WO2019182017A1 - バリア性積層フィルム及び該バリア性積層フィルムを用いた包装材料 - Google Patents
バリア性積層フィルム及び該バリア性積層フィルムを用いた包装材料 Download PDFInfo
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- WO2019182017A1 WO2019182017A1 PCT/JP2019/011720 JP2019011720W WO2019182017A1 WO 2019182017 A1 WO2019182017 A1 WO 2019182017A1 JP 2019011720 W JP2019011720 W JP 2019011720W WO 2019182017 A1 WO2019182017 A1 WO 2019182017A1
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- WIPO (PCT)
- Prior art keywords
- film
- aluminum oxide
- barrier
- vapor deposition
- plastic substrate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Definitions
- the present invention has excellent barrier properties against oxygen and water vapor, which can be suitably used as a packaging material for retort processing such as foods, pharmaceuticals, and pet foods, and improves the adhesion between the plastic substrate after retort processing and the aluminum oxide deposited film
- the present invention relates to a barrier laminated film having a barrier property and retort resistance and a packaging material.
- a barrier laminate film having a multilayer structure in which a barrier layer composed of a thin film of a deposited film such as silicon oxide and aluminum oxide and a barrier coat layer is laminated has been developed.
- the plastic substrate of a laminated film having a vapor deposited film with excellent barrier properties that is easily affected by temperature, humidity, etc. is likely to undergo dimensional changes. Further, it is difficult to follow a deposited film such as a silicon oxide deposited film or an aluminum oxide deposited film provided thereon. Therefore, the delamination phenomenon often occurs between the plastic substrate and the vapor deposition film such as the silicon oxide vapor deposition film or the aluminum oxide vapor deposition film in a severe environment of high temperature and high humidity. Furthermore, cracks, pinholes, etc. appear. As a result, there is a problem that the original barrier performance is remarkably lost and it is extremely difficult to maintain the barrier performance.
- the in-line plasma processing method using a parallel plate type apparatus generally used in Patent Document 1 introduces a functional group such as a hydroxyl group or a carbonyl group to the plastic surface and interposes between the deposited films via the functional group. Adhesiveness is expressed. However, those that have developed adhesiveness by hydrogen bonding with hydroxyl groups are markedly adherent because the hydrogen bonding is broken in high-temperature and high-humidity environments required for applications such as electronic devices such as electronic paper and retort packaging materials. There is a problem that decreases. In addition, since the film only passes through the plasma atmosphere generated in the air in the above-mentioned plasma treatment, adhesion in a severe environment such as a high temperature and high humidity between the substrate and the deposited film is not obtained. Is the actual situation.
- a functional group such as a hydroxyl group or a carbonyl group
- the undercoat treatment method described in Patent Document 2 is a method in which an undercoat layer is provided as an adhesive layer on the surface of a plastic film, and is generally practiced.
- a technique for improving the adhesion is performed by pre-treating the surface of the plastic substrate using a reactive ion etching (RIE) method in which plasma is generated with the electrode for generating the plasma facing the substrate.
- RIE reactive ion etching
- Patent Document 3 The plasma RIE method simultaneously obtains two effects: a chemical effect such as giving a functional group to the surface of the base material, and a physical effect of performing ion etching on the surface to remove impurities and smoothing. It exhibits adhesion.
- a barrier laminate film that can stably exhibit higher barrier properties, and has a multilayer structure in which a barrier layer made of a thin film of aluminum oxide such as silicon oxide and aluminum oxide and a barrier coating layer are laminated.
- a barrier laminated film excellent in retort resistance is desired.
- JP-A-7-233463 JP 2000-43182 A Japanese Patent Laying-Open No. 2005-335109 Japanese Patent No. 4461737 Japanese Patent No. 4135496
- the retorting process by the hydrothermal treatment gives a large mechanical and chemical stress to the interface between the plastic substrate and the aluminum oxide deposited film. This stress deteriorates the barrier property. This part is stressed because it is the most fragile in the laminated configuration. Therefore, in order to obtain retort resistance, it is important to firmly coat the vapor deposition film on the interface with the base material.
- aluminum hydroxide has good adhesion to a plastic substrate due to its chemical structure, and has a high water vapor barrier property because it itself forms a network and is dense.
- the bonding structure based on the hydrogen bond between the aluminum hydroxide and the base material is easily broken microscopically against a powerful environment such as retorting. Also, it easily penetrates into the membrane due to the affinity of the water molecule and aluminum hydroxide grain interface to the aluminum hydroxide network.
- the present invention has been made in view of the above-mentioned problems and knowledge, and the object is that the adhesiveness between the plastic substrate and the aluminum oxide vapor deposition film is good even after the hot water treatment, And a laminated film having a vapor-deposited film having excellent barrier properties, and further comprising the laminated film, a barrier-type laminated film comprising an aluminum oxide vapor-deposited film having excellent so-called retort resistance, and the barrier-type laminated film, It is to provide a packaging material excellent in barrier properties and retort resistance.
- the laminated film of the present invention is formed on the surface of a base film in a laminated film having a barrier property in which an aluminum oxide vapor deposition film mainly composed of aluminum oxide is formed on the surface of a plastic substrate.
- a transition region of the vapor deposition film that defines the adhesion strength with the vapor deposition film mainly composed of the aluminum oxide vapor deposition film is formed, and the transition region is formed using time-of-flight secondary ion mass spectrometry (TOF-SIMS).
- the transition rate of the transition region defined by the ratio of the transition region to be defined is 5% or more and 60% or less. Is shall.
- Secondary ion mass spectrometry is a method for analyzing element concentration distribution by irradiating the surface of the sample to be analyzed with a primary ion beam and mass-analyzing secondary ions sputtered from the sample surface. It is.
- the secondary ion intensity is detected while sputtering is progressing. Therefore, by converting the transition time into depth with respect to the data of the time transition of the ion intensity of the secondary ion, that is, the detected element ion or the molecular ion bonded to the detected element, the depth direction of the sample surface
- the concentration distribution of the element to be detected can be known.
- the transition time is converted into the depth by measuring the depth of the depression formed on the sample surface by irradiation of the primary ions using a surface roughness meter, and calculating the average from the depth of the depression and the transition time.
- the sputtering speed is calculated, and the irradiation time (that is, the transition time) is converted into the depth (spatter amount) under the assumption that the sputtering speed is constant.
- time-of-flight secondary ion mass spectrometry is used for the aluminum oxide deposited film of the laminated film while repeating soft etching at a constant rate with a Cs (cesium) ion gun.
- Transition that defines the adhesion strength between the surface of the base film and the deposited film composed mainly of the deposited aluminum oxide film by measuring ions derived from the deposited aluminum oxide film and ions derived from the plastic substrate A region is formed.
- the transition region includes elementally bonded Al 2 O 4 H that transforms into aluminum hydroxide detected by etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS).
- Ratio of the transition region to be transformed defined using time-of-flight secondary ion mass spectrometry, with respect to the aluminum oxide deposition film, which is defined by etching using secondary ion mass spectrometry (TOF-SIMS)
- TOF-SIMS secondary ion mass spectrometry
- the present invention performs etching from the outermost surface of the aluminum oxide vapor deposition film by Cs using a time-of-flight secondary ion mass spectrometer, and element bonding at the interface between the aluminum oxide vapor deposition film and the plastic substrate Then, the element bond of the deposited film is measured, and an actual measurement graph is obtained for each of the measured element and element bond (FIG.
- the transition rate of the transition region of the aluminum oxide vapor-deposited film is set to 5% or more and 60% or less, whereby a barrier coating layer is further formed on the laminated film, and the plastic substrate of the barrier laminated film is oxidized.
- the adhesion strength at the interface with the deposited aluminum film is 2.1 N / min even after hot water treatment (high retort treatment) at 135 ° C. for 40 minutes or after hot water treatment (semi-retort treatment) at 121 ° C. for 40 minutes. It can be made 15 mm or more, delamination does not occur during retort pouch molding or retort processing, adhesion is improved, and a barrier laminated film having retort resistance can be produced.
- the transition rate of the transition region of the aluminum oxide vapor-deposited film is set to 5% or more and 60% or less, so that the oxygen permeability and water vapor permeability after high retort treatment, semi-retort are 0.2 cc, respectively.
- 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 barrier heat resistance, moist heat resistance and hot water resistance after retort treatment, and can improve retort resistance. It is.
- the present invention is characterized by the following points. 1.
- a laminated film having a barrier property an aluminum oxide vapor deposition film mainly composed of aluminum oxide is formed on the surface of a plastic substrate, and a barrier coating layer is laminated on the surface of the aluminum oxide vapor deposition film.
- a transition region that defines the adhesion strength between the surface of the plastic substrate and the aluminum oxide vapor deposition film is formed, and the transition region is a time-of-flight secondary ion mass spectrometry method.
- TOF-SIMS includes element-bonded Al 2 O 4 H converted to aluminum hydroxide, which is detected by etching, and the barrier coating layer and the aluminum oxide vapor-deposited film are combined with TOF-SIMS.
- the transition region transformation rate defined by the proportion of the transition region to be transformed, defined using TOF-SIMS, with respect to the aluminum oxide vapor deposition film, which is defined by performing etching using, is 5% or more,
- the barrier laminate film which is 60% or less.
- the barrier laminate film according to 1 above, wherein the plastic substrate is a polyethylene terephthalate film. 3.
- the barrier laminate film according to 1 above, wherein the plastic substrate is a polybutylene terephthalate film. 5).
- the barrier laminate film according to 1 above, wherein the plastic substrate is a biomass-derived polyester film. 6).
- barrier laminate film according to any one of 1 to 9 above, wherein the barrier coating layer is a layer formed by applying a mixed solution of a metal alkoxide, a silane coupling agent, and a water-soluble polymer and drying by heating.
- a packaging material obtained by laminating a heat-sealing thermoplastic resin on the barrier laminate film according to any one of 1 to 10 above. 12 The packaging material according to the above 11, which is used for packaging for retort sterilization.
- the transition rate of the transition region of the aluminum oxide vapor deposition film in the laminated film is set to 60% or less, and by increasing the proportion of the aluminum oxide film that is relatively low in aluminum hydroxide, It greatly suppresses the destruction of the vapor-deposited film and the interface with the plastic substrate. Thereby, the adhesiveness is improved, and a multilayer film having retort resistance unprecedented and a barrier multilayer film including the sex layer film can be provided.
- the barrier laminate film of the present invention has an adhesion strength at the interface between the plastic substrate and the aluminum oxide vapor deposition film of 2.1 N / 15 mm or more even after high retort treatment and semi-retort treatment, and high retort treatment.
- Oxygen permeability and water vapor permeability after semi-retort have barrier performances 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.
- FIG. 1a Sectional drawing which shows an example of the barriering laminated film A (FIG. 1a) by which the barriering coating layer of this invention was laminated
- the figure which shows an example of the apparatus which forms the aluminum oxide vapor deposition film in this invention.
- FIG. 5 is a cross-sectional view of the loop stiffness measuring device of FIG. 4 along line VV.
- FIG. 1a is a cross-sectional view showing an example of a barrier laminate film of the present invention
- FIG. 1b is a cross-sectional view showing an example of a laminate film in which a base material layer is composed of multiple layers
- FIG. It is a figure which shows typically the structure of the roller type continuous vapor deposition film forming apparatus suitable for forming into a film the aluminum oxide vapor deposition film
- the barrier coating agent coating apparatus is continuously arranged in the vapor deposition film forming apparatus.
- a known roller coating apparatus is connected in series, and is illustrated here. Was omitted.
- a barrier laminate film A having an aluminum oxide vapor deposition film having a barrier property with improved adhesion and a barrier coating layer according to the present invention is adhered to one surface of a plastic substrate 1.
- the basic structure is a laminated structure in which an aluminum oxide vapor deposition film 2 having improved barrier properties is laminated, and a barrier coating layer 3 is further laminated on the aluminum oxide vapor deposition film 2.
- it has excellent barrier properties and retort resistance.
- the plastic substrate is not particularly limited, and a known plastic film or sheet can be used.
- polyester resins such as polyethylene terephthalate, polyester derived from biomass, polybutylene terephthalate, polyethylene naphthalate, recycled polyethylene terephthalate, polyamide resin 6, polyamide resin 66, polyamide resin 610, polyamide resin 612, polyamide resin 11, polyamide resin 12
- a film made of a polyamide-based resin such as a polyolefin resin such as a polymer of ⁇ -olefin such as polyethylene or polypropylene can be used.
- a polyester resin known as a polyethylene terephthalate film is particularly preferably used.
- Polybutylene terephthalate film (Polybutylene terephthalate film (PBT)) Polybutylene terephthalate film has a high thermal deformation temperature, excellent mechanical strength and electrical characteristics, and good moldability. For this reason, when used for packaging bags containing foods and other contents, It is possible to prevent the packaging bag from being deformed or its strength from being lowered.
- the polybutylene terephthalate film has high strength. For this reason, when a polybutylene terephthalate film is used, the packaging bag can have puncture resistance as in the case where the packaging material constituting the packaging bag includes a nylon film. In addition, polybutylene terephthalate film is hydrolyzed in a high temperature and high humidity environment, and thus the adhesion strength and barrier property after retort treatment are reduced. However, the polybutylene terephthalate film has a characteristic that it hardly absorbs moisture compared to nylon.
- the polybutylene terephthalate film is arrange
- the polybutylene terephthalate film is a film containing polybutylene terephthalate (hereinafter also referred to as PBT) as a main component, and is preferably a resin film containing 60% by mass or more of PBT. And a polybutylene terephthalate film is divided into two aspects from the structure.
- PBT polybutylene terephthalate
- 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.
- PBT used as a main constituent component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, most preferably 100 mol% or more of terephthalic acid as a dicarboxylic acid component. Mol%.
- 1,4-butanediol 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 a polyester resin other than PBT.
- Polyester resins other than PBT include polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polypropylene terephthalate (PPT), as well as isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, and biphenyldicarboxylic acid.
- PBT resin copolymerized with dicarboxylic acid such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, polycarbonate diol Min can be mentioned copolymerized PBT resin.
- dicarboxylic acid such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid
- ethylene glycol 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 -Diols
- the amount of the polyester resin other than 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 as PBT may be impaired, and impact strength, pinhole resistance, and drawability may be insufficient.
- the layer structure of the polybutylene terephthalate film according to the first aspect is produced by casting a resin in multiple layers by a casting method, and includes a multilayer structure portion including a plurality of unit layers.
- Each of the plurality of unit layers includes PBT as a main component.
- each of the plurality of unit layers includes 60% by mass or more of PBT.
- the (n + 1) th unit layer is directly stacked on the nth unit layer. That is, no adhesive layer or adhesive layer is interposed between the plurality of unit layers.
- Such a polybutylene terephthalate film is composed of a multilayer structure part including at least 10 layers, preferably 60 layers or more, more preferably 250 layers or more, and still more preferably 1000 layers or more.
- the polybutylene terephthalate film according to the second aspect is composed of a single layer containing polyester having PBT as a main repeating unit.
- Polyesters having PBT as the main repeating unit are mainly composed of 1,4-butanediol as a glycol component, or an ester-forming derivative thereof, and terephthalic acid as a dibasic acid component, or an ester-forming derivative thereof.
- the content of PBT according to the second configuration is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more.
- the polybutylene terephthalate film according to the second aspect may contain a polyester resin other than PBT in a range of 30% by mass or less.
- a polyester resin other than PBT By including the polyester resin, PBT crystallization can be suppressed, and the stretchability of the polybutylene terephthalate film can be improved.
