, as a graph as shown in FIG. In the graph of FIG. 4, the unit on the vertical axis (intensity) is the measured ionic strength, and the unit on the horizontal axis (cycle) is the number of etchings.

Then, the depth in the aluminum oxide vapor deposition layer in each cycle, Al ₃ ⁻ strength, and Al ₂ O ₃ ⁻ strength were obtained, and when the maximum Al ₃ ⁻ strength was shown, the Al ₃ ⁻ maximum intensity ratio Al ₃ ⁻ /. al ₂ O ₃ ^- and × 100, it is possible to calculate the ratio of the aluminum layer thickness depth.

Maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) If is less than 1, Al ₃ of aluminum oxide vapor deposited layer ^- in structure is too small, the barrier property tends to decrease. Maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) when is 20 exceeds tend transparency of the aluminum oxide vapor deposition layer is lowered, it is impaired printability as a packaging material and packaging The problem of poor visibility of the contents of aluminum products and the like is likely to occur. The maximum strength ratio is preferably 2 or more, and more preferably 10 or less.

When the maximum strength ratio (Al ₃ ⁻ / Al ₂ O ₃ ⁻ × 100) is 1 or more and 20 or less, the oxygen permeability is 0.02 cc / m when the barrier resin film contains a barrier coating layer. It has a barrier property of ² / day / atm or more and 0.15 cc / m ² / day / atm or less, and the water vapor permeability is 0.02 g / m ² / day or more and 0.2 g / m ² / day or less. can do.

Hereinafter, each layer constituting the barrier film 1 will be described.

[Base layer]
The base material layer 2 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-based resins including polyethylene terephthalate-based resins, polybutylene terephthalate-based resins, polyethylene naphthalate-based resins, and polyamide-based resins; polyolefin-based 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 even among polyester-based resins, polyethylene terephthalate-based resins and polybutylene terephthalate-based resins are preferably used.

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 layer 2.

<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.

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

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 performing an esterification reaction and / or a transesterification reaction between the above dicarboxylic acid component and a diol component and then performing 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 diol unit and dicarboxylic acid unit, and is obtained by polycondensation reaction using ethylene glycol of fossil fuel-derived diol as diol unit and dicarboxylic acid derived from fossil fuel as 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. Examples include agents and coloring pigments. 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. In addition, in this specification, Tm means a melting point.

Since 14C is contained in carbon dioxide in the atmosphere at a constant ratio (105.5 pMC), the 14C content in a plant that grows by taking in 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 biomass degree 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. In addition, in this specification, Tg means a glass transition point.

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, 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 polyester derived from biomass should be suitably used for packaging products such as bags, lid materials, lamitubes, various label materials, sheet molded products, etc., in addition to the adhesive barrier film application of this case. Can be done. 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)". ..

Of the PET contained in the base material layer, the content of the isophthalic acid component is preferably 0.5 mol% or more and 5 mol% or less, preferably 1.0 mol%, in the total dicarboxylic acid components constituting the PET. It is more preferably 2.5 mol% or more. 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 to 100 mol of the dicarboxylic acid or its derivative, but generally, esterification and / or transesterification reaction and / or polycondensation. 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, 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 one hour to several tens of hours in 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 to 40 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, dimer 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 recycled PET may be composed of only recycled PET, or may contain virgin PET in addition to 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 used as two layers, one layer is 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. 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. Examples include agents and coloring pigments. 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 performed 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, the heat fixing treatment is subsequently performed, and the preferable temperature range of the 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 the intended 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 not only for the adhesive barrier film of the present case, but also for packaging products such as bags, lids 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 or more in a width of 15 mm of the test piece 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. 5 to 10. 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 layer formed on the single-layer film. The laminated film is a film containing a plurality of laminated films.

FIG. 5 is a plan view showing the test piece 40 and the loop stiffness measuring instrument 45, and FIG. 6 is a cross-sectional view of the test piece 40 and the loop stiffness measuring instrument 45 of FIG. 5 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. 5 and 6, 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 produced by cutting the film to be measured. You may. Further, the test piece 40 may be produced by cutting a packaging product produced 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. 5 and 6, 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. 7, 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. 8, 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. 8 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. 8, 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 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. 9, 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. 9, 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 61 and then the load cell 48 pushes the loop portion 41 toward the chuck portion 46, as shown in FIGS. 9 and 10. 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. 10, 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. As a result, in the laminated film provided with the high stiffness film, the piercing 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. it 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, the value obtained by dividing the tensile strength of the high stiffness film by the tensile elongation in at least one direction 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, and 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, 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 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 thin-film deposition layer is provided. For example, a high-stiffness film provided with the aluminum oxide-deposited layer 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 layer, it has the same mechanical properties as a single high-stiffness film. For example, the high stiffness film provided with the aluminum oxide vapor deposition layer 3 and the organic coating layer 4 has a loop stiffness of 0.0017 N or more in at least one direction.

In the process of producing a high-stiffness film, for example, first, a plastic film obtained by melting and molding polyester is stretched 3 to 4.5 times at 90 to 145 ° C. in the flow direction and the vertical direction, respectively. The first stretching step is carried out. Subsequently, a second stretching step is carried out in which the plastic film is stretched 1.1 to 3.0 times at 100 to 145 ° C. in the flow direction and the vertical direction, respectively. Then, heat fixing is performed at a temperature of 190 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 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 resin base material may have a single layer or a multi-layer structure of two or more layers, and in the case of a multi-layer 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.

