JP2018192693A - Gas barrier film and manufacturing method thereof - Google Patents

Abstract

To provide a gas barrier film that strengthens adhesion of a base material and an inorganic oxide vapor-deposited film, that can avoid delamination even if heat sterilization such as retort is carried out, without deterioration of oxygen permeability and steam permeability.SOLUTION: A gas barrier film includes: a base material made of a high polymeric material; a pretreatment layer laminated at least on one side of the base material and being a layer of a metal or an oxide thereof; a gas barrier layer laminated on the pretreatment layer and being an inorganic oxide layer or an organic-inorganic hybrid layer; and a composite coating film layer laminated on the gas barrier layer and being a layer of a water-soluble polymer and a metalalkoxide or a hydrolyzate thereof. The pretreatment layer is composed of one or a plurality of alloys selected from aluminum, silicon, copper, iron, niobium and titanium, or an oxide thereof, and has average film thickness of 0.01-10 nm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film used in the packaging field of foods, pharmaceuticals, precision electronic parts and the like.

  Packaging materials used for packaging foods, pharmaceuticals, precision electronic components and the like are required to have sufficient gas barrier properties. The gas barrier packaging material suppresses the alteration of the contents, for example, the oxidation and alteration of proteins and oils and fats in food, and further maintains the taste and freshness. In order to suppress the deterioration of the active ingredient and maintain its efficacy, and in the precision electronic parts, in order to prevent corrosion of metal parts, insulation failure, etc., oxygen and water vapor that permeate the packaging material are blocked, The influence by the gas which changes the contents can be prevented.

  Conventionally, polymer resin compositions that are generally said to have relatively high gas barrier properties such as polypropylene (KOP), polyethylene terephthalate (KPET), or ethylene vinyl alcohol copolymer (EVOH) coated with vinylidene chloride resin are used as gas barrier packaging materials. A metal or metal compound such as Al is vapor-deposited on a wrapping film, a foil of a metal or metal compound such as Al, or an appropriate polymer resin composition (which may be a resin that does not have high gas barrier properties alone). Metal vapor deposited films have been commonly used. The packaging film using the above-described polymer resin composition is inferior in gas barrier properties as compared to a foil using a metal such as Al or a metal compound, or a metal vapor-deposited film in which a vapor-deposited layer of these metal or metal compound is formed. Further, it is easily affected by temperature and humidity, and the gas barrier property may be further deteriorated depending on the change. On the other hand, a metal vapor deposition film in which a foil or a vapor deposition layer using a metal or a metal compound such as Al is formed is less affected by temperature, humidity, and the like, and has excellent gas barrier properties. However, there are drawbacks such as the fact that the contents of the package cannot be seen through, the metal detector cannot be used during inspection, and the microwave cannot be used.

  Therefore, as a packaging material that achieves both gas barrier properties and transparency, a ceramic thin film such as a metal oxide and silicon oxide has recently been deposited on a substrate substantially made of a polymer material having transparency. The vapor deposition film formed by the formation means is marketed. However, these films have a drawback in that delamination is caused by heat sterilization treatment such as boil and retort treatment performed in the food field. Further, there has been a problem that gas barrier properties such as oxygen permeability and water vapor permeability are also deteriorated due to a decrease in adhesion.

  In order to overcome these drawbacks, a method of forming an anchor coat layer by wet coating or a metal layer by sputtering between the base material and the vapor deposition layer has been proposed (Patent Documents 1 and 2). However, in the method of Patent Document 1, productivity is not high because the number of steps for forming the anchor coat increases. Further, the method described in Patent Document 2 has a problem that the vapor deposition layer is aluminum, and the transparency is low and the contents cannot be confirmed. On the other hand, a method for improving a decrease in adhesion and gas barrier properties after boiling or retorting by forming a metal by sputtering has been proposed (Patent Documents 3, 4, and 5). However, the method described in Patent Document 3 has insufficient gas barrier properties after the retort treatment. Moreover, when the silicon oxide is used for the vapor deposition layer, the method described in Patent Document 4 has a problem that the laminate strength and oxygen permeability after the retort treatment are lowered. The method described in Patent Document 5 has a problem that the inorganic oxide layer and the organic material layer are formed in two layers, and the cost increases. In addition, a method has been proposed for improving the decrease in adhesion and gas barrier properties after boil and retort treatment by plasma treatment (Patent Document 6). However, in the case of the method described in Patent Document 6, there is a problem that the apparatus becomes complicated because of the special plasma processing.

