JPWO2019087960A1 - Laminated film, barrier laminated film, gas barrier packaging material using the barrier laminated film, gas barrier packaging - Google Patents

Abstract

A laminated film having an aluminum oxide vapor-deposited film having good adhesion between a plastic base material and an aluminum oxide vapor-deposited film and having high barrier performance, so-called retort-resistant aluminum oxide film, even after hot water treatment, and the laminated film. It is an object of the present invention to provide a barrier laminated film containing the above, a gas barrier packaging material using the barrier laminated film, and a gas barrier packaging. Mainly the aluminum oxide vapor deposition film formed on the surface of the base film by using the flight time type secondary ion mass spectrometry (TOF-SIMS) with a Cs (cesium) ion gun for the aluminum oxide vapor deposition film of the laminated film. A transition region that defines the adhesion strength is formed between the vapor-deposited film and the transition region, and the transition region contains element-bonded Al2O4H that transforms into aluminum hydroxide detected by etching using TOF-SIMS, and TOF- By defining the transformation rate of the transition region that transforms into aluminum hydroxide as defined by the ratio of the transition region that is transformed with respect to the aluminum oxide vapor deposition film defined by etching using SIMS, it is 45% or less. It identifies a laminated film having a barrier property with improved adhesion strength.

Description

INDUSTRIAL APPLICABILITY The present invention is excellent in barrier properties against oxygen and water vapor, which can be suitably used as a packaging material for retort treatment of foods, pharmaceuticals, pet foods, etc., and improves the adhesion between the plastic base material after retort treatment and the aluminum oxide vapor deposition film. The present invention relates to a laminated film having a barrier property, a barrier-type laminated film using the laminated film having a retort-resistant property, and a packaging material.

In fields that require retort treatment such as foods and pharmaceuticals, stable higher barrier properties that are not affected by temperature, humidity, etc., so that deterioration of the contents can be prevented and functions and properties can be maintained. A barrier-type laminated film that can be exhibited is required, and a multi-layered barrier-type laminated film in which a barrier layer made of a thin film of a vapor-deposited film such as silicon oxide or aluminum oxide and a barrier-type coating film layer are laminated has also been developed.

However, the plastic base material of the laminated film having a vapor-deposited film having an excellent barrier property that is easily affected by temperature, humidity, etc. is liable to cause a dimensional change. Therefore, the plastic base material can be expanded and contracted due to the dimensional change. , It is difficult to follow a vapor-deposited film such as a silicon oxide-deposited film or an aluminum oxide-deposited film provided on the film.
Therefore, an delamination phenomenon often occurs between the plastic substrate and the vapor-deposited film such as a silicon oxide vapor-deposited film or an aluminum oxide-deposited film in a harsh environment of high temperature and humidity, and further, cracks, pinholes, etc. Occur.
As a result, there is a problem that the original barrier performance is significantly impaired and it is extremely difficult to maintain the barrier performance.

In the case of forming a thin-film deposition film of an inorganic oxide such as aluminum oxide on a plastic base material by the method using the above-mentioned thin-film deposition film, in order to obtain high adhesion between the plastic base material and the formed thin-film deposition film, Methods for modifying the surface of a plastic substrate, such as in-line plasma pretreatment with a parallel plate type apparatus and formation of an undercoat treatment layer, have been carried out (see, for example, Patent Document 1 and Patent Document 2).

However, in the in-line plasma treatment method using a generally used parallel plate type apparatus of Patent Document 1, a functional group such as a hydroxyl group or a carbonyl group is introduced into the plastic surface, and the functional group is interposed between the vapor-deposited films. Adhesion is expressed. However, those that develop adhesion by hydrogen bonds with hydroxyl groups have remarkable adhesion because the hydrogen bonds are broken in the high temperature and high humidity environment required for applications such as electronic devices such as electronic paper and retort packaging materials. There is a problem of decline.
Further, since the above plasma treatment only allows the film to pass under a plasma atmosphere generated in the air, sufficient adhesion between the base material and the vapor-deposited film in a harsh environment of high temperature and humidity is not obtained. Is the reality.

Further, the undercoat treatment method described in Patent Document 2 is to provide an undercoat layer as an adhesive layer on the surface of a plastic film, and is generally practiced. However, as a manufacturing method, the number of steps is increased, which increases the cost.

Therefore, a technique for improving adhesion is implemented by pretreating the surface of a plastic base material using a reactive ion etching (RIE) method in which the electrode for plasma generation is placed on the base material side to generate plasma. (Patent Document 3).
The plasma RIE method simultaneously obtains two effects: a chemical effect such as giving a functional group to the surface of a base material, and a physical effect of ion-etching the surface to remove impurities and smooth it. It develops adhesion.

In the RIE method, unlike the above-mentioned in-line plasma treatment, the adhesion is not exhibited by hydrogen bonding, so that the adhesion is not deteriorated in a high temperature and high humidity environment.
However, in the RIE method, since a functional group is provided on the plastic base material, the water resistance and water resistance that cause hydrolysis at the interface are still insufficient. Further, in order to obtain sufficient adhesion by 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 by this method, a method of increasing the plasma density and a method of lengthening the processing time can be considered, but in order to increase the plasma density, a high output power supply is required. There is a problem that the damage of the base material becomes large, and when the processing time is lengthened, a decrease in productivity becomes a problem (see Patent Documents 4 and 5).

Therefore, the problem in forming the vapor-deposited film of inorganic oxide on the surface of the transported plastic base material as described above is solved, and the adhesion between the plastic base material and the vapor-deposited film is good even after the retort treatment. A laminated film having excellent barrier properties is desired.

In particular, in fields such as foods and pharmaceuticals that require high-temperature and high-pressure retort treatment and sterilization treatment, the contents are not affected by temperature, humidity, etc. so as to prevent deterioration of the contents and maintain their functions and properties. A barrier-type laminated film capable of stably exhibiting higher barrier properties is required, and has a multilayer structure in which a barrier layer made of a thin film of aluminum oxide such as silicon oxide and aluminum oxide and a barrier-type coating film layer are laminated. A barrier laminated film having excellent retort resistance is desired.

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

In the problem of the prior art, the retort treatment by hot water treatment imposes a large mechanical and chemical stress on the interface between the plastic substrate and the aluminum oxide vapor deposition film. This stress deteriorates the barrier property. This part is stressed because it is the most vulnerable in the laminated configuration. Therefore, in order to obtain retort resistance, it is important to firmly coat the interface with the substrate with a thin-film deposition film.
On the other hand, aluminum hydroxide has good adhesion to a plastic base material due to its chemical structure, and also has a high water vapor barrier property because it forms a network and is dense. However, in a strong environment such as retort treatment, the bond structure based on the hydrogen bond between aluminum hydroxide and the base material is microscopically easily broken. Further, the network of aluminum hydroxide also easily penetrates into the membrane due to the affinity between the water molecule and the grain interface of aluminum hydroxide.

The present invention has been made in view of the above problems and findings, and an object of the present invention is that the adhesion between the plastic base material and the aluminum oxide vapor-deposited film is good even after hot water treatment. In addition, a laminated film having a vapor-deposited film having excellent barrier properties, a barrier-based laminated film including the laminated film and having a so-called aluminum oxide vapor-deposited film having excellent retort resistance, and the barrier-related laminated film are used to provide adhesion and adhesion. It is an object of the present invention to provide a gas barrier packaging material and a gas barrier packaging material having excellent barrier properties and excellent retort resistance.

In order to achieve these objects, the laminated film of the present invention is formed on the surface of a base film in a laminated film having a barrier property in which an aluminum oxide vapor-deposited film containing aluminum oxide as a main component is formed on the surface of a plastic base material. A transition region of the vapor-deposited film that defines the adhesion strength with the vapor-deposited film mainly composed of the aluminum oxide vapor-deposited film is formed, and the transition region uses the flight time type secondary ion mass spectrometry (TOF-SIMS). includes elements coupled _Al 2 _{O 4} H for transforming the aluminum hydroxide that is detected by performing etching Te, for the aluminum oxide deposited film as defined by performing etching using TOF-SIMS, using TOF-SIMS The transformation rate of the transition region defined by the ratio of the transformation region defined in the above is 45% or less.

Secondary ion mass spectrometry (SIMS) is a method for analyzing the element concentration distribution by irradiating the surface of a sample to be analyzed with a primary ion beam and performing mass spectrometry on the secondary ions emitted by sputtering from the sample surface. Is. In this secondary ion mass spectrometry method, the secondary ionic strength is detected while sputtering is allowed to proceed. Therefore, by converting the transition time into the depth of the data of the ionic strength of the secondary ion, that is, the ion to be detected or the molecular ion bonded to the element to be detected, in the depth direction of the sample surface. It is possible to know the concentration distribution of the element to be detected.

