JP6239409B2 - Vapor deposition film - Google Patents

Description

  The present invention relates to a vapor deposition film that suppresses a decrease in gas barrier properties during processing such as lamination.

  Conventionally, heat insulating materials using polyurethane foam have been used as heat insulating materials for refrigerators, heat insulating panels for residential heat insulating walls, and hot water storage tanks. As a superior material to replace this, a vacuum heat insulating body composed of a laminate film having a gas barrier property even under high humidity and a core material has begun to be used. As the gas barrier material, aluminum foil is mainly used. However, since aluminum is a good conductor of heat, there is a drawback in that the amount of heat passing through the aluminum portion in the film is large and the heat insulation performance is lowered. In order to eliminate this drawback, high gas barrier films such as a polyester film having a thin aluminum vapor deposition layer instead of an aluminum foil, an ethylene-vinyl alcohol copolymer film, and a silica vapor deposition film have been studied.

Since these vapor-deposited layers are thin layers having a thickness of several tens to hundreds of nanometers, there is an inconvenience that gas barrier properties due to bending in a laminate film manufacturing process or a vacuum heat insulator manufacturing process are lowered. As a solution to this problem, a technique for improving the pinhole resistance by adding a filler to a gas barrier resin is known (see Patent Document 1). Moreover, the technique which surface-treats a base film and expresses stable barrier property is known (refer patent document 2).
However, even if such a technique is used, vapor deposition is lost during vapor deposition, and the gas barrier property of the vapor deposited film is lowered. Therefore, an improvement in workability during vapor deposition has been desired.

JP 2002-310385 A JP-A-2005-290108

  It is an object of the present invention to suppress the occurrence of vapor deposition omission during vapor deposition as described above, and cracks during vapor deposition film processing such as lamination, to provide an excellent vapor deposition layer adhesion strength, and to suppress a decrease in gas barrier properties and production thereof It is to provide a method and use.

  The invention made in order to solve the above-mentioned problems is a vapor deposition film having a metal vapor deposition layer on a base film made of a resin composition containing a vinyl alcohol polymer (A), which is not contained in the base film. It is a vapor deposition film which contains a saturated aldehyde (B) 0.01ppm or more and 100ppm or less.

  The vapor-deposited film of the present invention is a vapor-deposited film having a metal vapor-deposited layer on a base film made of a resin composition containing a vinyl alcohol polymer (A), and an unsaturated aldehyde (B) in the base film. Is contained in the above-mentioned specific range, it suppresses the occurrence of vapor deposition loss during vapor deposition, cracks during vapor deposition film processing such as lamination, and is excellent in adhesion strength of the vapor deposition layer. The reason why the resin composition has the above-described configuration provides the above-mentioned effect is not necessarily clear, but can be inferred as follows, for example. That is, by setting the content of the unsaturated aldehyde (B) within the above specific range, it is possible to suppress the occurrence of gels and blisters during the production of the base film. As a result, the occurrence of vapor deposition defects is suppressed at the time of vapor deposition on the base film, and the surface of the base film is not disturbed, so that the adhesion strength between the vapor deposition layer and the base film is improved.

  The unsaturated aldehyde (B) is preferably an unsaturated aliphatic aldehyde, and the unsaturated aliphatic aldehyde comprises crotonaldehyde, 2,4-hexadienal, and 2,4,6-octatrienal. It is preferably at least one selected from the group. The said resin composition can improve the vapor deposition defect inhibitory property and the adhesion strength of a vapor deposition layer more by containing unsaturated aldehyde.

  The vapor deposition film which the said metal vapor deposition layer has on both sides of a base film may be sufficient. By having a metal vapor-deposited layer on both sides of the base film, that is, on both two opposing faces of the film, further improvement in gas barrier properties and stability can be obtained.

  The vapor deposition film which has a metal vapor deposition layer of 2 or more layers on the single side | surface or both surfaces of a base film may be sufficient. By further depositing two or more metal deposition layers, further improvement in gas barrier properties and stability can be obtained.

  15 nm or more and 150 nm or less may be sufficient as the sum total of the average thickness of the metal vapor deposition layer of the single side | surface of the said vapor deposition film.

  The packaging material provided with the said vapor deposition film or a vacuum heat insulating body may be sufficient.

  The vapor deposition film is preferably manufactured at a surface temperature of the base film at the time of vapor deposition of 60 ° C. or less from the viewpoints of economics and stability of vapor deposition such as suppression of deformation of the base film.

  An object of the present invention is to provide a vapor deposition film that suppresses vapor deposition defects such as vapor deposition loss occurring during vapor deposition as described above, has high adhesion strength of the vapor deposition layer, and suppresses a decrease in gas barrier properties, a method for producing the same, and uses. There is.

<Vapor deposition film>
The vapor-deposited film of the present invention is a vapor-deposited film having a metal vapor-deposited layer on a base film made of a resin composition containing a vinyl alcohol polymer (A), and an unsaturated aldehyde (B) in the base film. In an amount of 0.01 ppm to 100 ppm. Hereinafter, it demonstrates in order of a base film, an unsaturated aldehyde, and a metal vapor deposition layer.

<Base film>
(Vinyl alcohol polymer (A))
The vinyl alcohol polymer (A) contained in the resin composition is a vinyl ester homopolymer or a copolymer of vinyl ester and other monomers (hereinafter referred to as vinyl ester homopolymer, vinyl ester and others). And a copolymer of both of the monomer and the monomer are abbreviated as a vinyl ester polymer) and saponified using an alkali catalyst or the like. The content of vinyl ester in the copolymer of vinyl ester and other monomers is preferably 40 mol% or more. Examples of the vinyl ester include vinyl acetate, but other fatty acid vinyl esters (such as vinyl propionate and vinyl pivalate) can also be used. In addition, the vinyl alcohol polymer (A) may be other monomers such as ethylene, propylene, butylene, isobutene, 4-methyl-1-pentene, as long as the effects of the present invention are not impaired. Α-olefins such as hexene and 1-octene; unsaturated carboxylic acids such as (meth) acrylic acid or esters thereof; vinylsilane compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or salts thereof; alkylthiols; One or a plurality of vinyl pyrrolidones such as N-vinyl pyrrolidone may be copolymerized. Among these, as the monomer to be copolymerized, ethylene is more preferable from the viewpoint of enabling melt molding of the resulting vinyl alcohol polymer (A). The vinyl alcohol polymer (A) is preferably an ethylene-vinyl alcohol copolymer.

  When the other monomer is ethylene, the content of the ethylene unit with respect to all the units constituting the vinyl alcohol polymer (A) is 0 mol% to 60 mol%, and 3 mol% to 60 mol. % Is more preferable, 10 mol% to 60 mol% is more preferable, and 20 mol% to 55 mol% is still more preferable. The vinyl alcohol polymer (A) contained in the resin composition can be produced by a known method. A chain transfer agent may be used during the production, and examples of the chain transfer agent include alkylthiols.

  The saponification degree of the vinyl ester component of the vinyl alcohol polymer (A) (ratio of vinyl alcohol units to the total of vinyl alcohol units and vinyl ester units (mol%)) is 85 mol% or more, 90 The mol% or more is preferable, 95 mol% or more is more preferable, and 99 mol% or more is more preferable. If the saponification degree is less than 85 mol%, the gas barrier property of the vapor-deposited film under high humidity may be lowered. When the vinyl alcohol polymer (A) contains two or more types of vinyl alcohol polymers (A) having different degrees of saponification, it is calculated based on the content ratio of the respective vinyl alcohol polymers (A). Let the average value be the degree of saponification. The saponification degree of the vinyl alcohol polymer (A) can be determined by a nuclear magnetic resonance (NMR) method.

In the base film, the upper limit of the oxygen permeability coefficient measured at 20 ° C.-65% RH is preferably 50 ml · 20 μm / m ² · day · atm or less, preferably 10 ml · 20 μm / m ² · day · atm or less. More preferably, 5 ml · 20 μm / m ² · day · atm or less is more preferred, and 1 ml · 20 μm / m ² · day · atm or less is particularly preferred. When the oxygen permeability coefficient is 50 ml · 20 μm / m ² · day · atm or less, the thickness of the base film constituting the vacuum heat insulator can be reduced, and the cost can be reduced.
Here, “20 ° C.-65% RH” means that the relative humidity is 65% at 20 ° C., and “50 ml · 20 μm / m ² · day · atm” means that the film thickness is converted to 20 μm. In addition, it represents that 50 ml of oxygen permeates per day under a pressure difference of 1 m ^{2 of} film and 1 atmosphere of oxygen gas.

  The average thickness of the substrate film is not particularly limited, but is preferably 30 μm or less, more preferably 25 μm or less, and further preferably 20 μm or less. Moreover, as said average thickness, 5 micrometers or more are preferable, 7 micrometers or more are more preferable, and 10 micrometers or more are further more preferable.

(Unsaturated aldehyde (B))
Said resin composition contains unsaturated aldehyde (B) as an essential component. As a minimum of content of unsaturated aldehyde (B), it is 0.01 ppm or more with respect to a resin composition, and 0.05 ppm or more is more preferred. On the other hand, as an upper limit of content of unsaturated aldehyde (B), it is 100 ppm or less with respect to a resin composition, and 50 ppm or less is more preferable. When the content of the unsaturated aldehyde (B) is less than the lower limit, it is insufficient to suppress an increase in the generation of gels and punctures over time in melt molding. Conversely, if the content of the unsaturated aldehyde (B) exceeds the above upper limit, the condensation of unsaturated aldehydes (B) or the condensate of unsaturated aldehydes (B) with the vinyl alcohol polymer (A) during melt molding. May cause the generation of fish eyes and streaks, and the resin composition may be easily colored. Here, the content of the unsaturated aldehyde (B) in the resin composition is expressed as a ratio to the total solid mass of the resin composition, and specifically, contained in the dried resin composition. The value obtained by quantifying the unsaturated aldehyde (B).