JP 2007-69456 A JP-A-7-233462 Japanese Patent No. 8-267642 Japanese Patent No. 5145800 Japanese Patent No. 5040491 Japanese Patent No. 4385835

  The present invention has been made in order to solve the above-mentioned problems, strengthening the adhesion between the base material and the inorganic oxide vapor-deposited film, in particular, delamination does not occur even when heat sterilization such as retort is performed, and oxygen permeability Another object of the present invention is to provide a gas barrier film without deterioration of water vapor permeability.

  In order to achieve the above object, one aspect of the present invention includes a base material made of a polymer material and a pretreatment layer that is a layer of a metal or an oxide thereof laminated on at least one surface of the base material. And a gas barrier layer that is an inorganic oxide layer or an organic-inorganic hybrid layer laminated on the pretreatment layer, and a composite film that is a layer of a water-soluble polymer and a metal alkoxide or a hydrolyzate thereof laminated on the gas barrier layer And the pretreatment layer is one or a plurality of alloys selected from aluminum, silicon, copper, iron, niobium, and titanium, or an oxide thereof, and has an average film thickness of 0.01 nm to 10 nm. This is a gas barrier film.

  Further, the base material made of a polymer material may be polyethylene terephthalate.

  Further, by forming the pretreatment layer, the full width at half maximum of the C—C bond waveform obtained from the C1s waveform separation by X-ray photoelectron spectroscopy measurement on the substrate surface may be 1.50 eV or more and 1.70 eV or less.

  The gas barrier layer is made of an inorganic oxide such as aluminum oxide, silicon oxide, or a mixture thereof, or aluminum, oxygen, carbon, hydrogen, silicon, oxygen, carbon, hydrogen or aluminum, silicon, oxygen, carbon, hydrogen. It may be an organic / inorganic hybrid.

  Further, the water-soluble polymer may be composed of one or more of polyvinyl alcohol, cellulose, and starch.

  Further, the metal alkoxide or a hydrolyzate thereof may contain either a silane alkoxide or a silane coupling agent.

The oxygen permeability after retorting at 121 ° C. for 30 minutes was 1.0 cc / m ² * day or less, the water vapor permeability was 1 g / m ² * day or less, and the laminate strength was 2.0 N / 15 mm or more. May be.

  Another aspect of the present invention is obtained from C1s waveform separation by X-ray photoelectron spectroscopy measurement of a substrate surface by forming a pretreatment layer which is a layer of a metal or an oxide thereof on a substrate made of a polymer material. A step of setting the full width at half maximum of the waveform of CC bond to 1.50 eV or more and 1.70 eV or less, a step of forming a gas barrier layer that is an inorganic oxide layer or an organic-inorganic hybrid layer on the pretreatment layer, and a gas barrier And a step of forming a composite coating layer, which is a layer of a water-soluble polymer and a metal alkoxide or a hydrolyzate thereof, on the layer.

  According to the present invention, it is possible to obtain a strong adhesion vapor deposition film in which the substrate and the inorganic oxide layer exhibit extremely good adhesion. Furthermore, when this laminated film is used as a packaging material, even when heat sterilization such as retort is performed, delamination does not occur, and a gas barrier film having high oxygen permeability and water vapor permeability can be provided. it can.

Cross-sectional block diagram of the gas barrier film which concerns on one Embodiment of this invention The figure which shows an example of the C1s waveform separation analysis spectrum obtained by XPS of general PET

  Details of one embodiment of the present invention will be described below.

