Vapor-deposited film, multilayer structure, molded body, food container, and vapor-deposited film production method

Abstract

Provided are: a vapor-deposited film having excellent surface smoothness; a multilayer structure including the same; a molded body; a food container; and a vapor-deposited film production method.　This vapor-deposited film comprises: a base material film having a layer that contains a composition containing an ethylene-vinyl alcohol copolymer and a titanium compound; and a metal vapor-deposited layer laminated on the base material film. The contained amount of the titanium compound in terms of metals is not less than 0.001 ppm but less than 3 ppm with respect to the mass of the composition.

Description

Vapor-deposited film, multilayer structure, molded body, food container, and method for manufacturing vapor-deposited film

[0001] The present invention relates to a vapor-deposited film, a multilayer structure, a molded article, a food container, and a method for producing a vapor-deposited film, and more particularly to a vapor-deposited film, a multilayer structure, a molded article, a food container, and a method for producing a vapor-deposited film that have excellent surface smoothness.

[0002] Ethylene-vinyl alcohol copolymers (hereinafter sometimes referred to as "EVOH resins") have very strong intermolecular forces due to hydrogen bonds between hydroxyl groups present in polymer side chains. Therefore, they are highly crystalline, and the intermolecular forces are strong even in the amorphous portions. Therefore, films using EVOH resins are difficult for gas molecules to pass through, and exhibit excellent gas barrier properties. Therefore, EVOH resins are used as gas barrier layers to impart gas barrier properties to multilayer structures such as films and containers in a wide range of fields, such as food packaging.

[0003] Aluminum foil has traditionally been used primarily as a gas barrier material in high-humidity environments, but because aluminum has high thermal conductivity and poor heat insulation performance, high-gas barrier films with thin metal vapor-deposited layers are being considered as an alternative to aluminum foil.

[0004] For example, Patent Documents 1 and 2 disclose a vapor-deposited film that can suppress the occurrence of pinholes and cracks during processing such as lamination and suppress deterioration of gas barrier properties. The vapor-deposited film has a metal vapor-deposited layer on a substrate film containing EVOH resin, and the average particle size of the metal vapor-deposited layer is within a specific range. These technologies also state that the EVOH resin may contain 0.001 to 1 mass % of an inorganic oxide (equivalent to 10 to 10,000 ppm) (Patent Documents 1 and 2: paragraphs

[0017] and

[0018] ).

[0005] JP 2017-100451 A International Publication No. 2013 / 125564

[0006] However, Patent Documents 1 and 2 do not consider the surface smoothness of the vapor-deposited film, and there is a risk of minute irregularities occurring on the surface of the vapor-deposited film. A vapor-deposited film with excellent surface smoothness reduces stress concentration due to external stress during transportation, can prevent cracking, suppresses deterioration of gas barrier properties, and can maintain stable performance over a long period of time. Therefore, the vapor-deposited films of Patent Documents 1 and 2 have room for improvement in surface smoothness.

[0007] The present invention has been made in view of the above problems, and provides a vapor-deposited film having excellent surface smoothness on the vapor-deposited surface, a multilayer structure, a molded article, a food container, and a method for producing the vapor-deposited film, each of which includes the vapor-deposited film.

[0008] However, in view of these circumstances, the present inventors have conducted extensive research and have found that the surface smoothness of the vapor-deposited surface of the resulting vapor-deposited film can be improved by adding a specific trace amount of a titanium compound to the EVOH resin in the base film.

[0009] That is, the present invention has the following aspects. [1] A vapor-deposited film comprising a substrate film having a layer containing a composition containing an ethylene-vinyl alcohol copolymer and a titanium compound, and a metal vapor-deposited layer laminated on the substrate film, wherein the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. [2] The vapor-deposited film according to [1], wherein the composition further contains at least one selected from the group consisting of a lubricant, an alkali metal compound, an alkaline earth metal compound, and a boron compound. [3] The vapor-deposited film according to [1] or [2], wherein the water content of the composition before melt molding is 1% by mass or less. [4] The vapor-deposited film according to [2] or [3], wherein the content of the lubricant is 500 ppm or less relative to the mass of the composition. [5] The vapor-deposited film according to any of [2] to [4], wherein the mass ratio of the content of the lubricant to the content of the titanium compound in terms of metal is 0.3 to 500,000. [6] The vapor-deposited film according to any one of [2] to [5], wherein the content of the alkali metal compound in terms of metal is 1 to 1,000 ppm relative to the mass of the composition. [7] The vapor-deposited film according to any one of [2] to [6], wherein the mass ratio of the metal content of the alkali metal compound to the metal content of the titanium compound in terms of metal is 0.2 to 1,000,000. [8] The vapor-deposited film according to any one of [2] to [7], wherein the content of the alkaline earth metal compound in terms of metal is 0.1 to 800 ppm relative to the mass of the composition. [9] The vapor-deposited film according to any one of [2] to [8], wherein the mass ratio of the content of the alkaline earth metal compound in terms of metal to the content of the titanium compound in terms of metal is 0.03 to 500,000.

[10] The vapor-deposited film according to any one of [2] to [9], wherein the content of the boron compound in terms of boron is 1 to 500 ppm relative to the mass of the composition.

[11] The vapor-deposited film according to any one of [2] to

[10] , wherein the mass ratio of the boron-equivalent content of the boron compound to the metal content of the titanium compound is 1 to 200000.

[12] The vapor-deposited film according to any one of [3] to

[11] , wherein the water content of the composition before melt molding is 0.12 mass% or more.

[13] The vapor-deposited film according to any one of [1] to

[12] , wherein the base film is a multilayer film further having a layer containing a thermoplastic resin.

[14] The vapor-deposited film according to any one of [1] to

[13] , wherein the metal of the metal vapor-deposited layer is at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium.

[15] A multilayer structure comprising the vapor-deposited film according to any one of [1] to

[14] .

[16] A molded product comprising the vapor-deposited film according to any one of [1] to

[14] .

[17] A food container comprising the multilayer structure according to

[15] .

[18] A method for producing the vapor-deposited film according to any one of [1] to

[14] , comprising a step of laminating an inorganic vapor-deposited layer on the base film.

[0010] The vapor-deposited film of the present invention has excellent surface smoothness of the vapor-deposited surface. Furthermore, multilayer structures, molded articles, and food containers containing such a vapor-deposited film also have excellent surface smoothness of the vapor-deposited surface.

[0011] The present invention will be described below based on examples of embodiments for carrying out the present invention, but the present invention is not limited to the embodiments described below.

[0012] In this specification, when "X to Y" (X and Y are any numbers) is used, it means "X or more and Y or less," unless otherwise specified, and also includes "preferably more than X" or "preferably less than Y." Furthermore, when "X or more" (X is any number) or "Y or less" (Y is any number) is used, it also includes "preferably more than X" or "preferably less than Y." Furthermore, "x and / or y (x and y are any configurations)" means at least one of x and y, and can mean three possibilities: x only, y only, or x and y. Regarding the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of the numerical range can also be replaced with the values ​​shown in the examples.

[0013] In this specification, the term "film" includes "tape" and "sheet."

[0014] Hereinafter, a monomer unit contained in an EVOH resin or a thermoplastic resin may be simply referred to as a “unit.” For example, a monomer unit based on ethylene may be referred to as an “ethylene unit.”

[0015] A vapor-deposited film according to one embodiment of the present invention (hereinafter, sometimes referred to as "the vapor-deposited film") comprises a substrate film having a layer containing an ethylene-vinyl alcohol copolymer and a composition containing a titanium compound, and a vapor-deposited metal layer laminated on the substrate film.

[0016] In addition to the first aspect, the vapor-deposited film further includes a vapor-deposited film in which the composition contains at least one selected from the group consisting of a lubricant, an alkali metal compound, an alkaline earth metal compound, and a boron compound, and in which the moisture content of the composition before melt-forming is not more than a specific amount. The vapor-deposited film will be described in the following order: a vapor-deposited film in which the composition contains a lubricant is referred to as a "second aspect," a vapor-deposited film in which the composition contains an alkali metal compound is referred to as a "third aspect," a vapor-deposited film in which the composition contains an alkaline earth metal compound is referred to as a "fourth aspect," a vapor-deposited film in which the composition contains a boron compound is referred to as a "fifth aspect," and a vapor-deposited film in which the moisture content of the composition before melt-forming is not more than a specific amount is referred to as a "sixth aspect."

[0017] <<First Aspect>> The first aspect includes the following aspects <I-1> to <I-7>. <I-1> A vapor-deposited film including a substrate film having a layer containing a composition containing an EVOH resin and a titanium compound, and a metal vapor-deposited layer laminated on the substrate film, wherein the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. <I-2> The vapor-deposited film according to <I-1>, wherein the substrate film is a multilayer film further having a layer containing a thermoplastic resin. <I-3> The vapor-deposited film according to <I-1> or <I-2>, wherein the metal of the metal vapor-deposited layer is at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium. <I-4> A multilayer structure comprising the vapor-deposited film according to any one of <I-1> to <I-3>. <I-5> A molded article comprising the vapor-deposited film according to any one of <I-1> to <I-3>. <I-6> A food container comprising the multilayer structure according to <I-4>. <I-7> A method for producing the vapor-deposited film according to any one of <I-1> to <I-3>, comprising a step of laminating an inorganic vapor-deposited layer on the base film.

[0018] The present invention will be described below based on examples of modes for carrying out the first aspect, although the present invention is not limited to the embodiments described below.

[0019] <Vapor-deposited film> A vapor-deposited film according to a first aspect of the present invention (hereinafter sometimes referred to as "the vapor-deposited film") comprises a substrate film having a layer containing an ethylene-vinyl alcohol copolymer and a composition containing a titanium compound, and a vapor-deposited metal layer laminated on the substrate film. Each component will be described below.

[0020] [Base Film] The base film has a layer containing an EVOH resin (hereinafter referred to as an "EVOH layer") The components of the base film will be described below.

[0021] [EVOH Layer] The EVOH layer is formed from a composition containing an EVOH resin (hereinafter, sometimes referred to as "the composition"). The composition will be described below.

[0022] The present composition contains an EVOH resin as a main component and a specific trace amount of a titanium compound. That is, the base resin of the present composition is an EVOH resin, and the content of the EVOH resin in the present composition is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Each component will be described below.

[0023] (EVOH Resin) The EVOH resin used in the present embodiment is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble thermoplastic resin.

[0024] Vinyl acetate is typically used as the vinyl ester monomer because of its commercial availability and the efficiency of impurity removal during production. Examples of vinyl ester monomers other than vinyl acetate include aliphatic vinyl esters such as vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl versatate, and aromatic vinyl esters such as vinyl benzoate. Typically, an aliphatic vinyl ester having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms, is used. These are typically used alone, but multiple types may be used simultaneously as necessary.

[0025] The copolymerization of ethylene and vinyl ester monomers can be carried out using any known polymerization method, such as solution polymerization, suspension polymerization, or emulsion polymerization, but solution polymerization using methanol as a solvent is generally used. The resulting ethylene-vinyl ester copolymer can also be saponified by a known method. The EVOH resin produced in this manner is primarily composed of ethylene-derived structural units and vinyl alcohol structural units, with a small amount of vinyl ester structural units remaining unsaponified.

[0026] The content of ethylene structural units in the EVOH resin is usually 20 to 60 mol%, preferably 25 to 50 mol%, and particularly preferably 25 to 35 mol%. The content of the ethylene structural units can be controlled by the ethylene pressure when copolymerizing the vinyl ester monomer with ethylene. If the content is too low, the gas barrier properties and melt moldability under high humidity conditions tend to decrease, while if the content is too high, the gas barrier properties tend to decrease. The content of the ethylene structural units can be measured in accordance with ISO 14663.

[0027] The saponification degree of the EVOH resin is usually 90 to 100 mol%, preferably 95 to 100 mol%, and particularly preferably 99 to 100 mol%. The saponification degree can be controlled by the amount, temperature, time, etc. of the saponification catalyst (usually an alkaline catalyst such as sodium hydroxide) used when saponifying the ethylene-vinyl ester copolymer. If the saponification degree is too low, the gas barrier properties, thermal stability, moisture resistance, etc. tend to decrease. The saponification degree of the EVOH resin can be measured in accordance with JIS K6726 (wherein the EVOH resin is used as a solution uniformly dissolved in a water / methanol solvent).

[0028] The melt flow rate (MFR) (210°C, 2160 g load) of the EVOH resin is typically 0.5 to 100 g / 10 min, preferably 1 to 50 g / 10 min, and particularly preferably 3 to 35 g / 10 min. If the MFR is too high, stability during film formation tends to be impaired, while if it is too low, the viscosity tends to be too high, making melt extrusion difficult. The MFR is an indicator of the degree of polymerization of the EVOH resin and can be adjusted by the amount of polymerization initiator and the amount of solvent used when copolymerizing ethylene and vinyl ester monomers. In this specification, the MFR can be determined by measuring the flow rate of a sample through an orifice with a length of 8 mm and a diameter of 2.095 mm under conditions of a temperature of 210°C and a load of 2160 g using an automatic melt flow rate tester (manufactured by Toyo Seiki Seisakusho, Ltd.).

[0029] The EVOH resin may further contain structural units derived from the comonomers shown below (for example, 10 mol % or less of the EVOH resin) within the range that does not impair the effects of the present invention.Examples of the comonomer include olefins such as propylene, 1-butene, and isobutene; hydroxy group-containing α-olefins such as 3-butene-1-ol, 3-butene-1,2-diol, 4-pentene-1-ol, and 5-hexene-1,2-diol, and derivatives thereof such as esters and acylation products; hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, and 1,3-dibutyl hydroxyalkylvinylidene diacetates such as methyloxy-2-methylenepropane; unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, or their salts or mono- or di-alkyl esters in which the alkyl group has 1 to 18 carbon atoms; acrylamide, N-alkylacrylamide in which the alkyl group has 1 to 18 carbon atoms, N,N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salts, acrylamidopropyldimethylamine or its acid salts or quaternary salts thereof acrylamides such as methacrylamide, N-alkylmethacrylamides in which the alkyl group has 1 to 18 carbon atoms, N,N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or its salts, methacrylamidepropyldimethylamine or its acid salts or its quaternary salts; N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; alkyl vinyl ethers in which the alkyl group has 1 to 18 carbon atoms, hydrochloric acid vinyl ethers such as alkoxyalkyl vinyl ether and alkoxyalkyl vinyl ether; halogenated vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide; vinyl silanes such as trimethoxyvinylsilane; halogenated allyl compounds such as allyl acetate and allyl chloride; allyl alcohols such as allyl alcohol and dimethoxyallyl alcohol; and comonomers such as trimethyl-(3-acrylamido-3-dimethylpropyl)-ammonium chloride and acrylamido-2-methylpropanesulfonic acid.These may be used alone or in combination of two or more.

[0030] Among these, hydroxy group-containing α-olefins are preferred, and 3-butene-1,2-diol and 5-hexene-1,2-diol are particularly preferred. When the hydroxy group-containing α-olefins are copolymerized, the resulting EVOH resin has primary hydroxyl groups in the side chains. Such EVOH resins having primary hydroxyl groups in the side chains, particularly EVOH resins having a 1,2-diol structure in the side chains, are preferred in that they exhibit good secondary moldability while maintaining gas barrier properties.

[0031] When the EVOH resin has a primary hydroxyl group in a side chain, the content of the structural unit derived from the monomer having the primary hydroxyl group is usually 0.1 to 20 mol %, preferably 0.5 to 15 mol %, particularly preferably 1 to 10 mol %, of the EVOH resin.

[0032] Furthermore, as the EVOH resin, EVOH resins that have been "post-modified" by esterification, urethanization, acetalization, cyanoethylation, oxyalkylenation, or the like can also be used.

[0033] When the post-modified EVOH resin is used, the modification rate is usually 10 mol % or less, and preferably 4 mol % or less. If the modification rate of the EVOH resin is too high, the resin tends to be susceptible to thermal degradation and the long-run properties tend to be reduced.

[0034] Furthermore, the EVOH resin may be a mixture of EVOH resins having different ethylene structural unit contents, saponification degrees, polymerization degrees, copolymerization components, and the like.

[0035] (Titanium Compound) Examples of the titanium compound include inorganic titanium compounds and organic titanium compounds. The titanium compounds may be used alone or in combination of two or more. Among these, inorganic titanium compounds are preferred.

[0036] Examples of the inorganic titanium compounds include titanium oxide, titanium hydroxide, titanium chloride, and inorganic salts of titanium. Examples of the titanium oxides include titanium(II) oxide, titanium(III) oxide, titanium(IV) oxide, and titanium suboxide. Examples of the titanium hydroxides include titanium(I) hydroxide and titanium(II) hydroxide. Examples of the titanium chlorides include titanium(I) chloride and titanium(II) chloride. Examples of the inorganic salts of titanium include those other than the titanium chlorides, such as titanium phosphate and titanium sulfate. Among these, titanium oxide is preferred, titanium(IV) oxide is more preferred, and rutile titanium(IV) oxide is particularly preferred.

[0037] Examples of the organic titanium compounds include titanium carboxylates such as titanium acetate, titanium butyrate, and titanium stearate.

[0038] The titanium compound may exist in the composition as a titanium compound, or may exist in an ionized state or in the form of a complex interacting with the EVOH resin or other ligands.

[0039] The average particle size of the titanium compound is usually 0.001 to 100 μm, preferably 0.01 to 50 μm, and more preferably 0.015 to 20 μm. When the average particle size of the titanium compound is within the above range, the effect of suppressing surface irregularities tends to be excellent. The average particle size of the titanium compound can be measured using a laser diffraction particle size distribution measuring device or the like. The average particle size referred to here is the median diameter.

[0040] The content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. It is preferably 0.01 to 1 ppm, more preferably 0.03 to 0.5 ppm, and particularly preferably 0.05 to 0.2 ppm. By setting the content of the titanium compound within this range, the titanium compound fills up minute depressions in the surface of the EVOH film, resulting in excellent surface smoothness. If the content of the titanium compound is too low, the minute depressions will not be filled up, leaving minute irregularities on the surface. If the content is too high, the remaining titanium oxide will appear on the surface, forming protrusions and causing the surface to become rough. The content of the titanium compound in terms of metal is, in other words, the content of elemental titanium.

[0041] Furthermore, by setting the content of the titanium compound within the above range, it is possible to suppress the generation of microgels due to thermal degradation during melt molding, and the film surface tends to have excellent smoothness. If the content of the titanium compound is too low, the effect of suppressing the generation of microgels will decrease, and the surface smoothness will tend to decrease, while if the content is too high, the EVOH resin will be more susceptible to thermal decomposition, and the surface smoothness will tend to decrease due to the generation of microgels.

[0042] The content of the titanium compound in terms of metal can be quantified by weighing out the composition into a platinum crucible, ashing it successively using a burner and an electric furnace, thermally decomposing the ashed material with nitric acid and hydrofluoric acid, treating it with a mixed acid of dilute nitric acid and dilute hydrofluoric acid, and measuring the titanium in the resulting constant-volume solution by ICP mass spectrometry using an ICP mass spectrometer (Agilent 8800, manufactured by Agilent Technologies).

[0043] Normally, when a titanium compound is added to a resin composition containing EVOH resin, it is thought that the titanium ions will cause thermal degradation of the resin composition and the generation of microgels, and therefore it is common technical knowledge for those in the industry to avoid using titanium compounds. However, in this embodiment, contrary to this common technical knowledge, it has been discovered that when a specific trace amount of titanium compound is used, the titanium in the titanium compound coordinates to the double bond in the main chain of the EVOH resin to form a chelate, thereby improving thermal stability, suppressing the generation of microgels due to thermal degradation, and resulting in an EVOH film with excellent surface smoothness.

[0044] Furthermore, EVOH resins become discolored due to thermal degradation. This is thought to be because EVOH resins deteriorate due to heat, generating radicals, which dehydrate hydroxyl groups in the EVOH resin, forming double bonds in the main chain of the EVOH resin. These sites then become reaction initiation sites, further accelerating dehydration and forming conjugated polyene structures in the main chain of the EVOH resin. Furthermore, in the present resin composition, titanium in the specific trace amount of titanium compound is stabilized as a tetravalent ion, and even in trace amounts, it is stabilized by coordinating to the double bonds in the main chain of the EVOH resin to form a chelate, thereby suppressing the formation of polyene structures.

[0045] (Other Thermoplastic Resins) The composition may contain thermoplastic resins other than EVOH resins within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the composition, preferably 20% by mass or less, particularly preferably 10% by mass or less, the lower limit being typically 0% by mass). Examples of other thermoplastic resins that may be used include known thermoplastic resins, such as polyester resins, polystyrene resins, polyvinyl chloride resins, polycarbonate resins, ionomers, polyvinylidene chloride, polyester elastomers, polyurethane elastomers, chlorinated polyethylene, and chlorinated polypropylene. These may be used alone or in combination of two or more.

[0046] (Other Compounding Agents) The composition may also contain compounding agents (excluding titanium compounds) that are generally compounded with EVOH resins, within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the resin composition, preferably 20% by mass or less, more preferably 10% by mass or less, the lower limit being typically 0% by mass). Examples of such compounding agents include inorganic double salts (e.g., hydrotalcite, etc.), plasticizers (e.g., aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), oxygen absorbers [e.g., inorganic oxygen absorbers such as aluminum powder and potassium sulfite; ascorbic acid, its fatty acid esters and metal salts, etc.; gallic acid; polyhydric phenols such as hydroxyl group-containing phenolaldehyde resins; terpene compounds; blends of tertiary hydrogen-containing resins and transition metals (e.g., a combination of polypropylene and cobalt); and blends of carbon-carbon unsaturated bond-containing resins and transition metals. Polymeric oxygen absorbers such as blends with transition metals (e.g., a combination of polybutadiene and cobalt), photooxidatively degradable resins (e.g., polyketones), anthraquinone polymers (e.g., polyvinyl anthraquinone), and combinations thereof with the addition of photoinitiators (e.g., benzophenone), antioxidants other than those mentioned above, and deodorizers (e.g., activated carbon) may also be added, as well as heat stabilizers, light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants (excluding those used as lubricants), antibacterial agents, antiblocking agents, and fillers (e.g., inorganic fillers). These compounds may be used alone or in combination of two or more.

[0047] (Method for Producing the Composition) The composition can be produced, for example, by mixing the EVOH resin and the titanium compound by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, it is preferable to produce the composition by a method including a step of melt mixing the composition raw materials containing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0048] The dry blending method may be, for example, (i) a method in which a pelletized EVOH resin and a titanium compound are dry blended using a tumbler or the like.

[0049] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with a titanium compound, and the resulting dry blend is melt-kneaded; and (iii) a method in which a titanium compound is added to a molten EVOH resin, and the resulting mixture is melt-kneaded.

[0050] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, a titanium compound is blended therein, the solution is coagulated and molded, and then the resulting mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which a titanium compound is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production process of EVOH resin, the resulting mixture is coagulated and molded, and then the resulting mixture is subjected to solid-liquid separation by known means and dried.

