TW202000953A - Vapor deposition film and production method of vapor deposition film - Google Patents

Abstract

The present invention provides a vapor deposition film exhibiting excellent adhesiveness allowing a laminated metal film not to be peeled off at hot water treatment of a content (especially in the case of food or the like) while maintaining a barrier property for preventing transmission of oxygen, steam and the like, and a production method of the vapor deposition film. The vapor deposition film comprises a substrate and a vapor deposition layer provided on the substrate, in which the vapor deposition layer comprises a metal and an average concentration of oxygen atoms measured by an X-ray photoelectron spectroscopy in a thickness direction of the vapor deposition layer is 8.0 atomic percent or less.

Description

Vapor deposition film and method for manufacturing vapor deposition film

The invention relates to a vapor-deposited film and a method for manufacturing the vapor-deposited film. More specifically, it relates to a vapor-deposited film excellent in barrier properties and sealing properties, and a method for manufacturing a vapor-deposited film.

In the field of film technology, a variety of packaging films for packaging food and other contents have been developed since it was known. The packaging film may be, for example, a laminated metal film for imparting various characteristics. In addition, the laminated film needs to be useful for preventing deterioration of the content, barrier properties for preventing the penetration of oxygen or water vapor, or for hydrothermal treatment of the content (especially in the case of food, etc.) The peeling tightness of the deposited metal film, etc.

As a method for depositing a metal film or the like on a substrate, there is known a sputtering method using a vacuum deposition method, a DC (direct current) power supply, or an RF (high frequency) power supply, or a method in which plasma is used on the surface of a substrate IE (ion etching) treatment method (Patent Document 1).

Patent Literature 1: Japanese Patent Laid-Open No. 2004-203022

[Problems to be solved by the invention]

However, any of the aforementioned methods has a problem that the sealability of the resulting laminated film (vapor-deposited film) after hydrothermal treatment decreases. Therefore, the above-mentioned conventional vapor-deposited thin film has a barrier property, and at the same time, in order to be used in a field in which sealing performance is required (for example, a food field requiring hydrothermal treatment), there is still room for improvement.

The present invention is an invention developed in light of such conventional knowledge, and its object is to provide a method for hydrothermal treatment of contents (especially in the case of food, etc.) while maintaining barrier properties against penetration of oxygen, water vapor, etc. Vapor-deposited thin film with excellent sealing performance without delamination of the deposited metal and method for manufacturing the deposited thin film.

As a result of discussion by the inventors, when a metal-containing vapor deposition layer is provided on a substrate, and the concentration of oxygen atoms contained in the vapor deposition layer is below a certain amount, water is displayed while maintaining excellent barrier properties of the vapor-deposited film Excellent sealability after heat treatment, and completed the present invention. In addition, the inventors completed the present invention by applying an electrode to the substrate before the deposition layer with a negative high-voltage pulse at a predetermined load ratio as a pretreatment in order to make the vapor deposition layer have the above-mentioned oxygen atom concentration. That is, in order to solve the above-mentioned problems, the vapor-deposited thin film and the method for manufacturing the vapor-deposited thin film of the present invention include the following configurations.

[Means to solve the problem]

(1) A vapor-deposited film comprising: a substrate; and a vapor-deposited layer provided on the substrate; the vapor-deposited layer contains a metal, and the average concentration of oxygen atoms is measured by X-ray photoelectron spectroscopy in the thickness direction It is 8.0 atomic% or less.

According to the above configuration, the vapor-deposited thin film has excellent barrier properties against penetration of oxygen, water vapor, or the like. In addition, the vapor-deposited thin film has excellent sealing properties in the vapor-deposited layer during hydrothermal treatment. Therefore, the vapor-deposited film seeks barrier properties and can be suitably used in applications requiring hydrothermal treatment (for example, applications such as packaging films for food requiring hydrothermal treatment).

(2) The vapor-deposited thin film as described in (1), wherein the aforementioned average concentration is 4.0 to 6.0 atomic %.

According to the above configuration, the resulting vapor-deposited thin film has more excellent barrier properties and sealing properties.

(3) The vapor-deposited thin film according to claim (1) or (2), wherein the peak concentration of oxygen atoms measured by X-ray photoelectron spectroscopy in the thickness direction of the deposited layer is 15.0 atomic% or less.

According to the above configuration, the resulting vapor-deposited thin film has more excellent barrier properties and sealing properties.

(4) The vapor-deposited film as described in any one of claims (1) to (3), wherein the bonding strength after hydrothermal treatment is 50gf/15mm or more.

According to the above configuration, the resulting vapor-deposited thin film has more excellent barrier properties and sealing properties.

(5) The vapor-deposited thin film according to any one of claims (1) to (4), wherein the carbon content ratio in the peeling interface on the vapor deposition layer side is 50 atomic% or more.

According to the above configuration, the resulting vapor-deposited thin film has more excellent barrier properties and sealing properties.

(6) The vapor-deposited film according to any one of claims (1) to (5), wherein the vapor-deposited layer contains aluminum.

According to the above configuration, the resulting vapor-deposited thin film has more excellent barrier properties and sealing properties.

(7) The vapor-deposited film according to any one of claims (1) to (6), wherein the substrate is a resin-made substrate.

