WO2018062329A1

WO2018062329A1 - Film and film production method, and packaging material equipped with film

Info

Publication number: WO2018062329A1
Application number: PCT/JP2017/035076
Authority: WO
Inventors: 田中　大介; 満武士田; 鈴木　梓; 和弘多久島
Original assignee: 大日本印刷株式会社
Priority date: 2016-09-30
Filing date: 2017-09-27
Publication date: 2018-04-05
Also published as: JP2018058355A; JP7098900B2

Abstract

The present invention provides a film that exhibits piercing resistance and heat resistance, and has gas-barrier properties. This film is provided with: a substrate; and a deposition layer which is disposed on the substrate and contains a metal or an alloy. The substrate contains at least 51 mass% of polybutylene terephthalate. Formed at the interface between the substrate and the deposition layer is a covalent bond between a metal atom and a carbon atom.

Description

Film, film manufacturing method, and packaging material provided with film

The present invention relates to a base material and a film having a vapor deposition layer provided on the base material and a film manufacturing method. The present invention also relates to a packaging material comprising a film and a thermoplastic resin layer laminated on the film via an adhesive layer.

Conventionally, various packaging materials have been developed and proposed for filling and packaging various articles such as foods and drinks, pharmaceuticals, chemicals, cosmetics, and others. In such packaging materials, various physical properties are required as packaging materials, although they vary depending on the packaging purpose, contents to be filled, storage / distribution of packaged products, and others. For example, as one of those physical properties, there is a gas barrier property that prevents permeation of oxygen, water vapor, and the like.

Conventionally, various gas barrier materials that prevent permeation of oxygen and water vapor have been developed and proposed. For example, gas barrier materials such as aluminum foil or nylon film or polyethylene terephthalate film having a polyvinylidene chloride resin coating film, polyvinyl alcohol film, saponified ethylene-vinyl acetate copolymer film, polyacrylonitrile resin film, etc. Has been developed and proposed.

Further, in recent years, a transparent barrier film having a structure in which a vapor-deposited layer of an inorganic oxide such as silicon oxide or aluminum oxide is provided on a plastic substrate, or a vapor-deposited layer of a metal such as aluminum is provided. Barrier films and the like have also been proposed. For example, Patent Document 1 proposes producing a barrier film by forming an inorganic oxide vapor deposition layer on a nylon film.

JP 2007-303000 A

The packaging material is required to have so-called stab resistance that prevents the bag from tearing when a sharp member with a sharp tip contacts the packaging bag. The nylon film described in Patent Document 1 is known as a film having high puncture resistance. On the other hand, nylon is easy to absorb moisture and has poor heat resistance. Therefore, it is difficult to use the nylon film as a film constituting the outer surface of the packaging material. For example, in Patent Document 1, a base film containing a polyester-based resin or the like is laminated on an outer surface side of a nylon film via an adhesive layer. Thus, since the packaging material includes two plastic films, that is, a nylon film and a base film, the cost of the packaging material is increased.

The present invention aims to provide a bag that can effectively solve such problems.

The present invention comprises a base material and a vapor deposition layer provided on the base material and containing a metal or an alloy, the base material containing 51% by mass or more of polybutylene terephthalate, and the base material and the vapor deposition In this film, a covalent bond between a metal atom and a carbon atom is formed at the interface with the layer.

In the film according to the present invention, the base material may contain 60% by mass or more of polybutylene terephthalate.

The film according to the present invention may further include a gas barrier coating film provided on the vapor deposition layer.

In the film according to the present invention, the vapor deposition layer may be a transparent vapor deposition layer.

In the film according to the present invention, the vapor deposition layer may be composed of an inorganic oxide containing aluminum oxide or a mixture of a plurality of inorganic oxides.

In the film according to the present invention, the inorganic oxide may be a mixture of aluminum oxide and one or more inorganic oxides selected from silicon oxide, magnesium oxide, tin oxide, and zinc oxide.

In the film according to the present invention, the thickness of the vapor deposition layer may be 5 nm and 200 nm or less.

The present invention comprises a step of preparing a base material, and a vapor deposition step of depositing a metal or an alloy on the base material to form a vapor deposition layer on the base material, wherein the base material is 60% by mass or more. And a covalent bond of a metal atom and a carbon atom is formed at the interface between the base material and the vapor deposition layer.

The film manufacturing method according to the present invention may further include a plasma pretreatment step in which a plasma treatment is performed on the substrate to form a plasma treatment surface on the substrate. In this case, the said vapor deposition process forms the said vapor deposition layer on the said plasma processing surface of the said base material.

In the film manufacturing method according to the present invention, in the plasma pretreatment step, the substrate is held between the plasma pretreatment roller and the plasma supply unit in a state where a voltage is applied between the plasma pretreatment roller and the plasma supply unit. And the process of forming a plasma processing surface in the said base material may be included. In this case, the said vapor deposition process forms the said vapor deposition layer on the said plasma processing surface of the said base material following the said plasma pretreatment process.

In the film manufacturing method according to the present invention, in the plasma pretreatment step, a roller-type film formation facility in which a pretreatment section for performing plasma treatment on the substrate and a film formation section for forming the vapor deposition layer are continuously arranged. May be implemented. In this case, preferably, the roller-type film-forming facility is configured such that the surface of the substrate is between the plasma pretreatment roller and the plasma supply unit and the magnetic field formation unit disposed to face the plasma pretreatment roller. When the plasma source gas is introduced as plasma, a gap for containing the plasma is formed.

In the film production method according to the present invention, the plasma pretreatment step, the surface of the substrate, 100W · sec / m ² or more as the plasma intensity per unit area and at 8000W · sec / m ² under the following conditions plasma treatment May be.

In the film manufacturing method according to the present invention, the plasma raw material gas may be argon alone or a mixed gas of one or more of oxygen, nitrogen, and carbon dioxide.

In the film manufacturing method according to the present invention, the plasma pretreatment step may be performed using a plasma source gas composed of a mixed gas of at least one of oxygen, nitrogen, and carbon dioxide and argon.

In the film manufacturing method according to the present invention, the vapor deposition step may form the vapor deposition layer on the plasma-treated surface of the substrate by physical vapor deposition.

The present invention is a packaging material, comprising: a base material; a film provided on the base material; and a vapor deposition layer containing a metal or an alloy; and a thermoplastic resin layer laminated on the film. The base material is a packaging material in which 60% by mass or more of polybutylene terephthalate is included, and a covalent bond between a metal element and a carbon element is formed at an interface between the base material and the vapor deposition layer.

The packaging material according to the present invention may have a puncture strength of 11 N or more.

In the packaging material according to the present invention, the thermoplastic resin layer may be laminated on the film via an adhesive layer. In this case, the laminate strength between the base material and the thermoplastic resin layer at a width of 15 mm is preferably 4N or more.

In the packaging material according to the present invention, the thermoplastic resin layer may have a light shielding property.

The packaging material according to the present invention may be used for a boil packaging bag or a retort sterilization packaging bag.

According to the present invention, a gas barrier film including a base material and a vapor deposition layer can be provided with puncture resistance and heat resistance.

It is sectional drawing which shows an example of the base film in embodiment of this invention. It is sectional drawing which shows an example of the base material of a base film. It is sectional drawing which shows another example of the base film in embodiment of this invention. It is sectional drawing which shows an example of the packaging material provided with a base film. It is sectional drawing which shows one modification of the packaging material. It is sectional drawing which shows one modification of the packaging material. It is sectional drawing which shows one modification of the packaging material. It is a figure which shows the film-forming equipment which forms a vapor deposition layer on a base material. It is a figure which shows an example of the measuring method of adhesion strength. It is a figure which shows an example of the measuring method of adhesion strength. It is a figure which shows the change of the tensile stress with respect to the space | interval between a pair of grips which pulls a part of packaging material in order to measure adhesion strength. It is a figure which shows an example of the measuring method of piercing strength. It is a figure which shows the evaluation result of Example 1,2,3 and Comparative Example 1,2.

Hereinafter, a film forming facility for forming a base film and a vapor deposition layer of the base film according to an embodiment of the present invention will be described in detail with reference to the drawings. In addition, this Example is only a mere illustration and does not limit this invention at all.

FIG. 1 is a cross-sectional view showing an example of a base film 5 obtained by forming a vapor deposition layer 2 on a base 1, and FIG. 2 is a cross-sectional view showing an example of the base 1. FIG. 3 is a cross-sectional view showing another example of the base film 5. FIG. 4 is a cross-sectional view showing an example of the packaging material 8 obtained by laminating the thermoplastic resin layer 7 on the base film 5 via the adhesive layer 6. FIG. 8 is a diagram schematically showing the configuration of the film forming facility 10 for forming the vapor deposition layer 2 of the base film 5. When the base film 5 includes the gas barrier coating film 4 shown in FIG. 3, a gas barrier coating apparatus for forming the gas barrier coating film 4 is continuously arranged in the film forming facility 10. Although not shown, a known roller coating device can be used as the gas barrier coating device.

Base Film First, the base film 5 will be described with reference to FIGS. As shown in FIG. 1, the base film 5 includes at least a base 1 and a vapor deposition layer 2 provided on the base 1. The vapor deposition layer 2 contains a metal or an alloy. Examples of the vapor deposition layer 2 containing a metal include aluminum (Al), magnesium (Mg), tin (Sn), sodium (Na), titanium (Ti), lead (Pb), zirconium (Zr), and yttrium (Y). , Gold (Au), chromium (Cr), or the like can be used. In particular, for packaging bags, it is preferable to provide an aluminum vapor deposition layer. As a vapor deposition layer containing an alloy, the vapor deposition layer of the above-mentioned metal oxide can be used. For example, as the vapor deposition layer 2 containing an alloy, a vapor deposition layer containing an inorganic oxide such as aluminum oxide as a main component can be used.

A covalent bond between a metal atom and a carbon atom is formed at the interface between the substrate 1 and the vapor deposition layer 2. For example, when the vapor deposition layer 2 contains aluminum oxide, a covalent bond between an aluminum atom and a carbon atom is formed at the interface between the substrate 1 and the vapor deposition layer 2. Such a covalent bond can be formed, for example, by depositing the vapor deposition layer 2 on the surface of the substrate 1 that has been subjected to plasma pretreatment using the film deposition facility 10 shown in FIG. Covalent bonds can be detected by X-ray photoelectron spectroscopy (hereinafter abbreviated as “XPS measurement”) measurement.