[0051] The impregnation method includes, for example, (vi) a method in which pellets of EVOH resin are brought into contact with an aqueous solution containing a titanium compound to incorporate the titanium compound into the EVOH resin, followed by drying. The aqueous solution containing a titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0052] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0053] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0054] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0055] The shape of the present composition obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, cubic, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. Furthermore, in the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0056] The water content of the composition before melt molding is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass. Here, "melt molding" before melt molding refers to melting and forming a certain shape, and examples include melting the resin composition and forming it into pellets, or melting the resin composition and forming it into a film.

[0057] The moisture content of the composition is measured and calculated by the following method: The mass (W1) of the composition before drying is weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and then cooled in a desiccator for 30 minutes, after which the mass (W2) is weighed and calculated using the following formula: Moisture content (mass%) = [(W1 - W2) / W1] x 100

[0058] When the composition is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds may be used alone or in combination of two or more. The content of such lubricants in the composition is usually 5% by mass or less, preferably 1% by mass or less. The lower limit is usually 0% by mass.

[0059] The composition thus obtained is prepared into various forms, such as pellets, powder, or liquid, and provided as a molding material for various molded products. In particular, in this embodiment, when the composition is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable. Note that the composition also includes resin compositions obtained by mixing resins other than the EVOH resin used in the composition.

[0060] The substrate film may be, for example, a single-layer film (EVOH layer) formed from the composition of the present invention, or a multi-layer film having at least one EVOH layer.

[0061] [Layer containing thermoplastic resin] The substrate film preferably has a layer containing a thermoplastic resin (hereinafter, sometimes referred to as a "thermoplastic resin layer"). When the substrate film has a thermoplastic resin layer, the mechanical strength and water vapor barrier properties of the vapor-deposited film tend to be further improved. In addition, properties such as heat sealability and mechanical strength can be imparted depending on the type of thermoplastic resin constituting the thermoplastic resin layer.

[0062] Examples of the thermoplastic resins are those other than the EVOH resins, and include polyolefins such as polyethylenes such as linear low-density polyethylene, low-density polyethylene, very low-density polyethylene, medium-density polyethylene, and high-density polyethylene, ethylene-vinyl acetate copolymers, ionomers, ethylene-propylene (block or random) copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid ester copolymers, polypropylene, propylene-α-olefin copolymers, polybutene, and polypentene, as well as polyolefins graft-modified with unsaturated carboxylic acids or their esters; polyesters; polyamides (including copolymerized polyamides); polyvinyl chloride; polyvinylidene chloride; acrylic resins; polystyrene; polyvinyl esters; polyester elastomers; polyurethane elastomers; chlorinated polystyrene; chlorinated polypropylene; aromatic polyketones or aliphatic polyketones, and polyalcohols obtained by reducing these; polyacetals; and polycarbonates. Among these, polyolefins are preferred from the viewpoint of excellent heat-sealing properties and mechanical properties, with polypropylene and polyethylene being more preferred, and polyethylene being particularly preferred. These may be used alone or in combination of two or more. The terms linear low density polyethylene, low density polyethylene, very low density polyethylene, medium density polyethylene, and high density polyethylene are commonly used terms to represent types of polyethylene.

[0063] When polyethylene is used as the thermoplastic resin, the melt flow rate (MFR) of the polyethylene, measured (190°C, 2.16 kg load) in accordance with JIS K 7210: 2014, is preferably 0.10 to 7.5 g / 10 min, more preferably 0.15 to 5.0 g / 10 min, and particularly preferably 0.2 to 2.5 g / 10 min. When the MFR of the polyethylene is within the above range, molding stability tends to be better.

[0064] The content of the thermoplastic resin in the thermoplastic resin layer is not particularly limited, but preferably the thermoplastic resin is the main component (i.e., the content of the thermoplastic resin contained in the thermoplastic resin layer is 50% by mass or more), more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0065] The thermoplastic resin layer may contain other components besides the thermoplastic resin, such as antiblocking agents, processing aids, resins other than thermoplastic resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, UV absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0066] [Layer Containing Adhesive Resin] The substrate film may have a layer containing an adhesive resin (hereinafter, sometimes referred to as an "adhesive resin layer"). When the substrate film has an adhesive resin layer, the appearance properties (film surface) of the vapor-deposited film tend to be better.

[0067] The adhesive resin is not particularly limited, but is preferably a polyolefin having a carboxy group, a carboxylic anhydride group, or an epoxy group, and more preferably a polyolefin having a carboxylic anhydride group, since such adhesive resins tend to have excellent adhesion to the EVOH layer and / or the thermoplastic resin layer.

[0068] Examples of polyolefins containing carboxyl groups include polyolefins copolymerized with acrylic acid or methacrylic acid. In this case, all or part of the carboxyl groups contained in the polyolefin may be present in the form of a metal salt, as typified by ionomers. Examples of polyolefins having carboxylic acid anhydride groups include polyolefins graft-modified with maleic anhydride or itaconic acid. Examples of polyolefins having epoxy groups include polyolefins copolymerized with glycidyl methacrylate. Among these, polyolefins having carboxylic acid anhydride groups such as maleic anhydride are preferred, and polyethylenes having carboxylic acid anhydride groups are particularly preferred. These may be used alone or in combination of two or more.

[0069] The melt flow rate (MFR) of the adhesive resin measured (190°C, 2.16 kg load) according to JIS K 7210: 2014 is not particularly limited, but is preferably 0.1 to 20.0 g / 10 min, and more preferably 1.0 to 10.0 g / 10 min. When the MFR of the adhesive resin is in the above range, molding stability tends to be better.

[0070] The content of the adhesive resin in the adhesive resin layer is not particularly limited, but it is preferable that the adhesive resin be the main component (i.e., the content of the adhesive resin contained in the adhesive resin layer is 50% by mass or more). In particular, the content of the adhesive resin is more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0071] The adhesive resin layer may contain other components other than the adhesive resin, such as antiblocking agents, processing aids, resins other than adhesive resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0072] [Method for Producing Substrate Film] The substrate film can usually be produced by extruding the composition through a die, forming it into a film, and stretching it as needed. When the substrate film has a thermoplastic resin layer or an adhesive resin layer, the raw material compositions forming the EVOH layer, the thermoplastic resin layer, and the adhesive resin layer are extruded through separate dies or a common die to form a film by conventional co-extrusion, and then laminating them, followed by stretching as needed. Examples of the die that can be used include a circular die and a T-die. Examples of the molding method include melt-molding methods such as extrusion molding, blow molding, injection molding, thermoforming, and inflation molding, and solution-molding methods such as cast molding.

[0073] The substrate film may have any other layer configuration as long as it has an EVOH layer, but the other layer configuration is not particularly limited. Since the substrate film has an EVOH layer, it is possible to obtain a vapor-deposited film having excellent transparency. The base film is preferably multilayered. When the EVOH layer is defined as the "(A) layer," the thermoplastic resin layer as the "(B) layer," and the adhesive resin layer as the "(C) layer," examples of the layer configuration include (B) layer / (A) layer, (B) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (B) layer / (A) layer / (B) layer / (A) layer / (B) layer, (B) layer / (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, and the like.

[0074] In the above examples, layers (B) and (C) are exemplified as layers other than layer (A), but layers other than layer (A) are not limited to these. Furthermore, it is preferable that the substrate film does not include a layer formed from a resin composition containing a polyamide resin as a main component (i.e., a resin composition containing 50% by mass or more of polyamide resin). Furthermore, the " / " shown in the above examples means that the layers on both sides of it are directly laminated.

[0075] The substrate film thus obtained is preferably stretched as necessary, and more preferably uniaxially stretched. The stretching ratio in the uniaxially stretched film is preferably 3 times or more, more preferably 4 times or more, and particularly preferably 5 times or more. If the stretching ratio is less than 3 times, thickness unevenness due to stretching tends to occur and gas barrier properties tend to deteriorate. The upper limit of the stretching ratio is preferably 12 times or less, more preferably 10 times or less, and particularly preferably 8 times or less. If the stretching ratio is more than 12 times, the film surface after stretching tends to deteriorate. The use of a uniaxially stretched film has advantages such as economic efficiency, ease of tearing the multilayer structure (making it easy to open the packaging material when used as a packaging material), and improved gas barrier properties.

[0076] The stretching direction of the uniaxially stretched film is not particularly limited and may be either the longitudinal direction (MD direction) or the transverse direction (TD direction), but uniaxial stretching in the longitudinal direction (MD direction) is preferred, and it is particularly preferred that the film is not substantially stretched in a direction different from the stretching direction. The stretched state of the substrate film (unstretched, uniaxially stretched, biaxially stretched, etc.) can be confirmed by using a general method for analyzing the orientation of a resin (for example, wide-angle X-ray scattering (WAXS), etc.).

[0077] The stretching method for the uniaxially stretched film is not particularly limited, but examples thereof include tenter stretching, tubular stretching, and roll stretching. Among these, from the viewpoint of production costs, uniaxial stretching by roll stretching is preferred. Furthermore, when the base film is obtained by inflation molding, roll stretching is preferred.

[0078] The stretching temperature during uniaxial stretching is not particularly limited, but is generally 50 to 130°C.

[0079] The total thickness of the substrate film is not particularly limited and can be appropriately set depending on the application. The thickness of the substrate film is preferably 10 μm or more, more preferably 15 μm or more. When the thickness of the substrate film is 10 μm or more, industrial productivity and mechanical properties tend to be further improved. Furthermore, the thickness of the substrate film is preferably 100 μm or less, more preferably 50 μm or less. When the thickness of the substrate film is 100 μm or less, industrial productivity and economic efficiency tend to be further improved. The thickness of the substrate film, which is a uniaxially stretched film, means the thickness after stretching.

[0080] Furthermore, when the base film is a multilayer film, the thickness of the EVOH layer is preferably 0.5 μm or more, more preferably 0.8 μm or more, and particularly preferably 1 μm or more. When the thickness of the EVOH layer is 0.5 μm or more, the gas barrier property tends to be improved. On the other hand, the thickness of the EVOH layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the EVOH layer is 20 μm or less, the appearance characteristics (film surface) tend to be good. Note that the thickness of the multilayer film, which is a uniaxially stretched film, means the thickness after stretching. When the base film has multiple EVOH layers provided thereon, it is preferable that the total thickness of all EVOH layers is within the above range.

[0081] When the base film is a multilayer film, the ratio of the thickness of the EVOH layer to the total thickness of all layers is preferably 30% or less, more preferably 20% or less, and may be 10% or less, or 5% or less, from the viewpoints of industrial productivity and mechanical properties.

[0082] When the base film has a thermoplastic resin layer, the thickness thereof is preferably 7 to 100 μm, more preferably 10 to 50 μm, from the viewpoints of industrial productivity and mechanical properties. In a base film that is a uniaxially stretched film, the thickness of the thermoplastic resin layer refers to the thickness after stretching. When the base film has multiple thermoplastic resin layers, the total thickness of all the thermoplastic resin layers is preferably within the above range.

[0083] When the substrate film has an adhesive resin layer, the thickness thereof is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, from the viewpoints of industrial productivity and quality stability. In a substrate film that is a uniaxially stretched film, the thickness of the adhesive resin layer refers to the thickness after stretching. When the substrate film has multiple adhesive resin layers, the total thickness of all the adhesive resin layers is preferably within the above range.

[0084] The internal haze value of the substrate film is preferably less than 0.4%, more preferably 0.3% or less, even more preferably 0.2% or less, and particularly preferably 0%. Such measurement can be performed using a substrate film having a thickness of 33 μm and a haze meter in accordance with ASTM D1003.

[0085] [Metal Vapor Deposited Layer] The metal vapor deposition layer laminated on the base film is obtained by vapor depositing a single metal or an alloy of two or more metals. From the viewpoint of gas barrier properties, the metal vapor deposition layer is preferably laminated on the EVOH layer of the base film.

[0086] Examples of metals used in the metal vapor deposition layer include those classified as aluminum group elements (aluminum, gallium, indium, etc.), tin group elements (titanium, zirconium, tin, hafnium, etc.), noble metals (copper, silver, gold, etc.), chromium group elements (chromium, molybdenum, tungsten, etc.), and iron group elements (iron, cobalt, nickel, etc.), as well as alloys thereof. Among these, at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium is preferred because it is commonly available and easy to handle, and aluminum is particularly preferred.

[0087] The metal used in the metal vapor deposition layer preferably contains a metal compound such as a metal oxide, a metal carbide, or a metal nitride, and among these metal compounds, a metal oxide is preferred. The content of such a metal compound is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass, of the metal used in the metal vapor deposition layer.

[0088] The metal vapor deposition layer can be identified by analyzing the cross section of the laminate by energy dispersive spectroscopy (EDS).

[0089] [Method for Producing the Present Vapor-Deposited Film] The present vapor-deposited film can be produced by laminating the above-described metal vapor-deposited layer on the above-described substrate film.

[0090] The method for laminating the metal vapor deposition layer on the substrate film is not particularly limited, and any known vapor deposition method may be appropriately adopted, for example, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD method).

[0091] The thickness of the metal vapor deposition layer is usually 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 20 nm. If the thickness of the metal vapor deposition layer is less than 1 nm, the gas barrier property tends to be insufficient, while if the thickness exceeds 100 nm, the effect of improving the gas barrier property cannot be obtained, and the bending resistance and production costs tend to increase.

[0092] The vapor-deposited film thus obtained has excellent surface smoothness of the vapor-deposited surface. The root-mean-square height (Sq) of the vapor-deposited surface of the vapor-deposited film is preferably 0.10 μm or less, more preferably 0.09 μm or less, and even more preferably 0.08 μm or less. The smaller the root-mean-square height (Sq), the smoother the surface, which is preferable. The root-mean-square height (Sq) can be measured using the method specified in ISO 25178, specifically, by the method described in the Examples below.

[0093] The oxygen permeability of this vapor-deposited film at 20°C and 90% RH is 8 cc / m 2 ·day·atm or less, and 7cc / m 2 ·day·atm or less is more preferable, 5 cc / m 2 ·day·atm or less is particularly preferred.

[0094] The vapor-deposited film can be suitably used as a molding for packaging general foods, as well as seasonings such as mayonnaise and dressings, fermented foods such as miso, oily foods such as salad oil, snacks, beverages, cosmetics, pharmaceuticals, etc., as well as packaging materials such as packaging films, or as part of multilayer structures for forming these.

[0095] <Multilayer structure> The multilayer structure is obtained by laminating another layer on the present vapor-deposited film. The other layer to be laminated on the present vapor-deposited film is not particularly limited, and may be a layer formed from a resin composition containing a thermoplastic resin exemplified above as the thermoplastic resin or an adhesive resin exemplified above as the adhesive resin.

[0096] As a method for producing the multilayer structure, various known production methods can be used, such as dry lamination, sand lamination, extrusion lamination, coextrusion lamination, and solution coating.

[0097] <Molded Articles> Cup- or tray-shaped molded articles can be obtained using the vapor-deposited film or the multilayer structure. In this case, a drawing method is typically employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, the multilayer structure can be used to obtain molded articles such as tube- or bottle-shaped multilayer containers (laminate structure) and food containers from a multilayer parison (a hollow tubular preform before blowing). In this case, a blow molding method is typically employed, specifically extrusion blow molding (two-head, mold-moving, parison-shift, rotary, accumulator, horizontal parison, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0098] <<Second Aspect>> The second aspect includes the following aspects <II-1> to <II-9>. <II-1> A vapor-deposited film including a substrate film having a layer containing a composition containing an EVOH resin, a lubricant, and a titanium compound, and a metal vapor-deposited layer laminated on the substrate film, wherein the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. <II-2> The vapor-deposited film according to <II-1>, wherein the content of the lubricant is 500 ppm or less relative to the mass of the composition. <II-3> The vapor-deposited film according to <II-1> or <II-2>, wherein the mass ratio of the content of the lubricant to the content of the titanium compound in terms of metal is 0.3 to 500,000. <II-4> The vapor-deposited film according to any one of <II-1> to <II-3>, wherein the substrate film is a multilayer film further having a layer containing a thermoplastic resin. <II-5> The vapor-deposited film according to any one of <II-1> to <II-4>, wherein the metal in the metal vapor-deposited layer is at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium. <II-6> A multilayer structure comprising the vapor-deposited film according to any one of <II-1> to <II-5>. <II-7> A molded article comprising the vapor-deposited film according to any one of <II-1> to <II-5>. <II-8> A food container comprising the multilayer structure according to <II-6>. <II-9> A method for producing the vapor-deposited film according to any one of <II-1> to <II-5>, comprising a step of laminating an inorganic vapor-deposited layer on the base film.

[0099] The present invention will be described below based on examples of modes for carrying out the second aspect, although the present invention is not limited to the embodiments described below.

[0100] <Vapor-deposited film> A vapor-deposited film according to a second aspect of the present invention (hereinafter sometimes referred to as "the vapor-deposited film") comprises a substrate film having a layer containing a composition that includes an ethylene-vinyl alcohol copolymer, a lubricant, and a titanium compound, and a vapor-deposited metal layer laminated on the substrate film. Each component will be described below.

[0101] [Base Film] The base film has a layer containing an EVOH resin (hereinafter referred to as an "EVOH layer") The components of the base film will be described below.

[0102] [EVOH Layer] The EVOH layer is formed from a composition containing an EVOH resin (hereinafter, sometimes referred to as "the composition"). The composition will be described below.

[0103] The present composition contains an EVOH resin as a main component, a lubricant, and a specific trace amount of a titanium compound. That is, the base resin of the present composition is an EVOH resin, and the content of the EVOH resin in the present composition is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Each component will be described below.

[0104] (EVOH Resin) The EVOH resin used in the present embodiment is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble thermoplastic resin. The same EVOH resin as that described in the first embodiment can be used.

[0105] (Lubricant) Examples of the lubricant include higher fatty acids having 12 to 25 carbon atoms, preferably 13 to 23 carbon atoms, and more preferably 15 to 20 carbon atoms. Examples of the higher fatty acids include higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid; metal salts of higher fatty acids such as aluminum salts, calcium salts, zinc salts, magnesium salts, and barium salts of these higher fatty acids; esters of higher fatty acids such as methyl esters, isopropyl esters, butyl esters, and octyl esters of the higher fatty acids; saturated higher fatty acid amides such as stearamide and behenamide; unsaturated higher fatty acid amides such as oleamide and erucamide; and amides of higher fatty acids such as bis-higher fatty acid amides such as ethylene bisstearamide, ethylene bisoleamide, ethylene biserucamide, and ethylene bislauamide. Examples of lubricants other than the higher fatty acids include low-molecular-weight polyolefins such as low-molecular-weight polyethylene and low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof, higher alcohols, ester oligomers, fluorinated ethylene resins, etc. These lubricants can be used alone or in combination of two or more.

[0106] From the viewpoint of extrusion stability and commercial availability, the valence of the higher fatty acids is usually 1 to 5, preferably 1 to 3, and particularly preferably 1 to 2. The valence refers to the number of structures derived from higher fatty acids contained in one molecule of the compound used in the lubricant; for example, when bisstearic acid amide is used as the lubricant, it has two structures derived from higher fatty acid molecules having 18 carbon atoms in one molecule, and therefore is an amide of a higher fatty acid having 18 carbon atoms, and the valence of the higher fatty acid is considered to be 2.

[0107] Among the above-mentioned lubricants, preferred are higher fatty acids, metal salts of higher fatty acids, esters of higher fatty acids, and amides of higher fatty acids, and particularly preferred are metal salts of higher fatty acids and amides of higher fatty acids, and from the viewpoint of extrusion stability, more preferably amides of higher fatty acids, and particularly preferably ethylene bisstearamide.

[0108] The lubricant may be in any form, such as a solid (powder, fine powder, flakes, etc.), semi-solid, liquid, paste, solution, or emulsion (aqueous dispersion). Of these, a powder form is preferred. The particle size of the powder lubricant is usually 0.1 to 100 μm, preferably 1 to 75 μm, and particularly preferably 5 to 50 μm.

[0109] By incorporating an appropriate amount of lubricant into the composition, thermal stability is improved, the occurrence of streaks and microgels is suppressed, and the surface becomes smooth. The content of the lubricant is preferably 500 ppm or less, more preferably 300 ppm or less, and particularly preferably 200 ppm or less, relative to the mass of the composition. If the content of the lubricant exceeds the above-mentioned value, the surface smoothness tends to decrease due to a decrease in thermal stability (gel formation). The lower limit of the content of the lubricant is usually 1 ppm, preferably 10 ppm or more, and particularly preferably 50 ppm or more. If no lubricant is added or if too little, the moldability of the composition tends to decrease.

[0110] The content of the lubricant can be measured, for example, by the following method. When the lubricant is attached to the surface of the EVOH resin, the amount of the lubricant added can be considered as the content. When the lubricant is contained in the composition, if the lubricant is, for example, a higher fatty acid amide, the total amount of nitrogen in the composition can be measured using a trace total nitrogen analyzer and converted into the lubricant content, thereby measuring the content of the lubricant in the composition.

[0111] (Titanium Compound) As the titanium compound, the same titanium compounds as those explained in the first embodiment can be used.

[0112] The content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. It is preferably 0.01 to 1 ppm, more preferably 0.03 to 0.5 ppm, and particularly preferably 0.05 to 0.2 ppm. By setting the content of the titanium compound within this range, the titanium compound fills up minute depressions in the surface of the EVOH film, resulting in excellent surface smoothness. If the content of the titanium compound is too low, the minute depressions will not be filled up, leaving minute irregularities on the surface. If the content is too high, the remaining titanium oxide will appear on the surface, forming protrusions and causing the surface to become rough. The content of the titanium compound in terms of metal is, in other words, the content of elemental titanium.

[0113] Furthermore, by setting the content of the titanium compound within the above range, it is possible to suppress the generation of microgels due to thermal degradation during melt molding, and the film surface tends to have excellent smoothness. If the content of the titanium compound is too low, the effect of suppressing the generation of microgels will decrease, and the surface smoothness will tend to decrease, while if the content is too high, the EVOH resin will be more susceptible to thermal decomposition, and the surface smoothness will tend to decrease due to the generation of microgels.

[0114] The content of the titanium compound in terms of metal can be quantified by weighing out the composition into a platinum crucible, ashing it successively using a burner and an electric furnace, thermally decomposing the ashed material with nitric acid and hydrofluoric acid, treating it with a mixed acid of dilute nitric acid and dilute hydrofluoric acid, and measuring the titanium in the resulting constant-volume solution by ICP mass spectrometry using an ICP mass spectrometer (Agilent 8800, manufactured by Agilent Technologies).

[0115] The mass ratio of the content of the lubricant to the content of the titanium compound in terms of metal [lubricant content / titanium compound in terms of metal] is usually 0.3 to 500,000, preferably 1 to 50,000, more preferably 20 to 10,000, particularly preferably 250 to 4,000, and especially preferably 900 to 3,000. If this value is too large, thermal stability tends to be impaired, and if it is too small, surface smoothness tends to decrease.

[0116] Normally, when a titanium compound is added to a resin composition containing EVOH resin, it is thought that the titanium ions will cause thermal degradation of the resin composition and the generation of microgels, and therefore it is common technical knowledge for those in the industry to avoid using titanium compounds. However, in this embodiment, contrary to this common technical knowledge, it has been discovered that when a specific trace amount of titanium compound is used, the titanium in the titanium compound coordinates to the double bond in the main chain of the EVOH resin to form a chelate, thereby improving thermal stability, suppressing the generation of microgels due to thermal degradation, and resulting in an EVOH film with excellent surface smoothness.