According to the above configuration, the obtained vapor-deposited film-based substrate is a resin-made substrate. Therefore, the vapor-deposited film can be suitably used in various applications of resin substrates (such as packaging films for food containers).

(8) The vapor-deposited film described in any one of claims (1) to (7), which is a packaging film used for packaging food.

According to the above configuration, the vapor-deposited film has excellent barrier properties and sealing properties. Therefore, the packaging film used for packaging food is used, thereby preventing the penetration of oxygen, water vapor, etc. into the content, that is, food, and It also makes it difficult to produce defects after hydrothermal treatment.

(9) A method for manufacturing a vapor-deposited thin film, which includes a substrate; and a vapor-deposited layer, which is provided on the aforementioned substrate; and includes: a pretreatment process in which the aforementioned substrate is subjected to plasma treatment; and a vapor deposition process The vapor deposition layer is formed on the substrate after the pretreatment process; the vapor deposition process is to form a metal-containing vapor deposition layer on the substrate after the pretreatment process; the pretreatment process includes the following processes: The maximum power density of 0.5~20 (W/cm ² ) pulse to pulse recurrence time (T _on + T _off ) pulse time (T _on ) ratio (T _on / T _on + T _off ) is less than 0.15 The negative electrode is supplied to generate plasma.

According to the above configuration, the base material is subjected to the aforementioned plasma treatment as a pretreatment process. The substrate subjected to the above-mentioned pretreatment uses a vapor deposition process described later to form a vapor-deposited layer having excellent sealing properties on the substrate. In addition, the resulting vapor-deposited film has excellent barrier properties against penetration of oxygen, water vapor, and the like. Therefore, the vapor-deposited film seeks barrier properties and can be suitably used in applications requiring hydrothermal treatment (for example, applications such as packaging films for food requiring hydrothermal treatment).

(10) The method for manufacturing a vapor-deposited thin film as described in claim (9), wherein the maximum current value of the pulse in the pretreatment is 6.0 (A) or less.

According to the above configuration, the resulting vapor-deposited thin film has more excellent barrier properties and sealing properties.

(11) The method of manufacturing a vapor-deposited thin film as described in claim (9) or (10), wherein the surface roughness of the substrate measured by an atomic force microscope during the pretreatment process is Ra 0.7-2.0 nm, Rz is 8.0 to 20.0 nm and the surface treatment of the aforementioned substrate is performed.

According to the above configuration, the resulting vapor-deposited thin film has more excellent barrier properties and sealing properties.

[Invention Effect]

As described above, according to the present invention, it is possible to provide a metal film that is deposited during hydrothermal treatment of the contents (especially in the case of food, etc.) while maintaining the barrier property against the penetration of oxygen, water vapor, etc. without peeling Vapor-deposited film with excellent sealing performance and method for manufacturing vapor-deposited film.

<Vapor Deposition Film>

A vapor-deposited thin film according to an embodiment of the present invention includes: a substrate; and a vapor-deposited layer, which is provided on the substrate. The vapor deposition layer system contains metal. In addition, the average concentration of oxygen atoms in the metal layer measured by X-ray photoelectron spectroscopy in the thickness direction is 8.0 atomic% or less. The vapor-deposited film of this embodiment has excellent barrier properties against the penetration of oxygen, water vapor, and the like. In addition, the vapor-deposited thin film has excellent sealing properties in the vapor-deposited layer during hydrothermal treatment. Therefore, the vapor-deposited film seeks barrier properties and can be suitably used in applications requiring hydrothermal treatment (for example, applications such as packaging films for food requiring hydrothermal treatment). Each structure will be described below.

(Substrate)

The substrate is not particularly limited. The substrate may also be a substrate that can form a vapor-deposited layer described later. For example, the substrate is polyethylene terephthalate (PET; polyethylene terephthalate), nylon, unoriented polypropylene (CPP; unoriented polypropylene), biaxially oriented polypropylene film (OPP; Biaxially oriented polypropylene film), Linear low-density polyethylene (LLDPE; linear low-density polyethylene), high-density polyethylene (HDPE; high density polyethylene), polyethylene naphthalate (PEN; polyethylene naphthalate), polyene (COP; polyolefin), Polycarbonate (PC; polycarbonate), polystyrene film, polyethersulfone (PES; polyethersulfone), decomposable resin (lactic acid BDP), polyacrylonitrile, polyimide (PI; polyimide), liquid crystal polymer ( LCP; liquid crystal polymer), ethylene vinyl alcohol (EVOH), fluorine-based resin (FL; fluorine-based resin), polyamide-amide imide (PAI; polyamide imide), polyarylate (PAR; polyarylate), polyallyl sulfone (PASF; Polyallyl sulfone), polyether ether ketone (PEEK; polyether ether ketone), polyether imide (PEI; polyether imide), methacrylic resin (PMMA; methacrylic resin), Polyvinyl chloride (PVC; polyvinyl chloride), polybutylene terephthalate (PBT; polybutylene terephthalate), etc. Among these substrates, it is known from the obtained vapor-deposited film that it has excellent barrier properties and excellent sealability after hydrothermal treatment, and it is preferably a resin substrate, more preferably PET, PP, nylon, and very preferably PET . In addition, since the base material is made of resin, the vapor-deposited film is used for various applications of the resin base material (for example, packaging film for food containers, etc.), and can be suitably used. Well-known additives such as antistatic agents, ultraviolet absorbers, plasticizers, lubricants, colorants, etc. can also be added to these organic polymers.