The base film 5 may further include a printing layer 3 provided on the vapor deposition layer 2 as shown in FIG. The printed layer 3 is a layer printed on the base material 1 in order to show product information or impart aesthetics to a packaging bag made up of a packaging material 8 to be described later provided with the base film 5. The print layer 3 expresses characters, numbers, symbols, figures, patterns, and the like. As a material constituting the printing layer 3, gravure printing ink or flexographic printing ink can be used. As a specific example of the ink for gravure printing, FINAT manufactured by DIC Graphics Corporation can be given.

As shown in FIG. 3, the base film 5 may further include a gas barrier coating film 4 provided on the vapor deposition layer 2. The gas barrier coating film 4 is a film formed by coating a gas barrier composition on the vapor deposition layer 2. In the example shown in FIG. 3, the above-described printing layer 3 is provided on the gas barrier coating film 4.

Hereinafter, the material used for the base film 5, the manufacturing method of the base film 5, and an apparatus therefor will be described.

(Base material)
The base material 1 used for the base film 5 contains polybutylene terephthalate (hereinafter also referred to as PBT) as a main component. For example, the base material 1 contains 51 mass% or more of PBT. Hereinafter, the advantage that the substrate 1 includes PBT will be described.

PBT has excellent heat resistance. For this reason, it can suppress that the base material 1 deform | transforms or the intensity | strength of the base material 1 falls when performing a boil process and a retort process to the packaging bag which accommodates contents, such as foodstuffs. The retort process is a process of heating the packaging bag in a pressurized state using steam or heated hot water after filling the packaging bag with the contents and sealing the packaging bag. The temperature of retort processing is 120 degreeC or more, for example. The boil process is a process of filling the bag 10 with the contents and sealing the bag 10 and then bathing the bag 10 under atmospheric pressure. The temperature of boil processing is 90 degreeC or more and 100 degrees C or less, for example.

Also, PBT has high strength. For this reason, the packaging bag can be provided with puncture resistance, similarly to the case where the packaging material 8 constituting the packaging bag contains nylon.

Also, PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 1 containing PBT is arrange | positioned on the outer surface of the packaging material 8, it suppresses that the base material 1 absorbs a water | moisture content and the laminate strength of the packaging material 8 falls. be able to.

Hereinafter, the configuration of the base material 1 including PBT will be described in detail. As the configuration of the substrate 1 containing PBT in the present embodiment, any of the following first configuration or second configuration may be adopted.

[First Configuration of Substrate]
The content of PBT in the substrate 1 according to the first configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further 70% by mass or more, particularly preferably 75% by mass or more, and most preferably. 80% by mass or more. By setting the content of PBT to 51% by mass or more, the first film 40 can have excellent impact strength and pinhole resistance.

PBT used as a main constituent component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, most preferably 100 mol% or more of terephthalic acid as a dicarboxylic acid component. Mol%. 1,4-butanediol as the glycol component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 97 mol% or more, and most preferably 1,4-butanediol during polymerization. It is not included except by-products generated by the ether bond of butanediol.

The base material 1 may contain a polyester resin other than PBT. Thereby, for example, the film formability when the film-like substrate 1 is biaxially stretched and the mechanical properties of the substrate 1 can be adjusted.
Polyester resins other than PBT include polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polypropylene terephthalate (PPT), as well as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid. , PBT resin copolymerized with dicarboxylic acid such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, polycarbonate diol Min can be mentioned copolymerized PBT resin.

The amount of the polyester resin other than PBT is preferably 49% by mass or less, and more preferably 40% by mass or less. If the addition amount of the polyester resin other than PBT exceeds 49% by mass, the mechanical properties as PBT may be impaired, and impact strength, pinhole resistance, and drawability may be insufficient.

The substrate 1 may contain, as an additive, a polyester-based and polyamide-based elastomer obtained by copolymerizing at least one of a flexible polyether component, a polycarbonate component, and a polyester component. Thereby, the pinhole resistance at the time of bending can be improved. The additive amount of the additive is, for example, 20% by mass. When the addition amount of the additive exceeds 20% by mass, the effect as the additive may be saturated or the transparency of the substrate 1 may be reduced.

An example of a method for producing the film-like substrate 1 according to the first configuration will be described. Here, a method for producing the film-like substrate 1 by a casting method will be described. More specifically, a method of casting a resin having the same composition in multiple layers during casting will be described.

Since PBT has a high crystallization speed, crystallization proceeds even during casting. At this time, when cast as a single layer without being multi-layered, there is no barrier that can suppress the growth of the crystal, so the crystal grows to a large size, and the resulting unstretched original fabric is obtained. The yield stress of becomes higher. For this reason, it becomes easy to fracture when the unstretched original fabric is biaxially stretched. Moreover, it is possible that the yield stress of the obtained biaxially stretched film becomes high and the moldability of the biaxially stretched film becomes insufficient.
On the other hand, if the same resin is multilayered at the time of casting, the stretching stress of the unstretched sheet can be reduced. For this reason, stable biaxial stretching is possible, and the yield stress of the obtained biaxially stretched film is reduced. Thereby, a flexible and high breaking strength film can be obtained.

FIG. 2 is a cross-sectional view showing an example of the layer structure of the substrate 1. When the base material 1 is produced by casting the resin in multiple layers, as shown in FIG. 2, the base material 1 is composed of a multilayer structure including a plurality of layers 1a. Each of the plurality of layers 1a includes PBT as a main component. For example, each of the plurality of layers 1a preferably includes 51% by mass or more of PBT, and more preferably includes 60% by mass or more of PBT. In the plurality of layers 1a, the (n + 1) th layer 1a is directly stacked on the nth layer 1a. That is, no adhesive layer or adhesive layer is interposed between the plurality of layers 1a.

The reason why the properties of the PBT film are improved by multilayering is estimated as follows. When the resins are laminated, even if the resin composition is the same, a layer interface exists, and crystallization is accelerated by the interface. On the other hand, the growth of large crystals beyond the layer thickness is suppressed. For this reason, it is considered that the size of the crystal (spherulite) becomes small.

As a specific method for reducing the size of spherulites by multilayering, a general multilayering apparatus (multilayer feed block, static mixer, multilayer multimanifold, etc.) can be used. For example, a method of laminating thermoplastic resins sent from different flow paths using two or more extruders in multiple layers using a feed block, a static mixer, a multi-manifold die, or the like can be used. In addition, when multilayering resin of the same composition, it is also possible to introduce the above multilayering apparatus into the melt line from the extruder to the die using only one extruder.

The substrate 1 is composed of a multilayer structure including at least 10 layers, preferably 60 layers or more, more preferably 250 layers or more, and still more preferably 1000 layers or more. By increasing the number of layers, the size of spherulites in the unstretched raw PBT can be reduced, and the subsequent biaxial stretching can be carried out stably. Moreover, the yield stress of PBT in the state of a biaxially stretched film can be made small. Preferably, the diameter of the spherulite in the unstretched raw PBT is 500 nm or less.

The stretching temperature (hereinafter also referred to as MD stretching temperature) in the longitudinal stretching direction (hereinafter referred to as MD) when producing a biaxially stretched film by biaxially stretching the unstretched raw material of PBT is preferably 40 ° C. or higher. Yes, more preferably 45 ° C or higher. By setting the MD stretching temperature to 40 ° C. or higher, the film can be prevented from being broken. Moreover, MD extending | stretching temperature becomes like this. Preferably it is 100 degrees C or less, More preferably, it is 95 degrees C or less. The phenomenon that the orientation of the biaxially stretched film does not occur can be suppressed by setting the MD stretching temperature to 100 ° C. or lower.

The draw ratio in MD (hereinafter also referred to as MD draw ratio) is preferably 2.5 times or more. Thereby, a biaxially stretched film can be oriented and a favorable mechanical characteristic and uniform thickness can be implement | achieved. MD stretch ratio is 5 times or less, for example.

The stretching temperature (hereinafter also referred to as TD stretching temperature) in the transverse stretching direction (hereinafter also referred to as TD) is preferably 40 ° C. or higher. By setting the TD stretching temperature to 40 ° C. or higher, the film can be prevented from being broken. The TD stretching temperature is preferably 100 ° C. or lower. By setting the TD stretching temperature to 100 ° C. or lower, the phenomenon that the orientation of the biaxially stretched film does not occur can be suppressed.

The stretching ratio in TD (hereinafter also referred to as TD stretching ratio) is preferably 2.5 times or more. Thereby, a biaxially stretched film can be oriented and a favorable mechanical characteristic and uniform thickness can be implement | achieved. MD stretch ratio is 5 times or less, for example.

TD relaxation rate is preferably 0.5% or more. Thereby, it can suppress that a fracture | rupture arises at the time of heat setting of the biaxially stretched film of PBT. The TD relaxation rate is preferably 10% or less. Thereby, sagging etc. arise in a biaxially stretched film of PBT, and it can control that thickness unevenness generate | occur | produces.

The thickness of the layer 1a of the base material 1 shown in FIG. 2 is preferably 3 nm or more, more preferably 10 nm or more. The thickness of the layer 1a is preferably 200 nm or less, more preferably 100 nm or less.
Further, the thickness of the substrate 1 is preferably 9 μm or more, more preferably 12 μm or more. Moreover, the thickness of the base material 1 is preferably 25 μm or less, and more preferably 20 μm or less. By setting the thickness of the substrate 1 to 9 μm or more, the substrate 1 has sufficient strength. Moreover, the base material 1 comes to show the moldability which was excellent by making the thickness of the base material 1 into 25 micrometers or less. For this reason, the process which processes the packaging material 8 containing the base material 1 and manufactures a packaging bag can be implemented efficiently.

[Second Configuration of Base Material]
The base material 1 which concerns on a 2nd structure consists of a single layer film containing polyester which has butylene terephthalate as a main repeating unit. For example, the substrate 1 is mainly composed of 1,4-butanediol as a glycol component or an ester-forming derivative thereof and terephthalic acid as a dibasic acid component or an ester-forming derivative thereof as a main component. Homo- or copolymer-type polyester obtained. The content of PBT in the substrate 1 according to the second configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 80% by mass or more, and most preferably. Is 90% by mass or more. Moreover, it is preferable that the base material 1 which concerns on a 2nd structure is comprised only with the polybutylene terephthalate and the additive.

In order to impart mechanical strength to the substrate 1, a PBT having a melting point of 200 ° C. or more and 250 ° C. or less and an IV value (intrinsic viscosity) of 1.10 dl / g or more and 1.35 dl / g or less. Is preferred. Furthermore, those having a melting point of 215 ° C. or more and 225 ° C. or less and an IV value of 1.15 dl / g or more and 1.30 dl / g or less are particularly preferable. These IV values may be satisfied by the entire material constituting the substrate 1. The IV value can be calculated based on JIS K 7367-5: 2000.