  Unsaturated aldehyde (B) is an aldehyde having a carbon-carbon double bond or triple bond in the molecule. The unsaturated aldehyde (B) is preferably an unsaturated aliphatic aldehyde, such as acrylic aldehyde (acrolein), crotonaldehyde, methacrylaldehyde, 2-methyl-2-butenal, 2-pentenal, 2-hexenal, 2,6- Aldehydes having a carbon-carbon double bond in the molecule such as nonadienal, 2,4-hexadienal, 2,4,6-octatrienal, 3-methyl-2-hexenal, 5-methyl-2-hexenal Aldehydes having a carbon-carbon triple bond such as propioaldehyde, 2-butyn-1-al and 2-pentyne-1-al are preferred, and unsaturated having a straight-chain or branched carbon-carbon double bond Aliphatic aldehydes are more preferred, crotonaldehyde, 2,4-hexadienal and , 4,6-octatrienal is more preferable, and crotonaldehyde having a high solubility in water and a boiling point of around 100 ° C. is used in, for example, a washing step and a drying step. It is further preferable because it is easy to remove the excess or add the deficiency as necessary. As carbon number including the aldehyde part of unsaturated aldehyde (B), 3-10 are preferable, 4-8 are more preferable, 4, 6, and 8 are more preferable.

(Boron compound)
The resin composition preferably further contains 100 ppm or more and 5,000 ppm or less of a boron compound. The boron compound content is converted to boric acid.

Examples of the boron compound include boric acids such as orthoboric acid, metaboric acid, and tetraboric acid;
Borate esters such as triethyl borate and trimethyl borate;
Borate salts such as alkali metal salts or alkaline earth metal salts of borates, borax;
Examples thereof include borohydrides. Of these, boric acids are preferable, and orthoboric acid (hereinafter sometimes simply referred to as “boric acid”) is more preferable.

  The content of the boron compound is 100 ppm to 5,000 ppm, preferably 100 ppm to 4,000 ppm, and more preferably 150 ppm to 3,000 ppm. In the resin composition, by making the content of the boron compound within the above specific range, it is difficult to cause gelation during melt molding, and effectively suppresses torque fluctuations of an extruder during heat melting. Can do. Thereby, the said resin composition can form the container etc. which are excellent in external appearance property, and can improve long run property. The said resin composition cannot fully exhibit the said effect as content of a boron compound is less than 100 ppm, and when it exceeds 5,000 ppm, it may become easy to gelatinize and the external appearance of a molded product may become inadequate. is there.

(Conjugated polyene compound)
It is preferable that the said resin composition further contains 0.01 ppm or more and 1,000 ppm or less of conjugated polyene compounds. Here, the conjugated polyene compound does not include a conjugated polyene compound corresponding to the unsaturated aldehyde (B). The resin composition can further suppress oxidative degradation during melt molding by further containing the specific amount of the conjugated polyene compound. Thereby, the said resin composition can suppress generation | occurrence | production and coloring of defects, such as a fish eye, can improve the external appearance property of a molded article, and is also excellent in long run property.

  The conjugated polyene compound is a compound having a so-called conjugated double bond in which the number of carbon-carbon double bonds is 2 or more. The conjugated polyene compound may be a conjugated diene having two conjugated double bonds, a conjugated triene having three, or a conjugated polyene having more than that number. Further, a plurality of sets of the conjugated double bonds may be present in one molecule without being conjugated with each other. For example, a compound having three conjugated triene structures in the same molecule such as tung oil is also included in the conjugated polyene compound.

  The conjugated polyene compound preferably has 7 or less conjugated double bonds. When the resin composition contains a conjugated polyene compound having 8 or more conjugated double bonds, the molded product may be colored.

  In addition to conjugated double bonds, the conjugated polyene compounds include carboxyl groups and salts thereof, hydroxyl groups, ester groups, carbonyl groups, ether groups, amino groups, imino groups, amide groups, cyano groups, diazo groups, nitro groups, sulfones. And other salts such as sulfonyl groups, sulfoxide groups, sulfide groups, thiol groups, phosphate groups and salts thereof, phenyl groups, halogen atoms, non-conjugated double bonds, triple bonds, etc. Good.

Examples of the conjugated polyene compound include isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 1,3- Pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, 2- Methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4- Hexadiene, 1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-phenyl-1,3-butadiene, 1,4-diphenyl-1,3-butyl Diene, 1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene, 1-ethoxy-1,3-butadiene, 2-ethoxy-1,3-butadiene, 2-nitro-1,3-butadiene Butadiene, chloroprene, 1-chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 2-bromo-1,3-butadiene, fulvene, tropone, oximene, ferrandrene, myrcene, farnesene, semblene, sorbine Conjugated diene compounds such as acids, sorbic acid esters, sorbates, and abietic acid;
Conjugated triene compounds such as 1,3,5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, cholecalciferol;
Examples thereof include conjugated polyene compounds such as cyclooctatetraene, 2,4,6,8-decatetraene-1-carboxylic acid, retinol, and retinoic acid. In addition, the said conjugated polyene compound may be used individually by 1 type, and can also use 2 or more types together.

  As carbon number of a conjugated polyene compound, 4-30 are preferable and 4-10 are preferable.

  Among these, sorbic acid, sorbic acid ester, sorbate, myrcene and a mixture of any of these are preferable, and sorbic acid, sorbate and a mixture thereof are more preferable. Sorbic acid, sorbate and a mixture thereof are highly effective in suppressing oxidative degradation at high temperatures, and are also widely used industrially as food additives, and thus are preferable from the viewpoint of hygiene and availability.

  The molecular weight of the conjugated polyene compound is usually 1,000 or less, preferably 500 or less, and more preferably 300 or less. When the molecular weight of the conjugated polyene compound exceeds 1,000, the dispersion state in the vinyl alcohol polymer (A) is poor, and the appearance after melt molding may be poor.

  The content of the conjugated polyene compound is from 0.01 ppm to 1,000 ppm, preferably from 0.1 ppm to 1,000 ppm, preferably from 0.5 ppm to 800 ppm, and more preferably from 1 ppm to 500 ppm. When the content of the conjugated polyene compound is less than 0.01 ppm, the resin composition cannot sufficiently obtain an effect of suppressing oxidative deterioration during melt molding. On the other hand, if it exceeds 1,000 ppm, gelation of the resin composition is promoted and the appearance of the molded product tends to be poor.

  It is disclosed in Japanese Patent Application Laid-Open No. 9-71620 that a resin composition with less generation of gel-like spots at the time of molding can be obtained by adding a conjugated polyene compound in the subsequent step of polymerization. In addition to the addition of unsaturated aldehyde (B), the occurrence of defects such as fish eyes and coloring can be further suppressed, and the appearance of molded products can be improved. An excellent resin composition is obtained.

(Acetic acid and / or acetate)
The resin composition preferably contains 50 ppm to 1,000 ppm of acetic acid and / or acetate. The said resin composition can prevent coloring of a molded article by further containing the said specific amount of acetic acid and / or acetate. The acetic acid and / or acetate content is converted to acetic acid.

  As the acetic acid and / or acetate, it is preferable to use both acetic acid and acetate, and it is more preferable to use acetic acid and sodium acetate.

  The content of acetic acid and / or acetate is preferably from 50 ppm to 1,000 ppm, preferably from 100 ppm to 1,000 ppm, preferably from 150 ppm to 500 ppm, more preferably from 200 ppm to 400 ppm. If the content of acetic acid and / or acetate is less than 50 ppm, a sufficient anti-coloring effect cannot be obtained, and yellowing may be observed in a molded product formed from the resin composition. When the content of acetic acid and / or acetate exceeds 1,000 ppm, the resin composition tends to gel during melt molding, particularly during long melt molding, and the appearance of the molded product may be poor. is there.

(Phosphorus compound)
The resin composition preferably contains 1 ppm or more and 200 ppm or less of a phosphorus compound. The resin composition further contains the above-mentioned specific amount of the phosphorus compound, thereby further suppressing the generation and coloring of defects such as fish eyes and improving the appearance of the molded product, and also has a long run property. Even better. The phosphorus compound content is converted to phosphorus element.

  Examples of the phosphorus compound include various phosphoric acids such as phosphoric acid and phosphorous acid, and phosphates.

  As said phosphate, any form of a 1st phosphate, a 2nd phosphate, and a 3rd phosphate may be sufficient. The cation species is not particularly limited, but is preferably an alkali metal salt or an alkaline earth metal salt. Among these, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate Dipotassium hydrogen phosphate is more preferable, and sodium dihydrogen phosphate and dipotassium hydrogen phosphate are more preferable.

  As content of the phosphorus compound in the said resin composition, 1 ppm or more and 200 ppm or less are preferable, 2 ppm or more and 150 ppm or less are preferable, 3 ppm or more and 150 ppm or less are preferable, and 5 ppm or more and 100 ppm or less are more preferable. When the content of the phosphorus compound is less than 1 ppm or more than 200 ppm, the resin composition has a reduced thermal stability, and the occurrence of gelled spots and coloration during long-time melt molding Problems are likely to arise.

(Other optional ingredients)
The resin composition may contain an alkali metal as another optional component as long as the effects of the present invention are not impaired. Examples of the alkali metal include lithium, sodium, and potassium. Moreover, the said alkali metal can also be contained as an alkali metal salt. Examples of the alkali metal salt include a monovalent metal aliphatic carboxylate, aromatic carboxylate, and metal complex. Specific examples include sodium stearate, potassium stearate, and sodium salt of ethylenediaminetetraacetic acid. Of these, sodium stearate and potassium stearate are preferred. As content in the said resin composition of the said alkali metal, 20-1,000 ppm is preferable and 50-500 ppm is more preferable.