The thickness of the substrate is not particularly limited. For example, the thickness of the substrate is preferably 5 μm or more, and more preferably 8 μm or more. In addition, the thickness of the substrate is preferably 200 μm or less, and more preferably 30 μm or less. Since the thickness of the substrate is within the above range, the substrate becomes difficult to break during a preprocessing process or a vapor deposition process described later. In addition, the resulting vapor-deposited thin film has appropriate flexibility and is easy to use.

The manufacturing method of the vapor-deposited thin film will be described later. The substrate of the present embodiment is used as a pretreatment process before forming a vapor-deposited layer, and the electrode is applied in such a manner that the pulse of negative high voltage becomes a predetermined duty ratio or less. According to the above method, the base material will become difficult to impart large thermal energy and become difficult to break. Therefore, even if the substrate of the present embodiment is a relatively weak resin film of the aforementioned film, a vapor-deposited layer can be formed, and a vapor-deposited film having excellent barrier properties or sealing properties can be obtained.

The base material of this embodiment is preferably provided on the surface of the vapor-deposited layer and processed with a predetermined surface roughness. That is, the surface of the substrate before the vapor deposition layer was observed using an atomic force microscope (PSM-0600, manufactured by Shimadzu Corporation, scanning probe microscope) in a 1 μm square interior (but protrusions such as fillers should be removed The measured surface roughness is best to be processed in such a way that Ra is 0.7 to 2.0 nm and Rz is 8.0 to 20.0 nm. The surface of the substrate is processed with the aforementioned surface roughness, whereby the vapor-deposited thin-film substrate and the vapor-deposited layer have excellent sealing properties.

(Deposited layer)

The vapor deposition layer system contains metal. The metal is not particularly limited. For example, the metal system is at least one metal selected from various light metals, silicon, tin, zinc, indium, and the like. Light metals are aluminum, magnesium, beryllium, titanium, alkali metals, alkaline earth metals, etc. Among these metals, the metal is preferably aluminum, titanium, silicon, copper, and more preferably aluminum. The vapor-deposited layer is made of aluminum, and the resulting vapor-deposited film has excellent barrier properties and excellent sealing properties between the substrate and the vapor-deposited layer.

The average concentration of oxygen atoms in the vapor-deposited layer system of this embodiment is 8.0 atomic% or less. The average concentration of oxygen atoms may also be 8.0 atom% or less, and most preferably 6.0 atom% or less. In addition, the average concentration of oxygen atoms is preferably 2.0 atom% or more, and more preferably 4.0 atom% or more.

Here, in the present embodiment, the average concentration of the oxygen atoms can be measured by X-ray photoelectron spectroscopy (XPS; X-ray photoelectron spectrometer). Specifically, the average concentration of oxygen atoms is measured by the next method. The sample is sputtered and etched every 30 seconds. The etching process will be described in detail later. Thereafter, the atomic concentration was measured by X-ray photoelectron spectroscopy (XPS) (detailed measurement conditions are as follows.). By repeating this process, the average concentration (atomic %) of oxygen atoms in the thickness direction and the peak concentration of oxygen atoms in the thickness direction can be measured. In addition, in this embodiment, the area from the bottom of the oxygen content ratio measured on the vapor deposition surface to the interface between the substrate and the vapor deposition layer is defined as the vapor deposition layer. The portion where the carbon content ratio is 5 atomic% is defined as the interface between the base material and the vapor deposition layer. The average concentration of oxygen atoms calculated from the bottom of the oxygen content ratio on the vapor deposition surface side is used to remove the oxygen contained in the oxidation area on the outermost surface of the vapor deposition layer.

(Determination conditions of X-ray photoelectron spectroscopy (XPS) depth direction analysis) ・Device: X-ray photoelectron spectrum analyzer (XPS) ・Manufacturer/model: ULVAC-PHI (share)/PHI5000VersaProbe II ・X-ray beam diameter (measurement range): φ100μm Etching conditions (sputtering conditions from the vapor-deposited layer side toward the depth of the substrate) ・Acceleration voltage of argon (Ar) ion gun: 4kV ・Etching range: 3mm×3mm square inside ・Etching time: 30 seconds/1 time

FIG. 1 is a graph showing the results of measuring the average concentration of oxygen atoms using the XPS to measure the average concentration of the oxygen vapor deposited film (aluminum vapor deposition layer formed on the PET substrate) (the embodiment 1 will be described later) . FIG. 2 is a graph showing the results of measuring the average concentration of oxygen atoms using a vapor deposited film of an aluminum vapor deposition layer on a PET substrate that has not been subjected to a pretreatment process (comparative example 1 will be described later). In FIGS. 1 and 2, the horizontal axis indicates the sputtering time (minutes), and the vertical axis indicates the atomic %. Sputtering time is from 0 to 30 minutes. Figure 1 shows that the calculated average concentration of oxygen atoms is 4.9 atomic %. On the other hand, FIG. 2 shows that the calculated average concentration of oxygen atoms is 10.5 atomic %.