The base material 1 which concerns on a 2nd structure may contain polyester resins other than PBT, such as PET, in 30 mass% or less. When the base material 1 contains PET in addition to PBT, PBT crystallization can be suppressed, and the stretchability of the PBT film can be improved. As PET mix | blended with PBT of the base material 1, the polyester which uses ethylene terephthalate as a main repeating unit can be used. For example, a homotype mainly composed of ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component can be preferably used. In order to impart good mechanical strength characteristics, among PET, those having a melting point of 240 ° C. or more and 265 ° C. or less and an IV value of 0.55 dl / g or more and 0.90 dl / g or less are preferable. Furthermore, those having a melting point of 245 ° C. or more and 260 ° C. or less and an IV value of 0.60 dl / g or more and 0.80 dl / g or less are particularly preferable.
By setting the blending amount of PET to 30% by mass or less, it is possible to suppress the unstretched raw fabric and the stretched film from becoming too rigid. Thereby, a stretched film becomes brittle and it can suppress that the pressure resistance strength, impact strength, puncture strength, etc. of a stretched film fall. Moreover, it is possible to suppress the occurrence of stretching failure when the unstretched raw fabric is stretched.

The base material 1 is made of a lubricant, an antiblocking agent, an inorganic extender, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a plasticizer, a colorant, a crystallization inhibitor, and a crystallization accelerator as necessary. Etc. may be contained. Further, the polyester resin pellet used as a raw material of the substrate 1 has a moisture content of 0.05% by weight or less, preferably 0.01% by weight or less before heating and melting in order to avoid a decrease in viscosity due to hydrolysis during heating and melting. It is preferable to use after sufficiently pre-drying so that

An example of a method for producing the film-like substrate 1 according to the second configuration will be described.

In order to stably produce the film of the base material 1 having the above-described configuration, it is important to suppress the crystal growth in the unstretched raw fabric state. Specifically, when forming the film by cooling the extruded PBT melt, the crystallization temperature region of the polymer is cooled at a certain rate or more, that is, the raw fabric cooling rate is an important factor. The raw fabric cooling rate is, for example, 200 ° C./second or more, preferably 250 ° C./second or more, particularly preferably 350 ° C./second or more. Since the unstretched original film formed at a high cooling rate maintains a low crystalline state, the stability of the bubbles during stretching is improved. Furthermore, since film formation at high speed is possible, film productivity is also improved. When the cooling rate is less than 200 ° C./sec, it is considered that the crystallinity of the obtained unstretched original fabric is increased and the stretchability is lowered. In extreme cases, the stretching bubble may burst and stretching may not continue.

It is preferable that the unstretched raw material containing PBT as a main component is conveyed to a space where biaxial stretching is performed while maintaining the atmospheric temperature at 25 ° C. or lower, preferably 20 ° C. or lower. Thereby, even if it is a case where residence time becomes long, the crystallinity of the unstretched original fabric immediately after film-forming can be maintained.

The biaxial stretching method for obtaining a stretched film by stretching an unstretched raw fabric is not particularly limited. For example, the longitudinal direction and the lateral direction may be simultaneously stretched by the tubular method or the tenter method, or the longitudinal direction and the lateral direction may be sequentially stretched. Among these, the tubular method can obtain a stretched film having a good balance of physical properties in the circumferential direction, and is particularly preferably employed.

In the tubular method, the unstretched raw material introduced into the stretching space is inserted between a pair of low-speed nip rolls, and then heated by a stretching heater while air is being pressed therein. After stretching, air is blown onto the stretched film by a cooling shoulder air ring. The stretching ratio is preferably 2.7 times or more and 4.5 times or less for MD and TD, respectively, in consideration of stretching stability, strength physical properties of the stretched film, transparency, and thickness uniformity. By setting the draw ratio to 2.7 times or more, it is possible to sufficiently ensure the tensile elastic modulus and impact strength of the stretched film. In addition, by setting the draw ratio to 4.5 times or less, it is possible to suppress the occurrence of excessive molecular chain distortion due to stretching, and to suppress the occurrence of breakage and puncture during the stretching process, so that the stretched film can be stabilized. Can be produced.

The stretching temperature is preferably 40 ° C. or higher and 80 ° C. or lower, and particularly preferably 45 ° C. or higher and 65 ° C. or lower. Since the unstretched original fabric produced at the above-described high cooling rate has low crystallinity, the unstretched original fabric can be stably stretched even when the stretching temperature is relatively low. Further, by setting the stretching temperature to 80 ° C. or less, it is possible to suppress stretching bubble shaking and obtain a stretched film with good thickness accuracy. In addition, by setting the stretching temperature to 40 ° C. or higher, it is possible to suppress the occurrence of excessive stretch-oriented crystallization due to low-temperature stretching, thereby preventing whitening of the film.

The base material 1 produced as described above is constituted by a single layer containing, for example, polyester having butylene terephthalate as a main repeating unit. According to the above-described production method, since the unstretched raw film is formed at a high cooling rate, even when the unstretched raw fabric is constituted by a single layer, a low crystalline state can be maintained, For this reason, an unstretched original fabric can be extended | stretched stably.

In both the first configuration and the second configuration described above, the base material 1 includes PBT as a main component. For this reason, the heat resistance of the packaging material 8 including the base film 5 and the base film 5 can be increased. For example, the tensile elastic modulus of the base film 5 and the packaging material 8 can be sufficiently increased. In particular, the tensile elastic modulus (hereinafter also referred to as hot tensile elastic modulus) of the base film 5 and the packaging material 8 in a high temperature atmosphere, for example, in an atmosphere of 100 ° C., can be sufficiently increased.

(Deposition layer)
Next, the vapor deposition layer 2 will be described.

In the present embodiment, when the vapor deposition layer 2 is formed on the substrate 1, the surface of the substrate 1 is subjected to plasma treatment using plasma as a pretreatment in order to improve adhesion to the vapor deposition layer 2 and the like. Is preferably performed as a pretreatment.

8, partition walls 35 a to 35 c are formed in the decompression chamber 12. The partition walls 35a to 35c form a base material transfer chamber 12A, a plasma pretreatment chamber 12B, and a film formation chamber 12C. In particular, the plasma pretreatment chamber 12B and the film formation chamber are surrounded by the partition walls and the partition walls 35a to 35c. 12C is formed, and an exhaust chamber is further formed inside each chamber as necessary.

In the plasma pretreatment chamber 12B, a part of the plasma pretreatment roller 20 that conveys the base material 1 to be pretreated and enables plasma treatment is provided so as to be exposed to the base material conveyance chamber 12A. The base material 1 is moved from the base material transfer chamber 12A to the plasma pretreatment chamber 12B while being wound up.

The plasma pretreatment chamber 12B and the film formation chamber 12C are provided in contact with the base material transfer chamber 12A, and can be moved without exposing the base material 1 to the atmosphere. Further, the plasma pretreatment chamber 12B and the base material transfer chamber 12A are connected by a rectangular hole, and a part of the plasma pretreatment roller 20 protrudes toward the base material transfer chamber 12A through the rectangular hole. A gap is opened between the wall of the transfer chamber and the plasma pretreatment roller 20, and the substrate 1 can be moved from the substrate transfer chamber 12A to the film forming chamber 12C through the gap. The structure between the base material transfer chamber 12A and the film forming chamber 12C is similar, and the base material 1 can be moved without being exposed to the atmosphere.

In the base material transport chamber 12A, the base material 1 having the vapor deposition layer 2 formed on one side, which has been moved again to the base material transport chamber 12A by the film forming roller 25, is wound in a roll shape. The take-up roller is provided, and the substrate 1 on which the vapor deposition layer 2 is formed can be taken up.

The vacuum chamber 12 is provided with a vacuum pump through a pressure adjustment valve. Therefore, the entire base material transfer chamber 12A, plasma pretreatment chamber 12B, and film formation chamber 12C, which are partitioned by the partition walls 35a to 35c, can be decompressed.

When manufacturing the base film 5, in the plasma pretreatment chamber 12B, it is preferable to partition the space in which plasma is generated from other regions so that the opposing space can be efficiently evacuated. This facilitates control of the plasma gas concentration and improves productivity. The pressure in the space where the plasma is generated is preferably set and maintained at about 0.1 Pa to 100 Pa.

A plasma pretreatment roller 20 is disposed so as to straddle the substrate transport chamber 12A and the plasma pretreatment chamber 12B, and guide

rollers

14a and 14b are provided between the unwinding roll 13 and the plasma pretreatment roller 20.
Further, a film forming roller 25 is disposed in the film forming chamber 12C, and guide

rollers

14c and 14d are provided between the plasma pretreatment roller 20 and the film forming roller 25 and between the film forming roller 25 and the take-up roller. It is provided, and the conveyance path | route of the base material 1 is formed with these guide roller groups.

The conveyance speed of the substrate 1 is not particularly limited, but is preferably 200 m / min or more, more preferably 480 m / min or more and 1000 m / min or less from the viewpoint of production efficiency.

The plasma pretreatment chamber 12B is provided with a plasma pretreatment roller 20 for plasma pretreatment of the transported substrate 1 and a plasma pretreatment apparatus including plasma pretreatment means for pretreatment of the substrate 1. It has been.

The purpose of the plasma pretreatment roller 20 is to prevent shrinkage or breakage of the substrate 1 due to heat during the plasma treatment by the plasma pretreatment means, and to apply the plasma P to the substrate 1 uniformly and over a wide range. It is provided.
It is preferable that the plasma pretreatment roller 20 can be adjusted to a constant temperature between −20 ° C. and 100 ° C. by adjusting the temperature of the temperature adjustment medium circulating in the plasma pretreatment roller 20. . Electrical insulating portions are provided on both sides of the central portion of the roller body and around the rotation shaft, and the base material 1 is wound around the central portion of the roller body.

The plasma pretreatment roller 20 may be installed at an electrical ground level. In this case, it is realizable by using a metal electroconductive material for a roller main body, a rotating shaft, a bearing, and a roller support body.

Further, the plasma pretreatment roller 20 may be installed at an electrically floating level, that is, an insulation potential. By setting the potential of the plasma pretreatment roller 20 to the floating level, it is possible to prevent power leakage, to increase the input power of the plasma pretreatment, and to increase the utilization efficiency for the plasma pretreatment.

The plasma pretreatment means includes a plasma supply means and a magnetic formation means. The plasma pretreatment means cooperates with the plasma pretreatment roller 20 to confine the plasma P near the surface of the substrate 1. Thereby, the chemical property of the surface of a base material is changed by changing the shape of the surface of a base material, a chemical bond state, or a functional group. This makes it possible to improve the adhesion between the substrate 1 and the vapor deposition layer 2 during subsequent film formation.