[0117] Furthermore, EVOH resins become discolored due to thermal degradation. This is thought to be because EVOH resins deteriorate due to heat, generating radicals, which dehydrate hydroxyl groups in the EVOH resin, forming double bonds in the main chain of the EVOH resin. These sites then become reaction initiation sites, further accelerating dehydration and forming conjugated polyene structures in the main chain of the EVOH resin. Furthermore, in the present resin composition, titanium in the specific trace amount of titanium compound is stabilized as a tetravalent ion, and even in trace amounts, it is stabilized by coordinating to the double bonds in the main chain of the EVOH resin to form a chelate, thereby suppressing the formation of polyene structures.

[0118] (Other Thermoplastic Resins) The present composition may contain thermoplastic resins other than EVOH resins within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the present composition, preferably 20% by mass or less, particularly preferably 10% by mass or less, the lower limit being typically 0% by mass). As the other thermoplastic resins, the same ones as those described in the first embodiment above as (other thermoplastic resins) can be used.

[0119] (Other Compounding Agents) The composition may also contain compounding agents generally compounded in EVOH resins (excluding titanium compounds and lubricants) within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the resin composition, preferably 20% by mass or less, more preferably 10% by mass or less, the lower limit being typically 0% by mass). As the compounding agents, the same compounds as those described in the first aspect above can be used.

[0120] (Method for Producing the Composition) The composition can be produced, for example, by mixing the EVOH resin, lubricant, and titanium compound by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, it is preferable to produce the composition by a method including a step of melt mixing the composition raw materials containing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0121] The dry blending method may be, for example, (i) a method in which pelletized EVOH resin, a lubricant, and a titanium compound are dry blended using a tumbler or the like.

[0122] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with a lubricant and a titanium compound, and the resulting dry blend is melt-kneaded; and (iii) a method in which a lubricant and a titanium compound are added to a molten EVOH resin, and the resulting mixture is melt-kneaded.

[0123] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, a lubricant and a titanium compound are blended therein, the solution is coagulated and molded, and then the resulting mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which a lubricant and a titanium compound are added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production of EVOH resin, the resulting mixture is coagulated and molded, and then the resulting mixture is subjected to solid-liquid separation by known means and dried.

[0124] The impregnation method includes, for example, (vi) a method in which pelletized EVOH resin is brought into contact with an aqueous solution containing a lubricant and a titanium compound to incorporate the lubricant and titanium compound into the EVOH resin, followed by drying. The aqueous solution containing the titanium compound may be an aqueous solution of a lubricant and a titanium compound, or one in which titanium ions have been eluted by immersing a lubricant and a titanium compound in water containing various chemicals.

[0125] In the impregnation method, the contents of the lubricant and titanium compound (in terms of metal) can be controlled by the concentrations of the lubricant and titanium compound in the aqueous solution in which the EVOH resin is immersed, as well as the immersion temperature, immersion time, etc. The immersion temperature and immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0126] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0127] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0128] The shape of the present composition obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, cubic, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. Furthermore, in the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0129] The water content of the composition before melt molding is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass. Here, "melt molding" before melt molding refers to melting and forming a certain shape, and examples include melting the resin composition and forming it into pellets, or melting the resin composition and forming it into a film.

[0130] The moisture content of the composition is measured and calculated by the following method: The mass (W1) of the composition before drying is weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and then cooled in a desiccator for 30 minutes, after which the mass (W2) is weighed and calculated using the following formula: Moisture content (mass%) = [(W1 - W2) / W1] x 100

[0131] The composition thus obtained is prepared into various forms, such as pellets, powder, or liquid, and provided as a molding material for various molded products. In particular, in this embodiment, when the composition is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable. Note that the composition also includes resin compositions obtained by mixing resins other than the EVOH resin used in the composition.

[0132] The substrate film may be, for example, a single-layer film (EVOH layer) formed from the composition of the present invention, or a multi-layer film having at least one EVOH layer.

[0133] [Layer containing thermoplastic resin] The substrate film preferably has a layer containing a thermoplastic resin (hereinafter, sometimes referred to as a "thermoplastic resin layer"). When the substrate film has a thermoplastic resin layer, the mechanical strength and water vapor barrier properties of the vapor-deposited film tend to be further improved. In addition, properties such as heat sealability and mechanical strength can be imparted depending on the type of thermoplastic resin constituting the thermoplastic resin layer.

[0134] As the thermoplastic resin, the same thermoplastic resins as those described in the [Layer containing thermoplastic resin] of the first embodiment can be used.

[0135] The content of the thermoplastic resin in the thermoplastic resin layer is not particularly limited, but preferably the thermoplastic resin is the main component (i.e., the content of the thermoplastic resin contained in the thermoplastic resin layer is 50% by mass or more), more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0136] The thermoplastic resin layer may contain other components besides the thermoplastic resin, such as antiblocking agents, processing aids, resins other than thermoplastic resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, UV absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0137] [Layer Containing Adhesive Resin] The substrate film may have a layer containing an adhesive resin (hereinafter, sometimes referred to as an "adhesive resin layer"). When the substrate film has an adhesive resin layer, the appearance properties (film surface) of the vapor-deposited film tend to be better.

[0138] The adhesive resin may be the same as the adhesive resin described in the [Layer containing adhesive resin] in the first embodiment.

[0139] The content of the adhesive resin in the adhesive resin layer is not particularly limited, but it is preferable that the adhesive resin be the main component (i.e., the content of the adhesive resin contained in the adhesive resin layer is 50% by mass or more). In particular, the content of the adhesive resin is more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0140] The adhesive resin layer may contain other components other than the adhesive resin, such as antiblocking agents, processing aids, resins other than adhesive resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0141] [Method for Producing Substrate Film] The substrate film can usually be produced by extruding the composition through a die, forming it into a film, and uniaxially stretching it as needed. When the substrate film has a thermoplastic resin layer or an adhesive resin layer, the raw material compositions forming the EVOH layer, the thermoplastic resin layer, and the adhesive resin layer can be formed into a film by conventional co-extrusion, in which the raw material compositions are extruded through separate dies or a common die and laminated, and then stretched as needed. Examples of the die that can be used include a circular die and a T-die. Examples of the molding method include melt-molding methods such as extrusion molding, blow molding, injection molding, thermoforming, and inflation molding, and solution-molding methods such as cast molding.

[0142] The substrate film may have any other layer configuration as long as it has an EVOH layer, but the other layer configuration is not particularly limited. Since the substrate film has an EVOH layer, it is possible to obtain a vapor-deposited film having excellent transparency. The base film is preferably multilayered. When the EVOH layer is defined as the "(A) layer," the thermoplastic resin layer as the "(B) layer," and the adhesive resin layer as the "(C) layer," examples of the layer configuration include (B) layer / (A) layer, (B) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (B) layer / (A) layer / (B) layer / (A) layer / (B) layer, (B) layer / (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, and the like.

[0143] In the above examples, layers (B) and (C) are exemplified as layers other than layer (A), but layers other than layer (A) are not limited to these. Furthermore, it is preferable that the substrate film does not include a layer formed from a resin composition containing a polyamide resin as a main component (i.e., a resin composition containing 50% by mass or more of polyamide resin). Furthermore, the " / " shown in the above examples means that the layers on both sides of it are directly laminated.

[0144] The substrate film thus obtained is preferably stretched as necessary, and more preferably uniaxially stretched. The stretching ratio in the uniaxially stretched film is preferably 3 times or more, more preferably 4 times or more, and particularly preferably 5 times or more. If the stretching ratio is less than 3 times, thickness unevenness due to stretching tends to occur and gas barrier properties tend to deteriorate. The upper limit of the stretching ratio is preferably 12 times or less, more preferably 10 times or less, and particularly preferably 8 times or less. If the stretching ratio is more than 12 times, the film surface after stretching tends to deteriorate. The use of a uniaxially stretched film has advantages such as economic efficiency, ease of tearing the multilayer structure (making it easy to open the packaging material when used as a packaging material), and improved gas barrier properties.

[0145] The stretching direction of the uniaxially stretched film is not particularly limited and may be either the longitudinal direction (MD direction) or the transverse direction (TD direction), but uniaxial stretching in the longitudinal direction (MD direction) is preferred, and it is particularly preferred that the film is not substantially stretched in a direction different from the stretching direction. The stretched state of the substrate film (unstretched, uniaxially stretched, biaxially stretched, etc.) can be confirmed by using a general method for analyzing the orientation of a resin (for example, wide-angle X-ray scattering (WAXS), etc.).

[0146] The stretching method for the uniaxially stretched film is not particularly limited, but examples thereof include tenter stretching, tubular stretching, and roll stretching. Among these, from the viewpoint of production costs, uniaxial stretching by roll stretching is preferred. Furthermore, when the base film is obtained by inflation molding, roll stretching is preferred.

[0147] The stretching temperature during uniaxial stretching is not particularly limited, but is generally 50 to 130°C.

[0148] The total thickness of the substrate film is not particularly limited and can be appropriately set depending on the application. The thickness of the substrate film is preferably 10 μm or more, more preferably 15 μm or more. When the thickness of the substrate film is 10 μm or more, industrial productivity and mechanical properties tend to be further improved. Furthermore, the thickness of the substrate film is preferably 100 μm or less, more preferably 50 μm or less. When the thickness of the substrate film is 100 μm or less, industrial productivity and economic efficiency tend to be further improved. The thickness of the substrate film, which is a uniaxially stretched film, means the thickness after stretching.

[0149] Furthermore, when the base film is a multilayer film, the thickness of the EVOH layer is preferably 0.5 μm or more, more preferably 0.8 μm or more, and particularly preferably 1 μm or more. When the thickness of the EVOH layer is 0.5 μm or more, the gas barrier property tends to be improved. On the other hand, the thickness of the EVOH layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the EVOH layer is 20 μm or less, the appearance characteristics (film surface) tend to be good. Note that the thickness of the multilayer film, which is a uniaxially stretched film, means the thickness after stretching. When the base film has multiple EVOH layers provided thereon, it is preferable that the total thickness of all EVOH layers is within the above range.

[0150] When the base film is a multilayer film, the ratio of the thickness of the EVOH layer to the total thickness of all layers is preferably 30% or less, more preferably 20% or less, and may be 10% or less, or 5% or less, from the viewpoints of industrial productivity and mechanical properties.

[0151] When the base film has a thermoplastic resin layer, the thickness thereof is preferably 7 to 100 μm, more preferably 10 to 50 μm, from the viewpoints of industrial productivity and mechanical properties. In a base film that is a uniaxially stretched film, the thickness of the thermoplastic resin layer refers to the thickness after stretching. When the base film has multiple thermoplastic resin layers, the total thickness of all the thermoplastic resin layers is preferably within the above range.

[0152] When the substrate film has an adhesive resin layer, the thickness thereof is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, from the viewpoints of industrial productivity and quality stability. In a substrate film that is a uniaxially stretched film, the thickness of the adhesive resin layer refers to the thickness after stretching. When the substrate film has multiple adhesive resin layers, the total thickness of all the adhesive resin layers is preferably within the above range.

[0153] The internal haze value of the substrate film is preferably less than 0.4%, more preferably 0.3% or less, even more preferably 0.2% or less, and particularly preferably 0%. Such measurement can be performed using a substrate film having a thickness of 33 μm and a haze meter in accordance with ASTM D1003.

[0154] [Metal Vapor Deposited Layer] The metal vapor deposition layer laminated on the base film is obtained by vapor depositing a single metal or an alloy of two or more metals. From the viewpoint of gas barrier properties, the metal vapor deposition layer is preferably laminated on the EVOH layer of the base film.

[0155] Examples of metals used in the metal vapor deposition layer include those classified as aluminum group elements (aluminum, gallium, indium, etc.), tin group elements (titanium, zirconium, tin, hafnium, etc.), noble metals (copper, silver, gold, etc.), chromium group elements (chromium, molybdenum, tungsten, etc.), and iron group elements (iron, cobalt, nickel, etc.), as well as alloys thereof. Among these, at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium is preferred because it is commonly available and easy to handle, and aluminum is particularly preferred.

[0156] The metal used in the metal vapor deposition layer preferably contains a metal compound such as a metal oxide, a metal carbide, or a metal nitride, and among these metal compounds, a metal oxide is preferred. The content of such a metal compound is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass, of the metal used in the metal vapor deposition layer.

[0157] The metal vapor deposition layer can be identified by analyzing the cross section of the laminate by energy dispersive spectroscopy (EDS).

[0158] [Method for Producing the Present Vapor-Deposited Film] The present vapor-deposited film can be produced by laminating the above-described metal vapor-deposited layer on the above-described substrate film.

[0159] The method for laminating the metal vapor deposition layer on the substrate film is not particularly limited, and any known vapor deposition method may be appropriately adopted, for example, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD method).

[0160] The thickness of the metal vapor deposition layer is usually 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 20 nm. If the thickness of the metal vapor deposition layer is less than 1 nm, the gas barrier property tends to be insufficient, while if the thickness exceeds 100 nm, the effect of improving the gas barrier property cannot be obtained, and the bending resistance and production costs tend to increase.

[0161] The vapor-deposited film thus obtained has excellent surface smoothness of the vapor-deposited surface. The root-mean-square height (Sq) of the vapor-deposited surface of the vapor-deposited film is preferably 0.080 μm or less, more preferably 0.070 μm or less, and even more preferably 0.065 μm or less. The smaller the root-mean-square height (Sq), the smoother the surface, which is preferable. The root-mean-square height (Sq) can be measured using the method specified in ISO 25178, specifically, by the method described in the Examples below.

[0162] The arithmetic mean height (Sa) of the vapor-deposited surface of the vapor-deposited film is preferably 0.060 μm or less, more preferably 0.055 μm or less, and even more preferably 0.050 μm or less. A smaller arithmetic mean height (Sa) indicates a smoother surface, which is preferable. The arithmetic mean height (Sa) can be measured by the method described in the Examples below. In this specification, the arithmetic mean height (Sa) refers to the average absolute value of the height differences at each point relative to the average plane of the surface of the vapor-deposited film.

[0163] The oxygen permeability of this vapor-deposited film at 20°C and 90% RH is 8 cc / m 2 ·day·atm or less, and 7cc / m 2 ·day·atm or less is more preferable, 5 cc / m 2 ·day·atm or less is particularly preferred.

[0164] The vapor-deposited film can be suitably used as a molding for packaging general foods, as well as seasonings such as mayonnaise and dressings, fermented foods such as miso, oily foods such as salad oil, snacks, beverages, cosmetics, pharmaceuticals, etc., as well as packaging materials such as packaging films, or as part of multilayer structures for forming these.

[0165] <Multilayer structure> The multilayer structure is obtained by laminating another layer on the present vapor-deposited film. The other layer to be laminated on the present vapor-deposited film is not particularly limited, and may be a layer formed from a resin composition containing a thermoplastic resin exemplified above as the thermoplastic resin or an adhesive resin exemplified above as the adhesive resin.

[0166] As a method for producing the multilayer structure, various known production methods can be used, such as dry lamination, sand lamination, extrusion lamination, coextrusion lamination, and solution coating.

[0167] <Molded Articles> Cup- or tray-shaped molded articles can be obtained using the vapor-deposited film or the multilayer structure. In this case, a drawing method is typically employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, the multilayer structure can be used to obtain molded articles such as tube- or bottle-shaped multilayer containers (laminate structure) and food containers from a multilayer parison (a hollow tubular preform before blowing). In this case, a blow molding method is typically employed, specifically extrusion blow molding (two-head, mold-moving, parison-shift, rotary, accumulator, horizontal parison, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0168] <<Third Aspect>> The third aspect includes the following aspects <III-1> to <III-9>. <III-1> A vapor-deposited film including a substrate film having a layer containing a composition containing an EVOH resin, an alkali metal compound, an alkali metal compound, and a titanium compound, and a metal vapor-deposited layer laminated on the substrate film, wherein the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. <III-2> The vapor-deposited film according to <III-1>, wherein the content of the alkali metal compound in terms of metal is 1 to 1,000 ppm relative to the mass of the composition. <III-3> The vapor-deposited film according to <III-1> or <III-2>, wherein the mass ratio of the metal content of the alkali metal compound to the content of the titanium compound in terms of metal is 0.2 to 1,000,000. <III-4> The vapor-deposited film according to any one of <III-1> to <III-3>, wherein the substrate film is a multilayer film further having a layer containing a thermoplastic resin. <III-5> The vapor-deposited film according to any one of <III-1> to <III-4>, wherein the metal in the metal vapor-deposited layer is at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium. <III-6> A multilayer structure comprising the vapor-deposited film according to any one of <III-1> to <III-5>. <III-7> A molded article comprising the vapor-deposited film according to any one of <III-1> to <III-5>. <III-8> A food container comprising the multilayer structure according to <III-6>. <III-9> A method for producing the vapor-deposited film according to any one of <III-1> to <III-5>, comprising a step of laminating an inorganic vapor-deposited layer on the base film.

[0169] The present invention will be described below based on examples of modes for carrying out the third aspect, although the present invention is not limited to the embodiments described below.

[0170] <Vapor-deposited film> A vapor-deposited film according to a third aspect of the present invention (hereinafter sometimes referred to as "the vapor-deposited film") comprises a substrate film having a layer containing a composition that includes an ethylene-vinyl alcohol copolymer, an alkali metal compound, and a titanium compound, and a vapor-deposited metal layer laminated on the substrate film. Each component will be described below.

[0171] [Base Film] The base film has a layer containing an EVOH resin (hereinafter referred to as an "EVOH layer") The components of the base film will be described below.

[0172] [EVOH Layer] The EVOH layer is formed from a composition containing EVOH (hereinafter, sometimes referred to as "the composition"), which will be described below.

[0173] The present composition contains an EVOH resin as a main component, an alkali metal compound, and a specific trace amount of a titanium compound. That is, the base resin of the present composition is an EVOH resin, and the content of the EVOH resin in the present composition is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Each component will be described below.

[0174] (EVOH Resin) The EVOH resin used in the present embodiment is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble thermoplastic resin. The same EVOH resin as that described in the first embodiment can be used.

[0175] (Alkali Metal Compound) Examples of the alkali metal compound include salts and hydroxides of alkali metals. These may be used alone or in combination of two or more. Among these, the alkali metal compound is preferably water-soluble, and from the viewpoint of dispersibility, alkali metal salts are preferred.

[0176] Examples of the alkali metal salt include inorganic salts of alkali metals and carboxylates of alkali metals, among which carboxylates of alkali metals are preferred.

[0177] Examples of the inorganic salts of alkali metals include alkali metal carbonates, hydrogencarbonates, phosphates, borates, sulfates, chlorides, etc. Examples of the carboxylates of alkali metals include monocarboxylates having 2 to 11 carbon atoms, such as acetate, butyrate, propionate, enanthate, and caprate; dicarboxylates having 2 to 11 carbon atoms, such as oxalate, malonate, succinate, adipate, suberate, and sebacate; monocarboxylates having 12 or more carbon atoms, such as laurate, palmitate, stearate, 12-hydroxystearate, behenate, and montanate; and carboxylates with the polymerization terminal carboxy group of EVOH resin. Among these, monocarboxylates having 2 to 11 carbon atoms are preferred, and acetate is particularly preferred.

[0178] Examples of the alkali metal species of the alkali metal compound include lithium, sodium, potassium, rubidium, and cesium. Of these, sodium and potassium are preferred, and sodium is particularly preferred.

[0179] The molecular weight of the alkali metal compound is usually 20 to 10,000, preferably 20 to 1,000, and particularly preferably 20 to 500.

[0180] Of these, sodium acetate is preferred as the alkali metal compound. From the standpoints of economy and dispersibility, it is preferred that the alkali metal compound does not include inorganic layered compounds and double salts.

[0181] The inclusion of an appropriate amount of alkali metal compound in the composition improves thermal stability, suppresses the occurrence of streaks and microgels, and results in a smooth surface. The metal-equivalent content of the alkali metal compound is preferably 1 to 1,000 ppm, more preferably 5 to 800 ppm, even more preferably 10 to 700 ppm, particularly preferably 100 to 600 ppm, and especially preferably 150 to 400 ppm, based on the mass of the composition. If the alkali metal compound content is too high, thermal stability (the occurrence of streaks and microgels) tends to decrease, resulting in a decrease in surface smoothness. If the alkali metal compound content is too low or not added, the formability of the composition tends to decrease. The metal-equivalent content of the alkali metal compound can be measured, for example, by heating and ashing the composition, treating the resulting solution with an acid such as hydrochloric acid, adding pure water to the resulting solution, and measuring the volume using an atomic absorption spectrophotometer.

[0182] (Titanium Compound) Examples of the titanium compound include inorganic titanium compounds and organic titanium compounds. The titanium compounds may be used alone or in combination of two or more. Among these, inorganic titanium compounds are preferred.

[0183] As the inorganic titanium compound, the same titanium compounds as those explained in the first embodiment can be used.

[0184] The content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. It is preferably 0.01 to 1 ppm, more preferably 0.03 to 0.5 ppm, and particularly preferably 0.05 to 0.2 ppm. By setting the content of the titanium compound within this range, the titanium compound fills up minute depressions in the surface of the EVOH film, resulting in excellent surface smoothness. If the content of the titanium compound is too low, the minute depressions will not be filled up, leaving minute irregularities on the surface. If the content is too high, the remaining titanium oxide will appear on the surface, forming protrusions and causing the surface to become rough. The content of the titanium compound in terms of metal is, in other words, the content of elemental titanium.

[0185] Furthermore, by setting the content of the titanium compound within the above range, it is possible to suppress the generation of microgels due to thermal degradation during melt molding, and the film surface tends to have excellent smoothness. If the content of the titanium compound is too low, the effect of suppressing the generation of microgels will decrease, and the surface smoothness will tend to decrease, while if the content is too high, the EVOH resin will be more susceptible to thermal decomposition, and the surface smoothness will tend to decrease due to the generation of microgels.

[0186] The content of the titanium compound in terms of metal can be quantified by weighing out the composition into a platinum crucible, ashing it successively using a burner and an electric furnace, thermally decomposing the ashed material with nitric acid and hydrofluoric acid, treating it with a mixed acid of dilute nitric acid and dilute hydrofluoric acid, and measuring the titanium in the resulting constant-volume solution by ICP mass spectrometry using an ICP mass spectrometer (Agilent 8800, manufactured by Agilent Technologies).

[0187] The mass ratio of the content of the alkali metal compound to the content of the titanium compound in terms of metal is usually 1 to 360,000, preferably 18 to 100,000, and particularly preferably 100 to 50,000. When the mass ratio is within the above range, color change due to thermal degradation tends to be further suppressed.

[0188] The mass ratio of the alkali metal compound content in terms of metal to the titanium compound content in terms of metal is preferably 0.2 to 1,000,000, more preferably 0.3 to 100,000, more preferably 5 to 27,000, particularly preferably 20 to 14,000, particularly preferably 100 to 7,000, and most preferably 300 to 4,000. When the mass ratio is within the above range, color change due to thermal degradation tends to be more effectively suppressed. Furthermore, if the mass ratio is too large, thermal stability tends to decrease, and if it is too small, the molded product tends to be colored.