The thickness of the base material layer 2 is not particularly limited, but is preferably 5 μm or more and 25 μm or less, and more preferably 8 μm or more and 15 μm or less. When it is 5 μm or more, the strength of the barrier film can be made preferable. When the thickness is 25 μm or less, the thickness of the entire barrier film can be reduced, so that the transparency is increased and the visibility of the contents is improved.

[Aluminum oxide vapor deposition layer]
The aluminum oxide vapor deposition layer 3 is a thin film of an inorganic oxide containing aluminum oxide as a main component. The aluminum oxide vapor deposition layer 3 has an element-bonded structural portion represented by an Al ₂ O ₃ ^- structure portion and an Al ₃ ^- structure portion, and the Al ₂ O ₃ ^- structure portion and the above-mentioned Al ₃ ^- maximum intensity ratio between the structural unit ^{_{(Al 3 - / Al 2 O}} 3 - × 100) is, and wherein a is 1 or more and 20 or less.

Thus, simply Al ₂ O ₃ ^- rather than the aluminum oxide consisting of only a structural unit, Al ₂ O ₃ ^- improving the barrier properties of the barrier film by controlling the maximum intensity ratio between the structural unit ^- structure and Al ₃ Can be made to.

Specifically, the intensity ratio Al ₃ ⁻ / Al, which is the ratio of the intensity of Al ₃ ⁻ detected by the time-of-flight secondary ion mass spectrometry (TOF-SIMS) to the intensity of Al ₂ O ₃ ^−. ₂ O ₃ ^- it can be represented by. In the present invention, the Al ₃ ⁻ structural part and the Al ₂ O ₃ ⁻ structural part are the strength of Al ₃ ⁻ (strength derived from the element bond Al ₃ ) and the strength of Al ₂ O ₃ ⁻ in TOF-SIMS, respectively. It means the strength derived from the bond Al ₂ O ₃ ). The strength of Al ₃ ⁻ is derived from aluminum, and the strength of Al ₂ O ₃ ⁻ is derived from aluminum oxide.

Here, the time-of-flight secondary ion mass spectrometry (TOF-SIMS) is an ion (secondary) in which a solid sample is irradiated with an ion beam (primary ion) and some of the molecules constituting the surface are ionized and released. Ions) are mass-separated using the time-of-flight difference (the flight time is proportional to the square root of the weight). In the present specification, the intensity ratio Al ₃ ⁻ / Al ₂ O ₃ ⁻ is obtained by irradiating an ion beam from the organic coating layer side of the barrier film to obtain the Al ₂ O ₃ ⁻ structural part derived from the aluminum oxide vapor deposition layer and Al. It is identified by the secondary ions of ₃ ^- structural part.

Judgment of the aluminum oxide vapor deposition layer in the measurement result of TOF-SIMS is that the position where the strength of SiO ₂ , which is a constituent element of the organic coating layer, becomes half of the maximum strength is defined as the interface between the barrier organic coating layer and the aluminum oxide vapor deposition layer. Next, the position where the strength of C6, which is a constituent material of the base material layer, becomes half of the maximum strength is set as the interface between the film base material and the aluminum oxide vapor deposition layer, and the aluminum oxide vapor deposition is performed from the first interface to the second interface. Make a layer.

Then, Al ₃ with an aluminum oxide vapor deposition layer ^- maximum ^- Al ₃ is the intensity of the ratio ^- between the strength and the _Al 2 _{O 3} ^- _{Al 3} in the strength seeking the highest peak position (maximum intensity), its position Calculate the strength ratio (Al ₃ ⁻ / Al ₂ O ₃ ⁻ × 100) and the ratio of the maximum strength of Al ₃ ^{− to} the thickness of the aluminum oxide vapor deposition layer (depth of the aluminum oxide vapor deposition layer from the organic coating layer side). ..

Further, the maximum strength of the Al ₃ ^- structure portion is a depth position of 4% or more and 45% or less of the film thickness of the aluminum oxide vapor deposition layer from the surface of the organic coating layer side (ion beam irradiation side) of the aluminum oxide vapor deposition layer. It is preferably present at a depth of 10% or more and 25% or less. This will be described with reference to FIG. FIG. 11 is a graph analysis diagram showing the measurement results by TOF-SIMS in the barrier film having the structure of the base material / thin-film deposition layer. FIG. 4, which will be described later, shows the measurement results (base material / thin-film deposition layer / organic coating layer) by TOF-SIMS of Example 1, and although there is a difference in the layer structure that the organic coating layer does not exist in FIG. 11, FIG. It can be understood in a pseudo manner as an enlarged view of the vicinity of the vapor deposition film. In FIG. 11, the maximum strength of the Al ₃ ⁻ structural part has a peak between 0 cycle and 10 cycles on the horizontal axis, while the Al ₂ O ₃ ⁻ structural part is widely present from 0 cycle to a little less than 100 cycles. ing. This means that in the aluminum oxide vapor-deposited layer, the Al ₃ ^- structured portion is unevenly distributed on the organic coating layer side, and specifically, it exists at a depth position of 4% or more and 45% or less of the film thickness. doing. Conversely, it means that the maximum strength of the Al ₃ ⁻ structural part does not exist in the vicinity of the substrate interface in the thin-film deposition film, and the Al ₂ O ₃ ⁻ structural part mainly exists. In this way, despite being a single vapor deposition film, the main region of the Al ₃ ⁻ structural part exists in addition to the region of the Al ₂ O ₃ ⁻ structural part on the organic coating layer side of the vapor deposition film, and vapor deposition By adopting a configuration in which the region of the Al ₂ O ₃ ⁻ structural part is mainly present on the base material layer side of the film, the high barrier property derived from the Al ₃ ⁻ structural part and the Al ₂ O ₃ ⁻ structural part have a high barrier property. We have succeeded in achieving both the transparent properties derived from the material and the adhesion to the base material layer, which are contradictory to each other.