  In addition to the alkali metal, the resin composition includes antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, heat stabilizers, other resins, and higher aliphatic carboxylic acid metals. You may contain a salt, a hydrotalcite compound, etc. as another arbitrary component. The resin composition may contain one or more of these optional components, and the total content is 1% by mass or less.

  Examples of the antioxidant include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis- (6-t-butylphenol), 2, 2′-methylene-bis- (4-methyl-6-tert-butylphenol), octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 4,4′-thiobis -(6-t-butylphenol) and the like.

  Examples of the ultraviolet absorber include ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-). Methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-oxybenzophenone and the like.

  Examples of the antistatic agent include pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, polyethylene oxide, carbowax (trade name), and the like.

  Examples of the lubricant include ethylene bisstearamide and butyl stearate.

  Examples of the colorant include carbon black, phthalocyanine, quinacridone, indoline, azo pigments, and bengara.

  Examples of the heat stabilizer include hindered phenol compounds and hindered amine compounds.

  Examples of the other resin include polyamide and polyolefin.

  Examples of the metal salt of the higher aliphatic carboxylic acid include calcium stearate and magnesium stearate.

  In addition, as a measure against gel generation, 0.01 to 1% by mass of one or more of the above hydrotalcite compounds, hindered phenols, hindered amine heat stabilizers, and higher fatty acid carboxylic acid metal salts are added. can do.

  Examples of the filler include glass fiber, wollastonite, calcium silicate, talc, and montmorillonite.

  The vinyl alcohol polymer (A) may contain an inorganic oxide. The inorganic oxide is not particularly limited, and silicon oxide, aluminum oxide, magnesium oxide, zirconium oxide, cerium oxide, tungsten oxide, molybdenum oxide, and a complex thereof can be used. Among these inorganic oxides, silicon oxide and silicon oxide-magnesium oxide are preferable, and silicon oxide is more preferable.

  As content of the said inorganic oxide, 0.001 mass% or more is preferable with respect to 100 mass% of vinyl alcohol-type polymers, 0.005 mass% or more is more preferable, 0.01 mass% or more is further more preferable. . Moreover, as content of an inorganic oxide, 1 mass% or less is preferable, 0.75 mass% or less is more preferable, and 0.5 mass% or less is further more preferable. When the content of the inorganic oxide exceeds 1% by mass, gels, fish eyes and the like are likely to be generated, and gas barrier properties may be deteriorated due to vapor deposition.

  As an average particle diameter measured by the laser diffraction scattering method of the inorganic oxide, 2 μm or more is preferable, and 2.5 μm or more is more preferable. The average particle size of the inorganic oxide is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3.5 μm or less. When the average particle diameter of the inorganic oxide exceeds 10 μm, gels, fish eyes and the like are likely to occur. Moreover, gas barrier property may fall that it is less than 2 micrometers. The method for adding the inorganic oxide is not particularly limited. For example, when the vinyl alcohol polymer (A) is produced, it is added as an aqueous dispersion and then precipitated and dried in a coagulation bath. Examples thereof include a method, a method of dry blending, and a method of mixing a master batch.

<Method for producing resin composition>
As a manufacturing method of said resin composition, unsaturated aldehyde (B) can be uniformly blended in vinyl alcohol polymer (A), and the range of 0.01 ppm or more and 100 ppm or less of the resin composition finally obtained. Although it will not specifically limit if it is a method in which unsaturated aldehyde (B) of this is contained,
(1) A method for producing a vinyl alcohol polymer (A), which comprises a step of polymerizing vinyl ester and the like, and (2) a step of saponifying the copolymer obtained in step (1).
A method for producing a resin composition, wherein 0.01 to 100 ppm of unsaturated aldehyde (B) is contained in the resin composition, is preferred.

The method for containing the specific amount of unsaturated aldehyde (B) in the resin composition is not particularly limited. For example, in the step (1), a method of adding the specific amount of unsaturated aldehyde (B),
A method of adding a specific amount of the unsaturated aldehyde (B) in the step (2),
Examples thereof include a method of adding a specific amount of unsaturated aldehyde (B) to the vinyl alcohol polymer (A) obtained by the step (2).
However, when the method of adding a specific amount of unsaturated aldehyde (B) in the above step (1) or the method of adding a specific amount of unsaturated aldehyde (B) in the above step (2) is adopted, In order to contain the desired amount of unsaturated aldehyde (B) in the resin composition obtained, the amount added in consideration of the amount consumed in the polymerization reaction in the step (1) and the saponification reaction in the step (2) However, if the amount of unsaturated aldehyde (B) is large, these reactions may be inhibited. In addition, since the amount consumed varies depending on the reaction conditions of the polymerization reaction and saponification reaction, it is difficult to adjust the content of the unsaturated aldehyde (B) in the resin composition. Therefore, a method of adding a specific amount of the unsaturated aldehyde (B) to the EVOH (A) obtained by the step (2) after the step (2) is preferable.

  As a method for adding a specific amount of the unsaturated aldehyde (B) to the vinyl alcohol polymer (A), for example, the unsaturated aldehyde (B) is previously blended with the vinyl alcohol polymer (A) to produce pellets. The method of granulating, the method of impregnating the unsaturated aldehyde (B) in the strand deposited in the step of depositing the paste after saponification of the vinyl ester polymer, and impregnating the unsaturated aldehyde (B) after cutting the precipitated strand A method of adding an unsaturated aldehyde (B) to a redissolved chip of a dry resin composition, melting a blend of two components of a vinyl alcohol polymer (A) and an unsaturated aldehyde (B) Method of kneading and feeding the unsaturated aldehyde (B) to the melt of the vinyl alcohol polymer (A) from the middle of the extruder A master batch is prepared by blending unsaturated aldehyde (B) with a part of vinyl alcohol polymer (A) at a high concentration and granulated, and then dry blended with vinyl alcohol polymer (A) and melt-kneaded. The method etc. are mentioned.

  Among these, from the viewpoint that a small amount of unsaturated aldehyde (B) can be uniformly dispersed in the vinyl alcohol polymer (A), the unsaturated aldehyde (B) mixing step includes an unsaturated aldehyde (B). ) In advance in the vinyl alcohol polymer (A) to pelletize the pellet. Specifically, the unsaturated aldehyde (B) is added to a solution obtained by dissolving the vinyl alcohol polymer (A) in a good solvent such as a water / methanol mixed solvent, and the mixed solution is added to the poor solvent from a nozzle or the like. It is possible to obtain pellets in which the unsaturated aldehyde (B) is homogeneously mixed with the vinyl alcohol polymer (A) by extruding into a polymer and precipitating and / or solidifying it, and washing and / or drying it.

  Moreover, a conjugated polyene compound can also be added simultaneously with unsaturated aldehyde (B) at the process of granulating the said pellet. By adding the unsaturated aldehyde (B) and the conjugated polyene compound, it is possible to further suppress the occurrence of defects such as fish eyes and coloring, and to improve the appearance of the molded product, and also to provide long run properties. An excellent resin composition can be obtained.

  Examples of the method of adding each component other than the unsaturated aldehyde (B) to the resin composition include, for example, a method of mixing and melting and kneading the pellet together with the components, and an unsaturated aldehyde (B ) And a method of mixing each component at the same time, a method of immersing the pellet in a solution containing each component, and the like. In addition, a ribbon blender, a high-speed mixer / conical mixer, a mixing roll, an extruder, an intensive mixer, or the like can be used for the mixing.

<Method for producing base film>
The method for producing the base film is not particularly limited, and may be any of non-stretching and stretching by a casting method, and the base film stretching method may be any of biaxial stretching, uniaxial stretching, and inflation. Also good. In addition, when manufacturing a base film, components, such as the said unsaturated aldehyde (B), may be mixed and a film may be obtained. The component concentration such as the unsaturated aldehyde (B) in the base film is preferably the component concentration in the resin composition described above.

  The method of stretching the substrate film is not particularly limited, and any of simultaneous stretching and sequential stretching is possible. The stretching ratio is preferably 12 times or less, more preferably 11 times or less as the upper limit of the area ratio. Moreover, as a draw ratio, 8 times or more are preferable as an area magnification, and 9 times or more are more preferable. The lower limit of the area magnification is preferably 8 times or more, more preferably 9 times or more. The area magnification is preferably 8 to 12 times from the viewpoint of the uniformity of the thickness of the obtained film, gas barrier properties, and mechanical strength. If the area magnification is less than 8 times, stretch spots may remain easily, and if it exceeds 12 times, the film may be easily broken during stretching.

  In addition, continuous stretching is facilitated by preliminarily containing water before stretching. The moisture content of the raw fabric before stretching is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. The moisture content of the raw fabric before stretching is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. When the moisture content is less than 2% by mass, stretch spots are likely to remain, and particularly when the film is stretched with a tenter, the stretch ratio in the portion close to the grip becomes high, so that tearing near the grip may easily occur. On the other hand, when the moisture content exceeds 30% by mass, the elastic modulus of the stretched portion is low, the difference from the unstretched portion is not sufficient, and stretched spots may easily remain.

  The stretching temperature varies somewhat depending on the moisture content of the original fabric before stretching, but a range of 50 ° C to 130 ° C is generally used. In particular, in simultaneous biaxial stretching, a biaxially stretched film with little thickness unevenness is easily obtained in the range of 70 ° C. to 100 ° C., and in sequential biaxial stretching, 70 ° C. to 100 ° C. in longitudinal stretching with a roll. When the film is stretched in the width direction with a tenter at 80 ° C., a biaxially stretched film with few thickness spots is easily obtained in the temperature range of 80 ° C. to 120 ° C.

