WO2019087960A1

WO2019087960A1 - Laminate film, barrier laminate film, and gas-barrier packaging material and gas-barrier packaged body each using said barrier laminate film

Info

Publication number: WO2019087960A1
Application number: PCT/JP2018/039877
Authority: WO
Inventors: 岸本　好弘; 鈴木　梓; 可成青野; 雄一郎浅井; 翔平伊丹
Original assignee: 大日本印刷株式会社
Priority date: 2017-10-30
Filing date: 2018-10-26
Publication date: 2019-05-09
Also published as: JPWO2019087960A1; JP7192781B2

Abstract

Provided are: a laminate film in which the adhesion between a plastic base member and an aluminum oxide-deposited film is good even after a hot water treatment, and which is provided with an aluminum oxide-deposited film having high barrier performance, i.e., excellent retort resistance; a barrier laminate film including the laminate film; and a gas barrier packaging material and a gas barrier packaged body, in each of which the barrier laminate film is used. A laminate film having improved adhesion strength and barrier performance is specified as follows: an aluminum oxide-deposited film in the laminate film is subjected to a time-of-flight secondary ion mass spectrometry (TOF-SIMS) method using a Cs (cesium) ion gun to form a transition region, which specifies adhesion strength, between the surface of a base film and a deposited film mainly composed of the formed aluminum oxide-deposited film; the transition region contains an elemental bond Al2O4H which can be modified into aluminum hydroxide that can be detected by carrying out etching employing TOF-SIMS; and the modification rate of the transition region that is modified into aluminum hydroxide, which is defined by the ratio of the modified transition region to the aluminum oxide-deposited film specified by carrying out etching employing TOF-SIMS, is specified to 45% or less.

Description

Laminated film, barrier laminate film, gas barrier packaging material using the barrier laminate film, gas barrier package

INDUSTRIAL APPLICABILITY The present invention has excellent barrier properties against oxygen and water vapor, which can be suitably used as packaging materials for retort treatment such as food, medicine, pet food, etc., and improves the adhesion between the plastic substrate after retort treatment and the aluminum oxide deposited film. The present invention relates to a laminated film having the above-mentioned barrier property, and a barrier film and a packaging material using the laminated film having resistance to retort.

In fields requiring retort treatment of food and pharmaceuticals, etc., the higher barrier property, which is not affected by temperature and humidity, is stabilized so that deterioration of contents can be prevented and the function and properties can be maintained. There is a demand for a barrier laminate film that can be exhibited, and a barrier laminate film having a multilayer structure in which a barrier layer consisting of a thin film of a deposited film of silicon oxide, aluminum oxide or the like and a barrier coating layer are laminated has also been developed.

However, the plastic substrate of a laminated film having a vapor-deposited film with excellent barrier properties susceptible to temperature, humidity, etc. is prone to dimensional change, and therefore, corresponds to expansion and contraction accompanying dimensional change of the plastic substrate. It is difficult to follow a vapor deposition film such as a silicon oxide vapor deposition film or an aluminum oxide vapor deposition film provided thereon.
Therefore, delamination often occurs in the severe environment of high temperature and humidity, etc. between the plastic substrate and the deposited film such as silicon oxide deposited film or aluminum oxide deposited film, and cracks, pinholes, etc. are also generated. Occur.
As a result, there is a problem that the original barrier performance is significantly lost and it is extremely difficult to maintain the barrier performance.

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

However, the in-line plasma treatment method using the generally used parallel plate type device of Patent Document 1 introduces functional groups such as hydroxyl groups and carbonyl groups on the plastic surface, and interposes the same functional groups between the deposited films. Adhesion is expressed. However, if the adhesion is expressed by the hydrogen bond due to the hydroxyl group, the adhesion is remarkable because the hydrogen bond is broken in the high temperature and high humidity environment required for the application such as electronic paper such as electronic paper and retort packaging material There is a problem that falls.
In addition, since the film only passes through the plasma atmosphere generated in the air in the above-mentioned plasma treatment, sufficient adhesion between the substrate and the deposited film in a severe environment with high temperature and humidity can not be obtained. Is the reality.

Moreover, although the undercoat processing method of patent document 2 provides an undercoat layer as a contact bonding layer on a plastic film surface and is generally implemented, since the number of processes is increased as a manufacturing method, the cost increases.

Therefore, the technology to improve adhesion is implemented by performing pretreatment on the surface of the plastic substrate using a reactive ion etching (RIE) method that generates plasma with the electrode for plasma generation on the substrate side. (Patent Document 3).
In the plasma RIE method, two effects of chemical effect, such as giving a functional group to the surface of a substrate, and physical effect, such as ion etching of the surface to fly away impurities and the like and smoothing, are obtained simultaneously. It develops adhesion.

In the RIE method, unlike the in-line plasma treatment described above, the adhesion is not exhibited by the hydrogen bond, and therefore, the decrease in the adhesion under a high temperature and high humidity environment is not observed.
However, in the RIE method, since a functional group is provided on a plastic substrate, the water resistance and the hot water resistance which cause hydrolysis and the like at the interface are still insufficient. Further, in order to obtain sufficient adhesion by the RIE method, an Ed value (= plasma density × processing time) equal to or more than a predetermined value is required.
In order to obtain the Ed value of a certain value or more by the same method, a method of increasing the plasma density and a method of lengthening the processing time can be considered, but in the case of increasing the plasma density, a high output power source is required. There is a problem that the damage to the base material becomes large, and in the case of prolonging the treatment time, the decrease in productivity becomes a problem (see Patent Document 4 and Patent Document 5).

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

In particular, in fields requiring retort treatment and sterilization treatment at high temperature and high pressure such as food and medicine, it is not affected by temperature, humidity, etc. so that deterioration of contents can be prevented and function and properties can be maintained. A barrier laminate film capable of stably exhibiting higher barrier properties is required, and has a multilayer structure in which a barrier layer composed of a thin film of aluminum oxide such as silicon oxide or aluminum oxide is laminated with a barrier coating layer. A barrier laminate film excellent in retort resistance is desired.

Unexamined-Japanese-Patent No. 7-233463 JP 2000-43182 A JP, 2005-335109, A Patent No. 4461737 Patent 4135496 gazette

In the problems of the prior art, retort treatment by hot water treatment gives great mechanical and chemical stress to the interface between the plastic substrate and the aluminum oxide vapor deposition film. This stress degrades the barrier property. This site is stressed because this site is the most vulnerable in the stack configuration. Therefore, in order to obtain retort resistance, it is important to firmly coat the deposited film at the interface with the substrate.
On the other hand, aluminum hydroxide has high water vapor barrier properties because it has good adhesion to a plastic substrate due to its chemical structure, and itself forms a network and is compact. However, in a strong environment such as retort treatment, the bonding structure based on hydrogen bonding between aluminum hydroxide and the substrate is easily microscopically broken. In addition, it also easily penetrates into the film due to the affinity of the water particle / aluminum hydroxide particle interface to the aluminum hydroxide network.

The present invention has been made in view of the above problems and findings, and the object of the present invention is that adhesion between a plastic substrate and a deposited aluminum oxide film is good even after hot water treatment, And, a laminated film having a vapor deposited film excellent in barrier property, a barrier film laminated film including the laminated film and a so-called aluminum oxide vapor deposited film excellent in retort resistance, and the barrier film laminated film It is providing the gas-barrier packaging material excellent in barrier property excellent in retort resistance, and a gas-barrier package.

In order to achieve these objects, the laminate film of the present invention is a laminate film having a barrier property in which an aluminum oxide deposited film mainly composed of aluminum oxide is formed on the surface of a plastic substrate, and is formed with the substrate film surface. A transition region of the deposited film is formed which defines adhesion strength with the deposited film mainly comprising the deposited aluminum oxide film, and the transition region is formed using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Using TOF-SIMS to an aluminum oxide vapor deposition film defined by performing etching using TOF-SIMS, containing an element-bound Al ₂ O ₄ H that is transformed into aluminum hydroxide detected by performing etching The transition rate of the transition zone defined by the percentage of the transition zone to be transformed being 45% or less. is there.