In order to make the maximum strength of the Al ₃ ^- structure part 4% or more and 45% or less of the film thickness of the aluminum oxide vapor deposition layer from the surface of the organic coating layer side (ion beam irradiation side) of the aluminum oxide vapor deposition layer. It can be adjusted by controlling the oxygen concentration during vapor deposition during the formation of the aluminum oxide vapor deposition layer, and in order to make it more preferably 10% or more and 25% or less, the conditions of pretreatment, especially oxygen plasma treatment, and the aluminum oxide vapor deposition layer It can be adjusted by controlling the combination with the oxygen concentration at the time of vapor deposition at the time of formation. It is presumed that the pretreatment with an appropriate oxygen plasma promotes the oxidation of Al on the substrate layer side of the vapor-deposited film as compared with the organic coating layer side, and as a result, it is presumed that Al ₃ ^- structured parts are less likely to be formed. It has succeeded in maintaining transparency as a whole.

The aluminum oxide vapor deposition layer contains a small amount of aluminum compounds such as aluminum nitrides, carbides, and hydroxides alone or a mixture thereof, silicon oxides, silicon nitrides, silicon oxide nitrides, silicon carbides, and oxidations. It may contain metal oxides such as magnesium, titanium oxide, tin oxide, indium oxide, zinc oxide and zirconium oxide, or metal nitrides, carbides and mixtures thereof.

The thickness of the aluminum oxide vapor-deposited layer is not particularly limited, but is preferably 5 nm or more and 100 nm or less, and more preferably 8 nm or more and 30 nm or less. When the thickness of the aluminum oxide vapor-deposited layer is 5 nm or more, the barrier property of the barrier film is improved. When the thickness of the aluminum oxide vapor-deposited layer is 100 nm or less, the transparency of the adhesive barrier film can be further improved.

Further, the Al ₃ ⁻ structural part is not as transparent as the Al ₂ O ₃ ⁻ structural part. Therefore, in addition to the above-mentioned maximum intensity ratio, the Al ₃ ^- structure part can be quantified by the total light transmittance (total light transmittance), haze, and color difference (L value of the Lab color system). Specifically, the total light transmittance of the barrier film in which the base material layer, the aluminum oxide vapor deposition layer, and the organic coating layer are laminated is preferably 85% or more and 89.0% or less, and 86% or more and 88. 5% or less is more preferable. The haze of the barrier film in which the base material layer, the aluminum oxide vapor deposition layer, and the organic coating layer are laminated is preferably 2.15% or more and 3.0% or less, and 2.2% or more and 2.5% or less. More preferred. As for the color difference (L ^* a ^* b ^* color system), it is preferable that L ^* is 98 or more and less than 100. b ^* is preferably 0.50 or more and 1.00 or less, more preferably 0.80 or more and 1.00 or less, and particularly preferably 0.90 or more and 1.00 or less. The total light transmittance is measured based on JIS K7361, and the haze is measured based on JIS K7136. The color difference (L ^* a ^* b ^* color system) is measured based on JIS Z8722.

[Organic coating layer]
The organic coating layer 4 mechanically and chemically protects the aluminum oxide vapor-deposited layer and improves the barrier performance of the barrier film.

The organic coating layer 4 is formed of a coating agent for an organic coating layer containing a metal alkoxide and preferably a hydroxyl group-containing water-soluble resin having a saponification degree of 90% or more and 100% or less. In the organic coating layer, the metal alkoxide produces a condensation reaction product, but a copolymer may be produced with a hydroxyl group-containing water-soluble resin.

The mass ratio hydroxyl group-containing water-soluble resin / metal alkoxide is preferably 5/95 or more and 20/80 or less, and more preferably 8/92 or more and 15/85 or less. If it is smaller than the above range, the barrier effect of the organic coating layer tends to be insufficient, and if it is larger than the above range, the rigidity and brittleness of the organic coating layer tend to increase.

The metal alkoxide is represented by the general formula R _1n M (OR ₂ ) _m (wherein R ₁ and R ₂ represent a hydrogen atom or an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n. Represents an integer of 0 or more, and m represents an integer of 1 or more. Each of a plurality of R ₁ and R _{2 in} one molecule may be the same or different). To.

Specific examples of the metal atom represented by M of the metal alkoxide include silicon, zirconium, titanium, aluminum, tin, lead, borane, and the like. For example, alkoxy in which M is Si (silicon). It is preferable to use silane.

The alkoxysilane is represented by the general formula R _1n Si (OR ₂ ) _m (where n + m = 4). Therefore, when alkoxysilane is used, the organic coating layer has an elemental bond structure represented by a SiO ₂ structure.

In the above, specific examples of OR ₂ include a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an i-propoxy group, a butoxy group, and a 3-methacryloxy group. Examples thereof include an alkoxy group such as a 3-acryloxy group and a phenoxy group, or a phenoxy group.