  FIG. 1 is a cross-sectional view illustrating a gas barrier film according to an embodiment of the present invention. The gas barrier film has a structure in which a pretreatment layer 2, a gas barrier layer 3, and a composite coating layer 4 are formed on the surface of a base material 1 made of a polymer material. The pretreatment layer 2, the gas barrier layer 3, and the composite coating layer 4 may be formed on both sides of the substrate, or may be multilayered.

  A PET (polyethylene terephthalate) film as an example of the substrate 1 may be either unstretched or stretched, and the stretching ratio is not particularly limited in the case of stretching. Moreover, what has the mechanical strength and dimensional stability more than fixed is good. The thickness of the film is not particularly limited, and a film obtained by laminating films having different properties in addition to a single film can be used in consideration of suitability as a packaging material. In consideration of workability in forming a primer layer, a gas barrier layer, a composite coating layer, etc., a range of 3 μm to 200 μm is preferable, and a range of 6 μm to 30 μm is particularly preferable. Various known additives and stabilizers such as an antistatic agent, an anti-ultraviolet agent, a plasticizer, and a lubricant may be used on the surface opposite to the surface on which the vapor deposition layer of the PET film is provided.

  The metal of the pretreatment layer 2 or its oxide is at least one of aluminum, silicon, copper, iron, niobium, titanium, or an alloy or oxide thereof. The method for forming the metal or its oxide is not particularly limited, and for example, vacuum deposition, sputtering, ion plating, ion beam, plasma vapor deposition (CVD), or the like is used. By forming the metal or its oxide, the anchor effect by nucleation and the chemical change of the surface structure of the PET film, the mixed layer (mixing layer) of the base and the metal or its oxide is formed. The boundary of the barrier layer becomes ambiguous and the adhesion energy increases. The appropriate range of the processing degree of the base PET film will be described later. The average film thickness of the metal or its oxide on the substrate surface is preferably 0.01 nm to 10 nm. If it is less than 0.01 nm, the substrate may not be sufficiently modified, and if it is more than 10 nm, the adhesion may be lowered.

  As a method for verifying the degree of treatment that can achieve good adhesion, measurement by X-ray photoelectron spectroscopy (XPS measurement) can be mentioned. This method can analyze the type and concentration of atoms in the depth range of several nanometers from the surface of the substance to be measured, the type of atoms bonded to the atoms and their bonding state, and the element ratio, functional group ratio, etc. Can be sought. However, as in the case of the gas barrier film of the present invention, this state is maintained in the case of a PET film provided with a vapor deposition layer made of an inorganic oxide or the like to be described later having a thickness greater than or equal to a depth that can be analyzed by XPS measurement. Thus, it is impossible to measure the surface of the PET film. There is also a method of measuring by digging a vapor deposition layer by Ar ion etching, but since the PET is etched even a little, the measurement result becomes meaningless. Therefore, it is necessary to first remove the inorganic oxide vapor deposition layer on the PET film.

  As this method, there is a method of immersing a film in treated water for removing the inorganic oxide vapor deposition layer. The water used for the treatment is not particularly limited, such as tap water, ion exchange water, and distilled water. The water temperature is not particularly limited, but preferably 50 ° C. or higher. Furthermore, it is necessary to add at least one or more kinds of weakly alkaline amines such as ammonia, triethanolamine, trimethanolamine, diethanolamine, triethylamine, and trimethylamine to the water. By adding such amines, it is possible to completely remove the inorganic oxide in a short time. The addition amount is preferably in the range of 0.01% to 10%. If it is less than 0.01%, it takes a long time to complete removal and cannot be completely removed. On the other hand, if it exceeds 10%, the PET film itself is also affected, the surface after the inorganic oxide layer is removed may be contaminated, and the PET structure may be destroyed.