<Metal vapor deposition layer>
The vapor deposition film of this invention has a metal vapor deposition layer on the base film which consists of a resin composition containing a vinyl alcohol-type polymer (A). Aluminum is preferable as the metal to be deposited on the base film because it has advantages of being light, flexible and glossy. The upper limit of the average particle diameter of the deposited metal particles when observed from the surface of the deposited layer with a scanning electron microscope is 150 nm or less, preferably 125 nm or less, more preferably 100 nm or less, more preferably 75 nm or less, and more preferably 50 nm or less. Is particularly preferred. Although the minimum of the average particle diameter of the said metal vapor deposition layer does not have limitation in particular, 10 nm or more is preferable, 15 nm or more is more preferable, and 20 nm or more is further more preferable. The average particle diameter of the metal vapor deposition layer is measured with an electron microscope such as a scanning electron microscope. When the metal vapor deposition layer is formed of metal particles, the particle diameter of the metal particles When it is formed as a lump, it means the particle diameter of the metal particles that give this agglomerate. Moreover, the average particle diameter of a metal vapor deposition layer means what averaged each maximum length about the same direction, such as a metal particle observed with an electron microscope.

  As average thickness of the said metal vapor deposition layer, 150 nm or less is preferable per vapor deposition layer, 130 nm or less is more preferable, and 100 nm or less is further more preferable. Moreover, as average thickness of the said metal vapor deposition layer, 15 nm or more is preferable per vapor deposition layer, 20 nm or more is more preferable, 30 nm or more is further more preferable. When the average thickness of the metal vapor deposition layer per vapor deposition layer exceeds 150 nm, a heat bridge tends to occur in the vacuum heat insulating body, and the heat insulation effect may be reduced. Moreover, when the average thickness of the metal vapor deposition layer per vapor deposition layer is less than 15 nm, there exists a possibility that gas-barrier property may become inadequate. In addition, the average thickness of the said metal vapor deposition layer is an average value of the thickness in arbitrary 10 points | pieces of the metal vapor deposition layer cross section measured with an electron microscope. The vapor deposition film having a plurality of metal vapor deposition layers is preferably such that each of the metal vapor deposition layers is within the range of the average thickness of the metal vapor deposition layer, and the sum of the thicknesses of the metal vapor deposition layers (the total thickness of the metal vapor deposition layers) Is more preferably in the range of the average thickness of the metal deposition layer.

As a method of setting the average particle diameter of the metal vapor deposition layer to 150 nm or less, in the production of the vapor deposition film, the content of volatile components contained in the base film before vapor deposition is 1.1% by mass or less. For example, the surface temperature of the base film may be set to 60 ° C. or lower, or the surface of the base film before vapor deposition may be modified by plasma treatment.
As content of the volatile matter contained in the base film before the said vapor deposition, 1.1 mass% or less is preferable, 0.5 mass% or less is more preferable, and 0.3 mass% or less is further more preferable. Moreover, as content of the said volatile matter, although a minimum is not specifically limited, 0.01 mass% or more is preferable, 0.03 mass% or more is more preferable, 0.05 mass% or more is further more preferable. Here, the content of the volatile component is obtained from the mass change before and after drying at 105 ° C. by the following formula.
Volatile content (% by mass) = [(mass before drying−mass after drying) / mass after drying] × 100

  As surface temperature of the base film at the time of metal vapor deposition, 60 degrees C or less is preferred, 55 degrees C or less is more preferred, and 50 degrees C or less is still more preferred. Moreover, as a surface temperature of the base film at the time of vapor deposition, although a minimum is not specifically limited, 0 degreeC or more is preferable, 10 degreeC or more is more preferable, and 20 degreeC or more is further more preferable. By setting the surface temperature to 60 ° C. or less, the gas barrier property is improved by suppressing the average particle diameter of the metal deposited on the base film to the above range, and deformation of the base film can be suppressed.

The vapor-deposited film of the present invention may have a metal vapor-deposited layer on both sides of the base film, that is, on both two opposite sides of the film. By disposing the metal vapor-deposited layer on both surfaces of the substrate, further improvement in gas barrier properties and stability can be obtained. Here, the term “stability” means that even if a certain vapor deposition layer is defective due to physical impact or the like, the other vapor deposition layer maintains the barrier property, thereby maintaining the gas barrier property of the film.

The deposited film of the present invention may be a deposited film having two or more metal deposited layers on one side or both sides of the base film.
In addition, in this specification, let the vapor deposition layer of the single side | surface of a base film be a 1st layer vapor deposition layer, a 2nd layer vapor deposition layer ... nth layer vapor deposition layer in order from the base film side. Here, n represents an integer.

  One or more metal vapor deposition layers may be sufficient, Preferably it is 1-5 layers from an economical surface, More preferably, it is 1-3 layers. By having one or more metal deposited layers on one or both sides of the base film, improvement in gas barrier properties and stability can be obtained.

  As a method for plasma-treating the surface of the substrate film before vapor deposition, known methods can be used, and among these, atmospheric pressure plasma treatment is preferable. In the atmospheric pressure plasma treatment, nitrogen gas, helium, neon, argon, krypton, xenon, radon, or the like is used as a discharge gas. Among these, nitrogen, helium, and argon are preferably used, and particularly nitrogen is preferable because it can reduce the cost.

In addition to the above plasma treatment, as a pretreatment on the surface of the base film before the vapor deposition treatment is applied to the base film, for example, a method of accelerating the activation of the base material itself such as corona treatment, and polyethylene or polyether A method of forming a thin film layer with a coating agent that uses a urethane-based curing agent as the main agent can be mentioned.

  The vapor deposition film of this invention may further have the resin coat layer containing the vinyl alcohol-type polymer (A) laminated | stacked on the said metal vapor deposition layer. By further including the resin coat layer, it is possible to further suppress a decrease in gas barrier properties due to bending in film processing such as lamination in a subsequent process, which may occur in the vapor deposition film production. The material of the resin coat layer is preferably a water-soluble or water-dispersible polymer, that is, a polymer that can be completely dissolved or finely dispersed in a solvent containing water as a main component at room temperature. Such a polymer is not particularly limited, and examples thereof include water-soluble or water-dispersible polymers among those exemplified as the vinyl alcohol polymer (A) that can be used for the base film.

  A swellable inorganic layered silicate may be dispersed in the resin coat layer. The content of the swellable inorganic layered silicate with respect to the vinyl alcohol polymer (A) in the resin coat layer is not particularly limited, but is preferably 0.5% by mass to 55% by mass in terms of solid content. When it exceeds 55% by mass, the flexibility of the resin coat layer is lowered and defects such as cracks are liable to occur. The content of the swellable inorganic layered silicate is more preferably 1% by mass to 40% by mass, further preferably 3% by mass to 30% by mass, and particularly preferably 5% by mass to 20% by mass.

  The method for laminating the resin coating layer on the metal vapor deposition layer is not particularly limited, but a coating liquid of the resin composition is applied on the surface of the base film side by coating, drying and heat treatment on the metal vapor deposition layer. The method and the method of laminating the resin coating layer on the metal vapor deposition layer side are preferable. Further, the interface between the metal vapor deposition layer and the resin coat layer may be subjected to a corona treatment, a treatment with an anchor coating agent, or the like. Examples of the coating method include a direct gravure method, a reverse gravure method, a micro gravure method, a two roll beat coat method, a roll feed method such as a bottom feed three reverse coat method; a doctor knife method, a die coat method, a dip coat method, Examples thereof include a bar coating method and a coating method combining these. Although it does not specifically limit as average thickness of a resin coat layer, 10 micrometers or less are preferable and 2 micrometers or less are more preferable. The average thickness of the resin coat layer is not particularly limited, but is preferably 0.001 μm or more in order to obtain effective gas barrier properties.

  The vapor-deposited film of the present invention may further include a layer containing a thermoplastic resin other than the vinyl alcohol polymer (A). Examples of the thermoplastic resin include polyolefins such as polyethylene and polypropylene, and polyesters such as polyethylene terephthalate, and these may be stretched. The layer made of the thermoplastic resin may be laminated on any of the base film, the metal vapor-deposited layer, and the resin coat layer of the vapor-deposited film, or these layers and an adhesive layer may be interposed therebetween.

  In addition, the above-mentioned multilayer film may have multiple layers of the metal vapor deposition film of this invention, for example, the base material which consists of thermoplastic resins other than the vapor deposition film of this invention and a vinyl alcohol-type polymer (A). By having a plurality of layers having a film having a metal vapor deposition layer thereon, higher barrier properties can be stably obtained. As a film which has a metal vapor deposition layer on the base material which consists of thermoplastic resins other than a vinyl alcohol-type polymer (A), a metal vapor deposition polyester film is mentioned, for example.

The vapor deposition film preferably has an upper limit of oxygen permeability measured at 40 ° C., a humidity of 90% RH on the vapor deposition layer side and a humidity of 0% RH on the base film side, of 5 ml / m ² · day · atm, more preferably not more than ^{3ml / m 2 · day · atm} , more preferably less ^{2ml / m 2 · day · atm} , and particularly preferably ^{1ml / m 2 · day · atm} . When the oxygen permeability is 5 ml / m ² · day · atm or less, the period during which the degree of vacuum of the heat insulator constituting the vacuum heat insulator can be maintained is extended, and the useful life of the vacuum heat insulator can be extended.