In the above, specific examples of R ₁ include methyl group, ethyl group, n-propyl group, isopropyl group, phenyl group, p-styryl group, 3-chloropropyl group, trifluoromethyl group, vinyl group and γ-gly. Examples thereof include a sidoxylpropyl group, a methacryl group and a γ-aminopropyl group.

Specific examples of the alkoxysilane include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and the like. Methyltributoxysilane, methyltriphenoxysilane, phenylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxy Silane, isopropyltriethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltri Examples thereof include various alkoxysilanes such as ethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, and 1,6-bis (trimethoxysilyl) hexane, and phenoxysilane.

In alkoxysilane, when R ₁ is an organic group having a functional group such as a vinyl group, an epoxy group, a methacryl group and an amino group, it is generally called a silane coupling agent.

Specific examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Therefore, γ-glycidoxypropyltrimethoxysilane is suitable.

The above metal alkoxide may be used alone or in combination of two or more, and it is particularly preferable to use a silane coupling agent in combination. When a silane coupling agent is used in combination, it is preferable to use 2% by mass or more and 15% by mass or less of the total metal alkoxide as the silane coupling agent.

(Hydroxy group-containing water-soluble resin)
The hydroxyl group-containing water-soluble resin can be dehydrated and copolymerized with a metal alkoxide, and the degree of saponification is preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, and 99% or more and 100. % Or less is more preferable. If the degree of saponification is smaller than the above range, the hardness of the organic coating layer tends to decrease.

Specific examples of the hydroxyl group-containing water-soluble resin include polyvinyl alcohol-based resins, ethylene / vinyl alcohol copolymers, polymers of bifunctional phenol compounds and bifunctional epoxy compounds, and the like, each of which is used alone. It may be used, two or more kinds may be mixed and used, or may be copolymerized and used. Among these, polyvinyl alcohol is particularly preferable, and polyvinyl alcohol-based resin is preferable because it is excellent in flexibility and affinity.

Specifically, for example, a polyvinyl alcohol-based resin obtained by saponifying polyvinyl acetate or an ethylene / vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate is used. can do.

Examples of such polyvinyl alcohol-based resins include "RS-110 (degree of polymerization = 99%, degree of polymerization = 1000)", which is an RS resin manufactured by Kuraray Co., Ltd., and "Gosenol NM-" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 14 (degree of saponification = 99%, degree of polymerization = 1400) ”and the like.

The thickness of the organic coating layer is not particularly limited, but is preferably 150 nm or more and 800 nm or less, and more preferably 250 nm or more and 600 nm or less. When the thickness of the organic coating layer is 150 nm or more, the barrier property can be more effectively imparted. When the thickness of the organic coating layer is 800 nm or less, the transparency can be further improved.

Next, the sealant layer constituting the laminated film will be described.

[Sealant layer]
The sealant layer is a layer in which the sealant layers are joined to each other mainly by heat-sealing the sealant layers. The sealant layer is mainly composed of a resin, and the melting point of the resin is usually lower than that of the resin constituting another layer such as a base material layer.

As the sealant layer, for example, one kind or two or more kinds of resins selected from polyethylene such as low density polyethylene and linear low density polyethylene, polypropylene, and the like can be used. The sealant layer may be a single layer or may be a multi-layer.

The thickness of the sealant layer is preferably 20 μm or more and 100 μm or less, and more preferably 30 μm or more and 80 μm or less.

Next, the metal products packaged in the packaging bag will be described.

[Metal products]
A metal product is a metal product that rusts due to oxidation. The metal product is a product containing at least a part of metal, and examples thereof include various electric appliances and electronic devices.

Then, this metal product is hermetically packaged in a packaging bag. As described above, since this packaging bag has excellent barrier properties, it is possible to prevent rusting of the metal product to be packaged by sealing and packaging the bag.

It is preferable that this sealed packaging is packaged in a state where the metal product is kept out of contact with oxygen and / or water vapor as much as possible. For example, a method of packaging a metal product in a packaging bag and sealing while sucking air in the packaging bag, a method of sealing and packaging in the presence of an oxygen scavenger and / or a hygroscopic agent, or a low oxygen and low humidity state ( For example, a method of sealing and packaging with air having an oxygen concentration of 10% by mass or less, preferably 1% by mass or less, or air having a humidity of 10% or less, preferably 1% or less, or in the presence of nitrogen or a rare gas) can be mentioned. In addition, you may combine these methods.

Next, a method for producing the barrier film will be described.

<Manufacturing method of barrier film>
In the method of producing a barrier film, for example, a resin film (base material layer) is subjected to oxygen plasma treatment, and aluminum is vapor-deposited on the surface of the plasma-treated resin film in an oxygen atmosphere to form an aluminum oxide vapor-deposited layer for oxidation. Examples thereof include a method in which a coating agent composition for a coating layer is applied to the surface of an aluminum vapor-deposited layer, dried to form a coating layer, and a sealant layer is laminated on the coating layer by a melt extrusion method.

[Plasma processing]
In the barrier film according to the present embodiment, the adhesion between the aluminum oxide vapor-deposited layer and the base material tends to be easily lowered by increasing the Al ₃ ^- structure portion in the aluminum oxide-deposited layer. Therefore, by treating the resin film (base material layer) with oxygen plasma, the degree of oxidation of the aluminum oxide-deposited layer on the surface of the base material can be increased, and the adhesion between the aluminum oxide-deposited layer and the base material can be improved.

