JP7441433B2 - Vapor deposition film forming apparatus and vapor deposition film forming method - Google Patents

Description

The present invention relates to a vapor deposition film forming apparatus and a vapor deposition film forming method for forming a vapor deposited film on a base material.

BACKGROUND OF THE INVENTION Laminated films including a vapor-deposited film formed on a base material by a vapor-deposition method are used for various purposes. For example, in fields that require retort processing of foods, pharmaceuticals, etc., higher barrier properties that are unaffected by temperature and humidity are needed to prevent the contents from deteriorating and maintain their functions and properties. Laminated films that can stably perform are required as packaging materials.

However, the plastic base material of the laminated film, which has a vapor-deposited film with excellent barrier properties that are easily affected by temperature and humidity, is susceptible to dimensional changes. It is difficult to follow the deposited film provided thereon, such as a silicon oxide deposited film or an aluminum oxide deposited film. Therefore, delamination often occurs between the plastic base material and the vapor deposited film such as silicon oxide vapor deposition film or aluminum oxide vapor deposition film in harsh environments of high temperature and humidity, and cracks and pinholes may also occur. Occur. As a result, there is a problem in that the original barrier performance is significantly impaired and it is extremely difficult to maintain the barrier performance.

When forming a vapor-deposited film of an inorganic oxide such as aluminum oxide on a plastic substrate using the method using the above-mentioned vapor-deposited film, in order to obtain high adhesion between the plastic substrate and the formed vapor-deposited film, Methods for modifying the surface of plastic substrates, such as in-line plasma pretreatment using a parallel plate type device and formation of an undercoat treatment layer, have been implemented (see, for example, Patent Document 1 and Patent Document 2).

For example, in the in-line plasma processing method using a commonly used parallel plate device as described in Patent Document 1, functional groups such as hydroxyl groups and carbonyl groups are introduced onto the plastic surface, and the functional groups are interposed between the deposited films. It exhibits adhesion. However, the adhesion of products that develop adhesion through hydrogen bonds due to hydroxyl groups deteriorates significantly in the high temperature and humidity environments required for electronic devices such as electronic paper, retort packaging materials, etc., as the hydrogen bonds are destroyed. There is a problem of deterioration. In addition, since the above plasma treatment simply passes the film through a plasma atmosphere generated in the air, sufficient adhesion between the substrate and the deposited film may not be achieved in harsh environments of high temperature and humidity. is the reality.

Further, the undercoat treatment method described in Patent Document 2 provides an undercoat layer as an adhesive layer on the surface of a plastic film, and is commonly practiced, but the manufacturing method increases the number of steps, resulting in an increase in cost.

Therefore, a technology has been implemented to improve adhesion by pre-treating the surface of the plastic substrate using a reactive ion etching (RIE) method in which plasma is generated with the electrode for plasma generation on the substrate side. (Patent Document 3). The plasma RIE method achieves two effects at the same time: a chemical effect such as adding functional groups to the surface of the base material, and a physical effect such as ion etching the surface to remove impurities and smooth it. It exhibits adhesion.

In the RIE method, unlike the above-mentioned in-line plasma treatment, adhesion is not developed by hydrogen bonding, so no decrease in adhesion is observed in a high temperature and humid environment. However, in the RIE method, since functional groups are provided on the plastic base material, water resistance and hot water resistance are still insufficient due to hydrolysis at the interface. Furthermore, in order to obtain sufficient adhesion using the RIE method, an Ed value (=plasma density×processing time) of a certain value or more is required. In order to obtain an Ed value above a certain value using this method, there are two possible methods: increasing the plasma density and lengthening the processing time, but increasing the plasma density requires a high-output power source. There is a problem of increased damage to the base material, and if the processing time is increased, a decrease in productivity becomes a problem (see Patent Document 4 and Patent Publication 5).

Therefore, we have solved the problem of forming an inorganic oxide vapor deposited film on the surface of the plastic substrate being transported as described above, and the adhesion between the plastic substrate and the vapor deposited film is good even after retort treatment. , a laminated film with excellent barrier properties is desired.

In particular, in fields that require high temperature, high pressure retort processing and sterilization of foods, pharmaceuticals, etc., it is necessary to prevent the contents from deteriorating and to maintain their functions and properties. There is a need for a barrier multilayer film that can stably exhibit higher barrier properties, and has a multilayer structure consisting of a barrier layer made of a thin film of aluminum oxide such as silicon oxide or aluminum oxide, and a barrier coating layer. A barrier laminated film with excellent retort resistance is desired.

Japanese Patent Application Publication No. 7-233463 Japanese Patent Application Publication No. 2000-43182 Japanese Patent Application Publication No. 2005-335109 Patent No. 4461737 Patent No. 4135496

A problem with the prior art is that retort treatment using hot water imposes large mechanical and chemical stress on the interface between the plastic substrate and the deposited film. This stress deteriorates the barrier properties. This area is stressed because it is the weakest part of the stack. Therefore, in order to obtain retort resistance, it is important to firmly cover the interface with the base material with a deposited film.

The present invention has been made in view of the above-mentioned problems and knowledge, and its purpose is to improve the bond between the plastic substrate and the plastic substrate even after a treatment that applies stress to the deposited film, such as hot water treatment. An object of the present invention is to provide a vapor deposition film forming apparatus and a vapor deposition film forming method for forming a vapor deposited film having good adhesion and excellent barrier properties on a plastic substrate.

The present invention is a film forming apparatus for forming a vapor-deposited film of an inorganic oxide on the surface of a plastic base material, comprising a film forming roller that conveys the wrapped plastic base material, and a film forming roller that faces the film forming roller. a film-forming mechanism having a film-forming source in which a target containing an inorganic material serving as a raw material for the vapor-deposited film is arranged; Alternatively, there is provided a vapor deposition film forming apparatus comprising: a water vapor supply mechanism having at least a water vapor emitting section that emits water vapor or water vapor plasma so that the water vapor plasma reaches the surface of the plastic base material.

In the vapor deposition film forming apparatus according to the present invention, the water vapor supply mechanism includes a water vapor generation unit that generates water vapor or water vapor plasma, and a water vapor delivery unit that supplies the water vapor or water vapor plasma generated by the water vapor generation unit to the water vapor release unit. a water vapor control unit that controls the water vapor feeding unit based on the detected amount of water vapor or water vapor plasma around the plastic base material to adjust the amount of water vapor or water vapor plasma fed to the water vapor release unit; and may further include.

In the vapor deposition film forming apparatus according to the present invention, the water vapor generation section includes a tank containing water, and the water vapor supply section is connected to the tank above the liquid level of the water contained in the tank. It may also include pipes that have been installed.

In the vapor deposition film forming apparatus according to the present invention, the water vapor discharge section may include a plurality of discharge ports that are arranged in the width direction of the plastic base material perpendicular to the conveying direction of the plastic base material and that discharge water vapor or water vapor plasma. good.

In the vapor deposition film forming apparatus according to the present invention, the vapor deposition film forming apparatus is separated from a film forming chamber in which the film forming mechanism is arranged by a partition wall, and is upstream of the film forming chamber in the transport direction of the plastic base material. The plasma pretreatment mechanism further includes a plasma pretreatment mechanism disposed in a plasma pretreatment chamber located on the side, and the plasma pretreatment mechanism is configured to treat the plastic material wound on the upstream side of the film forming roller in the conveyance direction of the plastic base material. It has a pre-treatment roller that conveys the substrate, and a plasma supply means that generates plasma around the pre-treatment roller, and the water vapor emitting section is configured to perform pre-treatment that emit water vapor or water vapor plasma in the plasma pre-treatment chamber. It may also have a room water vapor release section.

In the vapor deposition film forming apparatus according to the present invention, the vapor deposition film forming apparatus further includes a substrate transport mechanism arranged in a substrate transport chamber separated by a partition from the film forming chamber in which the film forming mechanism is arranged. , the water vapor emitting section has a water vapor emitting section for a substrate transfer chamber that emits water vapor or water vapor plasma at an upstream side of the film forming source in the transfer direction of the plastic substrate in the substrate transfer chamber. Good too.