The plasma pretreatment means is provided so as to cover a part of the plasma pretreatment roller 20. For example, the plasma pretreatment means includes a plasma supply means and a magnetic formation means. The plasma supply means includes

plasma supply nozzles

22a and 22b that serve as electrodes for supplying plasma source gas and generating plasma P. The magnetic forming means has a magnet 21 and the like for promoting the generation of plasma P. The plasma supply unit and the magnetic forming unit are arranged along the surface in the vicinity of the outer periphery of the plasma pretreatment roller 20. The plasma supply means and the magnetism forming means are installed so as to form a gap for containing the plasma between the plasma pretreatment roller 20 and the surface in the vicinity of the outer periphery.
Thereby, the

plasma supply nozzles

22a and 22b are opened in the space of the gap to form a plasma formation region, and further, a region having a high plasma density is formed in the vicinity of the surface of the plasma pretreatment roller 20 and the substrate 1, A plasma processing surface is formed on one surface of the substrate 1.

The plasma supply means of the plasma pretreatment means includes a raw material gas volatilization supply device 18 connected to a plasma supply nozzle provided outside the decompression chamber 12 and a raw material gas supply nozzle that supplies the raw material gas from the raw material gas volatilization supply device 18. 19a to 19d. As the plasma source gas, an inert gas such as argon alone or a mixed gas of oxygen, nitrogen, carbon dioxide and one or more of them is measured from the gas reservoir through a flow controller to measure the gas flow rate. However, it is supplied.

These supplied gases are mixed at a predetermined ratio as necessary, formed into a plasma raw material gas alone or a plasma forming mixed gas, and supplied to the plasma supply means. The single or mixed gas is supplied to the

plasma supply nozzles

22a and 22b of the plasma supply means, and is supplied to the vicinity of the outer periphery of the plasma pretreatment roller 20 where the supply ports of the

plasma supply nozzles

22a and 22b open.
The nozzle opening is directed to the base material 1 on the plasma pretreatment roller 20, and the plasma P can be uniformly diffused and supplied to the surface of the base material 1, and the uniform plasma is applied to a large area of the base material 1. Pre-processing is possible.

The

plasma supply nozzles

22a and 22b function as counter electrodes of the plasma pretreatment roller 20 and have an electrode function. The supplied plasma source gas is excited by the potential difference caused by the high frequency voltage supplied to the plasma pretreatment roller 20, and the plasma P is generated and supplied.

In the plasma pretreatment apparatus, a mechanism for generating an arbitrary direct electric field between the plasma pretreatment roller and the plasma pretreatment means to enhance or weaken the plasma P implantation effect on the substrate 1 is installed. Is preferred. In order to enhance the plasma implantation effect, it is preferable to apply a negative potential to the substrate 1, and in order to weaken the plasma implantation effect, it is preferable to apply a positive plus potential to the substrate 1.
By adjusting the plasma intensity as described above, it is possible to adjust the plasma implantation effect on the base material 1 to reduce the damage to the base material 1 and, on the contrary, to increase the adhesion rate of the film to the base material 1. It becomes.

Specifically, the plasma supply means of the plasma pretreatment means can be in a state where an arbitrary voltage is applied between the plasma pretreatment roller 20 and the physical properties of the surface of the substrate 1 are physically or A power source 32 is provided that can apply a bias voltage that makes the plasma P that can be chemically modified a positive potential.
Such a plasma supply means can supply a desired plasma P at a desired density in the vicinity of the outer periphery of the plasma pretreatment roller 20, and can improve the power efficiency of the plasma pretreatment.

Employed in the present embodiment, the plasma intensity per unit area of the surface of the substrate 1 is preferably not 100W · sec / m ² or more and 8000W · sec / m ² or less. If it is less than 100 W · sec / m ² , the effect of the plasma pretreatment is not observed, and if it exceeds 8000 W · sec / m ² , the deterioration of the substrate 1 due to plasma such as consumption, damage coloring, and firing of the substrate 1 is caused. It tends to happen.

The plasma pretreatment means has magnetic formation means. As magnetic forming means, an insulating spacer and a base plate are provided in a magnet case, and a magnet 21 is provided on the base plate. An insulating shield plate is provided on the magnet case, and an electrode is attached to the insulating shield plate.
Therefore, the magnet case and the electrode are electrically insulated, and the electrode can be brought to an electrically floating level even if the magnet case is installed and fixed in the decompression chamber 12.

The power supply wiring 31 is connected to the electrode, and the power supply wiring 31 is connected to the power source 32. Further, a temperature control medium pipe for cooling the electrode and the magnet 21 is provided inside the electrode.

The magnet 21 is provided to concentrate and apply the plasma P from the

plasma supply nozzles

22a and 22b, which are electrode and plasma supply means, to the substrate 1. By providing the magnet 21, the reactivity in the vicinity of the surface of the substrate 1 is increased, and the plasma processing surface can be formed at a high speed.

The magnet 21 has a magnetic flux density of 10 gauss or more and 10000 gauss or less at the surface position of the substrate 1. If the magnetic flux density on the substrate surface is 10 gauss or more, the reactivity in the vicinity of the substrate surface can be sufficiently increased, and the pretreatment surface can be formed at high speed.

Due to the arrangement structure of the electrode magnet 21, ions and electrons formed during the plasma pretreatment move according to the arrangement structure. For this reason, for example, even when the plasma pretreatment is performed on the substrate 1 having a large area of 1 m ² or more, electrons, ions, and decomposition products of the substrate are uniformly diffused over the entire electrode surface. Therefore, even when the substrate 1 has a large area, a uniform and stable pretreatment can be performed with a desired plasma intensity.

The substrate 1 having a plasma treatment surface formed on one side by the plasma pretreatment roller 20 is moved from the substrate transfer chamber 12A to the film formation chamber 12C by the guide rollers 14a to 14d for guiding to the next film formation chamber 12C. A vapor deposition layer 2 is formed in the film section.

The vapor deposition layer 2 is a thin film having a gas barrier performance that blocks or blocks permeation of oxygen gas, water vapor, and the like. For example, the vapor deposition layer 2 is formed by forming an aluminum oxide layer on the substrate 1 using a physical vapor deposition method or the like. Can be formed.

The inorganic oxide layer which forms the vapor deposition layer 2 is a layer which contains an aluminum compound as a main component including at least aluminum oxide, aluminum nitride, carbide alone or a mixture thereof, for example. For example, the inorganic oxide layer contains aluminum oxide as a main component.
Furthermore, the vapor deposition layer 2 contains an aluminum compound such as the above-described aluminum oxide as a main component, and further includes silicon oxide (silicon oxide), silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, and oxidation. A layer comprising a metal oxide such as tin, indium oxide, zinc oxide, zirconium oxide or the like, or a mixture of inorganic oxides containing these metal nitrides, carbides and mixtures thereof, and containing a covalent bond between an aluminum atom and a carbon atom. It may be.

The vapor deposition layer 2 indicates the presence of a covalent bond between an aluminum atom and a carbon atom at the peak measured by ion etching in the depth direction using an X-ray photoelectron spectrometer (measurement conditions: X-ray source AlKα, X-ray output 120 W). In addition, it has transparency and gas barrier properties that prevent permeation of oxygen, water vapor and the like.

Further, in the vapor deposition layer 2, the abundance ratio of the covalent bond between the aluminum atom and the carbon atom includes all carbon atoms observed when the interface between the substrate 1 and the vapor deposition layer 2 is measured by X-ray photoelectron spectroscopy. It is desirable to be within the range of 0.3% or more and 30% or less of the bonds. Thereby, the adhesiveness of the vapor deposition layer 2 and the base material 1 is strengthened, the transparency is excellent, and a gas barrier vapor deposition film having a well-balanced performance is obtained.

When the abundance ratio of the covalent bond between the aluminum atom and the carbon atom is less than 0.3%, the adhesion of the vapor deposition layer 2 is not sufficiently improved, and it is difficult to stably maintain the barrier property. Further, when the abundance ratio of the covalent bond between aluminum atoms and carbon atoms exceeds 30%, the surface of the substrate 1 is decomposed by the plasma treatment, the surface is roughened, and the decomposed components are adhered, rather than the adhesion improvement by the plasma pretreatment. The adverse effects of the surface treatment such as a decrease in the adhesive improvement ratio and a decrease in transparency caused by the surface treatment are large, and the effect of the pretreatment is reduced.

Furthermore, the AL (aluminum) / O (oxygen) ratio of the vapor deposition layer 2 mainly composed of aluminum oxide is such that the vapor deposition layer 2 on the opposite side of the base material 1 from the interface between the base material 1 and the vapor deposition layer 2. In the range up to 3 nm toward the surface, it is preferably 1.0 or less.
If the AL / O ratio exceeds 1.0 within the range from the interface between the vapor deposition layer 2 and the substrate 1 to the surface of the vapor deposition layer 2 on the opposite side of the substrate 1, the plasma treatment surface of the substrate 1 Adhesiveness with the vapor deposition layer 2 becomes inadequate, the ratio of aluminum increases, and the transparency of the vapor deposition layer 2 falls.

The thickness of the vapor deposition layer 2 formed with one film forming apparatus is, for example, 5 nm or more and 200 nm or less, preferably 10 nm or more and 100 nm or less. In the case of the aluminum vapor deposition layer 2, the thickness of the vapor deposition layer 2 is, for example, 5 nm to 60 nm, preferably 10 nm to 45 nm. In the case of the vapor deposition layer 2 of aluminum oxide or silicon oxide, the thickness of the vapor deposition layer 2 is, for example, not less than 5 nm and not more than 50 nm, preferably not less than 10 nm and not more than 30 nm.

A film forming apparatus including a film forming roller 25 and a film forming unit 26 is provided in the film forming chamber 12C. The film forming unit 26 forms the vapor deposition layer 2 on the plasma processing surface of the substrate 1 pretreated by the plasma pretreatment unit.

The film forming apparatus is arranged so as to form the vapor deposition layer 2 on the surface of the substrate 1 that has been plasma pretreated. As a vapor deposition method for forming the vapor deposition layer 2, various vapor deposition methods can be applied among physical vapor deposition and chemical vapor deposition.
The physical vapor deposition method can be selected from the group consisting of vapor deposition method, sputtering method, ion plating method, ion beam assist method, and cluster ion beam method. Chemical vapor deposition methods include plasma CVD method, plasma polymerization method, thermal method. It can be selected from the group consisting of CVD method and catalytic reaction type CVD method.