[0189] Normally, when a titanium compound is added to a resin composition containing EVOH resin, it is thought that the titanium ions will cause thermal degradation of the resin composition and the generation of microgels, and therefore it is common technical knowledge for those in the industry to avoid using titanium compounds. However, in this embodiment, contrary to this common technical knowledge, it has been discovered that when a specific trace amount of titanium compound is used, the titanium in the titanium compound coordinates to the double bond in the main chain of the EVOH resin to form a chelate, thereby improving thermal stability, suppressing the generation of microgels due to thermal degradation, and resulting in an EVOH film with excellent surface smoothness.

[0190] Furthermore, EVOH resins become discolored due to thermal degradation. This is thought to be because EVOH resins deteriorate due to heat, generating radicals, which dehydrate hydroxyl groups in the EVOH resin, forming double bonds in the main chain of the EVOH resin. These sites then become reaction initiation sites, further accelerating dehydration and forming conjugated polyene structures in the main chain of the EVOH resin. Furthermore, in the present resin composition, titanium in the specific trace amount of titanium compound is stabilized as a tetravalent ion, and even in trace amounts, it is stabilized by coordinating to the double bonds in the main chain of the EVOH resin to form a chelate, thereby suppressing the formation of polyene structures.

[0191] (Other Thermoplastic Resins) The present composition may contain thermoplastic resins other than EVOH resins within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the present composition, preferably 20% by mass or less, particularly preferably 10% by mass or less, the lower limit being typically 0% by mass). As the other thermoplastic resins, the same ones as those described in the first embodiment above as (other thermoplastic resins) can be used.

[0192] (Other Compounding Agents) The composition may also contain compounding agents generally compounded in EVOH resins (excluding titanium compounds and alkali metal compounds) within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the resin composition, preferably 20% by mass or less, more preferably 10% by mass or less, the lower limit being typically 0% by mass). As the compounding agents, the same compounds as those described in the first aspect above can be used.

[0193] (Method for Producing the Composition) The composition can be produced, for example, by mixing the EVOH resin, alkali metal compound, and titanium compound by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, it is preferable to produce the composition by a method including a step of melt mixing a composition raw material containing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0194] The dry blending method may be, for example, (i) a method in which pelletized EVOH resin, an alkali metal compound, and a titanium compound are dry blended using a tumbler or the like.

[0195] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with an alkali metal compound and a titanium compound, and the dry-blended product is melt-kneaded; and (iii) a method in which an alkali metal compound and a titanium compound are added to a molten EVOH resin, and the resulting mixture is melt-kneaded.

[0196] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, an alkali metal compound and a titanium compound are blended therein, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which an alkali metal compound and a titanium compound are added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production of EVOH resin, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried.

[0197] The impregnation method includes, for example, (vi) a method in which pellets of EVOH resin are brought into contact with an aqueous solution containing an alkali metal compound and a titanium compound to incorporate the alkali metal compound and titanium compound into the EVOH resin, followed by drying. The aqueous solution containing the titanium compound may be an aqueous solution of an alkali metal compound and a titanium compound, or an aqueous solution in which titanium ions have been eluted by immersing an alkali metal compound and a titanium compound in water containing various chemicals.

[0198] In the impregnation method, the content (in terms of metal) of the alkali metal compound or titanium compound can be controlled by the concentration of the alkali metal compound or titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0199] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0200] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0201] The shape of the present composition obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, cubic, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. Furthermore, in the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0202] The water content of the composition before melt molding is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass. Here, "melt molding" before melt molding refers to melting and forming a certain shape, and examples include melting the resin composition and forming it into pellets, or melting the resin composition and forming it into a film.

[0203] The moisture content of the composition is measured and calculated by the following method: The mass (W1) of the composition before drying is weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and then cooled in a desiccator for 30 minutes, after which the mass (W2) is weighed and calculated using the following formula: Moisture content (mass%) = [(W1 - W2) / W1] x 100

[0204] When the composition is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds may be used alone or in combination of two or more. The content of such lubricants in the composition is usually 5% by mass or less, preferably 1% by mass or less. The lower limit is usually 0% by mass.

[0205] The composition thus obtained is prepared into various forms, such as pellets, powder, or liquid, and provided as a molding material for various molded products. In particular, in this embodiment, when the composition is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable. Note that the composition also includes resin compositions obtained by mixing resins other than the EVOH resin used in the composition.

[0206] The substrate film may be, for example, a single-layer film (EVOH layer) formed from the composition of the present invention, or a multi-layer film having at least one EVOH layer.

[0207] [Layer containing thermoplastic resin] The substrate film preferably has a layer containing a thermoplastic resin (hereinafter, sometimes referred to as a "thermoplastic resin layer"). When the substrate film has a thermoplastic resin layer, the mechanical strength and water vapor barrier properties of the vapor-deposited film tend to be further improved. In addition, properties such as heat sealability and mechanical strength can be imparted depending on the type of thermoplastic resin constituting the thermoplastic resin layer.

[0208] As the thermoplastic resin, the same thermoplastic resins as those described in the [Layer containing thermoplastic resin] of the first embodiment can be used.

[0209] The content of the thermoplastic resin in the thermoplastic resin layer is not particularly limited, but preferably the thermoplastic resin is the main component (i.e., the content of the thermoplastic resin contained in the thermoplastic resin layer is 50% by mass or more), more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0210] The thermoplastic resin layer may contain other components besides the thermoplastic resin, such as antiblocking agents, processing aids, resins other than thermoplastic resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, UV absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0211] [Layer Containing Adhesive Resin] The substrate film may have a layer containing an adhesive resin (hereinafter, sometimes referred to as an "adhesive resin layer"). When the substrate film has an adhesive resin layer, the appearance properties (film surface) of the vapor-deposited film tend to be better.

[0212] The adhesive resin may be the same as the adhesive resin described in the [Layer containing adhesive resin] in the first embodiment.

[0213] The content of the adhesive resin in the adhesive resin layer is not particularly limited, but it is preferable that the adhesive resin be the main component (i.e., the content of the adhesive resin contained in the adhesive resin layer is 50% by mass or more). In particular, the content of the adhesive resin is more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0214] The adhesive resin layer may contain other components other than the adhesive resin, such as antiblocking agents, processing aids, resins other than adhesive resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0215] [Method for Producing Substrate Film] The substrate film can usually be produced by extruding the composition through a die, forming it into a film, and stretching it as needed. When the substrate film has a thermoplastic resin layer or an adhesive resin layer, the raw material compositions forming the EVOH layer, the thermoplastic resin layer, and the adhesive resin layer are extruded through separate dies or a common die to form a film by conventional co-extrusion, and then laminating them, followed by stretching as needed. Examples of the die that can be used include a circular die and a T-die. Examples of the molding method include melt-molding methods such as extrusion molding, blow molding, injection molding, thermoforming, and inflation molding, and solution-molding methods such as cast molding.

[0216] The substrate film may have any other layer configuration as long as it has an EVOH layer, but the other layer configuration is not particularly limited. Since the substrate film has an EVOH layer, it is possible to obtain a vapor-deposited film having excellent transparency. The base film is preferably multilayered. When the EVOH layer is defined as the "(A) layer," the thermoplastic resin layer as the "(B) layer," and the adhesive resin layer as the "(C) layer," examples of the layer configuration include (B) layer / (A) layer, (B) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (B) layer / (A) layer / (B) layer / (A) layer / (B) layer, (B) layer / (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, and the like.

[0217] In the above examples, layers (B) and (C) are exemplified as layers other than layer (A), but layers other than layer (A) are not limited to these. Furthermore, it is preferable that the substrate film does not include a layer formed from a resin composition containing a polyamide resin as a main component (i.e., a resin composition containing 50% by mass or more of polyamide resin). Furthermore, the " / " shown in the above examples means that the layers on both sides of it are directly laminated.

[0218] The substrate film thus obtained is preferably stretched as necessary, and more preferably uniaxially stretched. The stretching ratio in the uniaxially stretched film is preferably 3 times or more, more preferably 4 times or more, and particularly preferably 5 times or more. If the stretching ratio is less than 3 times, thickness unevenness due to stretching tends to occur and gas barrier properties tend to deteriorate. The upper limit of the stretching ratio is preferably 12 times or less, more preferably 10 times or less, and particularly preferably 8 times or less. If the stretching ratio is more than 12 times, the film surface after stretching tends to deteriorate. The use of a uniaxially stretched film has advantages such as economic efficiency, ease of tearing the multilayer structure (making it easy to open the packaging material when used as a packaging material), and improved gas barrier properties.

[0219] The stretching direction of the uniaxially stretched film is not particularly limited and may be either the longitudinal direction (MD direction) or the transverse direction (TD direction), but uniaxial stretching in the longitudinal direction (MD direction) is preferred, and it is particularly preferred that the film is not substantially stretched in a direction different from the stretching direction. The stretched state of the substrate film (unstretched, uniaxially stretched, biaxially stretched, etc.) can be confirmed by using a general method for analyzing the orientation of a resin (for example, wide-angle X-ray scattering (WAXS), etc.).

[0220] The stretching method for the uniaxially stretched film is not particularly limited, but examples thereof include tenter stretching, tubular stretching, and roll stretching. Among these, from the viewpoint of production costs, uniaxial stretching by roll stretching is preferred. Furthermore, when the base film is obtained by inflation molding, roll stretching is preferred.

[0221] The stretching temperature during uniaxial stretching is not particularly limited, but is generally 50 to 130°C.

[0222] The total thickness of the substrate film is not particularly limited and can be appropriately set depending on the application. The thickness of the substrate film is preferably 10 μm or more, more preferably 15 μm or more. When the thickness of the substrate film is 10 μm or more, industrial productivity and mechanical properties tend to be further improved. Furthermore, the thickness of the substrate film is preferably 100 μm or less, more preferably 50 μm or less. When the thickness of the substrate film is 100 μm or less, industrial productivity and economic efficiency tend to be further improved. The thickness of the substrate film, which is a uniaxially stretched film, means the thickness after stretching.

[0223] Furthermore, when the base film is a multilayer film, the thickness of the EVOH layer is preferably 0.5 μm or more, more preferably 0.8 μm or more, and particularly preferably 1 μm or more. When the thickness of the EVOH layer is 0.5 μm or more, the gas barrier property tends to be improved. On the other hand, the thickness of the EVOH layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the EVOH layer is 20 μm or less, the appearance characteristics (film surface) tend to be good. Note that the thickness of the multilayer film, which is a uniaxially stretched film, means the thickness after stretching. When the base film has multiple EVOH layers provided thereon, it is preferable that the total thickness of all EVOH layers is within the above range.

[0224] When the base film is a multilayer film, the ratio of the thickness of the EVOH layer to the total thickness of all layers is preferably 30% or less, more preferably 20% or less, and may be 10% or less, or 5% or less, from the viewpoints of industrial productivity and mechanical properties.

[0225] When the base film has a thermoplastic resin layer, the thickness thereof is preferably 7 to 100 μm, more preferably 10 to 50 μm, from the viewpoints of industrial productivity and mechanical properties. In a base film that is a uniaxially stretched film, the thickness of the thermoplastic resin layer refers to the thickness after stretching. When the base film has multiple thermoplastic resin layers, the total thickness of all the thermoplastic resin layers is preferably within the above range.

[0226] When the substrate film has an adhesive resin layer, the thickness thereof is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, from the viewpoints of industrial productivity and quality stability. In a substrate film that is a uniaxially stretched film, the thickness of the adhesive resin layer refers to the thickness after stretching. When the substrate film has multiple adhesive resin layers, the total thickness of all the adhesive resin layers is preferably within the above range.

[0227] The internal haze value of the substrate film is preferably less than 0.4%, more preferably 0.3% or less, even more preferably 0.2% or less, and particularly preferably 0%. Such measurement can be performed using a substrate film having a thickness of 33 μm and a haze meter in accordance with ASTM D1003.

[0228] [Metal Vapor Deposited Layer] The metal vapor deposition layer laminated on the base film is obtained by vapor depositing a single metal or an alloy of two or more metals. From the viewpoint of gas barrier properties, the metal vapor deposition layer is preferably laminated on the EVOH layer of the base film.

[0229] Examples of metals used in the metal vapor deposition layer include those classified as aluminum group elements (aluminum, gallium, indium, etc.), tin group elements (titanium, zirconium, tin, hafnium, etc.), noble metals (copper, silver, gold, etc.), chromium group elements (chromium, molybdenum, tungsten, etc.), and iron group elements (iron, cobalt, nickel, etc.), as well as alloys thereof. Among these, at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium is preferred because it is commonly available and easy to handle, and aluminum is particularly preferred.

[0230] The metal used in the metal vapor deposition layer preferably contains a metal compound such as a metal oxide, a metal carbide, or a metal nitride, and among these metal compounds, a metal oxide is preferred. The content of such a metal compound is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass, of the metal used in the metal vapor deposition layer.

[0231] The metal vapor deposition layer can be identified by analyzing the cross section of the laminate by energy dispersive spectroscopy (EDS).

[0232] [Method for Producing the Present Vapor-Deposited Film] The present vapor-deposited film can be produced by laminating the above-described metal vapor-deposited layer on the above-described substrate film.

[0233] The method for laminating the metal vapor deposition layer on the substrate film is not particularly limited, and any known vapor deposition method may be appropriately adopted, for example, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD method).

[0234] The thickness of the metal vapor deposition layer is usually 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 20 nm. If the thickness of the metal vapor deposition layer is less than 1 nm, the gas barrier property tends to be insufficient, while if the thickness exceeds 100 nm, the effect of improving the gas barrier property cannot be obtained, and the bending resistance and production costs tend to increase.

[0235] The vapor-deposited film thus obtained has excellent surface smoothness of the vapor-deposited surface. The root-mean-square height (Sq) of the vapor-deposited surface of the vapor-deposited film is preferably 0.090 μm or less, more preferably 0.080 μm or less, and even more preferably 0.070 μm or less. The smaller the root-mean-square height (Sq), the smoother the surface, which is preferable. The root-mean-square height (Sq) can be measured using the method specified in ISO 25178, specifically, by the method described in the Examples below.

[0236] The oxygen permeability of this vapor-deposited film at 20°C and 90% RH is 8 cc / m 2 ·day·atm or less, and 7cc / m 2 ·day·atm or less is more preferable, 5 cc / m 2 ·day·atm or less is particularly preferred.

[0237] The vapor-deposited film can be suitably used as a molding for packaging general foods, as well as seasonings such as mayonnaise and dressings, fermented foods such as miso, oily foods such as salad oil, snacks, beverages, cosmetics, pharmaceuticals, etc., as well as packaging materials such as packaging films, or as part of multilayer structures for forming these.

[0238] <Multilayer structure> The multilayer structure is obtained by laminating another layer on the present vapor-deposited film. The other layer to be laminated on the present vapor-deposited film is not particularly limited, and may be a layer formed from a resin composition containing a thermoplastic resin exemplified above as the thermoplastic resin or an adhesive resin exemplified above as the adhesive resin.

[0239] As a method for producing the multilayer structure, various known production methods can be used, such as dry lamination, sand lamination, extrusion lamination, coextrusion lamination, and solution coating.

[0240] <Molded Articles> Cup- or tray-shaped molded articles can be obtained using the vapor-deposited film or the multilayer structure. In this case, a drawing method is typically employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, the multilayer structure can be used to obtain molded articles such as tube- or bottle-shaped multilayer containers (laminate structure), food containers, etc. from a multilayer parison (a hollow tubular preform before blowing). In this case, a blow molding method is typically employed, specifically extrusion blow molding (two-head, mold-moving, parison-shift, rotary, accumulator, horizontal parison, etc.), cold parison blow molding, injection blow molding, biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0241] <<Fourth Aspect>> The fourth aspect includes the following aspects <IV-1> to <IV-9>. <IV-1> A vapor-deposited film including a substrate film having a layer containing a composition containing an EVOH resin, an alkaline earth metal compound, and a titanium compound, and a metal vapor-deposited layer laminated on the substrate film, wherein the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. <IV-2> The vapor-deposited film according to <IV-1>, wherein the content of the alkaline earth metal compound in terms of metal is 0.1 to 800 ppm relative to the mass of the composition. <IV-3> The vapor-deposited film according to <IV-1> or <IV-2>, wherein the mass ratio of the content of the alkaline earth metal compound in terms of metal to the content of the titanium compound in terms of metal is 0.03 to 500,000. <IV-4> The vapor-deposited film according to any one of <IV-1> to <IV-3>, wherein the substrate film is a multilayer film further having a layer containing a thermoplastic resin. <IV-5> The vapor-deposited film according to any one of <IV-1> to <IV-4>, wherein the metal in the metal vapor-deposited layer is at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium. <IV-6> A multilayer structure comprising the vapor-deposited film according to any one of <IV-1> to <IV-5>. <IV-7> A molded article comprising the vapor-deposited film according to any one of <IV-1> to <IV-5>. <IV-8> A food container comprising the multilayer structure according to <IV-6>. <IV-9> A method for producing the vapor-deposited film according to any one of <IV-1> to <IV-5>, comprising a step of laminating an inorganic vapor-deposited layer on the base film.

[0242] The present invention will be described below based on examples of modes for carrying out the fourth aspect, although the present invention is not limited to the embodiments described below.

[0243] <Vapor-deposited film> A vapor-deposited film according to a fourth aspect of the present invention (hereinafter sometimes referred to as "the present vapor-deposited film") comprises a substrate film having a layer containing a composition that includes an ethylene-vinyl alcohol copolymer, an alkaline earth metal compound, and a titanium compound, and a vapor-deposited metal layer laminated on the substrate film. Each component will be described below.

[0244] [Base Film] The base film has a layer containing an EVOH resin (hereinafter referred to as an "EVOH layer") The components of the base film will be described below.

[0245] [EVOH Layer] The EVOH layer is formed from a composition containing an EVOH resin (hereinafter, sometimes referred to as "the composition"). The composition will be described below.

[0246] The present composition contains an EVOH resin as a main component, an alkaline earth metal compound, and a specific trace amount of a titanium compound. That is, the base resin of the present composition is an EVOH resin, and the content of the EVOH resin in the present composition is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Each component will be described below.

[0247] (EVOH Resin) The EVOH resin used in the present embodiment is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble thermoplastic resin. The same EVOH resin as that described in the first embodiment can be used.

[0248] (Alkaline earth metal compound) Examples of the alkaline earth metal compound include salts, oxides, and hydroxides of alkaline earth metals. These may be used alone or in combination of two or more. Among these, from the viewpoints of economy and dispersibility, alkaline earth metal salts and alkaline earth metal oxides are preferred, and alkaline earth metal oxides are particularly preferred.

[0249] Examples of the alkaline earth metal salt include inorganic salts of alkaline earth metals and carboxylates of alkaline earth metals.

[0250] Examples of the inorganic salts of alkaline earth metals include alkaline earth metal carbonates, hydrogencarbonates, phosphates, borates, sulfates, chlorides, etc. Examples of the carboxylates of alkaline earth metals include saturated or unsaturated carboxylates having 2 to 25 carbon atoms, preferably 2 to 22, and particularly preferably 6 to 20 carbon atoms, and specific examples include monocarboxylic acid salts such as acetate, butyrate, propionate, enanthate, caprate, laurate, palmitate, stearate, 12-hydroxystearate, behenate, and montanate, and dicarboxylic acid salts such as oxalate, malonate, succinate, adipate, suberate, and sebacate. Among these, linear saturated carboxylates are preferred in terms of commercial availability, and monocarboxylic acid salts are more preferred.

[0251] Examples of the alkaline earth metal species of the alkaline earth metal compound include beryllium, magnesium, calcium, strontium, barium, and radium. Among these, magnesium and calcium are preferred in terms of market availability and economic efficiency, and magnesium is particularly preferred.

[0252] Among these, magnesium oxide is preferred as the alkaline earth metal compound. From the viewpoints of economy and dispersibility, it is preferred that the alkaline earth metal compound does not include layered inorganic compounds such as montmorillonite and double salts such as hydrotalcite.

[0253] The alkaline earth metal compound may be in any form, such as a solid (powder, fine powder, flakes, etc.), a semi-solid, a liquid, a paste, a solution, or an emulsion (aqueous dispersion), with a powder being preferred.

[0254] The inclusion of an appropriate amount of alkaline earth metal compound in the composition improves thermal stability, suppresses the occurrence of streaks and microgels, and results in a smooth surface. The metal-equivalent content of the alkaline earth metal compound is preferably 0.1 to 800 ppm, more preferably 0.3 to 500 ppm, even more preferably 0.5 to 300 ppm, particularly preferably 1 to 200 ppm, especially preferably 2 to 150 ppm, even more preferably 3 to 80 ppm, and most preferably 5 to 40 ppm, based on the mass of the composition. If the metal-equivalent content of the alkaline earth metal compound is too high, the thermal stability (the occurrence of streaks and microgels) tends to decrease, resulting in a decrease in surface smoothness. If no alkaline earth metal compound is added or if the amount is too low, the formability of the composition tends to decrease. The metal-equivalent content of the alkaline earth metal compound can be measured, for example, by heating and ashing the composition, treating the resulting solution with an acid such as hydrochloric acid, adding pure water to the resulting solution, and measuring the volume using an atomic absorption spectrophotometer.

[0255] (Titanium Compound) Examples of the titanium compound include inorganic titanium compounds and organic titanium compounds. The titanium compounds may be used alone or in combination of two or more. Among these, inorganic titanium compounds are preferred.

[0256] As the inorganic titanium compound, the same titanium compounds as those explained in the first embodiment can be used.

[0257] The content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. It is preferably 0.01 to 1 ppm, more preferably 0.03 to 0.5 ppm, and particularly preferably 0.05 to 0.2 ppm. By setting the content of the titanium compound within this range, the titanium compound fills up minute depressions in the surface of the EVOH film, resulting in excellent surface smoothness. If the content of the titanium compound is too low, the minute depressions will not be filled up, leaving minute irregularities on the surface. If the content is too high, the remaining titanium oxide will appear on the surface, forming protrusions and causing the surface to become rough. The content of the titanium compound in terms of metal is, in other words, the content of elemental titanium.

[0258] Furthermore, by setting the content of the titanium compound within the above range, it is possible to suppress the generation of microgels due to thermal degradation during melt molding, and the film surface tends to have excellent smoothness. If the content of the titanium compound is too low, the effect of suppressing the generation of microgels will decrease, and the surface smoothness will tend to decrease, while if the content is too high, the EVOH resin will be more susceptible to thermal decomposition, and the surface smoothness will tend to decrease due to the generation of microgels.

[0259] The content of the titanium compound in terms of metal can be quantified by weighing out the composition into a platinum crucible, ashing it successively using a burner and an electric furnace, thermally decomposing the ashed material with nitric acid and hydrofluoric acid, treating it with a mixed acid of dilute nitric acid and dilute hydrofluoric acid, and measuring the titanium in the resulting constant-volume solution by ICP mass spectrometry using an ICP mass spectrometer (Agilent 8800, manufactured by Agilent Technologies).