- polyester resin blended with PBT polyester having ethylene terephthalate as a main repeating unit can be used.
- a homotype mainly composed of ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component can be preferably used.
- the polybutylene terephthalate film according to the second configuration can be produced by a tubular method or a tenter method.
- the tubular method or the tenter method the unstretched original fabric may be stretched in the machine direction and the transverse direction simultaneously, or the machine direction and the transverse direction may be successively drawn.
- the tubular method can obtain a stretched film having a good balance of physical properties in the circumferential direction, and is particularly preferably employed.
- the biomass-derived polyester film is composed of a resin composition comprising as a main component a polyester composed of a diol unit and a dicarboxylic acid unit, and the resin composition is ethylene glycol derived from biomass and the dicarboxylic acid unit is a fossil.
- a resin composition of dicarboxylic acid derived from fuel is preferable, and a resin composition of ethylene glycol derived from biomass and terephthalic acid derived from fossil fuel is more preferable.
- Biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol, so the polyester film synthesized using biomass-derived ethylene glycol is the same as conventional fossil fuel-derived polyester film and machinery. There is no inferiority in physical properties such as physical properties. Therefore, the barrier laminate film of the present invention using a biomass-derived polyester film has a layer made of a carbon neutral material, and therefore, compared to a barrier laminate film manufactured from a raw material obtained from a conventional fossil fuel, The amount of fossil fuel used can be reduced, and the environmental load can be reduced.
- Biomass-derived ethylene glycol is made from ethanol (biomass ethanol) produced from biomass such as sugar cane and corn.
- biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide.
- biomass ethylene glycol marketed from India Glycol can be used conveniently.
- the dicarboxylic acid unit of the polyester uses a dicarboxylic acid derived from fossil fuel.
- dicarboxylic acid aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used.
- aromatic dicarboxylic acid include terephthalic acid and isophthalic acid
- aromatic dicarboxylic acid derivative include lower alkyl esters of aromatic dicarboxylic acid, specifically methyl ester, ethyl ester, propyl ester, and butyl. Examples include esters.
- terephthalic acid is preferable, and dimethyl terephthalate is preferable as an aromatic dicarboxylic acid derivative.
- a single film made of biomass-derived polyester can be used as the plastic base material of the present invention.
- a film made of biomass-derived polyester, a fossil fuel-derived polyester, a recycled polyester of a fossil fuel-derived polyester product, a recycled polyester of a biomass-derived polyester product, or a film comprising a resin containing two or more types can be used.
- biomass degree indicates the weight ratio of biomass-derived components. Taking PET as an example, since PET is a polymer of ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1, only those derived from biomass are used as ethylene glycol.
- the plastic substrate of the present invention one containing polyethylene terephthalate recycled by mechanical recycling (hereinafter, polyethylene terephthalate is also referred to as PET) can be used.
- the plastic substrate includes PET obtained by recycling a PET bottle by mechanical recycling.
- the diol component is ethylene glycol
- the dicarboxylic acid component includes terephthalic acid and isophthalic acid.
- mechanical recycling generally means that collected polyethylene terephthalate resin products such as PET bottles are crushed and washed with alkali to remove dirt and foreign matter on the surface of PET resin products, and then dried for a certain period of time under high temperature and reduced pressure.
- contaminants remaining inside the PET resin are diffused and decontaminated to remove stains on the resin product made of the PET resin, and then returned to the PET resin again.
- polyethylene terephthalate obtained by recycling PET bottles is referred to as “recycled polyethylene terephthalate (hereinafter also referred to as recycled PET)”, and polyethylene terephthalate that is not recycled is referred to as “virgin polyethylene terephthalate (hereinafter referred to as virgin PET). ) ".
- the content of the isophthalic acid component is preferably 0.5 mol% or more and 5 mol% or less in all dicarboxylic acid components constituting the PET, and is 1.0 mol%. More preferably, it is 2.5 mol% or less.
- the content of the isophthalic acid component is less than 0.5 mol%, the flexibility may not be improved.
- it exceeds 5 mol% the melting point of PET may be lowered and the heat resistance may be insufficient.
- biomass PET in addition to normal fossil fuel-derived PET.
- biomass PET includes biomass-derived ethylene glycol as the diol component and fossil fuel-derived dicarboxylic acid as the dicarboxylic acid component.
- This biomass PET may be formed only of PET having biomass-derived ethylene glycol as a diol component and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid component, or biomass-derived ethylene glycol and fossil fuel-derived diol. It may be formed of PET having a diol component and a dicarboxylic acid component derived from a fossil fuel.
- PET used for PET bottles can be obtained by a conventionally known method in which the above-described diol component and dicarboxylic acid component are polycondensed.
- a general method of melt polymerization in which an esterification reaction and / or transesterification reaction between 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 heating dehydration condensation method using
- the amount of the diol component used in the production of the PET is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof.
- esterification and / or transesterification and / or polycondensation are performed. Since there is distillation during the reaction, it is used in an excess of 0.1 mol% or more and 20 mol% or less.
- the polycondensation reaction is preferably performed in the presence of a polymerization catalyst.
- the addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction.
- PET that has been recycled from PET bottles is polymerized and solidified as described above, and is further subjected to solid-phase polymerization as necessary in order to further increase the degree of polymerization or to remove oligomers such as cyclic trimers.
- solid-phase polymerization is performed by making PET into chips and drying, followed by heating at a temperature of 100 ° C. or higher and 180 ° C. or lower for 1 to 8 hours to pre-crystallize the PET, followed by 190 ° C. It is carried out by heating at a temperature of 230 ° C. or lower for 1 hour to several tens of hours in an inert gas atmosphere or under reduced pressure.
- the intrinsic viscosity of PET contained in recycled PET is preferably 0.58 dl / g or more and 0.80 dl / g or less.
- the intrinsic viscosity is measured at 35 ° C. with an orthochlorophenol solution.
- Recycled PET preferably contains recycled PET at a ratio of 50 wt% or more and 95 wt% or less, and may contain virgin PET in addition to recycled PET.
- the diol component as described above may be ethylene glycol
- the dicarboxylic acid component may be PET containing terephthalic acid and isophthalic acid
- the dicarboxylic acid component may be PET not containing isophthalic acid.
- the resin base material layer may contain polyesters other than PET.
- the dicarboxylic acid component an aliphatic dicarboxylic acid or the like may be contained in addition to the aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.
- aliphatic dicarboxylic acid examples include chains having usually 2 to 40 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid.
- alicyclic dicarboxylic acids examples include lower alkyl esters such as methyl esters, ethyl esters, propyl esters, and butyl esters of the aliphatic dicarboxylic acids, and cyclic acid anhydrides of the aliphatic dicarboxylic acids such as succinic anhydride.
- aliphatic dicarboxylic acid adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and those having succinic acid as a main component are particularly preferable.
- succinic acid a main component of succinic acid
- derivative of the aliphatic dicarboxylic acid methyl esters of adipic acid and succinic acid, or a mixture thereof are more preferable.
- Such a plastic substrate made of PET may be a single layer or a multilayer.
- it in the case of using recycled PET as described above for the plastic substrate, it may be a resin substrate including three layers of the first layer 1a, the second layer 1b, and the third layer 1c.
- the second layer 1b is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET
- the first layer 1a and the third layer 1c are layers composed only of virgin PET. Is preferred.
- the resin base material layer may be a plastic base material provided with two layers of the second layer 1b and the third layer 1c without providing the first layer 1a shown in FIG. 1b.
- the plastic substrate may be a plastic substrate provided with two layers of the first layer 1a and the second layer 1b without providing the third layer 1c shown in FIG. 1b.
- 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 that
- the PET constituting the resin base material can contain various additives in the production process or after the production, as long as the characteristics are not impaired.
- additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, and ions.
- exchange agents and coloring pigments include exchange agents and coloring pigments.
- the additive is preferably contained in the entire resin composition containing PET in a range of 5% by mass to 50% by mass, preferably 5% by mass to 20% by mass.
- the resin base material can be formed by forming a film by using the above-described PET, for example, by a T-die method. Specifically, after drying the above-mentioned PET, it is supplied to a melt extruder heated to a temperature not lower than the melting point of PET (Tm) to a temperature of Tm + 70 ° C. to melt the resin composition.
- Tm melting point of PET
- a film can be formed by extruding into a sheet from a die such as the above, and rapidly solidifying the extruded sheet with a rotating cooling drum or the like.
- the melt extruder a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.
- the film obtained as described above is preferably biaxially stretched.
- Biaxial stretching can be performed by a conventionally known method.
- the film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the longitudinal direction to obtain a longitudinally stretched film.
- This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls.
- the longitudinal stretching is usually performed in a temperature range of 50 ° C. or more and 100 ° C. or less.
- the ratio of the longitudinal stretching is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the film application. When the draw ratio is less than 2.5, the thickness unevenness of the PET film becomes large and it is difficult to obtain a good film.
- the longitudinally stretched film is successively subjected to the transverse stretching, heat setting, and thermal relaxation treatment steps to form a biaxially stretched film.
- the transverse stretching is usually performed in a temperature range of 50 ° C. or more and 100 ° C. or less.
- the transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the required characteristics of this application. If it is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage tends to occur during film formation.
- a heat setting treatment is subsequently performed.
- a preferable temperature range for heat setting is Tg + 70 to Tm-10 ° C. of PET.
- the heat setting time is preferably 1 second or more and 60 seconds or less. Furthermore, for applications that require a low thermal shrinkage rate, heat relaxation treatment may be performed as necessary.
- the thickness of the PET film obtained as described above is arbitrary depending on its use, but is usually about 5 ⁇ m to 100 ⁇ m, preferably 5 ⁇ m to 25 ⁇ m. 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 % To 350%, and 50% to 300% in the TD direction. Further, the shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1% or more and 5% or less.
- the virgin PET may be fossil fuel polyethylene terephthalate (hereinafter also referred to as fossil fuel PET) or biomass PET.
- 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.
- the recycled PET may be obtained by recycling a PET resin product formed using fossil fuel PET, or may be obtained by recycling a PET resin product formed using biomass PET. There may be.
- the high stiffness PET film is a stretched plastic film having a loop stiffness of 0.0017 N / 15 mm or more in the flow direction (MD) and the vertical direction (TD) and containing 51 mass% or more of PET.
- the thickness of the high stiffness PET film is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more.
- the thickness of the high stiffness PET film is preferably 25 ⁇ m or less, and more preferably 20 ⁇ m or less.
- the loop stiffness is a parameter representing the strength of the film.
- a method for measuring loop stiffness will be described with reference to FIGS.
- a vapor deposition film is a film containing the single layer film like the above-mentioned barrier property laminated film A, and the vapor deposition layer currently formed on the single layer film.
- the laminated film is a film including a plurality of laminated films such as a packaging material described later.
- FIG. 4 is a plan view showing the test piece 40 and the loop stiffness measuring device 45
- FIG. 5 is a cross-sectional view taken along the line IV-IV of the test piece 40 and the loop stiffness measuring device 45 of FIG.
- the test piece 40 is a rectangular film having a long side and a short side.
- the long side length L1 of the test piece 40 is 150 mm
- the short side length L2 is 15 mm.
- the loop stiffness measuring instrument 45 for example, No. manufactured by Toyo Seiki Co., Ltd. 581 Loop Stiffness Tester (registered trademark) LOOP STIFFNESS TESTER DA type can be used.
- the long side length L1 of the test piece 40 can be adjusted as long as the test piece 40 can be gripped by a pair of chuck portions 46 described later.
- the loop stiffness measuring instrument 45 includes a pair of chuck portions 46 for gripping a pair of end portions in the long side direction of the test piece 40, and a support member 47 for supporting the chuck portion 46.
- the chuck portion 46 includes a first chuck 461 and a second chuck 462. In the state shown in FIGS. 4 and 5, the test piece 40 is disposed on the pair of first chucks 461, and the second chuck 462 still holds the test piece 40 with the first chuck 461. Not. As will be described later, at the time of measurement, the test piece 40 is held between the first chuck 461 and the second chuck 462 of the chuck portion 46.
- the second chuck 462 may be connected to the first chuck 461 via a hinge mechanism.
- the test piece 40 is produced by cutting the film to be measured. May be. Moreover, the test piece 40 may be produced by cutting a packaged product produced from a packaging material such as a bag and taking out a film to be measured.
- the test piece 40 is placed on the first chuck 461 of the pair of chuck portions 46 arranged with a gap L3.
- the interval L3 is set so that the length of the loop portion 41 (to be described later) (hereinafter also referred to as loop length) is 60 mm.
- the test piece 40 includes an inner surface 40x located on the first chuck 461 side and an outer surface 40y located on the opposite side of the inner surface 40x.
- the second chuck 462 is disposed on the test piece 40 so as to grip the end portion of the test piece 40 in the long side direction with the first chuck 461.
- a test piece 40 shown in FIG. 7 includes a loop portion 41, a pair of intermediate portions 42, and a pair of fixing portions 43.
- the pair of fixing portions 43 are portions that are gripped by the pair of chuck portions 46 in the test piece 40.
- the pair of intermediate portions 42 is a portion located between the loop portion 41 and the pair of intermediate portions 42 in the test piece 40.
- the chuck portion 46 is slid on the support member 47 until the inner surfaces 40x of the pair of intermediate portions 42 come into contact with each other.
- the loop part 41 which has a loop length of 60 mm can be formed.
- the loop length of the loop portion 41 is such that the position P1 where the surface on the loop portion 41 side of one second chuck 462 and the test piece 40 intersect, the surface on the loop portion 41 side of the other second chuck 462, and the test piece 40. Is the length of the test piece 40 between the position P2 and the position P2.
- the distance L3 described above is a value obtained by adding 2 ⁇ t to the length of the loop portion 41 when the thickness of the test piece 40 is ignored.
- t is the thickness of the second chuck 462 of the chuck portion 46.
- the posture of the chuck portion 46 is adjusted so that the protruding direction Y of the loop portion 41 with respect to the chuck portion 46 is horizontal.
- the posture of the chuck portion 46 supported by the support member 47 is adjusted by moving the support member 47 so that the normal direction of the support member 47 faces the horizontal direction.
- the protruding direction Y of the loop portion 41 coincides with the thickness direction of the chuck portion.
- the load cell 48 is prepared at a position away from the second chuck 462 by a distance Z1 in the projecting direction Y of the loop portion 41. In the present application, the distance Z1 is 50 mm.
- the load cell 48 is moved toward the loop portion 41 of the test piece 40 at the speed V by the distance Z2 shown in FIG.
- the distance Z2 is set so that the load cell 48 comes into contact with the loop portion 41 and then the load cell 48 pushes the loop portion 41 toward the chuck portion 46 as shown in FIGS.
- the distance Z2 is 40 mm.
- the distance Z3 between the load cell 48 and the second chuck 462 of the chuck portion 46 in a state where the load cell 48 pushes the loop portion 41 toward the chuck portion 46 is 10 mm.
- the speed V for moving the load cell 48 was 3.3 mm / second.
- the load cell 48 is moved by the distance Z ⁇ b> 2 toward the chuck portion 46, and the load cell 48 is added to the load cell 48 from the loop portion 41 in a state where the loop portion 41 of the test piece 40 is pushed in. After the load value stabilizes, record the load value.
- the load value thus obtained is employed as the loop stiffness of the film constituting the test piece 40.
- the environment at the time of measuring loop stiffness is a temperature of 23 ° C. and a relative humidity of 50%.
- the puncture strength of the high stiffness PET film is preferably 9.5 N or more, more preferably 10.0 N or more.