As described above, the vapor-deposited thin film of this embodiment (FIG. 1) has a low average concentration of oxygen atoms in the vapor deposition layer and is 8.0 atomic% or less. On the other hand, the average concentration of oxygen atoms in the vapor-deposited layer (Figure 2) of the vapor-deposited film without the pretreatment process is high. The vapor-deposited film of the present embodiment is an average concentration of oxygen atoms in the vapor-deposited layer of 8.0 atomic% or less, and as a result, compared with the conventional vapor-deposited film, the vapor-deposited film after hydrothermal treatment The sealing is excellent. The vapor-deposited film of the present embodiment reduces the oxygen contained in the substrate by surface modification of the substrate, thereby reducing the influence of oxygen on the vapor deposition layer, and speculates the tightness of the vapor-deposited film Variety.

In the vapor deposition layer of this embodiment, in the thickness direction of the vapor deposition layer, the peak concentration of oxygen atoms is preferably 15.0 atomic% or less, more preferably 13.0 atomic% or less. In addition, the peak concentration of oxygen atoms is preferably 7.0 atomic% or more. The vapor-deposited film of the present embodiment is in the range of the peak concentration of oxygen atoms in the vapor-deposited layer, whereby, as a result, compared with the conventional vapor-deposited film, the vapor-deposited film after hydrothermal treatment The sealing is excellent.

The manufacturing method of the vapor-deposited thin film will be described later. The vapor-deposited thin film of this embodiment is used as a pretreatment process, and the electrode is applied in such a manner that the pulse of negative high voltage is set to a predetermined load ratio below, based on the above pretreatment A vapor-deposited layer is formed on the material. Although the mechanism is not clear, as mentioned above, the vapor-deposited thin film of the present embodiment performs the pretreatment of the substrate, whereby the concentration of oxygen atoms contained in the vapor deposition layer formed on the substrate is more than that set by a conventional method The concentration of oxygen atoms contained in the vapor-deposited film is still low. Next, although the mechanism is not clear, as a result, since the concentration of oxygen atoms contained in the vapor-deposited thin film is low, not only the barrier property but also the sealability after hydrothermal treatment becomes excellent.

The thickness of the vapor-deposited layer is not particularly limited. For example, the thickness of the deposited layer is preferably 7 nm or more, and more preferably 20 nm or more. In addition, the thickness of the vapor-deposited layer is preferably 100 nm or less, and more preferably 80 nm or less. The thickness of the vapor-deposited layer is within the above range, and the resulting vapor-deposited layer has excellent barrier properties, is moderately flexible, and is easy to use.

As described above, the vapor-deposited thin film of this embodiment has excellent barrier properties against the penetration of oxygen, water vapor, and the like. In addition, the vapor-deposited film has excellent sealing properties of the vapor-deposited layer after hydrothermal treatment. Therefore, the vapor-deposited thin film seeks barrier properties and can be suitably used in applications requiring hydrothermal treatment. In particular, the vapor-deposited film is a food produced by a manufacturing method including a hydrothermal treatment process (for example, a retort sterilization process), or a food subjected to hydrothermal treatment at the time of eating and is packaged as a packaging film Used properly. That is, the vapor-deposited film has excellent barrier properties and sealing properties, so it is used as a packaging film for packaging such foods, thereby preventing the penetration of oxygen, water vapor, etc. into the contents, that is, food, It also makes it difficult to produce defects after hydrothermal treatment.

Specifically, the vapor-deposited film of this embodiment is subjected to hydrothermal treatment (sterilizer test, that is, the condition of immersion in hot water at 125°C every 30 minutes), and the T-shaped condition is peeled at a stretching speed of 300 mm/min. , Laminate strength when peeling the vapor deposited film can be more than 50gf/15mm. The best bonding strength is 50gf/15mm or more, more preferably 100gf/15mm or more.

In addition, regarding the peeled-off vapor-deposited layer, the carbon content ratio of the vapor-deposited film on the peeling interface on the side of the vapor-deposited layer is preferably at least 50 atom%, more preferably at least 80 atom%. In addition, the carbon content ratio was measured by X-ray photoelectron spectroscopy (XPS) on the peeling interface and surface light on the vapor deposited layer side after peeling. The relatively high carbon content means that the non-substrate and the vapor-deposited layer are peeled off near the interface, which means that the substrate is broken. (X-ray photoelectron spectroscopy (XPS) measurement conditions) XPS measurement conditions ・Device: X-ray photoelectron spectrum analyzer (XPS) ・Manufacturer/model: ULVAC-PHI (share)/PHI5000VersaProbe II ・X-ray beam diameter (measurement range): φ100μm