In the present invention, the conversion of the transition time to the depth is obtained by measuring the depth of the depression formed on the sample surface by irradiation with the primary ion using a surface roughness meter, and averaging the depth of the depression and the transition time. The sputtering rate is calculated, and the irradiation time (that is, transition time) is converted into the depth (sputtering amount) under the assumption that the sputtering rate is constant.

In the present invention, the flight time type secondary ion mass spectrometry (TOF-SIMS) is used while repeating soft etching of the aluminum oxide vapor-deposited film of the laminated film with a Cs (cesium) ion gun at the above-mentioned constant speed. By measuring the ions derived from the aluminum oxide vapor deposition film and the ions derived from the plastic substrate, the transition that defines the adhesion strength between the surface of the substrate film and the vapor deposition film mainly composed of the formed aluminum oxide vapor deposition film. A region is formed. The transition region contains an elemental bond Al ₂ O ₄ H that transforms into aluminum hydroxide detected by etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS). The ratio of the transformed transition region defined by using the time-of-flight secondary ion mass spectrometry to the aluminum hydroxide vapor deposition film defined by etching using the secondary ion mass spectrometry (TOF-SIMS). It is based on the finding that a laminated film having a barrier property with improved adhesion strength can be specified by defining the transformation rate of the transition region transformed into aluminum hydroxide defined by.

Specifically, in the present invention, etching is performed from the outermost surface of the aluminum oxide vapor deposition film by Cs using a flight time type secondary ion mass analyzer, and the elemental bond at the interface between the aluminum oxide vapor deposition film and the plastic substrate is performed. And the elemental bond of the vapor deposition film was measured, and the measured element and the elemental bond were obtained from each actual measurement graph (Fig. 3 graph analysis diagram), and the plastic substrate and the vapor deposition film formed by aluminum hydroxide in the aluminum oxide vapor deposition film. In order to make the transition region of the interface of the element as narrow as possible, pay attention to the elemental bond Al ₂ O ₄ H, and 1) set the position where the strength of the graph of the element C6 is halved as the interface between the plastic base material and aluminum oxide from the surface. Find the peak up to the interface as an aluminum oxide vapor deposition film, 2) find the peak in the graph representing the elemental bond Al ₂ O ₄ H, and find the transition region from that peak to the interface, and 3) (element bond Al ₂ O ₄ H) The transformation rate of the transition region to aluminum hydroxide is determined as the transition region from the peak to the interface / aluminum oxide vapor deposition film) × 100 (%).

In the present invention, by setting the alteration rate of the transition region of the aluminum oxide vapor-deposited film to 45% or less, a barrier coating layer is further formed on the laminated film, and the plastic base material of the barrier laminated film and the aluminum oxide vapor-deposited film are combined. Adhesion strength at the interface shall be 2.1 N / 15 mm or more even after hot water treatment (high retort treatment) at 135 ° C. for 40 minutes or hot water treatment (semi-retort treatment) at 121 ° C. for 40 minutes. It is possible to produce a barrier laminated film having retort resistance, which does not cause delamination during molding or retort processing of the retort pouch, and has improved adhesion.

The present invention, by which the modified ratio of the transition region of the aluminum oxide deposited film was 45% or less, high retort treatment, the oxygen transmission rate after the semi-retort, the water vapor permeability, respectively, 0.2cc / m 2 ^· 24hr hereinafter, the following 0.9g / m 2 ^· 24hr, to produce a barrier laminate film that exhibits sufficient barrier to the extent not to or causing deterioration of the quality deterioration and shelf life of the contents after the retort processing minute Can be done.
Therefore, the aluminum oxide vapor-deposited film of the present invention not only improves the adhesion at the interface with the plastic base material, but also has excellent barrier performance such as moisture heat resistance and heat resistance after retort treatment, and can improve retort resistance. Is.

The present invention is characterized by the following points.
1. 1. In a laminated film having a barrier property in which an aluminum oxide vapor-deposited film containing aluminum oxide as a main component is formed on the surface of a plastic base material, the adhesion strength between the base film surface and the formed vapor-deposited aluminum oxide film-based film is improved. A defined transition region of the vapor-deposited film is formed, and the transition region is transformed into aluminum hydroxide detected by etching using the flight time type secondary ion mass spectrometry (TOF-SIMS). Defined by the ratio of the transformed transition region defined using TOF-SIMS to the aluminum oxide vapor deposition film containing the element-bonded Al ₂ O ₄ H and defined by etching with TOF-SIMS. The laminated film having a transformation rate of 45% or less in the transition region.
2. 2. The laminated film according to 1 above, wherein the plastic base material is a polyethylene terephthalate film.
3. 3. The laminated film according to 1 above, wherein the plastic base material contains a recycled polyethylene terephthalate film.
4. The laminated film according to 1 above, wherein the plastic base material is a polybutylene terephthalate film.
5. The laminated film according to 1 above, wherein the plastic base material is a polyester film derived from biomass.
6. The laminated film according to 1 above, wherein the plastic base material is a high-stiffness polyester film.
7. The laminated film according to any one of 1 to 6 above, wherein the surface of the plastic base material is an oxygen plasma-treated surface.
8. The laminated film according to 7 above, wherein an aluminum oxide vapor-deposited film is laminated in-line on an oxygen plasma-treated surface.
9. A barrier laminated film obtained by laminating a barrier coating layer on the surface of the aluminum oxide vapor-deposited film of the laminated film according to any one of 1 to 8 above.
10. The barrier laminated film according to 9 above, wherein the barrier coating layer is a layer formed by applying a mixed solution of a metal alkoxide and a water-soluble polymer and drying the mixture by heating.
11. The barrier laminated film according to 9 above, wherein the barrier coating layer is a layer formed by applying a mixed solution of a metal alkoxide, a silane coupling agent, and a water-soluble polymer and drying the mixture by heating.
12. A gas barrier packaging material obtained by laminating a thermoplastic resin having a heat seal property on the barrier laminated film according to any one of 9 to 11 above.
13. The gas barrier packaging material according to 12 above, which is used for packaging for retort sterilization.
14. A gas-barrier package made from the gas-barrier packaging material according to 12 or 13 above.

In the present invention, in order to narrow the transition region of the interface between the aluminum hydroxide vapor-deposited film and the plastic substrate on which aluminum hydroxide is formed as much as possible and to optimize the rate of modification to aluminum hydroxide, the element-bonded Al ₂ O ₄ Focusing on H, by setting the transformation rate of the transition region of the aluminum oxide vapor-deposited film in the laminated film to 45% or less and increasing the ratio of the aluminum oxide film, which has a relatively small amount of aluminum hydroxide, fine particles due to water molecules by retort treatment are used. It greatly suppresses the visual destruction of the vapor-deposited film and the interface destruction with the plastic substrate. As a result, it is possible to provide a laminated film having improved adhesion and having unprecedented retort resistance, and a barrier laminated film containing the sex layer film.
The barrier laminated film of the present invention has a adhesion strength at the interface between the plastic base material and the aluminum oxide vapor-deposited film of 2.1 N / 15 mm or more even after the high retort treatment and the semi-retort treatment, and the high retort treatment. oxygen transmission rate after the semi-retort, the water vapor permeability, respectively, 0.2cc ^/ m 2 · 24hr or less, has the following barrier properties 0.9g ^/ m 2 · 24hr, has excellent retort resistance.

Cross-sectional view showing an example of the laminated film A (FIG. 1a) of the present invention, the barrier laminated film B (FIG. 1b) in which the barrier coating layer is laminated, and the laminated film A (FIG. 1c) of another aspect. The figure which shows an example of the apparatus which deposits the aluminum oxide vapor deposition film of this invention. An example of a graph analysis diagram of the analysis result by the time-of-flight type secondary ion mass spectrometry of the aluminum oxide vapor-deposited film laminated film of the present invention.

Hereinafter, a laminated film having an aluminum oxide vapor-deposited film having a barrier property with improved adhesion according to an embodiment of the present invention and a barrier-type laminated film including the laminated film will be described in detail with reference to the drawings. It should be noted that this embodiment is merely an example and does not limit the present invention in any way.
FIG. 1a is a cross-sectional view showing an example of a laminated film of the present invention, and FIG. 1b is a cross-sectional view showing an example of a barrier laminated film containing the laminated film and having a barrier coating layer laminated on the surface. FIG. 1c is a cross-sectional view showing an example of a laminated film in which the base material layer is composed of multiple layers, and FIG. 2 is a roller suitable for forming an aluminum oxide vapor-deposited film of the laminated film having a barrier property of the present invention. It is a figure which shows typically the structure of the formula continuous vapor deposition film formation apparatus. In addition, in order to form the barrier laminated film in which the barrier coating layer is laminated, the barrier coating agent coating apparatus is continuously arranged in the vapor deposition film forming apparatus, but a known roller coating apparatus is continuously provided. Yes, it is omitted here.