Secondary ion mass spectrometry (SIMS) is an analysis method of an elemental concentration distribution in which a primary ion beam is irradiated to the surface of a sample to be analyzed, and secondary ions emitted by being sputtered from the sample surface are mass analyzed It is. In this secondary ion mass spectrometry, secondary ion intensity is detected while advancing sputtering. Therefore, by converting the transition time into the depth with respect to the data of the time transition of the ion intensity of the secondary ion, that is, the ion ion of the to-be-detected element ion or the to-be-detected element The concentration distribution of the element to be detected can be known.

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

In the present invention, time-of-flight secondary ion mass spectrometry (TOF-SIMS) is performed on the aluminum oxide vapor deposited film of the laminated film while repeating soft etching at a constant speed as described above with a Cs (cesium) ion gun. A transition defining an adhesion strength between the substrate film surface and the vapor deposition film mainly comprising the aluminum oxide vapor deposition film formed by measuring the ions derived from the aluminum oxide vapor deposition film and the ions derived from the plastic substrate An area is formed. The transition region includes an element-bound Al ₂ O ₄ H that is transformed into aluminum hydroxide, which is detected by performing etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Ratio of the transformed transition area defined using time-of-flight secondary ion mass spectrometry to an aluminum oxide vapor deposition film defined by performing etching using secondary ion mass spectrometry (TOF-SIMS) It is based on the finding that it is possible to specify a laminated film having a barrier property with improved adhesion strength by defining the transformation ratio of the transition region that is transformed to aluminum hydroxide as defined by the above.

Specifically, the present invention performs etching from the outermost surface of a deposited aluminum oxide film by Cs using a time-of-flight secondary ion mass spectrometer, and combines elements at the interface between the deposited aluminum oxide film and the plastic substrate. And measurement of the elemental bonds of the deposited film, and the obtained measurement graphs of the measured elements and elemental bonds (FIG. 3 graph analysis diagram), and the plastic substrate and the deposited film formed by aluminum hydroxide in the deposited aluminum oxide film In order to narrow the transition region of the interface as much as possible, attention is paid to element-bound Al ₂ O ₄ H, and 1) the position where the strength of the graph of element C6 is half is taken as the interface between the plastic substrate and aluminum oxide from the surface up to the interface determined as aluminum oxide deposited film, the peak in the graph representing two) elements bonded Al 2 _O 4 _H, peak Until Luo interface and transition region, determined, 3) (element binding Al 2 _O 4 transition region / aluminum oxide vapor deposited film from the peak of _H to the interface) × 100 (%) modified rate to aluminum hydroxide of the transition region as Seeks

In the present invention, a barrier coating layer is further formed on the laminated film by setting the conversion ratio of the transition region of the aluminum oxide vapor-deposited film to 45% or less, and the plastic base of the barrier laminated film and the aluminum oxide vapor-deposited film The adhesion strength at the interface should be 2.1 N / 15 mm or more after hot water treatment (high retort treatment) for 40 minutes at 135 ° C., or after 40 minutes of hot water treatment (semi retort treatment) at 121 ° C. It is possible to produce a barrier film having resistance to retort, which is improved in adhesion without the occurrence of delamination during molding or retorting of the retort pouch.

In the present invention, by setting the conversion ratio of the transition region of the aluminum oxide vapor deposition film to 45% or less, the oxygen permeability after high retort treatment and semi retort and the water vapor permeability are 0.2 cc / m ² · 24 hr respectively. Hereinafter, a barrier laminate film exhibiting sufficient barrier properties to such an extent that deterioration of contents after storage and deterioration of storage life do not occur at 0.9 g / m ² · 24 hours or less Can.
Therefore, the aluminum oxide vapor deposition film of the present invention not only can improve the adhesion at the interface with the plastic substrate, but also has excellent heat and moisture resistance after retort treatment and can improve retort resistance after retort treatment also in barrier performance. It is.

The present invention is characterized by the following points.
1. In a laminated film having a barrier property in which an aluminum oxide vapor deposition film mainly composed of aluminum oxide is formed on the surface of a plastic substrate, adhesion strength between the substrate film surface and the vapor deposition film mainly comprising the aluminum oxide vapor deposition film formed A transition region of the deposited film to be defined is formed, and the transition region is transformed into aluminum hydroxide detected by performing etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Defined by the ratio of the denatured transition region defined using TOF-SIMS to the aluminum oxide deposited film that contains elemental bound Al ₂ O ₄ H and is defined by performing etching using TOF-SIMS The above laminated film, wherein the transformation ratio of the transition region is 45% or less.
2. The laminated film according to the above 1, wherein the plastic substrate is a polyethylene terephthalate film.
3. The laminated film according to the above 1, wherein the plastic substrate comprises a recycled polyethylene terephthalate film.
4. The laminated film according to the above 1, wherein the plastic substrate is a polybutylene terephthalate film.
5. The laminated film according to the above 1, wherein the plastic substrate is a biomass-derived polyester film.
6. A laminated film according to the above 1, wherein the plastic substrate is a high stiffness polyester film.
7. The laminated film according to any one of the above 1 to 6, wherein the plastic substrate surface is an oxygen plasma treated surface.
8. 7. The laminated film as described in 7 above, wherein an aluminum oxide vapor deposition film is laminated inline on an oxygen plasma treated surface.
9. 8. A barrier laminate film comprising a barrier coating layer laminated on the surface of the aluminum oxide deposited film of the laminate film according to any one of 1 to 8 above.
10. 10. The barrier laminate film as described in 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 by heating.
11. 10. The barrier laminate film as described in 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 by heating.
12. A gas barrier packaging material comprising a thermoplastic resin having heat sealability laminated on the barrier laminate film according to any one of the above 9 to 11.
13. The gas barrier packaging material according to the above 12 which is used for packaging for retort sterilization.
14. The gas-barrier packaging body produced from the gas-barrier packaging material as described in said 12 or 13.

In the present invention, in order to narrow as much as possible the transition region of the interface between the aluminum oxide vapor-deposited film and the plastic base on which aluminum hydroxide is formed, and optimize the ratio of modification to aluminum hydroxide, elemental bonded Al ₂ O ₄ Focusing on H, making the conversion ratio of the transition region of the aluminum oxide vapor deposition film in the laminated film 45% or less, increasing the ratio of the aluminum oxide film relatively less aluminum hydroxide, the fineness by the water molecules by retort treatment It is a thing which suppresses a vapor deposition film visual observation visually and an interface destruction with a plastic base material greatly. As a result, it is possible to provide a laminated film having improved adhesion and having unconventional retort resistance, and a barrier laminated film including the above-mentioned layer film.
In the barrier laminate film of the present invention, the adhesion strength at the interface between the plastic substrate and the aluminum oxide vapor-deposited film is 2.1 N / 15 mm or more even after high retort treatment and semi retort treatment, and high retort treatment. The oxygen permeability and the water vapor permeability after semi-retort have barrier properties of 0.2 cc / m ² · 24 hr or less and 0.9 g / m ² · 24 hr or less, respectively, and are excellent in retort resistance.

Cross-sectional view showing an example of a barrier laminate film B (FIG. 1 b) in which the laminate film A of the present invention (FIG. 1 a) and the barrier coating layer are laminated, and another embodiment laminate film A (FIG. The figure which shows an example of the apparatus which forms the aluminum oxide vapor deposition film | membrane of this invention Example of analysis of graph of analysis result by time of flight type secondary ion mass spectrometry of aluminum oxide vapor deposition film laminated film of the present invention

Hereinafter, a laminated film having a deposited aluminum oxide film having a barrier property with improved adhesion according to an embodiment of the present invention and a barrier laminate film including the laminated film according to the embodiment of the present invention will be described in detail. Note that this embodiment is merely an example and does not limit the present invention.
FIG. 1 a is a cross-sectional view showing an example of the laminated film of the present invention, and FIG. 1 b is a cross-sectional view showing an example of a barrier laminate film including the laminate film and having a barrier coating layer laminated on the surface. FIG. 1 c is a cross-sectional view showing an example of a laminated film in which the base material layer is constituted of multiple layers, and FIG. 2 is a roller suitable for forming the aluminum oxide vapor deposition film of the laminated film having barrier properties of the present invention. It is a figure which shows typically the structure of Formula continuous vapor deposition film-forming apparatus. In addition, in order to form the barriering laminated film which laminated | stacked the barriering coating layer, although a barrier coating agent coating apparatus is arrange | positioned continuously with vapor deposition film film-forming apparatus, a well-known roller coating apparatus is provided in a row. Yes, I have omitted to illustrate here.