The film forming apparatus is placed in a reduced pressure film forming chamber, and the substrate 1 is wound and transported with the plasma processing surface of the substrate 1 pre-processed by the plasma pre-processing apparatus facing outside. A film roller 25 and a film forming unit 26 that evaporates a target of a film forming source disposed to face the film forming roller 25 to form a vapor deposition layer on the surface of the substrate. The film forming means 26 includes a vapor deposition film forming apparatus, a sputtering film forming apparatus, an ion plating film forming apparatus, an ion beam assisted film forming apparatus, a cluster ion beam film forming apparatus, a plasma CVD film forming apparatus, a plasma polymerization film forming apparatus, A CVD film forming apparatus, a catalytic reaction type CVD film forming apparatus, or the like.

In the film forming apparatus, various physical vapor deposition apparatuses can be applied by exchanging the evaporation means of the target of the film forming source, and it is possible to adopt an apparatus configuration capable of performing film formation by the chemical vapor deposition apparatus. The film forming method can be used properly.

As the film forming means 26, a physical vapor deposition apparatus such as a resistance heating vacuum film forming apparatus, a sputtering apparatus, an ion plating film forming apparatus, an ion beam assist film forming apparatus, a cluster ion beam film forming apparatus, a plasma CVD film forming apparatus, a plasma, etc. It can be produced by forming an inorganic oxide layer into a film using a chemical vapor deposition apparatus such as a polymerization film forming apparatus, a thermal CVD film forming apparatus, or a catalytic reaction type CVD film forming apparatus.

When a vacuum film forming apparatus is employed as the film forming means 26, the crucible as an evaporation source is filled with a single or plural types of target metal materials at a ratio of aluminum as a main component, heated to a high temperature, and contains aluminum metal. The metal vapor is oxidized by introducing oxygen gas supplied from the gas supply means into the metal vapor, and a metal oxide containing aluminum oxide is formed on the surface of the substrate 1.

In the case of resistance heating, a metal wire such as aluminum can be used to form a film on the substrate surface while being oxidized as metal vapor. As the evaporation source for film formation, a sputtering evaporation source, an arc evaporation source, or a plasma CVD film formation mechanism such as a plasma generating electrode or a raw material gas supply means can be employed.

At the time of film formation, the evaporation method of the target metal material may be adjusted based on the composition of the vapor deposition layer 2 to be formed. For example, depending on the easiness of evaporation of aluminum and other metals, the metal material is vaporized separately so that the aluminum oxide is a main component, or the metal material is set to a target ratio. The mixture can be vaporized.
In the film formation chamber, one film forming apparatus may be provided as the film forming unit 26 according to the vapor deposition layer 2 to be formed, or two or more of the same or different kinds of film forming apparatuses may be provided.

When a thin film is formed thick with one film forming apparatus, the thin film becomes brittle due to stress, cracks are generated, the gas barrier property is remarkably lowered, and the thin film is peeled off during transportation or winding. Therefore, in order to obtain a thick layer of a gas barrier thin film, it is preferable to provide a plurality of film forming apparatuses and form a thin film of the same substance a plurality of times.

Further, in the present embodiment, a gas barrier coating film 4 is further formed on the laminate of the base material 1 and the vapor deposition layer 2 by a known roller-type coating apparatus (not shown) provided continuously with the film forming facility 10. To do. Thin films of different materials may be formed by a plurality of film forming apparatuses. In that case, a multilayer multifunctional film having not only gas barrier properties but also various functions can be obtained.

In particular, in the film forming apparatus, it is preferable that the set temperature can be set to a constant temperature between −20 ° C. and 100 ° C. from the viewpoint of heat resistance restrictions of related mechanical parts and versatility.
In various film formation methods, the film formation pressure in the film formation chamber for continuously forming the vapor deposition layer is sufficient to form a vapor deposition layer having sufficient denseness of the vapor deposition layer and adhesion to the substrate. It is preferable to set and maintain at about 0.1 Pa to 100 Pa.

(Deposition layer deposition method)
Next, a method for forming the vapor deposition layer 2 by employing the film forming facility 10 in which the pretreatment section where the plasma pretreatment apparatus is disposed and the film formation section are separated will be described.
First, the roll-shaped raw material is installed on the unwinding roller 13 in the base material transport chamber 12A, and the pressure in the base material transport chamber 12A, the plasma pretreatment chamber 12B, and the film formation chamber 12C is reduced by a vacuum pump.

After reducing the pressure to a predetermined pressure, the substrate 1 is unwound from the original fabric by the unwinding roller 13, and the substrate 1 is wound around the plasma pretreatment roller 20 via the guide roller 14 a, so that the substrate 1 is The material moves from the material transfer chamber 12A to the plasma pretreatment chamber 12B and is guided to the plasma pretreatment apparatus.
Then, plasma is introduced in a state where an applied potential is applied between the plasma supply means and the pretreatment roller, and plasma pretreatment is performed. Thereby, a plasma processing surface is formed on one surface of the substrate 1 wound around the plasma preprocessing roller 20 by the plasma preprocessing means.

The substrate 1 having a plasma treatment surface formed on one side is moved again from the plasma pretreatment roller 20 around the guide roller 14b to move to the substrate conveyance chamber 12A again.
Thereafter, the

guide rollers

14b and 14c are used to move the inside of the substrate transport chamber 12A, wind around the film forming roller 25 so that the plasma-treated surface becomes the front, and move to the film forming chamber 12C. In the film forming chamber 12 </ b> C, the vapor deposition layer 2 is formed on the pretreatment surface of the substrate 1 by the film forming means 26.

Thus, the base material 1 on which the vapor deposition layer 2 is formed is moved again from the film formation roller 25 to the base material transfer chamber 12A, and is wound into a roll shape by the take-up roller via the guide roller 14d.

According to the roller-type film forming facility 10 according to the present embodiment, the substrate 1 is formed before the vapor deposition layer 2 is formed, and the gap formed by the plasma pretreatment roller 20, the plasma supply unit, and the magnetic forming unit 21 is formed. At that time, the plasma P is introduced from the

plasma supply nozzles

22a and 22b that also serve as the supply of the plasma source gas in the gap near the outer periphery of the plasma pretreatment roller 20 toward the substrate 1, and the plasma P and the plasma pretreatment are introduced. The atmosphere in the plasma pretreatment means is improved by performing the plasma pretreatment in a state where a positive applied voltage is applied to the roller 20.
Therefore, a uniform and high-quality plasma processing surface can be formed on the substrate 1. Thereafter, by depositing the vapor deposition layer 2 on the plasma processing surface by the film deposition means 26, it becomes possible to obtain the base film 5 having the uniform vapor deposition layer 2 having excellent adhesion and the like.
Moreover, it becomes possible to obtain the base film 5 having the uniform vapor-deposited layer 2 that has adhesiveness and excellent water-resistant adhesiveness even after hydrothermal treatment at 121 ° C. for 60 minutes.
Furthermore, it is possible to obtain a base material having a uniform vapor deposition layer 2 that has adhesiveness even in a high-temperature and high-humidity environment that is stored for 500 hours in a 60 ° C. × 90% RH environment and that has excellent wet heat resistance.

The base material transfer chamber 12A is partitioned by a partition wall 35a (zone seal) and has a different pressure from the plasma pretreatment chamber in which electrodes are present. By making the substrate transfer chamber 12A and the plasma pretreatment chamber 12B different spaces in terms of pressure, the plasma P in the plasma pretreatment chamber 12B leaks into the substrate transfer chamber 12A due to leakage of the plasma P in the plasma pretreatment chamber. It does not become unstable, damage the member of the base material transfer chamber 12A, or cause electrical damage to the electric circuit for controlling the base material transfer mechanism, thereby causing no control failure. Material conveyance becomes possible.

The plasma processing pressure in the added plasma pretreatment chamber 12B is, for example, 0.1 Pa or more and 100 Pa or less. By performing the pretreatment at such a pretreatment pressure, a stable plasma P can be formed.

According to the plasma pretreatment, it is possible to prevent an increase in the impedance of the plasma discharge, to easily form the plasma P, and to perform the discharge and the plasma treatment stably for a long time.

Further, since the discharge impedance of the plasma P does not increase, in the plasma processing, the processing speed is improved, the film stress is reduced, the damage to the base material is reduced (the occurrence of electrical charge-up is suppressed, the base material etching is reduced, It is possible to reduce material coloring.
Thus, the discharge impedance can be optimized, the ion implantation effect on the substrate 1 can be adjusted, the adhesion of the vapor deposition layer formed on the pretreatment surface can be improved, and Damage can be reduced and a favorable pre-processed surface can be formed.

(Gas barrier coating film)
Next, the gas barrier coating film 4 will be described. The gas barrier coating film 4 is a transparent coating film that retains gas barrier properties in a high temperature and high humidity environment. The general formula R ¹ _n M (OR ² ) _m (where R ¹ and R ² are carbon atoms) An organic group having a number of 1 to 8, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M. Gas barrier properties comprising at least one or more metal alkoxides represented and a water-soluble polymer, and further polycondensing by a sol-gel method in the presence of a sol-gel method catalyst, acid, water, and an organic solvent A coating film made of the composition.
A gas barrier composition is applied onto the vapor deposition layer 2 and heat-dried at a temperature of 20 ° C. to 180 ° C. and below the melting point of the substrate 1 for 10 seconds to 10 minutes to form a gas barrier coating film 4. be able to.

In addition, the gas barrier composition is coated on the vapor deposition layer 2 to form two or more layers of coating films, and heated at a temperature of 20 ° C. to 180 ° C. and below the melting point of the substrate 1 for 10 seconds to 10 minutes. You may dry-process and form the gas-barrier coating film 4 which laminated | stacked the coating film 2 or more layers.
In the metal alkoxide, examples of the metal atom represented by M in the general formula R ¹ _n M (OR ² ) _m include silicon, zirconium, titanium, aluminum, and the like.

The above alkoxides may be used in combination of two or more. For example, when alkoxysilane and zirconium alkoxide are mixed and used, the toughness and heat resistance of the resulting base film 5 can be improved, and a decrease in the retort resistance of the film during stretching can be avoided. Moreover, when alkoxysilane and titanium alkoxide are mixed and used, the heat conductivity of the gas barrier coating film obtained will become low, and heat resistance will improve remarkably.

As the water-soluble polymer of the gas barrier coating film 4, a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer can be used. Can be used in combination. By using a polyvinyl alcohol-based resin and / or an ethylene / vinyl alcohol copolymer, physical properties such as gas barrier properties, water resistance, weather resistance, and the like can be remarkably improved.

As the polyvinyl alcohol resin, those obtained by saponifying polyvinyl acetate can be generally used. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Well, not particularly limited.

As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used.
For example, it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain. However, it is preferable to use a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of gas barrier properties.
The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter also referred to as “ethylene content”) is usually 0 to 50 mol%, preferably 20 to 45 mol%. It is preferable.