  FIG. 2 is a spectrum obtained by performing peak separation analysis on the C1s waveform of untreated PET obtained by XPS measurement. The C1s waveform is separated into a C—C bond 5, a C—O bond 6, and a COO bond 7. In addition, the value of each bond energy is 285.0 eV (C—C bond), 286.6 eV to 286.7 eV (C—O bond), 288.9 eV to 289.0 eV (COO bond).

  When XPS measurement of the PET film surface after removing the inorganic oxide layer as described above is performed, the FWHM (half-value width) of the C—C bond obtained from the C1s waveform separation is 1.50 eV to 1.70 eV. In this case, the PET film and the inorganic oxide layer exhibit extremely good adhesion, and delamination does not occur even when heat sterilization treatment such as retort is performed.

  On the other hand, in the case of an untreated PET film, the half width of the C—C bond on the surface of the PET film after removing the inorganic oxide layer is about 1.45 eV. In such a case, the adhesion between the PET film and the inorganic oxide layer is poor, and delamination occurs when heat sterilization treatment such as retort is performed. When the half width is less than 1.50 eV, the film surface treatment is weak, the adhesion is deteriorated as in the case of the untreated PET film, and the gas barrier property after the heat sterilization treatment is also deteriorated. On the other hand, when the full width at half maximum is greater than 1.70 eV, the film surface is excessively processed and the surface deteriorates, resulting in poor adhesion.

  In order to obtain a PET film having good adhesion to the inorganic oxide layer as described above, the formation of a mechanical bond with the PET film or the surface structure of the PET film is chemically formed by forming a metal or its oxide. It is possible to control the full width at half maximum of the CC bond. Further, by performing this treatment, a dense thin film of inorganic oxide can be formed. As a result, the adhesion between the base material and the inorganic oxide layer can be strengthened, which not only improves gas barrier properties and prevents cracking, but also causes delamination even when heat sterilization such as retort is performed. There is nothing.

  Next, the gas barrier layer 3 will be described in detail. The gas barrier layer 3 may be an inorganic oxide layer made of aluminum oxide, silicon oxide, or a mixture thereof, or is made of silicon or aluminum alkoxide or alkyl group, has transparency, and has gas barrier properties such as oxygen and water vapor. An organic-inorganic hybrid layer which is a layer having Considering various sterilization resistances, it is more preferable to use aluminum oxide and silicon oxide among them. However, the gas barrier layer of the present invention is not limited to the inorganic oxide described above, and any material that meets the above conditions can be used.

  The optimum thickness of the gas barrier layer 3 varies depending on the type and configuration of the inorganic compound used, but generally it is preferably in the range of 3 nm to 300 nm, and the value is appropriately selected. However, if the film thickness is less than 3 nm, a uniform film may not be obtained or the film thickness may not be sufficient, and the function as a gas barrier material may not be sufficiently achieved. Further, when the film thickness exceeds 300 nm, the thin film cannot be kept flexible, and there is a problem because the thin film may be cracked due to external factors such as bending and pulling after the film formation. More preferably, it exists in the range of 6 nm-150 nm.

  The method for forming the gas barrier layer 3 is not particularly limited, and for example, a vacuum deposition method, a sputtering method, an ion plating method, an ion beam method, a plasma vapor deposition method (CVD), or the like is used. Further, a plasma assist method, an ion beam assist method, or the like may be combined as means for further densifying the gas barrier layer to be formed and improving the barrier property and adhesion.

  Next, the composite coating layer 4 will be described. The composite coating layer is a coating layer having a gas barrier property, and is formed by using a coating agent mainly composed of an aqueous solution or water / alcohol mixed solution containing a water-soluble polymer and one or more metal alkoxides or hydrolysates thereof. The For example, a solution obtained by mixing a water-soluble polymer dissolved in an aqueous (water or water / alcohol mixed) solvent with a metal alkoxide directly or previously hydrolyzed is used as a solution. After coating this solution on the vapor deposition thin film layer which consists of mineralized oxide, it heat-drys and forms. Each component contained in the coating agent will be described in more detail. The metal alkoxide or the hydrolyzate thereof includes, for example, any of a silane alkoxide, an aluminum alkoxide, a silane coupling agent, and an aluminum coupling agent.