The laminated film A having an aluminum oxide vapor deposition film having a barrier property with improved adhesion according to the present invention has a barrier property with improved adhesion to one surface of the plastic substrate 1, as shown in FIG. 1a. In the present invention, further, as shown in FIG. 1b, the barrier coating layer 3 is further formed on the deposited film 2 of the laminated film A. It is set as the laminated structure which is laminated | stacked, was excellent in adhesiveness and barrier property, and was set as the barrier property laminated film B excellent in retort resistance.

The plastic substrate is not particularly limited, and known plastic films or sheets can be used. For example, polyethylene terephthalate, polyester derived from biomass, polybutylene terephthalate, polyethylene naphthalate, recycled polyethylene terephthalate, polyester resin such as polyethylene furanoate, polyamide resin 6, polyamide resin 66, polyamide resin 610, polyamide resin 612, polyamide resin 11 A film made of a polyamide resin such as polyamide resin 12 or a polyolefin resin such as a polymer of α-olefin such as polyethylene or polypropylene can be used. Polyester-based resins known as polyethylene terephthalate films are particularly preferably used.

(Polybutylene terephthalate film (PBT))
A polybutylene terephthalate film has a high heat distortion temperature, is excellent in mechanical strength and electrical characteristics, and has good molding processability, etc., and therefore, when it is used for a packaging bag for containing contents such as food, when subjected to retort treatment It is possible to prevent the packaging bag from being deformed or its strength being reduced.

Polybutylene terephthalate film has high strength. For this reason, when a polybutylene terephthalate film is used, the packaging bag can have puncture resistance similarly to the case where the packaging material constituting the packaging bag contains a nylon film.
In addition, although polybutylene terephthalate film is degraded in adhesion strength after retort treatment and in barrier property because it is hydrolyzed under high temperature and high humidity environment, it has a characteristic of being less likely to absorb water than nylon. For this reason, even when the polybutylene terephthalate film is disposed on the outer surface of the packaging material, it is possible to suppress the reduction in the laminate strength between the packaging materials of the packaging bag. Since it has such a property, when a polybutylene terephthalate film is used for a retort packaging bag, it can be preferably used because it can be replaced with a conventional polyethylene terephthalate film and nylon film laminated packaging material.

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 mass% or more of PBT. And a polybutylene terephthalate film is divided into two aspects from the 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 component preferably contains 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 100 mol% or more of terephthalic acid as a dicarboxylic acid component. It is mol%. As a glycol component, 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably 97 mol% or more.

The polybutylene terephthalate film may contain polyester resins other than PBT. As polyester resins other than PBT, polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polypropylene terephthalate (PPT), and isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid , PBT resin in which dicarboxylic acid such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid is copolymerized, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol and polycarbonate diol Min can be mentioned copolymerized PBT resin.

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

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

The polybutylene terephthalate film according to the second aspect is constituted by a single layer containing a polyester having PBT as a main repeating unit. A polyester having PBT as a main repeating unit has, 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. And polyesters of the homo or copolymer type obtained by condensing them. 70 mass% or more is preferable, as for the content rate of PBT which concerns on a 2nd structure, 80 mass% or more is preferable, Most preferably, it is 90 mass% or more.

The polybutylene terephthalate film according to the second aspect may contain a polyester resin other than PBT in a range of 30% by mass or less. By including the polyester resin, PBT crystallization can be suppressed, and the stretchability of the polybutylene terephthalate film can be improved. As polyester resin compounded with PBT, polyester which has ethylene terephthalate as a main repeating unit can be used. For example, it is preferable to preferably use ethylene glycol as a glycol component and a homotype mainly composed of terephthalic acid as a dibasic acid component.

The polybutylene terephthalate film according to the second configuration can be produced by a tubular method or a tenter method. The unstretched raw fabric may be simultaneously stretched in the machine direction and the transverse direction by the tubular method or the tenter method, or may be sequentially stretched in the machine direction and the transverse direction. Among them, the tubular method can obtain a stretched film having a good balance of physical properties in the circumferential direction, and is particularly preferably employed.

(Polyester film derived from biomass)
The biomass-derived polyester film is composed of a resin composition comprising, as a main component, a polyester comprising a diol unit and a dicarboxylic acid unit, wherein the resin composition is ethylene glycol having a diol unit derived from biomass, and a dicarboxylic acid unit 50 to 95% by mass, preferably 50 to 90% by mass, of a polyester which is a dicarboxylic acid derived from fossil fuel, with respect to the entire resin composition.

Because biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol, polyester films synthesized using biomass-derived ethylene glycol are the same as conventional fossil fuel-derived polyester films and machines There is no inferiority in physical properties such as chemical 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 manufactured from the raw material obtained from the conventional fossil fuel and the barrier property using the same Compared to laminated films, the amount of fossil fuel used can be significantly reduced, and the environmental impact can be reduced.

Ethylene glycol derived from biomass is obtained by using ethanol (biomass ethanol) produced from biomass such as sugar cane and corn as a raw material. For example, biomass ethylene glycol can be obtained from biomass ethanol by a method known in the prior art, such as a method of producing ethylene glycol via ethylene oxide. Alternatively, commercially available biomass ethylene glycol may be used, and, for example, biomass ethylene glycol commercially available from Indyaglikol can be suitably used.

The dicarboxylic acid unit of polyester uses dicarboxylic acid derived from fossil fuel. As dicarboxylic acids, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid. Derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl ester, ethyl ester, propyl ester and butyl ester. Ester etc. are mentioned. Among these, terephthalic acid is preferable, and as a derivative of aromatic dicarboxylic acid, dimethyl terephthalate is preferable.

The polyester which may be contained in a proportion of 5 to 45% by mass in the resin composition forming the polyester film derived from biomass is a polyester derived from fossil fuel, a recycled polyester from polyester products derived from fossil fuel, a polyester product derived from biomass Is recycled polyester.

In the resin composition containing a polyester obtained as described above, the content of carbon derived from biomass as measured by radioactive carbon ( ¹⁴ C) is preferably 10 to 19% of the total carbon in the polyester. Since carbon dioxide in the atmosphere contains ¹⁴ C at a constant rate (105.5 pMC), plants that grow by incorporating carbon dioxide in the atmosphere, such as corn, also have a ¹⁴ C content of around 105.5 pMC It is known to be. It is also known that ¹⁴ C is hardly contained in fossil fuels. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of ¹⁴ C contained in all the carbon atoms in the polyester.

In the present invention, when the content of ¹⁴ C in the polyester is P ¹⁴ C, the content Pbio of carbon derived from biomass is defined as follows.
Pbio (%) = P ¹⁴ C / 10 5.5 × 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. When P is used, the content Pbio of biomass-derived carbon in the polyester is 20%. In the present invention, the content of carbon derived from biomass as measured by radioactive carbon ( ¹⁴ C) relative to total carbon in the resin composition is preferably 10 to 19%. 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 as close to 20% as possible, but from the viewpoint of problems in the film production process and physical properties, the 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, one containing polyethylene terephthalate recycled by mechanical recycling (hereinafter, polyethylene terephthalate is also described as PET) can be used.
Specifically, the resin base material includes PET obtained by mechanical recycling of a PET bottle, and in this PET, the diol component is ethylene glycol and the dicarboxylic acid component includes terephthalic acid and isophthalic acid.

Here, with mechanical recycling, generally, polyethylene terephthalate resin products such as recovered PET bottles are crushed and washed with alkali to remove dirt and foreign matter on the surface of the PET resin products, and then dried for a fixed time under high temperature and reduced pressure. Then, the contaminants remaining in the inside of the PET resin are diffused and decontaminated to remove the stains of the resin product made of the PET resin, and it 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). Shall be

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 in all the dicarboxylic acid components constituting the PET, and 1.0 mol% More preferably, it is at least 2.5 mol%.
If the content of the isophthalic acid component is less than 0.5 mol%, the flexibility may not be improved, while if it is more than 5 mol%, the melting point of PET may decrease and the heat resistance may be insufficient.