As content of the volatile matter contained in the vapor deposition film before the said vapor deposition, 1.1 mass% or less is preferable, 0.5 mass% or less is more preferable, and 0.3 mass% or less is further more preferable. Moreover, as content of the said volatile matter, although a minimum is not specifically limited, 0.01 mass% or more is preferable, 0.03 mass% or more is more preferable, 0.05 mass% or more is further more preferable. Here, the content of the volatile component is obtained from the mass change before and after drying at 105 ° C. by the following formula.
Volatile content (% by mass) = [(mass before drying−mass after drying) / mass after drying] × 100

  For example, in a vacuum insulator, volatile matter generated from the deposited film enters the vacuum portion of the vacuum insulator. As a result, the degree of vacuum in the vacuum insulator is lowered, and the heat insulation performance is lowered. For this reason, it is particularly preferable that the volatile content contained in the deposited film is as small as possible.

<Application>
The vapor deposition film having a metal vapor deposition layer on the base film made of the resin composition containing the vinyl alcohol polymer (A) of the present invention is a crack during vapor deposition film processing such as occurrence of vapor deposition loss during lamination or lamination. And the adhesion strength of the deposited layer is excellent. For this reason, the vapor deposition film of this invention is applicable to various uses. For example, a packaging material and a vacuum heat insulator are mentioned.

  The packaging material can be applied to various applications, and is preferably used for applications that require a barrier property against oxygen and for applications in which the inside of the packaging material is replaced with various functional gases. Moreover, the packaging material of the present invention can be preferably used as a packaging material for packaging food packaging materials, chemicals such as agricultural chemicals and pharmaceuticals; medical equipment; industrial materials such as machine parts and precision materials; and clothing.

  In addition, the packaging material of the present invention can be used after being processed into various molded products. Such a molded article may be a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, a container lid or a vacuum insulator.

  Heat sealing is performed on the molded product (for example, a vertical bag-filled seal bag). When heat sealing is performed, it is usually necessary to dispose a heat-sealable layer on the inner side of the molded product or on both the inner side and the outer side of the molded product. When the heat-sealable layer is only on the inner side of the molded product (bag), the seal of the body portion is usually a palm-sealed seal. When the heat-sealable layer is on both the inner side and the outer side of the molded product, the seal of the body part is usually an envelope sticker. As the heat-sealable layer, a polyolefin layer (hereinafter sometimes referred to as “PO layer”) is preferable.

  The molded product including the vapor deposition film of the present invention may be, for example, a vertical bag-filling sealed bag that wraps a liquid, a viscous body, a powder, a solid rose, or a food or beverage that combines these. Good. The vertical bag-filling-sealing bag including the vapor-deposited film of the present invention has excellent gas barrier properties and maintains the gas barrier properties even when subjected to physical stress such as deformation and impact. According to this, the quality deterioration of the contents can be suppressed over a long period of time.

  The vertical bag-filling seal bag may be formed by laminating at least one vapor-deposited film and at least one other layer. Examples of other layers include polyester layers, polyamide layers, polyolefin layers, paper layers, inorganic vapor deposition film layers, ethylene-vinyl alcohol copolymer layers (hereinafter sometimes referred to as EVOH layers), and adhesive layers. Is included. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted. Particularly preferable examples of the configuration of the vapor deposition film as the vertical bag-filling seal bag include the configurations of vapor deposition film / polyamide layer / PO layer, vapor deposition film / PO layer, and PO layer / vapor deposition film / PO layer. The vertical bag-filling-sealed seal bag maintains its gas barrier property even when subjected to physical stress such as deformation or impact. An adhesive layer may be provided between the layers constituting the vertical bag-filling seal bag. Moreover, when the vapor deposition layer of this invention exists in the single side | surface of a base material, the vapor deposition layer may face any direction of the outer side and inner side of this vertical bag making filling sealing bag.

  The molded product including the vapor deposition film of the present invention may be a vacuum packaging bag for packaging food containing solid content. The vacuum packaging bag may be formed by laminating at least one deposited film and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted.

  Particularly preferable examples of the configuration of the vapor deposition film as the vacuum packaging bag include a configuration of vapor deposition film / polyamide layer / PO layer and polyamide layer / vapor deposition film / PO layer. A vacuum packaging bag using such a deposited film is particularly excellent in gas barrier properties after vacuum packaging or after vacuum packaging and heat sterilization. An adhesive layer may be provided between the layers. Moreover, when the vapor deposition layer is laminated | stacked only on the single side | surface of a base material, a vapor deposition layer may be in the outer side of a vacuum packaging bag with respect to a base material, and may exist inside.

  The molded product including the vapor deposition film of the present invention may be a pouch with a spout for packaging various liquid substances. The pouch with a spout can be used as a container for liquid drinks (for example, soft drinks), jelly drinks, yogurts, fruit sauces, seasonings, functional water, and liquid foods. The pouch with a spout is excellent in gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. Therefore, by using the pouch with a spout, it is possible to prevent the contents from being altered even after transportation and after long-term storage.

  The pouch with a spout may be formed by laminating at least one deposited film and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted. Particularly preferable examples of the configuration of the vapor deposition film as the pouch with a spout include the configurations of vapor deposition film / polyamide layer / PO layer and polyamide layer / vapor deposition film / PO layer. An adhesive layer may be provided between the layers. Moreover, when the vapor deposition layer is laminated | stacked only on the single side | surface of a base material, a vapor deposition layer may exist in the outer side of a pouch with a spout with respect to a base material, and may exist inside.

  The molded article including the vapor deposition film of the present invention may be a laminated tube container for packaging cosmetics, medicines, pharmaceuticals, foods, dentifrices and the like. The laminated tube container has excellent gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact.

  The laminate tube container may be formed by laminating at least one vapor-deposited film and at least one other layer. Examples of other layers include a polyamide layer, a polyolefin layer (which may be a pigment-containing polyolefin layer), an inorganic vapor deposition film layer, an EVOH layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted. Particularly preferred configurations for the laminate tube container include PO layer / deposition film / PO layer and PO layer / pigment-containing PO layer / PO layer / deposition film / PO layer. An adhesive layer may be disposed between the layers. Moreover, when the vapor deposition layer is laminated | stacked only on the single side | surface of a base material, a vapor deposition layer may exist in the outer side of a laminate tube container with respect to a base material, and may exist inside.

  The molded product containing the vapor deposition film of the present invention may be a lid material for containers filled with food products such as processed meat products, processed vegetable products, processed fishery products, and fruits. The container lid material is excellent in gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact, so that deterioration of the quality of food as a content can be suppressed over a long period of time. And this container lid | cover material is preferably used as a lid | cover material of the container used for the preservation | save of contents, such as foodstuff.

  The container lid may be formed by laminating at least one layer of a vapor deposition film and at least one other layer. Examples of other layers include a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, a polyester layer, a paper layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted. Particularly preferable examples of the configuration of the vapor deposition film as the container cover material include the configurations of vapor deposition film / polyamide layer / PO layer and vapor deposition film / PO layer. An adhesive layer may be provided between the layers. Moreover, when a vapor deposition layer exists in the single side | surface of a base material, a vapor deposition layer may exist inside (container side) rather than a base material, and may exist outside a base material.

  The molded article including the vapor deposition film of the present invention may be a vacuum heat insulator that can be used for various applications that require cold insulation and heat insulation. Since the vacuum heat insulator can maintain a heat insulation effect over a long period of time, heat insulation for homes used for household appliances such as refrigerators, hot water supply facilities and rice cookers, wall portions, ceiling portions, attic portions, floor portions, etc. It can be used for heat insulation panels such as wood, vehicle roofing and vending machines.

  The vacuum insulator may be formed by laminating at least one deposited film and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer, and an adhesive layer. The number of these layers and the order of lamination are not particularly limited, but when heat sealing is performed, a configuration for that is adopted. Particularly preferable examples of the configuration of the vapor deposition film as the vacuum heat insulating body include the configurations of vapor deposition film / polyamide layer / PO layer and polyamide layer / vapor deposition film / PO layer. An adhesive layer may be provided between the layers. Moreover, when the vapor deposition layer is laminated | stacked only on one surface of a base material, a vapor deposition layer may be in the outer side of a vacuum heat insulating body with respect to a base material, and may exist inside.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In addition, each fixed_quantity | quantitative_assay in a present Example was performed using the following method.

[Ethylene content and saponification degree of vinyl alcohol polymer (A)]
It was determined by ¹ H-NMR (“JNM-GX-500 type” manufactured by JEOL Ltd.) using DMSO-d ₆ as a solvent.

[Quantification of unsaturated aldehyde (B)]
To 200 mg of a 50 mass% 2,4-dinitrophenylhydrazine (DNPH) solution, 50 ml of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), 11.5 ml of acetic acid and 8 ml of ion-exchanged water were added. A DNPH adjustment solution is prepared. Thereafter, 1 g of a sample (dry resin composition pellet, substrate film, or vapor-deposited film) is added to 20 ml of the DNPH adjusting solution, and stirred and dissolved at 35 ° C. for 1 hour. Acetonitrile is added to this solution to precipitate the vinyl alcohol polymer (A), and the solution is filtered and concentrated to obtain an extracted sample. The amount of unsaturated aldehyde (B) was quantified by quantitatively analyzing the extracted sample with high performance liquid chromatography. For quantification, a calibration curve prepared using a standard obtained by reacting each unsaturated aldehyde (B) with a DNPH preparation solution was used.

[Metal vapor deposition layer thickness]
The deposited film was cut with a microtome to expose the cross section. This cross section was observed using a scanning electron microscope (SEM), and the thickness of the metal deposition layer was measured. SEM observation was performed using a backscattered electron detector using ZEISS ULTRA 55 manufactured by SII Nano Technology.