<Manufacturing method of vapor deposited film>

A method for manufacturing a vapor-deposited film according to an embodiment of the present invention is composed of a pretreatment process and a vapor deposition process. The pretreatment process is to perform plasma treatment on a substrate; the vapor deposition process is to form a vapor-deposited layer On the substrate after the pretreatment process. The vapor deposition process is a process of forming a metal-containing vapor deposition layer on the substrate after the pretreatment process. Pre-treatment process line contains the maximum power density (power density) of ^{0.5 ~ 20 (W / cm 2} ) of pulses of the pulse recursive time (pulse-recurrence time) (T on + T off) of the pulse time (T _on) The ratio (T _on /T _on +T _off ) is a process of generating plasma by periodically applying electrodes in a manner of 0.15 or less. The manufacturing method of the vapor-deposited film of this embodiment is to perform the aforementioned plasma treatment on the substrate during the pretreatment process. The above-mentioned pre-treated substrate uses a vapor deposition process described later to form a vapor-deposited layer with excellent sealing properties on the substrate. In addition, the resulting vapor-deposited film has excellent barrier properties against penetration of oxygen, water vapor, and the like. Therefore, the vapor-deposited film seeks barrier properties and can be suitably used in applications requiring hydrothermal treatment (for example, applications such as packaging films for food requiring hydrothermal treatment). Each structure will be described below. In addition, in the following description, the detailed description of the base material and the vapor deposition layer is the same as the above-mentioned embodiment regarding the vapor-deposited thin film. Therefore, the repeated description is appropriately omitted. In addition, FIG. 3 is a schematic diagram for explaining plasma processing. As shown in FIG. 3, the plasma treatment is a treatment that uses plasma to perform surface treatment toward the substrate.

(Pretreatment process)

The pretreatment process is a process of plasma treatment of the substrate, including the ratio of the pulse with the maximum power density of 0.5~20 (W/cm ² ) to the pulse repetition time (T _on + T _off ) of the pulse time (T _on ) (T _on /T _on +T _off ) is a process of generating plasma by periodically applying electrodes in a manner below 0.15. FIG. 4 is a schematic diagram illustrating pulses applied to electrodes during the pretreatment process. The pulse shown in Fig. 4 is a square wave in which only a predetermined pulse time (T _on ) generates a negative high voltage. In addition, in this embodiment, it is characterized in that the square wave is generated in each predetermined pulse recurrence time (T _on + T _off ), and the pulse repetition time (T _on + T _off ) is the pulse time (T _on ) The ratio (T _on /T _on +T _off ) is adjusted in a way below 0.15.

Specifically, first of all, the pretreatment process is carried out in a vacuum chamber (Vacuum chamber) under the introduction of atmospheric gas (Atmospheric gas) and under the pressure of 1×10 ^-3 ～1×10 ^-1 Torr, Plasma treatment is performed on the surface of the substrate using high power density plasma.

The furnace atmosphere gas is not particularly limited. For example, the furnace atmosphere gas is Noble gas, nitrogen, oxygen, air, etc. Among these gases, the furnace atmosphere gas is preferably argon (Ar) from the viewpoint of the stability or economy of discharge. The furnace atmosphere system is introduced into the discharge space in the vacuum chamber, and is activated by the discharge between the electrodes.

Here, in this embodiment, it is preferable to use a pulse power supply in order to generate the aforementioned pulse. FIG. 5 is a schematic diagram for explaining the structure of the pulse power supply 1. The pulse power supply 1 is a power supply for applying a negative voltage of a pulse waveform between electrodes, and includes a pulse unit 5 including a DC power supply 2, a capacitor 3, and a switch 4. The pulse power supply 1 outputs the power charged by the capacitor 3 as an instantaneous negative high power. The pulse of this embodiment is generated by the pulse power supply 1 in the form of a pulse waveform (so-called square wave) having a predetermined static interval. The maximum power density of the pulse should be 0.5 (W/cm ² ) or more, and the best is 1.0 (W/cm ² ) or more. In addition, the maximum power density of the pulse may be 20 (W/cm ² ) or less, and preferably 15 (W/cm ² ) or less. If the maximum power density of the pulse is less than 0.5 (W/cm ² ), it will be difficult to generate a plasma with a high electron density. On the other hand, if the maximum power density exceeds 20 (W/cm ² ), the substrate will be easily damaged.

The average power density of the pulse is preferably 2.0 (W/cm ² ) or less, preferably 1.5 (W/cm ² ) or less. In addition, the average power density of the pulse is preferably 0.01 (W/cm ² ) or more, preferably 0.1 (W/cm ² ) or more. Since the average power density of the pulse is within the above range, the vapor-deposited film obtained by using the aforementioned pulse and performing pretreatment has more excellent barrier properties and sealing properties.

Moreover, the ratio of the maximum power density to the average power density of the pulse is preferably 5 or more, preferably 10 or more. In addition, the ratio of the maximum power density to the average power density of the pulse is preferably 200 or less, preferably 100 or less. Since the ratio of the maximum power density to the average power density of the pulse is within the above range, the resulting vapor-deposited film has more excellent barrier properties and sealing properties.

The maximum current value of the pulse is preferably 6.0 (A) or less, and more preferably 4.0 (A) or less. In addition, the maximum current value of the pulse is preferably 0.1 (A) or more, and more preferably 0.5 (A) or more. Since the maximum current value of the pulse is within the above range, and the vapor-deposited film obtained by performing the pretreatment using the aforementioned pulse has more excellent barrier properties and sealing properties.