As shown in FIG. 1a, the laminated film A having an aluminum oxide vapor-deposited film having a barrier property with improved adhesion according to the present invention has a barrier property with improved adhesion on one surface of the plastic base material 1. The basic configuration is a layer structure in which the aluminum oxide vapor-deposited film 2 comprising the above is laminated, and in the present invention, as further shown in FIG. 1b, the barrier coating layer 3 is further formed on the vapor-deposited film 2 of the laminated film A. The laminated structure is formed by laminating, and is a barrier-type laminated film B having excellent adhesion and barrier properties and excellent retort resistance.

The plastic base material is not particularly limited, and a known plastic film or sheet can be used. For example, polyester resins such as polyethylene terephthalate, biomass-derived polyester, polybutylene terephthalate, polyethylene naphthalate, recycled polyethylene terephthalate, and polyethylene furanoate, polyamide resin 6, polyamide resin 66, polyamide resin 610, polyamide resin 612, and polyamide resin 11. , Polyester-based resins such as polyamide resin 12, and polyolefin-based resins such as α-olefin polymers such as polyethylene and polypropylene can be used. A polyester resin known as a polyethylene terephthalate film is particularly preferably used.

(Polybutylene terephthalate film (PBT))
Polybutylene terephthalate film has a high thermal deformation temperature, excellent mechanical strength and electrical characteristics, and good molding processability. Therefore, when it is used as a packaging bag for storing contents such as food, it is used for retort treatment. It is possible to prevent the packaging bag from being deformed or its strength from being lowered.

Polybutylene terephthalate film has high strength. Therefore, when the polybutylene terephthalate film is used, the packaging bag can be made to have puncture resistance as in the case where the packaging material constituting the packaging bag contains a nylon film.
Further, since the polybutylene terephthalate film is hydrolyzed in a high temperature and high humidity environment, the adhesion strength and the barrier property after the retort treatment are lowered, but it has a characteristic that it is harder to absorb water than nylon. Therefore, even when the polybutylene terephthalate film is arranged 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 being lowered. Since it has such properties, when a polybutylene terephthalate film is used for a retort packaging bag, it can be replaced with a conventional laminated packaging material of a polyethylene terephthalate film and a nylon film, and is therefore preferably used.

The polybutylene terephthalate film is a film containing polybutylene terephthalate (hereinafter, also referred to as PBT) as a main component, and is preferably a resin film containing 60% by mass or more of PBT. The polybutylene terephthalate film is classified into two modes according to its 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 PBT used as the main constituent component preferably contains terephthalic acid in an amount of 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 100 as a dicarboxylic acid component. It is mol%. As the glycol component, 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 97 mol% or more.

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

The amount of the polyester resin other than PBT added is preferably 40% by mass or less. If the amount of the polyester resin other than PBT added exceeds 40% by mass, it is considered that the mechanical properties of PBT are impaired and the impact strength, pinhole resistance, and draw moldability are insufficient.

The layer structure of the polybutylene terephthalate film according to the first aspect is produced by casting a resin in multiple layers by a casting method, and comprises a multilayer structure portion 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 60% by mass or more of PBT. In the plurality of unit layers, the n + 1th unit layer is directly laminated on the nth unit layer. That is, no adhesive layer or adhesive layer is interposed between the plurality of unit layers. Such a polybutylene terephthalate film comprises a multilayer structure including at least 10 layers or more, preferably 60 layers or more, more preferably 250 layers or more, and further preferably 1000 layers or more.

The polybutylene terephthalate film according to the second aspect is composed of a single layer containing polyester having PBT as the main repeating unit. Polyester containing PBT as a main repeating unit contains, for example, 1,4-butanediol as a glycol component or an ester-forming derivative thereof and terephthalic acid as a dibasic acid component or an ester-forming derivative thereof as main components. , Includes homo or copolymer type polyesters obtained by condensing them. The content of PBT according to 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 containing 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 blended with PBT, polyester having ethylene terephthalate as a main repeating unit can be used. For example, a homotype containing ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component as main components can be preferably used.

The polybutylene terephthalate film according to the second configuration can be produced by a tubular method or a tenter method. By the tubular method or the tenter method, the unstretched raw fabric may be stretched simultaneously in the vertical and horizontal directions, or may be sequentially stretched in the vertical and horizontal directions. Of these, the tubular method is particularly preferably adopted because it is possible to obtain a stretched film having a good balance of physical properties in the circumferential direction.

(Biomass-derived polyester film)
The polyester film derived from biomass comprises a resin composition containing a polyester composed of a diol unit and a dicarboxylic acid unit as a main component, and the resin composition is an ethylene glycol whose diol unit is derived from biomass and is a dicarboxylic acid unit. Polyester, which is a dicarboxylic acid derived from fossil fuel, is contained 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 similar to conventional fossil fuel-derived polyester films. It is not inferior in terms of physical properties such as physical characteristics. Therefore, since the laminated film of the present invention and the barrier laminated film using the same have a layer made of a carbon-neutral material, the laminated film produced from a raw material obtained from a conventional fossil fuel and the barrier property using the same are obtained. Compared with the laminated film, the amount of fossil fuel used can be significantly reduced, and the environmental load can be reduced.

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

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

Polyesters that may be contained in the resin composition forming the polyester film derived from biomass in a proportion of 5 to 45% by mass include polyester derived from fossil fuel, recycled polyester of polyester product derived from fossil fuel, and polyester product derived from biomass. Recycled polyester.

The resin composition containing the polyester obtained as described above preferably contains 10 to 19% of carbon derived from biomass as measured by radiocarbon ( ¹⁴ C) with respect to the total carbon in the polyester. Since carbon dioxide in the atmosphere contains ¹⁴ C in a certain ratio (105.5 pMC), the ¹⁴ C content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. Is known to be. It is also known that fossil fuels contain almost no ¹⁴ C. Therefore, the proportion of biomass-derived carbon can be calculated by measuring the proportion of ¹⁴ C contained in all carbon atoms in polyester.

In the present invention, when the content of ¹⁴ C in polyester is P ¹⁴ C, the content of carbon derived from biomass Pbio is defined as follows.
Pbio (%) = P ¹⁴ C / 105.5 × 100
Taking polyethylene terephthalate as an example, polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1: 1. Therefore, only ethylene glycol derived from biomass is used. When is used, the content of carbon derived from biomass in polyester Pbio is 20%. In the present invention, the content of biomass-derived carbon as measured by radiocarbon ( ¹⁴ C) is preferably 10 to 19% with respect to the total carbon in the resin composition. If the carbon content derived from biomass in the resin composition is less than 10%, the effect as a carbon offset material becomes poor. On the other hand, as described above, the carbon content derived from biomass in the resin composition is preferably close to 20%, but due to problems in the film manufacturing process and physical properties, the resin contains recycled polyester as described above. Since it is preferable to include an additive, the actual upper limit is 18%.

(Recycled polyethylene terephthalate)
As the resin base material of the present invention, those containing polyethylene terephthalate recycled by mechanical recycling (hereinafter, polyethylene terephthalate is also referred to as PET) can be used.
Specifically, the resin base material contains PET in which a PET bottle is recycled by mechanical recycling, and the PET contains ethylene glycol as a diol component and terephthalic acid and isophthalic acid as a dicarboxylic acid component.

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

Hereinafter, in the present specification, polyethylene terephthalate obtained by recycling PET bottles is referred to as "recycled polyethylene terephthalate (hereinafter, also referred to as recycled PET)", and non-recycled polyethylene terephthalate is referred to as "virgin polyethylene terephthalate (hereinafter, also referred to as virgin PET)". ) ”.

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

The PET may be a biomass PET in addition to a PET derived from ordinary fossil fuels. "Biomass PET" contains ethylene glycol derived from biomass as a diol component and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component. This biomass PET may be formed only of PET having a biomass-derived ethylene glycol as a diol component and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid component, or a biomass-derived ethylene glycol and a fossil fuel-derived diol. It may be formed of PET having a diol component and a fossil fuel-derived dicarboxylic acid as the dicarboxylic acid component.

The PET used in the PET bottle can be obtained by a conventionally known method of polycondensing the above-mentioned diol component and dicarboxylic acid component.

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

The amount of the diol component used in producing the PET is substantially equimolar to 100 mol of the dicarboxylic acid or its derivative, but is generally esterification and / or transesterification reaction and / or polycondensation. Since there is distillation during the reaction, it is used in excess of 0.1 mol% or more and 20 mol% or less.
Further, the polycondensation reaction is preferably carried out in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added at the time of raw material preparation or at the start of reduced pressure.

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

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

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

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

The resin base material composed of such PET may be a single layer or a multilayer.
As shown in FIG. 1c, when the recycled PET as described above is used as the resin base material, the resin base material may be provided with three layers of the first layer 1a, the second layer 1b, and the third layer 1c.
In this case, the second layer 1b shall be a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 1a and the third layer 1c shall be a layer composed only of virgin PET. Is preferable.