[Evaluation of deposition defects of deposited film]
(1) Measurement of the number of vapor deposition defects The first roll of the vapor deposition film is placed on a slitter and unwound while applying a 100 W fluorescent lamp from the lower part of the film, and the number of vapor deposition defects is measured at n = 10 over a width of 0.5 m and a length of 2 m. The average value was counted as the number of vapor deposition defects per 1 m ² and judged as follows.
A: 0 to 20 pieces / m ²
B: 21-40 pieces / m ²
C: 41-60 pieces / m ²
D: 61-80 pieces / m ²
E: 81-100 pieces / m ²
F: 101 or more / m ²

(2) Temporal change in the number of vapor deposition defects In the continuous production of a vapor deposition film, the number of vapor deposition defects is evaluated for the 100th vapor deposition film by the same determination method as the first film, and the ranks of the vapor deposition defects between the first film and the 100th film are compared. Was used to determine the time course of the deposition defects.
(Criteria)
A: There was no rank difference in vapor deposition defects between the first and 100th vapor deposition films.
B: There was one rank difference in vapor deposition defects between the first and 100th deposited films.

[Evaluation of adhesion strength]
(1) Measurement of vapor deposition strength The adhesion strength between the vapor deposition layer and the resin layer in the vapor deposition film was evaluated as follows.
On the surface of the vapor deposition film on the metal vapor deposition layer side, a dry laminating adhesive (Mitsui Chemicals Takelac A-385 / A-50 was mixed at a mass ratio of 6/1, and a solid content concentration of 23 mass% ethyl acetate solution and Were coated with a bar coater, dried with hot air at 50 ° C. for 5 minutes, and then laminated with a PET film (Toyobo E5000) with a nip roll heated to 80 ° C. At this time, half of the film was also provided with a portion that was not pasted by sandwiching an aluminum foil between them. Thereafter, the film was cured at 40 ° C. for 72 hours to obtain a laminate film. The obtained laminate film was cut into strips of 100 mm × 15 mm around the boundary of aluminum deposition, and a T-type peel test was performed 5 times with a tensile tester at a pulling rate of 10 mm / min. The average value of the measured values obtained was defined as the adhesion strength. The adhesion strength was determined as follows.
(Criteria)
A: 500 g / 15 mm or more B: 450 or more and less than 500 g / 15 mm C: 400 or more and less than 450 g / 15 mm D: 350 or more and less than 400 g / 15 mm E: 350 g / 15 mm or less (2) Change in adhesion strength over time
In the continuous production of the vapor deposition film, the adhesion strength of the 100th vapor deposition film was evaluated by the same determination method as the first film, and the change in the adhesion strength with time was determined by comparing the ranks of the adhesion strength between the first film and the 100th film.
(Criteria)
A: There was no rank difference in vapor deposition defects between the first and 100th vapor deposition films.
B: There was one rank difference in vapor deposition defects between the first and 100th deposited films.
C: There were two rank differences in vapor deposition defects between the first and 100th deposited films.

[Volatile matter from base film and deposited film]
A small piece for measuring the volatile content was cut out from the central portion of the roll having a total width of 80 cm, dried at 105 ° C. for 3 hours using a hot air dryer, and the volatile content was determined from the mass before and after drying by the following formula.
Volatile content (mass%) = (mass before drying−mass after drying) / mass after drying × 100

[Oxygen permeability]
A part of the deposited film was cut out and measured using an oxygen transmission rate measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control Co., Ltd., detection limit value 0.01 ml / m ² · day · atm). The measurement conditions were JIS K7126 (isobaric method) where the temperature was 40 ° C., the humidity on the oxygen supply side was 90% RH, the humidity on the carrier gas side was 0% RH, the oxygen pressure was 1 atm, and the carrier gas pressure was 1 atm. ). In the method of installing the vapor deposition film on the oxygen permeability measuring device, when the vapor deposition film has a resin surface on one side, the vapor deposition layer side is the oxygen supply side and the resin surface side is the carrier gas side. When both sides of a vapor deposition film are metal vapor deposition layers, the surface is not chosen and installed.

<Synthesis of vinyl alcohol polymer (A)>
[Synthesis Example 1]
Polymerization of the ethylene-vinyl acetate copolymer was carried out under the following conditions using a 250 L pressurized reactor.
83.0 kg of vinyl acetate,
26.6 kg of methanol,
2,2′-Azobisisobutylnitrile supply amount 1119.5 ml / hr (concentration 1.5 g / l)
Polymerization temperature 60 ° C
Polymerization tank ethylene pressure 4.93 MPa
Polymerization time 5.0 hours The polymerization rate of vinyl acetate in the obtained copolymer was about 40%. After adding sorbic acid to this copolymerization reaction solution, the sorbic acid is supplied to the extraction tower, and unreacted vinyl acetate is removed from the top of the tower by introducing methanol vapor from the bottom of the tower. % Methanol solution was obtained. The ethylene content of this ethylene-vinyl acetate copolymer was 32 mol%. This methanol solution of ethylene-vinyl acetate copolymer is charged into a saponification reactor, and caustic soda / methanol solution (80 g / l) is added so as to be 0.4 equivalent to the vinyl ester component in the copolymer. Then, methanol was added to adjust the copolymer concentration to 20%. This solution was heated to 60 ° C. and reacted for about 4 hours while blowing nitrogen gas into the reactor. This solution was extruded into water from a metal plate having a circular opening, precipitated, and cut to obtain pellets having a diameter of about 3 mm and a length of about 5 mm. The obtained pellets were drained with a centrifuge, and the operation of adding a large amount of water and draining was repeated.

  20 kg of the pellets obtained by the above liquid removal were put into 180 kg of a mixed solvent of water / methanol = 40/60 (mass ratio) and stirred at 60 ° C. for 6 hours to completely dissolve. Unsaturated aldehyde (B) and sorbic acid were added to the resulting solution, and the mixture was further stirred for 1 hour to completely dissolve unsaturated aldehyde (B) and sorbic acid to obtain a resin composition solution. This resin composition solution was continuously extruded from a nozzle having a diameter of 4 mm into a coagulation bath of water / methanol = 90/10 (mass ratio) adjusted to 0 ° C. to be solidified into a strand. This strand was introduced into a pelletizer to obtain a porous resin composition chip. The obtained porous resin composition chip was washed with an aqueous acetic acid solution and ion-exchanged water, and then immersed in an aqueous solution containing acetic acid, sodium acetate, potassium dihydrogen phosphate and boric acid. The aqueous solution for immersion treatment and the resin composition chip are separated and drained, and then placed in a hot air dryer, dried at 80 ° C. for 4 hours, and further dried at 100 ° C. for 16 hours to obtain a resin composition (dried Resin composition pellets) were obtained. The content of each component in the obtained resin composition was quantified using the above quantification method. In addition, the resin composition was prepared so that content of each component might become as described in Table 1 by adjusting the addition amount of unsaturated aldehyde (B) and the density | concentration of each component of the aqueous solution for immersion treatment.

[Synthesis Example 2]
Polymerization, saponification, pelletization, and washing were performed in the same manner as in Synthesis Example 1 except that crotonaldehyde was supplied so that 0.5 ppm coexisted with the entire system during polymerization to obtain pellets. 20 kg of the obtained pellets were put into 180 kg of a mixed solvent of water / methanol = 40/60 (mass ratio) and stirred at 60 ° C. for 6 hours to completely dissolve the pellets. Unsaturated aldehyde (B) and sorbic acid were added to the resulting solution, and the mixture was further stirred for 1 hour to completely dissolve unsaturated aldehyde (B) and sorbic acid to obtain a resin composition solution. This resin composition solution was continuously extruded from a nozzle having a diameter of 4 mm into a coagulation bath of water / methanol = 90/10 (mass ratio) adjusted to 0 ° C. to be solidified into a strand. This strand was introduced into a pelletizer to obtain a porous resin composition chip. The obtained porous resin composition chip was washed with an aqueous acetic acid solution and ion-exchanged water, and then immersed in an aqueous solution containing acetic acid, sodium acetate, potassium dihydrogen phosphate and boric acid. The aqueous solution for immersion treatment and the resin composition chip are separated and drained, and then placed in a hot air dryer, dried at 80 ° C. for 4 hours, and further dried at 100 ° C. for 16 hours to obtain a resin composition (dried Resin composition pellets) were obtained. The content of each component in the obtained resin composition was quantified using the above quantification method. The unsaturated aldehyde (B) in the resin composition obtained in Synthesis Example 2 was below the detection limit.

<Example 1>
(1) Manufacture of base film With respect to 100 parts by mass of the resin composition obtained in Synthesis Example 1, 2.9 ppm of crotonaldehyde, synthetic silica manufactured by Fuji Silysia Chemical Co., Ltd. (“Silysia” 310P, measured by laser method) The resulting average particle size of 2.7 μ) is dry blended using a tumbler to 0.03 parts by mass, melted at 240 ° C., extruded from a die onto a casting roll, and simultaneously using an air knife. Air was blown at a wind speed of 30 m / sec to obtain an unstretched film having a thickness of 170 μm. This film was brought into contact with warm water at 80 ° C. for 10 seconds, stretched 3.2 times in the vertical direction and 3.0 times in the horizontal direction at 90 ° C. with a tenter-type simultaneous biaxial stretching equipment, and further set at 170 ° C. The film was heat-treated for 5 seconds to obtain a stretched heat-treated film having a total width of 3.6 m. While rewinding this film, a width of 80 cm was slit centered on the center position in the entire width of the film to obtain a roll having a length of 4000 m. Furthermore, a base film was continuously formed, and a total of 100 rolls having a length of 4000 m were collected.

  In this example, the volatile content was 0.15% by mass. The biaxially stretched film with reduced volatile content was promptly packed with an aluminum foil laminate film after film formation to prevent moisture absorption.