In the vapor deposition film forming apparatus according to the present invention, the water vapor discharge section is configured to generate water vapor or water vapor plasma in a film forming chamber in which the film forming mechanism is arranged, on the upstream side of the film forming source in the transport direction of the plastic base material. The film-forming chamber may have a water vapor emitting section for emitting water vapor.

In the vapor deposition film forming apparatus according to the present invention, the film forming mechanism includes an oxygen releasing section that releases oxygen gas so that the oxygen gas reaches the surface of the plastic base material, The target may include aluminum.

In the vapor deposition film forming apparatus according to the present invention, the film forming mechanism includes an oxygen releasing section that releases oxygen gas so that the oxygen gas reaches the surface of the plastic base material, The target may include silicon.

The present invention is a film-forming method for forming a vapor-deposited film of an inorganic oxide on the surface of a plastic base material, in which a water vapor discharge part is configured to generate water vapor or water vapor plasma so that the water vapor or water vapor plasma reaches the surface of the plastic base material. and the vapor deposition step, which is disposed at a film forming source facing a film forming roller around which the plastic base material is wound on the downstream side of the water vapor release part in the conveying direction of the plastic base material. This method includes a step of forming the vapor deposited film on the surface of the plastic base material by evaporating a target containing an inorganic material that is a raw material for the film.

According to the present invention, it is possible to form a deposited film on a plastic substrate that has good adhesion to the plastic substrate and has excellent barrier properties.

It is a sectional view showing an example of a laminated film provided with a vapor deposition film. It is a sectional view showing an example of a laminated film provided with a vapor deposition film. FIG. 2 is a cross-sectional view showing an example of a plastic base material of a laminated film. 1 is a diagram showing an example of a vapor deposition film forming apparatus according to an embodiment of the present invention. FIG. 3 is a diagram showing an example of a water vapor supply mechanism of the vapor deposition film forming apparatus. FIG. 3 is a diagram showing an example of a graphical analysis diagram of the analysis results of a laminated film using time-of-flight secondary ion mass spectrometry. It is a figure which shows the example of a modification of a vapor deposition film-forming apparatus. FIG. 3 is a perspective view showing an example of a water vapor discharge section of the water vapor supply mechanism. It is a figure which shows the example of a modification of a vapor deposition film-forming apparatus. It is a figure which shows the example of a modification of a vapor deposition film-forming apparatus. It is a figure which shows the example of a modification of a vapor deposition film-forming apparatus. It is a figure which shows the example of a modification of a vapor deposition film-forming apparatus. It is a figure which shows the example of a modification of a vapor deposition film-forming apparatus. It is a figure which shows the example of a modification of a vapor deposition film-forming apparatus.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a laminated film having a vapor-deposited film having barrier properties with improved adhesion and a barrier laminated film including the laminated film according to embodiments of the present invention will be described in detail with reference to the drawings. Note that this example is merely an illustration and does not limit the present invention in any way.
FIG. 1a is a cross-sectional view showing an example of a laminated film produced in the present invention, and FIG. 1b is a cross-sectional view showing an example of a barrier laminated film including the laminated film and having a barrier coating layer laminated on the surface. FIG. 2 is a diagram schematically showing the configuration of a roller-type continuous vapor deposition apparatus suitable for forming a vapor deposited film of a laminated film having barrier properties. In addition, in order to form a barrier laminated film in which barrier coating layers are laminated, a barrier coating agent coating device is placed in succession to a vapor deposition film forming device, but a known roller coating device is not installed in series. Yes, it is not shown here.

A laminated film A having a vapor deposited film with barrier properties with improved adhesion is, as shown in FIG. The basic structure is a laminated layer structure. Furthermore, as shown in FIG. 1b, a layered structure is formed in which a barrier coating layer 3 is further layered on the vapor deposited film 2 of the laminated film A, and a barrier coating layer 3 is further layered on the vapor deposited film 2 of the layered film A, and furthermore, the layered film A has a layered structure with excellent adhesion, barrier properties, and retort resistance. It may also be used as a multilayer film B. A vapor deposited film 2 formed on one surface of the plastic substrate 1 by a vapor deposition film forming apparatus described below is made of an inorganic oxide such as aluminum oxide or silicon oxide. When the vapor deposited film 2 contains aluminum oxide, the target of the film formation source described below contains aluminum. When the vapor deposited film 2 contains silicon oxide, the target of the film formation source described later contains silicon. In this embodiment, an example in which the deposited film 2 is made of aluminum oxide will be described.

The plastic base material is not particularly limited, and any known plastic film or sheet can be used. For example, polyester resins such as polyethylene terephthalate, biomass-derived polyester, polybutylene terephthalate, and polyethylene naphthalate; polyamide resins such as polyamide resin 6, polyamide resin 66, polyamide resin 610, polyamide resin 612, polyamide resin 11, and polyamide resin 12. A film made of a resin, a polyolefin resin such as a polymer of α-olefin such as polyethylene or polypropylene, etc. can be used. A polyester resin known as polyethylene terephthalate is particularly preferably used. As the polyethylene terephthalate, for example, polyethylene terephthalate recycled by mechanical recycling can be used.

(Polybutylene terephthalate film)
Polybutylene terephthalate film has a high heat distortion temperature, excellent mechanical strength and electrical properties, and good moldability, so it is suitable for use in packaging bags that contain food and other contents during retort processing. This can prevent the packaging bag from deforming or reducing its strength.

Polybutylene terephthalate film has high strength. Therefore, when a polybutylene terephthalate film is used, the packaging bag can be provided with puncture resistance, as in the case where the packaging material constituting the packaging bag includes a nylon film.
In addition, polybutylene terephthalate film hydrolyzes in a high temperature and high humidity environment, resulting in a decrease in adhesion strength and barrier properties after retort treatment, but it has the property of being less likely to absorb moisture than nylon. Therefore, even when the polybutylene terephthalate film is disposed on the outer surface of the packaging material, it is possible to prevent the lamination strength between the packaging materials of the packaging bag from decreasing. Since polybutylene terephthalate film has the above-mentioned properties, it is preferably used in retort packaging bags because it can replace the conventional packaging material made of polyethylene terephthalate film and nylon film.

A polybutylene terephthalate film is a film containing polybutylene terephthalate (hereinafter also referred to as PBT) as a main component, and is a resin film containing 51% by mass or more of PBT. Polybutylene terephthalate films can be divided into two types based on their structure.

The content of PBT in the polybutylene terephthalate film according to the first aspect is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 75% by mass or more, and most preferably 80% by mass or more.
The dicarboxylic acid component of PBT used as a main component is preferably 90 mol% or more of terephthalic acid, more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 100 mol% or more. It is mole%. As a glycol component, 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably 97 mol% or more.

The polybutylene terephthalate film may contain polyester resins other than PBT. Examples of polyester resins other than PBT include polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polypropylene terephthalate (PPT), as well as isophthalic acid, orthophthalic acid, and naphthalene dicarboxylic acid. , PBT resins copolymerized with dicarboxylic acids such as biphenyl dicarboxylic acid, cyclohexane dicarboxylic acid, adipic acid, azelaic acid, and sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, and neopentyl glycol. Examples include PBT resins in which diol components such as , 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, and polycarbonate diol are copolymerized.

The amount of polyester resin other than PBT added is preferably 40% by mass or less. If the amount of polyester resin other than PBT exceeds 40% by mass, the mechanical properties of PBT may be impaired, and impact strength, pinhole resistance, and drawing formability may become insufficient.

The layer structure of the polybutylene terephthalate film according to the first aspect is produced by casting a multilayered resin by a casting method, and is composed of a multilayer structure including a plurality of unit layers. Each of the plurality of unit layers contains PBT as a main component. For example, each of the plurality of unit layers contains at least 51% by mass or more, preferably 60% by mass or more of PBT. Note that in the plurality of unit layers, the (n+1)th unit layer is directly stacked on the nth unit layer. That is, no adhesive layer or bonding layer is interposed between the plurality of unit layers. Such a polybutylene terephthalate film consists of a multilayer structure including at least 10 or more unit layers, preferably 60 or more layers, more preferably 250 or more layers, still more preferably 1000 or more layers.