In the plasma treatment, it is preferable that the plasma raw material gas to be supplied is a gas alone or a mixed gas with an inert gas having a high oxygen partial pressure.

FIG. 3 shows an example (plan view) of an apparatus for plasma treatment and forming an aluminum oxide vapor deposition layer. A part of the plasma pretreatment roller 20 for transporting the resin base material S to be pretreated and enabling the plasma treatment is provided in the plasma pretreatment chamber 12B so as to be exposed to the resin base material transport chamber 12A. The resin base material S moves to the plasma pretreatment chamber 12B while being wound up.

The plasma pretreatment chamber 12B is configured so that the space generated by the plasma is separated from other regions and the facing space can be efficiently evacuated, so that the plasma gas concentration can be easily controlled and the productivity is improved. To do. The pretreatment pressure formed by reducing the pressure can be set and maintained at about 0.1 Pa or more and 100 Pa or less, and is particularly preferably 1 Pa or more and 20 Pa or less.

The transport speed of the resin base material S is not particularly limited, but can be 200 m / min or more and 1000 m / min or less from the viewpoint of production efficiency, and is particularly preferably 300 m / min or more and 800 m / min or less.

The plasma treatment includes a plasma supply means and a magnetizing means. The plasma treatment cooperates with the plasma pretreatment roller 20 to confine the oxygen plasma P in the vicinity of the surface of the resin base material S. Specifically, the plasma supply means and the magnetizing means constituting the plasma pretreatment means are arranged along the surface near the outer periphery of the pretreatment roller 20 to supply the pretreatment roller 20 and the plasma raw material gas, and the plasma P. It is installed so as to form a gap sandwiched between the plasma supply nozzles 22a to 22c, which also serve as electrodes for generating the plasma P, and a magnetic forming means having a magnet 21 or the like in order to promote the generation of the plasma P.

The voltage between the pretreatment roller 20 and the plasma supply nozzles 22a to 22c is a frequency of 10 Hz to 2.5 GHz, an AC voltage of 50 volts or more and 1000 volts or less, input power control, impedance control, etc. Therefore, the voltage is in an arbitrary stable applied state.

The plasma supply means in the plasma processing includes a raw material volatilization supply device 18 connected to a plasma supply nozzle provided outside the decompression chamber 12 and a raw material gas supply line for supplying the raw material gas from the device. As the plasma raw material gas to be supplied, 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.

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.

[Formation of aluminum oxide vapor deposition layer]
As the vapor deposition method for forming the aluminum oxide vapor deposition layer, various vapor deposition methods can be applied from physical vapor deposition and chemical vapor deposition. The physical vapor deposition method can be selected from the group consisting of a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, and a cluster ion beam method, and the chemical vapor deposition method includes a plasma CVD method, a plasma polymerization method, and a thermal vapor deposition method. It can be selected from the group consisting of the CVD method and the catalytic reaction type CVD method. In the adhesive barrier film according to the present embodiment, the vapor deposition method of the physical vapor deposition method is suitable.

The thin-film deposition film film forming apparatus is arranged in the depressurized film forming chamber 12C, and the resin substrate S is wound and conveyed with the treated surface of the resin substrate S pretreated by the plasma pretreatment apparatus on the outside. A vapor-deposited film (aluminum oxide vapor-deposited layer) is formed on the surface of the resin base material by evaporating the film-forming roller 23 to be film-formed and the target of the thin-film film forming means 24 arranged to face the film-forming roller.

The thin-film vapor deposition film forming means 24 is a resistance heating method, and uses an aluminum metal wire rod as an evaporation source of aluminum, supplies oxygen to oxidize aluminum vapor, and forms an aluminum oxide thin-film deposition layer on the surface of the resin base material S. Form.

Oxygen, even oxygen itself, or may be a supply of a mixed gas of an inert gas such as argon but, Al ₃ ^- Maximum intensity ratio of the structural unit ^{_{(Al 3 - / Al 2 O}} 3 - × 100) is 1 The amount of oxygen is controlled so as to be 20 or more and 20 or less. In one example of the examples, the oxygen supply amount is preferably 7,000 sccm or more and 12000 sccm or less, and more preferably 8000 sccm or more and 10000 sccm or less. Within this range, barrier properties, transparency, and adhesion can be achieved at the same time.

Further, the evaporation of aluminum can be performed, for example, by arranging a plurality of aluminum metal wires in the axial direction of the roller 23 in a boat-shaped (referred to as “boat type”) vapor deposition container and heating them by a resistance heating method.

In this way, aluminum is evaporated while adjusting the amount of heat and the amount of heat supplied, and the amount of oxygen supplied is adjusted to control the reaction between aluminum and oxygen to form an aluminum oxide vapor deposition layer. be able to.

[Formation of organic coating layer]
First, a metal alkoxide, a hydroxyl group-containing water-soluble resin, a reaction accelerator (Zolgel method catalyst, acid, etc.), and an organic solvent such as water as a solvent, an alcohol such as methyl alcohol, ethyl alcohol, or isopropanol are mixed, and the organic coating layer is mixed. Prepare a coating composition for use.

Next, the coating agent composition for an organic coating layer is applied to the surface of the aluminum oxide vapor deposition layer or the like by a conventional method and dried. By this drying step, the condensation or cocondensation reaction further proceeds to form a coating film. 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, heat treatment is carried out at a temperature in the range of 20 ° C. or higher and 200 ° C. or lower, preferably 50 ° C. or higher and 180 ° C. or lower, and a temperature of 3 seconds or longer and 10 minutes or shorter at a temperature equal to or lower than the melting point of the resin substrate. As a result, an organic coating layer made of the organic coating layer coating composition can be formed on the surface of the aluminum oxide vapor deposition layer.