- the tensile strength of the high stiffness PET film in the flow direction is preferably 250 MPa or more, more preferably 280 MPa or more.
- the tensile strength of the high stiffness PET film in the vertical direction is preferably 250 MPa or more, and more preferably 280 MPa or more.
- the tensile elongation of the high stiffness PET film in the flow direction is preferably 130% or less, more preferably 120% or less.
- the tensile elongation of the high stiffness PET film in the vertical direction is preferably 120% or less, more preferably 110% or less.
- the value obtained by dividing the tensile strength of the high stiffness PET film by the tensile elongation is 2.0 [MPa /%] or more.
- the value obtained by dividing the tensile strength of the high stiffness film in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa /%] or more, more preferably 2.2 [MPa /%] or more. It is.
- 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, more preferably 2.0 [MPa /%] or more. .
- the tensile strength and tensile elongation can be measured according to JIS K7127.
- a tensile tester STA-1150 manufactured by Orientec Corporation can be used.
- As the test piece a high stiffness PET film cut into a rectangular film having a width of 15 mm and a length of 150 mm can be used.
- the distance at the start of measurement between the pair of chucks holding the test piece is 100 mm, and the tensile speed is 300 mm / min.
- the environmental temperature during the test is 25 ° C. and the relative humidity is 50%.
- the tensile strength and tensile elongation of the barrier laminate film A including the high stiffness PET film, the tensile strength and tensile elongation of the PBT film, and the tensile strength and tensile elongation of the barrier laminate film A including the PBT film are also high stiffness.
- the measurement is the same as in the case of PET film.
- the thermal contraction rate of the high stiffness PET film in the flow direction is preferably 0.7% or less, and more preferably 0.5% or less.
- the thermal contraction rate of the high stiffness PET film in the vertical direction is preferably 0.7% or less, and more preferably 0.5% or less.
- the heating temperature when measuring the heat shrinkage rate is 100 ° C., and the heating time is 40 minutes.
- the Young's modulus of the high stiffness PET film in the flow direction is preferably 4.0 GPa or more, more preferably 4.5 MPa or more.
- the Young's modulus of the high stiffness PET film in the vertical direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more.
- a PET film obtained by melting and molding polyethylene terephthalate is subjected to three times to 4.5 times at 90 ° C. to 145 ° C. in the flow direction and the vertical direction, respectively.
- stretched twice is implemented.
- a second stretching step is performed in which the plastic film is stretched 1.1 to 3.0 times at 100 to 145 ° C. in the flow direction and the vertical direction, respectively.
- heat setting is performed at a temperature of 190 ° C. to 220 ° C.
- a relaxation treatment treatment for reducing the film width
- a high stiffness PET film having the above-mentioned mechanical properties can be obtained by adjusting the stretching ratio, stretching temperature, heat setting temperature, and relaxation treatment rate.
- the loop stiffness of the barrier laminate film A in the flow direction (MD) and the vertical direction (TD) is preferably 0.0017 N or more.
- the puncture strength of the barrier laminate film A is preferably 9.5 N or more, more preferably 10.0 N or more.
- the tensile strength of the barrier laminate film A in the flow direction is preferably 250 MPa or more, and more preferably 280 MPa or more.
- the tensile strength of the barrier laminate film A in the vertical direction is preferably 250 MPa or more, and more preferably 280 MPa or more.
- the tensile elongation of the barrier laminate film A in the flow direction is preferably 130% or less, more preferably 120% or less.
- the tensile elongation of the barrier laminate film A in the vertical direction is preferably 120% or less, and more preferably 110% or less.
- a value obtained by dividing the tensile strength of the barrier laminate film A by the tensile elongation is 2.0 [MPa /%] or more.
- the value obtained by dividing the tensile strength of the barrier laminate film A in the vertical direction (TD) by the tensile elongation is preferably 2.0 [MPa /%] or more, more preferably 2.2 [MPa /%]. That is all.
- the value obtained by dividing the tensile strength of the barrier laminate film A in the flow direction (MD) by the tensile elongation is preferably 1.8 [MPa /%] or more, more preferably 2.0 [MPa /%] or more. It is.
- the thermal contraction rate of the barrier laminate film A in the flow direction is preferably 0.7% or less, and more preferably 0.5% or less.
- the thermal contraction rate of the barrier laminate film A in the vertical direction is preferably 0.7% or less, and more preferably 0.5% or less.
- the heating temperature when measuring the heat shrinkage rate is 100 ° C., and the heating time is 40 minutes.
- the Young's modulus of the barrier laminate film A in the flow direction is preferably 4.0 GPa or more, more preferably 4.5 MPa or more.
- the Young's modulus of the barrier laminate film A in the vertical direction is preferably 4.0 GPa or more, more preferably 4.5 GPa or more.
- the thickness of the plastic film as the plastic substrate of the present invention as described above is not particularly limited, and pretreatment or formation when a vapor deposition film is formed by a roller-type continuous vapor deposition film forming apparatus described later. Any film can be used as long as the film can be treated. From the viewpoints of flexibility and shape retention, the thickness is preferably 6 to 400 ⁇ m, and more preferably 9 to 200 ⁇ m. When the thickness of the plastic film is within the above range, it is easy to bend and is not broken during transportation, and is used continuously for the production of a laminated film having an aluminum oxide vapor deposition film with improved barrier properties. Easy to handle with vapor deposition film forming equipment.
- the aluminum oxide vapor deposition film is formed 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. It is preferable to perform an oxygen plasma pretreatment using.
- the oxygen plasma treatment of the present invention is an oxygen plasma treatment performed with a bias voltage perpendicular to the plastic substrate.
- the oxygen plasma pretreatment of the present invention is a pretreatment for strengthening and improving the adhesion between various resin films or sheets and aluminum oxide vapor deposition films in the present invention, as compared with the conventional method. This is performed in a film forming apparatus.
- a roller-type continuous vapor deposition film forming apparatus 10 suitably used for manufacturing a laminated film having an aluminum oxide vapor deposition film having a barrier property with improved adhesion according to the present invention includes, as shown in FIG.
- the partition walls 35a to 35c are formed on the surface.
- the partition walls 35a to 35c form a base material transfer chamber 12A, a plasma pretreatment chamber 12B, and a film formation chamber 12C.
- the plasma pretreatment chamber 12B and the film formation chamber are surrounded by the partition walls and the partition walls 35a to 35c. 12C is formed, and an exhaust chamber is further formed inside each chamber as necessary.
- a plastic substrate S to be pretreated is conveyed, and a part of the plasma pretreatment roller 20 that enables the plasma treatment is provided in the substrate conveyance chamber 12A.
- the plastic substrate S moves to the plasma pretreatment chamber 12B while being wound up.
- the plasma pretreatment chamber 12B and the film formation chamber 12C are provided in contact with the substrate transfer chamber 12A, and can be moved without the plastic substrate S being exposed to the atmosphere.
- the pretreatment chamber 12B and the substrate transport chamber 12A are connected by a rectangular hole, and a part of the plasma pretreatment roller 20 protrudes to the substrate transport chamber 12A side 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 move from the substrate transfer chamber 12A to the film forming chamber 12C through the gap.
- the same structure is 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 again to the base material transfer chamber 12A by the film forming roller 23, and rolls up the plastic base material S having a deposited film formed on one side in a roll shape.
- a take-up roller is provided so that the plastic substrate S on which the deposited film is formed can be taken up.
- the plasma pretreatment chamber 12B separates a space where plasma is generated from other regions, By being configured so that it can be evacuated efficiently, the plasma gas concentration can be easily controlled and productivity can be improved.
- the pretreatment pressure formed by reducing the pressure can be set and maintained at about 0.1 Pa to 100 Pa.
- oxygen plasma pretreatment is performed.
- the processing pressure is preferably 1 to 20 Pa.
- the conveyance speed of the plastic substrate S is not particularly limited, but can be set to at least 200 to 1000 m / min from the viewpoint of production efficiency, and in particular, in order to achieve the transformation rate of the transition region of the aluminum oxide deposited film of the present invention.
- the conveyance speed of the oxygen plasma pretreatment is preferably 300 to 800 m / min.
- the plasma pretreatment roller 20 constituting the plasma pretreatment apparatus prevents the plastic base material S from shrinking or damaging the base material due to heat during the plasma processing by the plasma pretreatment means, and oxygen plasma P to the plastic base material S. It is intended to be applied uniformly and over a wide range. 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 adjusting medium circulating in the pretreatment roller.
- the plasma pretreatment means includes a plasma supply means and a magnetic formation means.
- the plasma pretreatment means cooperates with the plasma pretreatment roller 20 to confine the oxygen plasma P in the vicinity of the surface of the plastic substrate S.
- the plasma pretreatment means is provided so as to cover a part of the pretreatment roller 20.
- the plasma supply means and the magnetic forming means constituting the plasma pretreatment means are arranged along the surface near the outer periphery of the pretreatment roller 20 to supply the pretreatment roller 20 and the plasma raw material gas, and the plasma P Are installed so as to form a gap sandwiched between the plasma supply nozzles 22a to 22c, which also serve as electrodes for generating plasma, and the magnetic forming means having the magnet 21 and the like in order to promote the generation of the plasma P.
- the plasma supply nozzles 22a to 22c are opened in the space of the gap, and the plasma is sprayed toward the substrate surface, the inside of the gap is set as a plasma formation region, and further, the pretreatment roller 20 and the plastic substrate S By forming a region having a high plasma density in the vicinity of the surface, the oxygen plasma pretreatment of the present invention for forming a plasma treatment surface on one surface 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 a raw material gas supply from the device.
- the plasma source gas to be supplied is supplied while oxygen alone or a mixed gas of oxygen gas and inert gas is measured from the gas reservoir through a flow rate controller while measuring the gas flow rate.
- an inert gas 1 type, or 2 or more types of mixed gas chosen from the group which consists of argon, helium, and nitrogen is mentioned.
- These supplied gases are mixed at a predetermined ratio as necessary, formed into a plasma raw material gas alone or a plasma forming mixed gas, and supplied to the plasma supply means.
- the single or mixed gas is supplied to the plasma supply nozzles 22a to 22c of the plasma supply means, and is supplied to the vicinity of 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 so that the oxygen plasma P can be uniformly diffused and supplied to the entire surface of the plastic substrate S.
- a uniform plasma pretreatment can be performed on a large area of the material S.
- the oxygen plasma pretreatment includes a mixing ratio of oxygen gas to the inert gas, and oxygen gas / inert gas is 6/1 to 1/1. 5/2 to 3/2 is more preferable.
- the mixing ratio By setting the mixing ratio to 6/1 to 1/1, the film formation energy of the deposited aluminum on the plastic film substrate is increased, and when it is further set to 5/2 to 3/2, formation of aluminum hydroxide is achieved. Is formed in the vicinity of the interface of the base material, that is, the rate of transformation of the transition region is lowered.
- the plasma supply nozzles 22a to 22c function as counter electrodes of the pretreatment roller 20, and are configured to have an electrode function.
- the plasma raw material gas supplied by the potential difference due to the frequency voltage or the like is excited, and plasma P is generated and supplied.
- the plasma supply means of the plasma pretreatment means is provided with a plasma pretreatment roller as a plasma power source, and an AC voltage with a frequency of 10 Hz to 2.5 GHz is applied between the counter electrode and the input power control or , Impedance control, etc. can be performed, and an arbitrary voltage can be applied between the plasma pretreatment roller 20 and a physical or chemical modification of the surface physical properties of the substrate can be performed.
- a power supply 32 that can apply a bias voltage for making the oxygen plasma P positive is provided.
- the plasma intensity per unit area employed in the present invention is 50 to 8000 W ⁇ sec / m 2 , and if it is 50 W ⁇ sec / m 2 or less, no effect of plasma pretreatment is observed, and 8000 W ⁇ sec / m 2.
- the substrate tends to deteriorate due to plasma such as consumption of the substrate, damage coloring, and firing.
- the plasma intensity of the oxygen plasma pretreatment is preferably 100 to 1000 W ⁇ sec / m 2 in order to obtain the transformation rate of the transition region of the vapor deposited aluminum oxide film of the present invention.
- the plasma pretreatment means has magnetic formation means.
- magnetic forming means an insulating spacer and a base plate are provided in a magnet case, and a magnet 21 is provided on the base plate.
- An insulating shield plate is provided on the magnet case, and an electrode is attached to the insulating shield plate. Therefore, the magnet case and the electrode are electrically insulated, and the electrode can be brought to an electrically floating level even if the magnet case is installed and fixed in the decompression chamber 12.
- a power supply wiring 31 is connected to the electrode, and the power supply wiring 31 is connected to a power source 32. Further, a temperature control medium pipe for cooling the electrode and the magnet 21 is provided inside the electrode. The magnet 21 is provided so that the oxygen plasma P from the plasma supply nozzles 22a to 22c, which are electrode and plasma supply means, is concentrated on the substrate S and applied. By providing the magnet 21, the reactivity in the vicinity of the substrate surface is increased, and a good plasma pretreatment surface can be formed at a high speed.
- the magnet 21 has a magnetic flux density of 10 gauss to 10000 gauss at the surface position of the plastic substrate S. If the magnetic flux density on the surface of the plastic substrate S is 10 gauss or more, the reactivity in the vicinity of the substrate surface can be sufficiently increased, and a good pretreatment surface can be formed at high speed.
- the plasma pretreatment is performed on a plastic substrate S having a large area of 1 m 2 or more.
- electrons, ions, and decomposition products of the base material are uniformly diffused over the entire electrode surface, and even when the plastic base material S has a large area, a uniform and stable target pretreatment can be performed with a desired plasma intensity. Is.
- the plastic substrate S treated with the special oxidation plasma is moved from the substrate transfer chamber 12A to the film formation chamber 12C by guide rolls 14a to 14d for guiding to the next film formation chamber 12C, and an aluminum oxide vapor deposition film is formed in the film formation section. Is formed.
- An aluminum oxide vapor deposition film is a thin film of an inorganic oxide containing aluminum oxide as a main component, and can contain an aluminum compound such as aluminum oxide or aluminum nitride, carbide, hydroxide alone or a mixture thereof. It is a layer containing aluminum as a main component. Further, the aluminum oxide vapor-deposited film contains the 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. Metal oxides such as these, or metal nitrides, carbides and mixtures thereof.
- the aluminum oxide vapor deposition film of the present invention has a transition rate of 60% or less in the transition region of the aluminum oxide vapor deposition film.
- the transition rate of the transition region of the aluminum oxide vapor deposition film is such that the aluminum oxide vapor deposition film 2 of the laminated film A having a barrier property is subjected to a time-of-flight secondary while repeating soft etching with a Cs (cesium) ion gun at a constant rate.
- a graph analysis diagram as shown in FIG. 3 is obtained by measuring ions derived from an aluminum deposited film and ions derived from a plastic substrate by using ion mass spectrometry (TOF-SIMS).
- etching is performed from the outermost surface of the aluminum oxide vapor-deposited film under certain conditions with Cs using a time-of-flight secondary ion mass spectrometer, and element bonding at the interface between the aluminum oxide vapor-deposited film and the plastic substrate is performed. And the element bond of the aluminum oxide vapor deposition film was measured, and respective graphs were obtained for the measured element and element bond (FIG.
- the transition rate of the transition region of the aluminum oxide vapor deposition film layer of the present invention is desirably 60% or less. If it exceeds 60%, 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 lowered.
