JP2005059265A - Strongly adhered vapor deposition film and packaging material for retort using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a strongly adhered vapor deposition film causing no delamination even if subjected to heat sterilization especially such as retorting or the like by increasing the adhesion of a polyethylene terephthalate film and an inorganic oxide vapor deposition film, and a packaging material for a retort using it. <P>SOLUTION: The strongly adhered vapor deposition film is formed by providing a vapor deposition layer with a thickness of 5-100 nm comprising an inorganic oxide at least on one side of a polyethylene terephthalate film and characterized in that a functional group ratio (COO/C-C) is 0.23 or below. Herein, the functional group ratio is calculated from the analysis of a C1s waveform when an X-ray photoelectron spectroscopic measuring method (measuring condition: X-ray source MgKα, output of 100 W) is adapted to the surface of the film after the vapor deposition layer comprising the inorganic oxide is removed from the vapor deposition film. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a vapor-deposited film having transparency, and a packaging material using the same. More specifically, it is a packaging material with a wide range of practical use that is used for the packaging of non-food fields such as food and retort food fields, pharmaceuticals, and electronic components, and is particularly suitable for packaging fields that require heat sterilization such as retort sterilization. The present invention relates to a strong adhesion vapor deposition film used and a packaging material for retort using the same.

U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017 JP, 11-262970, A In recent years, packaging materials used for packaging of foods, non-foods, pharmaceuticals and the like are oxygen permeated through the packaging materials in order to suppress the deterioration of the contents and maintain their functions and properties, It is necessary to prevent the effects of water vapor and other gases that alter the contents, and it is required to have a gas barrier property or the like for blocking these. Therefore, conventionally, a packaging material using a metal foil such as aluminum, which is less affected by temperature and humidity, as a gas barrier layer has been generally used.

  However, packaging materials using metal foils such as aluminum are not affected by temperature and humidity and have excellent gas barrier properties. However, the contents cannot be confirmed through the packaging material. Have problems such as having to be treated as non-combustible material and not being able to use a metal detector for inspection.

  Therefore, as a packaging material that has overcome these drawbacks, silicon oxide, aluminum oxide, and the like are formed on a polymer film as described in, for example, Patent Documents 1 and 2 by means of formation such as vacuum deposition or sputtering. A film in which a deposited film of an inorganic oxide is formed has been developed. These vapor-deposited films are known to have transparency and gas barrier properties such as oxygen and water vapor, and are suitable as packaging materials having transparency and gas barrier properties that cannot be obtained with metal foil or the like. .

  However, a film in which an inorganic oxide is vapor-deposited on a base material that has not been subjected to pretreatment as in the prior art has poor adhesion between the base material and the vapor-deposited film. There was a drawback of causing lamination.

  In order to solve this problem, attempts have been made to improve the adhesion of metal oxide deposition on plastic substrates by in-line pretreatment by using plasma.

  However, as shown in Patent Document 3, conventionally, when plasma processing is performed in-line, an electrode for applying a voltage for generating plasma is installed on the opposite side instead of the drum side where the substrate is located. . In the case of this apparatus, since the base material is installed on the anode side, a high self-bias cannot be obtained, and as a result, a high processing effect cannot be exhibited.

In order to obtain a high self-bias, a DC discharge method can be used. However, if a high bias voltage is obtained by this method, the plasma mode changes from glow to arc, so a uniform treatment over a large area. Cannot be done.

  The present invention has been made in order to solve the above-mentioned problems, and strengthens the adhesion between the polyethylene terephthalate film and the inorganic oxide vapor deposition film, and particularly does not generate delamination even when heat sterilization such as retort is performed. An object is to provide a film and a packaging material for retort using the film.

  In order to achieve the above object, the invention according to claim 1 is characterized in that a polyethylene terephthalate film provided with a vapor deposition layer made of an inorganic oxide having a thickness of 5 to 100 nm on at least one surface is immersed in treated water, After removing the oxide deposition layer, the X-ray photoelectron spectroscopic measurement (measurement condition: X-ray source MgKα, output 100 W) of the film surface was performed, and the functional group ratio (COO / C—C) is a strongly adhered vapor-deposited film characterized by being 0.23 or less.