In addition, PET may be biomass PET other than PET derived from normal fossil fuel. The “biomass PET” is one that contains ethylene glycol derived from biomass as a diol component, and contains dicarboxylic acid derived from a fossil fuel as a dicarboxylic acid component. This biomass PET may be formed only of PET comprising ethylene glycol derived from biomass as a diol component and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component, or ethylene glycol derived from biomass and diol derived from fossil fuel It may be formed of PET, which is a diol component and a dicarboxylic acid component derived from a fossil fuel.

PET used for a PET bottle can be obtained by the conventionally well-known method of polycondensing the diol component and dicarboxylic acid component which were mentioned above.

Specifically, a general method of melt polymerization in which an esterification reaction and / or an ester exchange reaction of the diol component and the dicarboxylic acid component is performed, and then a polycondensation reaction under reduced pressure is performed, or an organic solvent It can be produced by a known solution heat dehydration condensation method using

The amount of the diol component used in producing the PET is substantially equimolar to 100 moles of the dicarboxylic acid or its derivative, but in general, the 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.
The polycondensation reaction is preferably carried out in the presence of a polymerization catalyst. The timing of addition of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and may be added at the time of feeding the raw materials, or may be added at the start of pressure reduction.

The PET obtained by recycling the PET bottle is polymerized and solidified as described above, and then the degree of polymerization is further increased, and oligomers such as cyclic trimers are removed, so solid phase polymerization is carried out as necessary. You may go.
Specifically, in solid-phase polymerization, after PET is chipped and dried, it is heated at a temperature of 100 ° C. or more and 180 ° C. or less for about 1 hour to 8 hours to pre-crystallize PET, and subsequently, 190 ° C. It is carried out by heating at a temperature of at least 230 ° C. and under an inert gas atmosphere or under reduced pressure for 1 hour to several tens of hours.

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

Recycled PET preferably contains recycled PET at a ratio of 50% by weight to 95% by weight, and may contain virgin PET in addition to recycled PET.
The virgin PET may be a PET in which the diol component as described above is ethylene glycol, the dicarboxylic acid component is terephthalic acid and isophthalic acid, and the dicarboxylic acid component is PET in which isophthalic acid is not contained. It is also good. Moreover, the resin base material layer may contain polyester other than PET. For example, as the dicarboxylic acid component, aliphatic dicarboxylic acids and the like may be contained in addition to aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.

Specific examples of aliphatic dicarboxylic acids include chains having a carbon number of usually 2 or more and 40 or less, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid and cyclohexanedicarboxylic acid. And cyclic or alicyclic dicarboxylic acids. Examples of derivatives of aliphatic dicarboxylic acids include lower alkyl esters such as methyl, ethyl, propyl and butyl esters of the above aliphatic dicarboxylic acids, and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride, etc. . 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 derivatives of aliphatic dicarboxylic acids, methyl esters of adipic acid and succinic acid, or mixtures thereof are more preferred.

The resin base composed of such PET may be a single layer or a multilayer.
As shown in FIG. 1c, in the case of using recycled PET as described above for the resin substrate, it may be a resin substrate provided with three layers of a first layer 1a, a second layer 1b, and a third layer 1c.
In this case, the second layer 1b should 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 should be a layer composed only of virgin PET Is preferred.

Thus, 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 surface or the back surface of the resin base layer. For this reason, the hygiene of a layered product is securable.
Further, the resin base layer may be a resin base layer provided with two layers of the second layer 1 b and the third layer 1 c without providing the first layer 1 a shown in FIG. 1 c. Furthermore, the resin base material layer may be a resin base material layer provided with two layers of 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 only of recycled PET or a mixed layer of recycled PET and virgin PET, and the first layer 1a and the third layer 1c are layers composed only of virgin PET It is preferable to

When mixing recycled PET and virgin PET and forming one layer, there are a method of separately supplying to a molding machine, a method of mixing after dry blending and the like, and the like. Among them, the method of mixing by dry blending is preferable from the viewpoint that the operation is simple.

PET which comprises a resin base material can contain various additives in the range which the characteristic does not impair in the manufacturing process, or after its manufacture. Additives include, for example, plasticizers, UV stabilizers, coloring inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, ions Exchangers, color pigments and the like can be mentioned. The additive is preferably contained in the range of 5% by mass to 50% by mass, preferably 5% by mass to 20% by mass, in the entire resin composition containing PET.

The resin substrate can be formed, for example, by film formation by the T-die method using the above-mentioned PET. Specifically, the above-described PET is dried and then supplied to a melt extruder heated to a temperature (Tm) to Tm + 70 ° C. higher than the melting point of PET to melt the resin composition, for example, T-die The film can be formed by extruding the die into a sheet shape and rapidly solidifying the extruded sheet material with a rotating cooling drum or the like. As a melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder etc. can be used according to the objective.

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 on the cooling drum as described above is subsequently heated by roll heating, infrared heating or the like, and stretched in the longitudinal direction to form a longitudinally stretched film. It is preferable to perform this stretching using the circumferential speed difference of two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 ° C. or more and 100 ° C. or less. Moreover, although the magnification of longitudinal stretch is based also on the required characteristic of a film use, it is preferable to set it as 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.

Subsequently, the longitudinally stretched film is sequentially subjected to each processing step of transverse stretching, heat setting and heat relaxation to form a biaxially stretched film. Transverse stretching is usually performed in a temperature range of 50 ° C. or more and 100 ° C. or less. Although the magnification of transverse stretching depends on the required characteristics of this application, it is preferably 2.5 times or more and 5.0 times or less. When it is less than 2.5 times, thickness unevenness of the film becomes large and a good film is difficult to be obtained. When it exceeds 5.0 times, breakage easily occurs during film formation.

After the transverse stretching, a heat setting treatment is subsequently performed, but a preferable heat setting temperature range is Tg + 70 to Tm-10 ° C. of PET. The heat setting time is preferably 1 second to 60 seconds. Furthermore, for applications requiring a reduction in heat shrinkage rate, a heat relaxation treatment may be performed as necessary.

The thickness of the PET film obtained as described above is arbitrary according to the application, but is usually about 5 μm to 100 μm, preferably 5 μm to 25 μm. 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 % And 350% or less, and 50% or more and 300% or less in the TD direction. In addition, the shrinkage rate when left for 30 minutes in a temperature environment of 150 ° C. 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 may be biomass PET. Here, "fossil fuel PET" refers to a diol derived from fossil fuel as a diol component and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component. In addition, recycled PET may be obtained by recycling a PET resin product formed using fossil fuel PET, and obtained by recycling a PET resin product formed using biomass PET. It 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 machine direction (MD) and the vertical direction (TD) and containing 51% by mass or more of polyester.
Loop stiffness is a parameter that represents the strength of the film. Hereinafter, the method of measuring the loop stiffness of the film will be described.

First, the film is cut into strips having long sides and short sides to prepare test pieces. Subsequently, the short side of each end of the strip in the long side direction is fixed in a state in which the strip is curved so that the strip draws a loop to form a circular loop having a predetermined diameter. Thereafter, 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 60 mm, and the pressing distance of the circular loop was 40 mm. The above-mentioned "0.0017 N / 15 mm" loop stiffness means that the load required to push 40 mm of the circular loop of a short strip having a short side length of 15 mm is 0.0017 N.

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

The preferred mechanical properties of high stiffness polyester films are further described.
The puncture strength of the high-stiffness polyester film is preferably 9.5 N or more, 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.

Furthermore, it is preferable that a value obtained by dividing the tensile strength of the high-stiffness polyester film by the tensile elongation in at least one direction is 2.0 MPa /% or more.
For example, the tensile strength of the high stiffness film in the vertical direction (TD) divided by the tensile elongation is preferably 2.0 MPa /% or more, 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 in accordance with JIS K7127. As a measuring instrument, a tensile tester STA-1150 manufactured by Orientec Co., Ltd. can be used. As a test piece, what cut out the film into the rectangular film of width 15 mm and length 150 mm can be used. The distance between the pair of chucks holding the test piece at the start of measurement is 100 mm, and the pulling 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. And the thermal contraction rate 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 at the time of measuring the thermal contraction 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. And, the Young's modulus of the high stiffness polyester film in the vertical direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more.