- the hot water treatment gives a large mechanical and chemical stress to the interface between the plastic substrate and the aluminum oxide deposited film. This stress deteriorates the barrier property. This part is stressed because it is the most fragile in the laminated configuration. Therefore, in order to obtain retort resistance, it is important to cover the vapor deposition film with a strong interface with the substrate.
- Aluminum hydroxide has good adhesion to a plastic substrate due to its chemical structure, and has a high water vapor barrier property because it itself forms a network and is dense. However, the bonding structure based on the hydrogen bond between the aluminum hydroxide and the base material is easily broken microscopically against a powerful environment such as retorting.
- the present invention in order to make the transition region at the interface with the plastic substrate formed by aluminum hydroxide in the aluminum oxide vapor deposited film as narrow as possible, attention is paid to element-bonded Al 2 O 4 H, and the abundance thereof is controlled.
- element-bonded Al 2 O 4 H By suppressing the aluminum hydroxide generated from element-bound Al 2 O 4 H by hot water treatment and increasing the aluminum oxide film ratio with relatively little aluminum hydroxide, the microscopic deposited film by water molecules by retort treatment Destruction and interface destruction with plastic substrate were greatly suppressed. Thereby, the laminated film provided with the retort tolerance which has adhesiveness and barrier property which are not in the past can be provided.
- the aluminum oxide vapor deposition film of the present invention can be formed by depositing a vapor deposition film on the surface of a plastic substrate pretreated with oxygen plasma.
- a vapor deposition method for forming a vapor deposition film various vapor deposition methods can be applied among physical vapor deposition and chemical vapor deposition.
- the physical vapor deposition method can be selected from the group consisting of vapor deposition method, sputtering method, ion plating method, ion beam assist method, and cluster ion beam method.
- Chemical vapor deposition methods include plasma CVD method, plasma polymerization method, thermal method. It can be selected from the group consisting of CVD method and catalytic reaction type CVD method. In the present invention, a physical vapor deposition method is preferred.
- the vapor deposition film forming apparatus is disposed in the decompressed film forming chamber 12C, and conveys the plastic base material S with the processing surface of the plastic base material S preprocessed by the plasma pretreatment apparatus facing outside, A vapor deposition film is formed on the surface of the plastic substrate by evaporating the film formation roller 23 for film formation and the target of the film formation source 24 arranged opposite to the film formation roller.
- the vapor deposition film forming means 24 is a resistance heating method, using an aluminum metal wire with aluminum as an evaporation source, and oxidizing aluminum vapor by supplying oxygen to form an aluminum oxide vapor deposition film on the surface of the plastic substrate S. Form a film.
- a plurality of aluminum metal wires are arranged in the axial direction of the roller 23 in a boat-shaped (called “boat type”) vapor deposition vessel and heated by a resistance heating method.
- the thickness of the deposited aluminum oxide film formed as described above is preferably 3 to 50 nm, more preferably 9 to 30 nm. Within this range, the barrier property can be maintained. However, when the deposited film of aluminum oxide is very thin, it is difficult to calculate the transition region transformation rate by TOF-SIMS measurement.
- the barrier coating layer laminated on the surface of the aluminum oxide vapor deposition film of the present invention protects the aluminum oxide vapor deposition film mechanically and chemically and improves the barrier performance of the laminated film having barrier properties. .
- the barrier coating layer coated to form a barrier laminated film having retort resistance excellent in barrier properties will be described.
- the barrier coating layer is formed by applying a barrier coating agent on an aluminum oxide vapor deposition film and solidifying it.
- the barrier coating agent is composed of a metal alkoxide, a water-soluble polymer, a silane coupling agent added if necessary, a sol-gel method catalyst, an acid, and the like.
- a general formula R 1 nM (OR 2 ) m (wherein R 1 and R 2 represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n represents Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.
- the metal atom represented by M of the metal alkoxide examples thereof include silicon, zirconium, titanium, aluminum, and the like.
- the alkoxysilane include those represented by the general formula Si (ORa) 4 (wherein Ra represents a lower alkyl group).
- Ra methyl group, ethyl group, n-propyl group, n-butyl group, etc.
- 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 , etc.
- the alkoxide may be used in combination of two or more.
- silane coupling agent one having a reactive group such as a vinyl group, an epoxy group, a methacryl group or an amino group can be used.
- An organoalkoxysilane having an epoxy group is particularly suitable, for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, or ⁇ - (3,4-epoxycyclohexyl) ethyltri Methoxysilane or the like can be used.
- the above silane coupling agents may be used alone or in combination of two or more.
- a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer can be used alone, or a combination of a polyvinyl alcohol resin and an ethylene / vinyl alcohol copolymer can be used. can do.
- a polyvinyl alcohol-based resin is suitable.
- polyvinyl alcohol resin those obtained by saponifying polyvinyl acetate can be generally used.
- Polyvinyl alcohol resins include partially saponified polyvinyl alcohol resins in which several tens of percent of acetate groups remain, completely saponified polyvinyl alcohols in which no acetate groups remain, and modified polyvinyl alcohol resins in which OH groups have been modified. Good.
- the saponification degree as the polyvinyl alcohol-based resin it is necessary to use at least the saponification degree that improves the film hardness of the gas barrier coating film.
- the saponification degree is 70% or more.
- the degree of polymerization can be used as long as it is in the range used in the conventional sol-gel method (about 100 to 5000).
- a saponified product of a copolymer of ethylene and vinyl acetate that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer
- it is not particularly limited, and includes a partially saponified product in which several tens mol% of acetic acid groups remain to a complete saponified product in which only several mol% of acetic acid groups remain or no acetic acid groups remain.
- a saponification degree that is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more from the viewpoint of barrier properties.
- the barrier coating layer can be produced by the following method. First, the above metal alkoxide, a silane coupling agent to be added as necessary, a water-soluble polymer, a sol-gel method catalyst, an acid, and water as a solvent, an organic solvent such as methyl alcohol, ethyl alcohol, isopropanol and other organic solvents are mixed. Then, a barrier coating agent is prepared. Next, the barrier coating agent is applied onto the aluminum oxide vapor-deposited film by a conventional method and dried. By this drying step, polycondensation of the metal alkoxide, the silane coupling agent and the water-soluble polymer further proceeds to form a coating film.
- the above coating operation may be further repeated to form a plurality of coating films composed of two or more layers. Further, heat treatment is performed at 20 to 200 ° C. and a temperature below the melting point of the plastic substrate, preferably 50 to 180 ° C. for 3 seconds to 10 minutes. Thereby, the barrier coating layer by the barrier coating agent can be formed on the aluminum oxide vapor deposition film.
- the composition of the barrier coating agent is 100 to 500 parts by weight of a water-soluble polymer such as a polyvinyl alcohol-based resin and 1 to 20 parts by weight of a silane coupling agent with respect to 100 parts by weight of alkoxysilane. can do.
- a silane coupling agent is used in excess of 20 parts by weight, the rigidity and brittleness of the formed barrier coating film are increased, which is not preferable.
- the barrier coating layer formed as described above has a layer thickness of 100 to 500 nm. If it is this range, since a coat film does not crack and coats the vapor deposition film surface enough, it is preferred.
- the barrier laminate film of the present invention has good adhesion between the plastic substrate and the aluminum oxide vapor-deposited film and excellent gas barrier properties even after the hot water treatment, particularly after the high temperature hot water treatment retort treatment.
- the packaging material of the present invention is obtained by laminating at least one heat-sealable layer on a barrier laminate film, and an innermost layer with or without a heat-sealable thermoplastic resin interposed or interposed therebetween. And heat sealability is imparted.
- a function desired as a packaging material for example, a light-shielding layer for imparting light-shielding properties, a decorative property, a printing layer for imparting printing, a pattern layer, a laser printing layer, Various functional layers such as an absorptive / adsorptive layer that absorbs or absorbs odor can be added as a layer structure to form a packaging material.
- the heat-sealable thermoplastic resin may be a resin layer, film, or sheet that can be melted by heat and fused to each other.
- the heat-sealable thermoplastic resin may be a resin layer, film, or sheet that can be melted by heat and fused to each other.
- low-density polyethylene medium-density polyethylene, high-density polyethylene, linear (linear Shape)
- a film or sheet of low density fat may be used.
- low density polyethylene low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, polymethylpentene, polystyrene, ethylene-vinyl acetate copolymer, ⁇ -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, or the like It is preferable to use a sheet made of a film, and among them, as a layer in contact with the contents of food, etc., a kind of olefinic resin such as polyethylene and polypropylene having hygienic, heat resistant, chemical resistant and fragrance retention properties Or more resin or these films It is more preferable to use the sheets.
- the thickness is preferably about 3 to 100 ⁇ m, more preferably
- the barrier laminate film produced under the conditions shown in each of the above Examples or Comparative Examples was used as a measurement sample, and the transition rate, oxygen permeability, water vapor permeability, and adhesion strength of the transition region of the deposited film were as follows. Measured using the method.
- the transition rate of the transition region of the deposited film is determined by time-of-flight secondary ion mass spectrometry while performing soft etching on the surface of the barrier coating layer of the barrier laminate film at a constant rate with a Cs (cesium) ion gun.
- the graph analysis diagram of FIG. 3 is obtained by measuring ions derived from the barrier coating layer, ions derived from the vapor deposited aluminum oxide film, and ions derived from the plastic substrate using the method (TOF-SIMS).
- the unit of the vertical axis (intensity) of the graph is the measured ion intensity
- the unit of the horizontal axis (cycle) is the number of etchings.
- a time-of-flight secondary ion mass spectrometer used in the TOF-SIMS is manufactured by ION TOF, TOF.
- the measurement was performed under the following measurement conditions using SIMS5. (TOF-SIMS measurement conditions)
- an ion gun for measuring ions derived from aluminum oxide to be measured it is usually necessary to separate the ions derived from other components from a plurality of ions derived from aluminum oxide, and sufficient.
- each graph of the measured element and element bond graph 1 was obtained.
- the position where the strength of SiO 2 (mass number 59.96), which is a constituent element of the barrier coating layer, is half that of the barrier coating layer is defined as the interface between the barrier coating layer and the aluminum oxide vapor deposition film.
- the position that becomes half of the layer portion of C 6 (mass number 72.00), which is the constituent material of the plastic substrate, is the interface between the film substrate and the aluminum oxide vapor deposition film.
- the aluminum oxide vapor deposition film was an aluminum oxide vapor deposition film.
- a peak in a graph representing the measured element bond Al 2 O 4 H (mass number 118.93) is obtained, and the transition from the peak to the interface can be obtained.
- the barrier coating layer is made of a material having the same mass number as Al 2 O 4 H (mass number 118.93), it is necessary to separate the waveform of 118.93.
- reaction product AlSiO 4 and the hydroxide Al 2 O 4 H generated at the interface with the coating layer are generated at the interface between the barrier coating layer and the aluminum oxide layer. Separate 2 O 4 H. This corresponds appropriately depending on the material of the barrier coating layer.
- An example of waveform separation method is shown below. The profile having a mass number of 118.93 obtained by TOF-SIMS is subjected to nonlinear curve fitting using a Gaussian function, and overlapping peaks are separated using a least square method Levenberg Marquardt algorithm.
- the above operation was performed, and the rate of transformation of the transition region of the aluminum oxide vapor deposition film was determined as (transition region thickness from the peak of the element-bound Al 2 O 4 H to the interface / aluminum oxide vapor deposition film thickness) ⁇ 100 (%).
- adhesion strength between base material and 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 and dried, and a two-component curable polyurethane adhesive and a thickness are applied to an unstretched polypropylene film having a thickness of 70 ⁇ m.
- a laminated composite film was produced by dry laminating a 15 ⁇ m stretched nylon film and a laminated film.
- the sample was pulled at a speed of 50 mm / min, and the average value of the tensile stress in the stable region was measured. Peeling occurs between the plastics substrate of the barrier laminate film having the weakest adhesive strength in the laminated composite film and the aluminum oxide vapor deposition film, and the above measured values are obtained from the plastic substrate of the barrier laminate film and the aluminum oxide. The adhesion strength of the deposited film was taken.
- a two-component curable polyurethane adhesive is applied to the barrier coating layer side of the barrier laminate film and dried, and a two-component curable polyurethane adhesive and a thickness are applied to an unstretched polypropylene film having a thickness of 70 ⁇ m.
- a 15 ⁇ m stretched nylon film and a laminated film were dry laminated to produce a laminated composite film. 100 mL of water was poured into a four-sided pouch produced to B5 size using the above laminated composite film, and hydrothermal retort treatment was performed at 135 ° C. for 40 minutes.
- adhesion strength after semi-retort treatment> A laminated composite film was prepared in the configuration of the adhesion strength measurement (2), without using a nylon film, with a polypropylene film thickness of 70 ⁇ m. 100 mL of water was poured into a four-sided pouch made to B5 size using the above laminated composite film, and hydrothermal retort treatment was performed at 121 ° C. for 40 minutes. After the retort treatment, a sample cut into a strip of 15 mm width was prepared from a four-sided pouch with drained water. Using this sample, the adhesion strength was measured in the same manner as in the measurement of the adhesion strength (1).
- An aluminum oxide vapor deposition film having a thickness of 12 nm was formed on the PET film by a resistance heating method.
- ⁇ Formation of barrier coating layer> In a solution prepared by mixing 385 g of water, 67 g of isopropyl alcohol and 9.1 g of 0.5N hydrochloric acid and adjusting the pH to 2.2, 175 g of tetraethoxysilane as a metal alkoxide and glycidoxypropyltrimethoxysilane as a silane coupling agent 9. Solution A was prepared by mixing 2 g while cooling to 10 ° C. As a water-soluble polymer, a solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of polymerization of 2400 with a ken number of 99% or more, 324 g of water, and 17 g of isopropyl alcohol.
- a solution obtained by mixing the liquid A and the liquid B so as to have a weight ratio of 6.5: 3.5 was used as a barrier coating agent.
- the barrier coating agent prepared above was coated on the aluminum oxide vapor deposition film of the PET film by a spin coating method. Then, it heat-processed in 180 degreeC for 60 second (s), the barrier property coating layer about 400 nm thick was formed on the aluminum oxide vapor deposition film, and the barrier property laminated
- Example 2 A barrier laminate film was obtained in the same manner as in Example 1 except that the oxygen plasma pretreatment conditions were changed to 100 W ⁇ sec / m 2 .
- Example 3 A barrier laminate film was obtained in the same manner as in Example 1 except that a biomass-derived PET film having a thickness of 12 ⁇ m was used as the plastic substrate and the plasma pretreatment conditions were changed to 150 W ⁇ sec / m 2. It was.
- Example 4 The use of petroleum-derived polybutylene terephthalate film (hereinafter referred to as PBT film) having a thickness of 12 ⁇ m as the plastic substrate, the thickness of the aluminum oxide deposition film was changed to 10 nm, and the oxygen plasma pretreatment conditions were 150 W ⁇ sec. A barrier laminate film was obtained in the same manner as in Example 1 except that it was changed to / m 2 . However, the retort conditions were semi-retort conditions.
- PBT film petroleum-derived polybutylene terephthalate film
- Example 5 The same as Example 1 except that a petroleum-derived PET film having a thickness of 12 ⁇ m, whose moisture content has been increased by long-term storage under high humidity, and that the thickness of the aluminum oxide deposited film was changed to 14 nm. Thus, a barrier laminate film was obtained.
- Example 1 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 was 7 nm.
- Example 2 A barrier laminate film was obtained in the same manner as in Example 1 except that the oxygen plasma pretreatment was not performed.