The polybutylene terephthalate film according to the second aspect is composed of a single layer containing polyester having PBT as a main repeating unit. A polyester having PBT as the main repeating unit, for example, has 1,4-butanediol or its ester-forming derivative as a glycol component and terephthalic acid or its ester-forming derivative as a dibasic acid component as its main components. , homo- or copolymer-type polyesters obtained by condensing them. The content of PBT in the second configuration is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more.

The polybutylene terephthalate film according to the second aspect may contain a polyester resin other than PBT in a range of 30% by mass or less. By including the polyester resin, PBT crystallization can be suppressed and the stretchability of the polybutylene terephthalate film can be improved. As the polyester resin to be mixed with PBT, a polyester having 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.

The polybutylene terephthalate film according to the second configuration can be manufactured by a tubular method or a tenter method. The unstretched original fabric may be stretched simultaneously in the machine direction and the transverse direction, or sequentially in the machine direction and the transverse direction, by a tubular method or a tenter method. Among these, the tubular method is particularly preferably employed because it can produce a stretched film with good balance of physical properties in the circumferential direction.

(Polyester film derived from biomass)
The biomass-derived polyester film is composed of a resin composition containing as a main component a polyester consisting of diol units and dicarboxylic acid units, and the resin composition has diol units that are biomass-derived ethylene glycol and dicarboxylic acid units. The polyester is a fossil fuel-derived dicarboxylic acid in an amount of 50 to 95% by mass, preferably 50 to 90% by mass, based on the entire resin composition.

Biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol, so polyester films synthesized using biomass-derived ethylene glycol are mechanically comparable to conventional fossil fuel-derived polyester films. There is no inferiority in terms of physical properties such as physical properties. Therefore, since the laminated film and the barrier laminated film using the same have a layer made of carbon-neutral material, the laminated film manufactured from raw materials obtained from conventional fossil fuels and the barrier laminated film using the same are In comparison, the amount of fossil fuel used can be significantly reduced, and the environmental impact can be reduced.

Biomass-derived ethylene glycol is made from ethanol produced from biomass such as sugarcane and corn (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene glycol via ethylene oxide using a conventionally known method. Moreover, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Corporation can be suitably used.

Dicarboxylic acid derived from fossil fuels is used as the dicarboxylic acid unit of the polyester. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and examples of derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters. Examples include esters. Among these, terephthalic acid is preferred, and as the aromatic dicarboxylic acid derivative, dimethyl terephthalate is preferred.

The polyester that may be contained in a proportion of 5 to 45% by mass in the resin composition forming the biomass-derived polyester film includes fossil fuel-derived polyester, recycled polyester of fossil fuel-derived polyester products, and biomass-derived polyester products. Made of recycled polyester.

The resin composition containing the polyester obtained as described above preferably contains 10 to 19% of biomass-derived carbon based on the total carbon in the polyester as determined by radiocarbon (C14) measurement. Since carbon dioxide in the atmosphere contains C14 at a certain rate (105.5 pMC), the C14 content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyester, the proportion of carbon derived from biomass can be calculated. The biomass-derived carbon content Pbio, where the C14 content in polyester is PC14, is defined as follows.
Pbio (%) = PC14/105.5×100
Taking polyethylene terephthalate as an example, polyethylene terephthalate is a polymerization of ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1, so only biomass-derived ethylene glycol can be used. When Pbio is used, the biomass-derived carbon content Pbio in the polyester is 20%. The content of biomass-derived carbon based on radiocarbon (C14) measurement is preferably 10 to 19% of the total carbon in the resin composition. If the biomass-derived carbon content in the resin composition is less than 10%, the effect as a carbon offset material will be poor. On the other hand, as mentioned above, the biomass-derived carbon content in the resin composition is preferably close to 20%, but due to problems in the film manufacturing process and physical properties, the resin may contain recycled polyester or Since it is preferable to include additives, the actual upper limit is 18%.

(Film containing recycled polyethylene terephthalate through mechanical recycling)
As the plastic base material 1 of the present invention, a film containing polyethylene terephthalate (hereinafter, polyethylene terephthalate is also referred to as PET) recycled by mechanical recycling can be used.

Specifically, the film used as the plastic substrate 1 includes PET obtained by mechanically recycling PET bottles, and this PET has diol units of ethylene glycol and dicarboxylic acid units of terephthalic acid and isophthalic acid. include.

Mechanical recycling here generally means that collected polyethylene terephthalate resin products such as PET bottles are crushed, washed with alkali to remove dirt and foreign matter from the surface of the PET resin product, and then dried for a certain period of time under high temperature and reduced pressure. In this method, contaminants remaining inside the PET resin are diffused and decontaminated, dirt is removed from resin products made of PET resin, and the product is returned to PET resin again.

Hereinafter, in this specification, polyethylene terephthalate made from recycled PET bottles will be referred to as "recycled polyethylene terephthalate (hereinafter also referred to as recycled PET)", and polyethylene terephthalate that has not been recycled will be referred to as "virgin polyethylene terephthalate (hereinafter also referred to as virgin PET)". )”.

The content of isophthalic acid in the PET contained in the film is preferably 0.5 mol% or more and 5 mol% or less, and 1.0 mol% or more and 2 More preferably, it is .5 mol% or less.
If the content of isophthalic acid is less than 0.5 mol%, the flexibility may not be improved, while if it exceeds 5 mol%, the melting point of PET may decrease and the heat resistance may become insufficient.

Note that PET may be biomass PET in addition to normal fossil fuel-derived PET. "Biomass PET" includes ethylene glycol derived from biomass as a diol unit and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid unit. This biomass PET may be formed only of PET in which biomass-derived ethylene glycol is used as a diol unit and fossil fuel-derived dicarboxylic acid is used as a dicarboxylic acid unit, or it may be formed only with PET in which biomass-derived ethylene glycol and fossil fuel-derived diol are used as diol units. It may be formed of PET having diol units and fossil fuel-derived dicarboxylic acids as dicarboxylic acid units.

PET used for PET bottles can be obtained by a conventionally known method of polycondensing the diol units and dicarboxylic acid units described above.
Specifically, a general method of melt polymerization in which the above-mentioned diol unit and dicarboxylic acid unit are subjected to an esterification reaction and/or a transesterification reaction, followed by a polycondensation reaction under reduced pressure, or an organic solvent It can be produced by a known solution heating dehydration condensation method using.
The amount of diol units used in producing the above PET is substantially equimolar to 100 moles of the dicarboxylic acid or its derivative, but in general, esterification and/or transesterification reaction and/or polycondensation reaction is used. Since distillation occurs during the reaction, it is used in an excess of 0.1 mol % or more and 20 mol % or less.
Further, the polycondensation reaction is preferably carried out in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added at the time of charging the raw materials or at the start of pressure reduction.

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

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

The film containing recycled PET preferably contains recycled PET in a proportion of 50% by weight or more and 95% by weight or less, and may contain virgin PET in addition to recycled PET. When the film containing recycled PET further contains virgin PET, the virgin PET may be PET in which the diol unit as described above is ethylene glycol and the dicarboxylic acid unit contains terephthalic acid and isophthalic acid, and PET in which the dicarboxylic acid unit does not contain isophthalic acid may also be used.
Moreover, the film containing recycled PET may contain polyester other than PET.

Recycled PET may contain, for example, aliphatic dicarboxylic acids and the like in addition to aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid as dicarboxylic acid units.
Specifically, aliphatic dicarboxylic acids include chains usually having 2 to 40 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. or alicyclic dicarboxylic acids. Examples of derivatives of aliphatic dicarboxylic acids include lower alkyl esters such as methyl esters, ethyl esters, propyl esters and butyl esters of the above aliphatic dicarboxylic acids, and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride. . Among these, adipic acid, succinic acid, dimer acid, or a mixture thereof is preferred as the aliphatic dicarboxylic acid, and those containing succinic acid as a main component are particularly preferred. As the aliphatic dicarboxylic acid derivative, methyl esters of adipic acid and succinic acid, or mixtures thereof are more preferred.
A film containing such recycled PET may be a single layer or a multilayer.