In addition, the ratio of the pulse to the pulse recurrence time (T _on + T _off ) pulse time (T _on ) (T _on /T _on + T _off , also known as the “load ratio”) is adjusted in such a way that 0.15 or less Period and continuous pulse interval. The load ratio may be 0.15 or less, and the optimal value is 0.1 or less. In addition, the load is preferably 0.005 or more, and more preferably 0.01 or more. If the load ratio is less than 0.15, the pretreatment of the substrate requires a long time, and the manufacturing efficiency of the vapor-deposited film is likely to decrease. On the other hand, if the load ratio is too large, the base material will easily become hot due to the pulse, and there is a risk of damage.

The pulse time (T _on ) can be adjusted in accordance with the aforementioned load ratio. For example, the pulse time (T _on ) is preferably 30 μs or more, and more preferably 50 μs or more. In addition, the pulse time (T _on ) is preferably 1000 μsec or less, and more preferably 500 μsec or less. Since the pulse time (T _on ) is within the above range, it is easier to generate pulses that meet the aforementioned duty ratio.

The frequency of the pulse (pulse recurrence time (T _on + T _off )) can be adjusted in a manner that conforms to the aforementioned load ratio. For example, the frequency of the pulse is preferably 50 Hz or more, and more preferably 100 Hz or more. In addition, the frequency of the pulse is preferably 1000 Hz or less, and more preferably 500 Hz or less. Since the pulse frequency is within the above range, it is easier to generate pulses that meet the aforementioned duty ratio.

In addition, the waveform of the pulse is not limited to the aforementioned square wave. As long as the pulse waveform conforms to the aforementioned maximum power density and load ratio, other waveforms may be used as appropriate. For example, the pulse waveform may also be a sawtooth wave, a triangle wave, and so on.

According to the aforementioned pretreatment process, the surface of the substrate can be processed to a predetermined surface roughness compared to the pretreatment process. Specifically, the pretreatment process was observed using an atomic force microscope (PSM-0600, manufactured by Shimadzu Corporation, scanning probe microscope), and measured in a 1 μm square interior (but protrusions such as fillers are to be removed) The best surface roughness at that time is to process Ra with 0.7~2.0nm and Rz as 8.0~20.0nm. Ra is preferably 0.7 nm or more, and more preferably 0.8 nm or more. Ra is preferably 2.0 nm or less, and more preferably 1.5 nm or less. Rz is preferably 8.0 nm or more, and more preferably 10 nm or more. In addition, Rz is preferably 20.0 nm or less, more preferably 15 nm or less. Since Ra and Rz process the surface roughness of the substrate in the above range, the resulting vapor-deposited thin-film substrate and the vapor-deposited layer have extremely excellent sealing properties.

The substrate processed by the pretreatment process then forms an evaporation layer.

(Vapor deposition process)

The vapor deposition process is a process of forming a vapor-deposited layer on the substrate after pretreatment, and a vapor-containing layer containing metal is formed on the substrate after the pretreatment process.

In the vapor deposition process, the method of vapor depositing the metal on the substrate is not particularly limited. As the vapor deposition method, a known physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a chemical vapor deposition method can be suitably used. Among these methods, the manufacturing method of the vapor-deposited thin film of the present embodiment is preferably provided with a vacuum vapor deposition method to provide a vapor-deposited layer due to high productivity. The vapor deposition conditions are based on the material of the vapor-deposited layer and the thickness of the desired vapor-deposited layer, and conventionally known conditions can be appropriately adopted. In addition, when it comes to vapor-depositing metals, the metal material preferably has less impurities and a purity of 99% by weight or more, and more preferably 99.5% by weight or more. In addition, the metal material is preferably granular, rod-shaped, flat, wire-shaped or crucible-shaped. The heating method for evaporating the metal material can be performed by placing the metal material in a crucible for resistance heating or high-frequency heating, performing an electron beam heating method, and placing the metal material in a ceramic plate made of boron nitride, etc. For the method of direct resistance heating, etc., known methods are used. The crucible using vacuum vapor deposition is ideally made of carbon, and can also be a crucible of alumina (alumina), magnesium oxide (Magnesia), titanium oxide (Titania), beryllium oxide (Beryllia).

By performing the vapor deposition process, a vapor-deposited film with a vapor-deposited layer formed on the substrate can be made. The resulting vapor-deposited thin film is as described above. Although the mechanism is not clear, the average concentration of oxygen atoms measured by X-ray photoelectron spectroscopy (XPS) in the vapor-deposited layer will be 8.0 atomic% or less. That is, the vapor-deposited thin film produced by the method for manufacturing a vapor-deposited thin film of this embodiment is subjected to the pretreatment of the substrate due to the aforementioned pretreatment process, and is formed on the substrate by a conventional method The concentration of oxygen atoms containing the vapor-deposited layer becomes lower than the concentration of oxygen atoms contained in the vapor deposited film. Next, as a result, the aforementioned vapor-deposited film not only has barrier properties but also has excellent sealing properties after hydrothermal treatment.