  Examples of the water-soluble polymer used in the coating agent in the present invention include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. In particular, when polyvinyl alcohol (hereinafter abbreviated as PVA) is used for the coating agent of the present invention, the gas barrier property is most excellent, which is preferable. PVA here is generally obtained by saponifying polyvinyl acetate. As PVA, for example, complete PVA in which only several percent of acetic acid groups remain can be used from so-called partially saponified PVA in which several tens percent of acetic acid groups remain, and other types may be used. .

The metal alkoxide is a compound represented by the general formula, M (OR) _n (M: Si, Al metal, R: alkyl group such as CH ₃ and C ₂ H ₅ ). Specific examples include tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], triisopropoxyaluminum Al [OCH (CH ₃ ) ₂ ] ₃ , and the silane coupling agent includes 3-glycidoxypropyl. Those having an epoxy group such as trimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, those having a mercapto group such as 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane Although what has an isocyanate group, a tris- (3-trimethoxysilylpropyl) isocyanurate, etc. are mentioned, It does not specifically limit.

  As a method for applying the coating agent, conventionally known methods such as a dipping method, a roll coating method, a screen printing method, a spray method, and a gravure printing method that are usually used can be used.

  The thickness of the composite coating layer 4 varies depending on the type of coating agent, the processing machine, and the processing conditions, and is not particularly limited. However, when the thickness after drying is 0.01 μm or less, a uniform coating film may not be obtained and sufficient gas barrier properties may not be obtained. On the other hand, if the thickness exceeds 50 μm, cracks are likely to occur in the film, which may be problematic. It is preferably in the range of 0.01 μm to 50 μm, more preferably in the range of 0.1 μm to 10 μm.

  A printing layer, an intervening film, a sealant layer, and the like can be laminated on the composite coating layer 4 to obtain a packaging material.

  The intervening film is provided in order to increase the bag breaking strength and puncture strength at the time of the bag-shaped packaging material, and is generally a biaxially stretched nylon film, a biaxially stretched polyethylene terephthalate film, in terms of mechanical strength and thermal stability, It is necessary to be one selected from among biaxially stretched polypropylene films. The thickness is determined according to the material and required quality, but is generally in the range of 10 μm to 30 μm.

  Further, the sealant layer is provided as an adhesive layer when forming a bag-like package or the like. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer and their Resins such as metal cross-linked products are used. The thickness is determined according to the purpose, but is generally in the range of 15 μm to 200 μm.

  A printing layer, an intervening film, a sealant layer, and the like can be laminated on the opposite surface of the substrate 1 as necessary.

  Examples and comparative examples of the strong adhesion vapor deposition film (gas barrier film) of the present invention will be specifically described below. The present invention is not limited to these examples. Table 1 shows the materials and film thicknesses of the pretreatment layer and the gas barrier layer in Examples and Comparative Examples.

  On the polyethylene terephthalate (PET) film (P60 made by Toray Industries, Inc.) having a thickness of 12 μm, pretreatment was performed by magnetron sputtering to form 0.3 nm of Al (pretreatment layer 2), and subsequently aluminum oxide was deposited in the same vacuum apparatus. It was formed by a 10 nm electron beam evaporation method (gas barrier layer 3).

  On this film, a solution in which the following (1) liquid and (2) liquid were mixed at a mixing ratio (wt%) of 6/4 was prepared to form a composite coating layer 4.

(1) Liquid: A hydrolyzed solution having a solid content of 3 wt% (in terms of SiO ₂ ) obtained by adding 89.6 g of hydrochloric acid (0.1N) to 10.4 g of tetraethoxysilane and stirring for 30 minutes for hydrolysis.
(2) Liquid: 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (90:10 by weight ratio of water: isopropyl alcohol).
This mixed solution was applied and dried by a gravure coating method to form a composite coating layer 4 having a thickness of 0.4 μm.