As described above, by using only virgin PET for the first layer 1a and the third layer 1c, it is possible to prevent the recycled PET from being exposed from the front surface or the back surface of the resin base material layer. Therefore, the hygiene of the laminated body can be ensured.
Further, the resin base material layer may be a resin base material layer having two layers, the second layer 1b and the third layer 1c, without providing the first layer 1a shown in FIG. 1c. Further, the resin base material layer may be a resin base material layer having two layers, the first layer 1a and the second layer 1b, without providing the third layer 1c shown in FIG. 1c. Also in these cases, the second layer 1b is a layer composed of only recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 1a and the third layer 1c are layers composed of only virgin PET. Is preferable.

When one layer is formed by mixing recycled PET and virgin PET, there are a method of separately supplying to a molding machine, a method of supplying after mixing with a dry blend or the like. Above all, the method of mixing by dry blend is preferable from the viewpoint of easy operation.

The PET constituting the resin base material can contain various additives in the manufacturing process thereof or after the manufacturing thereof as long as its properties are not impaired. Additives include, for example, plasticizers, UV stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, mold release agents, antioxidants, ions. Examples include replacement agents and coloring pigments. The additive is preferably contained in the entire resin composition containing PET in the range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less.

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

The 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 the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the vertical direction to obtain a vertically stretched film. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 ° C. or higher and 100 ° C. or lower. Further, the magnification of longitudinal stretching depends on the required characteristics of the film application, but is preferably 2.5 times or more and 4.2 times or less. When the draw ratio is less than 2.5 times, the thickness unevenness of the PET film becomes large and it is difficult to obtain a good film.

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

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

The thickness of the PET film obtained as described above is arbitrary depending on the intended use, but is usually about 5 μm or more and 100 μm or less, and preferably 5 μm or more and 25 μm or less. Further, the breaking strength of the PET film in the MD direction 5 kg / mm ² or more 40 kg / mm ² or less, in TD direction 5 kg / mm ² or more 35 kg / mm ² or less, also elongation at break 50 in the MD direction % Or more and 350% or less, and 50% or more and 300% or less in the TD direction. The shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1% or more and 5% or less.

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

(High stiffness polyester film)
The high-stiffness polyester film is a stretched plastic film having a loop stiffness of 0.0017 N / 15 mm or more in the flow direction (MD) and the vertical direction (TD) and containing 51% by mass or more of polyester.
Loop stiffness is a parameter that expresses the strength of the film. Hereinafter, a method for measuring the loop stiffness of the film will be described.

First, the film is cut into strips having long and short sides to prepare test pieces. Subsequently, the short sides of both ends of the strip in the long side direction are fixed in a state where the test piece of the strip is curved so that the long piece draws a loop to form a circular loop having a predetermined diameter. Then, the circular loop is pushed from the outside over a predetermined distance. Then, the load required for pushing is recorded as loop stiffness.

In the present embodiment, the length of the short side of the strip is 15 mm, and the length of the long side is 150 mm. Further, the diameter of the circular loop was set to 60 mm, and the pushing distance of the circular loop was set to 40 mm. The above-mentioned loop stiffness of "0.0017N / 15mm" means that the load required to push the circular loop of the strip test piece having a short side length of 15mm by 40mm is 0.0017N.

When measuring the loop stiffness in the flow direction, a test piece is prepared so that the flow direction of the film coincides with the long side direction of the strip. When measuring the loop stiffness in the vertical direction, the test piece is prepared so that the vertical direction of the film coincides with the long side direction of the strip. As the loop stiffness measuring instrument, for example, LOOP STIFFNESS TESTER manufactured by Toyo Seiki Co., Ltd. can be used.

The preferred mechanical properties of the high stiffness polyester film will be further described.
The piercing strength of the high-stiffness polyester film is preferably 9.5 N or more, and more preferably 10.0 N or more.

The tensile strength of the high-stiffness polyester film in the flow direction is preferably 250 MPa or more, more preferably 280 MPa or more. The tensile strength of the high stiffness polyester film in the vertical direction is preferably 250 MPa or more, more preferably 280 MPa or more.

The tensile elongation of the high-stiffness polyester film in the flow direction is preferably 130% or less, more preferably 120% or less. The tensile elongation of the high-stiffness polyester film in the vertical direction is preferably 120% or less, more preferably 110% or less.

Further, in at least one direction, the value obtained by dividing the tensile strength of the high stiffness polyester film by the tensile elongation is preferably 2.0 MPa /% or more.
For example, the value obtained by dividing the tensile strength of the high stiffness film in the vertical direction (TD) by the tensile elongation is preferably 2.0 MPa /% or more, and more preferably 2.2 MPa /% or more. The value obtained by dividing the tensile strength of the high-stiffness film in the flow direction (MD) by the tensile elongation is preferably 1.8 MPa /% or more, and more preferably 2.0 MPa /% or more.

Tensile strength and tensile elongation can be measured according to JIS K7127. As the measuring instrument, a tensile tester STA-1150 manufactured by Orientec can be used. As the test piece, a film cut out into a rectangular film having a width of 15 mm and a length of 150 mm can be used. The distance at the start of measurement between the pair of chucks holding the test piece is 100 mm, and the tensile speed is 300 mm / min. The environmental temperature during the test is 25 ° C.

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

The Young's modulus of the high stiffness polyester film in the flow direction is preferably 4.0 GPa or more, more preferably 4.5 MPa or more. The Young's modulus of the high-stiffness polyester film in the vertical direction is preferably 4.0 GPa or more, and more preferably 4.5 GPa or more.

In the manufacturing process of the high stiffness polyester film, for example, first, the polyester film obtained by melting and molding the polyester is 3 to 4.5 times at 90 ° C. to 145 ° C. in the flow direction and the vertical direction, respectively. The first stretching step is carried out.

Subsequently, a second stretching step of stretching the polyester film 1.1 to 3.0 times at 100 ° C. to 145 ° C. in the flow direction and the vertical direction is carried out.

Then, heat fixing is performed at a temperature of 190 ° C. to 220 ° C. Subsequently, in the flow direction and the vertical direction, a relaxation treatment for reducing the width of the polyester film by about 0.2% to 2.5% is performed at a temperature of 100 ° C. to 190 ° C.

As a type of polyester used for a high-stiffness polyester film, a high-stiffness polyester film having the above-mentioned mechanical properties can be obtained by adjusting the draw ratio, the draw temperature, the heat fixation temperature, and the relaxation treatment rate in these steps. Is preferably polyethylene terephthalate.

The thickness of the plastic film as the plastic base material of the present invention as described above is not particularly limited, and pretreatment and formation when the vapor-deposited film is formed by the roller-type continuous vapor-deposited film-forming apparatus described later. Any film can be treated, and from the viewpoint of flexibility and shape retention, a range of 6 to 400 μm, preferably 9 to 200 μm is desirable. However, in the case of a high-stiffness polyester film, the thickness is preferably 5 μm or more, more preferably 7 μm or more, further preferably 25 μm or less, and more preferably 20 μm or less. When the thickness of the plastic film is within the above range, it is easy to bend and does not tear during transportation, and is continuously used for producing a laminated film having an aluminum oxide vapor-deposited film having a barrier property with improved adhesion. Easy to handle with a thin film deposition device.
In particular, when a high-stiffness polyester film is used as the plastic base material, it is possible to obtain a laminated film having the same or higher rigidity, tensile strength, and piercing strength while reducing the thickness and weight of the laminated film.

Next, the aluminum oxide vapor deposition film will be described. In the present invention, the film formation of the aluminum oxide vapor-deposited film is performed on the surface of the film of the plastic base material in order to improve the adhesion between the plastic base material and the aluminum oxide vapor-deposited film. It is preferable to perform special oxygen plasma pretreatment using. The special oxygen plasma pretreatment is a pretreatment for strengthening and improving the adhesion between the film or sheet of various resins and the aluminum oxide vapor-deposited film in the present invention as compared with the conventional method, and the following vapor-film deposition film formation. It is carried out in the device.