[0260] The mass ratio of the alkaline earth metal compound content in terms of metal to the titanium compound content in terms of metal is preferably 0.03 to 500,000, more preferably 0.04 to 50,000, more preferably 0.5 to 10,000, particularly preferably 2 to 4,000, particularly preferably 9 to 1,000, and most preferably 50 to 500. When this mass ratio is within this range, the generation of microgels due to thermal degradation is suppressed, and the surface smoothness tends to be excellent. Furthermore, if this mass ratio is too large, thermal stability tends to decrease, and if it is too small, surface smoothness tends to decrease.

[0261] Normally, when a titanium compound is added to a resin composition containing EVOH resin, it is thought that the titanium ions will cause thermal degradation of the resin composition and the generation of microgels, and therefore it is common technical knowledge for those in the industry to avoid using titanium compounds. However, in this embodiment, contrary to this common technical knowledge, it has been discovered that when a specific trace amount of titanium compound is used, the titanium in the titanium compound coordinates to the double bond in the main chain of the EVOH resin to form a chelate, thereby improving thermal stability, suppressing the generation of microgels due to thermal degradation, and resulting in an EVOH film with excellent surface smoothness.

[0262] Furthermore, EVOH resins become discolored due to thermal degradation. This is thought to be because EVOH resins deteriorate due to heat, generating radicals, which dehydrate hydroxyl groups in the EVOH resin, forming double bonds in the main chain of the EVOH resin. These sites then become reaction initiation sites, further accelerating dehydration and forming conjugated polyene structures in the main chain of the EVOH resin. Furthermore, in the present resin composition, titanium in the specific trace amount of titanium compound is stabilized as a tetravalent ion, and even in trace amounts, it is stabilized by coordinating to the double bonds in the main chain of the EVOH resin to form a chelate, thereby suppressing the formation of polyene structures.

[0263] (Other Thermoplastic Resins) The present composition may contain thermoplastic resins other than EVOH resins within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the present composition, preferably 20% by mass or less, particularly preferably 10% by mass or less, the lower limit being typically 0% by mass). As the other thermoplastic resins, the same ones as those described in the first embodiment above as (other thermoplastic resins) can be used.

[0264] (Other Compounding Agents) The composition may also contain compounding agents generally compounded in EVOH resins (excluding titanium compounds and alkaline earth metal compounds) within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the resin composition, preferably 20% by mass or less, more preferably 10% by mass or less, the lower limit being typically 0% by mass). As the compounding agents, the same compounds as those described in the first aspect above can be used.

[0265] (Method for Producing the Composition) The composition can be produced by, for example, mixing the EVOH resin, alkaline earth metal compound, and titanium compound by a known method such as dry blending, melt mixing, solution mixing, impregnation, etc. Among these, it is preferable to produce the composition by a method including a step of melt mixing the composition raw materials containing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0266] The dry blending method may be, for example, (i) a method in which pelletized EVOH resin, an alkaline earth metal compound, and a titanium compound are dry blended using a tumbler or the like.

[0267] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with an alkaline earth metal compound and a titanium compound, and the dry-blended product is melt-kneaded; and (iii) a method in which an alkaline earth metal compound and a titanium compound are added to a molten EVOH resin, and the mixture is melt-kneaded.

[0268] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, an alkaline earth metal compound and a titanium compound are blended therein, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which an alkaline earth metal compound and a titanium compound are added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production of EVOH resin, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried.

[0269] The impregnation method includes, for example, (vi) a method in which pelletized EVOH resin is contacted with an aqueous solution containing an alkaline earth metal compound and a titanium compound to incorporate the alkaline earth metal compound and titanium compound into the EVOH resin, followed by drying. The aqueous solution containing the titanium compound can be an aqueous solution of an alkaline earth metal compound and a titanium compound, or an aqueous solution in which titanium ions have been eluted by immersing an alkaline earth metal compound and a titanium compound in water containing various chemicals.

[0270] In the impregnation method, the contents (in terms of metals) of the alkaline earth metal compound and titanium compound can be controlled by the concentrations of the alkaline earth metal compound and titanium compound in the aqueous solution in which the EVOH resin is immersed, as well as the immersion temperature, immersion time, etc. The immersion temperature and immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0271] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0272] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0273] The shape of the present composition obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, cubic, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. Furthermore, in the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0274] The water content of the composition before melt molding is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass. Here, "melt molding" before melt molding refers to melting and forming a certain shape, and examples include melting the resin composition and forming it into pellets, or melting the resin composition and forming it into a film.

[0275] The moisture content of the composition is measured and calculated by the following method: The mass (W1) of the composition before drying is weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and then cooled in a desiccator for 30 minutes, after which the mass (W2) is weighed and calculated using the following formula: Moisture content (mass%) = [(W1 - W2) / W1] x 100

[0276] When the composition is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds may be used alone or in combination of two or more. The content of such lubricants in the composition is usually 5% by mass or less, preferably 1% by mass or less. The lower limit is usually 0% by mass.

[0277] The composition thus obtained is prepared into various forms, such as pellets, powder, or liquid, and provided as a molding material for various molded products. In particular, in this embodiment, when the composition is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable. Note that the composition also includes resin compositions obtained by mixing resins other than the EVOH resin used in the composition.

[0278] The substrate film may be, for example, a single-layer film (EVOH layer) formed from the composition of the present invention, or a multi-layer film having at least one EVOH layer.

[0279] [Layer containing thermoplastic resin] The substrate film preferably has a layer containing a thermoplastic resin (hereinafter, sometimes referred to as a "thermoplastic resin layer"). When the substrate film has a thermoplastic resin layer, the mechanical strength and water vapor barrier properties of the vapor-deposited film tend to be further improved. In addition, properties such as heat sealability and mechanical strength can be imparted depending on the type of thermoplastic resin constituting the thermoplastic resin layer.

[0280] As the thermoplastic resin, the same thermoplastic resins as those described in the [Layer containing thermoplastic resin] of the first embodiment can be used.

[0281] The content of the thermoplastic resin in the thermoplastic resin layer is not particularly limited, but preferably the thermoplastic resin is the main component (i.e., the content of the thermoplastic resin contained in the thermoplastic resin layer is 50% by mass or more), more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0282] The thermoplastic resin layer may contain other components besides the thermoplastic resin, such as antiblocking agents, processing aids, resins other than thermoplastic resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, UV absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0283] [Layer Containing Adhesive Resin] The substrate film may have a layer containing an adhesive resin (hereinafter, sometimes referred to as an "adhesive resin layer"). When the substrate film has an adhesive resin layer, the appearance properties (film surface) of the vapor-deposited film tend to be better.

[0284] The adhesive resin may be the same as the adhesive resin described in the [Layer containing adhesive resin] in the first embodiment.

[0285] The content of the adhesive resin in the adhesive resin layer is not particularly limited, but it is preferable that the adhesive resin be the main component (i.e., the content of the adhesive resin contained in the adhesive resin layer is 50% by mass or more). In particular, the content of the adhesive resin is more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0286] The adhesive resin layer may contain other components other than the adhesive resin, such as antiblocking agents, processing aids, resins other than adhesive resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0287] [Method for Producing Substrate Film] The substrate film can usually be produced by extruding the composition through a die, forming it into a film, and stretching it as needed. When the substrate film has a thermoplastic resin layer or an adhesive resin layer, the raw material compositions forming the EVOH layer, the thermoplastic resin layer, and the adhesive resin layer are extruded through separate dies or a common die to form a film by conventional co-extrusion, and then laminating them, followed by stretching as needed. Examples of the die that can be used include a circular die and a T-die. Examples of the molding method include melt-molding methods such as extrusion molding, blow molding, injection molding, thermoforming, and inflation molding, and solution-molding methods such as cast molding.

[0288] The substrate film may have any other layer configuration as long as it has an EVOH layer, but the other layer configuration is not particularly limited. Since the substrate film has an EVOH layer, it is possible to obtain a vapor-deposited film having excellent transparency. The base film is preferably multilayered. When the EVOH layer is defined as the "(A) layer," the thermoplastic resin layer as the "(B) layer," and the adhesive resin layer as the "(C) layer," examples of the layer configuration include (B) layer / (A) layer, (B) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (B) layer / (A) layer / (B) layer / (A) layer / (B) layer, (B) layer / (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, and the like.

[0289] In the above examples, layers (B) and (C) are exemplified as layers other than layer (A), but layers other than layer (A) are not limited to these. Furthermore, it is preferable that the substrate film does not include a layer formed from a resin composition containing a polyamide resin as a main component (i.e., a resin composition containing 50% by mass or more of polyamide resin). Furthermore, the " / " shown in the above examples means that the layers on both sides of it are directly laminated.

[0290] The substrate film thus obtained is preferably stretched as necessary, and more preferably uniaxially stretched. The stretching ratio in the uniaxially stretched film is preferably 3 times or more, more preferably 4 times or more, and particularly preferably 5 times or more. If the stretching ratio is less than 3 times, thickness unevenness due to stretching tends to occur and gas barrier properties tend to deteriorate. The upper limit of the stretching ratio is preferably 12 times or less, more preferably 10 times or less, and particularly preferably 8 times or less. If the stretching ratio is more than 12 times, the film surface after stretching tends to deteriorate. The use of a uniaxially stretched film has advantages such as economic efficiency, ease of tearing the multilayer structure (making it easy to open the packaging material when used as a packaging material), and improved gas barrier properties.

[0291] The stretching direction of the uniaxially stretched film is not particularly limited and may be either the longitudinal direction (MD direction) or the transverse direction (TD direction), but uniaxial stretching in the longitudinal direction (MD direction) is preferred, and it is particularly preferred that the film is not substantially stretched in a direction different from the stretching direction. The stretched state of the substrate film (unstretched, uniaxially stretched, biaxially stretched, etc.) can be confirmed by using a general method for analyzing the orientation of a resin (for example, wide-angle X-ray scattering (WAXS), etc.).

[0292] The stretching method for the uniaxially stretched film is not particularly limited, but examples thereof include tenter stretching, tubular stretching, and roll stretching. Among these, from the viewpoint of production costs, uniaxial stretching by roll stretching is preferred. Furthermore, when the base film is obtained by inflation molding, roll stretching is preferred.

[0293] The stretching temperature during uniaxial stretching is not particularly limited, but is generally 50 to 130°C.

[0294] The total thickness of the substrate film is not particularly limited and can be appropriately set depending on the application. The thickness of the substrate film is preferably 10 μm or more, more preferably 15 μm or more. When the thickness of the substrate film is 10 μm or more, industrial productivity and mechanical properties tend to be further improved. Furthermore, the thickness of the substrate film is preferably 100 μm or less, more preferably 50 μm or less. When the thickness of the substrate film is 100 μm or less, industrial productivity and economic efficiency tend to be further improved. The thickness of the substrate film, which is a uniaxially stretched film, means the thickness after stretching.

[0295] Furthermore, when the base film is a multilayer film, the thickness of the EVOH layer is preferably 0.5 μm or more, more preferably 0.8 μm or more, and particularly preferably 1 μm or more. When the thickness of the EVOH layer is 0.5 μm or more, the gas barrier property tends to be improved. On the other hand, the thickness of the EVOH layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the EVOH layer is 20 μm or less, the appearance characteristics (film surface) tend to be good. Note that the thickness of the multilayer film, which is a uniaxially stretched film, means the thickness after stretching. When the base film has multiple EVOH layers provided thereon, it is preferable that the total thickness of all EVOH layers is within the above range.

[0296] When the base film is a multilayer film, the ratio of the thickness of the EVOH layer to the total thickness of all layers is preferably 30% or less, more preferably 20% or less, and may be 10% or less, or 5% or less, from the viewpoints of industrial productivity and mechanical properties.

[0297] When the base film has a thermoplastic resin layer, the thickness thereof is preferably 7 to 100 μm, more preferably 10 to 50 μm, from the viewpoints of industrial productivity and mechanical properties. In a base film that is a uniaxially stretched film, the thickness of the thermoplastic resin layer refers to the thickness after stretching. When the base film has multiple thermoplastic resin layers, the total thickness of all the thermoplastic resin layers is preferably within the above range.

[0298] When the substrate film has an adhesive resin layer, the thickness thereof is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, from the viewpoints of industrial productivity and quality stability. In a substrate film that is a uniaxially stretched film, the thickness of the adhesive resin layer refers to the thickness after stretching. When the substrate film has multiple adhesive resin layers, the total thickness of all the adhesive resin layers is preferably within the above range.

[0299] The internal haze value of the substrate film is preferably less than 0.4%, more preferably 0.3% or less, even more preferably 0.2% or less, and particularly preferably 0%. Such measurement can be performed using a substrate film having a thickness of 33 μm and a haze meter in accordance with ASTM D1003.

[0300] [Metal Vapor Deposited Layer] The metal vapor deposition layer laminated on the base film is obtained by vapor depositing a single metal or an alloy of two or more metals. From the viewpoint of gas barrier properties, the metal vapor deposition layer is preferably laminated on the EVOH layer of the base film.

[0301] Examples of metals used in the metal vapor deposition layer include those classified as aluminum group elements (aluminum, gallium, indium, etc.), tin group elements (titanium, zirconium, tin, hafnium, etc.), noble metals (copper, silver, gold, etc.), chromium group elements (chromium, molybdenum, tungsten, etc.), and iron group elements (iron, cobalt, nickel, etc.), as well as alloys thereof. Among these, at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium is preferred because it is commonly available and easy to handle, and aluminum is particularly preferred.

[0302] The metal used in the metal vapor deposition layer preferably contains a metal compound such as a metal oxide, a metal carbide, or a metal nitride, and among these metal compounds, a metal oxide is preferred. The content of such a metal compound is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass, of the metal used in the metal vapor deposition layer.

[0303] The metal vapor deposition layer can be identified by analyzing the cross section of the laminate by energy dispersive spectroscopy (EDS).

[0304] [Method for Producing the Present Vapor-Deposited Film] The present vapor-deposited film can be produced by laminating the above-described metal vapor-deposited layer on the above-described substrate film.

[0305] The method for laminating the metal vapor deposition layer on the substrate film is not particularly limited, and any known vapor deposition method may be appropriately adopted, for example, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD method).

[0306] The thickness of the metal vapor deposition layer is usually 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 20 nm. If the thickness of the metal vapor deposition layer is less than 1 nm, the gas barrier property tends to be insufficient, while if the thickness exceeds 100 nm, the effect of improving the gas barrier property cannot be obtained, and the bending resistance and production costs tend to increase.

[0307] The vapor-deposited film thus obtained has excellent surface smoothness of the vapor-deposited surface. The root-mean-square height (Sq) of the vapor-deposited surface of the vapor-deposited film is preferably 0.120 μm or less, more preferably 0.110 μm or less, and even more preferably 0.100 μm or less. The smaller the root-mean-square height (Sq), the smoother the surface, which is preferable. The root-mean-square height (Sq) can be measured using the method specified in ISO 25178, specifically, by the method described in the Examples below.

[0308] The oxygen permeability of this vapor-deposited film at 20°C and 90% RH is 8 cc / m 2 ·day·atm or less, and 7cc / m 2 ·day·atm or less is more preferable, 5 cc / m 2 ·day·atm or less is particularly preferred.

[0309] The vapor-deposited film can be suitably used as a molding for packaging general foods, as well as seasonings such as mayonnaise and dressings, fermented foods such as miso, oily foods such as salad oil, snacks, beverages, cosmetics, pharmaceuticals, etc., as well as packaging materials such as packaging films, or as part of multilayer structures for forming these.

[0310] <Multilayer structure> The multilayer structure is obtained by laminating another layer on the present vapor-deposited film. The other layer to be laminated on the present vapor-deposited film is not particularly limited, and may be a layer formed from a resin composition containing a thermoplastic resin exemplified above as the thermoplastic resin or an adhesive resin exemplified above as the adhesive resin.

[0311] As a method for producing the multilayer structure, various known production methods can be used, such as dry lamination, sand lamination, extrusion lamination, coextrusion lamination, and solution coating.

[0312] <Molded Articles> Cup- or tray-shaped molded articles can be obtained using the vapor-deposited film or the multilayer structure. In this case, a drawing method is typically employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, the multilayer structure can be used to obtain molded articles such as tube- or bottle-shaped multilayer containers (laminate structure) and food containers from a multilayer parison (a hollow tubular preform before blowing). In this case, a blow molding method is typically employed, specifically extrusion blow molding (two-head, mold-moving, parison-shift, rotary, accumulator, horizontal parison, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0313] <<Fifth Aspect>> The fifth aspect includes the following aspects <V-1> to <V-9>. <V-1> A vapor-deposited film including a substrate film having a layer containing a composition containing an EVOH resin, a boron compound, and a titanium compound, and a metal vapor-deposited layer laminated on the substrate film, wherein the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. <V-2> The vapor-deposited film according to <V-1>, wherein the content of the boron compound in terms of boron is 1 to 500 ppm relative to the mass of the composition. <V-3> The vapor-deposited film according to <V-1> or <V-2>, wherein the mass ratio of the content of the boron compound in terms of boron to the metal content of the titanium compound is 1 to 200,000. <V-4> The vapor-deposited film according to any one of <V-1> to <V-3>, wherein the substrate film is a multilayer film further having a layer containing a thermoplastic resin. <V-5> The vapor-deposited film according to any one of <V-1> to <V-4>, wherein the metal in the metal vapor-deposited layer is at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium. <V-6> A multilayer structure comprising the vapor-deposited film according to any one of <V-1> to <V-5>. <V-7> A molded product comprising the vapor-deposited film according to any one of <V-1> to <V-5>. <V-8> A food container comprising the multilayer structure according to <V-6>. <V-9> A method for producing the vapor-deposited film according to any one of <V-1> to <V-5>, comprising a step of laminating an inorganic vapor-deposited layer on the base film.

[0314] The present invention will be described below based on examples of modes for carrying out the fifth aspect, although the present invention is not limited to the embodiments described below.

[0315] <Vapor-deposited film> A vapor-deposited film according to a fifth aspect of the present invention (hereinafter sometimes referred to as "the vapor-deposited film") comprises a substrate film having a layer containing a composition that includes an ethylene-vinyl alcohol copolymer, a boron compound, and a titanium compound, and a vapor-deposited metal layer laminated on the substrate film. Each component will be described below.

[0316] [Base Film] The base film has a layer containing an EVOH resin (hereinafter referred to as an "EVOH layer") The components of the base film will be described below.

[0317] [EVOH Layer] The EVOH layer is formed from a composition containing an EVOH resin (hereinafter, sometimes referred to as "the composition"). The composition will be described below.

[0318] The present composition contains an EVOH resin as a main component, a boron compound, and a specific trace amount of a titanium compound. That is, the base resin of the present composition is an EVOH resin, and the content of the EVOH resin in the present composition is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Each component will be described below.

[0319] (EVOH Resin) The EVOH resin used in the present embodiment is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble thermoplastic resin. The same EVOH resin as that described in the first embodiment can be used.

[0320] (Boron Compound) Examples of the boron compound include boric acid or metal salts thereof, such as sodium borate (sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, and sodium octaborate), potassium borate (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, and potassium octaborate), lithium borate (lithium metaborate, lithium tetraborate, and lithium pentaborate), calcium borate, barium borate (barium orthoborate, barium metaborate, barium diborate, and barium tetraborate), magnesium borate (magnesium orthoborate, magnesium diborate, magnesium metaborate, trimagnesium tetraborate, and pentamagnesium tetraborate), manganese borate (monomer borate), and manganese borate (monomer borate). Examples of the borate include manganese, manganese metaborate, manganese tetraborate, etc.), cobalt borate, zinc borate (zinc tetraborate, zinc metaborate, etc.), cadmium borate (cadmium orthoborate, cadmium tetraborate, etc.), silver borates (silver metaborate, silver tetraborate, etc.), copper borates (cupric borate, copper metaborate, copper tetraborate, etc.), nickel borates (nickel orthoborate, nickel diborate, nickel tetraborate, nickel octaborate, etc.), aluminum potassium borate, ammonium borate (ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate, etc.), lead borates (lead metaborate, lead hexaborate, etc.), bismuth borate, and borate minerals such as borax, kernite, inyoite, cottite, suianite, and seiberite. These may be used alone or in combination of two or more. Among these, borax and boric acid are preferred, with boric acid being particularly preferred.

[0321] The boron compound may be in any form, such as a solid (powder, fine powder, flakes, etc.), semi-solid, liquid, paste, solution, or emulsion (aqueous dispersion), with powder being preferred. When the boron compound is in powder form, the particle size of the boron compound is usually 0.1 to 100 μm, preferably 1 to 75 μm, and particularly preferably 5 to 50 μm.

[0322] The inclusion of an appropriate amount of boron compound in the present composition improves thermal stability, suppresses the occurrence of streaks and microgels, and results in a smooth surface. The content of the boron compound, in terms of boron, is preferably 1 to 500 ppm, more preferably 5 to 400 ppm, even more preferably 10 to 300 ppm, and particularly preferably 50 to 200 ppm, based on the mass of the composition. If the content is too low, the moldability of the composition tends to decrease. If the boron compound content is too high, the thermal stability (the occurrence of streaks and microgels) tends to decrease, resulting in a decrease in surface smoothness. If no boron compound is added or if the boron compound is too low, the moldability of the composition tends to decrease. The boron-equivalent content of the boron compound can be measured, for example, by heating and ashing the present composition, treating the resulting solution with an acid such as hydrochloric acid, adding pure water to the resulting solution, and measuring the volume using an atomic absorption spectrophotometer.

[0323] (Titanium Compound) As the titanium compound, the same titanium compounds as those explained in the first embodiment can be used.

[0324] The content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. It is preferably 0.01 to 1 ppm, more preferably 0.03 to 0.5 ppm, and particularly preferably 0.05 to 0.2 ppm. By setting the content of the titanium compound within this range, the titanium compound fills up minute depressions in the surface of the EVOH film, resulting in excellent surface smoothness. If the content of the titanium compound is too low, the minute depressions will not be filled up, leaving minute irregularities on the surface. If the content is too high, the remaining titanium oxide will appear on the surface, forming protrusions and causing the surface to become rough. The content of the titanium compound in terms of metal is, in other words, the content of elemental titanium.

[0325] Furthermore, by setting the content of the titanium compound within the above range, it is possible to suppress the generation of microgels due to thermal degradation during melt molding, and the film surface tends to have excellent smoothness. If the content of the titanium compound is too low, the effect of suppressing the generation of microgels will decrease, and the surface smoothness will tend to decrease, while if the content is too high, the EVOH resin will be more susceptible to thermal decomposition, and the surface smoothness will tend to decrease due to the generation of microgels.

[0326] The content of the titanium compound in terms of metal can be quantified by weighing out the composition into a platinum crucible, ashing it successively using a burner and an electric furnace, thermally decomposing the ashed material with nitric acid and hydrofluoric acid, treating it with a mixed acid of dilute nitric acid and dilute hydrofluoric acid, and measuring the titanium in the resulting constant-volume solution by ICP mass spectrometry using an ICP mass spectrometer (Agilent 8800, manufactured by Agilent Technologies).

[0327] The mass ratio of the boron-equivalent content of the boron compound to the metal-equivalent content of the titanium compound (metal-equivalent content of titanium compound / boron-equivalent content of boron compound) is preferably 1 to 200,000, more preferably 2 to 15,000, more preferably 5 to 10,000, particularly preferably 30 to 4,000, particularly preferably 50 to 2,000, and most preferably 70 to 900. If the mass ratio is too large, thermal stability tends to decrease, and if it is too small, surface smoothness tends to decrease.