  A gas barrier film was prepared in the same manner as in Example 1 except that the film thickness of the pretreatment layer Al was 0.7 nm.

  A gas barrier film was prepared in the same manner as in Example 1 except that the film thickness of the pretreatment layer Al was 1.1 nm.

  A gas barrier film was prepared in the same manner as in Example 2 except that the gas barrier layer was made of SiOx and the film thickness was 30 nm.

  A gas barrier film was prepared in the same manner as in Example 2 except that the pretreatment layer was SiOx and the film thickness was 0.7 nm.

  A gas barrier film was prepared in the same manner as in Example 5 except that the gas barrier layer was SiOx and the film thickness was 30 nm.

  A gas barrier film was prepared in the same manner as in Example 1 except that the pretreatment layer was copper and the film thickness was 0.4 nm.

  A gas barrier film was prepared in the same manner as in Example 7 except that the gas barrier layer was made of SiOx and the film thickness was 30 nm.

  A gas barrier film was prepared in the same manner as in Example 1 except that the pretreatment layer was iron and the film thickness was 0.5 nm.

  A gas barrier film was prepared in the same manner as in Example 9 except that the gas barrier layer was made of SiOx and the film thickness was 30 nm.

  A gas barrier film was prepared in the same manner as in Example 1 except that the pretreatment layer was NbOx and the film thickness was 0.7 nm.

  A gas barrier film was prepared in the same manner as in Example 11 except that the gas barrier layer was made of SiOx and the film thickness was 30 nm.

  A gas barrier film was prepared in the same manner as in Example 1 except that the pretreatment layer was Ti and the film thickness was 0.7 nm.

  A gas barrier film was prepared in the same manner as in Example 13 except that the gas barrier layer was made of SiOx and the film thickness was 30 nm.

[Comparative Example 1]
A gas barrier film was prepared in the same manner as in Example 1 except that the pretreatment layer was not formed.

[Comparative Example 2]
A gas barrier film was prepared in the same manner as in Example 4 except that the pretreatment layer was not formed.

[Comparative Example 3]
A gas barrier film was prepared in the same manner as in Example 1 except that the film thickness of the pretreatment layer Al was 0.001 nm.

[Comparative Example 4]
A gas barrier film was prepared in the same manner as in Example 1 except that the film thickness of the pretreatment layer Al was 15.0 nm.

[Comparative Example 5]
A gas barrier film was prepared in the same manner as in Example 4 except that the film thickness of the pretreatment layer Al was 0.001 nm.

[Comparative Example 6]
A gas barrier film was prepared in the same manner as in Example 4 except that the film thickness of the pretreatment layer Al was 15.0 nm.

  Further, a retort packaging material (laminated film) of the above gas barrier film / stretched nylon (15 μm) / unstretched polypropylene (70 μm) was prepared by dry lamination using a two-component curable polyurethane adhesive.

[Evaluation 1]
The laminate strength between the vapor deposition film (gas barrier film) / stretched nylon of the laminated sample was measured using Orientec Tensilon Universal Tester RTC-1250 (based on JIS Z1707). The measurement was performed in a normal state and while the measurement site was wetted with water. The results are shown in Table 2.

[Evaluation 2]
A pouch having four sides as a seal portion was produced using the above laminated sample, and water was filled as the contents. Thereafter, retort sterilization at 121 ° C. for 30 minutes was performed. As an evaluation, oxygen permeability after retorting (unit: cm ³ / m ² * day, measurement condition: 30 ° C.-70% RH), water vapor permeability (unit: g / m ² * day, measurement condition: 40 ° C.-90) % RH) was evaluated. The results are shown in Table 2.