  The invention described in claim 2 is characterized in that the treated water described above is weakly alkaline amines such as at least one kind of ammonia, triethanolamine, trimethanolamine, diethanolamine, triethylamine, and trimethylamine in water having a temperature of 30 ° C. or higher. The strong adhesion vapor deposition film according to claim 1, wherein 0.01% to 10% is added.

  The invention according to claim 3 is characterized in that a plasma pretreatment using reactive ion etching (RIE) is performed on at least a surface of the polyethylene terephthalate film constituting the strong adhesion vapor deposition film. Item 3. The strong adhesion vapor deposition film according to Item 1 or 2.

  The invention according to claim 4 is the strongly adhered vapor-deposited film according to any one of claims 1 to 3, wherein the inorganic oxide is aluminum oxide, silicon oxide or a mixture thereof.

  According to a fifth aspect of the present invention, an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer and one or more metal alkoxides or a hydrolyzate thereof is further applied onto the vapor deposition layer made of the inorganic oxide and heated. The composite film layer formed by drying is provided, The strong adhesion vapor deposition film according to any one of claims 1 to 4.

  The invention according to claim 6 is the strong adhesion deposition film according to claim 5, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.

  The invention according to claim 7 is characterized in that the water-soluble polymer has at least one of polyvinyl alcohol or poly (vinyl alcohol-o-ethylene), cellulose and starch as a component. It is a strong adhesion vapor deposition film of description.

  The invention according to claim 8 is a packaging material for retort characterized by being produced using the strong adhesion vapor deposition film according to any one of claims 1 to 7.

According to the present invention, the PET film on which the inorganic oxide layer is deposited is immersed in an aqueous solution to which an amine-based alkali is added to remove only the inorganic oxide layer, and XPS measurement is performed on the surface of the removed PET film. Sometimes, when the functional group ratio (COO / C-C) obtained from C1s waveform separation is 0.23 or less, the PET film and the inorganic oxide layer exhibit very good adhesion. Furthermore, when this laminated film is used as a packaging material, it is possible to provide a strongly adhered vapor deposition film that does not cause delamination and the like and a packaging material for retort using the same even when heat sterilization such as retort is performed.

  DESCRIPTION OF THE PREFERRED EMBODIMENTS The best mode for carrying out the present invention will be described below with reference to the drawings.

  FIG. 1 is a cross-sectional view illustrating a strong adhesion vapor deposition film of the present invention. In this structure, an inorganic oxide layer 2 and a composite coating layer 3 are formed on the surface of a polyethylene terephthalate (PET) film 1. The inorganic oxide layer 2 and the composite coating layer 3 may be formed on both surfaces of the substrate, or may be multilayered. The plasma pretreatment layer 4 can also be provided on the surface of the PET film on the side where the inorganic oxide layer is to be formed, by performing plasma treatment using reactive ion etching (RIE). The plasma pretreatment layer 4 may be formed on both sides of the substrate.

  The PET film may be either unstretched or stretched, and the stretching ratio is not particularly limited in the case of stretching. Moreover, what has mechanical strength and dimensional stability 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 vapor-deposited thin film layer made of an inorganic oxide, and a gas barrier coating layer, a range of 3 to 200 μm is preferable, and a range of 6 to 30 μm is particularly preferable. Various known additives and stabilizers such as an antistatic agent, an ultraviolet ray preventing 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.