In the production process of the high-stiffness polyester film, for example, the polyester film obtained by melting and forming the polyester first 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 of stretching into

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

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

In these steps, by adjusting the draw ratio, the draw temperature, the heat setting temperature, and the relaxation treatment rate, it is possible to obtain a high stiffness polyester film having the above-mentioned mechanical properties. As a kind of polyester used for the high stiffness polyester film Is preferably polyethylene terephthalate.

The thickness of the plastic film as the plastic substrate of the present invention as described above is not particularly limited, and the pretreatment and formation when depositing a deposited film by a roller type continuous deposited film deposition apparatus described later Any film can be used, 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, the continuous film is used for producing a laminated film having an aluminum oxide vapor deposition film provided with a barrier property with improved adhesion without bending and being broken during transportation. Easy to handle with a deposited film deposition system.
In particular, when a high-stiffness polyester film is used as the plastic substrate, it is possible to obtain a laminated film having the same or higher rigidity, tensile strength and piercing strength after reducing the thickness and weight of the laminated film.

Next, the aluminum oxide vapor deposition film will be described. In the present invention, the deposition of the aluminum oxide vapor deposition film is performed on the surface of the plastic substrate film in order to improve the adhesion between the plastic substrate and the aluminum oxide vapor deposition film, and the like. 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 a film or sheet of various resins and an aluminum oxide vapor deposition film in the present invention, as compared with the conventional method. It is implemented in an apparatus.

The roller-type continuous vapor deposition film deposition apparatus 10 suitably used for the production of a laminated film having an aluminum oxide vapor deposition film having a barrier property with improved adhesion according to the present invention is, as shown in FIG. The partition walls 35a to 35c are formed on the The base material transfer chamber 12A, the plasma pretreatment chamber 12B, and the film formation chamber 12C are formed by the partition walls 35a to 35c, and in particular, the plasma pretreatment chamber 12B and the film formation chamber are spaces surrounded by the partition walls and the partition walls 35a to 35c. 12C is formed, and each chamber is further internally formed with an exhaust chamber as required.
(Special oxygen plasma pretreatment)

In the plasma pretreatment chamber 12B, a plastic substrate S to be subjected to pretreatment is conveyed, and a part of the plasma pretreatment roller 20 that enables plasma treatment is provided so as to be exposed to the substrate conveyance chamber 12A. The plastic substrate S is moved to the plasma pretreatment chamber 12B while being wound up.

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

The base material transfer chamber 12A is moved to the base material transfer chamber 12A again by the film forming roller 23, and rolls up the plastic base material S on which the vapor deposition film is formed on one side. A take-up roller is provided to enable take-up of the plastic substrate S on which the deposited film is formed.

When manufacturing a laminated film having an aluminum oxide vapor deposition film having a barrier property with improved adhesion according to the present invention, the plasma pretreatment chamber 12B divides the space generated by plasma from the other region, and the opposing space By being configured to be able to evacuate efficiently, control of plasma gas concentration becomes easy, and productivity is improved. The pretreatment pressure to be 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 to achieve the transformation rate of the preferable transition region of the aluminum oxide vapor deposition film of the present invention. The processing pressure of is preferably 1 to 20 Pa.

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

The plasma pretreatment roller 20 constituting the plasma pretreatment apparatus prevents the plastic substrate S from shrinking or breaking of the substrate due to heat during plasma treatment by the plasma pretreatment means, oxygen plasma P to the plastic substrate S It is intended to be applied 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 circulated in the pretreatment roller.

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

The plasma pretreatment means is provided so as to cover a part of the pretreatment roller 20. Specifically, the plasma supply means and the magnetic forming means constituting the plasma pretreatment means are disposed along the surface in the vicinity of the outer periphery of the pretreatment roller 20 to supply the pretreatment roller 20 and the plasma raw material gas and the plasma P Are formed so as to form an air gap sandwiched between the plasma supply nozzles 22a to 22c, which also serve as electrodes for generating the magnetic field, and the magnetic forming means having the magnet 21 etc., to promote the generation of the plasma P.
Thereby, the plasma supply nozzles 22a to 22c are opened in the space of the gap, and plasma is jetted toward the surface of the substrate to make the inside of the gap a plasma forming region. By forming a region with 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 substrate 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 from the device. The supplied plasma source gas is a mixture gas of oxygen alone or a mixture of oxygen gas with argon, helium, nitrogen and one or more of those gases, and the flow rate of the gas is measured from the gas storage unit via a flow controller. While being supplied.

These supplied gases are mixed at a predetermined ratio as needed, formed into a plasma source gas alone or a mixed gas for plasma formation, and supplied to the plasma supply means. The single or mixed gas is supplied to the plasma supply nozzles 22a to 22c of the plasma supply means, and is supplied near the outer periphery of the pretreatment roller 20 where the supply ports of the plasma supply nozzles 22a to 22c are opened.
The nozzle opening is directed to the plastic substrate S on the pretreatment roller 20, and is arranged and configured to be able to diffuse and supply the oxygen plasma P uniformly over the entire surface of the plastic substrate S, the plastic substrate A uniform plasma pretreatment can be performed on the large-area portion of the material S.

As a special oxygen plasma pretreatment to obtain a transformation rate of the transition region of the aluminum oxide vapor deposition film of the present invention, the mixing ratio of oxygen gas and argon or helium is 5: 1, preferably 2: 1. By setting the mixing ratio to 5: 1, the film formation energy of the deposited aluminum on the plastic film substrate is increased, and by further setting it to 2: 1, the formation of aluminum hydroxide is formed in the vicinity of the interface of the substrate That is, the transformation rate of the transition region is reduced.

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

Specifically, the plasma supply means of the plasma pretreatment means installs a plasma pretreatment roller as a plasma power source, applies an AC voltage with a frequency of 10 Hz to 2.5 GHz to the counter electrode, and controls input power or And impedance control etc., and an arbitrary voltage can be applied between the substrate and the plasma pretreatment roller 20, so that the surface physical properties of the substrate can be physically or chemically modified. A power supply 32 is provided that can apply a bias voltage that makes the oxygen plasma P a positive potential.
A 50 ~ 8000W · sec / ^{m 2} as the plasma intensity per unit area employed in the present invention, the 50W · sec / ^{m 2} or less, without the effect of the plasma pretreatment was observed, also, 8000W · sec / ^{m 2} In the above, there is a tendency for deterioration of the substrate due to plasma, such as consumption of the substrate, damage coloring, and firing. 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 ratio of the transition region of the aluminum oxide vapor deposition film of the present invention.

The plasma pretreatment means comprises magnetism forming means. As a magnetic formation 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 an electrode is attached to the insulating shield plate.
Therefore, the magnet case and the electrode are electrically insulated, and even if the magnet case is installed and fixed in the decompression chamber 12, the electrode can be made to have an electrically floating level.

A power supply wiring 31 is connected to the electrode, and the power supply wiring 31 is connected to a power 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 in order to apply the oxygen plasma P from the plasma supply nozzles 22a to 22c, which are electrode and plasma supply means, to the substrate S in a concentrated manner. By providing the magnet 21, the reactivity in the vicinity of the surface of the substrate becomes high, and it becomes possible to form a good plasma pretreatment surface at high speed.

The magnet 21 has a magnetic flux density at the surface position of the plastic substrate S of 10 gauss to 10000 gauss. If the magnetic flux density on the surface of the plastic substrate S is 10 gauss or more, the reactivity near the surface of the substrate can be sufficiently enhanced, and a good pretreatment surface can be formed at high speed.

Since the ions and electrons formed at the time of plasma pretreatment are moved according to the arrangement structure of the electrode 21 due to the arrangement structure of the magnets 21, for example, in the case of performing the plasma pretreatment on a large area plastic substrate S of 1 m ² or more Also, electrons, ions, and decomposition products of the substrate are uniformly diffused over the entire surface of the electrode, and even when the plastic substrate S has a large area, uniform and stable target pretreatment can be performed with desired plasma strength. It is a thing.

(Aluminum oxide deposited film)
The special oxidation plasma-treated plastic substrate S is moved from the substrate transfer chamber 12A to the film forming chamber 12C by the guide rolls 14a to 14d for leading to the next film forming chamber 12C, and the aluminum oxide deposited film is formed in the film forming section. Is formed.