As shown in FIG. 1c, when using a film containing recycled PET as described above for the plastic base material 1, a film including three layers, a first layer 1a, a second layer 1b, and a third layer 1c, is used. May be used.
In this case, the second layer 1b should be a layer made only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 1a and the third layer 1c should be made only of virgin PET. is preferred.
In this way, by using only virgin PET for the first layer 1a and the third layer 1c, it is possible to prevent recycled PET from coming out from the front or back surface of the plastic base material 1. Therefore, the hygiene of the laminate can be ensured.

Further, the film may not include the first layer 1a shown in FIG. 1c but may include two layers, the second layer 1b and the third layer 1c. Moreover, the film may not include the third layer 1c shown in FIG. 1c, but may include two layers, the first layer 1a and the second layer 1b. Even in these cases, the second layer 1b is a layer made only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 1a and the third layer 1c are made layers made only of virgin PET. It is preferable that

In the case of mixing recycled PET and virgin PET to form a mixed layer, there are a method of feeding them separately to a molding machine, a method of mixing them by dry blending, etc., and then feeding them. Among these, a method of mixing by dry blending is preferred from the viewpoint of easy operation.

Various additives can be added to the film containing recycled PET during or after its production process, within the range that does not impair its properties. Examples of additives include plasticizers, ultraviolet stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducers, mold release agents, antioxidants, Examples include ion exchange agents and colored pigments. The additive is preferably added in an amount of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less, based on the entire resin composition containing recycled PET contained in the film.

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

The film obtained as described above is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded onto a cooling drum as described above is then heated by roll heating, infrared heating, etc., and stretched in the longitudinal direction to form a longitudinally stretched film. This stretching is preferably carried out using the difference in circumferential speed between two or more rolls.
Longitudinal stretching is usually performed at a temperature range of 50°C or higher and 100°C or lower. Further, the longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the film application.
When the stretching ratio is less than 2.5 times, the thickness unevenness of the PET film becomes large and it is difficult to obtain a good film.
The longitudinally stretched film is then sequentially subjected to transverse stretching, heat setting, and heat relaxation to become a biaxially stretched film. The transverse stretching is usually performed at a temperature range of 50°C or higher and 100°C or lower. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the required characteristics of this use. If it is less than 2.5 times, the thickness of the film becomes uneven and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage tends to occur during film formation.
After the transverse stretching, heat setting is subsequently performed, and the preferred temperature range for heat setting is Tg+70 to Tm-10°C of PET. Further, the heat setting time is preferably 1 second or more and 60 seconds or less. Furthermore, for applications requiring a reduction in thermal shrinkage rate, a thermal relaxation treatment may be performed as necessary.

The thickness of the film containing recycled PET obtained as described above is arbitrary depending on its use, but is usually about 5 μm or more and 100 μm or less, preferably 5 μm or more and 25 μm or less. In addition, the breaking strength of the film containing recycled PET is 5 kg/ ^mm2 or more and 40 kg/ ^mm2 or less in the MD direction, and 5 kg/mm2 or more and 35 kg/mm2 or less in the TD direction, and the breaking elongation is 5 kg/ ^mm2 or more and 35 kg/ ^mm2 or less in the TD direction. It is 50% or more and 350% or less in the direction, and 50% or more and 300% or less in the TD direction. Further, the shrinkage rate when left in a temperature environment of 150° C. for 30 minutes is 0.1% or more and 5% or less.

Note that virgin PET may be fossil fuel polyethylene terephthalate (hereinafter also referred to as fossil fuel PET) or biomass PET. Here, "fossil fuel PET" is one in which the diol unit is a fossil fuel-derived diol and the dicarboxylic acid unit is a fossil fuel-derived dicarboxylic acid. Recycled PET may also be obtained by recycling PET resin products formed using fossil fuel PET, or may be obtained by recycling PET resin products formed using biomass PET. There may be.

The thickness of the plastic film as a plastic base material as described above is not particularly limited, and may be subject to pre-treatment or film-forming treatment when forming a vapor-deposited film using a roller-type continuous vapor-deposition film-forming apparatus described below. From the viewpoint of flexibility and shape retention, the thickness is preferably in the range of 6 to 400 μm, preferably 9 to 200 μm. When the thickness of the plastic film is within the above range, it is easy to bend, does not tear during transportation, and is a continuous vapor-deposited film used for producing a laminated film having a vapor-deposited film with barrier properties with improved adhesion. Easy to handle with film forming equipment.

Next, the deposited film will be explained. To form a vapor-deposited film, in order to improve the adhesion between the plastic base material and the vapor-deposited film, the surface of the film on the plastic base material is subjected to plasma pre-treatment using the plasma pre-treatment mechanism described below. is preferred. Plasma pretreatment is a pretreatment to strengthen and improve the adhesion between various resin films or sheets and vapor deposition films compared to conventional methods, and is carried out in the following vapor deposition film forming equipment. be.

As shown in FIG. 2, a film forming apparatus 10 suitably used for manufacturing a laminated film having a vapor deposited film having barrier properties with improved adhesion includes a base material transport mechanism 11A for transporting a plastic base material S. , a plasma pretreatment mechanism 11B that performs plasma treatment on the surface of the plastic substrate S, a film forming mechanism 11C that forms a vapor deposition film, and a water vapor supply mechanism 40 that supplies water vapor or water vapor plasma to the surface of the plastic substrate S. and.

The film forming apparatus 10 according to this embodiment will be described in more detail. As shown in FIG. 2, in the film forming apparatus 10, partition walls 35a to 35c are formed in the reduced pressure chamber 12. The partition walls 35a to 35c form a substrate transfer chamber 12A, a plasma pretreatment chamber 12B, and a film formation chamber 12C, and in particular, a plasma pretreatment chamber 12B and a film formation chamber are defined as spaces surrounded by the partition walls 35a to 35c. 12C is formed. The substrate transport mechanism 11A is arranged in the substrate transport chamber 12A, the plasma pretreatment mechanism 11B is arranged in the plasma pretreatment chamber 12B, and the film forming mechanism 11C is arranged in the film forming chamber 12C. Each chamber is further provided with an internal exhaust chamber, if necessary. In the example shown in FIG. 2, the water vapor supply mechanism 40 supplies water vapor or water vapor plasma to the surface of the plastic base material S in the plasma pretreatment chamber 12B.

(plasma pretreatment)
Inside the plasma pretreatment chamber 12B, a part of the pretreatment roller 20 that conveys the plastic substrate S to be pretreated and enables plasma treatment is provided so as to be exposed to the substrate conveyance chamber 12A. The plastic base material S is moved to the plasma pretreatment chamber 12B while being wound up.

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

The base material transport chamber 12A serves as a winding means for winding up into a roll the plastic base material S on which a vapor deposited film is formed on one side, which has been moved to the base material transport chamber 12A again by the film forming roller 23. A take-up roller is provided so that the plastic base material S on which the vapor-deposited film is formed can be taken up.

When manufacturing a laminated film having a vapor deposited film with improved adhesion and barrier properties, the plasma pretreatment chamber 12B separates the space in which plasma is generated from other regions, and efficiently evacuates the opposing space. With this configuration, the plasma gas concentration can be easily controlled and productivity can be improved. The pretreatment pressure for forming the reduced pressure can be set and maintained at about 0.1 Pa to 100 Pa, and in particular, the treatment pressure for plasma pretreatment is , 1 to 20 Pa is preferable.

The conveyance speed of the plastic substrate S is not particularly limited, but from the viewpoint of production efficiency, it can be at least 200 m/min to 1000 m/min. The transport speed for treatment is preferably 300 to 800 m/min.

The pre-treatment roller 20 constituting the plasma pre-treatment mechanism 11B prevents the plastic substrate S from shrinking or breaking due to heat during plasma treatment by the plasma pre-treatment means, and prevents the plasma P from being applied to the plastic substrate S. It is intended to be applied uniformly and over a wide range.
Preferably, the temperature of the pretreatment roller 20 can be adjusted to a constant temperature between -20° C. and 100° C. by adjusting the temperature of a temperature adjusting medium circulating within the pretreatment roller.