As shown in FIG. 2, the roller-type continuous vapor deposition film deposition apparatus 10 preferably used for producing a laminated film having an aluminum oxide vapor deposition film having a barrier property with improved adhesion of the present invention is inside the decompression chamber 12. The partition walls 35a to 35c are formed in the partition wall 35a to 35c. The partition walls 35a to 35c form a base material transfer chamber 12A, a plasma pretreatment chamber 12B, and a film forming chamber 12C. In particular, the plasma pretreatment chamber 12B and the film forming chamber are formed as a space surrounded by the partition walls and the partition walls 35a to 35c. 12C is formed, and each chamber is further formed with an exhaust chamber as needed.
(Special oxygen plasma pretreatment)

In the plasma pretreatment chamber 12B, a part of the plasma pretreatment roller 20 for transporting the plastic base material S to be pretreated and enabling the plasma treatment is provided so as to be exposed to the base material transport chamber 12A. The plastic base material S moves 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 base material transport chamber 12A, and the plastic base material S can be moved without being exposed to the atmosphere. Further, the pretreatment chamber 12B and the base material transfer chamber 12A are connected by a rectangular hole, and a part of the plasma pretreatment roller 20 protrudes to the base material transfer chamber 12A side through the rectangular hole. There is a gap between the wall of the transport chamber and the pretreatment roller 20, and the base material S can move from the base material transport chamber 12A to the film forming chamber 12C through the gap. The base material transport chamber 12A and the film forming chamber 12C have the same structure, and the plastic base material S can be moved without being exposed to the atmosphere.

The base material transfer chamber 12A is used as a winding means because the plastic base material S having a vapor-deposited film formed on one surface, which has been moved to the base material transfer chamber 12A again by the film forming roller 23, is wound into a roll shape. 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 producing a laminated film having an aluminum oxide vapor-deposited film having a barrier property with improved adhesion of the present invention, the plasma pretreatment chamber 12B divides the space generated by plasma from other regions and creates a facing space. By being configured so that vacuum exhaust can be performed efficiently, the plasma gas concentration can be easily controlled and the productivity can be improved. The pretreatment pressure formed by reducing the pressure can be set and maintained at about 0.1 Pa to 100 Pa, and in particular, special oxygen plasma pretreatment is performed in order to obtain a transformation rate of a preferable transition region of the aluminum oxide vapor-deposited film of the present invention. The processing pressure of is preferably 1 to 20 Pa.

The transport speed of the plastic base material S is not particularly limited, but can be at least 200 to 1000 m / min from the viewpoint of production efficiency, and in particular, the transformation rate of the transition region of the aluminum oxide vapor-deposited film of the present invention is used. The transport speed of the special oxygen plasma pretreatment is preferably 300 to 800 m / min.

In the plasma pretreatment roller 20 constituting the plasma pretreatment apparatus, the plastic base material S prevents the base material from shrinking or being damaged due to heat during plasma treatment by the plasma pretreatment means, and oxygen plasma P is applied to the plastic base material S. The purpose is to apply it uniformly and widely.
It is preferable that the pretreatment roller 20 can be adjusted to a constant temperature between −20 ° C. and 100 ° C. by adjusting the temperature of the temperature control medium circulating in the pretreatment roller.

The plasma pretreatment means includes a plasma supply means and a magnetizing means. The plasma pretreatment means cooperates with the plasma pretreatment roller 20 to confine the oxygen plasma P in the vicinity of the surface of the plastic base material S.

The plasma pretreatment means is provided so as to cover a part of the pretreatment roller 20. Specifically, the plasma supply means and the magnetizing means constituting the plasma pretreatment means are arranged along the surface near the outer periphery of the pretreatment roller 20 to supply the pretreatment roller 20 and the plasma raw material gas, and the plasma P. It is installed so as to form a gap sandwiched between the plasma supply nozzles 22a to 22c, which also serve as electrodes for generating the plasma P, and a magnetic forming means having a magnet 21 or the like in order to promote the generation of the plasma P.
As a result, the plasma supply nozzles 22a to 22c are opened in the space of the gap to inject plasma toward the surface of the base material, the inside of the gap is used as a plasma forming region, and further, the pretreatment roller 20 and the plastic base material S are formed. By forming a region having a high plasma density in the vicinity of the surface, the special oxygen plasma pretreatment of the present invention for forming a plasma-treated surface on one side of the plastic base material S can be performed.

The plasma supply means of the plasma pretreatment means includes a raw material volatilization supply device 18 connected to a plasma supply nozzle provided outside the decompression chamber 12, and a raw material gas supply line for supplying the raw material gas supply from the device. As the plasma raw material gas to be supplied, the flow rate of oxygen alone or a mixed gas of oxygen gas and argon, helium, nitrogen and one or more of these gases is measured from the gas storage unit via a flow rate controller. It is supplied while.

These supplied gases are mixed at a predetermined ratio as needed 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 to the vicinity of the outer periphery of the pretreatment roller 20 in which the supply port of the plasma supply nozzles 22a to 22c opens.
The nozzle opening is directed toward the plastic base material S on the pretreatment roller 20, and is arranged and configured so that the oxygen plasma P can be uniformly diffused and supplied over the entire surface of the plastic base material S. Uniform plasma pretreatment is possible on a large area of the material S.

In the special oxygen plasma pretreatment, the mixing ratio of oxygen gas and argon or helium is 5: 1, preferably 2: 1 in order to obtain the alteration rate of the transition region of the aluminum oxide vapor-deposited film of the present invention. By setting the mixing ratio to 5: 1, the film formation energy of the vapor-deposited aluminum on the plastic film base material increases, and by further setting it to 2: 1, the formation of aluminum hydroxide is formed near the interface of the base material. That is, the alteration rate of the transition region is reduced.

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

Specifically, the plasma supply means of the plasma pretreatment means is provided with a plasma pretreatment roller as a plasma power source, and an AC voltage having a frequency of 10 Hz to 2.5 GHz is applied between the plasma pretreatment means and the counter electrode to control the input power. , Impedance control, etc. can be performed so that an arbitrary voltage is applied between the plasma pretreatment roller 20 and the substrate, and the surface physical properties of the base material can be physically or chemically modified. A power source 32 capable of applying a bias voltage that makes the oxygen plasma P a positive potential is provided.
As plasma intensity per unit area employed in the present invention are 50~8000W · sec / ^{m 2,} the 50W · sec / ^{m 2} or less, without the effect of the plasma pretreatment was observed, also, 8000W · sec / ^{m 2} In the above, the base material tends to be deteriorated by plasma such as wear, damage coloring, and firing of the base material. In particular, the plasma intensity of the special oxygen plasma pretreatment is preferably 100 to 1000 W · sec / m ² in order to obtain the transformation rate of the transition region of the aluminum oxide vapor-deposited film of the present invention.

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

The power supply wiring 31 is connected to the electrode, and the power supply wiring 31 is connected to the power supply 32. Further, a temperature control medium pipe for cooling the electrode and the magnet 21 is provided inside the electrode.
The magnet 21 is provided so that the oxygen plasma P from the plasma supply nozzles 22a to 22c, which is an electrode and plasma supply means, is concentrated and applied to the base material S. By providing the magnet 21, the reactivity in the vicinity of the surface of the base material is increased, and a good plasma pretreatment surface can be formed at high speed.

The magnet 21 has a magnetic flux density of 10 to 10000 gauss at the surface position of the plastic base material S. When the magnetic flux density on the surface of the plastic base material S is 10 gauss or more, the reactivity in the vicinity of the surface of the base material can be sufficiently enhanced, and a good pretreated surface can be formed at high speed.

Ions and electrons formed during plasma pretreatment due to the arrangement structure of the magnet 21 of the electrode move according to the arrangement structure. Therefore, for example, when plasma pretreatment is performed on a plastic base material S having a large area of 1 m ² or more. In addition, electrons, ions, and decomposition products of the base material are uniformly diffused over the entire electrode surface, and even when the plastic base material S has a large area, uniform and stable pretreatment for the purpose is possible with the desired plasma intensity. It is a thing.

(Aluminum oxide vapor deposition film)
The plastic base material S treated with the special oxide plasma is moved from the base material transport chamber 12A to the film formation chamber 12C by the guide rolls 14a to 14d for guiding to the next film formation chamber 12C, and the aluminum oxide vapor deposition film is formed in the film formation section. Is formed.

The aluminum oxide vapor deposition film is a thin film of an inorganic oxide containing aluminum oxide as a main component, and can contain an aluminum compound such as aluminum oxide or an aluminum nitride, a carbide, a hydroxide alone or a mixture thereof. It is a layer containing aluminum as a main component.
Further, the aluminum oxide vapor deposition film contains the aluminum compound as a main component, and contains silicon oxide, silicon nitride, silicon oxide nitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, and zirconium oxide. Such as metal oxides, or metal nitrides, carbides and mixtures thereof thereof can be contained.