[0328] Normally, when a titanium compound is added to a resin composition containing EVOH resin, it is thought that the titanium ions will cause thermal degradation of the resin composition and the generation of microgels, and therefore it is common technical knowledge for those in the industry to avoid using titanium compounds. However, in this embodiment, contrary to this common technical knowledge, it has been discovered that when a specific trace amount of titanium compound is used, the titanium in the titanium compound coordinates to the double bond in the main chain of the EVOH resin to form a chelate, thereby improving thermal stability, suppressing the generation of microgels due to thermal degradation, and resulting in an EVOH film with excellent surface smoothness.

[0329] Furthermore, EVOH resins become discolored due to thermal degradation. This is thought to be because EVOH resins deteriorate due to heat, generating radicals, which dehydrate hydroxyl groups in the EVOH resin, forming double bonds in the main chain of the EVOH resin. These sites then become reaction initiation sites, further accelerating dehydration and forming conjugated polyene structures in the main chain of the EVOH resin. Furthermore, in the present resin composition, titanium in the specific trace amount of titanium compound is stabilized as a tetravalent ion, and even in trace amounts, it is stabilized by coordinating to the double bonds in the main chain of the EVOH resin to form a chelate, thereby suppressing the formation of polyene structures.

[0330] (Other Thermoplastic Resins) The present composition may contain thermoplastic resins other than EVOH resins within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the present composition, preferably 20% by mass or less, particularly preferably 10% by mass or less, the lower limit being typically 0% by mass). As the other thermoplastic resins, the same ones as those described in the first embodiment above as (other thermoplastic resins) can be used.

[0331] (Other Compounding Agents) The composition may also contain compounding agents generally compounded in EVOH resins (excluding titanium compounds and boron) within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the resin composition, preferably 20% by mass or less, more preferably 10% by mass or less, the lower limit being typically 0% by mass). As the compounding agents, the same compounds as those described in the first aspect above can be used.

[0332] (Method for Producing the Composition) The composition can be produced, for example, by mixing the EVOH resin, boron compound, and titanium compound by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, it is preferable to produce the composition by a method including a step of melt mixing a composition raw material containing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0333] The dry blending method may be, for example, (i) a method in which pelletized EVOH resin, a boron compound, and a titanium compound are dry blended using a tumbler or the like.

[0334] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with a boron compound and a titanium compound, and the resulting dry blend is melt-kneaded; and (iii) a method in which a boron compound and a titanium compound are added to a molten EVOH resin, and the resulting mixture is melt-kneaded.

[0335] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, a boron compound and a titanium compound are blended therein, the resulting mixture is coagulated and molded, and then the resulting mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which a boron compound and a titanium compound are added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production of EVOH resin, the resulting mixture is coagulated and molded, and then the resulting mixture is subjected to solid-liquid separation by known means and dried.

[0336] The impregnation method includes, for example, (vi) a method in which pelletized EVOH resin is contacted with an aqueous solution containing a boron compound and a titanium compound to incorporate the boron compound and titanium compound into the EVOH resin, followed by drying. The aqueous solution containing the titanium compound may be an aqueous solution of a boron compound and a titanium compound, or a solution obtained by immersing a boron compound and a titanium compound in water containing various chemicals to elute titanium ions.

[0337] In the impregnation method, the content of the boron compound (calculated as boron) and the content of the titanium compound (calculated as metal) can be controlled by the concentration of the boron compound and the titanium compound in the aqueous solution in which the EVOH resin is immersed, as well as the immersion temperature, immersion time, etc. The immersion temperature and immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0338] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0339] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0340] The shape of the present composition obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, cubic, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. Furthermore, in the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0341] The water content of the composition before melt molding is usually 0.01 to 0.5% by mass, preferably 0.05 to 0.35% by mass, and particularly preferably 0.1 to 0.3% by mass. Here, "melt molding" before melt molding refers to melting and forming a certain shape, and examples include melting the resin composition and forming it into pellets, or melting the resin composition and forming it into a film.

[0342] The moisture content of the composition is measured and calculated by the following method: The mass (W1) of the composition before drying is weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and then cooled in a desiccator for 30 minutes, after which the mass (W2) is weighed and calculated using the following formula: Moisture content (mass%) = [(W1 - W2) / W1] x 100

[0343] When the composition is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds may be used alone or in combination of two or more. The content of such lubricants in the composition is usually 5% by mass or less, preferably 1% by mass or less. The lower limit is usually 0% by mass.

[0344] The composition thus obtained is prepared into various forms, such as pellets, powder, or liquid, and provided as a molding material for various molded products. In particular, in this embodiment, when the composition is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable. Note that the composition also includes resin compositions obtained by mixing resins other than the EVOH resin used in the composition.

[0345] The substrate film may be, for example, a single-layer film (EVOH layer) formed from the composition of the present invention, or a multi-layer film having at least one EVOH layer.

[0346] [Layer containing thermoplastic resin] The substrate film preferably has a layer containing a thermoplastic resin (hereinafter, sometimes referred to as a "thermoplastic resin layer"). When the substrate film has a thermoplastic resin layer, the mechanical strength and water vapor barrier properties of the vapor-deposited film tend to be further improved. In addition, properties such as heat sealability and mechanical strength can be imparted depending on the type of thermoplastic resin constituting the thermoplastic resin layer.

[0347] As the thermoplastic resin, the same thermoplastic resins as those described in the [Layer containing thermoplastic resin] of the first embodiment can be used.

[0348] The content of the thermoplastic resin in the thermoplastic resin layer is not particularly limited, but preferably the thermoplastic resin is the main component (i.e., the content of the thermoplastic resin contained in the thermoplastic resin layer is 50% by mass or more), more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0349] The thermoplastic resin layer may contain other components besides the thermoplastic resin, such as antiblocking agents, processing aids, resins other than thermoplastic resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, UV absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0350] [Layer Containing Adhesive Resin] The substrate film may have a layer containing an adhesive resin (hereinafter, sometimes referred to as an "adhesive resin layer"). When the substrate film has an adhesive resin layer, the appearance properties (film surface) of the vapor-deposited film tend to be better.

[0351] The adhesive resin may be the same as the adhesive resin described in the [Layer containing adhesive resin] in the first embodiment.

[0352] The content of the adhesive resin in the adhesive resin layer is not particularly limited, but it is preferable that the adhesive resin be the main component (i.e., the content of the adhesive resin contained in the adhesive resin layer is 50% by mass or more). In particular, the content of the adhesive resin is more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0353] The adhesive resin layer may contain other components other than the adhesive resin, such as antiblocking agents, processing aids, resins other than adhesive resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0354] [Method for Producing Substrate Film] The substrate film can usually be produced by extruding the composition through a die, forming it into a film, and stretching it as needed. When the substrate film has a thermoplastic resin layer or an adhesive resin layer, the raw material compositions forming the EVOH layer, the thermoplastic resin layer, and the adhesive resin layer are extruded through separate dies or a common die to form a film by conventional co-extrusion, and then laminating them, followed by stretching as needed. Examples of the die that can be used include a circular die and a T-die. Examples of the molding method include melt-molding methods such as extrusion molding, blow molding, injection molding, thermoforming, and inflation molding, and solution-molding methods such as cast molding.

[0355] The substrate film may have any other layer configuration as long as it has an EVOH layer, but the other layer configuration is not particularly limited. Since the substrate film has an EVOH layer, it is possible to obtain a vapor-deposited film having excellent transparency. The base film is preferably multilayered. When the EVOH layer is defined as the "(A) layer," the thermoplastic resin layer as the "(B) layer," and the adhesive resin layer as the "(C) layer," examples of the layer configuration include (B) layer / (A) layer, (B) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (B) layer / (A) layer / (B) layer / (A) layer / (B) layer, (B) layer / (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, and the like.

[0356] In the above examples, layers (B) and (C) are exemplified as layers other than layer (A), but layers other than layer (A) are not limited to these. Furthermore, it is preferable that the substrate film does not include a layer formed from a resin composition containing a polyamide resin as a main component (i.e., a resin composition containing 50% by mass or more of polyamide resin). Furthermore, the " / " shown in the above examples means that the layers on both sides of it are directly laminated.

[0357] The substrate film thus obtained is preferably stretched as necessary, and more preferably uniaxially stretched. The stretching ratio in the uniaxially stretched film is preferably 3 times or more, more preferably 4 times or more, and particularly preferably 5 times or more. If the stretching ratio is less than 3 times, thickness unevenness due to stretching tends to occur and gas barrier properties tend to deteriorate. The upper limit of the stretching ratio is preferably 12 times or less, more preferably 10 times or less, and particularly preferably 8 times or less. If the stretching ratio is more than 12 times, the film surface after stretching tends to deteriorate. The use of a uniaxially stretched film has advantages such as economic efficiency, ease of tearing the multilayer structure (making it easy to open the packaging material when used as a packaging material), and improved gas barrier properties.

[0358] The stretching direction of the uniaxially stretched film is not particularly limited and may be either the longitudinal direction (MD direction) or the transverse direction (TD direction), but uniaxial stretching in the longitudinal direction (MD direction) is preferred, and it is particularly preferred that the film is not substantially stretched in a direction different from the stretching direction. The stretched state of the substrate film (unstretched, uniaxially stretched, biaxially stretched, etc.) can be confirmed by using a general method for analyzing the orientation of a resin (for example, wide-angle X-ray scattering (WAXS), etc.).

[0359] The stretching method for the uniaxially stretched film is not particularly limited, but examples thereof include tenter stretching, tubular stretching, and roll stretching. Among these, from the viewpoint of production costs, uniaxial stretching by roll stretching is preferred. Furthermore, when the base film is obtained by inflation molding, roll stretching is preferred.

[0360] The stretching temperature during uniaxial stretching is not particularly limited, but is generally 50 to 130°C.

[0361] The total thickness of the substrate film is not particularly limited and can be appropriately set depending on the application. The thickness of the substrate film is preferably 10 μm or more, more preferably 15 μm or more. When the thickness of the substrate film is 10 μm or more, industrial productivity and mechanical properties tend to be further improved. Furthermore, the thickness of the substrate film is preferably 100 μm or less, more preferably 50 μm or less. When the thickness of the substrate film is 100 μm or less, industrial productivity and economic efficiency tend to be further improved. The thickness of the substrate film, which is a uniaxially stretched film, means the thickness after stretching.

[0362] Furthermore, when the base film is a multilayer film, the thickness of the EVOH layer is preferably 0.5 μm or more, more preferably 0.8 μm or more, and particularly preferably 1 μm or more. When the thickness of the EVOH layer is 0.5 μm or more, the gas barrier property tends to be improved. On the other hand, the thickness of the EVOH layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the EVOH layer is 20 μm or less, the appearance characteristics (film surface) tend to be good. Note that the thickness of the multilayer film, which is a uniaxially stretched film, means the thickness after stretching. When the base film has multiple EVOH layers provided thereon, it is preferable that the total thickness of all EVOH layers is within the above range.

[0363] When the base film is a multilayer film, the ratio of the thickness of the EVOH layer to the total thickness of all layers is preferably 30% or less, more preferably 20% or less, and may be 10% or less, or 5% or less, from the viewpoints of industrial productivity and mechanical properties.

[0364] When the base film has a thermoplastic resin layer, the thickness thereof is preferably 7 to 100 μm, more preferably 10 to 50 μm, from the viewpoints of industrial productivity and mechanical properties. In a base film that is a uniaxially stretched film, the thickness of the thermoplastic resin layer refers to the thickness after stretching. When the base film has multiple thermoplastic resin layers, the total thickness of all the thermoplastic resin layers is preferably within the above range.

[0365] When the substrate film has an adhesive resin layer, the thickness thereof is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, from the viewpoints of industrial productivity and quality stability. In a substrate film that is a uniaxially stretched film, the thickness of the adhesive resin layer refers to the thickness after stretching. When the substrate film has multiple adhesive resin layers, the total thickness of all the adhesive resin layers is preferably within the above range.

[0366] The internal haze value of the substrate film is preferably less than 0.4%, more preferably 0.3% or less, even more preferably 0.2% or less, and particularly preferably 0%. Such measurement can be performed using a substrate film having a thickness of 33 μm and a haze meter in accordance with ASTM D1003.

[0367] [Metal Vapor Deposited Layer] The metal vapor deposition layer laminated on the base film is obtained by vapor depositing a single metal or an alloy of two or more metals. From the viewpoint of gas barrier properties, the metal vapor deposition layer is preferably laminated on the EVOH layer of the base film.

[0368] Examples of metals used in the metal vapor deposition layer include those classified as aluminum group elements (aluminum, gallium, indium, etc.), tin group elements (titanium, zirconium, tin, hafnium, etc.), noble metals (copper, silver, gold, etc.), chromium group elements (chromium, molybdenum, tungsten, etc.), and iron group elements (iron, cobalt, nickel, etc.), as well as alloys thereof. Among these, at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium is preferred because it is commonly available and easy to handle, and aluminum is particularly preferred.

[0369] The metal used in the metal vapor deposition layer preferably contains a metal compound such as a metal oxide, a metal carbide, or a metal nitride, and among these metal compounds, a metal oxide is preferred. The content of such a metal compound is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass, of the metal used in the metal vapor deposition layer.

[0370] The metal vapor deposition layer can be identified by analyzing the cross section of the laminate by energy dispersive spectroscopy (EDS).

[0371] [Method for Producing the Present Vapor-Deposited Film] The present vapor-deposited film can be produced by laminating the above-described metal vapor-deposited layer on the above-described substrate film.

[0372] The method for laminating the metal vapor deposition layer on the substrate film is not particularly limited, and any known vapor deposition method may be appropriately adopted, for example, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD method).

[0373] The thickness of the metal vapor deposition layer is usually 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 20 nm. If the thickness of the metal vapor deposition layer is less than 1 nm, the gas barrier property tends to be insufficient, while if the thickness exceeds 100 nm, the effect of improving the gas barrier property cannot be obtained, and the bending resistance and production costs tend to increase.

[0374] The vapor-deposited film thus obtained has excellent surface smoothness of the vapor-deposited surface. The root-mean-square height (Sq) of the vapor-deposited surface of the vapor-deposited film is preferably 0.85 μm or less, more preferably 0.80 μm or less, and even more preferably 0.75 μm or less. The smaller the root-mean-square height (Sq), the smoother the surface, which is preferable. The root-mean-square height (Sq) can be measured using the method specified in ISO 25178, specifically, by the method described in the Examples below.

[0375] The maximum height (Sz) of the vapor-deposited surface of the vapor-deposited film is preferably 1.1 μm or less, more preferably 1.0 μm or less, and even more preferably 0.9 μm or less. A smaller maximum height (Sz) indicates a smoother surface, which is preferable. The maximum height (Sz) can be measured by the method described in the Examples below. In this specification, the maximum height (Sz) refers to the distance from the highest point to the lowest point on the surface of the vapor-deposited film.

[0376] The oxygen permeability of this vapor-deposited film at 20°C and 90% RH is 8 cc / m 2 ·day·atm or less, and 7cc / m 2 ·day·atm or less is more preferable, 5 cc / m 2 ·day·atm or less is particularly preferred.

[0377] The vapor-deposited film can be suitably used as a molding for packaging general foods, as well as seasonings such as mayonnaise and dressings, fermented foods such as miso, oily foods such as salad oil, snacks, beverages, cosmetics, pharmaceuticals, etc., as well as packaging materials such as packaging films, or as part of multilayer structures for forming these.

[0378] <Multilayer structure> The multilayer structure is obtained by laminating another layer on the present vapor-deposited film. The other layer to be laminated on the present vapor-deposited film is not particularly limited, and may be a layer formed from a resin composition containing a thermoplastic resin exemplified above as the thermoplastic resin or an adhesive resin exemplified above as the adhesive resin.

[0379] As a method for producing the multilayer structure, various known production methods can be used, such as dry lamination, sand lamination, extrusion lamination, coextrusion lamination, and solution coating.

[0380] <Molded Articles> Cup- or tray-shaped molded articles can be obtained using the vapor-deposited film or the multilayer structure. In this case, a drawing method is typically employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, the multilayer structure can be used to obtain molded articles such as tube- or bottle-shaped multilayer containers (laminate structure) and food containers from a multilayer parison (a hollow tubular preform before blowing). In this case, a blow molding method is typically employed, specifically extrusion blow molding (two-head, mold-moving, parison-shift, rotary, accumulator, horizontal parison, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0381] <<Sixth Aspect>> The sixth aspect includes the following aspects <VI-1> to <VI-8>. <VI-1> A vapor-deposited film including a substrate film containing an EVOH resin and an ethylene-vinyl alcohol copolymer composition containing a titanium compound, and a metal vapor-deposited layer laminated on the substrate film, wherein the moisture content of the composition before melt-forming is 1% by mass or less, and the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm, relative to the mass of the composition. <VI-2> The vapor-deposited film according to <VI-1>, wherein the moisture content of the composition before melt-forming is 0.12% by mass or more. <VI-3> The vapor-deposited film according to <v1> or <VI-2>, wherein the substrate film is a multilayer film further comprising a layer containing a thermoplastic resin. <VI-4> The vapor-deposited film according to any one of <VI-1> to <VI-3>, wherein the metal of the metal vapor-deposited layer is at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium. <VI-5> A multilayer structure comprising the vapor-deposited film according to any one of <VI-1> to <VI-4>. <VI-6> A molded article comprising the vapor-deposited film according to any one of <VI-1> to <VI-4>. <VI-7> A food container comprising the multilayer structure according to <VI-5>. <VI-8> A method for producing the vapor-deposited film according to any one of <VI-1> to <VI-4>, comprising a step of laminating an inorganic vapor-deposited layer on the base film.

[0382] The present invention will be described below based on examples of modes for carrying out the sixth aspect, although the present invention is not limited to the embodiments described below.

[0383] <Vapor-deposited film> A vapor-deposited film according to a sixth aspect of the present invention (hereinafter sometimes referred to as "the present vapor-deposited film") is a vapor-deposited film comprising a substrate film having a layer containing a composition containing an ethylene-vinyl alcohol copolymer and a titanium compound, and a vapor-deposited metal layer laminated on the substrate film, wherein the moisture content of the composition before melt molding is not more than a specific amount. Each component will be described below.

[0384] [Base Film] The base film has a layer containing an EVOH resin (hereinafter referred to as an "EVOH layer") The components of the base film will be described below.

[0385] [EVOH Layer] The EVOH layer is formed from a composition containing an EVOH resin (hereinafter, sometimes referred to as "the composition"). The composition will be described below.

[0386] The present composition contains an EVOH resin as a main component and a specific trace amount of a titanium compound. That is, the base resin of the present composition is an EVOH resin, and the content of the EVOH resin in the present composition is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Each component will be described below.

[0387] (EVOH Resin) The EVOH resin used in the present embodiment is a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is a water-insoluble thermoplastic resin. The same EVOH resin as that described in the first embodiment can be used.

[0388] (Titanium Compound) Examples of the titanium compound include inorganic titanium compounds and organic titanium compounds. The titanium compounds may be used alone or in combination of two or more. Among these, inorganic titanium compounds are preferred.

[0389] As the inorganic titanium compound, the same titanium compounds as those explained in the first embodiment can be used.

[0390] The content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm relative to the mass of the composition. It is preferably 0.01 to 1 ppm, more preferably 0.03 to 0.5 ppm, and particularly preferably 0.05 to 0.2 ppm. By setting the content of the titanium compound within this range, the titanium compound fills up minute depressions in the surface of the EVOH film, resulting in excellent surface smoothness. If the content of the titanium compound is too low, the minute depressions will not be filled up, leaving minute irregularities on the surface. If the content is too high, the remaining titanium oxide will appear on the surface, forming protrusions and causing the surface to become rough. The content of the titanium compound in terms of metal is, in other words, the content of elemental titanium.

[0391] Furthermore, by setting the content of the titanium compound within the above range, it is possible to suppress the generation of microgels due to thermal degradation during melt molding, and the film surface tends to have excellent smoothness. If the content of the titanium compound is too low, the effect of suppressing the generation of microgels will decrease, and the surface smoothness will tend to decrease, while if the content is too high, the EVOH resin will be more susceptible to thermal decomposition, and the surface smoothness will tend to decrease due to the generation of microgels.

[0392] The content of the titanium compound in terms of metal can be quantified by weighing out the composition into a platinum crucible, ashing it successively using a burner and an electric furnace, thermally decomposing the ashed material with nitric acid and hydrofluoric acid, treating it with a mixed acid of dilute nitric acid and dilute hydrofluoric acid, and measuring the titanium in the resulting constant-volume solution by ICP mass spectrometry using an ICP mass spectrometer (Agilent 8800, manufactured by Agilent Technologies).

[0393] Normally, when a titanium compound is added to a resin composition containing EVOH resin, it is thought that the titanium ions will cause thermal degradation of the resin composition and the generation of microgels, and therefore it is common technical knowledge for those in the industry to avoid using titanium compounds. However, in this embodiment, contrary to this common technical knowledge, it has been discovered that when a specific trace amount of titanium compound is used, the titanium in the titanium compound coordinates to the double bond in the main chain of the EVOH resin to form a chelate, thereby improving thermal stability, suppressing the generation of microgels due to thermal degradation, and resulting in an EVOH film with excellent surface smoothness.

[0394] Furthermore, EVOH resins become discolored due to thermal degradation. This is thought to be because EVOH resins deteriorate due to heat, generating radicals, which dehydrate hydroxyl groups in the EVOH resin, forming double bonds in the main chain of the EVOH resin. These sites then become reaction initiation sites, further accelerating dehydration and forming conjugated polyene structures in the main chain of the EVOH resin. Furthermore, in the present resin composition, titanium in the specific trace amount of titanium compound is stabilized as a tetravalent ion, and even in trace amounts, it is stabilized by coordinating to the double bonds in the main chain of the EVOH resin to form a chelate, thereby suppressing the formation of polyene structures.

[0395] (Other Thermoplastic Resins) The present composition may contain thermoplastic resins other than EVOH resins within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the present composition, preferably 20% by mass or less, particularly preferably 10% by mass or less, the lower limit being typically 0% by mass). As the other thermoplastic resins, the same ones as those described in the first embodiment above as (other thermoplastic resins) can be used.

[0396] (Other Compounding Agents) The composition may also contain compounding agents (excluding titanium compounds) that are generally compounded in EVOH resins, within a range that does not impair the effects of the present invention (for example, typically 30% by mass or less of the resin composition, preferably 20% by mass or less, more preferably 10% by mass or less, the lower limit being typically 0% by mass). As the compounding agents, the same compounds as those described in the first aspect above can be used.

[0397] (Method for Producing the Composition) The composition can be produced, for example, by mixing the EVOH resin and the titanium compound by a known method such as a dry blending method, a melt mixing method, a solution mixing method, an impregnation method, etc. Among these, it is preferable to produce the composition by a method including a step of melt mixing the composition raw materials containing the EVOH resin and the titanium compound. Furthermore, these production methods can be used in any combination.