The plasma pretreatment means includes a plasma supply means and a magnetic formation means. The plasma pretreatment means cooperates with the pretreatment roller 20 to confine the plasma P near the surface of the plastic substrate S.

The plasma pretreatment means is provided so as to cover a part of the pretreatment roller 20. Specifically, the plasma pretreatment means includes a plasma supply means and a magnetic formation means arranged along the surface near the outer periphery of the pretreatment roller 20. The plasma supply means has plasma supply nozzles 22a to 22c that supply plasma source gas and also serve as electrodes for generating plasma P. The magnetic formation means includes a magnet 21 and the like. In the gap between the pretreatment roller 20 and the magnetic formation means such as the magnet 21, the density of the plasma P is made uniform by the action of the magnetic formation means.
Plasma supply nozzles 22a to 22c are opened in the void space to inject plasma toward the surface of the base material, and the inside of the void is used as a plasma formation region. By forming a region with high plasma density, the plasma pretreatment of the present invention in which a plasma treated surface is formed on one side of the plastic base material S can be performed.

The plasma supply means of the plasma pretreatment means includes a source gas volatilization supply device 18 connected to a plasma supply nozzle provided outside the decompression chamber 12, and a source gas supply line that supplies the source gas from the device. The supplied plasma source gas is oxygen alone or a mixture of oxygen gas, argon, helium, nitrogen, or one or more of these gases, and the flow rate of the gas is measured by passing it from a gas storage section through a flow rate controller. It is supplied with In this embodiment, an example will be described in which a mixed gas of oxygen gas and argon gas is used as the plasma source gas.

These supplied gases are mixed at a predetermined ratio as necessary to form a plasma raw material gas alone or a mixed gas for plasma formation, and are supplied to the plasma supply means. The single or mixed gas is supplied to the plasma supply nozzles 22a to 22c of the plasma supply means, and is supplied near the outer periphery of the pretreatment roller 20 where the supply ports of the plasma supply nozzles 22a to 22c are open.
The nozzle opening is directed toward the plastic substrate S on the pretreatment roller 20, and is arranged and configured so that the plasma P can be uniformly diffused and supplied to the entire surface of the plastic substrate S. Uniform plasma pretreatment can be applied to a large area of S.

Plasma pretreatment in order to make the deposited film made of aluminum oxide have a preferable configuration, that is, a configuration in which more aluminum hydroxide is formed on the plastic substrate S side in the deposited film, includes a mixing ratio of oxygen gas and argon or helium. is 5:1, preferably 2:1. By setting the mixing ratio to 5:1, the energy for forming a film of vapor-deposited aluminum on the plastic substrate S increases, and by setting the mixing ratio to 2:1, the formation of aluminum hydroxide occurs near the interface of the plastic substrate S. is formed.

The plasma supply nozzles 22a to 22c function as opposing electrodes of the pretreatment roller 20, and are designed to have an electrode function, and are supplied between the pretreatment roller 20 and the high frequency voltage, low The plasma raw material gas supplied is excited by a potential difference caused by a frequency voltage or the like, and plasma P is generated and supplied.

Specifically, the plasma supply means of the plasma pretreatment means is equipped with a pretreatment roller as a plasma power source, applies an AC voltage with a frequency of 10 Hz to 2.5 GHz between it and a counter electrode, and controls input power or It is a plasma P that can perform impedance control etc. and apply any voltage between it and the pre-treatment roller 20, and can perform treatment to physically or chemically modify the surface properties of the base material. It is equipped with a power supply 32 that can apply a bias voltage to bring the voltage to a positive potential.
The plasma intensity per unit area employed in the present invention is 10 to 8,000 W·sec/m ² , and below 10 W·sec/m ² , no effect of plasma pretreatment can be seen, and 8,000 W·sec/m ² In this case, deterioration of the base material due to plasma tends to occur, such as consumption of the base material, damage and discoloration, and sintering. In particular, in order to obtain a preferable structure of the deposited film made of aluminum oxide, the plasma intensity of the plasma pretreatment is preferably 50 to 1000 W·sec/m ² .

As the above-mentioned magnetism forming means, an insulating spacer and a base plate are provided inside the magnet case, and the magnet 21 is provided on this base plate. An insulating shield plate is provided in the magnet case, and an electrode is attached to this insulating shield plate.
Therefore, the magnet case and the electrode are electrically insulated, and even if the magnet case is installed and fixed in the decompression chamber 12, the electrode can be kept at an electrically floating level.

A power supply wiring 31 is connected to the electrode, and the power supply wiring 31 is connected to a power source 32. Further, a temperature regulating medium pipe for cooling the electrode and the magnet 21 is provided inside the electrode.
The magnet 21 is provided to apply the oxygen plasma P from the plasma supply nozzles 22a to 22c, which serve as electrodes and plasma supply means, to the plastic substrate S in a concentrated manner. By providing the magnet 21, the reactivity near the surface of the base material becomes high, and it becomes possible to form a good plasma pretreated surface at high speed.

The magnet 21 has a magnetic flux density of 10 Gauss to 10,000 Gauss at the surface position of the plastic base material S. If the magnetic flux density on the surface of the plastic base material S is 10 Gauss or more, it becomes possible to sufficiently increase the reactivity near the base material surface, and a good pretreated surface can be formed at high speed.

Because ions and electrons formed during plasma pretreatment move according to the arrangement structure of the magnet 21 of the electrode, for example, when performing plasma pretreatment on a plastic substrate S with a large area of 1 m ² or more. Electrons, ions, and decomposition products of the plastic base material S are uniformly diffused over the entire electrode surface, allowing uniform and stable pretreatment with the desired plasma intensity even when the plastic base material S has a large area. This is the result.

(Steam supply mechanism)
Next, the steam supply mechanism 40 will be explained. The water vapor supply mechanism 40 is a component for supplying water vapor or water vapor plasma to the surface of the plastic base material S. In the example shown in FIG. 2, the steam supply mechanism 40 includes a steam release section 41, a steam generation section 42, and a steam supply section 43.

The steam supply mechanism 40 shown in FIG. 2 will be described in detail with reference to FIG. 3. FIG. 3 is an enlarged view of a portion surrounded by a dashed-dotted line labeled III in FIG. 2, showing a specific form of the steam supply mechanism 40, which is omitted in FIG. 2. Note that, in FIG. 3, the illustration of the power supply wiring 31 that connects the power supply 32 and the plasma supply nozzles 22a to 22c shown in FIG. 2 is omitted.

In this embodiment, the water vapor generation unit 42 is a component for generating water vapor. The water vapor generation unit 42 shown in FIG. 3 includes a tank 42a that accommodates water W. In FIG. 3, liquid water W is stored below the tank 42a, and water vapor exists above the liquid level of the water W. The pressure of the water vapor is, for example, a saturated water vapor pressure depending on the temperature of the liquid water W. The tank 42a may be provided with a control section for controlling the temperature of the water W.

In the present embodiment, the water vapor supply unit 43 is a component for feeding the water vapor generated in the water vapor generation unit 42 to the water vapor release unit 41, which will be described later. In the example shown in FIG. 3, the water vapor supply unit 43 includes an MFC (mass flow controller) 43a and a pipe 43b.
As shown in FIG. 3, the pipe 43b is connected to the tank 42a above the level of the water W. The water vapor in the tank 42a is introduced from the tank 42a into the pipe 43b. The MFC 43a will be described later.

In this embodiment, the water vapor release section 41 is a component for releasing the water vapor fed from the water vapor feed section 43. The water vapor discharge section 41 shown in FIG. 3 is configured to introduce water vapor into the plasma pretreatment chamber 12B from the wall surface of the plasma pretreatment chamber 12B. For example, the water vapor release section 41 is connected to the pipe 43b and includes a hole formed in the wall surface of the plasma pretreatment chamber 12B. The water vapor discharge part 41 shown in FIG. 3 can discharge the water vapor supplied from the pipe 43b into the plasma pretreatment chamber 12B, and allow it to reach the surface of the plastic base material S. Further, the water vapor released into the plasma pretreatment chamber 12B may become water vapor plasma due to the action of the electric field for generating the plasma P described above. In this case, the water vapor plasma can be made to reach the surface of the plastic base material S. In this case, the surface of the plastic base material S will be plasma-treated with a mixed plasma of water vapor plasma and plasma of oxygen and argon, which are source gases. Note that when water vapor is introduced into the plasma pretreatment chamber 12B from the wall surface of the plasma pretreatment chamber 12B as shown in FIG. 3, the pressure of the water vapor can be made uniform within the plasma pretreatment chamber 12B.