The aluminum oxide vapor deposition film is a thin film of an inorganic oxide containing aluminum oxide as a main component, which can contain an aluminum compound such as aluminum oxide or aluminum nitride such as aluminum nitride, carbide or hydroxide alone or a mixture thereof It is a layer containing aluminum as a main component.
Furthermore, the aluminum oxide vapor deposition film contains the above-mentioned aluminum compound as a main component, and silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, zirconium oxide Etc., or metal nitrides thereof, carbides, and mixtures thereof.

The aluminum oxide vapor deposition film of the present invention has a conversion ratio of 45% or less of the transition region of the aluminum oxide vapor deposition film.
The transformation ratio of the transition region of the aluminum oxide vapor deposition film is a time-of-flight type secondary while repeating soft etching at a constant speed with a Cs (cesium) ion gun to the aluminum oxide vapor deposition 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 the ions derived from the aluminum vapor deposition film and the ions derived from the plastic substrate using ion mass spectrometry (TOF-SIMS).
Specifically, etching is performed from the outermost surface of a deposited aluminum oxide film under a constant condition using Cs using a time-of-flight secondary ion mass spectrometer, and element bonding at the interface between the deposited aluminum oxide film and the plastic base material And measure the elemental bonds of the vapor deposited aluminum oxide film, and obtain the respective graphs for the measured elements and elemental bonds (Fig. 3 graph analysis diagram); 1) the position at which the strength of the graph of the element C6 becomes half From the surface to the interface is determined as the deposited aluminum oxide film as the interface between the material and the aluminum oxide, 2) the peak in the graph representing the element-bound Al ₂ O ₄ H is determined, and the peak to the interface is determined as the transition region; ) (the transition region / aluminum oxide vapor deposited film from the peak of the elements bond _Al 2 _{O 4} H to the interface) × 100 (%) and the transition territory Determine the metamorphic rate is that determined.

The transformation ratio of the transition region of the aluminum oxide vapor deposition film layer of the present invention is preferably 45% or less. If it exceeds 45%, the adhesion between the plastic substrate and the 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.

Hydrothermal treatment (retort treatment) exerts a large mechanical and chemical stress on the interface between the plastic substrate and the deposited aluminum oxide film. This stress degrades the barrier property. This site is stressed because this site is the most vulnerable in the stack configuration.
Therefore, in order to obtain retort resistance, it is important to cover the deposited film firmly at the interface with the substrate.
Aluminum hydroxide has high water vapor barrier properties because it has good adhesion to a plastic substrate due to its chemical structure, and itself forms a network and is compact. However, in a strong environment such as retort treatment, the bonding structure based on hydrogen bonding between aluminum hydroxide and the substrate is easily broken microscopically. In addition, it also easily penetrates into the film due to the affinity of the water particle / aluminum hydroxide particle interface to the aluminum hydroxide network.

In the present invention, in order to narrow the transition region at the interface with the plastic base formed by aluminum hydroxide in the aluminum oxide vapor deposition film as narrow as possible, attention is paid to the element bonding Al ₂ O ₄ H, and the amount thereof is controlled. A microscopic vapor deposition film by water molecules by retort treatment by suppressing the aluminum hydroxide generated from the element-bound Al ₂ O ₄ H by the hydrothermal treatment and increasing the ratio of the aluminum oxide film relatively less in aluminum hydroxide The fracture and the interfacial fracture with the plastic substrate were greatly suppressed. As a result, it is possible to provide a laminated film with retort resistance having adhesion and barrier properties that have not been achieved conventionally.

The aluminum oxide vapor deposition film of the present invention can be formed by depositing a vapor deposition film on the surface of a special oxygen plasma pretreated plastic substrate. 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 vapor deposition method, sputtering method, ion plating method, ion beam assist method, cluster ion beam method, and as chemical vapor deposition method, plasma CVD method, plasma polymerization method, thermal It can be selected from the group consisting of CVD method and catalytic reaction type CVD method. In the present invention, a physical vapor deposition method is preferred.

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

The vapor deposition film forming apparatus is disposed in the film forming chamber 12C under reduced pressure, and transports the plastic substrate S by winding the plastic substrate S with the treated surface of the plastic substrate S pretreated by the plasma pretreatment apparatus outside. A deposition film is formed on the surface of the plastic substrate by evaporating a film forming roller 23 for film formation processing and a target of a film forming source 24 disposed opposite to the film forming roller.
The vapor deposition film forming means 24 is a resistance heating method, using a metal wire of aluminum with aluminum as an evaporation source, supplying oxygen to oxidize aluminum vapor, depositing an aluminum oxide vapor deposition film on the surface of the plastic substrate 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 (“boat type”) vapor deposition vessel, and heating is performed by resistance heating. In this way, the metal material of aluminum can be evaporated by suppressing the supplied heat and heat amount, and the aluminum oxide vapor deposition film can be formed while suppressing the thermal deformability of the plastic substrate S as much as possible. it can.

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

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

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

As a metal alkoxide, a general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² each represents an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents n) , M represents an integer of 1 or more, and n + m represents a valence of M) at least one metal alkoxide represented by M), a metal represented by M of a 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 alkoxysilane is, for example, one represented by the general formula Si (ORa) ₄ (wherein, Ra represents a lower alkyl group). In the above, as Ra, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and the like 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 , tetrabutoxysilane Si (OC ₄ H ₉ ) ₄ , others, etc. can be used.
The above alkoxide may be used in combination of two or more.

As a silane coupling agent, what has reactive groups, such as a vinyl group, an epoxy group, methacryl group, and an amino group, can be used. In particular, organoalkoxysilanes having an epoxy group are suitable, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, or β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane can be used. The silane coupling agents as described above may be used alone or in combination of two or more.

As the water-soluble polymer, polyvinyl alcohol resins or ethylene / vinyl alcohol copolymers can be used alone, or polyvinyl alcohol resins and ethylene / vinyl alcohol copolymers are used in combination. can do. In the present invention, polyvinyl alcohol resins are preferred.

Generally as a polyvinyl alcohol-type resin, what is obtained by saponifying polyvinyl acetate can be used. As a polyvinyl alcohol-based resin, a partially saponified polyvinyl alcohol-based resin in which several tens 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 the polyvinyl alcohol-based resin, with respect to the degree of saponification, it is necessary to use at least one that is subjected to crystallization to improve the film hardness of the gas barrier coating, and preferably the degree of saponification is 70% or more. Further, even if the polymerization degree is in the range (about 100 to 5000) used in the conventional sol-gel method, it can be used. As such polyvinyl alcohol-based resin, "RS-110 (saponification degree = 99%, polymerization degree = 1,000)" which is RS resin manufactured by Kuraray Co., Ltd., "Gosenol" manufactured by Japan 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 copolymer of ethylene and vinyl acetate, that is, one obtained by saponifying an ethylene-vinyl acetate random copolymer can be used.
For example, the partial saponification product in which several tens mol% of acetic acid groups remain, to completely saponified products in which only several mol% of acetic acid groups remain or no acetic acid groups remain, is not particularly limited. However, from the viewpoint of the barrier property, it is preferable to use one having a preferable degree of saponification of 80 mol% or more, more preferably 90 mol% or more, and 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 added as necessary, a water-soluble polymer, a sol-gel method catalyst, an acid, water as a solvent, and an organic solvent such as alcohol such as methyl alcohol, ethyl alcohol and isopropanol are mixed. And prepare a barrier coating agent.
Then, the above-mentioned barrier coating agent is applied onto the aluminum oxide vapor-deposited film by a conventional method and dried. By the drying step, polycondensation of the metal alkoxide, the silane coupling agent and the water-soluble polymer further proceeds to form a coating film. The above coating operation may be further repeated on the first coating film to form a plurality of coating films composed of two or more layers.
Furthermore, heat treatment is carried out at a temperature of 20 to 200 ° C. and a temperature below the melting point of the plastic substrate, preferably at a temperature in the range of 50 to 180 ° C., for 3 seconds to 10 minutes. Thereby, a barrier coating layer of the above-mentioned 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 100 to 20 parts by weight of a silane coupling agent based on 100 parts by weight of alkoxysilane can do. In the above, when the silane coupling agent is used in excess of 20 parts by weight, the rigidity and the brittleness of the barrier coating film formed become large, which is not preferable.