It is preferable that the organic coating layer is formed in-line after the aluminum oxide vapor deposition layer is formed without being exposed to the outside air.

[Lamination of sealant layer]
The sealant layer may be laminated on the surface of the organic coating layer by a melt extrusion method, or the sealant layer made of a thermoplastic resin film previously formed by a dry laminating method and the organic coating layer are bonded together. You may. Further, the sealant layer is preferably unstretched.

<Manufacturing method of packaging bag>
The packaging bag is manufactured by joining the sealant layers of the barrier film to each other, heat-sealing at a temperature equal to or higher than the melting point of the resin constituting the sealant layer, and sealing and joining the surroundings.

The shape of the packaging bag may be a conventionally known shape, for example, a gusset shape or a horizontal gusset shape, or a stand bag shape using another barrier film. It is preferably sealed for the purpose of improving the rust prevention property of the metal product.

<Manufacturing method of packaging>
The package according to the present embodiment is manufactured by sealing and packaging a metal product with the above-mentioned packaging bag. The method of sealing and packaging a metal product can be produced by sealing and joining the periphery of the sealant layers while sucking air. Further, the metal product may be hermetically sealed and packaged in a low oxygen state.

The package is not particularly limited as long as it seals and packages only the metal product, but it is preferable to seal and package the hygroscopic agent and / or the oxygen scavenger together with the metal product. This makes it possible to more effectively prevent rust on the packaged metal product.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these descriptions.

<Aluminum oxide vapor deposition layer formation>
First, a roll was prepared by winding a polyester film having a thickness of 12 μm (hereinafter referred to as PET film) as a resin base material.

Next, the following plasma conditions were set in the pretreatment section by using a continuous vapor deposition film deposition apparatus in which the pretreatment section in which the plasma pretreatment device was arranged and the film formation section were separated on the surface of the PET film on which the aluminum oxide vapor deposition layer was provided. Below, plasma is introduced from the plasma supply nozzle, plasma pretreatment is performed at a transport speed of 400 m / min, and in the film-forming section that is continuously transported, a reactive resistance is used as a heating means for the vacuum vapor deposition method on the plasma treated surface under the following conditions. An aluminum oxide vapor-deposited layer having a thickness of 12 nm was formed on a PET film by a heating method to obtain a roll-wound barrier film, and various evaluations were carried out.

(Plasma pretreatment conditions)
・ Plasma intensity: 150 W ・ sec / m2
-Plasma forming gas ratio: Oxygen / argon = 2/1
・ Voltage applied between pretreatment drum and plasma supply nozzle: 340V
・ Pretreatment pressure: 3.8 Pa

(Aluminum oxide film formation conditions)
・ Vacuum degree: 8.1 × 10 ^-2 Pa
・ Transport speed: 400m / min
・ Oxygen gas supply: 8000 sccm

<Preparation of coating composition for coating layer>
226 g of water, 39 g of isopropyl alcohol and 5.3 g of 0.5N hydrochloric acid were mixed, and 167 g of tetraethoxysilane and 9.2 g of glycidoxypropyltrimethoxysilane were cooled to 10 ° C. in a solution adjusted to pH 2.2. Solution A was prepared by mixing with each other.

A solution B was prepared by mixing 23.3 g of polyvinyl alcohol having a degree of polymerization of 99% or more, 513 g of water, and 27 g of isopropyl alcohol.

The solution obtained by mixing the solution A and the solution B so as to have a weight ratio of 4.4: 5.6 was used as a coating agent composition for an organic coating layer.

The coating agent composition for a coating layer prepared above was coated on the aluminum oxide vapor-deposited layer 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 coating layer having a thickness of about 400 nm on the aluminum oxide vapor-deposited layer to obtain a barrier film with an organic coating layer.

Intensity ratio in ^{_{TOF-SIMS Al 3 - / Al}} 2 O 3 - × 100]
For the barrier film with an organic coating layer, use a time-of-flight secondary ion mass spectrometer (OTOF.SIMS5, manufactured by ION TOF) from the organic coating layer side of the barrier film under the following measurement conditions, Cs (cesium). ) while repeating soft etching at a constant speed by an ion gun, _{C 6} (mass number 72.00 derived from the resin base material), Al ₃ from oxidation Arumiumu deposited layer ^- (mass number 80.94), _Al 2 _{O 3} ^- (Mass number 101.94), mass spectrometry of SiO ₂ (mass number 59.96) ions derived from the coating layer was performed. A graph analysis diagram of the measurement results is shown in FIG.

Strength of SiO ₂ is a constituent element of the organic coating layer, the position where the half of the maximum intensity as the interface of the coating layer and the aluminum oxide vapor deposition layer, then the intensity of C ₆ a constituent material of the resin substrate, the maximum The position where the strength was halved was defined as the interface between the resin base material and the aluminum oxide vapor deposition layer, and the interface from the first interface to the second interface was defined as the aluminum oxide vapor deposition layer.