As described above, according to the method of manufacturing a vapor-deposited thin film of this embodiment, the substrate is subjected to the aforementioned plasma treatment as a pretreatment process. The substrate subjected to the above-mentioned pretreatment uses a vapor deposition process described later to form a vapor-deposited layer having excellent sealing properties on the substrate. In addition, the resulting vapor-deposited film has excellent barrier properties against penetration of oxygen, water vapor, and the like. Therefore, the vapor-deposited film seeks barrier properties and can be suitably used in applications requiring hydrothermal treatment (for example, applications such as packaging films for food requiring hydrothermal treatment).

[Example]

Hereinafter, the present invention will be described more specifically in detail through examples. The invention is not limited to these embodiments. In addition, as long as it is not particularly limited, its "%" means "mass %" and its "department" means "quality department".

<Example 1>

Using a biaxially stretched polyethylene terephthalate film ("TETORON" (registered trademark) HPE, 12 μm thick made by TEIJIN FILM SOLUTION Co., Ltd.) as a substrate, in a vacuum chamber, Using high-voltage pulse power on the substrate, Ar plasma treatment (pretreatment process) under the following pretreatment conditions. Secondly, vacuum vapor deposition of aluminum (vapor deposition process) is performed using a resistance heating vapor deposition machine. The vacuum vapor deposition system fills a carbon crucible with granular aluminum (purity 99.99%) and evaporates the aluminum while it is hot-melted to form an aluminum film (evaporated layer) with a thickness of 80 nm. (Pretreatment conditions) Maximum pulse power density: 2.4 (W/cm ² ) Average pulse power density: 0.24 (W/cm ² ) The ratio of the maximum power density to the average power density of the pulse: 10.0 Maximum pulse current value: 0.9 ( A) Pulse recurrence time (T _on + T _off ): 5 ms Pulse time (T _on ): 500 μs Load ratio: 0.10 Frequency: 200 Hz Pulse waveform: Square wave pre-processing time: 6.5 (seconds)

<Example 2>

Except for the pretreatment time of 4.5 seconds, the vapor deposition film was prepared in the same way as in Example 1.

<Example 3>

Except for the following changes in pretreatment conditions, the same method as in Example 1 was used to form a vapor-deposited film. (Pretreatment conditions) Maximum pulse power density: 2.4 (W/cm ² ) Average pulse power density: 0.12 (W/cm ² ) The ratio of the maximum power density to the average power density of the pulse: 20.0 Maximum pulse current value: 0.9 ( A) Pulse recurrence time (T _on + T _off ): 10 ms Pulse time (T _on ): 500 μs Load ratio: 0.05 Frequency: 100 Hz Pulse waveform: Square wave pre-processing time: 4.5 (seconds)

<Comparative Example 1>

Except that no pretreatment was performed, a vapor-deposited film was formed in the same manner as in Example 1.

<Comparative example 2>

Except that the pretreatment process uses Ar pulse plasma treatment with non-pulse and stable direct current, the same method as in Example 1 is used to form a vapor-deposited film. (Pretreatment conditions) Average power density: 0.24 (W/cm2) DC voltage: 2 (kV) DC current: 0.1 (A) Pre-processing time: 4.5 (seconds)

Regarding the substrate after the pretreatment process obtained in Examples 1 to 3 and Comparative Examples 1 to 2 (Comparative Example 1 is a substrate that has not been subjected to the pretreatment process) and the resulting vapor-deposited film, various evaluations were conducted according to the following methods. The results are shown in Table 1.

(1) Oxygen content ratio in the deposited layer

The oxygen content ratio of the vapor-deposited layer measured under the following conditions. The oxygen content ratio is based on the minimum oxygen ratio (Oxygen ratio) of oxygen in the deposited layer. X-ray photoelectron spectroscopy (XPS) depth-direction analysis measurement conditions XPS measurement conditions ・Device: X-ray photoelectron spectrum analyzer (XPS) ・Manufacturer/model: ULVAC-PHI (share)/PHI5000VersaProbe II ・X-ray beam diameter (measurement range): φ100μm Etching conditions (sputtering conditions measured from the A1 evaporation layer toward the depth of the substrate) ・Ar ion gun acceleration voltage: 4kV ・Etching range: 3mm×3mm square inside ・Etching time: 30 seconds/1 time

(2) Surface roughness of substrate

A scanning probe microscope (AFM) (PSM-9600, manufactured by Shimadzu Corporation) was used to measure the surface roughness (Ra, Rz, nm) of the substrate after the pretreatment process.

(3) Oxygen barrier

Based on JIS K 7126-2, an oxygen transmission rate (oxygen transmission rate) measuring device (OX-TRAN2/20, manufactured by MODERN CONTORLS) was used to measure the oxygen transmission rate (cc/m ² day). When the oxygen permeability is 1.2 (cc/m ² day) or less, it is judged to be suitable as a packaging material.

(4) Water vapor barrier

The water vapor transmission rate (g/m ² day) was measured using a water vapor transmission rate measuring device (Permatran-W3/31, manufactured by MODERN CONTORLS Co., Ltd.) based on JIS K 7129B. When the water vapor transmission rate is 1.5 (g/m ² day) or less, it is judged to be suitable as a packaging material.