  Using the above-mentioned film as a raw material, aluminum was vapor-deposited on one side of the film at a film surface temperature of 38 ° C. and a film running speed of 200 m / min using a batch type vapor deposition equipment EWA-105 manufactured by Nippon Vacuum Technology Co., Ltd. to obtain a vapor deposited film. The thickness of the deposited aluminum was 70 nm. Furthermore, 100 4000-m rolls obtained by continuously forming the films were used as vapor deposition films. With respect to the first roll and the 100th roll of the vapor deposition film, the number of vapor deposition defects, the adhesion strength, and the oxygen permeability (OTR) were evaluated.

  The number of vapor deposition defects, the time-dependent change in the number of vapor deposition defects, the adhesion strength of the vapor deposition layer, and the time course change in the adhesion strength of the vapor deposition layer were all good. The volatile content from the deposited film was the same and good for all rolls.

<Examples 2 to 13>
As shown in Table 1, a vapor deposition film was prepared in the same manner as in Example 1 except that the content of crotonaldehyde, the film surface temperature during vapor deposition, and the thickness of the vapor deposition layer were changed. Changes, volatile matter from the deposited film, adhesion strength of the deposited layer, and changes with time of the deposited layer were evaluated. These results are shown in Table 1. Good performance was confirmed in all evaluation items.

<Example 14>
Using the film obtained in Example 1 as a raw material, aluminum was deposited on one side of the film at a film surface temperature of 38 ° C. and a film running speed of 200 m / min using a batch-type deposition facility EWBA-105 manufactured by Nippon Vacuum Technology Co., Ltd. A film was obtained. After sufficiently cooling the film to room temperature, again using the batch-type deposition equipment EWA-105 manufactured by Nippon Vacuum Technology Co., Ltd., opposite to the surface on which aluminum was previously deposited at a film surface temperature of 38 ° C. and a film running speed of 200 m / min. Aluminum was vapor-deposited on this surface to obtain a double-sided vapor-deposited film. The thickness of the deposited aluminum was 70 nm on both sides. Table 1 shows the results of evaluating the number of vapor deposition defects, the change with time in the number of vapor deposition defects, the adhesion strength of the vapor deposition layer, and the change with time in the adhesion strength of the vapor deposition layer in the same manner as in Example 1.

<Example 15>
Using the film obtained in Example 1 as a raw material, aluminum was deposited on one side of the film at a film surface temperature of 38 ° C. and a film running speed of 200 m / min using a batch-type deposition equipment EWA-105 manufactured by Nippon Vacuum Technology Co., Ltd. A film was obtained. After the film has been sufficiently cooled to room temperature, the same surface as previously subjected to aluminum deposition at a film surface temperature of 38 ° C. and a film running speed of 200 m / min using a batch type vapor deposition equipment EWA-105 manufactured by Nippon Vacuum Technology Co., Ltd. Aluminum was deposited on the surface to obtain a two-layer deposited film. The thickness of the deposited aluminum was 70 nm for each layer. Table 1 shows the results of evaluating the number of vapor deposition defects, the change with time in the number of vapor deposition defects, the adhesion strength of the vapor deposition layer, and the change with time in the adhesion strength of the vapor deposition layer in the same manner as in Example 1.

<Example 16>
Using the vapor-deposited film obtained in Example 1, a 50 μm thick unstretched polypropylene film (CPP, Mitsui Chemicals Tosero Co., Ltd., RXC-21) and a 12 μm thick polyester stretched film (PET, Toray Industries, Inc.) “Lumirror” P60) was laminated by dry lamination using an adhesive to obtain a multilayer film. The layer structure of this multilayer film was polyester stretched film / deposited film / unstretched polypropylene film, and the laminated film was laminated so that the deposition layer side of the deposited film was on the polyester stretched film side. As the adhesive, Mitsui Chemicals, Inc. “Takelac” A-385 / “Takenate” A-50 was used, the coating amount was 4 g / m ^2, and the coating was dried at 50 ° C. for 5 seconds. Further, after drying, it was further aged at 40 ° C. for 3 days. Using this multilayer film, the oxygen transmission rate (OTR) was measured and found to be 0.09 ml / m ² · day · atm.

<Example 17>
Using the vapor-deposited film obtained in Example 1, a 50 μm-thick unstretched polypropylene film (CPP, manufactured by Mitsui Chemicals, Inc., RXC-21) and a 12-μm thick vapor-deposited polyester stretched film (deposited PET, Toray Industries, Inc.) A multi-layer film was produced in the same manner as in Example 16 using “VM-PET” 1510). In addition, the multilayer film bonded together the vapor deposition surface of vapor deposition PET, and the vapor deposition surface of a vapor deposition film. As a result of measuring oxygen permeability, it was 0.04 ml / m ² · day · atm.

<Example 18>
The vapor-deposited film obtained in Example 1, the unstretched polypropylene film and the polyester stretched film used in Example 16 were laminated in the same manner as in Example 16, and the polyester stretched film / deposited film / deposited film / unstretched polypropylene film were laminated. A multilayer film was produced. Lamination was performed such that the vapor deposition layer side of the vapor deposition film was on the polyester stretched film side. In addition, the lamination | stacking of vapor deposition films bonded the base film and the vapor deposition layer. As a result of measuring oxygen permeability, it was below the detection limit (less than 0.01 ml / m ² · day · atm).

<Example 19>
The vapor-deposited film obtained in Example 14, the unstretched polypropylene film and the polyester stretched film used in Example 16 were laminated in the same manner as in Example 16, and the polyester stretched film / double-sided vapor-deposited film / unstretched polypropylene film was laminated. A multilayer film was produced. As a result of measuring oxygen permeability, it was 0.03 ml / m ² · day · atm.

<Example 20>
The vapor-deposited film obtained in Example 15, the unstretched polypropylene film and the polyester stretched film used in Example 16 were laminated in the same manner as in Example 16, and the polyester stretched film / 2-layer deposited film / unstretched polypropylene was laminated. A multilayer film called a film was produced. In addition, the multilayer film bonded together the vapor deposition surface of PET and a two-layer vapor deposition film. The oxygen permeability was 0.03 ml / m ² · day · atm.

<Example 21>
The vapor-deposited film obtained in Example 1, the unstretched polypropylene film and vapor-deposited polyester stretched film used in Example 17, and a stretched polyamide film having a thickness of 15 μm (ON, “Emblem” ONBC (trademark) manufactured by Unitika Ltd.) And laminated in the same manner as in Example 16 to produce a multilayer film of stretched polyamide film / deposited polyester stretched film / deposited film / unstretched polypropylene film. In addition, the multilayer film bonded together the vapor deposition surface of vapor deposition PET, and the vapor deposition surface of a vapor deposition film. As a result of measuring oxygen permeability, it was 0.04 ml / m ² · day · atm.

<Comparative Example 1>
The unsaturated aldehyde (B) was not added to the resin composition obtained in Synthesis Example 2. The volatile content of the base film before vapor deposition was 1.05% by mass. In the same manner as in Example 1, a vapor deposition film was prepared and the oxygen permeability was evaluated. The oxygen permeability of the first vapor deposited film was 0.19 ml / m ² · day · atm.

<Comparative example 2>
The unsaturated aldehyde (B) was not added to the resin composition obtained in Synthesis Example 2. The volatile content of the base film before vapor deposition was 0.13% by mass. In the same manner as in Example 1, a vapor deposition film was prepared and the oxygen permeability was evaluated. The oxygen permeability of the first vapor deposited film was 0.16 ml / m ² · day · atm.

<Comparative Example 3 and Comparative Example 4>
Using the resin composition prepared in Synthesis Example 1 except that the content of crotonaldehyde and the film surface temperature were 62 degrees as shown in Table 1, a vapor deposition film was prepared in the same manner as in Example 1. The oxygen permeability was evaluated.

<Comparative Example 5>
Lamination was performed in the same manner as in Example 16 using the vapor-deposited film obtained in Comparative Example 1, the unstretched polypropylene film and the polyester stretched film used in Example 16, and called polyester stretched film / deposited film / unstretched polypropylene film. A multilayer film was prepared. Lamination was performed such that the vapor deposition layer side of the vapor deposition film was on the polyester stretched film side. As a result of measuring oxygen permeability, it was 0.34 ml / m ² · day · atm.

<Comparative Example 6>
The vapor-deposited film obtained in Comparative Example 1, the unstretched polypropylene film used in Example 21, the vapor-deposited polyester stretched film, and the stretched polyamide film were laminated in the same manner as in Example 16, and stretched polyamide film / vapor-deposited polyester stretched. A multilayer film of film / deposited film / unstretched polypropylene film was produced. In addition, the multilayer film bonded together the vapor deposition surface of vapor deposition PET, and the vapor deposition surface of a vapor deposition film. As a result of measuring oxygen permeability, it was 0.19 ml / m ² · day · atm.

[Production and evaluation of pouch with spout]
Examples of packaging materials <Example 22>
(Production method of pouch with spout)
Two multilayer films having a size of 20 cm × 13 cm were cut from the multilayer film prepared in Example 16. Subsequently, the two multilayer films that were cut were overlapped so that the CPP was on the inside, the outer periphery was heat-sealed with a width of 0.5 cm, and a spout made of polypropylene was attached by heat sealing. In this manner, a flat pouch-type pouch with a spout was produced. The spout pouch was allowed to stand for 1 week in an atmosphere at a temperature of 20 ° C. and a humidity of 85% RH, and then the oxygen permeability was measured.

(Oxygen permeability of pouch with spout)
-Oxygen permeability of the entire pouch with spout First, set a metal jig with two metal pipes for carrier gas connected to the spout mouth of the pouch, and use an epoxy adhesive to fix the metal jig and the spout. A metal jig was fixed to the spout mouth so that no gas leaked from the gap. Next, the opposite end of one metal pipe was connected to an oxygen permeation amount measuring apparatus ("MOCON OX-TRAN 2/20" manufactured by Modern Control). That is, the carrier gas is released from one of the metal pipes into the pouch with the spout, circulates in the pouch with the spout, and then flows from the other metal pipe into the oxygen gas sensor of the oxygen permeation measuring device.