- the barrier laminated film having a transition rate of 5% or more and 60% or less in the transition region of the aluminum oxide vapor deposition film of the present invention has an oxygen permeability even after good retorting. And water vapor permeability, and good adhesion.
- the element-bonded Al 2 O 4 H peak was too small to be hidden on the substrate interface side and could not be separated, so that the metamorphic rate of the transition region could not be calculated (0% or less) Numerical value).
- the water vapor barrier property after the retort treatment was poor, or the occurrence of delamination was observed due to the rapid deterioration of the peel strength.
- Experiment II an aluminum oxide vapor deposition film was formed using the film forming apparatus 60 shown in FIG.
- a high stiffness PET film having a loop stiffness of 0.0017 N / 15 mm or more and made of petroleum-derived PET was prepared. Specifically, XP-55 manufactured by Toray Industries, Inc. was used as a high stiffness PET film. The thickness of the high stiffness PET film was 16 ⁇ m. The measured value of the loop stiffness of the high stiffness PET film was 0.0021 N / 15 mm in both the flow direction and the vertical direction. The Young's modulus of the high stiffness PET film in the flow direction was 4.8 GPa, and the Young's modulus of the high stiffness polyester film in the vertical direction was 4.7 GPa.
- the tensile strength of the high stiffness PET film in the flow direction was 292 MPa, and the tensile strength of the high stiffness polyester film in the vertical direction was 257 MPa. Further, the tensile elongation of the high stiffness PET film in the flow direction was 107%, and the tensile elongation of the high stiffness polyester film in the vertical direction was 102%.
- the value obtained by dividing the tensile strength of the high stiffness PET film in the flow direction by the tensile elongation is 2.73 [MPa /%], and the tensile strength of the high stiffness PET film in the vertical direction is divided by the tensile elongation. The value is 2.52 [MPa /%].
- the thermal shrinkage rate of the high stiffness PET film in the flow direction and the vertical direction was both 0.4%.
- the puncture strength of the high stiffness PET film was measured according to JIS Z1707 7.4.
- Tensilon universal material testing machine RTC-1310 manufactured by A & D was used as a measuring instrument. Specifically, a semi-circular needle having a diameter of 1.0 mm and a tip shape radius of 0.5 mm is applied to the test piece of the high stiffness PET film in a fixed state from the outer surface 30y side at 50 mm / min (1 The maximum value of the stress until the needle penetrated the high stiffness PET film was measured at a speed of 50 mm per minute). About five or more test pieces, the maximum value of stress was measured, and the average value was defined as the piercing strength of the high stiffness PET film. The environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%. As a result, the piercing strength was 10.2N.
- Example B1 An example in which an aluminum oxide vapor deposition film 2 is formed on a plastic substrate 1 and a barrier coating layer 3 is formed on the aluminum oxide vapor deposition film 2 to produce a barrier laminate film A will be described.
- a roll around which a high stiffness PET film having a thickness of 16 ⁇ m and used in Example A1 described above was wound up was prepared as the plastic substrate 1. Subsequently, after performing the oxygen plasma treatment on the plastic substrate 1 using the above-described film forming apparatus 60 shown in FIGS. 6 and 10, the aluminum oxide having a thickness of 12 nm containing aluminum oxide is formed on the oxygen plasma treatment surface. A vapor deposition film 2 was formed.
- the oxygen plasma process and the film forming process will be described in detail.
- plasma is introduced from the plasma supply nozzle 72 to the surface of the plastic substrate 1 on which the aluminum oxide vapor deposition film 2 is provided in the plasma pretreatment chamber 62B under the following conditions, and is transported at a transport speed of 400 m / min.
- Plasma pretreatment was performed on the plastic substrate 1 to be formed. Thereby, the oxygen plasma processing surface was formed in the surface in which the aluminum oxide vapor deposition film 2 was provided among the plastic base materials 1.
- aluminum is used as a target on the oxygen plasma processing surface of the plastic substrate 1 in the film forming chamber 62C into which the plastic substrate 1 continuously conveyed from the plasma pretreatment chamber 62B is carried.
- An aluminum oxide vapor deposition film 2 containing aluminum oxide having a thickness of 12 nm was formed on the plastic substrate 1 by a vacuum vapor deposition method.
- a heating means of the vacuum deposition method a reactive resistance heating method was adopted.
- the film forming conditions are as follows. [Aluminum oxide deposition conditions] ⁇ Degree of vacuum: 8.1 ⁇ 10 ⁇ 2 Pa ⁇ Conveying speed: 400m / min ⁇ Oxygen gas supply amount: 20000 sccm
- a barrier coating layer 3 was formed on the aluminum oxide vapor deposition film 2. Specifically, first, 385 g of water, 67 g of isopropyl alcohol, and 9.1 g of 0.5N hydrochloric acid were mixed and adjusted to pH 2.2, and then 175 g of tetraethoxysilane as a metal alkoxide and glycid as a silane coupling agent. A solution A was prepared by mixing 9.2 g of xylpropyltrimethoxysilane while cooling to 10 ° C.
- a solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a degree of polymerization of 2400 with a ken number of 99% or more, 324 g of water, and 17 g of isopropyl alcohol. Then, A liquid and B liquid were mixed so that it might become a weight ratio 6.5: 3.5. The solution thus obtained was used as a coating agent for a gas barrier coating film.
- the above-prepared coating agent for gas barrier coating film was coated on the aluminum oxide vapor-deposited film 2 by a spin coating method. Then, the barrier coating layer 3 having a thickness of about 400 nm was formed on the aluminum oxide deposited film 2 by heat treatment in an oven at 180 ° C. for 60 seconds. Thus, the barriering laminated film A having the plastic substrate 1, the aluminum oxide vapor deposition film 2, and the barrier coating layer 3 was obtained.
- the barrier laminate film A of Example B1 was measured for modification rate, oxygen permeability, water vapor permeability, and loop stiffness.
- time-of-flight secondary ion mass spectrometry is applied to the surface of the barrier coating layer 3 of the barrier laminate film A while repeating soft etching with a Cs (cesium) ion gun at a constant rate.
- -SIMS time-of-flight secondary ion mass spectrometry
- ions derived from the barrier coating layer 3 ions derived from the aluminum oxide vapor deposition film 2
- ions derived from the plastic substrate 1 were measured.
- mass analysis of C 6 (mass number 72.00) derived from the resin film of the plastic substrate 1 and Al 2 O 4 H (mass number 118.93) ions derived from the aluminum oxide deposited film of the aluminum oxide deposited film 2 is performed. went.
- a time-of-flight secondary ion mass spectrometer used for TOF-SIMS is manufactured by ION TOF, TOF. The measurement was performed under the following measurement conditions using SIMS5. As a result, graphs as shown in FIG. 4 and FIG. 10 were obtained.
- the position at which the strength of SiO 2 (mass number 59.96), which is a constituent element of the barrier coating layer 3, is half the strength of the barrier coating layer 3 is indicated by the barrier coating layer 3 and the aluminum oxide vapor deposition film. Identified as the interface of 2. Further, the position where the strength of C 6 (mass number 72.00), which is a constituent material of the plastic substrate 1, is half the strength of the plastic substrate 1 is defined as the interface between the plastic substrate 1 and the aluminum oxide vapor deposition film 2. Identified. Further, the distance in the thickness direction between the two interfaces was adopted as the thickness of the aluminum oxide vapor deposition film 2.
- AlSiO 4 and hydroxide Al 2 O 4 H are generated at the interface between the barrier coating layer 3 and the aluminum oxide vapor deposition film 2, and between them, the plastic substrate 1 and the aluminum oxide vapor deposition film 2.
- Al 2 O 4 H present at the interface can be separated. As described above, the waveform separation can be appropriately handled according to the material of the barrier coating layer 3.
- waveform separation for example, a profile with a mass number of 118.93 obtained by TOF-SIMS is subjected to nonlinear curve fitting using a Gaussian function, and overlapping peaks are separated using a least square method Levenberg Marquardt algorithm. You may go.
- the above-mentioned rectangular test piece 40 was created from the barrier laminate film A of Example B1, and the loop stiffness in the flow direction and the vertical direction was measured.
- a measuring instrument No. manufactured by Toyo Seiki Co., Ltd.
- a 581 loop step tester (registered trademark) LOOP STIFFNESS TESTER DA type was used.
- the environment during the measurement was a temperature of 23 ° C. and a relative humidity of 50%.
- the loop stiffness in the flow direction of the barrier laminate film A was 0.0021 N
- the loop stiffness in the vertical direction was 0.0.0021N.
- the barrier laminate film A produced as described above and an unstretched polypropylene film (CPP film) having a thickness of 60 ⁇ m are bonded together by a dry laminating method via a two-component curable polyurethane adhesive, and the packaging material 8 was made.
- CPP film unstretched polypropylene film ZK207 manufactured by Toray Film Processing Co., Ltd. was used.
- the packaging material 8 was subjected to an aging treatment for 48 hours, and then a sample for evaluating the oxygen permeability before the retort treatment was prepared from the packaging material 8.
- a B5 size four-sided seal pouch was produced using the packaging material 8. Subsequently, 100 mL of water was injected into the inside of the four-way seal pouch from the opening at the top of the four-way seal pouch, and then a seal portion was formed on the upper portion to seal the four-way seal pouch. Subsequently, the four-side seal pouch was subjected to a retort treatment at 121 ° C. for 40 minutes. Then, the packaging material 8 which comprises the single side
- the sample before the retort treatment and the sample after the retort treatment are set so that the plastic plastic substrate 1 is on the oxygen supply side, and measured under a measurement condition of 23 ° C. and 100% RH under JIS K 7126 B.
- the oxygen permeability was measured according to the law.
- an oxygen permeability measuring device manufactured by Modern Control (MOCON) [model name: OX-TRAN 2/21]
- MOCON Modern Control
- the oxygen permeability of the sample after retort treatment was 0.20cc / m 2 / 24hr / atm .
- the oxygen transmission rate was 0.50cc / m 2 / 24hr / atm .
- the water vapor permeability was measured using the same sample as that used for measuring the oxygen permeability. Specifically, each sample was set so that the plastic substrate 1 would be on the sensor side, and under conditions of 37.8 ° C. and 100% RH, water vapor transmission was performed in accordance with the JIS K 7126 B method. The degree was measured.
- a water vapor permeability measuring device (a measuring machine manufactured by MOCON [model name, PERMATRAN 3/33]) was used. Result, the water vapor transmission rate of the retorting previous sample was 0.61g / m 2 / 24hr.
- water vapor permeability of the sample after retort treatment was 1.05g / m 2 / 24hr.
- water vapor transmission rate less than 1.5g / m 2 / 24hr.
- Example B2 The plastic substrate 1 and the aluminum oxide vapor deposition film provided on the plastic substrate 1 are the same as in Example B1 except that the barrier coating layer 3 is not formed on the aluminum oxide vapor deposition film 2. 2 was produced. Subsequently, in the same manner as in Example B1, two samples were prepared from the barrier laminate film A of Example B2, and for each of the two samples, the conversion rate of the aluminum oxide deposited film 2 was expressed as (transition region). Thickness W1 / thickness of aluminum oxide vapor deposition film 2) ⁇ 100 (%). As a result, the modification rate in the second sample was 37.8%, and the modification rate in the second sample was 42.2%.
- the above-described rectangular test piece 40 was prepared from the barrier laminate film A of Example B2, and the loop stiffness in the flow direction and the vertical direction was measured in the same manner as in Example B1.
- the loop stiffness in the flow direction of the barrier laminate film A was 0.0021N
- the loop stiffness in the vertical direction was 0.0021N.
- Example B1 As the plastic substrate 1, except for using a biaxially stretched PET film having a loop stiffness of less than 0.0017 N in both the flow direction and the vertical direction and made of petroleum-derived PET, and in the case of Example B1 Similarly, a barrier laminate film A comprising a plastic substrate 1, an aluminum oxide vapor deposition film 2 provided on the plastic substrate 1, and a barrier coating layer 3 provided on the aluminum oxide vapor deposition film 2. was made. Subsequently, in the same manner as in Example B1, the above-described rectangular test piece 40 was prepared from the barrier laminate film A of Comparative Example B1, and the loop stiffness in the flow direction and the vertical direction was measured. As a result, the loop stiffness in the flow direction of the barrier laminate film A was 0.0014N, and the loop stiffness in the vertical direction was 0.0016N.
- the present invention includes an aluminum oxide vapor deposition film having improved barrier properties and an improved adhesion property obtained by appropriately setting the transition rate of the transition region of the aluminum oxide vapor deposition film between the vapor deposition film and the plastic substrate.
- a barrier laminate film can be obtained.
- it can be a barrier laminated film having barrier properties and adhesion properties that prevent permeation of oxygen gas, water vapor, etc. ,
- Packaging materials for foods, pharmaceuticals, etc. that require laminated materials that can withstand processing associated with processing such as retort processing and sterilization processing, and use that requires durability and barrier properties such as packaging for electrical and electronic parts, protective sheets, etc. It can be applied to industrial materials in fields with severe environments.