[0398] The dry blending method may be, for example, (i) a method in which a pelletized EVOH resin and a titanium compound are dry blended using a tumbler or the like.

[0399] Examples of the melt-mixing method include (ii) a method in which a pellet-shaped EVOH resin is dry-blended with a titanium compound, and the resulting dry blend is melt-kneaded; and (iii) a method in which a titanium compound is added to a molten EVOH resin, and the resulting mixture is melt-kneaded.

[0400] Examples of the solution mixing method include (iv) a method in which a solution is prepared using a commercially available EVOH resin, a titanium compound is blended therein, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried; and (v) a method in which a titanium compound is added to an ethylene-vinyl ester copolymer solution before saponification or a homogeneous solution of EVOH resin (such as a water / alcohol solution) during the production process of EVOH resin, the mixture is coagulated and molded, and then the mixture is subjected to solid-liquid separation by known means and dried.

[0401] The impregnation method includes, for example, (vi) a method in which pellets of EVOH resin are brought into contact with an aqueous solution containing a titanium compound to incorporate the titanium compound into the EVOH resin, followed by drying. The aqueous solution containing a titanium compound may be an aqueous solution of a titanium compound or a titanium compound immersed in water containing various chemicals to elute titanium ions.

[0402] In the impregnation method, the content of the titanium compound (in terms of metal) can be controlled by the concentration of the titanium compound in the aqueous solution in which the EVOH resin is immersed, the immersion temperature, the immersion time, etc. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40°C, preferably 20 to 35°C.

[0403] As the drying method in each of the above-mentioned production methods, various drying methods can be used, and either static drying or fluidized drying may be used, or these may be used in combination.

[0404] As described above, in this embodiment, the above-mentioned different methods can be combined. Among them, the melt mixing method is preferred, and method (ii) is particularly preferred, in terms of productivity and the fact that a resin composition with more pronounced effects of the present invention can be obtained. Furthermore, when using the other thermoplastic resins and other compounding agents, they may be compounded by a conventional method according to the above-mentioned manufacturing method.

[0405] The shape of the present composition obtained by each of the above-mentioned production methods may be any shape, but is preferably pellets. The pellets may be, for example, spherical, oval, cylindrical, cubic, or rectangular, but are typically oval or cylindrical. From the viewpoint of convenience when subsequently used as a molding material, the size of the pellets is such that, in the case of an oval shape, the minor axis is typically 1 to 10 mm, preferably 2 to 6 mm, and more preferably 2.5 to 5.5 mm, and the major axis is typically 1.5 to 30 mm, preferably 3 to 20 mm, and more preferably 3.5 to 10 mm. Furthermore, in the case of a cylindrical shape, the diameter of the base is typically 1 to 6 mm, preferably 2 to 5 mm, and the length is typically 1 to 6 mm, preferably 2 to 5 mm. The shape and size of the pelletized EVOH resin used in each of the above-mentioned production methods are also preferably similar.

[0406] The water content of the present composition before melt molding is 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.7% by mass or less, even more preferably 0.5% by mass or less, particularly preferably 0.4% by mass or less, and especially preferably 0.3% by mass. On the other hand, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 0.12% by mass or more, and especially preferably 0.15% by mass or more. That is, it is preferably 0.01 to 0.8% by mass, more preferably 0.05 to 0.7% by mass, even more preferably 0.1 to 0.5% by mass, particularly preferably 0.12 to 0.4% by mass, and especially preferably 0.15 to 0.3% by mass. The present composition contains a specific amount of titanium compound, and by setting the water content within a specific range, the surface smoothness is improved. If the water content is too high, the thermal stability of the composition at high temperatures will be reduced due to the thermal conductivity of the water molecules themselves. On the other hand, if the water content is too low, the long-run properties of the composition will tend to be reduced. Here, the term "melt molding" before melt molding refers to melting and forming a certain shape, and examples thereof include melting a resin composition and forming it into pellets, or melting a resin composition and forming it into a film.

[0407] The moisture content of the composition is measured and calculated by the following method: The mass (W1) of the composition before drying is weighed on an electronic balance, dried in a hot air dryer at 150°C for 5 hours, and then cooled in a desiccator for 30 minutes, after which the mass (W2) is weighed and calculated using the following formula: Moisture content (mass%) = [(W1 - W2) / W1] x 100

[0408] Examples of methods for adjusting the moisture content of the composition include (1) increasing the drying temperature, (2) lengthening the drying time, (3) adjusting the humidity of the drying gas to a low level, and (4) spraying water in the aforementioned method for producing the composition. In the present invention, these methods can be used alone or in combination to adjust the moisture content of the resin composition to a specific range. Among these, method (4) of spraying water is preferred.

[0409] When the composition is in the form of pellets, it is also preferable to apply a known lubricant to the surface of the pellets in order to stabilize the feedability during melt molding. Examples of lubricants include higher fatty acids having 12 or more carbon atoms (e.g., lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl esters, isopropyl esters, butyl esters, octyl esters of higher fatty acids, etc.), higher fatty acid amides (e.g., saturated higher fatty acid amides such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc.; unsaturated higher fatty acid amides such as oleic acid amide, erucic acid amide, etc.; bis-higher fatty acid amides such as ethylene bisstearic acid amide, ethylene bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, etc.), low-molecular-weight polyolefins (e.g., low-molecular-weight polyethylene or low-molecular-weight polypropylene having a molecular weight of about 500 to 10,000, or acid-modified products thereof), higher alcohols having 6 or more carbon atoms, ester oligomers, and fluorinated ethylene resins. These compounds may be used alone or in combination of two or more. The content of such lubricants in the composition is usually 5% by mass or less, preferably 1% by mass or less. The lower limit is usually 0% by mass.

[0410] The composition thus obtained is prepared into various forms, such as pellets, powder, or liquid, and provided as a molding material for various molded products. In particular, in this embodiment, when the composition is provided as a material for melt molding, the effects of the present invention tend to be more efficiently obtained, which is preferable. Note that the composition also includes resin compositions obtained by mixing resins other than the EVOH resin used in the composition.

[0411] The substrate film may be, for example, a single-layer film (EVOH layer) formed from the composition of the present invention, or a multi-layer film having at least one EVOH layer.

[0412] [Layer containing thermoplastic resin] The substrate film preferably has a layer containing a thermoplastic resin (hereinafter, sometimes referred to as a "thermoplastic resin layer"). When the substrate film has a thermoplastic resin layer, the mechanical strength and water vapor barrier properties of the vapor-deposited film tend to be further improved. In addition, properties such as heat sealability and mechanical strength can be imparted depending on the type of thermoplastic resin constituting the thermoplastic resin layer.

[0413] As the thermoplastic resin, the same thermoplastic resins as those described in the [Layer containing thermoplastic resin] of the first embodiment can be used.

[0414] The content of the thermoplastic resin in the thermoplastic resin layer is not particularly limited, but preferably the thermoplastic resin is the main component (i.e., the content of the thermoplastic resin contained in the thermoplastic resin layer is 50% by mass or more), more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0415] The thermoplastic resin layer may contain other components besides the thermoplastic resin, such as antiblocking agents, processing aids, resins other than thermoplastic resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, UV absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0416] [Layer Containing Adhesive Resin] The substrate film may have a layer containing an adhesive resin (hereinafter, sometimes referred to as an "adhesive resin layer"). When the substrate film has an adhesive resin layer, the appearance properties (film surface) of the vapor-deposited film tend to be better.

[0417] The adhesive resin may be the same as the adhesive resin described in the [Layer containing adhesive resin] in the first embodiment.

[0418] The content of the adhesive resin in the adhesive resin layer is not particularly limited, but it is preferable that the adhesive resin be the main component (i.e., the content of the adhesive resin contained in the adhesive resin layer is 50% by mass or more). In particular, the content of the adhesive resin is more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass or more.

[0419] The adhesive resin layer may contain other components other than the adhesive resin, such as antiblocking agents, processing aids, resins other than adhesive resins, carboxylic acid compounds, phosphoric acid compounds, boron compounds, metal salts, stabilizers, antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, colorants, fillers, surfactants, desiccants, crosslinking agents, reinforcing agents such as various fibers, etc., within a range that does not impair the effects of the present invention, generally within a range of 20 mass % or less. These may be used alone or in combination of two or more.

[0420] [Method for Producing Substrate Film] The substrate film can usually be produced by extruding the composition through a die, forming it into a film, and stretching it as needed. When the substrate film has a thermoplastic resin layer or an adhesive resin layer, the raw material compositions forming the EVOH layer, the thermoplastic resin layer, and the adhesive resin layer are extruded through separate dies or a common die to form a film by conventional co-extrusion, and then laminating them, followed by stretching as needed. Examples of the die that can be used include a circular die and a T-die. Examples of the molding method include melt-molding methods such as extrusion molding, blow molding, injection molding, thermoforming, and inflation molding, and solution-molding methods such as cast molding.

[0421] The substrate film may have any other layer configuration as long as it has an EVOH layer, but the other layer configuration is not particularly limited. Since the substrate film has an EVOH layer, it is possible to obtain a vapor-deposited film having excellent transparency. The base film is preferably multilayered. When the EVOH layer is defined as the "(A) layer," the thermoplastic resin layer as the "(B) layer," and the adhesive resin layer as the "(C) layer," examples of the layer configuration include (B) layer / (A) layer, (B) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (B) layer, (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (B) layer / (A) layer / (B) layer / (A) layer / (B) layer, (B) layer / (B) layer / (C) layer / (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, (A) layer / (C) layer / (B) layer, (A) layer / (B) layer / (C) layer / (B) layer, and the like.

[0422] In the above examples, layers (B) and (C) are exemplified as layers other than layer (A), but layers other than layer (A) are not limited to these. Furthermore, it is preferable that the substrate film does not include a layer formed from a resin composition containing a polyamide resin as a main component (i.e., a resin composition containing 50% by mass or more of polyamide resin). Furthermore, the " / " shown in the above examples means that the layers on both sides of it are directly laminated.

[0423] The substrate film thus obtained is preferably stretched as necessary, and more preferably uniaxially stretched. The stretching ratio in the uniaxially stretched film is preferably 3 times or more, more preferably 4 times or more, and particularly preferably 5 times or more. If the stretching ratio is less than 3 times, thickness unevenness due to stretching tends to occur and gas barrier properties tend to deteriorate. The upper limit of the stretching ratio is preferably 12 times or less, more preferably 10 times or less, and particularly preferably 8 times or less. If the stretching ratio is more than 12 times, the film surface after stretching tends to deteriorate. The use of a uniaxially stretched film has advantages such as economic efficiency, ease of tearing the multilayer structure (making it easy to open the packaging material when used as a packaging material), and improved gas barrier properties.

[0424] The stretching direction of the uniaxially stretched film is not particularly limited and may be either the longitudinal direction (MD direction) or the transverse direction (TD direction), but uniaxial stretching in the longitudinal direction (MD direction) is preferred, and it is particularly preferred that the film is not substantially stretched in a direction different from the stretching direction. The stretched state of the substrate film (unstretched, uniaxially stretched, biaxially stretched, etc.) can be confirmed by using a general method for analyzing the orientation of a resin (for example, wide-angle X-ray scattering (WAXS), etc.).

[0425] The stretching method for the uniaxially stretched film is not particularly limited, but examples thereof include tenter stretching, tubular stretching, and roll stretching. Among these, from the viewpoint of production costs, uniaxial stretching by roll stretching is preferred. Furthermore, when the base film is obtained by inflation molding, roll stretching is preferred.

[0426] The stretching temperature during uniaxial stretching is not particularly limited, but is generally 50 to 130°C.

[0427] The total thickness of the substrate film is not particularly limited and can be appropriately set depending on the application. The thickness of the substrate film is preferably 10 μm or more, more preferably 15 μm or more. When the thickness of the substrate film is 10 μm or more, industrial productivity and mechanical properties tend to be further improved. Furthermore, the thickness of the substrate film is preferably 100 μm or less, more preferably 50 μm or less. When the thickness of the substrate film is 100 μm or less, industrial productivity and economic efficiency tend to be further improved. The thickness of the substrate film, which is a uniaxially stretched film, means the thickness after stretching.

[0428] Furthermore, when the base film is a multilayer film, the thickness of the EVOH layer is preferably 0.5 μm or more, more preferably 0.8 μm or more, and particularly preferably 1 μm or more. When the thickness of the EVOH layer is 0.5 μm or more, the gas barrier property tends to be improved. On the other hand, the thickness of the EVOH layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. When the thickness of the EVOH layer is 20 μm or less, the appearance characteristics (film surface) tend to be good. Note that the thickness of the multilayer film, which is a uniaxially stretched film, means the thickness after stretching. When the base film has multiple EVOH layers provided thereon, it is preferable that the total thickness of all EVOH layers is within the above range.

[0429] When the base film is a multilayer film, the ratio of the thickness of the EVOH layer to the total thickness of all layers is preferably 30% or less, more preferably 20% or less, and may be 10% or less, or 5% or less, from the viewpoints of industrial productivity and mechanical properties.

[0430] When the base film has a thermoplastic resin layer, the thickness thereof is preferably 7 to 100 μm, more preferably 10 to 50 μm, from the viewpoints of industrial productivity and mechanical properties. In a base film that is a uniaxially stretched film, the thickness of the thermoplastic resin layer refers to the thickness after stretching. When the base film has multiple thermoplastic resin layers, the total thickness of all the thermoplastic resin layers is preferably within the above range.

[0431] When the substrate film has an adhesive resin layer, the thickness thereof is preferably 0.5 to 20 μm, more preferably 1 to 10 μm, from the viewpoints of industrial productivity and quality stability. In a substrate film that is a uniaxially stretched film, the thickness of the adhesive resin layer refers to the thickness after stretching. When the substrate film has multiple adhesive resin layers, the total thickness of all the adhesive resin layers is preferably within the above range.

[0432] The internal haze value of the substrate film is preferably less than 0.4%, more preferably 0.3% or less, even more preferably 0.2% or less, and particularly preferably 0%. Such measurement can be performed using a substrate film having a thickness of 33 μm and a haze meter in accordance with ASTM D1003.

[0433] [Metal Vapor Deposited Layer] The metal vapor deposition layer laminated on the base film is obtained by vapor depositing a single metal or an alloy of two or more metals. From the viewpoint of gas barrier properties, the metal vapor deposition layer is preferably laminated on the EVOH layer of the base film.

[0434] Examples of metals used in the metal vapor deposition layer include those classified as aluminum group elements (aluminum, gallium, indium, etc.), tin group elements (titanium, zirconium, tin, hafnium, etc.), noble metals (copper, silver, gold, etc.), chromium group elements (chromium, molybdenum, tungsten, etc.), and iron group elements (iron, cobalt, nickel, etc.), as well as alloys thereof. Among these, at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium is preferred because it is commonly available and easy to handle, and aluminum is particularly preferred.

[0435] The metal used in the metal vapor deposition layer preferably contains a metal compound such as a metal oxide, a metal carbide, or a metal nitride, and among these metal compounds, a metal oxide is preferred. The content of such a metal compound is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass, of the metal used in the metal vapor deposition layer.

[0436] The metal vapor deposition layer can be identified by analyzing the cross section of the laminate by energy dispersive spectroscopy (EDS).

[0437] [Method for Producing the Present Vapor-Deposited Film] The present vapor-deposited film can be produced by laminating the above-described metal vapor-deposited layer on the above-described substrate film.

[0438] The method for laminating the metal vapor deposition layer on the substrate film is not particularly limited, and any known vapor deposition method may be appropriately adopted, for example, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical vapor deposition method (CVD method).

[0439] The thickness of the metal vapor deposition layer is usually 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 20 nm. If the thickness of the metal vapor deposition layer is less than 1 nm, the gas barrier property tends to be insufficient, while if the thickness exceeds 100 nm, the effect of improving the gas barrier property cannot be obtained, and the bending resistance and production costs tend to increase.

[0440] The vapor-deposited film thus obtained has excellent surface smoothness of the vapor-deposited surface. The root-mean-square gradient (Sdq) of the vapor-deposited surface of the vapor-deposited film is preferably 0.18 μm or less, more preferably 0.175 μm or less, and even more preferably 0.17 μm or less. The smaller the root-mean-square gradient (Sdq), the smoother the surface, which is preferable. The root-mean-square height (Sq) and root-mean-square gradient (Sdq) can be measured using the method specified in ISO 25178, specifically, by the method described in the Examples below.

[0441] The oxygen permeability of this vapor-deposited film at 20°C and 90% RH is 8 cc / m 2 ·day·atm or less, and 7cc / m 2 ·day·atm or less is more preferable, 5 cc / m 2 ·day·atm or less is particularly preferred.

[0442] The vapor-deposited film can be suitably used as a molding for packaging general foods, as well as seasonings such as mayonnaise and dressings, fermented foods such as miso, oily foods such as salad oil, snacks, beverages, cosmetics, pharmaceuticals, etc., as well as packaging materials such as packaging films, or as part of multilayer structures for forming these.

[0443] <Multilayer structure> The multilayer structure is obtained by laminating another layer on the present vapor-deposited film. The other layer to be laminated on the present vapor-deposited film is not particularly limited, and may be a layer formed from a resin composition containing a thermoplastic resin exemplified above as the thermoplastic resin or an adhesive resin exemplified above as the adhesive resin.

[0444] As a method for producing the multilayer structure, various known production methods can be used, such as dry lamination, sand lamination, extrusion lamination, coextrusion lamination, and solution coating.

[0445] <Molded Articles> Cup- or tray-shaped molded articles can be obtained using the vapor-deposited film or the multilayer structure. In this case, a drawing method is typically employed, specifically vacuum forming, pressure forming, vacuum-pressure forming, plug-assisted vacuum-pressure forming, etc. Furthermore, the multilayer structure can be used to obtain molded articles such as tube- or bottle-shaped multilayer containers (laminate structure) and food containers from a multilayer parison (a hollow tubular preform before blowing). In this case, a blow molding method is typically employed, specifically extrusion blow molding (two-head, mold-moving, parison-shift, rotary, accumulator, horizontal parison, etc.), cold parison blow molding, injection blow molding, and biaxial stretch blow molding (extrusion-type cold parison biaxial stretch blow molding, injection-type cold parison biaxial stretch blow molding, injection-molding in-line biaxial stretch blow molding, etc.). The resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making, deep drawing, box processing, tube processing, splitting processing, etc. as required.

[0446] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. In the examples, "parts" and "%" are based on mass.

[0447] <<First Aspect>>

[0448] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. In the examples, "parts" and "%" are based on mass.

[0449] Example I-1 Preparation of Pellets of Composition Pellets of EVOH resin having an ethylene structural unit content of 29 mol% and a saponification degree of 99.6 mol% were used as the EVOH resin. Titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the titanium compound. The titanium oxide was dry-blended with the EVOH resin pellets so that the metal equivalent amount relative to the mass of the composition was 0.1 ppm to obtain a mixture. The mixture was fed into a twin-screw extruder (20 mmφ) equipped with a two-hole die and extruded under the following extrusion conditions. The extruded strands were air-cooled and solidified on a belt conveyor. The solidified strands were then cut to obtain pellets of the composition. (Extrusion Conditions) Extruder set temperatures (°C): C1 / C2 / C3 / C4 / C5 / C6 = 150 / 200 / 210 / 210 / 210 / 210

[0450] [Preparation of Melt-Extruded Monolayer Film] The pellets of the obtained composition were extruded under the following conditions to obtain a melt-extruded monolayer film. (Film Preparation Conditions) Extruder: Plastograph EC-plus manufactured by Brabender Screw: Single screw, 20 mm diameter, full flight Cylinder temperature setting: 190 to 210°C Chill roll temperature setting: 80°C Film thickness: 30 μm

[0451] [Formation of Metal Vapor Deposition Layer] Using a batch-type vapor deposition facility manufactured by Showa Shinku K.K., the above-mentioned monolayer film was used as a substrate film, and a metal vapor deposition layer of aluminum was laminated thereon while the surface temperature of the substrate film was kept at 40°C or lower, to obtain the vapor deposition film of Example I-1.

[0452] Example I-2 A vapor-deposited film was obtained in the same manner as in Example I-1, except that the content of titanium oxide in terms of metal was changed to 1 ppm relative to the mass of the composition.

[0453] Comparative Example I-1 A vapor-deposited film was obtained in the same manner as in Example I-1, except that titanium oxide was not used.

[0454] Comparative Example I-2 A vapor-deposited film was obtained in the same manner as in Example I-1, except that the content of titanium oxide in terms of metal was changed to 10 ppm based on the mass of the composition.

[0455] Comparative Example I-3: Pellets of EVOH resin having an ethylene structural unit content of 29 mol% and a saponification degree of 99.7 mol% were used as the EVOH resin. Furthermore, zinc oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the zinc compound. The zinc oxide was dry-blended with the EVOH resin pellets so that the metal equivalent amount relative to the mass of the resin composition was 0.1 ppm, thereby obtaining a mixture. Using this mixture, a vapor-deposited film was obtained in the same manner as in Example I-1.

[0456] The surface smoothness of the deposited films of Examples I-1 and I-2 and Comparative Examples I-1 to I-3 obtained in this manner was measured as follows, and the measurement results are shown in Table I-1 below.

[0457] [Surface Smoothness] The surface of the vapor-deposited film on the side of the metal vapor-deposited layer (vapor-deposited surface) was observed using a laser microscope (Olympus, LEXTOLS5000) under the following conditions: Light source: 405 nm wavelength light source Objective lens: 100x magnification Optical zoom: 1.0x Image area: 129 μm × 129 μm Resolution: 1024 × 1024 pixels The root mean square height (Sq) of the vapor-deposited surface was measured from any point on the vapor-deposited surface using the method of ISO 25178. The smaller the root mean square height (Sq), the smoother the surface.

[0458]

[0459] The results shown in Table I-1 above indicate that the vapor-deposited films of Examples I-1 and I-2, which contained a specific trace amount of titanium compound, had small root-mean-square heights (Sq) and smooth vapor-deposited surfaces. On the other hand, the vapor-deposited films of Comparative Examples I-1 and I-3, which contained no titanium compound, and Comparative Example I-2, which contained a titanium compound in excess of the specific range, had large root-mean-square heights (Sq), indicating that the vapor-deposited surfaces were not smooth.

[0460] Furthermore, even when the substrate film constituting the vapor-deposited films of Examples I-1 and I-2 is a multilayer film obtained by co-extruding the composition and a thermoplastic resin (such as a polyethylene resin) instead of the monolayer film, the effect of excellent surface smoothness of the vapor-deposited surface can be obtained. Furthermore, the effect of excellent surface smoothness of the vapor-deposited surface can also be obtained in multilayer structures, molded articles, and food containers formed using the vapor-deposited films of Examples I-1 and I-2.