(5) Lamination strength (sealing)

For the vapor deposition layer, a polyester two-component adhesive (Polyester two-component adhesive) is applied in a coating thickness of 2 μm, and is laminated on an unstretched PP film of 60 μm, and is cooked in a 40°C atmosphere for 72 hours ( After aging), cut out a size of 15mm × 200mm, using a T-type peeling tester (AGS-100A, manufactured by Shimadzu Corporation), and measuring the adhesion strength at the time of T-type peeling at a tensile speed of 300mm/min as Fit strength. Next, the samples obtained by the same method as described above were immersed in hot water at 100°C, 115°C, and 125°C for 30 minutes, respectively, and the bonding strength was also measured. When the dry bonding strength is 100 (gf/15mm) or more and the wet bonding strength is 100 (gf/15mm) or more, it is judged to be suitable as a packaging material. In addition, when dropping 2 to 3 drops of distilled water at 90° peeling off the interface, and wiping the peeling interface with a cotton stick to keep it in a wet state, the wet bonding strength was also evaluated.

(6) Carbon content ratio in the peeling interface on the side of the vapor-deposited layer

X-ray photoelectron spectroscopy (XPS) was used to measure the peeling interface and surface light on the vapor deposited layer side after peeling. A relatively high carbon content means that the peeling is not near the interface between the substrate and the vapor-deposited layer, but means that cracks occurred inside the substrate. (X-ray photoelectron spectroscopy (XPS) measurement conditions) XPS measurement conditions ・Device: X-ray photoelectron spectrum analyzer (XPS) ・Manufacturer/model: ULVAC-PHI (share)/PHI5000VersaProbe II ・X-ray beam diameter (measurement range): φ100μm

[Table 1]

As shown in Table 1, the vapor-deposited films of Examples 1 to 3 with an average concentration of oxygen atoms of 8.0 atomic% or less showed excellent bonding strength and barrier properties. On the other hand, the vapor-deposited thin film of Comparative Example 1 without the pretreatment process greatly reduces the bonding strength by hydrothermal treatment, and the barrier properties cannot be possessed at the same time.

1‧‧‧Pulse power supply 2‧‧‧DC power supply 3‧‧‧Capacitor 4‧‧‧switch 5‧‧‧Pulse unit

FIG. 1 is a graph showing the results of measuring the average concentration of oxygen atoms using a vapor deposited film (aluminum vapor deposited layer formed on a PET substrate) according to an embodiment of the present invention. 2 is a graph showing a vapor deposition film (a vapor deposition film described in Patent Document 1) provided with an aluminum vapor deposition layer on a PET substrate that has not been subjected to a pretreatment process, and using XPS to measure the average concentration of oxygen atoms Chart. FIG. 3 is a schematic diagram for explaining plasma processing. FIG. 4 is a schematic diagram illustrating pulses applied to electrodes during the pretreatment process. 5 is a schematic diagram for explaining the structure of a pulse power supply.

Claims (11)

A vapor deposited film includes: Substrate; and The vapor deposited layer is provided on the aforementioned substrate; The vapor deposition layer system contains metal, and the average concentration of oxygen atoms measured by X-ray photoelectron spectroscopy in the thickness direction is 8.0 atomic% or less. The vapor-deposited thin film as described in item 1 of the patent application, wherein the aforementioned average concentration is 4.0 to 6.0 atomic %. The vapor-deposited thin film as described in claim 1 or 2, wherein the peak concentration of oxygen atoms measured by X-ray photoelectron spectroscopy in the thickness direction of the vapor deposition layer is 15.0 atomic% or less. As for the vapor-deposited film described in any one of claims 1 to 3 of the patent application, the bonding strength after hydrothermal treatment is 50gf/15mm or more. The vapor-deposited thin film as described in any one of claims 1 to 4 of the patent application, wherein the carbon content ratio in the peeling interface on the side of the vapor deposition layer is 50 atomic% or more. The vapor-deposited thin film as described in any one of claims 1 to 5 of the patent application, wherein the vapor deposition layer contains aluminum. The vapor-deposited thin film as described in any one of claims 1 to 6 of the patent application, wherein the aforementioned substrate is a resin-made substrate. The vapor-deposited film as described in any of items 1 to 7 of the patent application, which is a packaging film for packaging food. A method for manufacturing a vapor-deposited film, comprising: a substrate; and a vapor-deposited layer, which is provided on the aforementioned substrate; the manufacturing method includes: a pre-treatment process in which the aforementioned substrate is subjected to plasma treatment; and a vapor deposition process The vapor deposition layer is formed on the substrate after the pretreatment process; the vapor deposition process is to form a metal-containing vapor deposition layer on the substrate after the pretreatment process; the pretreatment process includes the following processes: The maximum power density of 0.5~20 (W/cm ² ) pulse to pulse recurrence time (T _on + T _off ) pulse time (T _on ) ratio (T _on / T _on + T _off ) is less than 0.15 The negative electrode is supplied to generate plasma. The method for manufacturing a vapor-deposited thin film as described in item 9 of the patent application, wherein the maximum current value of the pulse in the pretreatment is 6.0 (A) or less. The method for manufacturing a vapor-deposited thin film as described in item 9 or 10 of the patent application, wherein the surface roughness of the substrate measured by an atomic force microscope during the pretreatment process is Ra 0.7-2.0 nm and Rz 8.0- The surface treatment of the aforementioned substrate is performed up to 20.0 nm.

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