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Abstract
Description
そのため、プラスチック基材と、酸化ケイ素蒸着膜あるいは酸化アルミニウム蒸着膜等の蒸着膜との層間において、高温多湿の厳しい環境下等において、しばしば層間剥離現象が生じ、更に、クラックやピンホ-ル等も発生する。
その結果、本来のバリア性能を著しく棄損し、そのバリア性能を保持することが極めて困難であるという問題がある。
また、上記プラズマ処理は空気中で発生させたプラズマ雰囲気下をフィルムが通過するだけであることから基材と蒸着膜間で十分な高温多湿の厳しい環境下等における密着性が得られていないのが実情である。
前記プラズマRIE法は、基材の表面に官能基を持たせるなどの化学的効果と、表面をイオンエッチングして不純物等を飛ばし平滑化するという物理的効果の、2つの効果を同時に得ることで密着性を発現するものである。
しかし、RIE法では、プラスチック基材上に官能基を持たせるため、界面での加水分解等を生じる耐水、耐熱水性が依然として不十分である。また、RIE法で十分な密着性を得るためには、一定値以上のEd値(=プラズマ密度×処理時間)が必要である。
同法で一定値以上のEd値を得るためにはプラズマ密度を高くする方法と、処理時間を長くする方法が考えられるが、プラズマ密度を高くする場合は、高出力の電源が必要であり、基材のダメージが大きくなる問題があり、処理時間を長くする場合は、生産性の低下が問題となる(特許文献4、特許文献5参照)。
一方で、水酸化アルミニウムは、その化学構造によりプラスチック基材との密着性がよく、またそれ自体がネットワークを作り緻密なため、高い水蒸気バリア性を有する。しかし、レトルト処理のような強力な環境に対して、水酸化アルミニウムと基材との水素結合に基づく結合構造は微視的に崩れやすい。また、水酸化アルミニウムのネットワークに対しても、水分子と水酸化アルミニウムの粒界面の親和性から膜中に浸透しやすい。
本発明は、上記の課題及び知見に鑑みてなされたものであり、その目的とするところは、熱水処理後であっても、プラスチック基材と酸化アルミニウム蒸着膜との密着性が良好で、かつバリア性に優れた蒸着膜を有する積層フィルム、さらには該積層フィルムを含み、いわゆる耐レトルト性に優れた酸化アルミニウム蒸着膜を備えるバリア性積層フィルム並びに該バリア性積層フィルムを用い、密着性及びバリア性に優れた耐レトルト性に優れた包装材料を提供することである。
したがって、本発明の酸化アルミニウム蒸着膜は、プラスチック基材との界面における密着性を改善できるだけでなく、バリア性能においてもレトルト処理後の耐湿熱性、耐熱水性に優れており耐レトルト性を改善できるものである。
1.プラスチック基材の表面に酸化アルミニウムを主成分とする酸化アルミニウム蒸着膜を形成し、前記酸化アルミニウム蒸着膜の表面にバリア性被覆層が積層されてなる、バリア性を備える積層フィルムにおいて、
前記酸化アルミニウム蒸着膜中には、前記プラスチック基材の表面と前記酸化アルミニウム蒸着膜との密着強度を規定する遷移領域が形成されており、該遷移領域は、飛行時間型二次イオン質量分析法(TOF-SIMS)を用いてエッチングを行うことで検出される、水酸化アルミニウムに変成する元素結合Al2O4Hを含み、前記バリア性被覆層と前記酸化アルミニウム蒸着膜とをTOF-SIMSを用いてエッチングを行うことで規定される前記酸化アルミニウム蒸着膜に対する、TOF-SIMSを用いて規定される該変成される前記遷移領域の割合により定義される遷移領域の変成率が、5%以上、60%以下である、上記バリア性積層フィルム。
2.前記プラスチック基材が、ポリエチレンテレフタレートフィルムである、上記1に記載のバリア性積層フィルム。
3.前記プラスチック基材が、リサイクルポリエチレンテレフタレートフィルムを含む、上記1に記載の積層フィルム。
4.前記プラスチック基材が、ポリブチレンテレフタレートフィルムである、上記1に記載のバリア性積層フィルム。
5.前記プラスチック基材が、バイオマス由来のポリエステルフィルムである、上記1に記載のバリア性積層フィルム。
6.前記プラスチック基材が、高スティフネスPETフィルムである、上記1に記載のバリア性積層フィルム。
7.前記プラスチック基材の表面が、酸素プラズマ処理面である、上記1~6のいずれかに記載のバリア性積層フィルム。
8.酸素プラズマ処理面にインラインで酸化アルミニウム蒸着膜が積層された、上記7に記載のバリア性積層フィルム。
9.バリア性被覆層が、金属アルコキシドと水溶性高分子の混合溶液を塗布し、加熱乾燥してなる層である、上記1~8の何れかに記載のバリア性積層フィルム。
10.バリア性被覆層が、金属アルコキシドとシランカップリング剤と水溶性高分子の混合溶液を塗布し、加熱乾燥してなる層である、上記1~9のいずれかに記載のバリア性積層フィルム。
11.上記1~10のいずれかに記載のバリア性積層フィルムに、ヒートシール性を有する熱可塑性樹脂が積層されてなる、包装材料。
12.レトルト殺菌用包装に用いられる、上記11に記載の包装材料。
本発明のバリア性積層フィルムは、プラスチック基材と酸化アルミニウム蒸着膜との界面における密着強度が、ハイレトルト処理、セミレトルト処理後においても、2.1N/15mm以上で、かつ、ハイレトルト処理、セミレトルト後の酸素透過度、水蒸気透過度が、それぞれ、0.2cc/m2・24hr以下、0.9g/m2・24hr以下のバリア性能を有し、耐レトルト性に優れている。
図1aは、本発明のバリア性積層フィルムの一例を示す断面図であり、図1bは基材層が多層で構成されている積層フィルムの一例を示す断面図であり、図2は、本発明のバリア性積層フィルムの酸化アルミニウム蒸着膜を成膜するに好適なローラー式連続蒸着成膜装置の構成を模式的に示す図である。なお、バリア性被覆層を形成するために、バリアコート剤塗布装置が蒸着膜成膜装置に連続して配置されるが、公知のローラー塗布装置を連設するものであり、ここでは図示するのを省略した。
ポリブチレンテレフタレートフィルムは、熱変形温度が高く、機械的強度、電気的特性にすぐれ、成型加工性も良いことなどから、食品などの内容物を収容する包装袋に用いると、レトルト処理を施す際に包装袋が変形したり、その強度が低下したりすることを抑制することができる。
また、ポリブチレンテレフタレートフィルムは、高温高湿度環境下で加水分解するためレトルト処理後の密着強度、バリア性の低下がみられるが、ナイロンに比べて水分を吸収しにくいという特性を有する。このため、ポリブチレンテレフタレートフィルムを包装用材料の外面に配置した場合であっても、包装袋の包装用材料間のラミネート強度が低下してしまうことを抑制することができる。このような性質を持つので、ポリブチレンテレフタレートフィルムをレトルト包装袋に用いると、従来のポリエチレンテレフタレートフィルムとナイロンフィルムの貼り合せ包装材に置き換えることができることから、好ましく用いられる。
主たる構成成分として用いるPBTは、ジカルボン酸成分として、テレフタル酸が90モル%以上であることが好ましく、より好ましくは95モル%以上であり、さらに好ましくは98モル%以上であり、最も好ましくは100モル%である。グリコール成分として1,4-ブタンジオールが90モル%以上であることが好ましく、より好ましくは95モル%以上であり、さらに好ましくは97モル%以上である。
バイオマス由来のポリエステルフィルムは、ジオール単位とジカルボン酸単位とからなるポリエステルを主成分として含んでなる樹脂組成物からなり、前記樹脂組成物はジオール単位がバイオマス由来のエチレングリコールで、ジカルボン酸単位が化石燃料由来のジカルボン酸の樹脂組成物が好ましく、さらに好ましくはバイオマス由来のエチレングリコールと化石燃料由来のテレフタル酸の樹脂組成物である。
本発明において、「バイオマス度」とは、バイオマス由来成分の重量比率を示すものである。PETを例にとると、PETは、2炭素原子を含むエチレングリコールと8炭素原子を含むテレフタル酸とがモル比1:1で重合したものであるため、エチレングリコールとしてバイオマス由来のもののみを使用した場合、PET中のバイオマス由来成分の重量比率は31.25%であるため、バイオマス度は31.25%となる(バイオマス由来のエチレングリコール由来の分子量/ポリエステルの重合1単位の分子量=60÷192)。
また、化石燃料由来のポリエステルのバイオマス由来成分の重量比率は0%であり、化石燃料由来のポリエステルのバイオマス度は0%となる。本発明において、プラスチック基材中のバイオマス度は、5.0%以上であることが好ましく、さらに好ましくは10.0%以上であり、好ましくは30.0%以下である。
本発明のプラスチック基材として、メカニカルリサイクルによりリサイクルされたポリエチレンテレフタレート(以下、ポリエチレンテレフタレートをPETとも記す)を含むものを使用できる。
具体的には、プラスチック基材は、PETボトルをメカニカルリサイクルによりリサイクルしたPETを含み、このPETは、ジオール成分がエチレングリコールであり、ジカルボン酸成分がテレフタル酸およびイソフタル酸を含む。
イソフタル酸成分の含有量が0.5モル%未満であると柔軟性が向上しない場合があり、一方、5モル%を超えるとPETの融点が下がり耐熱性が不十分となる場合がある。
また、重縮合反応は、重合触媒の存在下で行うことが好ましい。重合触媒の添加時期は、重縮合反応以前であれば特に限定されず、原料仕込み時に添加しておいてもよく、減圧開始時に添加してもよい。
具体的には、固相重合は、PETをチップ化して乾燥させた後、100℃以上180℃以下の温度で1時間から8時間程度加熱してPETを予備結晶化させ、続いて、190℃以上230℃以下の温度で、不活性ガス雰囲気下または減圧下において1時間~数十時間加熱することにより行われる。
ヴァージンPETとしては、上記したようなジオール成分がエチレングリコールであり、ジカルボン酸成分がテレフタル酸およびイソフタル酸を含むPETであってもよく、また、ジカルボン酸成分がイソフタル酸を含まないPETであってもよい。また、樹脂基材層は、PET以外のポリエステルを含んでいてもよい。例えば、ジカルボン酸成分として、テレフタル酸およびイソフタル酸などの芳香族ジカルボン酸以外にも、脂肪族ジカルボン酸等が含まれていてもよい。
図1bに示すように、プラスチック基材に上記したようなリサイクルPETを用いる場合は、第1層1a、第2層1b、および第3層1cの3層を備えた樹脂基材としてもよい。
この場合、第2層1bをリサイクルPETのみから構成される層またはリサイクルPETとヴァージンPETとの混合層とし、第1層1aおよび第3層1cは、ヴァージンPETのみから構成される層とすることが好ましい。
また、樹脂基材層は、図1bに示す第1層1aを設けることなく、第2層1bおよび第3層1cの2層を備えたプラスチック基材としてもよい。さらに、プラスチック基材は、図1bに示す第3層1cを設けることなく、第1層1aおよび第2層1bの2層を備えたプラスチック基材としてもよい。これらの場合においても、第2層1bをリサイクルPETのみから構成される層またはリサイクルPETとヴァージンPETとの混合層とし、第1層1aおよび第3層1cは、ヴァージンPETのみから構成される層とすることが好ましい。
高スティフネスPETフィルムの突き刺し強度は、好ましくは9.5N以上であり、より好ましくは10.0N以上である。
流れ方向における高スティフネスPETフィルムの引張伸度は、好ましくは130%以下であり、より好ましくは120%以下である。垂直方向における高スティフネスPETフィルムの引張伸度は、好ましくは120%以下であり、より好ましくは110%以下である。
好ましくは、上述のとおり、少なくとも1つの方向において、高スティフネスPETフィルムの引張強度を引張伸度で割った値が2.0〔MPa/%〕以上である。例えば、垂直方向(TD)における高スティフネスフィルムの引張強度を引張伸度で割った値は、好ましくは2.0〔MPa/%〕以上であり、より好ましくは2.2〔MPa/%〕以上である。流れ方向(MD)における高スティフネスフィルムの引張強度を引張伸度で割った値は、好ましくは1.8〔MPa/%〕以上であり、より好ましくは2.0〔MPa/%〕以上である。
引張強度及び引張伸度は、JIS K7127に準拠して測定され得る。測定器としては、オリエンテック社製の引張試験機 STA-1150を用いることができる。試験片としては、高スティフネスPETフィルムを幅15mm、長さ150mmの矩形状のフィルムに切り出したものを用いることができる。試験片を保持する一対のチャックの間の、測定開始時の間隔は100mmであり、引張速度は300mm/分である。試験の際の環境温度は25℃であり、相対湿度は50% である。高スティフネスPETフィルムを備えるバリア性積層フィルムAの引張強度及び引張伸度、PBTフィルムの引張強度及び引張伸度、及びPBTフィルムを備えるバリア性積層フィルムAの引張強度及び引張伸度も、高スティフネスPETフィルムの場合と同様に測定される。
流れ方向における高スティフネスPETフィルムのヤング率は、好ましくは4.0GPa以上であり、より好ましくは4.5MPa以上である。垂直方向における高スティフネスPETフィルムのヤング率は、好ましくは4.0GPa以上であり、より好ましくは4.5GPa以上である。
バリア性積層フィルムAの流れ方向(MD)及び垂直方向(TD)におけるループスティフネスは、好ましくは0.0017N以上である。
バリア性積層フィルムAの突き刺し強度は、好ましくは9.5N以上であり、より好ましくは10.0N以上である。
流れ方向におけるバリア性積層フィルムAの引張強度は、好ましくは250MPa以上であり、より好ましくは280MPa以上である。垂直方向におけるバリア性積層フィルムAの引張強度は、好ましくは250MPa以上であり、より好ましくは280MPa以上である。
流れ方向におけるバリア性積層フィルムAの引張伸度は、好ましくは130%以下であり、より好ましくは120%以下である。垂直方向におけるバリア性積層フィルムAの引張伸度は、好ましくは120%以下であり、より好ましくは110%以下である。
好ましくは、少なくとも1つの方向において、バリア性積層フィルムAの引張強度を引張伸度で割った値が2.0〔MPa/%〕以上である。例えば、垂直方向(TD)におけるバリア性積層フィルムAの引張強度を引張伸度で割った値は、好ましくは2.0〔MPa/%〕以上であり、より好ましくは2.2〔MPa/%〕以上である。流れ方向(MD)におけるバリア性積層フィルムAの引張強度を引張伸度で割った値は、好ましくは1.8〔MPa/%〕以上であり、より好ましくは2.0〔MPa/%〕以上である。
流れ方向におけるバリア性積層フィルムAの熱収縮率は、0.7%以下であることが好ましく、0.5%以下であることがより好ましい。垂直方向におけるバリア性積層フィルムAの熱収縮率は、0.7%以下であることが好ましく、0.5%以下であることがより好ましい。熱収縮率を測定する際の加熱温度は100℃であり、加熱時間は40分である。
流れ方向におけるバリア性積層フィルムAのヤング率は、好ましくは4.0GPa以上であり、より好ましくは4.5MPa以上である。垂直方向におけるバリア性積層フィルムAのヤング率は、好ましくは4.0GPa以上であり、より好ましくは4.5GPa以上である。
プラスチックフィルムの厚さが前記範囲内にあると、曲げやすい上に搬送中に破けることもなく、密着性が改善されたバリア性を備える酸化アルミニウム蒸着膜を有する積層フィルムの製造に用いられる連続蒸着膜成膜装置で取り扱いやすい。
(酸素プラズマ前処理)
前処理ローラー20は、前処理ローラー内を循環させる温度調節媒体の温度を調整することにより、-20℃から100℃の間で、一定温度に調節することが可能であることが好ましい。
それにより、該空隙の空間にプラズマ供給ノズル22a~22cを開口させてプラズマを基材表面に向かって噴射し、該空隙内をプラズマ形成領域とし、さらに、前処理ローラー20とプラスチック基材Sの表面近傍にプラズマ密度の高い領域を形成することで、プラスチック基材Sの片面にプラズマ処理面を形成する本発明の酸素プラズマ前処理が行えるように構成されている。