[Evaluation 3]
Immersion at 80 ° C. for 5 minutes in distilled water to which 1.0 wt% of triethanolamine was added to the intermediate product obtained up to the formation of the gas barrier layers of the gas barrier films of Examples 1 to 12 and Comparative Examples 1 to 6 After removing the gas barrier layer, XPS measurement of the film surface was performed to measure the surface state. The X-ray photoelectron spectrometer used for the measurement was JPS-90MXV manufactured by JEOL Ltd., non-monochromated MgKα ray (1253.6 eV) was used as the X-ray source, and the output was measured at 100 W (10 kV-10 mA). did. For quantitative analysis, calculation was performed using a relative sensitivity factor of 2.28 for O1s and 1.00 for C1s. A mixed function of a Gaussian function and a Lorentz function was used for the waveform separation analysis of the C1s waveform, and the charge correction was performed by correcting the CC bond peak derived from the benzene ring as 285.0 eV. The results are shown in Table 2.

  In Examples, a high barrier property was confirmed in both oxygen and water vapor before and after retort. It was also confirmed that sufficient laminate strength could be maintained. Further, in the examples, it was confirmed that the FWHM (half-value width) of the C—C coupling waveform was in the range of 1.50 eV to 1.70 eV.

  INDUSTRIAL APPLICABILITY The present invention can be used as a packaging material with a wide practical range used for packaging in the food and retort food fields, non-food fields such as pharmaceuticals and electronic components.

DESCRIPTION OF SYMBOLS 1 Base material 2 Pretreatment layer 3 Gas barrier layer 4 Composite film layer 5 CC bond peak 6 CO bond peak 7 COO bond peak

Claims (8)

A base material made of a polymer material;
A pretreatment layer that is a layer of a metal or an oxide thereof laminated on at least one surface of the substrate;
A gas barrier layer, which is an inorganic oxide layer or an organic-inorganic hybrid layer, laminated on the pretreatment layer;
A water-soluble polymer and a composite coating layer that is a layer of a metal alkoxide or a hydrolyzate thereof laminated on the gas barrier layer,
The pretreatment layer is one or a plurality of alloys selected from aluminum, silicon, copper, iron, niobium, and titanium, or an oxide thereof, and has an average film thickness of 0.01 nm to 10 nm. A gas barrier film.   The gas barrier film according to claim 1, wherein the base material made of the polymer material is polyethylene terephthalate.   Due to the formation of the pretreatment layer, the full width at half maximum of the waveform of the C—C bond obtained from the C1s waveform separation by X-ray photoelectron spectroscopy measurement on the surface of the base material is 1.50 eV or more and 1.70 eV or less. The gas barrier film according to claim 1 or 2. The gas barrier layer is
Inorganic oxides that are aluminum oxide, silicon oxide, or mixtures thereof,
Or an organic-inorganic hybrid comprising aluminum, oxygen, carbon, hydrogen or silicon, oxygen, carbon, hydrogen or aluminum, silicon, oxygen, carbon, hydrogen. Gas barrier film.   The gas-barrier film according to any one of claims 1 to 4, wherein the water-soluble polymer comprises one or more of polyvinyl alcohol, cellulose, and starch.   The gas barrier film according to claim 1, wherein the metal alkoxide or a hydrolyzate thereof includes any one of silane alkoxide, aluminum alkoxide, silane coupling agent, and aluminum coupling agent. The oxygen permeability after retorting at 121 ° C. for 30 minutes is 1.0 cc / m ² * day or less, the water vapor permeability is 1 g / m ² * day or less, and the laminate strength is 2.0 N / 15 mm or more. The gas barrier film according to claim 1, wherein the gas barrier film is characterized by the following. The waveform of the C—C bond obtained from the C1s waveform separation by X-ray photoelectron spectroscopy measurement of the surface of the substrate by forming a pretreatment layer that is a layer of a metal or its oxide on a substrate made of a polymer material. A full width at half maximum of 1.50 eV to 1.70 eV,
Forming a gas barrier layer which is an inorganic oxide layer or an organic-inorganic hybrid layer on the pretreatment layer;
Forming a composite coating layer, which is a layer of a water-soluble polymer and a metal alkoxide or a hydrolyzate thereof, on the gas barrier layer.

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