As shown in FIG. 3, the steam supply mechanism 40 may further include a steam control section 45. The water vapor control unit 45 includes a detection unit that detects water vapor or water vapor plasma around the plastic base material S, and controls the water vapor supply unit 43 to release water vapor based on the detected amount of water vapor or water vapor plasma detected by the detection unit. It has an adjustment section that adjusts the amount of water vapor or water vapor plasma supplied to the section 41.

In the example shown in FIG. 3, the detection unit is not particularly limited as long as it can detect water vapor. For example, a quadrupole mass spectrometer can be used as the detection section. In this case, quadrupole mass spectrometry (Q-MAS) can be performed to determine the partial pressure of water vapor, which can be used as the detected amount.
Alternatively, the water vapor plasma may be detected by using a spectrometer as the detection unit and performing plasma spectroscopic analysis of the water vapor plasma generated by the plasma pretreatment mechanism 11B. In addition, on the premise that the partial pressure of gases other than water vapor among the total pressure in the plasma pretreatment chamber 12B is constant, the total pressure in the plasma pretreatment chamber 12B is determined using a vacuum gauge as a detection part, The partial pressure of water vapor may be calculated based on the total pressure and may be used as the detected amount.

In the example shown in FIG. 3, a method for controlling the steam supply section 43 by the adjustment section of the steam control section 45 will be described. The above-mentioned MFC 43a of the water vapor supply section 43 is connected to the adjustment section of the water vapor control section 45 so that it can be controlled by the adjustment section. The MFC 43a includes, for example, a valve provided in the piping 43b that can continuously change the degree of opening. By controlling the MFC 43a by the adjustment unit based on the detected amount and adjusting the amount of water vapor passing through the pipe 43b, the partial pressure of water vapor in the plasma pretreatment chamber 12B can be controlled to a predetermined target value. The target value is, for example, 0.1 Pa or more, preferably 0.5 Pa or more. Further, the target value is, for example, 200 Pa or less, preferably 50 Pa or less.

(Aluminum oxide vapor deposited film)
The plasma-treated plastic substrate S is moved from the substrate transport chamber 12A to the film forming chamber 12C by guide rolls 14a to 14d for guiding it to the next film forming chamber 12C, and an aluminum oxide vapor deposited film is formed in the film forming section. be done.

The aluminum oxide vapor deposited film is a thin film of an inorganic oxide containing aluminum oxide as a main component, and may contain an aluminum compound such as aluminum oxide or aluminum nitride, carbide, or hydroxide alone or in a mixture thereof. This is a layer containing aluminum as a main component.
Furthermore, the aluminum oxide vapor deposited film contains the above aluminum compound as a main component, including silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, and zirconium oxide. metal oxides such as metal oxides, metal nitrides, carbides, and mixtures thereof.

In the aluminum oxide vapor-deposited film in this embodiment, a large amount of aluminum hydroxide is formed on the plastic substrate side of the vapor-deposited film.

The formation state of aluminum hydroxide in the aluminum oxide vapor deposited film is determined by repeating soft etching at a constant rate with a Cs (cesium) ion gun on the aluminum oxide vapor deposited film of the multilayer film A having barrier properties, using a time-of-flight type method. It is determined from a graphical analysis diagram obtained by measuring ions derived from the aluminum deposited film and ions derived from the plastic substrate using secondary ion mass spectrometry (TOF-SIMS).

An example of a graph analysis diagram is shown in FIG. The unit (intensity) of the vertical axis of the graph is the common logarithm of the ion intensity. The unit (cycle) of the horizontal axis of the graph is the number of times of etching. Specifically, using a time-of-flight secondary ion mass spectrometer, etching is performed from the outermost surface of the aluminum oxide deposited film under certain conditions using Cs, and the elemental bonds at the interface between the aluminum oxide deposited film and the plastic base material are etched. and the elemental bonds of the aluminum oxide vapor-deposited film, and obtained graphs for each of the measured elements and elemental bonds (Figure 4, an example of a graph analysis diagram). 1) Find the position where the intensity of the graph for element C6 is half, The interface between the plastic base material and aluminum oxide is determined as an aluminum oxide vapor deposited film from the surface to the interface.

In FIG. 4, the position T ₀ on the horizontal axis corresponds to the outermost surface of the laminated film, that is, the outermost surface of the vapor deposited film 2. Further, the position _T1 on the horizontal axis is the position where the strength of the element C6 becomes _H1 , which is half of the strength _H0 in the plastic base material S. Here, position T ₁ is considered to be the interface between the plastic base material S and the aluminum oxide vapor deposited film. Further, the position T ₂ on the horizontal axis is an intermediate position between T ₀ and T ₁ and corresponds to the center of the deposited film 2 in the thickness direction.

As shown in FIG. 4, in the laminated film formed using the film forming apparatus 10 of this embodiment, the plastic base material is located between T ₁ and T ₂ , that is, from the center in the thickness direction of the vapor deposited film 2. An intensity peak of aluminum hydroxide (Al2O4H) exists on the S interface side. In other words, a large amount of aluminum hydroxide is formed near the interface of the plastic base material S. Thereby, the adhesion of the vapor deposited film 2 to the plastic base material S can be improved.

The aluminum oxide vapor-deposited film can be formed by forming a vapor-deposited film on the surface of a plastic substrate that has been subjected to plasma pretreatment. As the vapor deposition method for forming the vapor deposited film, various vapor deposition methods can be applied from among physical vapor deposition method and chemical vapor deposition method.
Physical vapor deposition methods can be selected from the group consisting of vapor deposition, sputtering, ion plating, ion beam assist, and cluster ion beam methods, and chemical vapor deposition methods include plasma CVD, plasma polymerization, and thermal It can be selected from the group consisting of CVD method and catalytic reaction type CVD method. In the present invention, physical vapor deposition is preferred.

Formation of an aluminum oxide vapor-deposited film using a roller-type film-forming mechanism 11C shown in FIG. 2, which can perform vapor deposition by a physical vapor deposition method suitable for the present invention, will be described below.

The film forming mechanism 11C is arranged in a reduced pressure film forming chamber 12C. The film forming mechanism 11C includes a film forming roller 23 that wraps around and conveys the plastic base material S pretreated in the plasma pretreatment mechanism 11B with the treated surface of the plastic base material S facing outward, and performs a film forming process. The film forming mechanism 11C forms a vapor deposited film on the surface of the plastic substrate S by evaporating the target of the film forming source 24 disposed opposite to the film forming roller 23.
The film forming mechanism 11C is of a resistance heating type, uses an aluminum metal wire as an evaporation source, and uses an oxygen supply mechanism 50 to supply oxygen to oxidize the aluminum vapor while oxidizing the surface of the plastic base material S. An aluminum vapor deposition film is formed.

Here, the oxygen supply mechanism 50 in the example of FIG. It has an oxygen release part 51 that releases the supplied oxygen gas so that the oxygen gas reaches the surface of the plastic base material S.
In the example of FIG. 2, the oxygen releasing section 51 has a discharge port upstream of the film forming source 24 in the transport direction of the plastic base material S, and thereby the film forming source 24 in the transport direction of the plastic base material S The oxygen gas is released so that it reaches the surface of the plastic base material S on the upstream side. However, the arrangement of the discharge ports of the oxygen discharge section 51 is not limited to this.
For example, the oxygen release section 51 may have a release port between the film forming source 24 and the plastic base material S. In this case as well, by controlling the amount of oxygen released from the oxygen release section 51 and the amount of water vapor released from the water vapor release section 41 described above, aluminum hydroxide can be increased on the plastic substrate S side in the vapor deposited film. can be formed.
Further, the oxygen release section 51 may have a release port on the downstream side of the film forming source 24 in the transport direction of the plastic base material S. In this case as well, by controlling the amount of oxygen released from the oxygen release section 51 and the amount of water vapor released from the water vapor release section 41 described above, aluminum hydroxide can be increased on the plastic substrate S side in the vapor deposited film. can be formed.