そのノズル開口は前処理ローラー20上のプラスチック基材Sに向けられ、プラスチック基材Sの表面全体に均一に酸素プラズマPを拡散、供給させることが可能となるように配置、構成され、プラスチック基材Sの大面積の部分に均一なプラズマ前処理が可能となる。
混合比率を6/1~1/1とすることで、プラスチックフィルム基材上での蒸着アルミニウムの膜形成エネルギーが増加し、更に5/2~3/2とすることで、水酸化アルミニウムの形成が基材の界面近傍で形成される、すなわち該遷移領域の変成率が低下する。
本発明で採用する単位面積あたりのプラズマ強度として50~8000W・sec/m2であり、50W・sec/m2以下では、プラズマ前処理の効果がみられず、また、8000W・sec/m2以上では、基材の消耗、破損着色、焼成などプラズマによる基材の劣化が起きる傾向にある。特に、本発明の酸化アルミウム蒸着膜の遷移領域の変成率とするため酸素プラズマ前処理のプラズマ強度としては、100~1000W・sec/m2が好ましい。プラスチック基材に垂直にバイアス電圧を持ち上記プラズマ強度を与えることにより、安定的に酸化アルミニウム蒸着膜との密着性等を従来法より強化される。
したがって、マグネットケースと電極は電気的に絶縁されており、マグネットケースを減圧チャンバ12内に設置、固定しても電極は電気的にフローティングレベルとすることが可能である。
マグネット21は、電極兼プラズマ供給手段であるプラズマ供給ノズル22a~22cからの酸素プラズマPが基材Sに集中して適用するために設けられる。マグネット21を設けることにより、基材表面近傍での反応性が高くなり、良好なプラズマ前処理面を高速で形成することが可能となる。
特殊酸化プラズマ処理されたプラスチック基材Sは、次の成膜室12Cに導くためのガイドロール14a~14dにより基材搬送室12Aから成膜室12Cに移動し、成膜区画で酸化アルミニウム蒸着膜が形成される。
さらに、酸化アルミニウム蒸着膜は、前記アルミニウム化合物を主成分として含み、ケイ素酸化物、ケイ素窒化物、ケイ素酸化窒化物、ケイ素炭化物、酸化マグネシウム、酸化チタン、酸化スズ、酸化インジウム、酸化亜鉛、酸化ジルコニウム等の金属酸化物、またはこれらの金属窒化物、炭化物及びその混合物などを含むことができる。
酸化アルミニウム蒸着膜の遷移領域の変成率は、バリア性を有する積層フィルムAの酸化アルミニウム蒸着膜2に対し、Cs(セシウム)イオン銃により一定の速度でソフトエッチングを繰り返しながら、飛行時間型二次イオン質量分析法(TOF-SIMS)を用いて、アルミニウム蒸着膜由来のイオンと、プラスチック基材に由来するイオンを測定することにより図3のようなグラフ解析図が得られるものである。
具体的には、飛行時間型二次イオン質量分析計を用いてCsにより、一定の条件で酸化アルミニウム蒸着膜の最表面からエッチングを行い、酸化アルミニウム蒸着膜とプラスチック基材との界面の元素結合及び酸化アルミニウム蒸着膜の元素結合を測定し、測定された元素および元素結合についてそれぞれのグラフを得(図3 グラフ解析図)、
1)元素C6のグラフの強度が半分になる位置を、プラスチック基材と酸化アルミニウムの界面として、表面から界面までを酸化アルミニウム蒸着膜として求め、
2)元素結合Al2O4Hを表すグラフにおけるピークを求め、そのピークから界面までを遷移領域とし、求め、
3)(元素結合Al2O4Hのピークから界面までの遷移領域厚/酸化アルミニウム蒸着膜厚)×100(%)を、遷移領域の変成率であると定め、求めたものである。
従って、レトルト耐性を得るためには、基材との界面を強固に、蒸着膜を被覆することが重要である。
水酸化アルミニウムは、その化学構造によりプラスチック基材との密着性がよく、またそれ自体がネットワークを作り緻密なため、高い水蒸気バリア性を有する。しかし、レトルト処理のような強力な環境に対して、水酸化アルミと基材との水素結合に基づく結合構造は微視的に崩れやすい。また、水酸化アルミニウムのネットワークに対しても、水分子と水酸化アルミニウムの粒界面の親和性から膜中に浸透しやすい。
本発明では、酸化アルミニウム蒸着膜における水酸化アルミニウムが形成するプラスチック基材との界面における遷移領域を極力狭くするために、元素結合Al2O4Hに注目し、その存在量を制御することで、熱水処理によって元素結合Al2O4Hから発生する水酸化アルミニウムを抑え、相対的に水酸化アルミニウムが少ない酸化アルミニウム膜比率を上げることにより、レトルト処理による水分子による微視的な蒸着膜破壊、プラスチック基材との界面破壊を大きく抑制した。それにより従来にない密着性、バリア性を有するレトルト耐性を備える積層フィルムを提供することができる。
物理蒸着法としては、蒸着法、スパッタリング法、イオンプレーティング法、イオンビームアシスト法、クラスターイオンビーム法からなる群から選ぶことができ、化学蒸着法としては、プラズマCVD法、プラズマ重合法、熱CVD法、触媒反応型CVD法からなる群から選ぶことができる。本発明においては、物理蒸着法の蒸着法が好適である。
蒸着膜成膜手段24は抵抗加熱方式であり、アルミニウムを蒸発源としてアルミニウムの金属線材を用い、 酸素を供給ししてアルミニウム蒸気を酸化しつつ、プラスチック基材Sの表面に酸化アルミニウム蒸着膜を成膜させる。
本発明の酸化アルミニウム蒸着膜の表面上に積層されるバリア性被覆層は、酸化アルミニウム蒸着膜を機械的・化学的に保護するとともに、バリア性を有する積層フィルムのバリア性能を向上させるものである。以下、バリア性に優れたレトルト耐性を備えるバリア性積層フィルムを形成するためコートされるバリア性被覆層について説明する。
上記のアルコキシシランとしては、例えば、一般式Si(ORa)4(ただし、式中、Raは、低級アルキル基を表す。)で表されるものである。上記において、Raとしては、メチル基、エチル基、n-プロピル基、n-ブチル基、その他等が用いられる。上記のアルコキシシランの具体例としては、例えば、テトラメトキシシラン Si(OCH3)4、テトラエトキシシラン Si(OC2H5)4、テトラプロポキシシラン Si(OC3H7)4、テトラブトキシシラン Si(OC4H9)4、その他等を使用することができる。上記アルコキシドは、2種以上を併用してもよい
例えば、酢酸基が数十モル%残存している部分ケン化物から、酢酸基が数モル%しか残存していないかまたは酢酸基が残存しない完全ケン化物まで含み、特に限定されるものではない。ただし、バリア性の観点から好ましいケン化度は、80モル%以上、より好ましくは、90モル%以上、さらに好ましくは、95モル%以上であるものを使用することが好ましい。
まず、上記金属アルコキシド、必要に応じて添加するシランカップリング剤、水溶性高分子、ゾルゲル法触媒、酸、及び溶媒としての水、メチルアルコール、エチルアルコール、イソプロパノール等のアルコール等の有機溶媒を混合し、バリアコート剤を調製する。
次いで、酸化アルミニウム蒸着膜の上に、常法により、上記のバリアコート剤を塗布し、乾燥する。この乾燥工程によって、上記金属アルコキシド、シランカップリング剤および水溶性高分子の重縮合が更に進行し、塗膜が形成される。第一の塗膜の上に、更に上記塗布操作を繰り返して、2層以上からなる複数の塗膜を形成してもよい。
さらに、20~200℃、かつプラスチック基材の融点以下の温度、好ましくは、50~180℃の範囲の温度で、3秒~10分間加熱処理する。これによって、酸化アルミニウム蒸着膜の上に、上記バリアコート剤によるバリア性被覆層を形成することができる。
本発明のバリア性積層フィルムは、熱水処理、特に高温熱水処理のレトルト処理後においても、プラスチック基材と酸化アルミニウム蒸着膜との密着性が良好で、かつガスバリア性にも優れているので、食品用のレトルト包装材、医療用の高温熱水処理包装材だけでなく、ペットフード等のレトルト処理を行う内容物の包装材として好適に使用できる。
本発明の包装材料は、バリア性積層フィルムに少なくとも1層のヒートシール可能な層を積層したものであって、ヒートシール可能な熱可塑性樹脂が接着層を介して、あるいは介することなく、最内層として積層され、ヒートシール性が付与されたものである。包装材料としは、さらに必要に応じて、包装材料として付与したい機能、例えば、遮光性を付与するための遮光性層、装飾性、印字を付与するための印刷層、絵柄層、レーザー印刷層、臭気を吸収又は吸着する吸収性・吸着性層など各種機能層を層構成として追加し、包装材料とすることもできる。
そして、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状(線状)低密度ポリエチレン、ポリプロピレン、ポリメチルペンテン、ポリスチレン、エチレン-酢酸ビニル共重合体、α-オレフィン共重合体、アイオノマー樹脂、エチレンーアクリル酸共重合体、エチレンーアクリル酸エチル共重合体、エチレンーメタクリル酸メチル共重合体、エチレンープロピレン共重合体、エラストマー等の樹脂の一種ないしそれ以上からなる樹脂ないしはこれらをフィルム化したシートを使用することが好ましく、中でも、食品等の内容物に接する層としては、衛生性、耐熱性、耐薬品性、保香性を有するポリエチレン、ポリプロピレン等のオレフィン系樹脂の一種ないしそれ以上からなる樹脂ないしはこれらをフィルム化したシートを使用することがより好ましい。
その厚さとしては3~100μm位が好ましく、15~70μm位がより好ましい。
上記各実施例又は比較例に示した条件下で製造したバリア性積層フィルムを測定用のサンプルとし、蒸着膜の遷移領域の変成率、酸素透過度、水蒸気透過度、及び密着強度について、下記の方法を用いて測定した。
本発明において、蒸着膜の遷移領域の変成率は、バリア性積層フィルムのバリア性被覆層表面にCs(セシウム)イオン銃により一定の速度でソフトエッチングを繰り返しながら、飛行時間型二次イオン質量分析法(TOF-SIMS)を用いて、バリア性被覆層由来のイオンと、酸化アルミウム蒸着膜由来のイオンと、プラスチック基材に由来するイオンを測定することにより図3のグラフ解析図が得られる。ここで、グラフの縦軸の単位(intensity)は、測定されたイオンの強度、横軸の単位(cycle)は、エッチングの回数である。
上記TOF-SIMSに用いられる飛行時間型二次イオン質量分析計としてはION TOF社製、TOF.SIMS5を用い、下記測定条件で測定を行なった。
(TOF-SIMS測定条件)
・一次イオン種類:Bi3 ++(0.2pA,100μs)、測定面積:150×150μm2
・Et銃種類:Cs(1keV、60nA)、Et面積:600×600μm2、Etレート:3sec/Cycle
なお、測定対象となる酸化アルミニウム由来のイオンを測定するためにイオン銃としては、通常、複数ある酸化アルミニウム由来のイオンの中から他の成分由来のイオンとの切り分けが必要であり、且つ十分な強度を有するものを選択する必要があること及び、特に元素結合Al2O4Hの濃度分布に近似換算できる深さ分布を得る目的から、本発明においては、Csイオンを選択することとした。
次に、測定された元素結合Al2O4H(質量数118.93)を表すグラフにおけるピークを求め、そのピークから界面までを遷移領域とし、求めることができる。
ただし、バリア性被覆層の成分がAl2O4H(質量数118.93)と同じ質量数の材料で構成させる場合、118.93の波形を分離する必要がある。
今回のケースでは、バリア性被覆層と酸化アルミ層の界面に、被覆層との界面に生じる反応物AlSiO4と、水酸化物Al2O4Hが生じるため、それらとフィルム界面に存在するAl2O4Hを分離する。これはバリア性被覆層の材料によって適宜対応する。
波形分離の方法例を以下に示す。
TOF-SIMSで得られた、質量数118.93のプロファイルを、Gaussian関数を用いて非線形のカーブフィッティングを行い最小二乗法Levenberg Marquardt アルゴリズムを使用して重複ピークの分離を行う。
以上の操作を行い、酸化アルミニウム蒸着膜の遷移領域の変成率を
(元素結合Al2O4Hのピークから界面までの遷移領域厚/酸化アルミニウム蒸着膜厚)×100(%)として求めた。
酸素透過度測定装置(モダンコントロール(MOCON)社製〔機種名:オクストラン(OX-TRAN)2/21〕)を用いて、測定のために作製したバリア性積層フィルム/接着剤/ナイロンフィルム15μm/接着剤/CPP70μmの複合積層フィルムとし、酸素供給側がバリア性積層フィルムのフィルム面となるように上記試験用サンプルをセットし、23℃、100%RH雰囲気下の測定条件で、JIS K 7126 B法に準拠して測定した。
測定サンプルとして、
1)レトルト処理前の複合積層フィルム
2)ハイレトルト処理条件:135℃、40分間の処理をした袋の状態にした複合積層フィルムの袋片面の複合積層フィルム
3)セミレトルト処理条件:121℃、40分間の処理をした袋の状態にした複合積層フィルムの袋片面の複合積層フィルム
を用いた。
水蒸気透過度測定装置(モコン(MOCON)社製の測定機〔機種名、パーマトラン(PERMATRAN)3/33〕)を用いて、センサー側がバリア性積層フィルムのフィルム面となるように上記試験用サンプルをセットし、37.8℃、100%RH雰囲気下の測定条件で、JIS K 7126 B法に準拠し、測定した。
測定サンプルとして、
1)レトルト処理前の複合積層フィルム
2)ハイレトルト処理条件:135℃、40分間の処理をした袋の状態にした複合積層フィルムの袋片面の複合積層フィルム
3)セミレトルト処理条件:121℃、40分間の処理をした袋の状態にした複合積層フィルムの袋片面の複合積層フィルム
を用いた。
<密着強度の測定(1);ハイレトルト・セミレトルト処理前の密着強度>
バリア性積層フィルムのバリア性被覆層側に2液硬化型ポリウレタン系接着剤を塗工し、乾燥処理したものと、厚さ70μmの無延伸ポリプロピレンフィルムに2液硬化型ポリウレタン系接着剤と厚さ15μmの延伸ナイロンフィルムと貼り合わせたフィルムとをドライラミネートした積層複合フィルムを作製した。
上記積層複合フィルムを48時間エージング処理した後、15mm巾の短冊状にカットしたサンプルについて、引張試験機(株式会社オリエンテック社製[機種名:テンシロン万能材料試験機])を用いてJIS K6854-2に準拠し、バリア性積層フィルム基材と酸化アルミウム蒸着膜との強度を測定した。
測定は、測定のために事前に剥離したポリプロピレンフィルム側とバリア性積層フィルム側をそれぞれ測定器のつかみ具で把持し、ポリプロピレンフィルムとバリア性積層フィルムとがまだ積層されている部分の面方向に対して直交する方向において互いに逆向きに(180°剥離:T字剥離法)、50mm/minの速度で引っ張り、安定領域における引張応力の平均値を測定した。
剥離は積層複合フィルムで密着強度が最も弱いバリア性積層フィルムのプラスチックス基材と酸化アルミニウム蒸着膜との間で生じており、上記の測定値を、バリア性積層フィルムのプラスチック基材と酸化アルミニウム蒸着膜の密着強度とした。
バリア性積層フィルムのバリア性被覆層側に2液硬化型ポリウレタン系接着剤を塗工し、乾燥処理したものと、厚さ70μmの無延伸ポリプロピレンフィルムに2液硬化型ポリウレタン系接着剤と厚さ15μmの延伸ナイロンフィルムと貼り合わせたフィルムとをドライラミネートし、積層複合フィルムを作製した。
上記積層複合フィルムを用いてB5サイズに作製した四方パウチに水100mLを注入し、135℃、40分間で熱水式レトルト処理を行った。該レトルト処理後、中身の水を抜いた四方パウチから15mm巾の短冊状にカットしたサンプルを作成した。このサンプルを用いて密着強度の測定(1)と同様にして、密着強度を測定した。
密着強度の測定(2)の構成にいて、ナイロンフィルムを使わずに、ポリプロピレンフィルムの厚みを70μmにして積層複合フィルムを作製した。
上記積層複合フィルムを用いてB5サイズに作製した四方パウチに水100mLを注入し、121℃、40分間で熱水式レトルト処理を行った。該レトルト処理後、中身の水を抜いた四方パウチから15mm巾の短冊状にカットしたサンプルを作成した。このサンプルを用いて密着強度の測定(1)と同様にして、密着強度を測定した。
[実施例1]
<酸化アルミニウム蒸着膜の形成>