  Measurement by X-ray photoelectron spectroscopy (XPS measurement) can analyze the type and concentration of atoms, the types of atoms bound to those atoms, and their bonding states in the depth region several nanometers from the surface of the substance to be measured. , Element ratio, functional group ratio, and the like. For this reason, in the case of a PET film provided with a vapor deposition layer made of an inorganic oxide having a thickness of 5 to 100 nm, such as the strong adhesion vapor deposition film of the present invention, it is not possible to measure the surface of the PET film in this state. Is possible. 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. Moreover, there is no problem if the water temperature is 30 ° 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 or it cannot be completely removed. On the other hand, if it exceeds 10%, the PET film itself is also affected, and the surface after the inorganic oxide layer is removed may be contaminated or the structure of the PET 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. Each bond energy value is 285.0 eV (C—C bond), 286.6-28.
It is 6.7 eV (C—O bond), 288.9 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, when the functional group ratio (COO / C-C) obtained from C1s waveform separation is 0.23 or less, this 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. More preferably, the functional group ratio is in the range of 0.05 to 0.23. If it is less than 0.05, the film surface is excessively treated, and the surface deteriorates.

  On the other hand, in the case of an untreated PET film, the functional group ratio (COO / C—C) is about 0.25 on the surface of the PET film after removing the inorganic oxide layer. 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.

  In order to obtain a PET film having good adhesion to the inorganic oxide layer as described above, it is effective to perform a plasma pretreatment using reactive ion etching (RIE) on the PET film surface. By performing plasma pretreatment using RIE, it is possible to chemically change the surface structure of PET film using the generated radicals and ions, and control the functional group ratio (COO / C-C). can do. Furthermore, by performing this treatment, a dense thin film of inorganic oxide can be formed during the vapor deposition. 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 inorganic oxide layer 2 will be described in detail. The vapor-deposited thin film layer made of an inorganic oxide is made of a vapor-deposited film of an inorganic oxide such as aluminum oxide, silicon oxide, tin oxide, magnesium oxide, or a mixture thereof, has transparency, and has oxygen, water vapor, etc. Any layer can be used. Considering various sterilization resistances, it is more preferable to use aluminum oxide and silicon oxide among them. However, the vapor-deposited thin film 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 vapor-deposited thin film layer varies depending on the type and configuration of the inorganic compound to be used, but is generally within the range of 5 to 300 nm, and the value is appropriately selected. However, if the film thickness is less than 5 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 10-150 nm.

  There are various methods for forming a vapor-deposited thin film layer made of an inorganic oxide on a plastic substrate, and it can be formed by a normal vacuum vapor deposition method. In addition, other thin film forming methods such as sputtering, ion plating, and plasma vapor deposition (CVD) can also be used. However, considering productivity, the vacuum deposition method is the best at present. As a heating means of the vacuum evaporation method, it is preferable to use any one of an electron beam heating method, a resistance heating method, and an induction heating method, but the electron beam heating method should be used in consideration of the wide selection of evaporation materials. Is more preferable. Moreover, in order to improve the adhesiveness of a vapor deposition thin film layer and a base material, and the denseness of a vapor deposition thin film layer, it is also possible to vapor-deposit using a plasma assist method or an ion beam assist method. In order to increase the transparency of the deposited film, it is possible to use reactive deposition in which various gases such as oxygen are blown during the deposition.

Next, the composite coating layer 3 will be described. The composite coating layer is a coating layer with gas barrier properties,
It is formed 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. 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.

  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 a general formula, M (OR) n (M: metal such as Si, Ti, Al, Zr, or alkyl group such as R: CH ₃ , C ₂ H ₅ ). Specific examples include tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] and triisopropoxyaluminum [Al (O-2′-C ₃ H ₇ ) ₃ ], among which tetraethoxysilane and triisopropoxy. Aluminum is preferable because it is relatively stable in an aqueous solvent after hydrolysis.

  It is also possible to add known additives such as isocyanate compounds, silane coupling agents, or dispersants, stabilizers, viscosity modifiers, and colorants to the solution as long as the gas barrier properties are not impaired. is there.

  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 varies depending on the optimum conditions 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 cannot 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 a problem. It is preferably in the range of 0.01 to 50 μm, more preferably in the range of 0.1 to 10 μm.

  A printing layer, an intervening film, a sealant layer, and the like can be laminated on the composite coating layer 3 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 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 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.