In the aluminum oxide vapor-deposited film of the present invention, the transformation rate of the transition region of the aluminum oxide-deposited film is 45% or less.
The alteration rate of the transition region of the aluminum oxide vapor-deposited film is a time-of-flight type secondary while repeating soft etching at a constant speed with a Cs (cesium) ion gun on the aluminum oxide vapor-deposited film 2 of the laminated film A having a barrier property. A graph analysis diagram as shown in FIG. 3 can be obtained by measuring ions derived from an aluminum vapor deposition film and ions derived from a plastic substrate by using an ion mass spectrometry method (TOF-SIMS).
Specifically, an elemental bond at the interface between the aluminum oxide vapor-deposited film and the plastic base material is etched from the outermost surface of the aluminum oxide vapor-deposited film by Cs using a flight-time type secondary ion mass analyzer. And the elemental bond of the aluminum oxide vapor deposition film was measured, and each graph was obtained for the measured element and elemental bond (Fig. 3 graph analysis diagram). 1) The position where the strength of the graph of element C6 is halved is the plastic group. As the interface between the material and aluminum oxide, the surface to the interface is determined as the aluminum oxide vapor deposition film, 2) the peak in the graph representing the elemental bond Al ₂ O ₄ H is obtained, and the peak to the interface is defined as the transition region, and 3 ) (Transition region from peak to interface of elemental bond Al ₂ O ₄ H / aluminum oxide vapor deposition film) × 100 (%) and the transformation rate of the transition region were determined and obtained.

The transformation rate of the transition region of the aluminum oxide vapor-deposited film layer of the present invention is preferably 45% or less. If it exceeds 45%, the adhesion between the plastic substrate and the vapor-deposited film after hot water treatment (high retort) at 135 ° C. for 40 minutes or after hot water treatment (semi-retort) at 121 ° C. for 40 minutes decreases. In addition, the barrier performance against water vapor is reduced.

Hot water treatment (retort treatment) imposes great mechanical and chemical stress on the interface between the plastic substrate and the aluminum oxide vapor deposition film. This stress deteriorates the barrier property. This part is stressed because it is the most vulnerable in the laminated configuration.
Therefore, in order to obtain retort resistance, it is important to firmly coat the vapor-deposited film at the interface with the base material.
Aluminum hydroxide has good adhesion to a plastic base material due to its chemical structure, and also has a high water vapor barrier property because it forms a network and is dense. However, in a strong environment such as retort treatment, the bond structure based on the hydrogen bond between aluminum hydroxide and the base material is microscopically easily broken. Further, the network of aluminum hydroxide also easily penetrates into the membrane due to the affinity between the water molecule and the grain interface of aluminum hydroxide.

In the present invention, in order to make the transition region at the interface between the aluminum hydroxide formed by aluminum hydroxide and the plastic base material in the aluminum oxide vapor deposition film as narrow as possible, the element bond Al ₂ O ₄ H is focused on and its abundance is controlled. to suppress the aluminum hydroxide generated from elements coupled Al 2 _O 4 _H by hydrothermal treatment, by raising the relative aluminum hydroxide is less aluminum oxide film ratio, microscopic deposition film by water molecules due to retort treatment Destruction and interface destruction with the plastic base material were greatly suppressed. This makes it possible to provide a laminated film having retort resistance having unprecedented adhesion and barrier properties.

The aluminum oxide vapor-deposited film of the present invention can be formed by forming a thin-film film on the surface of a plastic substrate pretreated with special oxygen plasma. As a vapor deposition method for forming a vapor deposition film, various vapor deposition methods can be applied from physical vapor deposition and chemical vapor deposition.
The physical vapor deposition method can be selected from the group consisting of a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, and a cluster ion beam method, and the chemical vapor deposition method includes a plasma CVD method, a plasma polymerization method, and a thermal vapor deposition method. It can be selected from the group consisting of the CVD method and the catalytic reaction type CVD method. In the present invention, the vapor deposition method of the physical vapor deposition method is suitable.

The film formation of the aluminum oxide vapor-deposited film will be described below using the roller-type continuous film-deposited film film-forming apparatus 10 shown in FIG. 2, which can be deposited by the physical vapor deposition method suitable for the present invention.

The vapor-deposited film film-forming apparatus is arranged in the depressurized film-forming chamber 12C, and the plastic substrate S is wound and conveyed with the processing surface of the plastic substrate S pretreated by the plasma pretreatment apparatus on the outside. The film-forming roller 23 to be film-formed and the target of the film-forming source 24 arranged to face the film-forming roller are evaporated to form a film-deposited film on the surface of the plastic substrate.
The thin-film vapor deposition film forming means 24 is a resistance heating method, and uses an aluminum metal wire rod as an evaporation source of aluminum, supplies oxygen to oxidize aluminum vapor, and forms an aluminum oxide thin-film film on the surface of the plastic base material S. Form a film.

In the present invention, a plurality of aluminum metal wires are arranged in the axial direction of the 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 metal material of aluminum by suppressing the heat and the amount of heat supplied, and it is possible to form an aluminum oxide vapor deposition film while suppressing the thermal deformability of the plastic base material S as much as possible. it can.

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

(Barrier coating layer)
The barrier coating layer laminated on the surface of the aluminum oxide vapor-deposited film of the laminated film of the present invention mechanically and chemically protects the aluminum oxide vapor-deposited film and improves the barrier performance of the laminated film having barrier properties. It is a thing. Hereinafter, the barrier coating layer coated to form the barrier laminated film having retort resistance having excellent barrier properties will be described.

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

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

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

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

As the water-soluble polymer, a polyvinyl alcohol-based resin or an ethylene / vinyl alcohol copolymer can be used alone, or a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer can be used in combination. can do. In the present invention, a polyvinyl alcohol-based resin is suitable.

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

As the ethylene-vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used.
For example, it includes, and is not particularly limited, from a partially saponified product in which several tens of mol% of acetic acid groups remain to a completely saponified product in which only a few mol% of acetic acid groups remain or no acetic acid groups remain. However, from the viewpoint of barrier properties, it is preferable to use a saponification degree of 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more.

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

The composition of the barrier coating agent is 100 to 500 parts by weight of a water-soluble polymer such as polyvinyl alcohol resin and 1 to 20 parts by weight of a silane coupling agent with respect to 100 parts by weight of alkoxysilane. can do. In the above, when the silane coupling agent is used in an amount of more than 20 parts by weight, the rigidity and brittleness of the formed barrier coating film are increased, which is not preferable.

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

(Gas barrier packaging material)
The barrier laminated film of the present invention has good adhesion between the plastic base material and the aluminum oxide vapor-deposited film even after retort treatment of hot water treatment, particularly high-temperature hot water treatment, and also has excellent gas barrier properties. It can be suitably used not only as a retort pouch packaging material for foods and a high-temperature hot water treatment packaging material for medical use, but also as a packaging material for contents to be retort-treated such as pet food.
The gas-barrier packaging material of the present invention is obtained by laminating at least one heat-sealable layer on a barrier-type laminated film, and the heat-sealable thermoplastic resin is formed through or without an adhesive layer. It is laminated as the innermost layer and has heat-sealing properties. The gas-barrier packaging material further includes functions to be imparted as the packaging material, for example, a light-shielding layer for imparting light-shielding property, decorativeness, a printing layer for imparting printing, a pattern layer, and laser printing, if necessary. Various functional layers such as a layer and an absorbent / adsorptive layer that absorbs or adsorbs odors can be added as a layer structure to form a gas barrier packaging material.

In addition, it can be produced by further laminating functional films according to the intended use. For example, in the case of a gas barrier packaging material for retort pouches, a gas barrier packaging material of a multilayer film in which a nylon film is laminated as a pinhole resistant structure and a heat resistant sealant CPP or the like is laminated as a heat resistant structure, or a gas barrier for a liquid paper container. As for the sex packaging material, a laminated packaging material in which paper is laminated can be mentioned.
In particular, in the case of a packaging material made from a laminated film using a high-stiffness polyester film as a plastic base material, the laminated film has the same or higher rigidity, tensile strength, and piercing strength after reducing the thickness and weight of the packaging material. Can be obtained.

The heat-sealable thermoplastic resin may be a resin layer, film or sheet that can be melted by heat and fused to each other. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (wire). Shape) Any film or sheet with low density fat may be used.
And, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, polymethylpentene, polystyrene, ethylene-vinyl acetate copolymer, α-olefin copolymer, A resin consisting of one or more resins such as ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, and elastomer, or these. It is preferable to use a sheet obtained by forming a film of ethylene, and among them, as a layer in contact with the contents of food or the like, a kind of olefin resin such as polyethylene and polypropylene having hygiene, heat resistance, chemical resistance and fragrance retention. It is more preferable to use a resin made of or more than that, or a sheet obtained by filming these.
The thickness is preferably about 3 to 100 μm, more preferably about 15 to 70 μm.

[Gas barrier packaging]
The gas barrier packaging material of the present invention is a packaging body made from the gas barrier packaging material of the present invention.
For example, a gas barrier packaging body in the form of a pillow packaging bag, a three-sided seal, a four-sided seal, a gusset type, or the like can be produced by heat-sealing processing such that the sealant layer of the gas-barrier packaging material made of a multilayer film is heat-sealed. Further, if it is a gas barrier packaging material made of a laminated film in which paper is laminated, a Goebel top type liquid paper container / packaging body for liquor, juice or the like can be produced.