Then, Al ₃ with an aluminum oxide vapor deposition layer ^- strength determine the highest position (maximum intensity) of, Al ₃ at that position ^- between the strength and the _Al 2 _{O 3} ^- is the intensity ratio between the Al ₃ ^- maximum intensity The ratio (Al ₃ ⁻ / Al ₂ O ₃ ⁻ × 100) and the ratio of Al ₃ ^{− to} the maximum strength aluminum oxide vapor deposition layer thickness (depth from the organic coating layer side in the aluminum oxide vapor deposition layer, unit%). Calculated.

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

Maximum intensity ratio between the structural unit ^{_{(Al 3 - - / Al 2}} O 3 - × 100) Al 2 O 3 aluminum oxide deposited layer ^- structure and Al ₃ was 5.1.

[Example 1]
<Manufacturing of laminated film>
A laminated film was produced by applying an adhesive to the surface of the organic coating layer of the barrier film produced as described above and laminating unstretched polypropylene (sealant layer) having a thickness of 70 μm.

<Manufacturing of packaging bags>
The packaging bag of Example 1 was produced by abutting the sealant layers of the two barrier films 1 against each other and heat-sealing the surroundings at a melting point equal to or higher than that of unstretched polypropylene.

[Example 2]
In the packaging bag of Example 1, the packaging bag of Example 2 in which a hygroscopic agent (5 g of Oasis silica gel manufactured by Oasis Planning Co., Ltd.) was packaged inside the packaging bag was manufactured.

[Example 3]
In the packaging bag of Example 1, the packaging bag of Example 3 in which an oxygen scavenger (Everfresh QJ-50 manufactured by Torishige Sangyo Co., Ltd.) was packaged inside the packaging bag was manufactured.

[Comparative Example 1]
Instead of the barrier film 1, the sealant layers of the vaporizable rust preventive films (PIPAK manufactured by Nihon Parkerizing Co., Ltd.) were brought into contact with each other and the surroundings were heat-sealed to produce the packaging bag of Comparative Example 1.

[Comparative Example 2]
In the packaging bag of Comparative Example 1, the packaging bag of Comparative Example 2 in which a hygroscopic agent (silica gel) was packaged inside the packaging bag was manufactured.

[Comparative Example 3]
In the packaging bag of Comparative Example 1, the packaging bag of Comparative Example 3 in which the oxygen scavenger was packaged inside the packaging bag was manufactured.

<Rust prevention test>
A rust preventive test was conducted using the packaging bags of Examples and Comparative Examples. Specifically, an iron plate (cold rolled steel plate (SPCC), 50 mm × 50 mm × 1 mm) and a copper plate (tough pitch copper plate C1100P-1 / 4H, 50 mm × 50 mm × 1 mm) are degreased in the packaging bags of Examples and Comparative Examples. After that, the package was packaged to produce a package, and a standing test (temperature: 60 ° C., humidity: 90% RH, 14 days) was performed, and the appearance after the standing test was evaluated according to the following evaluation criteria.
[Evaluation criteria]
◎: No rust, no discoloration ◎ ~ 〇: Spot rust, slight discoloration 〇: Rust occurs less than 10% of the area of the test piece ×: Rust occurs 10% or more and less than 50% of the area of the test piece XX: Rust occurs in 50% or more of the area of the test piece

From Table 1, it can be seen that the packaging bag (packaging body) of the example can prevent rust of the metal product to be packaged without adopting a multi-layer structure.

<Creation and evaluation of laminated film>
(Laminated film 3)
The laminated film 3 was obtained by producing the laminated film 1 in the same manner except that the amount of oxygen gas supplied was set to 10000 sccm. In the organic coating layer with barrier film, Al ₃ of aluminum oxide deposited layer ^- the maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) was measured in the same manner described above, it was 3.7.

(Laminated film 4)
The laminated film 1 was manufactured in the same manner except that the pretreatment (plasma treatment) was not performed, to obtain a laminated film 4. In the organic coating layer with barrier film, Al ₃ of aluminum oxide deposited layer ^- the maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) was measured in the same manner described above, it was 4.5.

(Laminated film 5)
The base material in the laminated film 1 was a biaxially stretched polyester film (biomass PET film) derived from the following biomass, and the laminated film 5 was produced in the same manner except that the plasma intensity of the pretreatment was 250 W · sec / m ^2. Obtained. In the organic coating layer with barrier film, Al ₃ of aluminum oxide deposited layer ^- the maximum intensity ratio _{^{(Al 3 - / Al 2 O}} 3 - × 100) was measured in the same manner described above, it was 4.9.
<Synthesis of biomass-derived polyester>
After performing an esterification reaction of 83 parts by mass of terephthalic acid and 62 parts by mass of biomass ethylene glycol (manufactured by India Glycol) by a conventional direct weight method, a polycondensation reaction was carried out under reduced pressure to carry out a biomass-derived polyethylene. Obtained terephthalate.
<Making resin film>
60 parts by mass of the above biomass-derived polyethylene terephthalate, 30 parts by mass of fossil fuel-derived polyethylene terephthalate, and 10 parts by mass of a masterbatch containing fossil fuel-derived polyethylene terephthalate are supplied to an extruder and sheet-shaped from a T-die. And solidified by cooling with a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was stretched in the longitudinal direction and then stretched in the lateral direction to obtain a biaxially stretched polyester film having a thickness of 12 μm. The biomass degree of the obtained biaxially stretched polyester film was measured and found to be 18.8%.