(Method for forming gas barrier coating film)
Hereinafter, an example of a method for forming the gas barrier coating film 4 will be described.

First, the metal alkoxide, silane coupling agent, water-soluble polymer, sol-gel catalyst, acid, water, organic solvent, etc. are mixed to prepare a gas barrier composition. Next, the gas barrier coating film 4 is applied on the vapor deposition layer 2 on the substrate 1 and dried. By this drying step, polycondensation of the metal alkoxide, the silane coupling agent, the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer further proceeds, and a coating film is formed. On the first coating film, the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers.

Next, the laminate of the base material 1 and the vapor deposition layer 2 coated with the gas barrier composition is 20 ° C. to 180 ° C. and a temperature below the melting point of the base material 1, preferably a temperature in the range of 50 ° C. to 160 ° C. And heat treatment for 10 seconds to 10 minutes. Moreover, the printing layer 3 is provided on the gas barrier coating film 4 as needed. In this way, the base film 5 can be manufactured.

As the method for applying the gas barrier composition, for example, it is applied once or a plurality of times by an application means such as a roll coat such as a gravure roll coater, a spray coat, a spin coat, a dipping, a brush, a barcode or an applicator. Thus, a coating film having a dry film thickness of 0.01 μm or more and 30 μm or less, preferably 0.1 μm or more and ˜10 μm or less can be formed. Condensation is carried out by heating and drying in a normal environment, for example, at a temperature of 50 to 300 ° C., preferably 70 to 200 ° C., for 0.005 to 60 minutes, preferably 0.01 to 10 minutes. In other words, the gas barrier coating film 4 can be formed.

(Effect of base film)

In the substrate film 5 of the present embodiment, a covalent bond between a metal atom and a carbon atom is formed at the interface between the substrate 1 and the vapor deposition layer 2. For this reason, the adhesiveness of the base material 1 and the vapor deposition layer 2 can be improved. For this reason, it can suppress that peeling of the base material 1 and the vapor deposition layer 2 arises in a hot and humid environment. Thereby, the gas barrier property of the base film 5 can be enhanced, and the occurrence of cracks, pinholes, and the like can be suppressed.

The base film 5 of the present embodiment further includes a gas barrier coating film 4. Thereby, the gas barrier property of the base film 5 can be further enhanced.

Moreover, according to the base film 5 of this Embodiment, the following effect can be show | played when the base film 5 contains the base material 1 which has PBT as a main component.
PBT is excellent in heat resistance. For this reason, when performing a retort process to the packaging bag comprised from the packaging material 8 containing the base film 5, it can suppress that the base material 1 deform | transforms or the intensity | strength of the base material 1 falls. .
PBT has high strength. For this reason, like the case where the packaging material 8 includes nylon, the packaging bag can have puncture resistance.
PBT has a characteristic that it is less likely to absorb moisture than nylon. For this reason, even if it is a case where the base material 1 containing PBT is arrange | positioned on the outer surface of the packaging material 8, it suppresses that the base material 1 absorbs a water | moisture content and the laminate strength of the packaging material 8 falls. be able to.

Wrapping material next with reference to FIG. 4, will be described wrapping material 8 for constituting a packaging bag. The packaging material 8 includes the above-described base film 5 and a thermoplastic resin layer 7 laminated on the base film 5 with an adhesive layer 6 interposed therebetween. In the example shown in FIG. 4, a thermoplastic resin layer 7 is laminated on the surface of the base film 5 on the vapor deposition layer 2 side. The thermoplastic resin layer 7 constitutes the inner surface of the packaging material 8 (the inner surface of the packaging bag constituted by the packaging material 8). Although not shown, a printing layer may be provided between the vapor deposition layer 2 and the adhesive layer 6.

(Thermoplastic resin layer)
The thermoplastic resin layer 7 may be any resin layer or film that can be melted by heat and fused to each other. For example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene. , Polypropylene, polymethylpentene, polystyrene, ethylene-vinyl acetate copolymer, α-olefin copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer It is preferable to use a resin consisting of one or more resins such as a polymer, an ethylene-propylene copolymer, an elastomer or the like, or a film thereof, and among them, since it is a layer in contact with contents such as food, hygiene, Olefies such as polyethylene and polypropylene with excellent heat resistance, chemical resistance, and fragrance retention It is more preferable to use a type or resin or these films consist more system resin.
Further, the thickness is preferably 13 μm or more and 100 μm or less, and more preferably 15 μm or more and 70 μm or less.
The thermoplastic resin layer 7 is preferably made of an unstretched film. “Unstretched” is a concept that includes not only a film that is not stretched at all, but also a film that is slightly stretched due to the tension applied during film formation.

The packaging bag composed of the packaging material 8 may be subjected to sterilization treatment such as boil treatment and retort treatment at a high temperature. Preferably, as the thermoplastic resin layer 7, one having heat resistance that can withstand these high-temperature treatments is used.

The melting point of the material constituting the thermoplastic resin layer 7 is preferably 150 ° C. or higher, and more preferably 160 ° C. or higher. By increasing the melting point of the thermoplastic resin layer 7, the packaging bag can be retorted at a high temperature, and therefore the time required for the retorting process can be shortened. Note that the melting point of the material constituting the thermoplastic resin layer 7 is lower than the melting point of the resin constituting the substrate 1.

When considering from the viewpoint of retort treatment, a material mainly composed of propylene can be used as the material constituting the thermoplastic resin layer 7. Here, the material having “propylene as a main component” means a material having a propylene content of 90% by mass or more. Specific examples of the material mainly composed of propylene include propylene / ethylene block copolymer, propylene / ethylene random copolymer, polypropylene such as homopolypropylene, or a mixture of polypropylene and polyethylene. Can do. Here, the “propylene / ethylene block copolymer” means a material having a structural formula represented by the following formula (I). The “propylene / ethylene random copolymer” means a material having a structural formula represented by the following formula (II). “Homopolypropylene” means a material having the structural formula shown by the following formula (III).

In the case of using a mixture of polypropylene and polyethylene as a material mainly composed of propylene, the material may have a sea-island structure. Here, the “sea-island structure” means a structure in which polyethylene is discontinuously dispersed in a region where polypropylene is continuous.

When considered from the viewpoint of the boil treatment, examples of the material constituting the thermoplastic resin layer 7 include polyethylene, polypropylene, or a combination thereof. Examples of polyethylene include medium density polyethylene, linear low density polyethylene, and combinations thereof. For example, it is also possible to use the materials mentioned as the material constituting the thermoplastic resin layer 7 from the viewpoint of the above retort processing. The material constituting the thermoplastic resin layer 7 has a melting point of, for example, 100 ° C. or higher, more preferably 105 ° C. or higher, and still more preferably 110 ° C. or higher. When polyethylene is used as a material constituting the thermoplastic resin layer 7, a melting point of 100 ° C. or higher can be realized, for example, when the density of polyethylene is 0.920 g / cm ³ or higher. Specific examples of the heat-sealable film for forming the thermoplastic resin layer 7 having a melting point of 100 ° C. or higher include TUX-HC manufactured by Mitsui Chemicals Tosero, L6101 manufactured by Toyobo, and LS700C manufactured by Idemitsu Unitech. it can. Specific examples of the heat-sealable film for forming the thermoplastic resin layer 7 having a melting point of 105 ° C. or higher include NB-1 manufactured by Tamapoly. Specific examples of the heat-sealable film for constituting the thermoplastic resin layer 7 having a melting point of 110 ° C. or higher include LS760C manufactured by Idemitsu Unitech, TUX-HZ manufactured by Mitsui Chemicals Tosero, and the like.

Furthermore, the thermoplastic resin layer 7 may have a light shielding property. In the present embodiment, as the thermoplastic resin layer 7 imparted with a light shielding property, a material having a property of shielding light from the outside can be used.
Specifically, as a material for the light-shielding heat seal layer, a metal such as aluminum can be used by forming a deposited film on the heat sealable film by vacuum deposition or sputtering.
Moreover, in order to provide light-shielding property, a white film may be used for a film and the film in which the light-shielding ink layer was formed can also be used.
Especially, what forms metal vapor deposition films, such as aluminum, can provide light-shielding property and barrier property in the state of the packaging material 8, and is preferable.
Specifically, as a material for the barrier layer, it is common to use a metal such as aluminum by forming a deposited film on a plastic film by vacuum deposition, but in addition, an aluminum foil may be used. .
As a metal for forming such a metal vapor deposition film, metals such as aluminum (Al), chromium (Cr), silver (Ag), copper (Cu), tin (Sn) can be used, It is desirable to use aluminum (Al).
Further, in the above, it is preferable to use an aluminum foil having a thickness of 5 μm or more and 30 μm or less, and a metal vapor deposition film having a thickness of 50 mm or more and ˜3000 mm or less, preferably 100 mm or more and The thing below 1000cm is desirable.
As the light-shielding ink layer, specifically, an ink containing a light-shielding pigment such as aluminum paste or carbon black can be used.
In the above, the thickness of the ink layer is preferably 1 μm or more and 8 μm or less, and more preferably 2 μm or more and 5 μm or less.
The white film contains a white pigment mainly giving a light shielding property to the polyolefin resin.
Specific examples of the white pigment used in the white film include titanium oxide, zinc oxide, extender pigments such as aluminum hydroxide, magnesium carbonate, calcium carbonate, precipitated barium sulfate, silica, and talc.
In the above, the content of the white pigment is preferably 10% or more and 40% or less.

Next, a method for forming a metal deposition film will be described. Examples of such a method include physical vapor deposition methods (Physical Vapor Deposition method, PVD method) such as vacuum deposition, sputtering, and ion plating, plasma enhanced chemical vapor deposition, and thermal chemical vapor deposition. And chemical vapor deposition methods such as photochemical vapor deposition (Chemical Vapor Deposition method, CVD method).
In this embodiment, a method for forming a metal vapor deposition film will be described in detail. A vacuum vapor deposition method in which a metal as described above is used as a raw material, and this is heated and vapor-deposited on a flexible film. Vapor deposition using oxidation reaction vapor deposition method that uses metal, introduces oxygen gas, etc., oxidizes and deposits on flexible film, and plasma-assisted oxidation reaction vapor deposition method that promotes oxidation reaction with plasma. A film can be formed.

(Adhesive layer)
The adhesive layer 6 may be an adhesive layer containing an adhesive or an anchor coat layer. Further, the adhesive layer 6 may be a layer containing an adhesive resin. As an example of adhesive resin, the same resin as the case of the above-mentioned thermoplastic resin layer 7 can be mentioned.