(Measurement method of evaluation items)
A laminated film having an aluminum oxide vapor-deposited film having improved adhesion and having a barrier property produced under the conditions shown in each of the above Examples or Comparative Examples, or a barrier laminated film having a barrier coating layer on the laminated film is measured. The transformation rate, oxygen permeability, water vapor permeability, and adhesion strength of the transition region of the vapor-deposited film were measured using the following methods.

(Metamorphism rate of transition region)
In the present invention, the transformation rate of the transition region of the vapor-deposited film is determined by a time-of-flight secondary ion mass spectrometry method while repeating soft etching on the surface of the aluminum oxide vapor-deposited film of the laminated film at a constant speed with a Cs (cesium) ion gun. The graph analysis diagram of FIG. 3 can be obtained by measuring the ions derived from the aluminum oxide vapor deposition film and the ions derived from the plastic substrate using TOF-SIMS). Here, the unit (intensity) on the vertical axis of the graph is the measured ionic strength, and the unit (cycle) on the horizontal axis is the number of etchings.
The time-of-flight secondary ion mass spectrometer used in the TOF-SIMS is manufactured by ION TOF, TOF. The measurement was carried out using SIMS5 under the following measurement conditions.

(TOFSIMS measurement conditions)
-Primary ion type: Bi ₃ ⁺⁺ (0.2 pA, 100 μs)
-Measurement area: 150 x 150 μm ²
-Et (etching) gun type: Cs (1keV, 60nA)
-Et (etching) area: 600 x 600 μm ²
-Et (etching) rate: 3 sec / Cycle
・ Vacuuming time: 15 hours or more at 1 × ^10-6 mbar or less ・ Measured within 30 hours after starting vacuuming

In order to measure the ions derived from aluminum oxide to be measured, it is usually necessary and sufficient for the ion gun to separate the ions derived from a plurality of aluminum oxides from the ions derived from other components. In the present invention, Cs ions are selected because it is necessary to select one having strength and in particular, for the purpose of obtaining a depth distribution that can be roughly converted to the concentration distribution of element-bonded Al ₂ O ₄ H.

Using Cs, etching was performed from the outermost surface of the aluminum oxide vapor deposition film, and the elemental bond at the interface between the aluminum oxide vapor deposition film and the film substrate such as a polyester film and the elemental bond of the vapor deposition film were analyzed and measured. Each graph of Graph 1 of the element and the element bond was obtained. In the graph, 118.93 of the measured mass number is Al ₂ O ₄ H, 101.94 is Al ₂ O ₃ , 72.00 is C 6, and so on. It was created by specifying. In the graph, the position where the strength of the element C6 is half of the plastic base material layer portion is defined as the interface between the film base material and aluminum oxide, and the surface to the interface is defined as the aluminum oxide vapor deposition film.
Next, the peak in the graph representing the measured elemental bond Al ₂ O ₄ H can be obtained, and the peak to the interface can be obtained as the transition region.
By performing the above operation, the transformation rate of the transition region of the aluminum oxide vapor deposition film is determined to be (transition region from the peak of the element-bonded Al ₂ O ₄ H to the interface / aluminum oxide vapor deposition film) × 100 (%).
Asked as.

(Oxygen permeability)
Barrier laminated film / adhesive / nylon film 15 μm / produced for measurement using an oxygen permeability measuring device (manufactured by Modern Control (MOCON) [model name: OX-TRAN 2/21]) Adhesive / CPP 70 μm composite laminated film, set the above test sample so that the oxygen supply side is the film surface of the barrier laminated film, and under the measurement conditions at 23 ° C and 100% RH atmosphere, JIS K 7126 B method. Measured according to.
As a measurement sample
1) Composite laminated film before retort treatment 2) High retort treatment condition: 135 ° C, 40 minutes treatment in the state of a bag of composite laminated film One side composite laminated film 3) Semi-retort treatment condition: 121 ° C, A composite laminated film on one side of the bag of the composite laminated film in the state of a bag treated for 40 minutes was used.

(Water vapor permeability)
Using a water vapor permeability measuring device (Measuring machine manufactured by MOCON (model name, PERMATRAN 3/33)), the above test sample so that the sensor side becomes the film surface of the barrier laminated film. Was set, and the measurement was performed in accordance with the JIS K 7126 B method under the measurement conditions of 37.8 ° C. and a 100% RH atmosphere.
As a measurement sample
1) Composite laminated film before retort treatment 2) High retort treatment condition: 135 ° C, 40 minutes treatment in the state of a bag of composite laminated film One side composite laminated film 3) Semi-retort treatment condition: 121 ° C, A composite laminated film on one side of the bag of the composite laminated film in the state of a bag treated for 40 minutes was used.

(Adhesion strength between base material and aluminum oxide vapor deposition film)
<Measurement of adhesion strength (1); Adhesion strength before high retort / semi-retort treatment>
A two-component curable polyurethane adhesive is applied to the barrier coating layer side of the barrier laminated film and dried, and a 70 μm-thick unstretched polypropylene film is coated with a two-component curable polyurethane adhesive and the thickness. A laminated composite film was produced by dry-laminating a 15 μm stretched nylon film and a bonded film.
After aging the laminated composite film for 48 hours, a sample cut into strips with a width of 15 mm was used with a tensile tester (manufactured by Orientec Co., Ltd. [model name: Tencilon universal material tester]) to JIS K6854-. In accordance with No. 2, the strengths of the barrier laminated film base material and the aluminum oxide vapor-deposited film were measured.

In the measurement, the polypropylene film side and the barrier laminated film side that have been peeled off in advance for measurement are gripped by the gripping tools of the measuring instrument, respectively, and the polypropylene film and the barrier laminated film are still laminated in the plane direction of the portion. The average value of the tensile stress in the stable region was measured by pulling at a speed of 50 mm / min in opposite directions (180 ° peeling: T-shaped peeling method) in the directions orthogonal to each other.
Peeling occurs between the plastic base material of the barrier-type laminated film, which has the weakest adhesion strength in the laminated composite film, and the aluminum oxide vapor-deposited film. The adhesion strength of the vapor-deposited film was used.

<Measurement of adhesion strength (2); Adhesion strength after high retort treatment>
A two-component curable polyurethane adhesive is applied to the barrier coating layer side of the barrier laminated film and dried, and a 70 μm-thick unstretched polypropylene film is coated with a two-component curable polyurethane adhesive and the thickness. A 15 μm stretched nylon film and a bonded film were dry-laminated to prepare a laminated composite film.
100 mL of water was injected into a four-sided pouch prepared in B5 size using the above laminated composite film, and hot water retort treatment was performed at 135 ° C. for 40 minutes. After the retort treatment, a sample cut into strips having a width of 15 mm was prepared from a four-sided pouch from which the contents were drained. Using this sample, the adhesion strength was measured in the same manner as in the measurement of the adhesion strength (1).

<Measurement of adhesion strength (3): Adhesion strength after semi-retort treatment>
In the configuration of the measurement of adhesion strength (2), a laminated composite film was produced by setting the thickness of the polypropylene film to 70 μm without using a nylon film.
100 mL of water was injected into a four-sided pouch prepared in B5 size using the above laminated composite film, and hot water retort treatment was performed at 121 ° C. for 40 minutes. After the retort treatment, a sample cut into strips having a width of 15 mm was prepared from a four-sided pouch from which the contents were drained. Using this sample, the adhesion strength was measured in the same manner as in the measurement of the adhesion strength (1).

Example 1
<Aluminum oxide vapor deposition film>
First, a roll was prepared by winding a polyester film having a thickness of 12 μm (hereinafter referred to as PET film) as a base material.
Next, a continuous vapor deposition film deposition apparatus in which the pretreatment section in which the plasma pretreatment device is arranged and the film formation section are separated on the surface on which the vapor deposition film of the PET film is provided is used, and the pretreatment section is subjected to the following plasma conditions. Reactive resistance as a heating means of the vacuum vapor deposition method on the plasma-processed surface under the following conditions in the film-forming section where plasma is introduced from the plasma supply nozzle, special oxygen plasma pretreatment is performed at a transport speed of 400 m / min, and the film is continuously transported. An aluminum oxide vapor-deposited film having a thickness of 12 nm was formed on the PET film by a heating method.

(Plasma pretreatment conditions)
・ Plasma intensity: 150 W ・ sec / m ²
-Plasma forming gas: Argon 1200 (sccm), Oxygen 3000 (sccm)
-Magnetic forming means: 1000 gauss permanent magnet-Pretreatment drum-plasma supply nozzle applied voltage: 340V
-Vacuum degree of pretreatment section: 3.8 Pa
(Aluminum oxide film formation conditions)
・ Vacuum degree: 8.1 × 10 ^-2 Pa
・ Transport speed: 400m / min
-Light transmittance at a wavelength of 366 nm: 92%

<Barrier coating layer>
While 385 g of water, 67 g of isopropyl alcohol and 9.1 g of 0.5N hydrochloric acid were mixed and 175 g of tetraethoxysilane and 9.2 g of glycidoxypropyltrimethoxysilane were cooled to 10 ° C. in a solution adjusted to pH 2.2. The mixture was mixed to prepare solution A.
A solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of polymerization of 99% or more, 324 g of water, and 17 g of isopropyl alcohol.
The solution obtained by mixing the solution A and the solution B so as to have a weight ratio of 6.5: 3.5 was used as a barrier coating agent.