The barrier coating layer formed as described above has a layer thickness of 100 to 500 nm. Within this range, it is preferable because the coating film does not break and the surface of the deposited film is sufficiently covered.

(Gas barrier packaging material)
The barrier laminate film of the present invention has good adhesion between the plastic substrate and the aluminum oxide deposited film even after retorting treatment with hot water, particularly high temperature hot water, and is also excellent in gas barrier property. It can be suitably used as a packaging material for retort packaging materials for food, high temperature hot water treatment packaging materials for medical use, and contents for performing retort processing 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 laminate film, and the heat sealable thermoplastic resin does not pass through or through the adhesive layer. It is laminated as the innermost layer and is provided with heat sealability. As a gas barrier packaging material, if desired, the function to be added as a packaging material, for example, a light shielding layer for giving a light shielding property, a decorative layer, a printing layer for giving a print, a pattern layer, a laser printing It is also possible to add various functional layers such as a layer, an absorbent / adsorbent layer that absorbs or adsorbs an odor as a layer configuration to make a gas barrier packaging material.

Moreover, the functional film according to a use can further be laminated | stacked and produced. For example, in the case of a gas barrier packaging material for retort, 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 as a heat resistant structure, or a gas barrier for liquid paper containers If it is an elastic packaging material, the packaging material of the laminated body which laminated | stacked paper is mentioned.
In particular, in the case of a packaging material made of a laminated film using a high-stiffness polyester film as a plastic substrate, a laminated film having the same or higher rigidity, tensile strength and piercing strength after reducing the thickness and weight of the packaging material You can get

The heat-sealable thermoplastic resin may be a resin layer or film or sheet which can be melted by heat and fused to each other, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear Shape) Low-density fat film or sheet 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, 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, elastomer, etc. It is preferable to use a sheet formed into a film, and among them, as a layer in contact with contents such as food, it is a type of olefin resin such as polyethylene, polypropylene, etc. having hygienicity, heat resistance, chemical resistance and aroma retention. Or resin consisting of them or films of these It is more preferable to use the sheets.
The thickness thereof is preferably about 3 to 100 μm, and more preferably about 15 to 70 μm.

[Gas barrier package]
The gas barrier package of the present invention is a package produced from the gas barrier packaging material of the present invention.
For example, a gas barrier package in the form of a pillow packaging bag, a three-way seal, a four-way seal, a gusset type or the like can be produced by heat sealing such that the sealant layer of the gas barrier packaging material made of a multilayer film is heat-sealed. Moreover, if it is a gas-barrier packaging material which consists of a laminated film which laminated | stacked paper, the liquid paper container package body of the goebel top type | molds of liquor, juice, etc. can be produced.

(Measuring method of evaluation item)
Measurement of a laminated film having a deposited aluminum oxide film having a barrier property with improved adhesion produced under the conditions shown in the respective examples or comparative examples or a barrier laminate film having a barrier coating layer on the laminated film As a sample for use, the transformation rate, the oxygen permeability, the water vapor permeability, and the adhesion strength of the transition region of the deposited film were measured using the following methods.

(Transformation rate of transition region)
In the present invention, the transformation rate of the transition region of the deposited film is time-of-flight secondary ion mass spectrometry (while repeating the soft etching at a constant speed with a Cs (cesium) ion gun on the aluminum oxide deposited film surface of the laminated film) The graph analysis diagram of FIG. 3 is 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) of the vertical axis of the graph is the measured ion intensity, and the unit (cycle) of the horizontal axis is the number of times of etching.
As a time-of-flight secondary ion mass spectrometer used for the above TOF-SIMS, ION TOF company TOF. The measurement was performed using SIMS 5 under the following measurement conditions.

(TOF SIMS measurement conditions)
Primary ion type: Bi ₃ ⁺⁺ (0.2 pA, 100 μs)
・ Measurement area: 150 × 150 μm ²
・ Et (etching) gun type: Cs (1 keV, 60 nA)
・ Et (etching) area: 600 × 600 μm ²
・ Et (etching) rate: 3 sec / cycle
・ Vacuum evacuation time: 15 h or more at 1 × 10 ^-6 mbar or less

In addition, in order to measure the ion derived from aluminum oxide used as a measuring object, it is usually necessary to separate the ions derived from other components from the plurality of aluminum oxide derived ions, and sufficient In the present invention, it is decided to select Cs ions in order to obtain a depth distribution which can be approximately converted to a concentration distribution of element-bound Al ₂ O ₄ H, in particular, since it is necessary to select one having strength.

Etching was performed from the outermost surface of the aluminum oxide vapor deposition film using Cs, and analysis of elemental bonding of the interface between the aluminum oxide vapor deposition film and the film substrate such as polyester film and elemental bonding of the vapor deposition film was carried out and measured. Graphs 1 of elemental and elemental bonds were obtained. The graph is the measured mass number of 118.93 were in _Al 2 _{O 4} H, the _Al 2 _{O 3} and 101.94, etc. 72.00 to C6, elemental and elemental coupled mass number measured Were identified and created. The position where the strength of the element C6 is half of the plastic base layer portion in the graph is the interface between the film base and the aluminum oxide, and the aluminum oxide vapor deposition film is from the surface to the interface.
Next, a peak in the graph representing the measured elemental bond Al ₂ O ₄ H can be determined, and the range from the peak to the interface can be determined as a transition region.
Performing the above operation, the transformation ratio of the transition region of the aluminum oxide deposition film (transition region from the peak of the element-bound Al ₂ O ₄ H to the interface / aluminum oxide deposition film) × 100 (%)
Asked as.

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

(Water vapor permeability)
Using the water vapor transmission rate measuring device (Model name made by Mocon (MOCON) [Model name, PERMATRAN 3/33]), the above-mentioned test sample so that the sensor side becomes the film surface of the barrier laminate film Were set, and measurement was performed in accordance with the JIS K 7126 B method under measurement conditions in an atmosphere of 37.8.degree. C. and 100% RH.
As a measurement sample
1) Composite laminate film before retort treatment 2) High retort treatment condition: Composite laminate film on one side of the composite laminate film bag treated at 135 ° C. for 40 minutes 3) Semi-retort treatment condition: 121 ° C. The composite laminated film on one side of the bag of the composite laminated film was used in the form of a bag treated for 40 minutes.

(Adhesive strength between substrate and deposited aluminum oxide 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 laminate film, dried and treated, and a two-component curable polyurethane adhesive and thickness on a 70 μm-thick non-oriented polypropylene film A laminated composite film was produced by dry laminating a 15 μm stretched nylon film and a film bonded to each other.
The above-mentioned laminated composite film was subjected to aging treatment for 48 hours, and then cut into a strip of 15 mm width using a tensile tester (Model name: Tensilon universal material tester made by ORIENTEC Co., Ltd.) JIS K6854- In accordance with 2, the strength of the barrier laminate film substrate and the aluminum oxide vapor deposition film was measured.

For measurement, the polypropylene film side and the barrier laminate film side that were peeled off in advance for measurement are held by the clamp of the measuring instrument, and in the surface direction of the part where the polypropylene film and the barrier laminate film are still laminated The film was pulled at a speed of 50 mm / min in directions opposite to each other in the direction orthogonal to each other (180 ° peeling: T-shaped peeling method), and the average value of tensile stress in the stable region was measured.
Peeling occurs between the plastic base material of the barrier laminate film and the aluminum oxide deposited film having the weakest adhesive strength in the laminate composite film, and the measured values described above are the plastic substrate of the barrier laminate film and aluminum oxide It was taken as the adhesion strength of the vapor deposition film.

<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 laminate film, dried and treated, and a two-component curable polyurethane adhesive and thickness on a 70 μm-thick non-oriented polypropylene film A film laminated with a 15 μm stretched nylon film was dry laminated to produce a laminated composite film.
100 mL of water was injected into a four-way pouch made of B5 size using the above laminated composite film, and a hot water retort treatment was performed at 135 ° C. for 40 minutes. After the retort treatment, a sample cut into strips of 15 mm width was made from the four-way pouch from which the water content was drained. The adhesion strength was measured in the same manner as in the adhesion strength measurement (1) using this sample.