Examples of adhesives include ether-based two-component reactive adhesives and ester-based two-component reactive adhesives. Examples of the ether-based two-component reactive adhesive include polyether polyurethane. The polyether polyurethane is a cured product produced by a reaction between a polyether polyol as a main agent and an isocyanate compound as a curing agent. Examples of the isocyanate compound include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI), and aromatic isocyanate compounds such as tolylene diisocyanate (TDI) and xylylene diisocyanate (XDI). Examples of the ester-based two-component reactive adhesive include polyester polyurethane and polyester. Polyester polyurethane is a cured product produced by a reaction between a polyester polyol as a main agent and an isocyanate compound as a curing agent. As the isocyanate compound, the above-described isocyanate compounds can be used. When an aliphatic compound is used as the isocyanate compound, components that cannot be used for food use do not elute under a high temperature environment such as during heat sterilization (boil treatment or retort treatment), which is suitable for food use.

Here, in the present embodiment, as described above, a covalent bond between a metal atom and a carbon atom is formed at the interface between the substrate 1 and the vapor deposition layer 2. For this reason, the adhesive strength between the base material 1 and the vapor deposition layer 2 can be raised. For this reason, the lamination strength between the base material 1 and the thermoplastic resin layer 7 can be increased. When an adhesive layer containing an adhesive is used as the adhesive layer 6, for example, the laminate strength between the base material 1 of the packaging material 8 and the thermoplastic resin layer 7 is 4.5 N or more, more preferably 5. It can be 0N or more. A method for measuring the laminate strength will be described in Examples described later.

In this embodiment, the packaging material 8 includes PBT having high strength. For this reason, the puncture strength of the packaging material 8 can be, for example, 11N or more, more preferably 13N or more, and further preferably 15N or more. The method for measuring the piercing strength will be described in the examples described later.

Moreover, in this Embodiment, the packaging material 8 is provided with the vapor deposition layer 2 provided on the base material 1. FIG. For this reason, the oxygen permeability and water vapor permeability of the packaging material 8 can be reduced. For example, the oxygen permeability of the packaging material 8 can be 1 cc / day · m ² or less, more preferably 0.6 cc / day · m ² or less. Further, the water vapor permeability of the packaging material 8 can be 1 g / day · m ² or less, and more preferably 0.6 g / day · m ² or less.

The packaging material 8 can be used, for example, as a boil packaging bag, a retort sterilization packaging bag, or a dry food packaging bag such as sweets. The packaging material 8 can also be used in the field of daily necessities or cosmetic packaging bags including shampoos, rinses and rinse-in shampoos. The packaging material 8 can also be used as a packaging material for industrial products such as ink cartridges. The packaging material 8 can also be used in the field of liquid soup packaging bags. The packaging material 8 can also be used as a material for constituting a paper cup, a liquid paper container, and a laminate tube.

When the packaging material 8 is used as a material for constituting the paper cup, the packaging material 8 is laminated on the base film 5 having the vapor deposition layer 2 on the side opposite to the thermoplastic resin layer 7 as shown in FIG. The paper layer 102 is further provided. The paper used as the paper layer 102 has a basis weight of 100 g / m ² or more and 700 g / m ² or less, preferably 150 g / m ² or more and 600 g / m ² or less, more preferably 200 g / m ² or more and 500 g / m ² or less. Is. As the paper layer 102, white paperboard is generally used, but ivory paper using natural pulp, milk carton base paper, cup base paper and the like are particularly preferable from the viewpoint of safety. As shown in FIG. 5, the paper layer 102 may be laminated via the adhesive layer 101. As the adhesive layer 101, a layer similar to the adhesive layer 6 described above can be used.

When the packaging material 8 is used as a material for constituting the liquid paper container, the packaging material 8 has the vapor deposition layer 2 on the side opposite to the first thermoplastic resin layer 7 as shown in FIG. The paper layer 102 laminated | stacked on the base film 5 which has, and the 2nd thermoplastic resin layer 104 laminated | stacked on the paper layer 102 are further provided. As shown in FIG. 6, the paper layer 102 may be laminated via the adhesive layer 101, and the second thermoplastic resin layer 104 may be laminated via the adhesive layer 103. As the adhesive layer 101 and the adhesive layer 103, the same layer as the above-mentioned adhesive layer 6 can be used, and as the second thermoplastic resin layer 104, the same layer as the above-mentioned first thermoplastic resin layer 7 is used. Can be used.

When the packaging material 8 is used as a material for constituting the laminate tube, the packaging material 8 has the vapor deposition layer 2 on the side opposite to the first thermoplastic resin layer 7 as shown in FIG. A second thermoplastic resin layer 104 laminated on the base film 5 is further provided. As shown in FIG. 7, the second thermoplastic resin layer 104 may be laminated via an adhesive layer 103.

As described above, with reference to the attached drawings, an AL-C covalent bond is formed at the interface between the base material 1 and the vapor deposition layer 2 which is manufactured using the film forming equipment 10 equipped with the plasma pretreatment apparatus according to the present invention. Although preferred embodiment of the base film 5 was described, this invention is not limited to this example.
It is obvious for those skilled in the art that various changes or modifications can be made within the scope of the technical idea disclosed in the present application, and these are naturally also within the technical scope of the film forming apparatus 10 of the present invention. Belonging to.

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.

(Example 1)
A film-like base material 1 including a plurality of layers 1a described in the first configuration and manufactured by a casting method was prepared. The content of PBT in each layer 1a was 80%, the number of layers 1a was 1024, and the thickness of the substrate 1 was 15 μm.

Subsequently, on the surface on which the vapor deposition layer 2 of the substrate 1 is provided, using the continuous vapor deposition film forming apparatus in which the pretreatment section in which the plasma pretreatment apparatus of the present invention is disposed and the film formation section are separated, the following in the pretreatment section: Plasma is introduced from a plasma supply nozzle under plasma conditions, and plasma pretreatment is performed at a transfer speed of 480 m / min. As a result, an aluminum oxide vapor deposition layer 2 having a thickness of 10 nm was formed by a reactive resistance heating method.
(Plasma pretreatment conditions)
High frequency power output: 4 kW
Plasma intensity: 550 W · sec / m ²
Plasma forming gas: Oxygen 300 (sccm), Argon 1000 (sccm)
Magnetic forming means: 1000 gauss permanent magnet Applied voltage between pretreatment drum and plasma supply nozzle: 420 V
Pretreatment compartment vacuum: 1.0 × 10 ^-1 Pa
(Conditions for deposition of aluminum oxide deposition layer)
Vacuum degree: 1.0 × 10 ^-2 Pa

Using an X-ray photoelectron spectrometer (Quantum 2000) manufactured by PHI, using AlKα (1486.6 eV) as an X-ray source, with an output of 120 W, the bonding state of the interface between the vapor deposition layer 2 and the substrate 1 containing PBT Analysis was performed. As a result, the presence of a bond of 283.5 ± 0.5 eV (CIS binding energy) derived from the covalent bond between the carbon element and the aluminum atom (AL-C covalent bond) was confirmed.

Next, to a mixed solution composed of polyvinyl alcohol, isopropyl alcohol, and ion-exchanged water of composition a prepared according to the composition table shown below, ethyl silicate, silane coupling agent, isopropyl alcohol, hydrochloric acid, and A hydrolyzate having a solid content of 4 wt% made of ion-exchanged water was added and stirred to obtain a colorless and transparent barrier coating solution.
Composition table a
Polyvinyl alcohol 2.30
Isopropyl alcohol 2.70
H2O 51.20
b
Ethyl silicate 16.60
Silane coupling agent 0.20
Isopropyl alcohol 3.90
0.5N hydrochloric acid aqueous solution 0.50
H2O 22.60
Total 100.00 (wt%)

Next, the gas barrier composition (barrier coating solution) manufactured above is coated on the aluminum oxide vapor deposition surface by using a gravure method, and then heated at 150 ° C. for 60 seconds by a sol-gel method. A gas barrier coating film 4 having a thickness of 0.3 μm (in a dry operation state) obtained by condensation polymerization was formed.

Subsequently, a thermoplastic resin layer 7 was laminated on the surface of the base film 5 on the gas barrier coating film 4 side through an adhesive layer 6. As the adhesive layer 6, a two-component polyurethane adhesive (main agent: RU-40, curing agent: H-4) manufactured by Rock Paint Co., Ltd. was used. The thickness of the adhesive layer 6 was 3 μm. RU-40 contains a polyester polyol. H-4 contains an aliphatic isocyanate compound. As the thermoplastic resin layer 7, an unstretched polypropylene film ZK99S manufactured by Toray Film Processing Co., Ltd. was used. The thickness of the thermoplastic resin layer 7 was 60 μm.

The layer structure of the packaging material 8 of the present embodiment can be expressed as follows in order from the outer surface side to the inner surface side. Note that “/” represents a boundary between layers.
Base material (multilayer PBT) / deposition layer / gas barrier coating film / adhesive layer / thermoplastic resin layer

[Evaluation of oxygen permeability and water vapor permeability]
The oxygen permeability of the packaging material 8 was measured using the MOCON method in a 23 ° C. × 90% RH environment in accordance with JIS K7126-1. As a result, the oxygen permeability was 0.5 cc / day · m ² . Moreover, the water vapor permeability of the packaging material 8 was measured using the MOCON method in a 40 ° C. × 90% RH environment in accordance with JISK7129B. As a result, the water vapor permeability was 0.2 g / day · m ² .

[Evaluation of laminate strength]
Subsequently, the laminate strength of the packaging material 8 was measured. As a measuring instrument, Tensilon universal material testing machine RTC-1310 manufactured by A & D was used. Specifically, first, the packaging material 8 is cut out and, as shown in FIG. 9, the base material 1 side member and the thermoplastic resin layer 7 side member are separated by 15 mm in the long side direction. A test piece was prepared. The width of the test piece (short side length) was 15 mm. Thereafter, as shown in FIG. 10, the already peeled portions of the member on the base material 1 side and the member on the thermoplastic resin layer 7 side were gripped by the gripping tool 71 and the gripping tool 72 of the measuring instrument, respectively. Further, the

grippers

71 and 72 are each set at a speed of 50 mm / min in directions opposite to each other in the direction perpendicular to the surface direction of the portion where the member on the substrate 1 side and the member of the vapor deposition layer 2 are still laminated. And the average value of the tensile stress in the stable region (see FIG. 11) was measured. The spacing S between the

gripping tools

71 and 72 when starting the tension was 30 mm, and the spacing S between the

gripping tools

71 and 72 when finishing the tensioning was 60 mm. FIG. 11 is a diagram illustrating a change in tensile stress with respect to the interval S between the

grippers

71 and 72. As shown in FIG. 11, the change in tensile stress with respect to the interval S enters the second region (stable region) having a smaller change rate than the first region through the first region.