(Laminated film 6)
The laminated film 6 was obtained by producing the laminated film 1 in the same manner except that the amount of oxygen gas supplied was set to 20000 sccm. The Al ₃ ⁻ maximum strength ratio (Al ₃ ⁻ / Al ₂ O ₃ ⁻ × 100) of the aluminum oxide vapor-deposited layer in the barrier film with an organic coating layer was measured in the same manner as described above and found to be 0.8.

(Laminated film 7)
The laminated film 1 was manufactured in the same manner except that the amount of oxygen gas supplied was set to 6000 sccm, to obtain a laminated film 7. In the organic coating layer with barrier film, Al ₃ of aluminum oxide deposited layer ^- the maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) was measured in the same manner described above, it was 25. Since it was visually colored and was inferior in printability, it was not used for further evaluation.

Regarding the barrier film with an organic coating layer before laminating the adhesive layer in the laminated films 1, 3 to 7, the vapor deposition pretreatment conditions, the vapor deposition conditions, the TOF-SIMS analysis values, and the evaluation results (oxygen / water vapor barrier, total light rays). (Transmittance, haze, color difference) are summarized in Table 2.

<Oxygen permeability>
Using an oxygen permeability measuring device (OX-TRAN2 / 21 manufactured by MOCON), set the barrier film with an organic coating layer so that the resin base material side is the oxygen supply side, and comply with the JIS K 7126 B method. The oxygen permeability was measured at 23 ° C. under a 90% RH atmosphere.

<Water vapor permeability>
Using a water vapor permeability measuring device (PERMATRAN 3/33, manufactured by MOCON), set the barrier film with an organic coating layer so that the resin substrate layer side is on the sensor side, and comply with the JIS K 7126 B method. The water vapor permeability was measured at 40 ° C. in a 100% RH atmosphere.

<Optical characteristics>
Total light transmittance was measured based on JIS K7136 using a haze meter. The color difference (L ^* a ^* b ^* color system) was measured based on JIS Z8722 using a spectrophotometer CM-700d. A barrier film with an organic coating layer was placed on a white plate for measurement. Regarding "visual coloring", a barrier film with an organic coating layer was placed on a white plate and visually observed, and those in which coloring was not observed were evaluated as ◯, and those in which coloring was observed were evaluated as x.

From Table 2, the maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) is, the laminated film 1 and 3 to 5 is 1 to 20 is seen to be both high barrier properties and transparency ..

On the other hand, the maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) is, oxygen permeability of the laminated film 6 is less than 1 is ^{0.2cc / m 2 / day / atm} , the water vapor permeability 0 It was .5 g / m ² / day. On the other hand, the maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) is 20 greater laminated film 7, although oxygen permeability and water vapor permeability was good, and darkened the barrier film, The transparency was reduced.

From the above, _Al 2 _{O 3} aluminum oxide deposited layer ^- structure and Al ₃ ^- maximum intensity ratio between the structural unit ^{_{(Al 3 - / Al 2 O}} 3 - × 100) is located according to the invention in 1 to 20 It can be seen that the barrier film is a package that has both high barrier properties and transparency and can prevent rusting of the metal product to be packaged, even if it does not have a multi-layer structure.

1 Barrier film 1a Laminated film 2 Base material layer 3 Aluminum oxide vapor deposition layer 4 Organic coating layer 5 Sealant layer 6 Package 10 Roller type continuous vapor deposition film deposition equipment S Resin base material P Plasma 12 Pressure reducing chamber 12A Resin base material transfer chamber 12B Plasma pretreatment chamber 12C Film deposition chamber 14a to d Guide roll 18 Raw material gas volatilization supply device 20 Pretreatment roller 21 Magnet 22 Plasma supply nozzle 23 Film formation roller 24 Thin film deposition film deposition means 31 Power supply wiring 32 Power supply 35a to 35c Partition

Claims (5)

A metal product that rusts due to oxidation is a package that is sealed and packaged in a packaging bag.
The packaging bag is composed of a laminated film in which at least a barrier film and a sealant layer are laminated, and the periphery of the sealant layers facing each other of the laminated film is hermetically bonded.
In the barrier film, a base material layer, an aluminum oxide vapor deposition layer, and an organic coating layer are laminated in this order.
The organic coating layer is formed of a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin.
The aluminum oxide vapor-deposited layer has an element-bonded structural portion represented by an Al ₂ O ₃ ^- structure portion and an Al ₃ ^- structure portion.
Maximum ^- the barrier film from the organic coating layer side is measured by the time-of-flight secondary ion mass spectrometry (TOF-SIMS), the _Al 2 _{O 3} ^- the relative strength of the structure Al ₃ structure it is the ratio of the intensity, Al ₃ ^- maximum intensity ratio ^{_{(Al 3 - / Al 2 O}} 3 - × 100) is 1 or more and 20 or less, packaging. The packaging according to claim 1, wherein the maximum strength of the Al ₃ ^- structured portion exists at a depth position of 4% or more and 45% or less from the surface on the organic coating layer side in the film thickness direction of the aluminum oxide vapor deposition layer. body. The packaging according to claim 1, wherein the maximum strength of the Al ₃ ^- structure portion exists at a depth position of 10% or more and 25% or less from the surface on the organic coating layer side in the film thickness direction of the aluminum oxide vapor deposition layer. body. The barrier film has an oxygen permeability of 0.15 cc / m ² / day / atm or less and a water vapor permeability of 0.2 g / m ² / day or less according to the JIS K 7126 B method, claims 1 to 3. The packaging described in any of. The package according to any one of claims 1 to 4, wherein the hygroscopic agent is hermetically packaged.

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