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

Example 1
<Aluminum oxide vapor deposition film>
First, a roll was prepared by winding a 12 μm thick polyester film (hereinafter referred to as a PET film) as a substrate.
Next, using the continuous vapor deposition film deposition apparatus in which the pretreatment section in which the plasma pretreatment apparatus is disposed and the deposition section are separated on the surface of the PET film on which the deposition film is to be provided, the pretreatment section under the following plasma conditions The plasma is introduced from the plasma supply nozzle, special oxygen plasma pretreatment is performed at a transfer speed of 400 m / min, and in the film forming section continuously transferred, reactive resistance as a heating means of vacuum deposition under the following conditions A 12 nm thick aluminum oxide vapor deposition film was formed on a PET film by a heating method.

(Plasma pretreatment conditions)
・ Plasma strength: 150 W · sec / m ²
Plasma forming gas: argon 1200 (sccm), oxygen 3000 (sccm)
Magnetic forming means: permanent magnet of 1000 gauss Applied voltage between pretreatment drum and plasma supply nozzle: 340 V
-Degree of vacuum in the pretreatment compartment: 3.8 Pa
(Aluminum oxide film formation conditions)
-Degree of vacuum: 8.1 × ^10-2 Pa
・ Conveying speed: 400 m / min
-Light transmittance of wavelength 366 nm: 92%

<Barrier coating layer>
A solution prepared by mixing 385 g of water, 67 g of isopropyl alcohol and 9.1 g of 0.5 N hydrochloric acid and adjusting the pH to 2.2 was cooled to 10 ° C. with 175 g of tetraethoxysilane and 9.2 g of glycidoxypropyltrimethoxysilane. Solution A was prepared by mixing.
A solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of saponification of 99% or more and a degree of polymerization of 2400, 324 g of water, and 17 g of isopropyl alcohol.
A solution obtained by mixing solution A and solution B so that the weight ratio was 6.5: 3.5 was used as a barrier coating agent.

<Barrier laminated film>
The barrier coating agent prepared above was coated by spin coating on the aluminum oxide deposited film of the PET film described above. Thereafter, the resultant 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 the aluminum oxide vapor deposition film, to obtain a barrier laminate film.

Example 2
A barrier laminate 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)
-Degree of vacuum: 8.1 × ^10-2 Pa
・ Conveying speed: 340 m / min
-Light transmittance of wavelength 366 nm: 92%

Example 3
A barrier laminate film was obtained in the same manner as in Example 1 except that a biomass-derived polyester film with a thickness of 12 μm was used as a substrate.
(Aluminum oxide film formation conditions)
-Degree of vacuum: 8.1 × ^10-2 Pa
・ Conveying speed: 400 m / min
-Light transmittance of wavelength 366 nm: 92%

Example 4
A barrier laminate 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 substrate and the thickness of the aluminum oxide vapor deposition film thickness was changed to 10 nm.
(Aluminum oxide film formation conditions)
-Degree of vacuum: 8.1 × ^10-2 Pa
・ Conveying speed: 400 m / min
-Light transmittance of wavelength 366 nm: 92%

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

Comparative Example 1
A barrier laminate 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 12 μm thick PET film as a substrate. Next, the surface of the PET film on which the vapor deposition layer is to be formed was plasma-treated under the following conditions using a direct plasma system to obtain a roll-up roll of plasma-treated PET film. Next, a 12 nm-thick aluminum oxide vapor deposition film was formed on the plasma-treated surface of this PET film by the 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 formation means: None Pretreatment drum-Applied voltage between plasma supply nozzles: None

(Aluminum oxide film formation conditions)
-Degree of vacuum: 8.1 × ^10-2 Pa
・ Conveying speed: 400 m / min
-Light transmittance of wavelength 366 nm: 92%

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

The measurement results are shown in Table 1. As shown in Examples 1 to 5, the transformation ratio of the transition region of the deposited aluminum oxide film of the laminated film in the present invention is 45% or less, and in Comparative Examples 1 and 2, the transformation ratio of the transition region is high. After high retort treatment and semi-retort treatment, Comparative Examples 1 and 2 have a low value of 1 N / 15 mm or less after retort treatment even if the peel strength before retort treatment is almost the same as that of the example. Deterioration is seen. In contrast to this, in the present invention, the peel strength is sufficiently maintained such that the peel strength is 2.1 N / 15 mm or more, and a significant decrease in the adhesion strength due to the retort treatment is not observed, and the deterioration is suppressed.

Also in barrier performance, Examples 1-5, high retort treatment, 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 permeability can be maintained at a constant level 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, in the laminated film in which the transformation ratio of the transition region of the aluminum oxide of the present invention is controlled, one showing excellent retort resistance is obtained.

According to the present invention, the adhesion is improved by appropriately setting the transformation ratio of the transition region of the aluminum oxide vapor deposition film between the vapor deposition film and the plastic substrate, and the aluminum oxide vapor deposition film having a barrier property is provided. A laminate film and a barrier laminate film can be obtained.
By improving the deterioration of the adhesion strength before and after the retort treatment between the vapor deposition film and the plastic substrate, it is possible to obtain a barrier laminate film having a barrier property and adhesion for blocking permeation of oxygen gas, water vapor, etc. , Foods that require laminated materials that can withstand processing accompanying processing such as retort processing, sterilization processing, packaging materials such as pharmaceuticals, and packaging of electric and electronic parts, uses that require durability and barrier properties such as protective sheets It can be applied to industrial materials in fields where the environment is severe.

1, S: Plastic base 2: Aluminum oxide vapor deposited film 3: Barrier coating layer A: ... Laminated film or vapor deposited film B: ...... Barrier laminated film P: ...... Plasma 10 ...... Roller-type continuous vapor deposition film deposition apparatus 12 ...... 減圧 Decompression chamber 12A ...... 基材 Substrate transfer chamber 12B ...... Plasma pretreatment chamber 12C ...... Film formation chambers 14a to 14d ...... Guide roll 18 ...... ... Source gas volatilization supply device 20 ... ... Pretreatment roller 21 ... ... Magnet 22 ... ... Plasma supply nozzle 23 ... ... Film formation roller 24 ... ... Vapor deposition film formation means 31 ... ... Power supply wiring 32 ... ...... Power supply 35a to 35c ......... Partition wall

Claims

In a laminated film having a barrier property in which an aluminum oxide vapor deposition film mainly composed of aluminum oxide is formed on the surface of a plastic substrate, adhesion strength between the substrate film surface and the vapor deposition film mainly comprising the aluminum oxide vapor deposition film formed A transition region of the deposited film to be defined is formed, and the transition region is transformed into aluminum hydroxide detected by performing etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Defined by the ratio of the denatured transition region defined using TOF-SIMS to the aluminum oxide deposited film that contains elemental bound Al 2 O 4 H and is defined by performing etching using TOF-SIMS The above laminated film, wherein the transformation ratio of the transition region is 45% or less.
The laminated film according to claim 1, wherein the plastic substrate is a polyethylene terephthalate film.
The laminated film according to claim 1, wherein the plastic substrate comprises a recycled polyethylene terephthalate film.
The laminated film according to claim 1, wherein the plastic substrate is a polybutylene terephthalate film.
The laminated film according to claim 1, wherein the plastic substrate is a biomass-derived polyester film.
The laminated film according to claim 1, wherein the plastic substrate is a high stiffness polyester film.
The laminated film according to any one of claims 1 to 6, wherein the plastic substrate surface is an oxygen plasma treated surface.
The laminated film according to claim 7, wherein an aluminum oxide vapor deposition film is laminated inline on the oxygen plasma treated surface.
A barrier laminate film comprising a barrier coating layer laminated on the surface of the aluminum oxide vapor deposited film of the laminate film according to any one of claims 1 to 8.
10. The barrier laminate 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 drying by heating.
10. The barrier laminate 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 by heating.
A gas barrier packaging material comprising a thermoplastic resin having heat sealability laminated on the barrier laminate film according to any one of claims 9 to 11.
The gas barrier packaging material according to claim 12, which is used for retort sterilization packaging.
A gas barrier package made from the gas barrier packaging material according to claim 12 or 13.