For the five test pieces, the average value of tensile stress in the stable region was measured, and the average value was defined as the laminate strength between the base material 1 of the packaging material 8 and the thermoplastic resin layer 7. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. As a result, the laminate strength at a width of 15 mm was 5.0 N.

[Evaluation of puncture strength]
Subsequently, the piercing strength of the packaging material 8 was measured according to JIS Z1707 7.4. As a measuring instrument, Tensilon universal material testing machine RTC-1310 manufactured by A & D was used. Specifically, a semicircular needle 80 having a diameter of 1.0 mm and a tip shape radius of 0.5 mm is applied to the test piece of the packaging material 8 in a fixed state from the base 1 side at 50 mm / min. The maximum value of the stress until the needle 80 penetrates the packaging material 8 was measured by piercing at a speed of (50 mm per minute). About five or more test pieces, the maximum value of stress was measured, and the average value was defined as the piercing strength of the packaging material 8. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. As a result, the piercing strength was 16N.

[Evaluation of retort suitability]
The two packaging materials 8 are stacked and heated at 190 ° C. for 1 second to heat-seal the thermoplastic resin layers 7 of the packaging material 8 and are filled with 200 g of water as a content to form a rectangular 4 A side-sealed bag was produced. The four-side seal bag had a height of 180 mm and a width of 130 mm. Subsequently, a retort sterilization treatment was performed in which the four-side sealed bag was heated at 121 ° C. for 40 minutes. Thereafter, it was confirmed whether or not the appearance of the four-side seal bag was whitened. As a result, no whitening was observed.

(Example 2)
A packaging material 8 was produced in the same manner as in Example 1 except that a film-like substrate 1 containing PBT and produced by a tubular method was used as the substrate 1. The substrate 1 was a single layer film composed only of PBT and additives, and the thickness of the substrate 1 was 15 μm. The layer structure of the packaging material 8 of the present embodiment can be expressed as follows in order from the outer surface side to the inner surface side. Note that “/” represents a boundary between layers.
Base material (single layer PBT) / deposition layer / gas barrier coating film / adhesive layer / thermoplastic resin layer

Further, in the same manner as in Example 1, the oxygen permeability and water vapor permeability, laminate strength, puncture strength, and retort suitability of the packaging material 8 were evaluated. As a result, the oxygen permeability was 0.3 cc / day · m ² , the water vapor permeability was 0.3 g / day · m ² , the laminate strength at 15 mm width was 5.3 N, and the piercing strength was 15 N. It was. Moreover, whitening was not seen when the retort sterilization process was performed.

(Example 3)
A base material 1 similar to that in Example 1 was prepared except that the content of PBT in each layer 1a was 70%. Subsequently, a packaging material 8 was produced in the same manner as in Example 1.

Further, in the same manner as in Example 1, the oxygen permeability and water vapor permeability, laminate strength, puncture strength, and retort suitability of the packaging material 8 were evaluated. As a result, the oxygen permeability was 0.3 cc / day · m ² , the water vapor permeability was 0.3 g / day · m ² , the laminate strength at 15 mm width was 5.3 N, and the piercing strength was 13 N. It was. Moreover, whitening was not seen when the retort sterilization process was performed.

(Comparative Example 1)
A packaging material 8 was produced in the same manner as in Example 1 except that a nylon film having a thickness of 15 μm (Bonil W manufactured by Kojin Holdings Co., Ltd.) was used as the substrate 1. The layer structure of the packaging material 8 of Comparative Example 1 can be expressed as follows in order from the outer surface side to the inner surface side. Note that “/” represents a boundary between layers.
Base material (nylon) / deposition layer / gas barrier coating film / adhesive layer / thermoplastic resin layer

Further, in the same manner as in Example 1, the oxygen permeability and water vapor permeability, laminate strength, puncture strength, and retort suitability of the packaging material 8 were evaluated. As a result, the oxygen permeability was 0.2 cc / day · m ² , the water vapor permeability was 1.3 g / day · m ² , the laminate strength at 15 mm width was 3.8 N, and the piercing strength was 15 N. It was. Moreover, whitening was seen when the retort sterilization process was performed.

(Comparative Example 2)
A packaging material 8 was produced in the same manner as in Example 1 except that a PET film having a thickness of 12 μm (T4102 manufactured by Toyobo Co., Ltd.) was used as the substrate 1. The layer structure of the packaging material 8 of Comparative Example 2 can be expressed as follows in order from the outer surface side to the inner surface side. Note that “/” represents a boundary between layers.
Base material (PET) / deposition layer / gas barrier coating film / adhesive layer / thermoplastic resin layer

Further, in the same manner as in Example 1, the oxygen permeability and water vapor permeability, laminate strength, puncture strength, and retort suitability of the packaging material 8 were evaluated. As a result, the oxygen permeability was 0.2 cc / day · m ² , the water vapor permeability was 0.4 g / day · m ² , the laminate strength at 15 mm width was 6.1 N, and the piercing strength was 10 N. It was. Moreover, whitening was not seen when the retort sterilization process was performed.

The evaluation results of Examples 1, 2, and 3 and Comparative Examples 1 and 2 are collectively shown in FIG. As can be seen from the comparison between Examples 1, 2, 3 and Comparative Example 1, the packaging material 8 is provided with PBT instead of nylon, so that the water vapor permeability of the packaging material 8 is reduced, and the packaging material is used. The laminate strength of 8 could be increased. Furthermore, it was possible to suppress the whitening of the packaging material 8 due to the retort sterilization treatment.

Further, as can be seen from the comparison between Examples 1, 2, and 3 and Comparative Example 2, the piercing strength of the packaging material 8 can be 11 N or more by providing the packaging material 8 with PBT instead of PET. More specifically, it could be 13N or more.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Deposition layer 3 Print layer 4 Gas barrier coating film 5 Base film 6 Adhesive layer 7 Thermoplastic resin layer 8 Packaging material P Plasma 10 Deposition equipment 12 Decompression chamber 12A Substrate transport chamber 12B Plasma pretreatment chamber 12C Deposition chamber 13 Unwind roller 14 Guide roller 15 Take-up roller 18 Raw material gas volatilization supply device 19 Raw material gas supply nozzle 20 Plasma pretreatment roller 21 Magnet 22 Plasma supply nozzle 25 Deposition roller 26 Deposition means 30 Vacuum pump 31 Power supply Wiring 32 Power supply 35a-35c Bulkhead

Claims

A substrate;
A vapor deposition layer provided on the base material and containing a metal or an alloy;
The base material contains 51% by mass or more of polybutylene terephthalate,
The film in which the covalent bond of a metal atom and a carbon atom is formed in the interface of the said base material and the said vapor deposition layer.
The film according to claim 1, wherein the base material contains 60% by mass or more of polybutylene terephthalate.
The film according to claim 1 or 2, further comprising a gas barrier coating film provided on the vapor deposition layer.
The film according to any one of claims 1 to 3, wherein the vapor deposition layer is a transparent vapor deposition layer.
The film according to any one of claims 1 to 4, wherein the vapor deposition layer is made of an inorganic oxide containing aluminum oxide or a mixture of a plurality of inorganic oxides.
The film according to claim 5, wherein the inorganic oxide is a mixture of aluminum oxide and one or more inorganic oxides selected from silicon oxide, magnesium oxide, tin oxide, and zinc oxide.
The film according to any one of claims 1 to 6, wherein a thickness of the vapor deposition layer is 5 nm and 200 nm or less.
Preparing a substrate;
A vapor deposition step of depositing a metal or an alloy on the base material to form a vapor deposition layer on the base material,
The base material contains 51% by mass or more of polybutylene terephthalate,
The film manufacturing method in which the covalent bond of a metal atom and a carbon atom is formed in the interface of the said base material and the said vapor deposition layer.
A plasma pretreatment step of performing plasma treatment on the substrate to form a plasma treatment surface on the substrate;
The said vapor deposition process is a film manufacturing method of Claim 8 which forms the said vapor deposition layer on the said plasma processing surface of the said base material.
In the plasma pretreatment step, the substrate is held between the plasma pretreatment roller and the plasma supply unit in a state where a voltage is applied between the plasma pretreatment roller and the plasma supply unit, and the substrate is subjected to plasma treatment. Forming a surface,
The film production method according to claim 9, wherein the vapor deposition step forms the vapor deposition layer on the plasma treatment surface of the base material in succession to the plasma pretreatment step.
The plasma pretreatment step is performed by a roller-type film forming facility in which a pretreatment section for performing a plasma treatment on the substrate and a film forming section for forming the vapor deposition layer are continuously arranged.
The roller-type film-forming facility is configured to plasma a plasma source gas on the surface of the substrate between the plasma pretreatment roller and the plasma supply unit and the magnetic field formation unit arranged to face the plasma pretreatment roller. The film manufacturing method according to claim 10, wherein the film manufacturing method is configured to form a void for containing the plasma when introduced as.
The plasma pretreatment step, the surface of the substrate, a plasma treatment with 100W · sec / m 2 or more and 8000W · sec / m 2 under the following conditions as the plasma intensity per unit area, in claim 10 or 11 The film manufacturing method of description.
The film manufacturing method according to any one of claims 9 to 12, wherein the plasma source gas is a mixed gas of argon alone and / or one or more of oxygen, nitrogen, and carbon dioxide.
14. The film manufacturing method according to claim 13, wherein the plasma pretreatment step performs plasma treatment using a plasma source gas composed of a mixed gas of at least one of oxygen, nitrogen and carbon dioxide and argon.
The film deposition method according to any one of claims 9 to 14, wherein the vapor deposition step forms the vapor deposition layer on the plasma-treated surface of the substrate by physical vapor deposition.
Packaging material,
A film having a base material and a vapor deposition layer provided on the base material and containing a metal or an alloy;
A thermoplastic resin layer laminated on the film,
The base material contains 51% by mass or more of polybutylene terephthalate,
A packaging material in which a covalent bond of a metal element and a carbon element is formed at an interface between the base material and the vapor deposition layer.
The packaging material according to claim 16, which has a puncture strength of 11N or more.
The thermoplastic resin layer is laminated to the film via an adhesive layer,
The packaging material according to claim 16 or 17, wherein a laminate strength between the base material and the thermoplastic resin layer in a width of 15 mm is 4 N or more.
The packaging material according to any one of claims 16 to 18, wherein the thermoplastic resin layer has a light shielding property.
The packaging material according to any one of claims 16 to 19, which is used for a boil packaging bag or a retort sterilization packaging bag.