A plurality of aluminum metal wires are arranged in the axial direction of the film forming roller 23 in a boat-shaped (referred to as "boat type") vapor deposition container, and heated by a resistance heating method. By doing so, it is possible to evaporate the aluminum metal material while suppressing the heat and amount of heat supplied, and it is possible to form an aluminum oxide vapor deposited film while minimizing thermal deformability of the plastic substrate S. can.

The thickness of the aluminum oxide vapor deposited film formed as described above is 3 to 50 nm, preferably 8 to 30 nm. Within this range, barrier properties can be maintained.

(barrier coating layer)
A barrier coating layer that is laminated on the surface of a vapor-deposited film such as an aluminum oxide vapor-deposited film of a laminated film mechanically and chemically protects the vapor-deposited film and improves the barrier performance of the laminated film that has barrier properties. It is. The barrier coating layer coated to form a barrier laminate film with excellent barrier properties and retort resistance will be described below.

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

The barrier coating layer can be manufactured by the following method.
First, the above metal alkoxide, a silane coupling agent added as necessary, a water-soluble polymer, a sol-gel method catalyst, an acid, and an organic solvent such as water, methyl alcohol, ethyl alcohol, or alcohol such as isopropanol as a solvent are mixed. and prepare a barrier coating agent.
Next, the above-mentioned barrier coating agent is applied onto the deposited film by a conventional method and dried. Through this drying step, the polycondensation of the metal alkoxide, silane coupling agent, and water-soluble polymer further progresses to form a coating film.

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

(packaging material)
A laminated film having a vapor-deposited film with barrier properties with improved adhesion according to an embodiment of the present invention and a barrier laminated film including the laminated film can be used after hot water treatment, particularly after retort treatment of high-temperature hot water treatment. It also has good adhesion between the plastic base material and the vapor-deposited film, and also has excellent gas barrier properties, so it can be used not only for retort packaging for food and high-temperature hot water treatment packaging for medical use, but also for pet food, etc. It can be suitably used as a packaging material for contents to be subjected to retort treatment.
The packaging material is a barrier laminated film laminated with at least one heat-sealable layer, and a heat-sealable thermoplastic resin is laminated as the innermost layer with or without an adhesive layer. , which has heat sealability. The packaging material may further include the functions desired to be imparted to the packaging material as necessary, such as a light-shielding layer for imparting light-shielding properties, decorativeness, a printing layer for imparting printing, a pattern layer, a laser printing layer, It is also possible to add various functional layers such as an absorbent/adsorbent layer that absorbs or adsorbs odors to the layer structure and use it as a packaging material.

(First modification)
In the above-described embodiment, an example has been described in which the water vapor release section 41 has a hole provided in the wall surface of the plasma pretreatment chamber 12B and connected to the pipe 43b. However, the present invention is not limited to this, and as shown in FIG. 5, the water vapor release section 41 may have a release port that releases water vapor at a position closer to the plastic substrate S than the wall surface of the plasma pretreatment chamber 12B. You can.
In the example shown in FIG. 5, the outlet of the water vapor emitting unit 41 is configured to emit water vapor toward the gap between the pretreatment roller 20 and the magnetic forming means such as the magnet 21, or toward the pretreatment roller 20. has been done.
In the example shown in FIG. 5, the water vapor release unit 41 has a release port for releasing water vapor in the plasma pretreatment chamber 12B on the upstream side of the plasma supply nozzles 22a to 22c in the transport direction of the plastic substrate S. An example with . However, when the water vapor emitting part 41 releases water vapor in the plasma pretreatment chamber 12B, the position of the outlet of the water vapor emitting part 41 is not particularly limited. For example, although not shown, the water vapor release section 41 may have a release port for releasing water vapor in the plasma pretreatment chamber 12B on the downstream side of the plasma supply nozzles 22a to 22c.

The water vapor release section 41 shown in FIG. 5 will be described in more detail with reference to FIG. 6. FIG. 6 is an enlarged view of the steam supply section 43, the steam discharge section 41, the pretreatment roller 20, and the magnet 21 in FIG. 5, and shows the specific shape of the steam discharge section 41, which was schematically shown in FIG. It is a diagram.

In the example shown in FIG. 6, the water vapor release section 41 has a plurality of release ports 41a lined up along the direction in which the rotational axis of the pretreatment roller 20 extends. Note that the rotation axis of the pretreatment roller 20 is a direction perpendicular to the conveyance direction of the plastic base material S that is wound around the pretreatment roller 20 and conveyed, and is also parallel to the width direction of the plastic base material S. be. Therefore, it can be said that the plurality of discharge ports 41a shown in FIG. 6 are lined up along the width direction of the plastic base material S. By discharging water vapor from such a plurality of discharge ports 41a, it is possible to suppress variations in the density of water vapor or water vapor plasma around the plastic base material S in the width direction of the plastic base material S. The distance between the discharge ports 41a is not particularly limited, but is, for example, 0.5 cm or more and 50 cm or less. Although not shown, the water vapor release section 41 may be divided into a plurality of parts in the width direction of the plastic base material S.

(Second modification)
As shown in FIG. 7, the water vapor release unit 41 releases water vapor toward the gap between the pretreatment roller 20 and the magnetic formation means through a through hole (not shown) provided in the magnetic formation means such as the magnet 21. It may be configured to do so.

(Third modification)
In the above-mentioned embodiment and each modification, the example in which the water vapor emitting section 41 releases water vapor in the plasma pretreatment chamber 12B has been described. However, the present invention is not limited to this, and as shown in FIGS. 8 and 9, the water vapor emitting section 41 may emit water vapor in the base material transfer chamber 12A. In the present application, the water vapor release unit 41 that releases water vapor in the plasma pretreatment chamber 12B is also referred to as a preprocessing chamber water vapor release unit, and the water vapor release unit 41 that releases water vapor in the substrate transfer chamber 12A is also referred to as a water vapor release unit for the substrate transfer chamber. Also called discharge section.

As long as water vapor or water vapor plasma is emitted upstream of the film-forming source 24 in the transport direction of the plastic substrate S, the discharge port of the water vapor emitting unit 41 in the substrate transport chamber 12A can be arranged arbitrarily. For example, as shown in FIG. 8, the water vapor release section 41 has a release port on the upstream side of the plasma pretreatment chamber 12B in the transport direction of the plastic substrate S in the substrate transport chamber 12A, and releases water vapor. You can. In this case, the water vapor attached to the surface of the plastic base material S or absorbed by the plastic base material S may become water vapor plasma in the plasma pretreatment chamber 12B. Further, as shown in FIG. 9, the water vapor emitting section 41 may emit water vapor on the downstream side of the plasma pretreatment chamber 12B and on the upstream side of the film forming chamber 12C.

(Fourth modification)
In the above-mentioned embodiment and each modified example, the example in which the water vapor emitting unit 41 releases water vapor in the substrate transfer chamber 12A or the plasma pretreatment chamber 12B has been described. However, the present invention is not limited to this, and as shown in FIG. 10, the water vapor release section 41 has a release port in the film forming chamber 12C on the upstream side of the film forming source 24 in the transport direction of the plastic substrate S. However, water vapor or water vapor plasma may be emitted. In the present application, the water vapor release unit 41 that releases water vapor in the film forming chamber 12C is also referred to as a film forming chamber water vapor release unit.