Hereinafter, examples of the strong adhesion vapor deposition film of the present invention will be described in detail. The present invention is not limited to these examples.
[Surface condition analysis method]
The X-ray photoelectron spectrometer used for the measurement was JPS-90MXV manufactured by JEOL Ltd., non-monochromated MgKα (1253.6 eV) was used as the X-ray source, and the output was measured at 100 W (10 kV-10 mA). . 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.

Plasma pretreatment using reactive ion etching (RIE) was performed on an untreated surface of a polyethylene terephthalate (PET) film having a thickness of 12 μm under the following conditions. At this time, a high frequency power source having a frequency of 13.56 MHz was used for the electrodes.
[Plasma treatment conditions]
Applied power: 120W
Processing time: 0.1 sec
Processing gas: Argon Processing unit pressure: 2.0 Pa
On top of this, aluminum oxide was formed into a film with a thickness of 15 nm by reactive vapor deposition using an electron beam heating method, and a strong adhesion vapor deposition film was prepared.

  Next, this film was added to 1.0 wt. After immersing in distilled water to which 80% triethanolamine was added at 80 ° C. for 5 minutes to remove the aluminum oxide vapor deposition layer, XPS measurement of the film surface was performed.

  A strongly adhered vapor deposition film was prepared in the same manner as in Example 1 except that the treatment time during the plasma pretreatment was 0.5 sec. Next, this film was added to 1.0 wt. After immersion in distilled water containing 90% triethanolamine at 90 ° C. for 3 minutes to remove the aluminum oxide deposition layer, XPS measurement of the film surface was performed.

  A strongly adhered vapor deposition film was prepared in the same manner as in Example 1 except that the processing gas at the time of plasma pretreatment was an argon / oxygen mixed gas. Next, this film was 2.0 wt. After immersing in distilled water to which 80% triethylamine was added at 80 ° C. for 10 minutes to remove the aluminum oxide deposition layer, XPS measurement of the film surface was performed.

  A strongly adhered vapor deposition film was prepared in the same manner as in Example 1 except that the applied voltage during plasma pretreatment was 250 W and the treatment gas was an argon / oxygen mixed gas. Next, this film was added to 1.0 wt. After immersing in distilled water to which 80% triethanolamine was added at 80 ° C. for 5 minutes to remove the aluminum oxide vapor deposition layer, XPS measurement of the film surface was performed.

  A pre-treatment by RIE on the base material was not performed, and a vapor deposition film was prepared in the same manner as in Example 1 for an untreated PET film. Next, this film was added to 1.0 wt. After immersing in distilled water to which 80% triethanolamine was added at 80 ° C. for 5 minutes to remove the aluminum oxide vapor deposition layer, XPS measurement of the film surface was performed.

  A vapor deposited film was prepared in the same manner as in Example 1 except that the PET film was subjected to corona treatment. Next, this film was 2.0 wt. After immersing in distilled water to which 80% triethanolamine was added at 80 ° C. for 5 minutes to remove the aluminum oxide vapor deposition layer, XPS measurement of the film surface was performed.

  A strongly adhered vapor-deposited film was prepared in the same manner as in Example 1 except that the applied voltage was 120 W, the treatment time was 0.1 sec, and the treatment gas was a plasma treatment (not RIE) using an argon / oxygen mixed gas. Next, this film was 2.0 wt. After immersing in distilled water to which 80% triethanolamine was added at 80 ° C. for 5 minutes to remove the aluminum oxide vapor deposition layer, XPS measurement of the film surface was performed.

  The same operation as in Example 7 was performed except that the processing time was 10 sec.

  On the vapor-deposited films of Examples 1 to 4 and Comparative Examples 5 to 8, a solution was prepared by mixing the following 1) liquid and 2) liquid at a blending ratio (wt%) of 6/4.