<Barrier laminated film>
The barrier coating agent prepared above was coated on the aluminum oxide vapor deposition film of the PET film by a spin coating method. Then, it was heat-treated in an oven at 180 ° C. for 60 seconds to form a barrier coating layer having a thickness of about 400 nm on an aluminum oxide vapor-deposited film to obtain a barrier laminated film.

Example 2
A barrier laminated film was obtained in the same manner as in Example 1 except that the thickness of the aluminum oxide vapor deposition film thickness was changed to 14 nm.
(Aluminum oxide film formation conditions)
・ Vacuum degree: 8.1 × 10 ^-2 Pa
-Transport speed: 340 m / min
-Light transmittance at a wavelength of 366 nm: 92%

Example 3
A barrier laminated film was obtained in the same manner as in Example 1 except that a biomass-derived polyester film having a thickness of 12 μm was used as a base material.
(Aluminum oxide film formation conditions)
・ Vacuum degree: 8.1 × 10 ^-2 Pa
・ Transport speed: 400m / min
-Light transmittance at a wavelength of 366 nm: 92%

Example 4
A barrier laminated film was obtained in the same manner as in Example 1 except that a polybutylene terephthalate film having a thickness of 12 μm was used as a base material and the thickness of the aluminum oxide vapor deposition film thickness was changed to 10 nm.
(Aluminum oxide film formation conditions)
・ Vacuum degree: 8.1 × 10 ^-2 Pa
・ Transport speed: 400m / min
-Light transmittance at a wavelength of 366 nm: 92%

Example 5
A barrier laminated film was obtained in the same manner as in Example 1 except that XP-55 (thickness 16 μm) manufactured by Toray Industries, Inc., which was a high-stiffness polyester film, was used as a base material.

Comparative Example 1
A barrier laminated film was obtained in the same manner as in Example 1 except that the plasma pretreatment was not performed.

Comparative Example 2
First, a roll was prepared by winding a PET film having a thickness of 12 μm as a base material. Next, the surface of the PET film on which the vapor-deposited layer was provided was subjected to plasma treatment using a direct plasma method under the following conditions to obtain a take-up roll of the plasma-treated PET film. Next, an aluminum oxide vapor-deposited film having a thickness of 12 nm was formed on the plasma-treated surface of this PET film by a reactive resistance heating method under the following conditions.

(Plasma pretreatment conditions)
・ DC plasma intensity: 150 W ・ sec / m ²
-Plasma forming gas: Argon 1200 (sccm), Oxygen 3000 (sccm)
・ Magnetic forming means: None ・ Voltage applied between pretreatment drum and plasma supply nozzle: None

(Aluminum oxide film formation conditions)
・ Vacuum degree: 8.1 × 10 ^-2 Pa
・ Transport speed: 400m / min
-Light transmittance at a wavelength of 366 nm: 92%

Next, a barrier coating layer was formed on the aluminum oxide vapor-deposited film in the same manner as in Example 1 to obtain a barrier laminated film.

The measurement results are shown in Table 1. As shown in Examples 1 to 5, the transformation rate of the transition region of the aluminum oxide vapor-deposited film of the laminated film in the present invention is 45% or less, and in Comparative Examples 1 and 2, the transformation rate of the transition region is high. After the high retort treatment and the semi-retort treatment, even if the peel strength before the retort treatment is almost the same as that in the examples in Comparative Examples 1 and 2, the value becomes as low as 1N / 15 mm or less after the retort treatment, and the peel strength is abrupt. Deterioration is seen. In contrast, in the present invention, the peel strength is 2.1 N / 15 mm or more, which is a sufficient adhesion strength, and the adhesion strength is not significantly reduced by the retort treatment, and the deterioration is suppressed.

Also in barrier performance, Examples 1-5, high retort processing, after semi retorting, deterioration of barrier performance water vapor transmission rate according to 0.9g ^/ m 2 / 24hr or less and retort treatment is suppressed, the oxygen The transparency can be maintained at a certain level even after any retort treatment. In contrast, Comparative Example 1 and the water vapor transmission rate of the retort pretreatment at 2 be substantially the same as in Example, after the high retort treatment showed deterioration becomes 1.2 g / m ^2/24 hr or a high value, also for even oxygen permeability, 0.5 cc ^/ m 2/24 hr or more and a high value of more than 2 times, degradation of barrier performance is occurring due to retort treatment.
As can be seen from these results, the laminated film in which the transformation rate of the transition region of aluminum oxide of the present invention is controlled can be obtained to exhibit excellent retort resistance.

The present invention provides an aluminum oxide vapor-deposited film having a barrier property, in which improved adhesion can be obtained by appropriately setting the transformation rate of the transition region of the aluminum oxide vapor-deposited film between the vapor-deposited film and the plastic substrate. A laminated film and a barrier laminated film can be obtained.
By improving the deterioration of the adhesion strength between the vapor-deposited film and the plastic base material before and after the retort treatment, it is possible to obtain a barrier-type laminated film having barrier properties and adhesions that prevent the permeation of oxygen gas, water vapor, etc., for example. , Packaging materials for foods, pharmaceuticals, etc. that require laminated materials that can withstand processing associated with processing such as retort treatment and sterilization treatment, and packaging for electrical and electronic parts, use that requires durability and barrier properties such as protective sheets It can be applied to industrial materials in fields where the environment is harsh.

1, S ………… Plastic base material 2 ………… Aluminum oxide vapor-deposited film 3 ………… Barrier coating layer A ………… Laminated film or vapor-deposited film film B ………… Barrier laminated film P ………… Plasma 10 …… …… Roller type continuous vapor deposition film film forming apparatus 12 ………… Pressure reducing chamber 12A ………… Substrate transfer chamber 12B ………… Plasma pretreatment chamber 12C ………… Film forming chamber 14a to d ………… Guide roll 18 ………… … Raw material gas volatilization supply device 20 ………… Pretreatment roller 21 ………… Magnet 22 ………… Plasma supply nozzle 23 ………… Formation roller 24 ………… Evaporation film film formation means 31 ………… Power supply wiring 32… …… Power supply 35a to 35c ………… Partition

Claims (14)

In a laminated film having a barrier property in which an aluminum oxide vapor-deposited film containing aluminum oxide as a main component is formed on the surface of a plastic base material, the adhesion strength between the base film surface and the formed vapor-deposited aluminum oxide film-based film is improved. A defined transition region of the vapor-deposited film is formed, and the transition region is transformed into aluminum hydroxide detected by etching using the flight time type secondary ion mass spectrometry (TOF-SIMS). Defined by the ratio of the transformed transition region defined using TOF-SIMS to the aluminum oxide vapor deposition film containing the element-bonded Al ₂ O ₄ H and defined by etching with TOF-SIMS. The laminated film having a transformation rate of 45% or less in the transition region. The laminated film according to claim 1, wherein the plastic base material is a polyethylene terephthalate film. The laminated film according to claim 1, wherein the plastic base material contains a recycled polyethylene terephthalate film. The laminated film according to claim 1, wherein the plastic base material is a polybutylene terephthalate film. The laminated film according to claim 1, wherein the plastic base material is a polyester film derived from biomass. The laminated film according to claim 1, wherein the plastic base material is a high-stiffness polyester film. The laminated film according to any one of claims 1 to 6, wherein the surface of the plastic base material is an oxygen plasma-treated surface. The laminated film according to claim 7, wherein an aluminum oxide vapor-deposited film is laminated in-line on the oxygen plasma-treated surface. A barrier laminated film obtained by laminating a barrier coating layer on the surface of an aluminum oxide vapor-deposited film of the laminated film according to any one of claims 1 to 8. The barrier laminated film according to claim 9, wherein the barrier coating layer is a layer formed by applying a mixed solution of a metal alkoxide and a water-soluble polymer and heating and drying the film. The barrier laminated film according to claim 9, wherein the barrier coating layer is a layer formed by applying a mixed solution of a metal alkoxide, a silane coupling agent, and a water-soluble polymer and drying the mixture by heating. A gas barrier packaging material obtained by laminating a thermoplastic resin having a heat seal property on the barrier laminated film according to any one of claims 9 to 11. The gas barrier packaging material according to claim 12, which is used for packaging for retort sterilization. A gas barrier package made from the gas barrier packaging material according to claim 12 or 13.

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