When the water vapor release unit 41 is arranged in the film forming chamber 12C, the water vapor release unit 41 has a release port on the upstream side of the oxygen release unit 51 in the film forming chamber 12C, and Plasma may be emitted. In the example shown in FIG. 10, the water vapor release section 41 has a release port on the upstream side of the oxygen release section 51, and releases water vapor or water vapor plasma. In this case, water vapor reaches the surface of the plastic substrate S earlier than oxygen gas, and aluminum hydroxide is formed on the surface of the plastic substrate S before the aluminum oxide vapor deposition film, so the aluminum oxide vapor deposition film It is possible to increase the formation of aluminum hydroxide near the interface of the plastic base material S. Although not shown, the oxygen emitting section 51 may emit water vapor or water vapor plasma together with oxygen gas. In this case, it can be said that the oxygen release section 51 also has the function of the water vapor release section 41. In this case, water vapor or water vapor plasma can be made to reach the surface of the plastic base material S together with oxygen gas, and aluminum hydroxide can be formed in a large amount near the interface of the plastic base material S.
In the example shown in FIG. 10, the oxygen releasing section 51 has a discharge port upstream of the film forming source 24 in the transport direction of the plastic base material S, and thereby has a discharge port located upstream of the film forming source 24 in the transport direction of the plastic base material S. Oxygen gas is released so that the oxygen gas reaches the surface of the plastic base material S on the upstream side of 24. However, the arrangement of the discharge ports of the oxygen discharge section 51 is not limited to this.
For example, the oxygen release section 51 may have a release port between the film forming source 24 and the plastic base material S. In this case as well, by controlling the amount of oxygen released from the oxygen release section 51 and the amount of water vapor released from the water vapor release section 41 described above, aluminum hydroxide can be increased on the plastic substrate S side in the vapor deposited film. can be formed.
Further, the oxygen release section 51 may have a release port on the downstream side of the film forming source 24 in the transport direction of the plastic base material S. In this case as well, by controlling the amount of oxygen released from the oxygen release section 51 and the amount of water vapor released from the water vapor release section 41 described above, aluminum hydroxide can be increased on the plastic substrate S side in the vapor deposited film. can be formed.

(Fifth modification)
The water vapor release section 41 having a hole formed in the wall surface shown in the example of FIG. The water vapor release section 41 having an outlet may be arranged in the same chamber. FIG. 11 is a diagram showing an example in which both the water vapor release section 41 shown in FIG. 2 and the water vapor release section 41 shown in FIG. 5 are arranged in the plasma pretreatment chamber 12B.

When the water vapor discharge section 41 in the example of FIG. 2 is used, the pressure of water vapor can be made uniform within the plasma pretreatment chamber 12B. Moreover, when the water vapor discharge part 41 in the example of FIG. 5 is used, more water vapor or water vapor plasma can be made to reach the surface of the plastic base material S. By using these water vapor release parts 41 in combination, more water vapor can be supplied to the plastic base material S uniformly in the width direction of the plastic base material S.

(Sixth modification)
In the above-mentioned embodiment and each modification, the water vapor discharge part 41 showed the example arrange|positioned in either 12 A of base material conveyance chambers, the plasma pretreatment chamber 12B, or 12 C of film-forming chambers. In this modification, an example will be described in which the water vapor release section 41 is arranged in a plurality of chambers among the substrate transfer chamber 12A, the plasma pretreatment chamber 12B, and the film forming chamber 12C. In the example shown in FIG. 12, water vapor release units 41 are arranged in the plasma pretreatment chamber 12B and the film forming chamber 12C.

When the water vapor release unit 41 releases water vapor in the substrate transfer chamber 12A or the plasma pretreatment chamber 12B, the surface of the plastic substrate S when transferred to the film forming chamber 12C is already affected by water vapor or water vapor plasma. I'm reading. Therefore, the water vapor released in the substrate transfer chamber 12A or the plasma pretreatment chamber 12B can contribute to making the intensity peak of aluminum hydroxide (Al2O4H) appear closer to the interface side of the plastic substrate S. . Thereby, the adhesion of the vapor deposited film to the plastic base material S can be improved.

On the other hand, the water vapor released in the film forming chamber 12C is used as a raw material for the vapor deposited film in the film forming process. Therefore, when the water vapor emitting unit 41 releases water vapor in the film forming chamber 12C, the concentration of structures caused by water vapor in the deposited film can be increased. Thereby, the barrier properties of the deposited film can be improved. Examples of structures caused by water vapor in the deposited film include hydroxyl groups, hydrates, and water molecules.

(Seventh modification)
In the above-described embodiment and each modification, a case has been described in which water vapor or water vapor plasma reaches the surface of the plastic base material by emitting water vapor by the water vapor emitting unit 41. However, the present invention is not limited to this, and water vapor may be turned into plasma in advance, and the water vapor emitting section 41 may emit water vapor plasma.

(Eighth modification)
In the above-described embodiment and each modified example, an example was shown in which the water vapor emitting section 41 emits water vapor or water vapor plasma. However, the present invention is not limited thereto, and the water vapor emitting section 41 may emit other gases in addition to water vapor or water vapor plasma. For example, in the plasma pretreatment chamber 12B, the water vapor release unit 41 releases plasma source gas such as oxygen alone or a mixed gas of oxygen gas, argon, helium, nitrogen, or one or more of these gases, in addition to water vapor. You may.

(Ninth modification)
Although not shown, the steam supply mechanism 40 may further include a carrier gas supply section that supplies a carrier gas for directing the steam or steam plasma released from the steam discharge section 41 toward the plastic substrate S. . As the carrier gas, oxygen gas, nitrogen gas, argon gas, helium gas, etc. can be used.

Although several modifications to the embodiment described above have been described, it is of course possible to apply a plurality of modifications in combination as appropriate.

1, S Plastic base material 1a First layer 1b Second layer 1c Third layer 2 Deposited film 3 Barrier coating layer A Laminated film or deposited film B Barrier laminated film P Plasma W Water 10 Film forming apparatus 11A Substrate transport Mechanism 11B Plasma pre-treatment mechanism 11C Film-forming mechanism 12 Decompression chamber 12A Substrate transport chamber 12B Plasma pre-treatment chamber 12C Film-forming chambers 14a-d Guide roll 18 Source gas volatilization supply device 20 Pre-treatment roller 21 Magnet 22a-c Plasma supply nozzle 23 Film forming roller 24 Film forming source 31 Power supply wiring 32 Power supply 35a to 35c Partition wall 40 Steam supply mechanism 41 Steam release section 41a Release port 42 Steam generation section 42a Tank 43 Steam supply section 43a MFC
43b Piping 45 Steam control section 50 Oxygen supply mechanism 51 Oxygen release section 52 Oxygen storage section 53 Oxygen supply section

Claims (2)

A film forming apparatus for forming a vapor-deposited film of an inorganic oxide on the surface of a plastic base material,
It has a film forming roller that conveys the wrapped plastic base material, and a film forming source that is located opposite to the film forming roller and includes a target containing an inorganic material that is a raw material for the vapor deposited film. A film forming mechanism;
a water vapor supply mechanism having at least a water vapor release section that releases water vapor so that the water vapor reaches the surface of the plastic base material on the upstream side of the film forming source in the transport direction of the plastic base material,
The target disposed in the film formation source contains aluminum, the vapor deposition film contains aluminum oxide,
When the strength of aluminum hydroxide (Al2O4H) in the thickness direction of the vapor deposited film is measured using time-of-flight secondary ion mass spectrometry, it is found that A vapor deposition film forming apparatus in which an intensity peak of aluminum hydroxide (Al2O4H) exists on the interface side. A film forming method for forming a vapor-deposited film of an inorganic oxide on the surface of a plastic base material, the method comprising:
a water vapor supplying step in which a water vapor release section releases water vapor so that the water vapor reaches the surface of the plastic base material;
An inorganic material that is a raw material for the vapor-deposited film is disposed in a film-forming source facing a film-forming roller around which the plastic base material is wound on the downstream side of the water vapor release part in the transport direction of the plastic base material. a film forming step of evaporating a target containing the vapor-deposited film on the surface of the plastic base material,
The target disposed in the film formation source contains aluminum, the vapor deposition film contains aluminum oxide,
When the strength of aluminum hydroxide (Al2O4H) in the thickness direction of the vapor deposited film is measured using time-of-flight secondary ion mass spectrometry, it is found that A vapor deposition film forming method in which an intensity peak of aluminum hydroxide (Al2O4H) exists on the interface side.