1) Liquid: 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% polyvinyl alcohol / isopropyl alcohol solution (90:10 by weight ratio of water: isopropyl alcohol)
This solution was applied and dried by a gravure coating method to form a 0.4 μm thick composite coating layer.

Furthermore, a retort packaging material of the above-mentioned vapor-deposited 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 deposited film and stretched nylon of the above laminated sample was measured using Orientec Tensilon Universal Tester RTC-1250 (conforming to JIS Z1707). However, the measurement was performed while the measurement site was wetted with water. The results are shown in Table 1.
[Evaluation 2]
Using the laminated sample, a pouch having four sides as a seal portion was prepared and filled with contents. Then, 121 degreeC-30 minute retort sterilization was performed, and the state after a retort was observed visually. The results are shown in Table 1.

表１より、実施例１〜４の本発明の強密着蒸着フィルムは、実施例５〜８の比較のための蒸着フィルムに比べて、ラミネート強度に優れ、かつレトルト処理後のデラミネーションの発生もなく、食品及びレトルト食品分野や医薬品、電子部材等の非食品分野の包装に用いられる実用範囲の広い包装材料を提供することが可能である。

From Table 1, the strong adhesion vapor deposition films of the present invention of Examples 1 to 4 are superior in laminate strength compared to the vapor deposition films for comparison of Examples 5 to 8, and the occurrence of delamination after retorting is also observed. In addition, it is possible to provide a packaging material with a wide practical range that is used for packaging in the non-food field such as food and retort food fields, pharmaceuticals, and electronic components.

  It is used as a packaging material with a wide range of practical use that is used for packaging in the non-food field such as food and retort food fields, pharmaceuticals, and electronic components.

It is sectional drawing which shows an example of the strong adhesion vapor deposition film of this invention. It is a C1s waveform separation analysis spectrum obtained by XPS of untreated PET.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Polyethylene terephthalate film (PET) base material layer 2 ... Inorganic oxide vapor deposition layer 3 ... Composite coating layer 4 ... Plasma treatment layer 5 ... CC bond peak 6 ... CO bond peak 7 ... COO bond peak

Claims (8)

  After immersing a polyethylene terephthalate film provided with a vapor deposition layer made of an inorganic oxide having a thickness of 5 to 100 nm on at least one surface in treated water and removing the vapor deposition layer made of an inorganic oxide, X-rays on the film surface The functional group ratio (COO / C-C) obtained from the analysis of the C1s waveform when performing photoelectron spectroscopy measurement (measurement condition: X-ray source MgKα, output 100 W) is 0.23 or less. Adhesive deposition film.   The treated water described above is prepared by adding at least one kind of ammonia, triethanolamine, trimethanolamine, diethanolamine, triethylamine, trimethylamine, or other weakly alkaline amines in water having a temperature of 30 ° C. or higher to 0.01% to 10%. The strongly adhered vapor-deposited film according to claim 1, characterized in that it is added in an amount of%.   The strong adhesion according to claim 1 or 2, wherein a plasma pretreatment using reactive ion etching (RIE) is performed on at least a surface of the polyethylene terephthalate film constituting the strong adhesion vapor deposition film. Deposition film.   The strong adhesion vapor deposition film according to any one of claims 1 to 3, wherein the inorganic oxide is aluminum oxide, silicon oxide, or a mixture thereof.   A composite film layer formed by applying an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer and one or more metal alkoxides or a hydrolyzate thereof on the vapor-deposited layer made of the inorganic oxide and drying by heating. The strong adhesion vapor deposition film according to any one of claims 1 to 4, which is provided.   The strong adhesion vapor deposition film according to claim 5, wherein the metal alkoxide is tetraethoxysilane, triisopropoxyaluminum, or a mixture thereof.   The strong adhesion vapor deposition film according to claim 5 or 6, wherein the water-soluble polymer has at least one of polyvinyl alcohol or poly (vinyl alcohol-o-ethylene), cellulose, and starch as a component.   A packaging material for retort, which is produced using the strong adhesion vapor deposition film according to any one of claims 1 to 7.

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