  Subsequently, the periphery of the pouch to which the metal pipe was attached was covered with a bag, the two metal pipes were pulled out from the bag, and the bag was fixed with a string at the metal pipe portion. The bag was produced by heat-sealing a laminate film having a laminated structure of polyester / adhesive layer / ethylene-vinyl alcohol copolymer (EVOH) layer / adhesive layer / PO layer. Next, the airtightness of the bag was enhanced by filling the gap between the bag and the metal pipe with an epoxy resin. Next, a hole is made in one location of the bag, a pipe for supplying gas is put in the hole, and the bag and gas are supplied using adhesive tape so that outside air does not flow in between the bag and the pipe. For fixing the pipe.

  Subsequently, nitrogen gas containing 2% by volume of hydrogen gas was allowed to flow as a gas and a carrier gas through the pipe and metal pipe in the bag and pouch. Part of the gas flowing into the bag passes through the pouch and flows into the inside of the pouch, the other part passes through the bag and flows out, and the other part is connected at two locations. It flowed out from (metal pipe and bag, pipe and bag connection). The concentration of oxygen gas contained in the carrier gas passing through the metal pipe was measured by an oxygen gas sensor of an oxygen transmission amount measuring device. Until the oxygen concentration reached a constant value, the gas and the carrier gas were continuously supplied into the bag and the pouch. The oxygen concentration at the time when the oxygen concentration became constant was set as the zero point of oxygen permeability.

Thereafter, the gas flowing in the bag was switched to a conditioned oxygen gas. That is, nitrogen gas flows inside the pouch and oxygen gas flows outside the pouch. Oxygen gas permeated from the outside to the inside of the pouch was carried to the oxygen gas sensor via the metal pipe by the carrier gas flowing inside the pouch, and the oxygen concentration was measured. From the oxygen concentration measured at this time, the oxygen permeability (unit: ml / (m ² · day · atm)) of the pouch with a spout was calculated. The measurement was performed under the conditions of a temperature of 20 ° C., a humidity of 85% RH, an oxygen pressure of 1 atm, and a carrier gas pressure of 1 atm.

-Oxygen permeability of spout itself The oxygen permeability of spout itself was measured by the following method. First, a spout portion outside the pouch was cut out from the pouch with the spout. Subsequently, one of the spout mouths cut out using aluminum foil was sealed. After that, set the metal jig to which the two metal pipes for carrier gas are connected to the other port not sealed with the aluminum foil of the spout, and use an epoxy adhesive to connect the metal jig and the spout. A metal jig was fixed to the spout so that gas did not leak from the gap. Next, the opposite end of the metal pipe is connected to an oxygen permeation measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control Co., Ltd.), and the carrier gas flows into the spout from one of the metal pipes. After flowing, the other metal pipe was allowed to flow into the oxygen gas sensor of the oxygen permeation measuring device.

  Subsequently, the spout to which the metal pipe was attached was covered with a bag, the two metal pipes were pulled out from the bag, and the bag was fixed with a string at the metal pipe portion. The bag was produced by heat-sealing a laminated film having a laminated structure of polyester / adhesive layer / EVOH layer / adhesive layer / PO layer. Next, the airtightness of the bag was enhanced by filling the gap between the bag and the metal pipe with an epoxy resin. Next, to make a hole in one place of the bag, put a pipe for supplying gas into the hole, and supply the bag and gas using adhesive tape so that outside air does not flow in between the bag and pipe The pipe was fixed.

  Subsequently, nitrogen gas containing 2% by volume of hydrogen gas was allowed to flow as a gas and carrier gas through the pipe and metal pipe in the bag and spout. Part of the carrier gas that has flowed into the bag passes through the spout and flows into the interior of the spout, the other part passes through the bag and flows out, and part of the carrier gas flows through the two connections ( The metal pipe and the bag, and the pipe and the bag were connected to the outside. The concentration of oxygen gas contained in the carrier gas passing through the metal pipe was measured by an oxygen gas sensor of an oxygen transmission amount measuring device. Until the oxygen concentration reached a constant value, the gas and the carrier gas were kept flowing in the bag and the spout. The oxygen concentration at the time when the oxygen concentration became constant was set as the zero point of oxygen permeability.

Thereafter, the gas flowing in the bag was switched to a conditioned oxygen gas. That is, nitrogen gas flows inside the spout and oxygen gas flows outside the spout. Oxygen gas permeated from the outside of the spout to the inside was carried to the oxygen gas sensor via the metal pipe by the carrier gas flowing inside the spout, and the oxygen concentration was measured. From the oxygen concentration measured at this time, the oxygen permeability of the spout (unit: ml / (m ² · day · atm)) was calculated. The measurement was performed under the conditions of a temperature of 20 ° C., a humidity of 85% RH, an oxygen pressure of 1 atm, and a carrier gas pressure of 1 atm.

-Oxygen permeability of multilayer film The oxygen permeability per unit area of the multilayer film was calculated from the oxygen permeability of each of the pouch with spout and the spout measured by the above method using the following formula.
[Oxygen permeability of pouch with spout] = ([oxygen permeability of multilayer film] × [surface area of multilayer film] + [oxygen permeability of spout] × [surface area of spout]) / ([surface area of multilayer film] + [Spout surface area]

<Comparative Example 7>
A spout with a spout of Comparative Example 7 was produced in the same manner as in Example 22 except that the multilayer film prepared in Comparative Example 5 was used instead of the multilayer film used in Example 22. The oxygen permeability of this pouch with a spout was determined in the same manner as in Example 22.

  Table 3 shows the evaluation results of the pouches with spouts of Examples and Comparative Examples.

[Production and evaluation of vacuum insulation]
<Example 23>
The multilayer film prepared in Example 21 was cut to obtain two multilayer films having a size of 70 cm × 30 cm. The two multilayer films were overlapped so that the CPP layers were the inner surfaces, and the three sides were heat-sealed with a width of 10 mm to produce a three-sided bag. Next, a heat insulating core material is filled from the opening of the three-sided bag, and the three-sided bag is sealed using a vacuum packaging machine (VAC-STAR 2500 type manufactured by Frimark GmbH) at a temperature of 20 ° C. and an internal pressure of 10 Pa. As a result, a vacuum insulator was obtained. Silica fine powder dried for 4 hours in an atmosphere at 120 ° C. was used as the heat insulating core material. The obtained vacuum insulator was allowed to stand at 40 ° C. and 15% RH for 360 days, and then the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge.

<Comparative Example 8>
A vacuum heat insulating material of Comparative Example 8 was produced in the same manner as in Example 23 except that the multilayer film prepared in Comparative Example 6 was used instead of the multilayer film used in Example 23. The vacuum insulator was allowed to stand at 40 ° C. and 15% RH for 360 days, and then the pressure inside the vacuum insulator was measured using a Pirani vacuum gauge.

  Table 4 shows the evaluation results of the vacuum heat insulating materials of Examples and Comparative Examples.

  As shown in Table 1, the base film made of the resin composition containing the vinyl alcohol polymer (A) was able to suppress vapor deposition omission that occurred during vapor deposition. The vapor deposition film which has the obtained metal vapor deposition layer was able to suppress the fall of gas barrier property.

  As shown in Table 2, the multilayer film exhibited high oxygen barrier properties by having an unsaturated aldehyde in the base film.

  As shown in Table 3, the pouch with a spout showed high oxygen barrier properties by having an unsaturated aldehyde in the base film.

  As shown in Table 4, the vacuum insulators of the examples were able to maintain a high degree of vacuum even after a storage test for 360 days at 40 ° C. and 15% RH.

  As described above, the vacuum insulator using the gas barrier layer of the present invention exhibited excellent characteristics over a long period of time.

  The vapor deposition film which has a metal vapor deposition layer on the base film which consists of a resin composition containing the vinyl alcohol polymer (A) of this invention suppresses the vaporization omission generate | occur | produced at the time of vapor deposition, and suppresses the fall of gas barrier property. Can do. Moreover, the said vapor deposition film is shape | molded in a film, a sheet | seat, etc., and is used suitably as various packaging materials and a vacuum heat insulating body.

Claims (9)

  A vapor-deposited film having a metal vapor-deposited layer on a base film made of a resin composition containing a vinyl alcohol polymer (A), the unsaturated aldehyde (B) being 0.01 ppm or more and 100 ppm or less in the base film Contains a deposited film.   The vapor-deposited film according to claim 1, wherein the unsaturated aldehyde (B) is an unsaturated aliphatic aldehyde.   The vapor-deposited film according to claim 2, wherein the unsaturated aliphatic aldehyde is at least one selected from the group consisting of crotonaldehyde, 2,4-hexadienal and 2,4,6-octatrienal.   The vapor deposition film in any one of Claims 1-3 which has a metal vapor deposition layer on both surfaces of a base film.   The vapor deposition film in any one of Claims 1-4 which has a metal vapor deposition layer of 2 or more layers on the single side | surface or both surfaces of a base film.   The vapor deposition film in any one of Claims 1-5 whose sum total of the average thickness of the metal vapor deposition layer of the single side | surface of the said base film is 15 nm or more and 150 nm or less.   A packaging material provided with the vapor deposition film in any one of Claims 1-6.   A vacuum heat insulating body provided with the vapor deposition film in any one of Claims 1-6.   The surface temperature of the base film at the time of vapor deposition is 60 degrees C or less, The manufacturing method of the vapor deposition film in any one of Claims 1-6.