まず、プラスチック基材である厚さ12μmの石油由来のポリエチレンテレフタレートフィルム(以下、PETフィルム)を巻き取ったロールを準備した。
次に、このPETフィルムの蒸着膜を設ける面に、酸素プラズマ前処理装置を配置した前処理区画と成膜区画を隔離した連続蒸着膜成膜装置を用いて、前処理区画において下記条件下でプラズマ供給ノズルからプラズマを導入し、搬送速度400m/minで酸素プラズマ前処理を施し、連続搬送した成膜区画内で、酸素プラズマ処理面上に、下記条件において真空蒸着法の加熱手段として反応性抵抗加熱方式により、厚さ12nmの酸化アルミニウム蒸着膜をPETフィルム上に形成した。
(酸素プラズマ前処理条件)
・プラズマ強度:200W・sec/m2
・プラズマ形成ガス比:酸素/アルゴン=2/1
・前処理ドラム-プラズマ供給ノズル間印加電圧:340V
・前処理区画の真空度:3.8Pa
(酸化アルミニウム成膜条件)
・真空度:8.1×10-2Pa
・搬送速度:400m/min
・酸素ガス供給量:20000sccm
水385g、イソプロピルアルコール67g及び0.5N塩酸9.1gを混合し、pH2.2に調整した溶液に、金属アルコキシドとしてテトラエトキシシラン175gと、シランカップリング剤としてグリシドキシプロピルトリメトキシシラン9.2gを10℃となるよう冷却しながら混合させて溶液Aを調製した。
水溶性高分子として、ケン価度99%以上の重合度2400のポリビニルアルコール14.7g、水324g、イソプロピルアルコール17gを混合した溶液Bを調製した。
A液とB液を重量比6.5:3.5となるよう混合して得られた溶液をバリアコート剤とした。
上記のPETフィルムの酸化アルミニウム蒸着膜上に、上記で調製したバリアコート剤をスピンコート法によりコーティングした。
その後、180℃で60秒間、オーブンにて加熱処理して、厚さ約400nmのバリア性被覆層を酸化アルミニウム蒸着膜上に形成して、バリア性積層フィルムを得た。
酸素プラズマ前処理条件を100W・sec/m2に変更したこと以外は、実施例1と同じにして、バリア性積層フィルムを得た。
プラスチック基材として厚さ12μmのバイオマス由来のPETフィルムを使用したこと、プラズマ前処理条件を150W・sec/m2に変更したこと以外は、実施例1と同じにして、バリア性積層フィルムを得た。
プラスチック基材として厚さ12μmの石油由来のポリブチレンテレフタレートフィルム(以下、PBTフィルム)を使用したことと、酸化アルミニウム蒸着膜の厚さを10nmに変更したこと、酸素プラズマ前処理条件を150W・sec/m2に変更したこと以外は、実施例1と同じにして、バリア性積層フィルムを得た。
但し、レトルト条件はセミレト条件で行った。
高湿度下で長期保管することで含水率の高まった、厚さ12μmの石油由来のPETフィルムを用いたことと、酸化アルミニウム蒸着膜の厚さを14nm変更したこと以外は、実施例1と同じにして、バリア性積層フィルムを得た。
酸化アルミニウム蒸着膜の厚さを7nmにしたこと以外は、実施例1と同じにしてバリア性積層フィルムを得た。
酸素プラズマ前処理を行わなかった以外は、実施例1と同じにしてバリア性積層フィルムを得た。
比較例1,2では、元素結合Al2O4Hピークが、ピークが小さすぎて基材界面側に隠れ、分離できなかった為に、該遷移領域の変成率が計算できない結果(0%以下の数値)となった。
そして、比較例1と2ではレトルト処理後の水蒸気バリア性が悪かったり、急激な剥離強度の劣化によりデラミネーションの発生が見られたりした。
実験IIにおいては、図10に示された成膜装置60を使って酸化アルミニウム蒸着膜の製膜を行った。
プラスチック基材1として、0.0017N/15mm以上のループスティフネスを有し、石油由来のPETからなる高スティフネスPETフィルムを準備した。具体的には、高スティフネスPETフィルムとして、東レ株式会社製のXP-55を用いた。高スティフネスPETフィルムの厚みは16μmであった。また、高スティフネスPETフィルムのループスティフネスの測定値は、流れ方向及び垂直方向のいずれにおいても0.0021N/15mmであった。また、流れ方向における高スティフネスPETフィルムのヤング率は4.8GPaであり、垂直方向における高スティフネスポリエステルフィルムのヤング率は4.7GPaであった。
また、流れ方向における高スティフネスPETフィルムの引張強度は292MPaであり、垂直方向における高スティフネスポリエステルフィルムの引張強度は257MPaであった。また、流れ方向における高スティフネスPETフィルムの引張伸度は107%であり、垂直方向における高スティフネスポリエステルフィルムの引張伸度は102%であった。この場合、流れ方向における高スティフネスPETフィルムの引張強度を引張伸度で割った値は2.73〔MPa/%〕であり、垂直方向における高スティフネスPETフィルムの引張強度を引張伸度で割った値は2.52〔MPa/%〕である。
また、流れ方向及び垂直方向における高スティフネスPETフィルムの熱収縮率はいずれも0.4%であった。
プラスチック基材1上に酸化アルミニウム蒸着膜2を形成し、酸化アルミニウム蒸着膜2上にバリア性被覆層3を形成してバリア性積層フィルムAを作製した例について説明する。
〔酸素プラズマ前処理条件〕
・プラズマ強度:200W・sec/m2
・プラズマ形成ガス比:酸素/アルゴン=2/1
・前処理ドラム-プラズマ供給ノズル間印加電圧:340V
・前処理区画の真空度:3.8Pa
〔酸化アルミニウム成膜条件〕
・真空度:8.1×10-2Pa
・搬送速度:400m/min
・酸素ガス供給量:20000sccm
水溶性高分子として、ケン価度99%以上の重合度2400のポリビニルアルコール14.7g、水324g、イソプロピルアルコール17gを混合した溶液Bを調製した。
続いて、A液とB液を重量比6.5:3.5となるよう混合した。このようにして得られた溶液を、ガスバリア性塗布膜用コート剤とした。
真空引きされた環境下で、バリア性積層フィルムAのバリア性被覆層3の表面にCs(セシウム)イオン銃により一定の速度でソフトエッチングを繰り返しながら、飛行時間型二次イオン質量分析法(TOF-SIMS)を用いて、バリア性被覆層3に由来するイオンと、酸化アルミニウム蒸着膜2に由来するイオンと、プラスチック基材1に由来するイオンを測定した。例えば、プラスチック基材1の樹脂フィルム由来のC6(質量数72.00)、酸化アルミニウム蒸着膜2の酸化アルミニウム蒸着膜由来のAl2O4H(質量数118.93)イオンの質量分析を行った。
(TOF-SIMS測定条件)
・一次イオン種類:Bi3 ++(0.2pA、100μs)
・測定面積:150×150μm2
・エッチング銃種類:Cs(1keV、60nA)
・エッチング面積:600×600μm2
・エッチングEtレート:3sec/Cycle
・真空引き時間:1×10-6mbar以下で15時間以上
飛行時間型二次イオン質量分析計を用いた測定は、真空引きを開始した後、30時間以内に実施した。
また、実施例B1のバリア性積層フィルムAから、上述の矩形状の試験片40を作成し、流れ方向及び垂直方向におけるループスティフネスを測定した。測定器としては、東洋精機社製のNo.581ループステフネステスタ(登録商標)LOOP STIFFNESS TESTER DA型を用いた。測定時の環境は、温度23℃、相対湿度50%とした。結果、バリア性積層フィルムAの流れ方向におけるループスティフネスは0.0021Nであり、垂直方向におけるループスティフネスは0.0.0021Nであった。
上述のように作製したバリア性積層フィルムAと、厚さ60μmの無延伸ポリプロピレンフィルム(CPPフィルム)とを、2液硬化型ポリウレタン系接着剤を介してドライラミネート法により貼り合わせて、包装材料8を作製した。CPPフィルムとしては、東レフィルム加工株式会社製の未延伸ポリプロピレンフィルム ZK207を用いた。
続いて、レトルト処理が施された後の四方シールパウチの片面を構成している包装材料8を切り出して、レトルト処理後の酸素透過度を評価するためのサンプルを作製した。
酸素透過度の測定の場合と同一のサンプルを用いて、水蒸気透過度の測定を行った。具体的には、各サンプルを、プラスチック基材1がセンサー側となるようにセットして、37.8℃、100%RH雰囲気下の測定条件で、JIS K 7126 B法に準拠して水蒸気透過度を測定した。測定器としては、水蒸気透過度測定装置(モコン(MOCON)社製の測定機〔機種名、パーマトラン(PERMATRAN)3/33〕)を用いた。結果、レトルト処理前のサンプルの水蒸気透過度は0.61g/m2/24hrであった。また、レトルト処理後のサンプルの水蒸気透過度は1.05g/m2/24hrであった。このように、レトルト処理前及びレトルト処理後のいずれの状態においても、水蒸気透過度を1.5g/m2/24hr未満にすることができた。
酸化アルミニウム蒸着膜2上にバリア性被覆層3を形成しなかったこと以外は、実施例B1の場合と同様にして、プラスチック基材1と、プラスチック基材1上に設けられた酸化アルミニウム蒸着膜2と、を備えるバリア性積層フィルムAを作製した。続いて、実施例B1の場合と同様にして、実施例B2のバリア性積層フィルムAから2つのサンプルを準備し、2つのサンプルのそれぞれについて、酸化アルミニウム蒸着膜2の変成率を、(遷移領域の厚みW1/酸化アルミニウム蒸着膜2の厚み)×100(%)として算出した。結果、第2のサンプルにおける変成率は37.8%であり、第2のサンプルにおける変成率は42.2%であった。
プラスチック基材1として、流れ方向及び垂直方向のいずれにおいても0.0017N未満のループスティフネスを有し、石油由来のPETからなる二軸延伸PETフィルムを用いたこと以外は、実施例B1の場合と同様にして、プラスチック基材1と、プラスチック基材1上に設けられた酸化アルミニウム蒸着膜2と、酸化アルミニウム蒸着膜2上に設けられたバリア性被覆層3と、を備えるバリア性積層フィルムAを作製した。続いて、実施例B1の場合と同様にして、比較例B1のバリア性積層フィルムAから、上述の矩形状の試験片40を作成し、流れ方向及び垂直方向におけるループスティフネスを測定した。結果、バリア性積層フィルムAの流れ方向におけるループスティフネスは0.0014Nであり、垂直方向におけるループスティフネスは0.0016Nであった。
蒸着膜とプラスチック基材間のレトルト処理前後における密着強度の劣化を改善することで、酸素ガス、水蒸気等の透過を阻止するバリア性及び密着性を有するバリア性積層フィルムとすることができ、例えば、レトルト処理、殺菌処理等の加工に伴う処理に耐える積層材を必要とする食品、医薬品などの包装材、及び電気・電子部品の包装、保護シートなどの耐久性、バリア性を必要とする使用環境が厳しい分野の産業資材等に適用できる。
2 ………酸化アルミニウム蒸着膜
3………バリア性被覆層
8………包装材料
A ………バリア性積層フィルム
P ………プラズマ
10 ………ローラー式連続蒸着膜成膜装置
12 ………減圧チャンバ
12A ………基材搬送室
12B ………プラズマ前処理室
12C ………成膜室
14a~d ………ガイドロール
18 ………原料ガス揮発供給装置
20 ………前処理ローラー
21 ………マグネット
22 ………プラズマ供給ノズル
23 ………成膜ローラー
24 ………蒸着膜成膜手段
31 ………電力供給配線
32 ………電源
35a~35c ………隔壁
60 成膜装置
62 減圧チャンバ
62A 基材搬送室
62B プラズマ前処理室
62C 成膜室
63 巻き出しローラー
64 ガイドローラー
65 巻き取りローラー
68 原料ガス揮発供給装置
69 原料ガス供給ノズル
70 プラズマ前処理ローラー
71 電極
72 プラズマ供給ノズル
75 成膜ローラー
76 成膜手段
80 真空ポンプ
81 電力供給配線
82 電源
85a~85c 隔壁
Claims (12)
- プラスチック基材の表面に酸化アルミニウムを主成分とする酸化アルミニウム蒸着膜を形成し、前記酸化アルミニウム蒸着膜の表面にバリア性被覆層が積層されてなる、バリア性を備える積層フィルムにおいて、
前記酸化アルミニウム蒸着膜中には、前記プラスチック基材の表面と前記酸化アルミニウム蒸着膜との密着強度を規定する遷移領域が形成されており、
該遷移領域は、飛行時間型二次イオン質量分析法(TOF-SIMS)を用いてエッチングを行うことで検出される、水酸化アルミニウムに変成する元素結合Al2O4Hを含み、
前記バリア性被覆層と前記酸化アルミニウム蒸着膜とをTOF-SIMSを用いてエッチングを行うことで規定される前記酸化アルミニウム蒸着膜に対する、TOF-SIMSを用いて規定される該変成される前記遷移領域の割合により定義される遷移領域の変成率が、5%以上、60%以下である、上記バリア性積層フィルム。 - 前記プラスチック基材が、ポリエチレンテレフタレートフィルムである、請求項1に記載のバリア性積層フィルム。
- 前記プラスチック基材が、リサイクルポリエチレンテレフタレートフィルムを含む、請求項1に記載のバリア性積層フィルム。
- 前記プラスチック基材が、ポリブチレンテレフタレートフィルムである、請求項1に記載のバリア性積層フィルム。
- 前記プラスチック基材が、バイオマス由来のポリエステルフィルムである、請求項1に記載のバリア性積層フィルム。
- 前記プラスチック基材が、高スティフネスPETフィルムである、請求項1に記載のバリア性積層フィルム。
- 前記プラスチック基材の表面が、酸素プラズマ処理面である、請求項1~6のいずれか1項に記載のバリア性積層フィルム。
- 酸素プラズマ処理面にインラインで酸化アルミニウム蒸着膜が積層された、請求項7に記載のバリア性積層フィルム。
- バリア性被覆層が、金属アルコキシドと水溶性高分子の混合溶液を塗布し、加熱乾燥してなる層である、請求項1~8の何れか1項に記載のバリア性積層フィルム。
- バリア性被覆層が、金属アルコキシドとシランカップリング剤と水溶性高分子の混合溶液を塗布し、加熱乾燥してなる層である、請求項1~9のいずれか1項に記載のバリア性積層フィルム。
- 請求項1~10のいずれか1項に記載のバリア性積層フィルムに、ヒートシール性を有する熱可塑性樹脂が積層されてなる、包装材料。
- レトルト殺菌用包装に用いられる、請求項11に記載の包装材料。
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JP2020049942A (ja) * | 2018-09-19 | 2020-04-02 | 大日本印刷株式会社 | ガスバリア性蒸着フィルム、および該ガスバリア性蒸着フィルムを用いた積層体、包装材料、包装体 |
JP2020049941A (ja) * | 2018-09-19 | 2020-04-02 | 大日本印刷株式会社 | ガスバリア性蒸着フィルム、ガスバリア性積層体、ガスバリア性包装材料及びガスバリア性包装体。 |
JP7434766B2 (ja) | 2018-09-19 | 2024-02-21 | 大日本印刷株式会社 | ガスバリア性蒸着フィルム、ガスバリア性積層体、ガスバリア性包装材料及びガスバリア性包装体。 |
JP7434767B2 (ja) | 2018-09-19 | 2024-02-21 | 大日本印刷株式会社 | ガスバリア性蒸着フィルム、および該ガスバリア性蒸着フィルムを用いた積層体、包装材料、包装体 |
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EP3769955A1 (en) | 2021-01-27 |
CN111867825B (zh) | 2023-06-27 |
EP3769955A4 (en) | 2021-06-09 |
CN111867825A (zh) | 2020-10-30 |
JPWO2019182017A1 (ja) | 2021-03-25 |
JP7248011B2 (ja) | 2023-03-29 |
US20200407136A1 (en) | 2020-12-31 |
KR20200135828A (ko) | 2020-12-03 |
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