[0461] <<Second Aspect>> <Example II-1> [Preparation of Pellets of Composition] Pellets of EVOH resin having an ethylene structural unit content of 29 mol% and a saponification degree of 99.6 mol% were used as the EVOH resin. Furthermore, ethylene bisstearamide (Alflo H50-FP, manufactured by NOF Corporation) was used as the lubricant, and titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the titanium compound. The EVOH resin pellets were dry-blended with the ethylene bisstearamide so that the content was 180 ppm relative to the mass of the composition, and the titanium oxide so that the metal content was 0.1 ppm relative to the mass of the composition, to obtain a mixture. The mixture was fed into a twin-screw extruder (20 mm diameter) equipped with a two-hole die, extruded under the following extrusion conditions, and the extruded strand was air-cooled and solidified on a belt conveyor. The solidified strand was then cut to obtain pellets of the composition. (Extrusion conditions) Extruder set temperatures (°C): C1 / C2 / C3 / C4 / C5 / C6 = 150 / 200 / 210 / 210 / 210 / 210

[0462] [Preparation of Melt-Extruded Monolayer Film] The pellets of the obtained composition were extruded under the following conditions to obtain a melt-extruded monolayer film. (Film Preparation Conditions) Extruder: Plastograph EC-plus manufactured by Brabender Screw: Single screw, 20 mm diameter, full flight Cylinder temperature setting: 190 to 210°C Chill roll temperature setting: 80°C Film thickness: 30 μm

[0463] [Formation of Metal Vapor Deposition Layer] Using a batch-type vapor deposition facility manufactured by Showa Shinku K.K., the above-mentioned monolayer film was used as a substrate film, and a metal vapor deposition layer of aluminum was laminated thereon while the surface temperature of the substrate film was kept at 40°C or lower, to obtain the vapor deposition film of Example II-1.

[0464] Example II-2 A vapor-deposited film was obtained in the same manner as in Example II-1, except that the content of titanium oxide in terms of metal was changed to 1 ppm relative to the mass of the composition.

[0465] Comparative Example II-1 A vapor-deposited film was obtained in the same manner as in Example II-1, except that titanium oxide was not used.

[0466] Comparative Example II-2 A vapor-deposited film was obtained in the same manner as in Example II-1, except that the content of titanium oxide in terms of metal was changed to 10 ppm based on the mass of the composition.

[0467] The surface smoothness of the deposited films of Examples II-1 and II-2 and Comparative Examples II-1 and II-2 thus obtained was measured as follows, and the measurement results are shown in Table II-1 below.

[0468] [Root-mean-square height (Sq)] and [Arithmetic mean height (Sa)] The metal vapor deposition layer side surface (deposited surface) of the vapor-deposited film was observed using a laser microscope (Olympus, LEXTOLS5000) under the following conditions: Light source: 405 nm wavelength light source Objective lens: 100x magnification Optical zoom: 1.0x Image area: 129 μm × 129 μm Resolution: 1024 × 1024 pixels The root-mean-square height (Sq) and arithmetic mean height (Sa) of the vapor-deposited surface were measured from any point on the vapor-deposited surface using the ISO 25178 method. The smaller the root-mean-square height (Sq), the smoother the surface. The smaller the arithmetic mean height (Sa), the smoother the surface.

[0469]

[0470] The results shown in Table II-1 above indicate that the vapor-deposited films of Examples II-1 and II-2, which contain a specific trace amount of titanium compound, have small root-mean-square heights (Sq) and arithmetic mean heights (Sa), and thus have smooth vapor-deposited surfaces. On the other hand, the vapor-deposited films of Comparative Example II-1, which does not contain a titanium compound, and Comparative Example II-2, which contains a titanium compound in excess of the specific range, have large root-mean-square heights (Sq) and arithmetic mean heights (Sa), and thus do not have smooth vapor-deposited surfaces.

[0471] Furthermore, even when the substrate film constituting the vapor-deposited films of Examples II-1 and II-2 is a multilayer film obtained by co-extruding the composition and a thermoplastic resin (e.g., polyethylene resin) instead of the monolayer film, the effect of excellent surface smoothness of the vapor-deposited surface can be obtained. Furthermore, the effect of excellent surface smoothness of the vapor-deposited surface can also be obtained in multilayer structures, molded articles, and food containers formed using the vapor-deposited films of Examples II-1 and II-2.

[0472] <<Third Aspect>> <Example III-1> [Preparation of Pellets of Composition] Pellets of EVOH resin having an ethylene structural unit content of 29 mol% and a saponification degree of 99.6 mol% were used as the EVOH resin. Sodium acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the alkali metal compound, and titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the titanium compound. The EVOH resin pellets were dry-blended with the sodium acetate so that the metal content was 200 ppm relative to the mass of the composition, and the titanium oxide so that the metal content was 0.1 ppm relative to the mass of the composition, to obtain a mixture. The mixture was fed into a twin-screw extruder (20 mm diameter) equipped with a two-hole die, and extruded under the following extrusion conditions. The extruded strand was air-cooled and solidified on a belt conveyor. The solidified strand was then cut to obtain pellets of the composition. (Extrusion conditions) Extruder set temperatures (°C): C1 / C2 / C3 / C4 / C5 / C6 = 150 / 200 / 210 / 210 / 210 / 210

[0473] [Preparation of Melt-Extruded Monolayer Film] The pellets of the obtained composition were extruded under the following conditions to obtain a melt-extruded monolayer film. (Film Preparation Conditions) Extruder: Plastograph EC-plus manufactured by Brabender Screw: Single screw, 20 mm diameter, full flight Cylinder temperature setting: 190 to 210°C Chill roll temperature setting: 80°C Film thickness: 30 μm

[0474] [Formation of Metal Vapor Deposition Layer] Using a batch-type vapor deposition facility manufactured by Showa Shinku K.K., the above-mentioned monolayer film was used as a substrate film, and a metal vapor deposition layer of aluminum was laminated thereon while the surface temperature of the substrate film was kept at 40°C or lower, to obtain the vapor deposition film of Example III-1.

[0475] Example III-2 A vapor-deposited film was obtained in the same manner as in Example III-1, except that the content of titanium oxide in terms of metal was changed to 1 ppm based on the mass of the composition.

[0476] Comparative Example III-1 A vapor-deposited film was obtained in the same manner as in Example III-1, except that titanium oxide was not used.

[0477] Comparative Example III-2 A vapor-deposited film was obtained in the same manner as in Example III-1, except that the content of titanium oxide in terms of metal was changed to 10 ppm based on the mass of the composition.

[0478] The surface smoothness of the deposited films of Examples III-1 and III-2 and Comparative Examples III-1 and III-2 thus obtained was measured as follows, and the results are shown in Table III-1 below.

[0479] [Surface Smoothness] The surface of the vapor-deposited film on the side of the metal vapor-deposited layer (vapor-deposited surface) was observed using a laser microscope (Olympus, LEXTOLS5000) under the following conditions: Light source: 405 nm wavelength light source Objective lens: 100x magnification Optical zoom: 1.0x Image area: 129 μm × 129 μm Resolution: 1024 × 1024 pixels The root mean square height (Sq) of the vapor-deposited surface was measured from any point on the vapor-deposited surface using the method of ISO 25178. The smaller the root mean square height (Sq), the smoother the surface.

[0480]

[0481] The results shown in Table III-1 above indicate that the vapor-deposited films of Examples III-1 and III-2, which contained a specific trace amount of titanium compound, had small root-mean-square heights (Sq) and smooth vapor-deposited surfaces. On the other hand, the vapor-deposited films of Comparative Example III-1, which contained no titanium compound, and Comparative Example III-2, which contained a titanium compound in excess of the specific range, had large root-mean-square heights (Sq), and thus did not have smooth vapor-deposited surfaces.

[0482] Furthermore, even when the substrate film constituting the vapor-deposited films of Examples III-1 and III-2 is a multilayer film obtained by co-extruding the composition and a thermoplastic resin (e.g., polyethylene resin) instead of the monolayer film, the effect of excellent surface smoothness of the vapor-deposited surface can be obtained. Furthermore, the effect of excellent surface smoothness of the vapor-deposited surface can also be obtained in multilayer structures, molded articles, and food containers formed using the vapor-deposited films of Examples III-1 and III-2.

[0483] <<Fourth Aspect>> <Example IV-1> [Preparation of Pellets of Composition] Pellets of EVOH resin having an ethylene structural unit content of 29 mol% and a saponification degree of 99.6 mol% were used as the EVOH resin. Magnesium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the alkaline earth metal compound, and titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the titanium compound. The EVOH resin pellets were dry-blended with the magnesium oxide so that the magnesium oxide content was 10 ppm, calculated as a metal, relative to the mass of the composition, and the titanium oxide content was 0.1 ppm, calculated as a metal, relative to the mass of the composition, to obtain a mixture. The mixture was fed into a twin-screw extruder (20 mm diameter) equipped with a two-hole die, and extruded under the following extrusion conditions. The extruded strand was air-cooled and solidified on a belt conveyor. The solidified strand was then cut to obtain pellets of the composition. (Extrusion conditions) Extruder set temperatures (°C): C1 / C2 / C3 / C4 / C5 / C6 = 150 / 200 / 210 / 210 / 210 / 210

[0484] [Preparation of Melt-Extruded Monolayer Film] The pellets of the obtained composition were extruded under the following conditions to obtain a melt-extruded monolayer film. (Film Preparation Conditions) Extruder: Plastograph EC-plus manufactured by Brabender Screw: Single screw, 20 mm diameter, full flight Cylinder temperature setting: 190 to 210°C Chill roll temperature setting: 80°C Film thickness: 30 μm

[0485] [Formation of Metal Vapor Deposition Layer] Using a batch-type vapor deposition facility manufactured by Showa Shinku K.K., the above-mentioned monolayer film was used as a substrate film, and a metal vapor deposition layer of aluminum was laminated thereon while the surface temperature of the substrate film was kept at 40°C or lower, to obtain the vapor deposition film of Example IV-1.

[0486] Example IV-2 A vapor-deposited film was obtained in the same manner as in Example IV-1, except that the content of titanium oxide in terms of metal was changed to 1 ppm relative to the mass of the composition.

[0487] Comparative Example IV-1 A vapor-deposited film was obtained in the same manner as in Example IV-1, except that titanium oxide was not used.

[0488] Comparative Example IV-2 A vapor-deposited film was obtained in the same manner as in Example IV-1, except that the content of titanium oxide in terms of metal was changed to 10 ppm based on the mass of the composition.

[0489] The surface smoothness of the deposited films of Examples IV-1 and IV-2 and Comparative Examples IV-1 and IV-2 thus obtained was measured as follows, and the results are shown in Table IV-1 below.

[0490] [Surface Smoothness] The surface of the vapor-deposited film on the side of the metal vapor-deposited layer (vapor-deposited surface) was observed using a laser microscope (Olympus, LEXTOLS5000) under the following conditions: Light source: 405 nm wavelength light source Objective lens: 100x magnification Optical zoom: 1.0x Image area: 129 μm × 129 μm Resolution: 1024 × 1024 pixels The root mean square height (Sq) of the vapor-deposited surface was measured from any point on the vapor-deposited surface using the method of ISO 25178. The smaller the root mean square height (Sq), the smoother the surface.

[0491]

[0492] The results shown in Table IV-1 above indicate that the vapor-deposited films of Examples IV-1 and IV-2, which contained a specific trace amount of titanium compound, had small root-mean-square heights (Sq) and smooth vapor-deposited surfaces. On the other hand, the vapor-deposited films of Comparative Example IV-1, which contained no titanium compound, and Comparative Example IV-2, which contained a titanium compound in excess of the specific range, had large root-mean-square heights (Sq), and therefore did not have smooth vapor-deposited surfaces.

[0493] Furthermore, even when the substrate film constituting the vapor-deposited films of Examples IV-1 and IV-2 is a multilayer film obtained by co-extruding the composition and a thermoplastic resin (e.g., polyethylene resin) instead of the monolayer film, the effect of excellent surface smoothness of the vapor-deposited surface can be obtained. Furthermore, the effect of excellent surface smoothness of the vapor-deposited surface can also be obtained in multilayer structures, molded articles, and food containers formed using the vapor-deposited films of Examples IV-1 and IV-2.

[0494] <<Fifth Aspect>>

[0495] Example V-1 Preparation of Pellets of Composition Pellets of EVOH resin having an ethylene structural unit content of 29 mol% and a saponification degree of 99.6 mol% were used as the EVOH resin. Boric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the boron compound, and titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the titanium compound. The EVOH resin pellets were dry-blended with the boric acid so that the boron content was 100 ppm relative to the mass of the composition, and the titanium oxide was 0.1 ppm relative to the mass of the composition, relative to the mass of the composition, in terms of metal, to obtain a mixture. The mixture was fed into a twin-screw extruder (20 mm diameter) equipped with a two-hole die, and extruded under the following extrusion conditions. The extruded strand was air-cooled and solidified on a belt conveyor. The solidified strand was then cut to obtain pellets of the composition. (Extrusion conditions) Extruder set temperatures (°C): C1 / C2 / C3 / C4 / C5 / C6 = 150 / 200 / 210 / 210 / 210 / 210

[0496] [Preparation of Melt-Extruded Monolayer Film] The pellets of the obtained composition were extruded under the following conditions to obtain a melt-extruded monolayer film. (Film Preparation Conditions) Extruder: Plastograph EC-plus manufactured by Brabender Screw: Single screw, 20 mm diameter, full flight Cylinder temperature setting: 190 to 210°C Chill roll temperature setting: 80°C Film thickness: 30 μm

[0497] [Formation of Metal Vapor Deposition Layer] Using a batch-type vapor deposition facility manufactured by Showa Shinku K.K., the above-mentioned monolayer film was used as a substrate film, and an aluminum metal vapor deposition layer was laminated thereon while the surface temperature of the substrate film was 40°C or lower, to obtain a vapor deposition film of Example V-1.

[0498] Example V-2 A vapor-deposited film was obtained in the same manner as in Example V-1, except that the content of titanium oxide in terms of metal was changed to 1 ppm relative to the mass of the composition.

[0499] Comparative Example V-1 A vapor-deposited film was obtained in the same manner as in Example V-1, except that titanium oxide was not used.

[0500] Comparative Example V-2 A vapor-deposited film was obtained in the same manner as in Example V-1, except that the content of titanium oxide in terms of metal was changed to 10 ppm based on the mass of the composition.

[0501] The surface smoothness of the deposited films of Examples V-1 and V-2 and Comparative Examples V-1 and V-2 thus obtained was measured as follows, and the results are shown in Table V-1 below.

[0502] [Root-mean-square height (Sq)] and [Maximum height (Sz)] The metal vapor deposition layer side surface (deposited surface) of the vapor-deposited film was observed using a laser microscope (Olympus, LEXTOLS5000) under the following conditions: Light source: 405 nm wavelength light source Objective lens: 100x magnification Optical zoom: 1.0x Image area: 129 μm × 129 μm Resolution: 1024 × 1024 pixels The root-mean-square height (Sq) and maximum height (Sz) of the vapor-deposited surface were measured from any point on the vapor-deposited surface using the method of ISO 25178. The smaller the root-mean-square height (Sq), the smoother the surface. The smaller the maximum height (Sz), the smoother the surface.

[0503]

[0504] The results shown in Table V-1 above indicate that the vapor-deposited films of Examples V-1 and V-2, which contained a specific trace amount of titanium compound, had small root-mean-square heights (Sq) and maximum heights (Sz), and thus had smooth vapor-deposited surfaces. On the other hand, the vapor-deposited films of Comparative Example V-1, which contained no titanium compound, and Comparative Example V-2, which contained a titanium compound in excess of the specific range, each had large root-mean-square heights (Sq) and / or maximum heights (Sz), and thus did not have smooth vapor-deposited surfaces.

[0505] Furthermore, even when the substrate film constituting the vapor-deposited films of Examples V-1 and V-2 is a multilayer film obtained by co-extruding the composition and a thermoplastic resin (such as a polyethylene resin) instead of the monolayer film, the effect of excellent surface smoothness of the vapor-deposited surface can be obtained. Furthermore, the effect of excellent surface smoothness of the vapor-deposited surface can also be obtained in multilayer structures, molded articles, and food containers formed using the vapor-deposited films of Examples V-1 and V-2.

[0506] <<Sixth Aspect>>

[0507] Example VI-1 Preparation of Pellets of Composition Pellets of EVOH resin having an ethylene structural unit content of 29 mol% and a saponification degree of 99.6 mol% were used as the EVOH resin. Titanium oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the titanium compound. The EVOH resin pellets were dry-blended with the titanium oxide so that the titanium oxide content, calculated as metal, was 0.1 ppm relative to the mass of the composition, and water was sprayed onto the EVOH resin pellets using a spray bottle to obtain a water content of 0.16%. The composition was fed into a twin-screw extruder (20 mm diameter) equipped with a two-hole die and extruded under the following extrusion conditions. The extruded strands were air-cooled and solidified on a belt conveyor. The solidified strands were then cut to obtain pellets of the composition. (Extrusion Conditions) Extruder set temperatures (°C): C1 / C2 / C3 / C4 / C5 / C6 = 150 / 200 / 210 / 210 / 210 / 210

[0508] [Preparation of Melt-Extruded Monolayer Film] The pellets of the obtained composition were extruded under the following conditions to obtain a melt-extruded monolayer film. (Film Preparation Conditions) Extruder: Plastograph EC-plus manufactured by Brabender Screw: Single screw, 20 mm diameter, full flight Cylinder temperature setting: 190 to 210°C Chill roll temperature setting: 80°C Film thickness: 30 μm

[0509] [Formation of Metal Vapor Deposition Layer] Using a batch-type vapor deposition facility manufactured by Showa Shinku K.K., the above-mentioned monolayer film was used as a substrate film, and a metal vapor deposition layer of aluminum was laminated thereon while the surface temperature of the substrate film was kept at 40°C or lower, to obtain the vapor deposition film of Example VI-1.

[0510] Example VI-2 A vapor-deposited film was obtained in the same manner as in Example VI-1, except that the content of titanium oxide in terms of metal was changed to 1 ppm relative to the mass of the composition.

[0511] Comparative Example VI-1 A vapor-deposited film was obtained in the same manner as in Example VI-1, except that titanium oxide was not used.

[0512] Comparative Example VI-2 A vapor-deposited film was obtained in the same manner as in Example VI-1, except that the content of titanium oxide in terms of metal was changed to 10 ppm based on the mass of the composition.

[0513] Comparative Example VI-3 A vapor-deposited film was obtained in the same manner as in Example VI-1, except that water was sprayed onto the film using an atomizer so that the water content became 1.5%.

[0514] The surface smoothness of the deposited films of Examples VI-1 and VI-2 and Comparative Examples VI-1 to VI-3 obtained in this manner was measured as follows, and the measurement results are shown in Table VI-1 below.

[0515] [Surface Smoothness] The surface of the vapor-deposited film on the side of the metal vapor-deposited layer (vapor-deposited surface) was observed using a laser microscope (Olympus, LEXTOLS5000) under the following conditions: Light source: 405 nm wavelength light source Objective lens: 100x magnification Optical zoom: 1.0x Image area: 129 μm × 129 μm Resolution: 1024 × 1024 pixels The root-mean-square gradient (Sdq) of the vapor-deposited surface was measured from any point on the vapor-deposited surface using the method of ISO 25178. The smaller the root-mean-square gradient (Sdq), the smoother the surface.

[0516]

[0517] The results shown in Table VI-1 above indicate that the vapor-deposited films of Examples VI-1 and VI-2, which contain a specific trace amount of titanium compound, have a small root-mean-square gradient (Sdq) and a smooth vapor-deposited surface. On the other hand, the vapor-deposited films of Comparative Example VI-1, which contains no titanium compound, Comparative Example VI-2, which contains a titanium compound in an amount exceeding the specific range, and Comparative Example VI-3, which has a water content exceeding the specific range, each have a large root-mean-square gradient (Sdq), and therefore do not have a smooth vapor-deposited surface.

[0518] Furthermore, even when the substrate film constituting the vapor-deposited films of Examples VI-1 and VI-2 is a multilayer film obtained by co-extruding the composition and a thermoplastic resin (e.g., polyethylene resin) instead of the monolayer film, the effect of excellent surface smoothness of the vapor-deposited surface can be obtained. Furthermore, the effect of excellent surface smoothness of the vapor-deposited surface can also be obtained in multilayer structures, molded articles, and food containers formed using the vapor-deposited films of Examples VI-1 and VI-2.

[0519] Although the above examples show specific embodiments of the present invention, the examples are merely illustrative and should not be construed as limiting. Various modifications that are obvious to those skilled in the art are intended to fall within the scope of the present invention.

[0520] The vapor-deposited film can be suitably used as a molding for packaging general foods, as well as seasonings such as mayonnaise and dressings, fermented foods such as miso, oily foods such as salad oil, snacks, beverages, cosmetics, pharmaceuticals, etc., as well as packaging materials such as packaging films, or as part of multilayer structures for forming these.

Claims

1. A vapor-deposited film comprising a substrate film having a layer containing a composition containing an ethylene-vinyl alcohol copolymer and a titanium compound, and a metal vapor-deposited layer laminated on the substrate film, in which the content of the titanium compound in terms of metal is 0.001 ppm or more and less than 3 ppm based on the mass of the composition.

2. The vapor-deposited film according to claim 1, wherein said composition further contains at least one selected from the group consisting of a lubricant, an alkali metal compound, an alkaline earth metal compound, and a boron compound.

3. The vapor-deposited film according to claim 1, wherein the moisture content of the composition before melt molding is 1% by mass or less.

4. The vapor-deposited film according to claim 2, wherein the content of the lubricant is 500 ppm or less based on the mass of the composition.

5. The vapor-deposited film according to claim 2 or 4, wherein the mass ratio of the content of said lubricant to the content of said titanium compound calculated as metal is 0.3 to 500,000.

6. The vapor-deposited film according to claim 2, wherein the content of the alkali metal compound in terms of metal is 1 to 1,000 ppm based on the mass of the composition.

7. The vapor-deposited film according to claim 2 or 6, wherein the mass ratio of the metal content of said alkali metal compound to the metal-equivalent content of said titanium compound is 0.2 to 1,000,000.

8. The vapor-deposited film according to claim 2, wherein the content of said alkaline earth metal compound in terms of metal is 0.1 to 800 pm based on the mass of said composition.

9. The vapor-deposited film according to claim 2 or 8, wherein the mass ratio of the content of said alkaline earth metal compound in terms of metal to the content of said titanium compound in terms of metal is 0.03 to 500,000.

10. The vapor-deposited film according to claim 2, wherein the boron compound has a boron content of 1 to 500 ppm based on the mass of the composition.

11. The vapor-deposited film according to claim 2 or 10, wherein the mass ratio of the boron content of said boron compound to the metal content of said titanium compound is 1 to 200,000.

12. The vapor-deposited film according to claim 3, wherein the water content of the composition before melt molding is 0.12% by mass or more.

13. The vapor-deposited film according to any one of claims 1 to 3, wherein the substrate film is a multilayer film further comprising a layer containing a thermoplastic resin.

14. The vapor-deposited film according to any one of claims 1 to 3, wherein the metal of the vapor-deposited metal layer is at least one selected from the group consisting of aluminum, gold, silver, copper, titanium, nickel, chromium, tin, and indium.

15. A multilayer structure comprising the vapor-deposited film according to any one of claims 1 to 3.

16. A molded article comprising the vapor-deposited film according to any one of claims 1 to 3.

17. A food container comprising the multi-layer structure of claim 15.

18. A method for producing the vapor-deposited film according to any one of claims 1 to 3, comprising a step of laminating an inorganic vapor-deposited layer on the substrate film.

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